Sample records for gap semiconductor tio2

  1. Band-engineering of TiO2 as a wide-band gap semiconductor using organic chromophore dyes

    NASA Astrophysics Data System (ADS)

    Wahyuningsih, S.; Kartini, I.; Ramelan, A. H.; Saputri, L. N. M. Z.; Munawaroh, H.

    2017-07-01

    Bond-engineering as applied to semiconductor materials refers to the manipulation of the energy bands in order to control charge transfer processes in a device. When the device in question is a photoelectrochemical cell, the charges affected by drift become the focus of the study. The ideal band gap of semiconductors for enhancement of photocatalyst activity can be lowered to match with visible light absorption and the location of conduction Band (CB) should be raised to meet the reducing capacity. Otherwise, by the addition of the chromofor organic dyes, the wide-band gab can be influences by interacation resulting between TiO2 surface and the dyes. We have done the impruvisation wide-band gap of TiO2 by the addition of organic chromophore dye, and the addition of transition metal dopand. The TiO2 morphology influence the light absorption as well as the surface modification. The organic chromophore dye was syntesized by formation complexes compound of Co(PAR)(SiPA)(PAR)= 4-(2-piridylazoresorcinol), SiPA = Silyl propil amine). The result showed that the chromophore groups adsorbed onto TiO2 surface can increase the visible light absorption of wide-band gab semiconductor. Initial absorption of a chromophore will affect light penetration into the material surfaces. The use of photonic material as a solar cell shows this phenomenon clearly from the IPCE (incident photon to current conversion efficiency) measurement data. Organic chromophore dyes of Co(PAR)(SiPA) exhibited the long wavelength absorption character compared to the N719 dye (from Dyesol).

  2. Band structure engineering of semiconductors for enhanced photoelectrochemical water splitting: The case of TiO2

    NASA Astrophysics Data System (ADS)

    Yin, Wan-Jian; Tang, Houwen; Wei, Su-Huai; Al-Jassim, Mowafak M.; Turner, John; Yan, Yanfa

    2010-07-01

    Here, we propose general strategies for the rational design of semiconductors to simultaneously meet all of the requirements for a high-efficiency, solar-driven photoelectrochemical (PEC) water-splitting device. As a case study, we apply our strategies for engineering the popular semiconductor, anatase TiO2 . Previous attempts to modify known semiconductors such as TiO2 have often focused on a particular individual criterion such as band gap, neglecting the possible detrimental consequence to other important criteria. Density-functional theory calculations reveal that with appropriate donor-acceptor coincorporation alloys with anatase TiO2 hold great potential to satisfy all of the criteria for a viable PEC device. We predict that (Mo, 2N) and (W, 2N) are the best donor-acceptor combinations in the low-alloy concentration regime whereas (Nb, N) and (Ta, N) are the best choice of donor-acceptor pairs in the high-alloy concentration regime.

  3. Increased visible-light photocatalytic activity of TiO2 via band gap manipulation

    NASA Astrophysics Data System (ADS)

    Pennington, Ashley Marie

    Hydrogen gas is a clean burning fuel that has potential applications in stationary and mobile power generation and energy storage, but is commercially produced from non-renewable fossil natural gas. Using renewable biomass as the hydrocarbon feed instead could provide sustainable and carbon-neutral hydrogen. We focus on photocatalytic oxidation and reforming of methanol over modified titanium dioxide (TiO2) nanoparticles to produce hydrogen gas. Methanol is used as a model for biomass sugars. By using a photocatalyst, we aim to circumvent the high energy cost of carrying out endothermic reactions at commercial scale. TiO2 is a semiconductor metal oxide of particular interest in photocatalysis due to its photoactivity under ultraviolet illumination and its stability under catalytic reaction conditions. However, TiO2 primarily absorbs ultraviolet light, with little absorption of visible light. While an effective band gap for absorbance of photons from visible light is 1.7 eV, TiO2 polymorphs rutile and anatase, have band gaps of 3.03 eV and 3.20 eV respectively, which indicate ultraviolet light. As most of incident solar radiation is visible light, we hypothesize that decreasing the band gap of TiO2 will increase the efficiency of TiO2 as a visible-light active photocatalyst. We propose to modify the band gap of TiO2 by manipulating the catalyst structure and composition via metal nanoparticle deposition and heteroatom doping in order to more efficiently utilize solar radiation. Of the metal-modified Degussa P25 TiO2 samples (P25), the copper and nickel modified samples, 1%Cu/P25 and 1%Ni/P25 yielded the lowest band gap of 3.05 eV each. A difference of 0.22 eV from the unmodified P25. Under visible light illumination 1%Ni/P25 and 1%Pt/P25 had the highest conversion of methanol of 9.9% and 9.6%, respectively.

  4. TiO2 film/Cu2O microgrid heterojunction with photocatalytic activity under solar light irradiation.

    PubMed

    Zhang, Junying; Zhu, Hailing; Zheng, Shukai; Pan, Feng; Wang, Tianmin

    2009-10-01

    Coupling a narrow-band-gap semiconductor with TiO(2) is an effective method to produce photocatalysts that work under UV-vis light irradiation. Usually photocatalytic coupled-semiconductors exist mainly as powders, and photocatalytic activity is only favored when a small loading amount of narrow-band-gap semiconductor is used. Here we propose a heavy-loading photocatalyst configuration in which 51% of the surface of the TiO(2) film is covered by a Cu(2)O microgrid. The coupled system shows higher photocatalytic activity under solar light irradiation than TiO(2) and Cu(2)O films. This improved performance is due to the efficient charge transfer between the two phases and the similar opportunity each has to be exposed to irradiation and adsorbates.

  5. n/p-Type changeable semiconductor TiO2 prepared from NTA

    NASA Astrophysics Data System (ADS)

    Li, Qiuye; Wang, Xiaodong; Jin, Zhensheng; Yang, Dagang; Zhang, Shunli; Guo, Xinyong; Yang, Jianjun; Zhang, Zhijun

    2007-10-01

    A novel kind of nano-sized TiO2 (anatase) was obtained by high-temperature (400-700°C) dehydration of nanotube titanic acid (H2Ti2O4(OH)2, NTA). The high-temperature (400-700°C) dehydrated nanotube titanic acids (HD-NTAs) with a unique defect structure exhibited a p-type semiconductor behavior under visible-light irradiation (λ≥420 nm, E photon=2.95 eV), whereas exhibited an n-type semiconductor behavior irradiated with UV light (λ=365 nm, E photon=3.40 eV).

  6. Effect of band gap engineering in anionic-doped TiO2 photocatalyst

    NASA Astrophysics Data System (ADS)

    Samsudin, Emy Marlina; Abd Hamid, Sharifah Bee

    2017-01-01

    A simple yet promising strategy to modify TiO2 band gap was achieved via dopants incorporation which influences the photo-responsiveness of the photocatalyst. The mesoporous TiO2 was successfully mono-doped and co-doped with nitrogen and fluorine dopants. The results indicate that band gap engineering does not necessarily requires oxygen substitution with nitrogen or/and fluorine, but from the formation of additional mid band and Ti3+ impurities states. The formation of oxygen vacancies as a result of modified color centres and Ti3+ ions facilitates solar light absorption and influences the transfer, migration and trapping of the photo-excited charge carriers. The synergy of dopants in co-doped TiO2 shows better optical properties relative to single N and F doped TiO2 with c.a 0.95 eV band gap reduction. Evidenced from XPS, the synergy between N and F in the co-doped TiO2 uplifts the valence band towards the conduction band. However, the photoluminescence data reveals poorer electrons and holes separation as compared to F-doped TiO2. This observation suggests that efficient solar light harvesting was achievable via N and F co-doping, but excessive defects could act as charge carriers trapping sites.

  7. Activities of Combined TiO2 Semiconductor Nanocatalysts Under Solar Light on the Reduction of CO2.

    PubMed

    Liu, Hongfang; Dao, Anh Quang; Fu, Chaoyang

    2016-04-01

    The materials based on TiO2 semiconductors are a promising option for electro-photocatalytic systems working as solar energy low-carbon fuels exchanger. These materials' structures are modified by doping metals and metal oxides, by metal sulfides sensitization, or by graphene supported membrane, enhancing their catalytic activity. The basic phenomenon of CO2 reduction to CH4 on Pd modified TiO2 under UV irradiation could be enhanced by Pd, or RuO2 co-doped TiO2. Sensitization with metal sulfide QDs is effective by moving of photo-excited electron from QDs to TiO2 particles. Based on characteristics of the catalysts various combinations of catalysts are proposed in order to creat catalyst systems with good CO2 reduction efficiency. From this critical review of the CO2 reduction to organic compounds by converting solar light and CO2 to storable fuels it is clear that more studies are still attractive and needed.

  8. Effect on Electron Structure and Magneto-Optic Property of Heavy W-Doped Anatase TiO2.

    PubMed

    Hou, Qingyu; Zhao, Chunwang; Guo, Shaoqiang; Mao, Fei; Zhang, Yue

    2015-01-01

    The spin or nonspin state of electrons in W-doped anatase TiO2 is very difficult to judge experimentally because of characterization method limitations. Hence, the effect on the microscopic mechanism underlying the visible-light effect of W-doped anatase TiO2 through the consideration of electronic spin or no-spin states is still unknown. To solve this problem, we establish supercell models of W-doped anatase TiO2 at different concentrations, followed by geometry optimization and energy calculation based on the first-principle planewave norm conserving pseudo-potential method of the density functional theory. Calculation results showed that under the condition of nonspin the doping concentration of W becomes heavier, the formation energy becomes greater, and doping becomes more difficult. Meanwhile, the total energy increases, the covalent weakens and ionic bonds strengthens, the stability of the W-doped anatase TiO2 decreases, the band gap increases, and the blue-shift becomes more significant with the increase of W doping concentration. However, under the condition of spin, after the band gap correction by the GGA+U method, it is found that the semimetal diluted magnetic semiconductors can be formed by heavy W-doped anatase TiO2. Especially, a conduction electron polarizability of as high as near 100% has been found for the first time in high concentration W-doped anatase TiO2. It will be able to be a promising new type of dilute magnetic semiconductor. And the heavy W-doped anatase TiO2 make the band gap becomes narrower and absorption spectrum red-shift.

  9. Semiconductor-to-metal transition in rutile TiO 2 induced by tensile strain

    DOE PAGES

    Benson, Eric E.; Miller, Elisa M.; Nanayakkara, Sanjini U.; ...

    2017-02-10

    Here, we report the first observation of a reversible, degenerate doping of titanium dioxide with strain, which is referred to as a semiconductor-to-metal transition. Application of tensile strain to a ~50 nm film of rutile TiO 2 thermally grown on a superelastic nitinol (NiTi intermetallic) substrate causes reversible degenerate doping as evidenced by electrochemistry, X-ray photoelectron spectroscopy (XPS), and conducting atomic force microscopy (CAFM). Cyclic voltammetry and impedance measurements show behavior characteristic of a highly doped n-type semiconductor for unstrained TiO 2 transitioning to metallic behavior under tensile strain. The transition reverses when strain is removed. Valence band XPS spectramore » show that samples strained to 5% exhibit metallic-like intensity near the Fermi level. Strain also induces a distinct transition in CAFM current-voltage curves from rectifying (typical of an n-type semiconductor) to ohmic (metal-like) behavior. We propose that strain raises the energy distribution of oxygen vacancies ( n-type dopants) near the conduction band and causes an increase in carrier concentration. As the carrier concentration is increased, the width of the depletion region is reduced, which then permits electron tunneling through the space charge barrier resulting in the observed metallic behavior.« less

  10. Effect on Electron Structure and Magneto-Optic Property of Heavy W-Doped Anatase TiO2

    PubMed Central

    Hou, Qingyu; Zhao, Chunwang; Guo, Shaoqiang; Mao, Fei; Zhang, Yue

    2015-01-01

    The spin or nonspin state of electrons in W-doped anatase TiO2 is very difficult to judge experimentally because of characterization method limitations. Hence, the effect on the microscopic mechanism underlying the visible-light effect of W-doped anatase TiO2 through the consideration of electronic spin or no-spin states is still unknown. To solve this problem, we establish supercell models of W-doped anatase TiO2 at different concentrations, followed by geometry optimization and energy calculation based on the first-principle planewave norm conserving pseudo-potential method of the density functional theory. Calculation results showed that under the condition of nonspin the doping concentration of W becomes heavier, the formation energy becomes greater, and doping becomes more difficult. Meanwhile, the total energy increases, the covalent weakens and ionic bonds strengthens, the stability of the W-doped anatase TiO2 decreases, the band gap increases, and the blue-shift becomes more significant with the increase of W doping concentration. However, under the condition of spin, after the band gap correction by the GGA+U method, it is found that the semimetal diluted magnetic semiconductors can be formed by heavy W-doped anatase TiO2. Especially, a conduction electron polarizability of as high as near 100% has been found for the first time in high concentration W-doped anatase TiO2. It will be able to be a promising new type of dilute magnetic semiconductor. And the heavy W-doped anatase TiO2 make the band gap becomes narrower and absorption spectrum red-shift. PMID:25955308

  11. Properties of TiO2 thin films and a study of the TiO2-GaAs interface

    NASA Technical Reports Server (NTRS)

    Chen, C. Y.; Littlejohn, M. A.

    1977-01-01

    Titanium dioxide (TiO2) films prepared by chemical vapor deposition were investigated in this study for the purpose of the application in the GaAs metal-insulator-semiconductor field-effect transistor. The degree of crystallization increases with the deposition temperature. The current-voltage study, utilizing an Al-TiO2-Al MIM structure, reveals that the d-c conduction through the TiO2 film is dominated by the bulk-limited Poole-Frenkel emission mechanism. The dependence of the resistivity of the TiO2 films on the deposition environment is also shown. The results of the capacitance-voltage study indicate that an inversion layer in an n-type substrate can be achieved in the MIS capacitor if the TiO2 films are deposited at a temperature higher than 275 C. A process of low temperature deposition followed by the pattern definition and a higher temperature annealing is suggested for device fabrications. A model, based on the assumption that the surface state densities are continuously distributed in energy within the forbidden band gap, is proposed to interpret the lack of an inversion layer in the Al-TiO2-GaAs MIS structure with the TiO2 films deposited at 200 C.

  12. Atomically engineered epitaxial anatase TiO 2 metal-semiconductor field-effect transistors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kim, Brian S. Y.; Minohara, Makoto; Hikita, Yasuyuki

    Here, anatase TiO 2 is a promising material for a vast array of electronic, energy, and environmental applications, including photocatalysis, photovoltaics, and sensors. A key requirement for these applications is the ability to modulate its electrical properties without dominant dopant scattering and while maintaining high carrier mobility. Here, we demonstrate the room temperature field-effect modulation of the conducting epitaxial interface between anatase TiO 2 and LaAlO 3 (001), which arises for LaO-terminated LaAlO 3, while the AlO 2-terminated interface is insulating. This approach, together with the metal-semiconductor field-effect transistor geometry, naturally bypasses the gate/channel interface traps, resulting in a highmore » field-effect mobility μ FE of 3.14 cm 2 (V s) –1 approaching 98% of the corresponding Hall mobility μ Hall. Accordingly, the channel conductivity is modulated over 6 orders of magnitude over a gate voltage range of ~4 V.« less

  13. Atomically engineered epitaxial anatase TiO 2 metal-semiconductor field-effect transistors

    DOE PAGES

    Kim, Brian S. Y.; Minohara, Makoto; Hikita, Yasuyuki; ...

    2018-03-26

    Here, anatase TiO 2 is a promising material for a vast array of electronic, energy, and environmental applications, including photocatalysis, photovoltaics, and sensors. A key requirement for these applications is the ability to modulate its electrical properties without dominant dopant scattering and while maintaining high carrier mobility. Here, we demonstrate the room temperature field-effect modulation of the conducting epitaxial interface between anatase TiO 2 and LaAlO 3 (001), which arises for LaO-terminated LaAlO 3, while the AlO 2-terminated interface is insulating. This approach, together with the metal-semiconductor field-effect transistor geometry, naturally bypasses the gate/channel interface traps, resulting in a highmore » field-effect mobility μ FE of 3.14 cm 2 (V s) –1 approaching 98% of the corresponding Hall mobility μ Hall. Accordingly, the channel conductivity is modulated over 6 orders of magnitude over a gate voltage range of ~4 V.« less

  14. Atomically engineered epitaxial anatase TiO2 metal-semiconductor field-effect transistors

    NASA Astrophysics Data System (ADS)

    Kim, Brian S. Y.; Minohara, Makoto; Hikita, Yasuyuki; Bell, Christopher; Hwang, Harold Y.

    2018-03-01

    Anatase TiO2 is a promising material for a vast array of electronic, energy, and environmental applications, including photocatalysis, photovoltaics, and sensors. A key requirement for these applications is the ability to modulate its electrical properties without dominant dopant scattering and while maintaining high carrier mobility. Here, we demonstrate the room temperature field-effect modulation of the conducting epitaxial interface between anatase TiO2 and LaAlO3 (001), which arises for LaO-terminated LaAlO3, while the AlO2-terminated interface is insulating. This approach, together with the metal-semiconductor field-effect transistor geometry, naturally bypasses the gate/channel interface traps, resulting in a high field-effect mobility μ FE of 3.14 cm2 (V s)-1 approaching 98% of the corresponding Hall mobility μ Hall . Accordingly, the channel conductivity is modulated over 6 orders of magnitude over a gate voltage range of ˜4 V.

  15. Effect of particle size on band gap and DC electrical conductivity of TiO2 nanomaterial

    NASA Astrophysics Data System (ADS)

    Avinash, B. S.; Chaturmukha, V. S.; Jayanna, H. S.; Naveen, C. S.; Rajeeva, M. P.; Harish, B. M.; Suresh, S.; Lamani, Ashok R.

    2016-05-01

    Materials reduced to the Nano scale can exhibit different properties compared to what they exhibit on a micro scale, enabling unique applications. When TiO2 is reduced to Nano scale it shows unique properties, of which the electrical aspect is highly important. This paper presents increase in the energy gap and decrease in conductivity with decrease in particle size of pure Nano TiO2 synthesized by hydrolysis and peptization of titanium isopropoxide. Aqueous solution with various pH and peptizing the resultant suspension will form Nano TiO2 at different particle sizes. As the pH of the solution is made acidic reduction in the particle size is observed. And it is confirmed from XRD using Scherer formula and SEM, as prepared samples are studied for UV absorbance, and DC conductivity from room temperature to 400°C. From the tauc plot it was observed, and calculated the energy band gap increases as the particle size decreases and shown TiO2 is direct band gap. From Arrhenius plot clearly we encountered, decrease in the conductivity for the decrease in particle size due to hopping of charge carriers and it is evident that, we can tailor the band gap by varying particle size.

  16. Synthesis and electronic properties of Fe2TiO5 epitaxial thin films

    NASA Astrophysics Data System (ADS)

    Osada, Motoki; Nishio, Kazunori; Hwang, Harold Y.; Hikita, Yasuyuki

    2018-05-01

    We investigate the growth phase diagram of pseudobrookite Fe2TiO5 epitaxial thin films on LaAlO3 (001) substrates using pulsed laser deposition. Control of the oxygen partial pressure and temperature during deposition enabled selective stabilization of (100)- and (230)-oriented films. In this regime, we find an optical gap of 2.1 eV and room temperature resistivity in the range of 20-80 Ω cm, which are significantly lower than α-Fe2O3, making Fe2TiO5 potentially an ideal inexpensive visible-light harvesting semiconductor. These results provide a basis to incorporate Fe2TiO5 in oxide heterostructures for photocatalytic and photoelectrochemical applications.

  17. Structure and Formation Mechanism of Black TiO 2 Nanoparticles

    DOE PAGES

    Tian, Mengkun; Mahjouri-Samani, Masoud; Eres, Gyula; ...

    2015-10-27

    The remarkable properties of black TiO 2 are due to its disordered surface shell surrounding a crystalline core. However, the chemical composition and the atomic and electronic structure of the disordered shell and its relationship to the core remain poorly understood. Using advanced transmission electron microscopy methods, we show that the outermost layer of black TiO 2 nanoparticles consists of a disordered Ti 2O 3 shell. The measurements show a transition region that connects the disordered Ti 2O 3 shell to the perfect rutile core consisting first of four to five monolayers of defective rutile, containing clearly visible Ti interstitialmore » atoms, followed by an ordered reconstruction layer of Ti interstitial atoms. Our data suggest that this reconstructed layer presents a template on which the disordered Ti 2O 3 layers form by interstitial diffusion of Ti ions. In contrast to recent reports that attribute TiO 2 band-gap narrowing to the synergistic action of oxygen vacancies and surface disorder of nonspecific origin, our results point to Ti 2O 3, which is a narrow-band-gap semiconductor. In conclusion, as a stoichiometric compound of the lower oxidation state Ti 3+ it is expected to be a more robust atomic structure than oxygen-deficient TiO 2 for preserving and stabilizing Ti 3+ surface species that are the key to the enhanced photocatalytic activity of black TiO 2.« less

  18. Diluted magnetic semiconductors with narrow band gaps

    NASA Astrophysics Data System (ADS)

    Gu, Bo; Maekawa, Sadamichi

    2016-10-01

    We propose a method to realize diluted magnetic semiconductors (DMSs) with p - and n -type carriers by choosing host semiconductors with a narrow band gap. By employing a combination of the density function theory and quantum Monte Carlo simulation, we demonstrate such semiconductors using Mn-doped BaZn2As2 , which has a band gap of 0.2 eV. In addition, we found a nontoxic DMS Mn-doped BaZn2Sb2 , of which the Curie temperature Tc is predicted to be higher than that of Mn-doped BaZn2As2 , the Tc of which was up to 230 K in a recent experiment.

  19. The effect of carbon nanotubes functionalization on the band-gap energy of TiO2-CNT nanocomposite

    NASA Astrophysics Data System (ADS)

    Shahbazi, Hessam; Shafei, Alireza; Sheibani, Saeed

    2018-01-01

    In this paper the morphology and structure of TiO2-CNT nanocomposite powder obtained by an in situ sol-gel process were investigated. The synthesized nanocomposite powders were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and diffuse reflectance spectroscopy (DRS). The effect of functionalizing of CNT on the properties was studied. XRD results showed amorphous structure before calcination. Also, anatase phase TiO2 was formed after calcination at 400 °C. The SEM results indicate different distributions of TiO2 on CNTs. As a result, well dispersed TiO2 microstructure on the surface of CNTs was observed after functionalizing, while compact and large aggregated particles were found without functionalizing. The average thickness of uniform and well-defined coated TiO2 layer was in the range of 30-40 nm. The DRS results have determined the reflective properties and band gap energies of nanocomposite powders and have shown that functionalizing of CNTs caused the change of band-gap energy from 2.98 to 2.87 eV.

  20. Synthesis and electronic properties of Fe 2TiO 5 epitaxial thin films

    DOE PAGES

    Osada, Motoki; Nishio, Kazunori; Hwang, Harold Y.; ...

    2018-05-02

    Here, we investigate the growth phase diagram of pseudobrookite Fe 2TiO 5 epitaxial thin films on LaAlO 3 (001) substrates using pulsed laser deposition. Control of the oxygen partial pressure and temperature during deposition enabled selective stabilization of (100)- and (230)-oriented films. In this regime, we find an optical gap of 2.1 eV and room temperature resistivity in the range of 20–80 Ω cm, which are significantly lower than α-Fe 2O 3, making Fe 2TiO 5 potentially an ideal inexpensive visible-light harvesting semiconductor. These results provide a basis to incorporate Fe 2TiO 5 in oxide heterostructures for photocatalytic and photoelectrochemicalmore » applications.« less

  1. Controlled synthesis and facets-dependent photocatalysis of TiO2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Roy, Nitish; Park, Yohan; Sohn, Youngku; Pradhan, Debabrata

    2015-04-01

    Titanium dioxide (TiO2) is a wide band gap semiconductor that has been extensively used in several environmental applications including degradation of organic hazardous chemicals, water splitting to generate hydrogen, dye sensitized solar cells, self cleaning agents, and pigments. Herein we demonstrate the synthesis of TiO2 nanocrystals (NCs) with the shapes of ellipsoids, rods, cuboids, and sheets with different exposed facets using a noncorrosive and nontoxic chemical (i.e. diethanolamine) as the shape controlling agent, unlike hydrofluoric acid commonly used. The TiO2 NCs of diverse shapes with different exposed facets were tested for photocatalytic hydroxyl radical (OH•) formation, which determines their photocatalytic behavior and the results were compared with the standard P-25 Degussa. The formation rate of OH• per specific surface area was found to be >6 fold higher for rod-shaped TiO2 NCs than that of commercial Degussa P25 catalyst. The highest photocatalytic activity of rod-shaped TiO2 NCs is ascribed to the unique chemical environment of {010} exposed facets which facilitates the electron/hole separation in presence of {101} facets.

  2. Narrow band gap amorphous silicon semiconductors

    DOEpatents

    Madan, A.; Mahan, A.H.

    1985-01-10

    Disclosed is a narrow band gap amorphous silicon semiconductor comprising an alloy of amorphous silicon and a band gap narrowing element selected from the group consisting of Sn, Ge, and Pb, with an electron donor dopant selected from the group consisting of P, As, Sb, Bi and N. The process for producing the narrow band gap amorphous silicon semiconductor comprises the steps of forming an alloy comprising amorphous silicon and at least one of the aforesaid band gap narrowing elements in amount sufficient to narrow the band gap of the silicon semiconductor alloy below that of amorphous silicon, and also utilizing sufficient amounts of the aforesaid electron donor dopant to maintain the amorphous silicon alloy as an n-type semiconductor.

  3. GW quasiparticle bandgaps of anatase TiO2 starting from DFT + U.

    PubMed

    Patrick, Christopher E; Giustino, Feliciano

    2012-05-23

    We investigate the quasiparticle band structure of anatase TiO(2), a wide gap semiconductor widely employed in photovoltaics and photocatalysis. We obtain GW quasiparticle energies starting from density-functional theory (DFT) calculations including Hubbard U corrections. Using a simple iterative procedure we determine the value of the Hubbard parameter yielding a vanishing quasiparticle correction to the fundamental bandgap of anatase TiO(2). The bandgap (3.3 eV) calculated using this optimal Hubbard parameter is smaller than the value obtained by applying many-body perturbation theory to standard DFT eigenstates and eigenvalues (3.7 eV). We extend our analysis to the rutile polymorph of TiO(2) and reach similar conclusions. Our work highlights the role of the starting non-interacting Hamiltonian in the calculation of GW quasiparticle energies in TiO(2) and suggests an optimal Hubbard parameter for future calculations.

  4. Semiconducting and quartz microbalance (QCM) humidity sensor properties of TiO2 by sol gel calcination method

    NASA Astrophysics Data System (ADS)

    Yakuphanoglu, Fahrettin

    2012-06-01

    Titanium dioxide (TiO2) material was synthesized using the sol gel calcination method. The structural properties of the TiO2 semiconductor were investigated by atomic force microscopy. The electrical conductivity of the TiO2 was measured as a function of temperature and TiO2 exhibits a conductivity of 2.55 × 10-6 S/m at room temperature with activation energy of 104 meV. The electrical conductivity of the TiO2 at room temperature is higher than that of nanocrystalline TiO2 (3 × 10-7 S/m) and TiO2 thin film in air (5 × 10-9 S/m) and in vacuum (8.8 × 10-10 S/m). It was found that the electrical transport mechanism of the TiO2 is controlled by thermally activated mechanism. The optical band gap of the TiO2 powder sample was determined to be 3.17 eV, which is good in agreement with the bulk TiO2 (Eg = 3.2 eV). Up to our knowledge, there is no any reported data about the band gap of TiO2 nanopowder based on the diffused reflectance calculation. Quartz crystal microbalance (QCM) TiO2 humidity sensor was prepared. The sensor indicates a large frequency change with an interaction occurred between TiO2 and humidity molecules. The sensor exhibits a good repeatability when it was exposed to the moist air of 65% RH.

  5. Low temperature RF plasma nitriding of self-organized TiO2 nanotubes for effective bandgap reduction

    NASA Astrophysics Data System (ADS)

    Bonelli, Thiago Scremin; Pereyra, Inés

    2018-06-01

    Titanium dioxide is a widely studied semiconductor material found in many nanostructured forms, presenting very interesting properties for several applications, particularly photocatalysis. TiO2 nanotubes have a high surface-to-volume ratio and functional electronic properties for light harvesting. Despite these manifold advantages, TiO2 photocatalytic activity is limited to UV radiation due to its large band gap. In this work, TiO2 nanotubes produced by electrochemical anodization were submitted to plasma nitriding processes in a PECVD reactor. The plasma parameters were evaluated to find the best conditions for gap reduction, in order to increase their photocatalytic activity. The pressure and RF power density were varied from 0.66 to 2.66 mbar and 0.22 to 3.51 W/cm2 respectively. The best gap reduction, to 2.80 eV, was achieved using a pressure of 1.33 mbar and 1.75 W/cm2 RF power at 320 °C, during a 2-h process. This leads to a 14% reduction in the band gap value and an increase of 25.3% in methylene blue reduction, doubling the range of solar photons absorption from 5 to 10% of the solar spectrum.

  6. The design, fabrication, and photocatalytic utility of nanostructured semiconductors: focus on TiO2-based nanostructures

    PubMed Central

    Banerjee, Arghya Narayan

    2011-01-01

    Recent advances in basic fabrication techniques of TiO2-based nanomaterials such as nanoparticles, nanowires, nanoplatelets, and both physical- and solution-based techniques have been adopted by various research groups around the world. Our research focus has been mainly on various deposition parameters used for fabricating nanostructured materials, including TiO2-organic/inorganic nanocomposite materials. Technically, TiO2 shows relatively high reactivity under ultraviolet light, the energy of which exceeds the band gap of TiO2. The development of photocatalysts exhibiting high reactivity under visible light allows the main part of the solar spectrum to be used. Visible light-activated TiO2 could be prepared by doping or sensitizing. As far as doping of TiO2 is concerned, in obtaining tailored material with improved properties, metal and nonmetal doping has been performed in the context of improved photoactivity. Nonmetal doping seems to be more promising than metal doping. TiO2 represents an effective photocatalyst for water and air purification and for self-cleaning surfaces. Additionally, it can be used as an antibacterial agent because of its strong oxidation activity and superhydrophilicity. Therefore, applications of TiO2 in terms of photocatalytic activities are discussed here. The basic mechanisms of the photoactivities of TiO2 and nanostructures are considered alongside band structure engineering and surface modification in nanostructured TiO2 in the context of doping. The article reviews the basic structural, optical, and electrical properties of TiO2, followed by detailed fabrication techniques of 0-, 1-, and quasi-2-dimensional TiO2 nanomaterials. Applications and future directions of nanostructured TiO2 are considered in the context of various photoinduced phenomena such as hydrogen production, electricity generation via dye-sensitized solar cells, photokilling and self-cleaning effect, photo-oxidation of organic pollutant, wastewater management, and

  7. Role of Fe doping in tuning the band gap of TiO2 for photo-oxidation induced cytotoxicity paradigm

    PubMed Central

    George, Saji; Pokhrel, Suman; Ji, Zhaoxia; Henderson, Bryana L.; Xia, Tian; Li, LinJiang; Zink, Jeffrey I.; Nel, André E.; Mädler, Lutz

    2014-01-01

    UV-Light induced electron-hole (e−/h+) pair generation and free radical production in TiO2 based nanoparticles is a major conceptual paradigm for biological injury. However, to date, this hypothesis has been difficult to experimentally verify due to the high energy of UV light that is intrinsically highly toxic to biological systems. Here, a versatile flame spray pyrolysis (FSP) synthetic process has been exploited to synthesize a library of iron doped (0–10 at wt%) TiO2 nanoparticles. These particles have been tested for photoactivation-mediated cytotoxicity using near-visible light exposure. The reduction in TiO2 band gap energy with incremental levels of Fe loading maintained the nanoparticle crystalline structure in spite of homogeneous Fe distribution (demonstrated by XRD, HRTEM, SAED, EFTEM, and EELS). Photochemical studies showed that band gap energy was reciprocally tuned proportional to the Fe content. The photo-oxidation capability of Fe-doped TiO2 was found to increase during near-visible light exposure. Use of a macrophage cell line to evaluate cytotoxic and ROS production showed increased oxidant injury and cell death in parallel with a decrease in band gap energy. These findings demonstrate the importance of band gap energy in the phototoxic response of the cell to TiO2 nanoparticles and reflect the potential of this material to generate adverse effects in humans and the environment during high intensity light exposure. PMID:21678906

  8. A urea biosensor based on pH-sensitive Sm2TiO5 electrolyte-insulator-semiconductor.

    PubMed

    Pan, Tung-Ming; Huang, Ming-De; Lin, Wan-Ying; Wu, Min-Hsien

    2010-06-11

    A urea biosensor based on pH-sensitive Sm(2)TiO(5) electrolyte-insulator-semiconductor (EIS) has been described. We used X-ray diffraction, Auger electron spectroscopy, and atomic force microscopy to investigate the structural and morphological features of high-k Sm(2)TiO(5) sensing membranes that had been subjected to annealing at different temperatures. The EIS device incorporating a high-k Sm(2)TiO(5) sensing film that had been annealed at 900 degrees C exhibited good sensing characteristics, including a high sensitivity of 60.5 mV/pH (in solutions from pH 2 to 12), a small hysteresis voltage of 2.72 mV (in the pH loop 7-->4-->7-->10-->7), and a low drift rate of 1.15 mV h(-1) (in the buffer solution at pH 7). The Sm(2)TiO(5) EIS device also showed a high selective response towards H(+). This improvement can be attributed to the small number of crystal defects and the large surface roughness. In addition, the urea biosensor based on pH-sensitive EIS incorporating a Sm(2)TiO(5) sensing membrane annealed at 900 degrees C allowed the potentiometric analysis of urea, at concentrations ranging from 0.1 to 32 mM, with a sensitivity of 72.85 mV/purea. Copyright 2010 Elsevier B.V. All rights reserved.

  9. Novel tiO2 nanocatalysts for wastewater purification: tapping energy from the sun.

    PubMed

    Liu, Y; Li, J; Qiu, X; Burda, C

    2006-01-01

    Water treatment using TiO2 semiconductor as a durable heterogeneous photocatalyst has been the focus of environmentalists in recent years. Currently, we developed an inexpensive and highly efficient approach for synthesizing nitrogen-doped TiO2 with lower band-gap energy that can respond to visible light. Doping on the molecular scale led to an enhanced nitrogen concentration of up to 21.8%. Reflectance measurements showed the synthesized N-doped TiO2 nanoparticles are catalytically active with the absorbance that extends into the visible region up to 600 nm. The water purification potential of this new class of compound was evaluated by studying the photodegradation of Acid Orange 7 (AO7) and E. coli. Experiments were conducted to compare the photocatalytic activities of N-doped TiO2 nanocatalysts and commercially available Degussa P25 power under identical solar light exposure. N-doped TiO2 demonstrated superior photocatalytic activities in both chemical compound degradation and bactericidal reactions. The result of this study shows the potential of applying new generations of catalyst for wastewater purification and disinfection.

  10. Piper Ornatum and Piper Betle as Organic Dyes for TiO2 and SnO2 Dye Sensitized Solar Cells

    NASA Astrophysics Data System (ADS)

    Hayat, Azwar; Putra, A. Erwin E.; Amaliyah, Novriany; Hayase, Shuzi; Pandey, Shyam. S.

    2018-03-01

    Dye sensitized solar cell (DSSC) mimics the principle of natural photosynthesis are now currently investigated due to low manufacturing cost as compared to silicon based solar cells. In this report, we utilized Piper ornatum (PO) and Piper betle (PB) as sensitizer to fabricate low cost DSSCs. We compared the photovoltaic performance of both sensitizers with Titanium dioxide (TiO2) and Tin dioxide (SnO2) semiconductors. The results show that PO and PB dyes have higher Short circuit current (Jsc) when applied in SnO2 compared to standard TiO2 photo-anode film even though the Open circuit voltage (Voc) was hampered on SnO2 device. In conclusion, from the result, higher electron injections can be achieved by choosing appropriate semiconductors with band gap that match with dyes energy level as one of strategy for further low cost solar cell.

  11. Heterostructured TiO2/NiTiO3 Nanorod Arrays for Inorganic Sensitized Solar Cells with Significantly Enhanced Photovoltaic Performance and Stability.

    PubMed

    Li, Yue-Ying; Wang, Jian-Gan; Sun, Huan-Huan; Wei, Bingqing

    2018-04-11

    Organic dyes used in the conventional dye-sensitized solar cells (DSSCs) suffer from poor light stability and high cost. In this work, we demonstrate a new inorganic sensitized solar cell based on ordered one-dimensional semiconductor nanorod arrays of TiO 2 /NiTiO 3 (NTO) heterostructures prepared via a facile two-step hydrothermal approach. The semiconductor heterostructure arrays are highly desirable and promising for DSSCs because of their direct charge transport capability and slow charge recombination rate. The low-cost NTO inorganic semiconductor possesses an appropriate band gap that matches well with TiO 2 , which behaves like a "dye" to enable efficient light harvesting and fast electron-hole separation. The solar cells constructed by the ordered TiO 2 /NTO heterostructure photoanodes show a significantly improved power conversion efficiency, high fill factor, and more promising, outstanding life stability. The present work will open up an avenue to design heterostructured inorganics for high-performance solar cells.

  12. Observation of shift in band gap with annealing in hydrothermally synthesized TiO2-thin films

    NASA Astrophysics Data System (ADS)

    Pawar, Vani; Jha, Pardeep K.; Singh, Prabhakar

    2018-05-01

    Anatase TiO2 thin films were synthesized by hydrothermal method. The films were fabricated on a glass substrate by spin coating unit and annealed at 500 °C for 2 hours in ambient atmosphere. The effect of annealing on microstructure and optical properties of TiO2 thin films namely, just deposited and annealed thin film were investigated. The XRD data confirms the tetragonal crystalline structure of the films with space group I41/amd. The surface morphology suggests that TiO2 particles are almost homogeneous in size and annealing of the film affect the grain growth of the particles. The band gap energy increases from 2.81 to 3.34 eV. On the basis of our observation, it can be concluded that the annealing of TiO2 thin films enhances the absorption range and it may find potential application in the field of solar cells.

  13. Pilot-plant evaluation of TiO2 and TiO2-based hybrid photocatalysts for solar treatment of polluted water.

    PubMed

    Andronic, Luminita; Isac, Luminita; Miralles-Cuevas, Sara; Visa, Maria; Oller, Isabel; Duta, Anca; Malato, Sixto

    2016-12-15

    Materials with photocatalytic and adsorption properties for advanced wastewater treatment targeting reuse were studied. Making use of TiO 2 as a well-known photocatalyst, Cu 2 S as a Vis-active semiconductor, and fly ash as a good adsorbent, dispersed mixtures/composites were prepared to remove pollutants from wastewater. X-ray diffraction, scanning electron microscopy, energy-dispersive X-Ray spectroscopy, atomic force microscopy, band gap energy, point of zero charge (pH pzc ) and BET porosity were used to characterize the substrates. Phenol, imidacloprid and dichloroacetic acid were used as pollutants for photocatalytic activity of the new photocatalysts. Experiments using the new dispersed powders were carried out at laboratory scale in two solar simulators and under natural solar irradiation at the Plataforma Solar de Almería, in a Compound Parabolic Collector (CPC) for a comparative analysis of pollutants removal and mineralization efficiencies, and to identify features that could facilitate photocatalyst separation and reuse. The results show that radiation intensity significantly affects the phenol degradation rate. The composite mixture of TiO 2 and fly ash is 2-3 times less active than sol-gel TiO 2 . Photodegradation kinetic data on the highly active TiO 2 are compared for pollutants elimination. Photodegradation of dichloroacetic acid was fast and complete after 90min in the CPC, while after 150min imidacloprid and phenol removal was 90% and 56% respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Codoped direct-gap semiconductor scintillators

    DOEpatents

    Derenzo, Stephen Edward [Pinole, CA; Bourret-Courchesne, Edith [Berkeley, CA; Weber, Marvin J [Danville, CA; Klintenberg, Mattias K [Berkeley, CA

    2008-07-29

    Fast, bright inorganic scintillators at room temperature are based on radiative electron-hole recombination in direct-gap semiconductors, e.g. CdS and ZnO. The direct-gap semiconductor is codoped with two different impurity atoms to convert the semiconductor to a fast, high luminosity scintillator. The codopant scheme is based on dopant band to dopant trap recombination. One dopant provides a significant concentration of carriers of one type (electrons or holes) and the other dopant traps carriers of the other type. Examples include CdS:In,Te; CdS:In,Ag; CdS:In,Na; ZnO:Ga,P; ZnO:Ga,N; ZnO:Ga,S; and GaN:Ge,Mg.

  15. Codoped direct-gap semiconductor scintillators

    DOEpatents

    Derenzo, Stephen E.; Bourret-Courchesne, Edith; Weber, Marvin J.; Klintenberg, Mattias K.

    2006-05-23

    Fast, bright inorganic scintillators at room temperature are based on radiative electron-hole recombination in direct-gap semiconductors, e.g. CdS and ZnO. The direct-gap semiconductor is codoped with two different impurity atoms to convert the semiconductor to a fast, high luminosity scintillator. The codopant scheme is based on dopant band to dopant trap recombination. One dopant provides a significant concentration of carriers of one type (electrons or holes) and the other dopant traps carriers of the other type. Examples include CdS:In,Te; CdS:In,Ag; CdS:In,Na; ZnO:Ga,P; ZnO:Ga,N; ZnO:Ga,S; and GaN:Ge,Mg.

  16. Fabrication of NIR-responsive NaYF4:Yb,Tm/anatase TiO2 composite aerogel

    NASA Astrophysics Data System (ADS)

    Li, Fu-Chih; Kitamoto, Yoshitaka

    2018-01-01

    3-dimensional interconnected network structure of TiO2 aerogel has attracted considerable attention to solve environmental issues due to an advanced oxidation process which uses abundant sunlight for the complete minimization of toxic pollutants. The TiO2 aerogel with high specific surface area, large pores, and low density has a potential to be used as photocatalyst for air and water purification. Nonetheless, due to the larger band gap, TiO2 semiconductor photocatalysts possess high oxidizing properties under UV light only which occupies 5% of solar energy. To expand the absorption spectrum of TiO2 aerogel under solar irradiation, the NaYF4:Yb,Tm nanoparticles (NPs) are introduced into the TiO2 aerogel matrix structure. The morphology and crystal structure of the composite aerogel are investigated by transmission electron microscopy and X-ray diffraction, respectively. The particle size of NaYF4:Yb,Tm NPs is approximately 40 nm and the crystallite size of TiO2 is around 10 nm. In addition, the NaYF4:Yb,Tm NPs are enclosed by anatase phase of TiO2 aerogel. The NaYF4:Yb,Tm NPs which exist in the TiO2 aerogel has a capability of transferring NIR light to UV region.

  17. Zero-gap semiconductor to excitonic insulator transition in Ta2NiSe5

    PubMed Central

    Lu, Y. F.; Kono, H.; Larkin, T. I.; Rost, A. W.; Takayama, T.; Boris, A. V.; Keimer, B.; Takagi, H.

    2017-01-01

    The excitonic insulator is a long conjectured correlated electron phase of narrow-gap semiconductors and semimetals, driven by weakly screened electron–hole interactions. Having been proposed more than 50 years ago, conclusive experimental evidence for its existence remains elusive. Ta2NiSe5 is a narrow-gap semiconductor with a small one-electron bandgap EG of <50 meV. Below TC=326 K, a putative excitonic insulator is stabilized. Here we report an optical excitation gap Eop ∼0.16 eV below TC comparable to the estimated exciton binding energy EB. Specific heat measurements show the entropy associated with the transition being consistent with a primarily electronic origin. To further explore this physics, we map the TC–EG phase diagram tuning EG via chemical and physical pressure. The dome-like behaviour around EG∼0 combined with our transport, thermodynamic and optical results are fully consistent with an excitonic insulator phase in Ta2NiSe5. PMID:28205553

  18. Characterization and Comparison of Photocatalytic Activity Silver Ion doped on TiO2(TiO2/Ag+) and Silver Ion doped on Black TiO2(Black TiO2/Ag+)

    NASA Astrophysics Data System (ADS)

    Kim, Jin Yi; Sim, Ho Hyung; Song, Sinae; Noh, Yeoung Ah; Lee, Hong Woon; Taik Kim, Hee

    2018-03-01

    Titanium dioxide (TiO2) is one of the representative ceramic materials containing photocatalyst, optic and antibacterial activity. The hydroxyl radical in TiO2 applies to the intensive oxidizing agent, hence TiO2 is suitable to use photocatalytic materials. Black TiO2was prepared through reduction of amorphous TiO2 conducting under H2 which leads to color changes. Its black color is proven that absorbs 100% light across the whole-visible light, drawing enhancement of photocatalytic property. In this study, we aimed to compare the photocatalytic activity of silver ion doped on TiO2(TiO2/Ag+) and silver ion doped on black TiO2(black TiO2/Ag+) under visible light range. TiO2/Ag+ was fabricated following steps. 1) TiO2 was synthesized by a sol-gel method from Titanium tetraisopropoxide (TTIP). 2) Then AgNO3 was added during an aging process step for silver ion doping on the surface of TiO2. Moreover, Black TiO2/Ag+ was obtained same as TiO2/Ag+ except for calcination under H2. The samples were characterized X-ray diffraction (XRD), UV-visible reflectance (UV-vis DRS), and Methylene Blue degradation test. XRD analysis confirmed morphology of TiO2. The band gap of black TiO2/Ag+ was confirmed (2.6 eV) through UV-vis DRS, which was lower than TiO2/Ag+ (2.9 eV). The photocatalytic effect was conducted by methylene blue degradation test. It demonstrated that black TiO2/Ag+ had a photocatalytic effect under UV light also visible light.

  19. Microwave-assisted synthesis of C-doped TiO2 and ZnO hybrid nanostructured materials as quantum-dots sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Rangel-Mendez, Jose R.; Matos, Juan; Cházaro-Ruiz, Luis F.; González-Castillo, Ana C.; Barrios-Yáñez, Guillermo

    2018-03-01

    The microwave-assisted solvothermal synthesis of C-doped TiO2 and ZnO hybrid materials was performed. Saccharose, titanium isopropoxide and zinc acetate were used as organic and inorganic sources for the synthesis. The influence of temperature and reaction time on the textural and optoelectronic properties of the hybrid materials was verified. Carbon quantum-dots of TiO2 and ZnO nanostructured spheres were obtained in a second pot by controlled calcination steps of the precursor hybrid materials. A carefully characterization by adsorption-desorption N2 isotherms, XRD, XPS, SEM, UV-vis/DR and electro- and photo-electrochemistry properties of the carbon quantum-dots TiO2 and ZnO spheres was performed. The photoelectrochemical activity of TiO2-C and ZnO-C films proved to be dependent on the conditions of synthesis. It was found a red-shift in the energy band gap of the semiconductors with values of 3.02 eV and 3.13 eV for the TiO2-C and ZnO-C, respectively, clearly lower than those on bare semiconductors, which is associated with the C-doping effect. From the photo-electrochemistry characterization of C-doped TiO2 and ZnO films can be concluded that the present materials have potential applications as photoelectrodes for quantum-dots sensitized solar cells.

  20. Zero-gap semiconductor to excitonic insulator transition in Ta2NiSe5.

    PubMed

    Lu, Y F; Kono, H; Larkin, T I; Rost, A W; Takayama, T; Boris, A V; Keimer, B; Takagi, H

    2017-02-16

    The excitonic insulator is a long conjectured correlated electron phase of narrow-gap semiconductors and semimetals, driven by weakly screened electron-hole interactions. Having been proposed more than 50 years ago, conclusive experimental evidence for its existence remains elusive. Ta 2 NiSe 5 is a narrow-gap semiconductor with a small one-electron bandgap E G of <50 meV. Below T C =326 K, a putative excitonic insulator is stabilized. Here we report an optical excitation gap E op ∼0.16 eV below T C comparable to the estimated exciton binding energy E B . Specific heat measurements show the entropy associated with the transition being consistent with a primarily electronic origin. To further explore this physics, we map the T C -E G phase diagram tuning E G via chemical and physical pressure. The dome-like behaviour around E G ∼0 combined with our transport, thermodynamic and optical results are fully consistent with an excitonic insulator phase in Ta 2 NiSe 5 .

  1. Hydrogen production by Tuning the Photonic Band Gap with the Electronic Band Gap of TiO2

    NASA Astrophysics Data System (ADS)

    Waterhouse, G. I. N.; Wahab, A. K.; Al-Oufi, M.; Jovic, V.; Anjum, D. H.; Sun-Waterhouse, D.; Llorca, J.; Idriss, H.

    2013-10-01

    Tuning the photonic band gap (PBG) to the electronic band gap (EBG) of Au/TiO2 catalysts resulted in considerable enhancement of the photocatalytic water splitting to hydrogen under direct sunlight. Au/TiO2 (PBG-357 nm) photocatalyst exhibited superior photocatalytic performance under both UV and sunlight compared to the Au/TiO2 (PBG-585 nm) photocatalyst and both are higher than Au/TiO2 without the 3 dimensionally ordered macro-porous structure materials. The very high photocatalytic activity is attributed to suppression of a fraction of electron-hole recombination route due to the co-incidence of the PBG with the EBG of TiO2 These materials that maintain their activity with very small amount of sacrificial agents (down to 0.5 vol.% of ethanol) are poised to find direct applications because of their high activity, low cost of the process, simplicity and stability.

  2. Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications

    NASA Astrophysics Data System (ADS)

    Pan, Xiaoyang; Yang, Min-Quan; Fu, Xianzhi; Zhang, Nan; Xu, Yi-Jun

    2013-04-01

    Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the synthesis of defective TiO2 with oxygen vacancies, and the defect related properties of TiO2 including structural, electronic, optical, dissociative adsorption and reductive properties, which are intimately related to the photocatalytic performance of TiO2. In particular, photocatalytic applications with regard to defective TiO2 are outlined. In addition, we offer some perspectives on the challenge and new direction for future research in this field. We hope that this tutorial minireview would provide some useful contribution to the future design and fabrication of defective semiconductor-based nanomaterials for diverse photocatalytic applications.Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the

  3. Toxicity of ZnO and TiO2 to Escherichia coli cells

    PubMed Central

    Leung, Yu Hang; Xu, Xiaoying; Ma, Angel P. Y.; Liu, Fangzhou; Ng, Alan M. C.; Shen, Zhiyong; Gethings, Lee A.; Guo, Mu Yao; Djurišić, Aleksandra B.; Lee, Patrick K. H.; Lee, Hung Kay; Chan, Wai Kin; Leung, Frederick C. C.

    2016-01-01

    We performed a comprehensive investigation of the toxicity of ZnO and TiO2 nanoparticles using Escherichia coli as a model organism. Both materials are wide band gap n-type semiconductors and they can interact with lipopolysaccharide molecules present in the outer membrane of E. coli, as well as produce reactive oxygen species (ROS) under UV illumination. Despite the similarities in their properties, the response of the bacteria to the two nanomaterials was fundamentally different. When the ROS generation is observed, the toxicity of nanomaterial is commonly attributed to oxidative stress and cell membrane damage caused by lipid peroxidation. However, we found that significant toxicity does not necessarily correlate with up-regulation of ROS-related proteins. TiO2 exhibited significant antibacterial activity, but the protein expression profile of bacteria exposed to TiO2 was different compared to H2O2 and the ROS-related proteins were not strongly expressed. On the other hand, ZnO exhibited lower antibacterial activity compared to TiO2, and the bacterial response involved up-regulating ROS-related proteins similar to the bacterial response to the exposure to H2O2. Reasons for the observed differences in toxicity and bacterial response to the two metal oxides are discussed. PMID:27731373

  4. Theoretical study of new potential semiconductor surfaces performance for dye sensitized solar cell usage: TiO2-B (001), (100) and H2Ti3O7 (100)

    NASA Astrophysics Data System (ADS)

    German, Estefania; Faccio, Ricardo; Mombrú, Álvaro W.

    2017-12-01

    Hydrogen titanate (H2Ti3O7) and TiO2-B polymorph are potential surfaces identified experimentally in the last years, which need to be analyzed. To study their performance as surfaces for dye sensitized solar cells (DSSC), a set of dye adsorption configurations were evaluated on them, as model dye the small and organic catechol molecule was used. We have calculated adsorption geometry, energy, electronic transfer from dye to semiconductor adsorbent and frontier orbitals by means of density functional theory (DFT). Results show that vacancy-like defected H2Ti3O7 (100) and TiO2-B (100) surfaces present favorable adsorption energies. Finally, an adequate energy level alignment make both surfaces prone to be adequate for direct electron transfer upon excitation, from catechol to the conduction band of the semiconductors, with bands located in the Visible region of the electromagnetic spectrum. Additionally, the band structure alignment indicates an increase in the open circuit voltage, in reference to I2/I3- redox pair potential. All these characteristics make hydrogen titanate (H2Ti3O7) and TiO2-B polymorph promising for DSSC applications.

  5. A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Li, L. H.; Deng, Z. X.; Xiao, J. X.; Yang, G. W.

    2015-06-01

    Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

  6. A metallic metal oxide (Ti5O9)-metal oxide (TiO2) nanocomposite as the heterojunction to enhance visible-light photocatalytic activity.

    PubMed

    Li, L H; Deng, Z X; Xiao, J X; Yang, G W

    2015-01-26

    Coupling titanium dioxide (TiO2) with other semiconductors is a popular method to extend the optical response range of TiO2 and improve its photon quantum efficiency, as coupled semiconductors can increase the separation rate of photoinduced charge carriers in photocatalysts. Differing from normal semiconductors, metallic oxides have no energy gap separating occupied and unoccupied levels, but they can excite electrons between bands to create a high carrier mobility to facilitate kinetic charge separation. Here, we propose the first metallic metal oxide-metal oxide (Ti5O9-TiO2) nanocomposite as a heterojunction for enhancing the visible-light photocatalytic activity of TiO2 nanoparticles and we demonstrate that this hybridized TiO2-Ti5O9 nanostructure possesses an excellent visible-light photocatalytic performance in the process of photodegrading dyes. The TiO2-Ti5O9 nanocomposites are synthesized in one step using laser ablation in liquid under ambient conditions. The as-synthesized nanocomposites show strong visible-light absorption in the range of 300-800 nm and high visible-light photocatalytic activity in the oxidation of rhodamine B. They also exhibit excellent cycling stability in the photodegrading process. A working mechanism for the metallic metal oxide-metal oxide nanocomposite in the visible-light photocatalytic process is proposed based on first-principle calculations of Ti5O9. This study suggests that metallic metal oxides can be regarded as partners for metal oxide photocatalysts in the construction of heterojunctions to improve photocatalytic activity.

  7. Hydrogen production by Tuning the Photonic Band Gap with the Electronic Band Gap of TiO2

    PubMed Central

    Waterhouse, G. I. N.; Wahab, A. K.; Al-Oufi, M.; Jovic, V.; Anjum, D. H.; Sun-Waterhouse, D.; Llorca, J.; Idriss, H.

    2013-01-01

    Tuning the photonic band gap (PBG) to the electronic band gap (EBG) of Au/TiO2 catalysts resulted in considerable enhancement of the photocatalytic water splitting to hydrogen under direct sunlight. Au/TiO2 (PBG-357 nm) photocatalyst exhibited superior photocatalytic performance under both UV and sunlight compared to the Au/TiO2 (PBG-585 nm) photocatalyst and both are higher than Au/TiO2 without the 3 dimensionally ordered macro-porous structure materials. The very high photocatalytic activity is attributed to suppression of a fraction of electron-hole recombination route due to the co-incidence of the PBG with the EBG of TiO2 These materials that maintain their activity with very small amount of sacrificial agents (down to 0.5 vol.% of ethanol) are poised to find direct applications because of their high activity, low cost of the process, simplicity and stability. PMID:24108361

  8. Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

    DOE PAGES

    Lichterman, Michael F.; Sun, Ke; Hu, Shu; ...

    2015-10-25

    Small-band-gap (E g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H 2 (g) or a reduced-carbon species such as CH 3 OH or CH 4 . To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O 2 (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. But, under water-oxidation conditions, the small-band-gap semiconductors required for efficient cell operation aremore » unstable, either dissolving or forming insulating surface oxides. Here, we describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO 2 /Ni and NiO x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for > 100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). Furthermore, the stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO 2 films, along with a discussion of the optical, catalytic, and electronic nature of NiO x films for stabilization of semiconductor photoanodes for water oxidation.« less

  9. Low-temperature magnetotransport of the narrow-gap semiconductor FeSb2

    NASA Astrophysics Data System (ADS)

    Takahashi, H.; Okazaki, R.; Yasui, Y.; Terasaki, I.

    2011-11-01

    We present a study of the magnetoresistance and Hall effect in the narrow-gap semiconductor FeSb2 at low temperatures. Both the electrical and Hall resistivities show unusual magnetic field dependence in the low-temperature range where a large Seebeck coefficient was observed. By applying a two-carrier model, we find that the carrier concentration decreases from 1 down to 10-4 ppm/unit cell and the mobility increases from 2000 to 28 000 cm2/Vs with decreasing temperature from 30 down to 4 K. At lower temperatures, the magnetoresistive behavior drastically changes and a negative magnetoresistance is observed at 3 K. These low-temperature behaviors are reminiscent of the low-temperature magnetotransport observed in doped semiconductors such as As-doped Ge, which is well described by a weak-localization picture. We argue a detailed electronic structure in FeSb2 inferred from our observations.

  10. Sonocatalytic degradation of humic acid by N-doped TiO2 nano-particle in aqueous solution.

    PubMed

    Kamani, Hossein; Nasseri, Simin; Khoobi, Mehdi; Nabizadeh Nodehi, Ramin; Mahvi, Amir Hossein

    2016-01-01

    Un-doped and N-doped TiO2 nano-particles with different nitrogen contents were successfully synthesized by a simple sol-gel method, and were characterized by X-ray diffraction, field emission scanning electron microscopy, Energy dispersive X-ray analysis and UV-visible diffuse reflectance spectra techniques. Then enhancement of sonocatalytic degradation of humic acid by un-doped and N-doped TiO2 nano-particles in aqueous environment was investigated. The effects of various parameters such as initial concentration of humic acid, N-doping, and the degradation kinetics were investigated. The results of characterization techniques affirmed that the synthesis of un-doped and N-doped TiO2 nano-particles was successful. Degradation of humic acid by using different nano-particles obeyed the first-order kinetic. Among various nano-particles, N-doped TiO2 with molar doping ratio of 6 % and band gap of 2.92 eV, exhibited the highest sonocatalytic degradation with an apparent-first-order rate constant of 1.56 × 10(-2) min(-1). The high degradation rate was associated with the lower band gap energy and well-formed anatase phase. The addition of nano-catalysts could enhance the degradation efficiency of humic acid as well as N-doped TiO2 with a molar ratio of 6 %N/Ti was found the best nano-catalyst among the investigated catalysts. The sonocatalytic degradation with nitrogen doped semiconductors could be a suitable oxidation process for removal of refractory pollutants such as humic acid from aqueous solution.

  11. Band-Gap Engineering at a Semiconductor-Crystalline Oxide Interface

    DOE PAGES

    Jahangir-Moghadam, Mohammadreza; Ahmadi-Majlan, Kamyar; Shen, Xuan; ...

    2015-02-09

    The epitaxial growth of crystalline oxides on semiconductors provides a pathway to introduce new functionalities to semiconductor devices. Key to integrating the functionalities of oxides onto semiconductors is controlling the band alignment at interfaces between the two materials. Here we apply principles of band gap engineering traditionally used at heterojunctions between conventional semiconductors to control the band offset between a single crystalline oxide and a semiconductor. Reactive molecular beam epitaxy is used to realize atomically abrupt and structurally coherent interfaces between SrZr xTi 1-xO₃ and Ge, in which the band gap of the former is enhanced with Zr content x.more » We present structural and electrical characterization of SrZr xTi 1-xO₃-Ge heterojunctions and demonstrate a type-I band offset can be achieved. These results demonstrate that band gap engineering can be exploited to realize functional semiconductor crystalline oxide heterojunctions.« less

  12. Crystal Growth and Characterization of the Narrow-Band-Gap Semiconductors OsPn 2 (Pn = P, As, Sb)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bugaris, Daniel E.; Malliakas, Christos D.; Shoemaker, Daniel P.

    2014-09-15

    Using metal fluxes, crystals of the binary osmium dipnictides OsPn(2) (Pn = P, As, Sb) have been grown for the first time. Single-crystal X-ray diffraction confirms that these compounds crystallize in the marcasite structure type with orthorhombic space group Pnnm. The structure is a three-dimensional framework of corner- and edge-sharing OsPn(6) octahedra, as well as [Pn(2)(-4)] anions. Raman spectroscopy shows the presence of PP single bonds, consistent with the presence of [Pn(2)(-4)] anions and formally Os4+ cations. Optical-band-gap and high-temperature electrical resistivity measurements indicate that these materials are narrow-band-gap semiconductors. The experimentally determined Seebeck coefficients reveal that nominally undoped OsP2more » and OsSb2 are n-type semiconductors, whereas OsAs2 is p-type. Electronic band structure using density functional theory calculations shows that these compounds are indirect narrow-band-gap semiconductors. The bonding p orbitals associated with the Pn(2) dimer are below the Fermi energy, and the corresponding antibonding states are above, consistent with a PnPn single bond. Thermopower calculations using Boltzmann transport theory and constant relaxation time approximation show that these materials are potentially good thermoelectrics, in agreement with experiment.« less

  13. Enhanced photocatalytic activity of Bi2WO6/TiO2 composite coated polyester fabric under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Du, Zoufei; Cheng, Cheng; Tan, Lin; Lan, Jianwu; Jiang, Shouxiang; Zhao, Ludan; Guo, Ronghui

    2018-03-01

    In this study, a visible-light-driven photocatalyst Bi2WO6/TiO2 composite was reported using one-step hydrothermal method and then coated on the polyester fabric. The samples were systematically characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area, UV-vis diffuse reflection spectroscopy and photoluminescence spectroscopy (PL). The photocatalytic activity of Bi2WO6/TiO2 coated polyester fabric was evaluated by degradation of Rhodamine B (RhB) and Methylene blue (MB) under visible light irradiation. The self-cleaning property of the fabrics was assessed through removing red wine stain. The results reveal that the Bi2WO6/TiO2 composites with irregular shape are coated on the polyester fabric successfully. The UV-vis absorption spectra show a broad absorption band in the visible region, which extends the scope of absorption spectrum and helps to improve the photocatalytic degradation efficiency. Photocatalytic activities of the Bi2WO6/TiO2 composite polyester fabric are associated with the content of TiO2. Bi2WO6/15%TiO2 coated polyester fabric exhibits the degradation efficiency for RhB and MB up to 98% and 95.1%, respectively, which is much higher than that of pure Bi2WO6 and TiO2 coated polyester fabric. Moreover, Bi2WO6/15%TiO2 coated polyester fabric shows good cycle stability toward continuous three cycles of photocatalytic experiment for dyes degradation. In addition, the Bi2WO6/TiO2 coated polyester fabric shows good self-cleaning property. This work could be extended to design of other composite photocatalyst coating on the fabric for enhancing activity by coupling suitable wide and narrow band-gap semiconductors.

  14. Two-dimensional wide-band-gap nitride semiconductors: Single-layer 1 T -X N2 (X =S ,Se , and Te )

    NASA Astrophysics Data System (ADS)

    Lin, Jia-He; Zhang, Hong; Cheng, Xin-Lu; Miyamoto, Yoshiyuki

    2016-11-01

    Recently, the two-dimensional (2D) semiconductors arsenene and antimonene, with band gaps larger than 2.0 eV, have attracted tremendous interest, especially for potential applications in optoelectronic devices with a photoresponse in the blue and UV range. Motivated by this exciting discovery, types of highly stable wide-band-gap 2D nitride semiconductors were theoretically designed. We propose single-layer 1 T -X N2 (X =S , Se, and Te) via first-principles simulations. We compute 1 T -X N2 (X =S , Se, and Te) with indirect band gaps of 2.825, 2.351, and 2.336 eV, respectively. By applying biaxial strain, they are able to induce the transition from a wide-band-gap semiconductor to a metal, and the range of absorption spectra of 1 T -X N2 (X =S , Se, and Te) obviously extend from the ultraviolet region to the blue-purple light region. With an underlying graphene, we find that 1 T -X N2 can completely shield the light absorption of graphene in the range of 1-1.6 eV. Our research paves the way for optoelectronic devices working under blue or UV light, and mechanical sensors based on these 2D crystals.

  15. MoSe2 modified TiO2 nanotube arrays with superior photoelectrochemical performance

    NASA Astrophysics Data System (ADS)

    Zhang, Yaping; Zhu, Haifeng; Yu, Lianqing; He, Jiandong; Huang, Chengxing

    2018-04-01

    TiO2 nanotube arrays (TNTs) are first prepared by anodization Ti foils in ethylene glycol electrolyte. Then, MoSe2 deposites electrochemically on TNTs. The as-synthesized MoSe2/TiO2 composite has a much higher photocurrent density of 1.07 mA cm‑2 at 0 V than pure TNTs of 0.38 mA cm‑2, which suggests that the MoSe2/TiO2 composite film has optimum photoelectrocatalysis properties. The electron transport resistances of the MoSe2/TiO2 decreases to half of pure TiO2, at 295.6 ohm/cm2. Both photocurrent-time and Mott-Schottky plots indicate MoSe2 a p-type semiconductor characteristics. MoSe2/TiO2 composite can achieve a maximum 5 orders of magnitude enhancement in carrier density (4.650 × 1027 cm‑3) than that of pure TiO2 arrays. It can be attributed to p-n heterojunction formed between MoSe2 and TiO2, and the composite can be potentially applied in photoelectrochemical, photocatalysis fields.

  16. Characterization of TiO2-based semiconductors for photocatalysis by electrochemical impedance spectroscopy

    NASA Astrophysics Data System (ADS)

    Ângelo, Joana; Magalhães, Pedro; Andrade, Luísa; Mendes, Adélio

    2016-11-01

    The photocatalytic activity of a commercial titanium dioxide (P25) and of an in-house prepared P25/graphene composite is assessed according to standard ISO 22197-1:2007. The photoactivity performances of bare and composite TiO2-based materials were further studied by electrochemical impedance spectroscopy (EIS) technique to better understand the function of the graphene in the composite. EIS experiments were performed using a three-electrode configuration, which allows obtaining more detailed information about the complex charge transfer phenomena at the semiconductor/electrolyte interface. The Randles equivalent circuit was selected as the most suitable for modelling the present photocatalysts. The use of the graphene composite allows a more effective charge separation with lower charge transfer resistance and less e-/h+ recombination on the composite photocatalyst, reflected in the higher values of NO conversion.

  17. Air-gating and chemical-gating in transistors and sensing devices made from hollow TiO2 semiconductor nanotubes

    NASA Astrophysics Data System (ADS)

    Alivov, Yahya; Funke, Hans; Nagpal, Prashant

    2015-07-01

    Rapid miniaturization of electronic devices down to the nanoscale, according to Moore’s law, has led to some undesirable effects like high leakage current in transistors, which can offset additional benefits from scaling down. Development of three-dimensional transistors, by spatial extension in the third dimension, has allowed higher contact area with a gate electrode and better control over conductivity in the semiconductor channel. However, these devices do not utilize the large surface area and interfaces for new electronic functionality. Here, we demonstrate air gating and chemical gating in hollow semiconductor nanotube devices and highlight the potential for development of novel transistors that can be modulated using channel bias, gate voltage, chemical composition, and concentration. Using chemical gating, we reversibly altered the conductivity of nanoscaled semiconductor nanotubes (10-500 nm TiO2 nanotubes) by six orders of magnitude, with a tunable rectification factor (ON/OFF ratio) ranging from 1-106. While demonstrated air- and chemical-gating speeds were slow here (˜seconds) due to the mechanical-evacuation rate and size of our chamber, the small nanoscale volume of these hollow semiconductors can enable much higher switching speeds, limited by the rate of adsorption/desorption of molecules at semiconductor interfaces. These chemical-gating effects are completely reversible, additive between different chemical compositions, and can enable semiconductor nanoelectronic devices for ‘chemical transistors’, ‘chemical diodes’, and very high-efficiency sensing applications.

  18. TiO2-Based Nanoheterostructures for Promoting Gas Sensitivity Performance: Designs, Developments, and Prospects

    PubMed Central

    Wang, Yuan; Wu, Tao; Zhou, Yun; Meng, Chuanmin; Zhu, Wenjun; Liu, Lixin

    2017-01-01

    Gas sensors based on titanium dioxide (TiO2) have attracted much public attention during the past decades due to their excellent potential for applications in environmental pollution remediation, transportation industries, personal safety, biology, and medicine. Numerous efforts have therefore been devoted to improving the sensing performance of TiO2. In those effects, the construct of nanoheterostructures is a promising tactic in gas sensing modification, which shows superior sensing performance to that of the single component-based sensors. In this review, we briefly summarize and highlight the development of TiO2-based heterostructure gas sensing materials with diverse models, including semiconductor/semiconductor nanoheterostructures, noble metal/semiconductor nanoheterostructures, carbon-group-materials/semiconductor nano- heterostructures, and organic/inorganic nanoheterostructures, which have been investigated for effective enhancement of gas sensing properties through the increase of sensitivity, selectivity, and stability, decrease of optimal work temperature and response/recovery time, and minimization of detectable levels. PMID:28846621

  19. Comparison study on photocatalytic oxidation of pharmaceuticals by TiO2-Fe and TiO2-reduced graphene oxide nanocomposites immobilized on optical fibers.

    PubMed

    Lin, Lu; Wang, Huiyao; Jiang, Wenbin; Mkaouar, Ahmed Radhi; Xu, Pei

    2017-07-05

    Incorporating reduced graphene oxide (rGO) or Fe 3+ ions in TiO 2 photocatalyst could enhance photocatalytic degradation of organic contaminants in aqueous solutions. This study characterized the photocatalytic activities of TiO 2 -Fe and TiO 2 -rGO nanocomposites immobilized on optical fibers synthesized by polymer assisted hydrothermal deposition method. The photocatalysts presented a mixture phase of anatase and rutile in the TiO 2 -rGO and TiO 2 -Fe nanocomposites. Doping Fe into TiO 2 particles (2.40eV) could reduce more band gap energy than incorporating rGO (2.85eV), thereby enhancing utilization efficiency of visible light. Incorporating Fe and rGO in TiO 2 decreased significantly the intensity of TiO 2 photoluminescence signals and enhanced the separation rate of photo-induced charge carriers. Photocatalytic performance of the synthesized nanocomposites was measured by the degradation of three pharmaceuticals under UV and visible light irradiation, including carbamazepine, ibuprofen, and sulfamethoxazole. TiO 2 -rGO exhibited higher photocatalytic activity for the degradation of pharmaceuticals under UV irradiation, while TiO 2 -Fe demonstrated more suitable for visible light oxidation. The results suggested that the enhanced photocatalytic performance of TiO 2 -rGO could be attributed to reduced recombination rate of photoexcited electrons-hole pairs, but for TiO 2 -Fe nanocomposite, narrower band gap would contribute to increased photocatalytic activity. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. TiO2-Based Nanomaterials for Gas Sensing-Influence of Anatase and Rutile Contributions.

    PubMed

    Zakrzewska, K; Radecka, M

    2017-12-01

    The paper deals with application of three nanomaterial systems: undoped TiO 2 , chromium-doped TiO 2 :Cr and TiO 2 -SnO 2 synthesized by flame spray synthesis (FSS) technique for hydrogen sensing. The emphasis is put on the role of anatase and rutile polymorphic forms of TiO 2 in enhancing sensitivity towards reducing gases. Anatase-to-rutile transformation is achieved by annealing of undoped TiO 2 in air at 700 °C, specific Cr doping and modification with SnO 2 . Undoped TiO 2 and TiO 2 -SnO 2 exhibit n-type behaviour and while TiO 2 : 5 at.% Cr is a p-type semiconductor. X-ray diffraction (XRD) has been applied to determine anatase-to-rutile weight ratio as well as anatase and rutile crystal size. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have been used to characterize the structure and morphological parameters. Optical reflectometry enabled to find and compare the band gaps E g of anatase and rutile predominated compositions. Electrical properties, i.e. the electrical conductivity and values of constant phase element (CPE), have been established on the basis of impedance spectroscopy. Dynamic responses of the electrical resistance as a function of hydrogen concentration revealed that predominance of rutile in anatase/rutile mixture is beneficial for gas sensing. Partial transformation to rutile in all three material systems under study resulted in an increased sensitivity towards hydrogen. It is proposed that this effect can be explained in a similar way as in photocatalysis, i.e. by specific band alignment and electron transfer from rutile to anatase to facilitate oxygen preadsorption on the surface of anatase grains.

  1. Electronic characterization of defects in narrow gap semiconductors

    NASA Technical Reports Server (NTRS)

    Patterson, James D.

    1993-01-01

    The study of point defects in semiconductors has a long and honorable history. In particular, the detailed understanding of shallow defects in common semiconductors traces back to the classic work of Kohn and Luttinger. However, the study of defects in narrow gap semiconductors represents a much less clear story. Here, both shallow defects (caused by long range potentials) and deep defects (from short range potentials) are far from being completely understood. In this study, all results are calculational and our focus is on the chemical trend of deep levels in narrow gap semiconductors. We study substitutional (including antisite), interstitial and ideal vacancy defects. For substitutional and interstitial impurities, the efects of relaxation are included. For materials like Hg(1-x)Cd(x)Te, we study how the deep levels vary with x, of particular interest is what substitutional and interstitial atoms yield energy levels in the gap i.e. actually produce deep ionized levels. Also, since the main technique utilized is Green's functions, we include some summary of that method.

  2. Reduction of chromium (VI) on the hetero-system CuBi2O4/TiO2 under solar light

    NASA Astrophysics Data System (ADS)

    Lahmar, H.; Benamira, M.; Akika, F. Z.; Trari, M.

    2017-11-01

    The CuBi2O4/TiO2 heterojunction was tested with success for the photo-catalytic reduction of chromate ions under sunlight. CuBi2O4, prepared by nitrate process, was characterised photo-electrochemically. The oxide is stable against photo corrosion by consumption of holes in presence of oxalic acid. The light absorption promotes electrons in the conduction band of the sensitizer (CuBi2O4) with a very negative potential (-1.74 VSCE) to participate in the exchange of the electron with HCrO4-. The enhanced activity is due to electron injection of activated CuBi2O4 into TiO2-CB (-0.97 VSCE). The band gap of the semiconductor CuBi2O4 is 1.50 eV with a direct optical transition. This compound is a p-type semiconductor with a flat band potential of -0.39 VSCE and activation energy of 0.18 eV. The electrochemical impedance spectroscopy was undertaken to study the semiconductor/electrolyte interfacial phenomena. The photoactivity on the heterojunction is strongly enhanced. A remarkable performance is obtained in less than 4 h for a concentration of 30 mg in (Cr (VI)) at pH ∼ 4 and a dose of 1 mg/mL; a 98% reduction has been obtained. The kinetic of chromate photoreduction is well described by the Langmuir-Hinshelwood model. The chromate elimination obeys to a pseudo-first order kinetic with an apparent rate constant of 0.014 min-1.

  3. Effect of TiO2 on the Gas Sensing Features of TiO2/PANi Nanocomposites

    PubMed Central

    Huyen, Duong Ngoc; Tung, Nguyen Trong; Thien, Nguyen Duc; Thanh, Le Hai

    2011-01-01

    A nanocomposite of titanium dioxide (TiO2) and polyaniline (PANi) was synthesized by in-situ chemical polymerization using aniline (ANi) monomer and TiCl4 as precursors. SEM pictures show that the nanocomposite was created in the form of long PANi chains decorated with TiO2 nanoparticles. FTIR, Raman and UV-Vis spectra reveal that the PANi component undergoes an electronic structure modification as a result of the TiO2 and PANi interaction. The electrical resistor of the nanocomposite is highly sensitive to oxygen and NH3 gas, accounting for the physical adsorption of these gases. A nanocomposite with around 55% TiO2 shows an oxygen sensitivity of 600–700%, 20–25 times higher than that of neat PANi. The n-p contacts between TiO2 nanoparticles and PANi matrix give rise to variety of shallow donors and acceptor levels in the PANi band gap which enhance the physical adsorption of gas molecules. PMID:22319389

  4. Influence of interface layer on optical properties of sub-20 nm-thick TiO2 films

    NASA Astrophysics Data System (ADS)

    Shi, Yue-Jie; Zhang, Rong-Jun; Li, Da-Hai; Zhan, Yi-Qiang; Lu, Hong-Liang; Jiang, An-Quan; Chen, Xin; Liu, Juan; Zheng, Yu-Xiang; Wang, Song-You; Chen, Liang-Yao

    2018-02-01

    The sub-20 nm ultrathin titanium dioxide (TiO2) films with tunable thickness were deposited on Si substrates by atomic layer deposition (ALD). The structural and optical properties were acquired by transmission electron microscopy, atomic force microscopy and spectroscopic ellipsometry. Afterwards, a constructive and effective method of analyzing interfaces by applying two different optical models consisting of air/TiO2/Ti x Si y O2/Si and air/effective TiO2 layer/Si, respectively, was proposed to investigate the influence of interface layer (IL) on the analysis of optical constants and the determination of band gap of TiO2 ultrathin films. It was found that two factors including optical constants and changing components of the nonstoichiometric IL could contribute to the extent of the influence. Furthermore, the investigated TiO2 ultrathin films of 600 ALD cycles were selected and then annealed at the temperature range of 400-900 °C by rapid thermal annealing. Thicker IL and phase transition cause the variation of optical properties of TiO2 films after annealing and a shorter electron relaxation time reveals the strengthened electron-electron and electron-phonon interactions in the TiO2 ultrathin films at high temperature. The as-obtained results in this paper will play a role in other studies of high dielectric constants materials grown on Si substrates and in the applications of next generation metal-oxide-semiconductor devices.

  5. Spectral characteristics and photosensitization of TiO2 nanoparticles in reverse micelles by perylenes.

    PubMed

    Hernández, Laura I; Godin, Robert; Bergkamp, Jesse J; Llansola Portolés, Manuel J; Sherman, Benjamin D; Tomlin, John; Kodis, Gerdenis; Méndez-Hernández, Dalvin D; Bertolotti, Sonia; Chesta, Carlos A; Mariño-Ochoa, Ernesto; Moore, Ana L; Moore, Thomas A; Cosa, Gonzalo; Palacios, Rodrigo E

    2013-04-25

    We report on the photosensitization of titanium dioxide nanoparticles (TiO2 NPs) synthesized inside AOT (bis(2-ethylhexyl) sulfosuccinate sodium salt) reverse micelles following photoexcitation of perylene derivatives with dicarboxylate anchoring groups. The dyes, 1,7-dibromoperylene-3,4,9,10-tetracarboxy dianhydride (1), 1,7-dipyrrolidinylperylene-3,4,9,10-tetracarboxy dianhydride (2), and 1,7-bis(4-tert-butylphenyloxy)perylene-3,4,9,10-tetracarboxy dianhydride (3), have considerably different driving forces for photoinduced electron injection into the TiO2 conduction band, as estimated by electrochemical measurements and quantum mechanical calculations. Fluorescence anisotropy measurements indicate that dyes 1 and 2 are preferentially solubilized in the micellar structure, creating a relatively large local concentration that favors the attachment of the dye to the TiO2 surface. The binding process was followed by monitoring the hypsochromic shift of the dye absorption spectra over time for 1 and 2. Photoinduced electron transfer from the singlet excited state of 1 and 2 to the TiO2 conduction band (CB) is indicated by emission quenching of the TiO2-bound form of the dyes and confirmed by transient absorption measurements of the radical cation of the dyes and free carriers (injected electrons) in the TiO2 semiconductor. Steady state and transient spectroscopy indicate that dye 3 does not bind to the TiO2 NPs and does not photosensitize the semiconductor. This observation was rationalized as a consequence of the bulky t-butylphenyloxy groups which create a strong steric impediment for deep access of the dye within the micelle structure to reach the semiconductor oxide surface.

  6. SYNTHESIZING ORGANIC COMPOUNDS USING LIGHT-ACTIVATED TIO2

    EPA Science Inventory

    High-value organic compounds have been synthesized successfully from linear and cyclic hydrocarbons, by photocatalytic oxidation using a semiconductor material, titanium dioxide (TiO2). Various hydrocarbons were partially oxgenated in both liquid and gaseous phase reactors usi...

  7. Continuum and atomistic description of excess electrons in TiO2

    NASA Astrophysics Data System (ADS)

    Maggio, Emanuele; Martsinovich, Natalia; Troisi, Alessandro

    2016-02-01

    The modelling of an excess electron in a semiconductor in a prototypical dye sensitised solar cell is carried out using two complementary approaches: atomistic simulation of the TiO2 nanoparticle surface is complemented by a dielectric continuum model of the solvent-semiconductor interface. The two methods are employed to characterise the bound (excitonic) states formed by the interaction of the electron in the semiconductor with a positive charge opposite the interface. Density-functional theory (DFT) calculations show that the excess electron in TiO2 in the presence of a counterion is not fully localised but extends laterally over a large region, larger than system sizes accessible to DFT calculations. The numerical description of the excess electron at the semiconductor-electrolyte interface based on the continuum model shows that the exciton is also delocalised over a large area: the exciton radius can have values from tens to hundreds of Ångströms, depending on the nature of the semiconductor (characterised by the dielectric constant and the electron effective mass in our model).

  8. The effect of TiO2 thin film thickness on self-cleaning glass properties

    NASA Astrophysics Data System (ADS)

    Mufti, Nandang; Laila, Ifa K. R.; Hartatiek; Fuad, Abdulloh

    2017-05-01

    TiO2 is one of semiconductor materials which are widely used as photocatalyst in the form of a thin film. The TiO2 thin film is prepared by using the spin coating sol-gel method. The researcher prepared TiO2 thin film with 3 coating variations and X-Ray Diffraction characterization, UV-Vis Spectrophotometer, Electron Microscopy Scanning, and examined its hydrophilic and anti-fogging properties. The result of X-Ray Diffraction showed that the phase formed is the anatase on 101crystal field. The Electron Microscopy Scanning images showed that TiO2 thin films had a homogeneous surface with the particle sizes as big as 235 nm, 179 nm, and 137 nm. The thickness of each thin film was 2.06μm, 3.33μm, and 5.20μm. The characterization of UV-Vis Spectrophotometer showed that the greatest absorption to the wavelength of visible light was in the thin film’s thickness of 3 coatings with the band-gap determined by using 3.30 eV, 3.33 eV, and 3.33 eV Plot Tuoc. These results indicated that the rate of absorption would be increased by increasing the thickness of film. The increasing thickness of the thin film makes the film hydrophilic able to be used as an anti-fogging substance.

  9. Superhydrophobicity construction with dye-sensitised TiO2 on fabric surface for both oil/water separation and water bulk contaminants purification

    NASA Astrophysics Data System (ADS)

    Yu, Linfeng; Zhang, Shengmiao; Zhang, Meng; Chen, Jianding

    2017-12-01

    For the promising material for both oil/water separation and water-soluble contaminants, the Dye@TiO2-TEOS/VTEO hybrid modified polyester fabric is developed by a simple dip-coating process, which combines Dye-sensitised TiO2 with silicon contained superhydrophobic coating to guarantee the long-term stability of Dye-sensitised TiO2 system as well as material's sustainability. The modified fabric possesses selective oil/water seperation properties towards water and oil, besides, mechanical, acid and alkali durability shows this material's appropriate performance on oil/water separation. UV-Vis absorption spectrum reveals the Dye 4-(2H-imidazol-2-ylazo) benzoic acid could sensitize the semiconductor TiO2 for visible light catalytic organic pollutant degradation that is also confirmed by methylene blue degradation experiment. Density Functional calculation (DFT) witnesses that HOMO, HOMO-1 of Dye contributed by oxygen bonding to TiO2 can insert into TiO2 band gap and result in low energy electron excitation. The ability of oil/water separation and water-soluble contaminants purification provides the material opportunity to practical applications in environmental restoration and human life.

  10. Cold sprayed WO3 and TiO2 electrodes for photoelectrochemical water and methanol oxidation in renewable energy applications.

    PubMed

    Haisch, Christoph; Schneider, Jenny; Fleisch, Manuel; Gutzmann, Henning; Klassen, Thomas; Bahnemann, Detlef W

    2017-10-03

    Films prepared by cold spray have potential applications as photoanodes in electrochemical water splitting and waste water purification. In the present study cold sprayed photoelectrodes produced with WO 3 (active under visible light illumination) and TiO 2 (active under UV illumination) on titanium metal substrates were investigated as photoanodes for the oxidation of water and methanol, respectively. Methanol was chosen as organic model pollutant in acidic electrolytes. Main advantages of the cold sprayed photoelectrodes are the improved metal-semiconductor junctions and the superior mechanical stability. Additionally, the cold spray method can be utilized as a large-scale electrode fabrication technique for photoelectrochemical applications. Incident photon to current efficiencies reveal that cold sprayed TiO 2 /WO 3 photoanodes exhibit the best photoelectrochemical properties with regard to the water and methanol oxidation reactions in comparison with the benchmark photocatalyst Aeroxide TiO 2 P25 due to more efficient harvesting of the total solar light irradiation related to their smaller band gap energies.

  11. Preparation of TiO2/(TiO2-V2O5)/polypyrrole nanocomposites and a study on catalytic activities of the hybrid materials under UV/Visible light and in the dark

    NASA Astrophysics Data System (ADS)

    Piewnuan, C.; Wootthikanokkhan, J.; Ngaotrakanwiwat, P.; Meeyoo, V.; Chiarakorn, S.

    2014-11-01

    Hybrid metal oxides/polymer nanocomposites, namely TiO2/(TiO2-V2O5)/polypyrrole (PPy), were synthesized via in situ polymerization. Structures of the products were characterized by SEM-EDX, XRD, and FTIR techniques. The light absorbance and band gap energy values of the materials were evaluated by UV/Visible spectroscopy. The catalytic activity of the materials was determined from a degradation of methylene blue. It was found that, regardless of the polymerization time, the absorbance of TiO2/(TiO2-V2O5)/PPy was greater than those of TiO2/PPy and the neat TiO2, respectively. This was in accordance with the decrease in the band gap energy of the materials. The catalytic activity of TiO2/(TiO2-V2O5) was also observed in the dark. After polymerization, the catalytic activity of nanocomposite under UV/Visible light and in the dark was compromised. The above effects are discussed in the light of the energy storage ability of V2O5 and capability of the polymer in acting as a binder for the system.

  12. Remediation of 17-α-ethinylestradiol aqueous solution by photocatalysis and electrochemically-assisted photocatalysis using TiO2 and TiO2/WO3 electrodes irradiated by a solar simulator.

    PubMed

    Oliveira, Haroldo G; Ferreira, Leticia H; Bertazzoli, Rodnei; Longo, Claudia

    2015-04-01

    TiO2 and TiO2/WO3 electrodes, irradiated by a solar simulator in configurations for heterogeneous photocatalysis (HP) and electrochemically-assisted HP (EHP), were used to remediate aqueous solutions containing 10 mg L(-1) (34 μmol L(-1)) of 17-α-ethinylestradiol (EE2), active component of most oral contraceptives. The photocatalysts consisted of 4.5 μm thick porous films of TiO2 and TiO2/WO3 (molar ratio W/Ti of 12%) deposited on transparent electrodes from aqueous suspensions of TiO2 particles and WO3 precursors, followed by thermal treatment at 450 (°)C. First, an energy diagram was organized with photoelectrochemical and UV-Vis absorption spectroscopy data and revealed that EE2 could be directly oxidized by the photogenerated holes at the semiconductor surfaces, considering the relative HOMO level for EE2 and the semiconductor valence band edges. Also, for the irradiated hybrid photocatalyst, electrons in TiO2 should be transferred to WO3 conduction band, while holes move toward TiO2 valence band, improving charge separation. The remediated EE2 solutions were analyzed by fluorescence, HPLC and total organic carbon measurements. As expected from the energy diagram, both photocatalysts promoted the EE2 oxidation in HP configuration; after 4 h, the EE2 concentration decayed to 6.2 mg L(-1) (35% of EE2 removal) with irradiated TiO2 while TiO2/WO3 electrode resulted in 45% EE2 removal. A higher performance was achieved in EHP systems, when a Pt wire was introduced as a counter-electrode and the photoelectrodes were biased at +0.7 V; then, the EE2 removal corresponded to 48 and 54% for the TiO2 and TiO2/WO3, respectively. The hybrid TiO2/WO3, when compared to TiO2 electrode, exhibited enhanced sunlight harvesting and improved separation of photogenerated charge carriers, resulting in higher performance for removing this contaminant of emerging concern from aqueous solution. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. A Molecular Cobalt Catalyst Architected and TiO2 Modified p-GaInP2 Photoelectrode for Hydrogen Production

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gu, Jing; Yan, Yong; Young, James

    2017-05-01

    We demonstrate that by employing a hybrid molecular/semiconductor interface with atomic layer deposited (ALD) TiO2 as an intermediate layer, a robust and corrosion resistant GaInP2-TiO2-cobaltoxime-TiO2 photocathode can be operated in alkaline media (pH =13).

  14. Using TiO2 as a conductive protective layer for photocathodic H2 evolution.

    PubMed

    Seger, Brian; Pedersen, Thomas; Laursen, Anders B; Vesborg, Peter C K; Hansen, Ole; Chorkendorff, Ib

    2013-01-23

    Surface passivation is a general issue for Si-based photoelectrodes because it progressively hinders electron conduction at the semiconductor/electrolyte interface. In this work, we show that a sputtered 100 nm TiO(2) layer on top of a thin Ti metal layer may be used to protect an n(+)p Si photocathode during photocatalytic H(2) evolution. Although TiO(2) is a semiconductor, we show that it behaves like a metallic conductor would under photocathodic H(2) evolution conditions. This behavior is due to the fortunate alignment of the TiO(2) conduction band with respect to the hydrogen evolution potential, which allows it to conduct electrons from the Si while simultaneously protecting the Si from surface passivation. By using a Pt catalyst the electrode achieves an H(2) evolution onset of 520 mV vs NHE and a Tafel slope of 30 mV when illuminated by the red part (λ > 635 nm) of the AM 1.5 spectrum. The saturation photocurrent (H(2) evolution) was also significantly enhanced by the antireflective properties of the TiO(2) layer. It was shown that with proper annealing conditions these electrodes could run 72 h without significant degradation. An Fe(2+)/Fe(3+) redox couple was used to help elucidate details of the band diagram.

  15. Synthesis and Characterization of Photocatalytic TiO 2 -ZnFe 2 O 4 Nanoparticles

    DOE PAGES

    Srinivasan, Sesha S.; Wade, Jeremy; Stefanakos, Elias K.

    2006-01-01

    A new coprecipimore » tation/hydrolysis synthesis route is used to create a TiO 2 -ZnFe 2 O 4 nanocomposite that is directed towards extending the photoresponse of TiO 2 from UV to visible wavelengths ( > 400   nm ). The effect of TiO 2 's accelerated anatase-rutile phase transformation due to the presence of the coupled ZnFe 2 O 4 narrow-bandgap semiconductor is evaluated. The transformation's dependence on pH, calcinations temperature, particle size, and ZnFe 2 O 4 concentration has been analyzed using XRD, SEM, and UV-visible spectrometry. The requirements for retaining the highly photoactive anatase phase present in a ZnFe 2 O 4 nanocomposite are outlined. The visible-light-activated photocatalytic activity of the TiO 2 -ZnFe 2 O 4 nanocomposites has been compared to an Aldrich TiO 2 reference catalyst, using a solar-simulated photoreactor for the degradation of phenol.« less

  16. One pot synthesis of nanosized anion doped TiO2: Effect of irradiation of sound waves on surface morphology and optical properties

    NASA Astrophysics Data System (ADS)

    Sharotri, Nidhi; Sud, Dhiraj

    2015-08-01

    Commercialization of AOP's for remediation of pollutants from environmental matrix required the process to be operated by solar light. Semiconductor TiO2 has emerged as an effective and preferred photocatalyst in the field of environmental photocatalysis due to its; (i) biological and chemical inertness (ii) resistance to chemical and photo corrosion, (iii) can absorb natural UV light due to appropriate energetic separation between its valence and conduction band. However, unfortunately the optical band gap of TiO2 (3.0-3.23 eV) with absorption cut off ˜ 380 nm, enables it to harness only a small fraction (˜ 5%) of the entire solar spectrum. One of the current areas of research is modification of TiO2 photocatalyst. In present paper one pot greener synthesis from titanium isopropoxide and hydroxylamine hydrochloride has been used as titanium and nitrogen precursor under ultrasonic waves. The as synthesized TiO2 nanomaterials were dried at 100°C and further calcinated at different temperatures. The effect of reaction parameters such as ultrasonication time on the yield, surface morphology, spectroscopic data and optical properties was also investigated. The results confirm that the anatase phase is a main phase with a crystallite size of 35-77 nm and the calculated band gap of nanomaterials varies from 2.10-3.1 eV.

  17. Ambiguous Role of Growth-Induced Defects on the Semiconductor-to-Metal Characteristics in Epitaxial VO2/TiO2 Thin Films.

    PubMed

    Mihailescu, Cristian N; Symeou, Elli; Svoukis, Efthymios; Negrea, Raluca F; Ghica, Corneliu; Teodorescu, Valentin; Tanase, Liviu C; Negrila, Catalin; Giapintzakis, John

    2018-04-25

    Controlling the semiconductor-to-metal transition temperature in epitaxial VO 2 thin films remains an unresolved question both at the fundamental as well as the application level. Within the scope of this work, the effects of growth temperature on the structure, chemical composition, interface coherency and electrical characteristics of rutile VO 2 epitaxial thin films grown on TiO 2 substrates are investigated. It is hereby deduced that the transition temperature is lower than the bulk value of 340 K. However, it is found to approach this value as a function of increased growth temperature even though it is accompanied by a contraction along the V 4+ -V 4+ bond direction, the crystallographic c-axis lattice parameter. Additionally, it is demonstrated that films grown at low substrate temperatures exhibit a relaxed state and a strongly reduced transition temperature. It is suggested that, besides thermal and epitaxial strain, growth-induced defects may strongly affect the electronic phase transition. The results of this work reveal the difficulty in extracting the intrinsic material response to strain, when the exact contribution of all strain sources cannot be effectively determined. The findings also bear implications on the limitations in obtaining the recently predicted novel semi-Dirac point phase in VO 2 /TiO 2 multilayer structures.

  18. Excess electrons in reduced rutile and anatase TiO2

    NASA Astrophysics Data System (ADS)

    Yin, Wen-Jin; Wen, Bo; Zhou, Chuanyao; Selloni, Annabella; Liu, Li-Min

    2018-05-01

    As a prototypical photocatalyst, TiO2 is a material of scientific and technological interest. In photocatalysis and other applications, TiO2 is often reduced, behaving as an n-type semiconductor with unique physico-chemical properties. In this review, we summarize recent advances in the understanding of the fundamental properties and applications of excess electrons in reduced, undoped TiO2. We discuss the characteristics of excess electrons in the bulk and at the surface of rutile and anatase TiO2 focusing on their localization, spatial distribution, energy levels, and dynamical properties. We examine specific features of the electronic states for photoexcited TiO2, for intrinsic oxygen vacancy and Ti interstitial defects, and for surface hydroxyls. We discuss similarities and differences in the behaviors of excess electrons in the rutile and anatase phases. Finally, we consider the effect of excess electrons on the reactivity, focusing on the interaction between excess electrons and adsorbates.

  19. Comparison of modification strategies towards enhanced charge carrier separation and photocatalytic degradation activity of metal oxide semiconductors (TiO2, WO3 and ZnO)

    NASA Astrophysics Data System (ADS)

    Kumar, S. Girish; Rao, K. S. R. Koteswara

    2017-01-01

    Metal oxide semiconductors (TiO2, WO3 and ZnO) finds unparalleled opportunity in wastewater purification under UV/visible light, largely encouraged by their divergent admirable features like stability, non-toxicity, ease of preparation, suitable band edge positions and facile generation of active oxygen species in the aqueous medium. However, the perennial failings of these photocatalysts emanates from the stumbling blocks like rapid charge carrier recombination and meager visible light response. In this review, tailoring the surface-bulk electronic structure through the calibrated and veritable approaches such as impurity doping, deposition with noble metals, sensitizing with other compounds (dyes, polymers, inorganic complexes and simple chelating ligands), hydrogenation process (annealing under hydrogen atmosphere), electronic integration with other semiconductors, modifying with carbon nanostructures, designing with exposed facets and tailoring with hierarchical morphologies to overcome their critical drawbacks are summarized. Taking into account the materials intrinsic properties, the pros and cons together with similarities and striking differences for each strategy in specific to TiO2, WO3 & ZnO are highlighted. These subtlety enunciates the primacy for improving the structure-electronic properties of metal oxides and credence to its fore in the practical applications. Future research must focus on comparing the performances of ZnO, TiO2 and WO3 in parallel to get insight into their photocatalytic behaviors. Such comparisons not only reveal the changed surface-electronic structure upon various modifications, but also shed light on charge carrier dynamics, free radical generation, structural stability and compatibility for photocatalytic reactions. It is envisioned that these cardinal tactics have profound implications and can be replicated to other semiconductor photocatalysts like CeO2, In2O3, Bi2O3, Fe2O3, BiVO4, AgX, BiOX (X = Cl, Br & I), Bi2WO6, Bi2MoO6

  20. Significantly enhanced visible light response in single TiO2 nanowire by nitrogen ion implantation

    NASA Astrophysics Data System (ADS)

    Wu, Pengcheng; Song, Xianyin; Si, Shuyao; Ke, Zunjian; Cheng, Li; Li, Wenqing; Xiao, Xiangheng; Jiang, Changzhong

    2018-05-01

    The metal-oxide semiconductor TiO2 shows enormous potential in the field of photoelectric detection; however, UV-light absorption only restricts its widespread application. It is considered that nitrogen doping can improve the visible light absorption of TiO2, but the effect of traditional chemical doping is far from being used for visible light detection. Herein, we dramatically broadened the absorption spectrum of the TiO2 nanowire (NW) by nitrogen ion implantation and apply the N-doped single TiO2 NW to visible light detection for the first time. Moreover, this novel strategy effectively modifies the surface states and thus regulates the height of Schottky barriers at the metal/semiconductor interface, which is crucial to realizing high responsivity and a fast response rate. Under the illumination of a laser with a wavelength of 457 nm, our fabricated photodetector exhibits favorable responsivity (8 A W-1) and a short response time (0.5 s). These results indicate that ion implantation is a promising method in exploring the visible light detection of TiO2.

  1. Significantly enhanced visible light response in single TiO2 nanowire by nitrogen ion implantation.

    PubMed

    Wu, Pengcheng; Song, Xianyin; Si, Shuyao; Ke, Zunjian; Cheng, Li; Li, Wenqing; Xiao, Xiangheng; Jiang, Changzhong

    2018-05-04

    The metal-oxide semiconductor TiO 2 shows enormous potential in the field of photoelectric detection; however, UV-light absorption only restricts its widespread application. It is considered that nitrogen doping can improve the visible light absorption of TiO 2 , but the effect of traditional chemical doping is far from being used for visible light detection. Herein, we dramatically broadened the absorption spectrum of the TiO 2 nanowire (NW) by nitrogen ion implantation and apply the N-doped single TiO 2 NW to visible light detection for the first time. Moreover, this novel strategy effectively modifies the surface states and thus regulates the height of Schottky barriers at the metal/semiconductor interface, which is crucial to realizing high responsivity and a fast response rate. Under the illumination of a laser with a wavelength of 457 nm, our fabricated photodetector exhibits favorable responsivity (8 A W -1 ) and a short response time (0.5 s). These results indicate that ion implantation is a promising method in exploring the visible light detection of TiO 2 .

  2. The Effects of Anchor Groups on (1) TiO2-Catalyzed Photooxidation and (2) Linker-Assisted Assembly on TiO2

    NASA Astrophysics Data System (ADS)

    Anderson, Ian Mark

    Quantum dot-sensitized solar cells (QDSSCs) are a popular target for research due to their potential for highly efficient, easily tuned absorption. Typically, light is absorbed by quantum dots attached to a semiconductor substrate, such as TiO2, via bifunctional linker molecules. This research aims to create a patterned monolayer of linker molecules on a TiO2 film, which would in turn allow the attachment of a patterned layer of quantum dots. One method for the creation of a patterned monolayer is the functionalization of a TiO2 film with a linker molecule, followed by illumination with a laser at 355 nm. This initiates a TiO 2-catalyzed oxidation reaction, causing loss of surface coverage. A second linker molecule can then be adsorbed onto the TiO2 surface in the illuminated area. Towards that end, the behaviors of carboxylic and phosphonic acids adsorbed on TiO2 have been studied. TiO2 films were functionalized by immersion in solutions a single adsorbate and surface coverage was determined by IR spectroscopy. It is shown that phosphonic acids attain higher surface coverage than carboxylic acids, and will displace them from TiO2 when in a polar solvent. Alkyl chain lengths, which can influence stabilities of monolayers, are shown not to have an effect on this relationship. Equilibrium binding data for the adsorption of n-hexadecanoic acid to TiO2 from a THF solution are presented. It is shown that solvent polarity can affect monolayer stability; carboxylates and phosphonates undergo more desorption into polar solvents than nonpolar. Through illumination, it was possible to remove nearly all adsorbed linkers from TiO2. However, the illuminated areas were found not to be receptive to attachment by a second adsorbate. A possible reason for this behavior is presented. I also report on the synthesis and characterization of a straight-chain, thiol-terminated phosphonic acid. Initial experiments involving monolayer formation and quantum dot attachment are presented

  3. Efficient solar light-driven degradation of Congo red with novel Cu-loaded Fe3O4@TiO2 nanoparticles.

    PubMed

    Arora, Priya; Fermah, Alisha; Rajput, Jaspreet Kaur; Singh, Harminder; Badhan, Jigyasa

    2017-08-01

    In this work, Cu-loaded Fe 3 O 4 @TiO 2 core shell nanoparticles were prepared in a single pot by coating of TiO 2 on Fe 3 O 4 nanoparticles followed by Cu loading. X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), thermogravimetric analysis (TGA), Brunauer-Emmett- Teller (BET), vibrating sample magnetometry (VSM), X-ray photoelectron spectroscopy (XPS), and valence band X-ray photoelectron spectroscopy (VB XPS) techniques were used for characterization of as prepared nanoparticles. Synergism between copper and titania was evaluated by studying the solar light-driven photodegradation of Congo red dye solution in the presence of Fe 3 O 4 @TiO 2 nanoparticles on one side and Cu-loaded Fe 3 O 4 @TiO 2 nanoparticles on the other side. The latter performed better than the former catalyst, indicating the enhanced activity of copper-loaded catalyst. Further photodegradation was studied by three means, i.e., under ultraviolet (UV), refluxing, and solar radiations. Cu-loaded Fe 3 O 4 @TiO 2 enhanced the degradation efficiency of Congo red dye. Thus, Cu act possibly by reducing the band gap of TiO 2 and widening the optical response of semiconductor, as a result of which solar light could be used to carry out photocatalysis. Graphical abstract Photodegradation of congo red over Cu-loaded Fe 3 O 4 @TiO 2 nanoparticles.

  4. Anhydrous crystals of DNA bases are wide gap semiconductors.

    PubMed

    Maia, F F; Freire, V N; Caetano, E W S; Azevedo, D L; Sales, F A M; Albuquerque, E L

    2011-05-07

    We present the structural, electronic, and optical properties of anhydrous crystals of DNA nucleobases (guanine, adenine, cytosine, and thymine) found after DFT (Density Functional Theory) calculations within the local density approximation, as well as experimental measurements of optical absorption for powders of these crystals. Guanine and cytosine (adenine and thymine) anhydrous crystals are predicted from the DFT simulations to be direct (indirect) band gap semiconductors, with values 2.68 eV and 3.30 eV (2.83 eV and 3.22 eV), respectively, while the experimentally estimated band gaps we have measured are 3.83 eV and 3.84 eV (3.89 eV and 4.07 eV), in the same order. The electronic effective masses we have obtained at band extremes show that, at low temperatures, these crystals behave like wide gap semiconductors for electrons moving along the nucleobases stacking direction, while the hole transport are somewhat limited. Lastly, the calculated electronic dielectric functions of DNA nucleobases crystals in the parallel and perpendicular directions to the stacking planes exhibit a high degree of anisotropy (except cytosine), in agreement with published experimental results.

  5. The strain induced band gap modulation from narrow gap semiconductor to half-metal on Ti{sub 2}CrGe: A first principles study

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Jia, E-mail: jiali@hebut.edu.cn; Research Institute for Energy Equipment Materials, Hebei University of Technology, Tianjin 300401; Zhang, Zhidong

    The Heusler alloy Ti{sub 2}CrGe is a stable L2{sub 1} phase with antiferromagnetic ordering. With band-gap energy (∼ 0.18 eV) obtained from a first-principles calculation, it belongs to the group of narrow band gap semiconductor. The band-gap energy decreases with increasing lattice compression and disappears until a strain of −5%; moreover, gap contraction only occurs in the spin-down states, leading to half-metallic character at the −5% strain. The Ti{sub 1}, Ti{sub 2}, and Cr moments all exhibit linear changes in behavior within strains of −5%– +5%. Nevertheless, the total zero moment is robust for these strains. The imaginary part ofmore » the dielectric function for both up and down spin states shows a clear onset energy, indicating a corresponding electronic gap for the two spin channels.« less

  6. Engineering the Band Gap States of the Rutile TiO2 (110) Surface by Modulating the Active Heteroatom.

    PubMed

    Yu, Yaoguang; Yang, Xu; Zhao, Yanling; Zhang, Xiangbin; An, Liang; Huang, Miaoyan; Chen, Gang; Zhang, Ruiqin

    2018-04-19

    Introducing band gap states to TiO 2 photocatalysts is an efficient strategy for expanding the range of accessible energy available in the solar spectrum. However, few approaches are able to introduce band gap states and improve photocatalytic performance simultaneously. Introducing band gap states by creating surface disorder can incapacitate reactivity where unambiguous adsorption sites are a prerequisite. An alternative method for introduction of band gap states is demonstrated in which selected heteroatoms are implanted at preferred surface sites. Theoretical prediction and experimental verification reveal that the implanted heteroatoms not only introduce band gap states without creating surface disorder, but also function as active sites for the Cr VI reduction reaction. This promising approach may be applicable to the surfaces of other solar harvesting materials where engineered band gap states could be used to tune photophysical and -catalytic properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. First-principles study of Mn-S codoped anatase TiO2

    NASA Astrophysics Data System (ADS)

    Li, Senlin; Huang, Jinliang; Ning, Xiangmei; Chen, Yongcha; Shi, Qingkui

    2018-04-01

    In this work, the CASTEP program in Materials Studio 2017 software package was applied to calculate the electronic structures and optical properties of pure anatase TiO2, S-doped, Mn-doped and Mn-S co-doped anatase TiO2 by GGA + U methods based on the density function theory (DFT). The results indicate that the lattice is distorted and the lattice constant is reduce due to doping. The doping also introduces impurity energy levels into the forbidden band. After substitution of Mn for Ti atom, band gap narrowing of anatase TiO2 is caused by the impurity energy levels appearance in the near Fermi surface, which are contributed by Mn-3d orbital, Ti-3d orbital and O-2p orbital hybridization. After substitution of S for O atom, band gap narrowing is creited with the shallow accepter level under the conduction hand of S-3p orbital. The Mn-S co-doped anatase TiO2 could be a potential candidate for a photocatalyst because of tis enhanced absorption ability of visible light. The results can well explain the immanent cause of a band gap narrowing as well as a red shift in the spectrum for doped anatase TiO2.

  8. Structural, Morphological, Optical and Photocatalytic Properties of Y, N-Doped and Codoped TiO2 Thin Films

    PubMed Central

    Hamden, Zeineb; Conceição, David; Boufi, Sami; Vieira Ferreira, Luís Filipe; Bouattour, Soraa

    2017-01-01

    Pure TiO2, Y-N single-doped and codoped TiO2 powders and thin films deposited on glass beads were successfully prepared using dip-coating and sol-gel methods. The samples were analyzed using grazing angle X-ray diffraction (GXRD), Raman spectroscopy, time resolved luminescence, ground state diffuse reflectance absorption and scanning electron microscopy (SEM). According to the GXRD patterns and micro-Raman spectra, only the anatase form of TiO2 was made evident. Ground state diffuse reflectance absorption studies showed that doping with N or codoping with N and Y led to an increase of the band gap. Laser induced luminescence analysis revealed a decrease in the recombination rate of the photogenerated holes and electrons. The photocatalytic activity of supported catalysts, toward the degradation of toluidine, revealed a meaningful enhancement upon codoping samples at a level of 2% (atomic ratio). The photocatalytic activity of the material and its reactivity can be attributed to a reduced, but significant, direct photoexcitation of the semiconductor by the halogen lamp, together with a charge-transfer-complex mechanism, or with the formation of surface oxygen vacancies by the N dopant atoms. PMID:28772962

  9. Photochemical Grafting of Organic Alkenes to Single-Crystal TiO2 Surfaces: A Mechanistic Study

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Franking, Ryan A.; Kim, Heesuk; Chambers, Scott A.

    2012-08-21

    The UV-induced photochemical grafting of terminal alkenes has emerged as a versatile way to form molecular layers on semiconductor surfaces. Recent studies have shown that grafting reactions can be initiated by photoelectron emission into the reactant liquid as well as by excitation across the semiconductor bandgap, but the relative importance of these two processes is expected to depend on the nature of the semiconductor and the reactant alkene and the excitation wavelength. Here we report a study of the wavelength-dependent photochemical grafting of alkenes onto single-crystal TiO2 samples. Trifluoroacetamide-protected 10-aminododec-1-ene (TFAAD), 10-N-BOC-aminodec-1-ene (t-BOC) and 1-dodecene were used as model alkenes.more » On rutile(110), photons with energy above the bandgap but below the expected work function are not effective at inducing grafting, while photons with energy sufficient to induce electronic transitions from the TiO2 Fermi level to electronic acceptor states of the reactant molecules induce grafting. A comparison of rutile (110), rutile(001), anatase (001), and anatase(101) samples shows slightly enhanced grafting for rutile but no difference between crystal faces for a given crystal phase. Hydroxylation of the surface increases the reaction rate by lowering the work function and thereby facilitating photoelectron ejection into the adjacent alkene. These results demonstrate that photoelectron emission is the dominant mechanism responsible for grafting when using short-wavelength (~254 nm) light and suggest that photoemission events beginning on mid-gap states may play a crucial role.« less

  10. Optical spectroscopy of rare earth ion-doped TiO2 nanophosphors.

    PubMed

    Chen, Xueyuan; Luo, Wenqin

    2010-03-01

    Trivalent rare-earth (RE3+) ion-doped TiO2 nanophosphors belong to one kind of novel optical materials and have attracted increasing attention. The luminescence properties of different RE3+ ions in various TiO2 nanomaterials have been reviewed. Much attention is paid to our recent progresses on the luminescence properties of RE3+ (RE = Eu, Er, Sm, Nd) ions in anatase TiO2 nanoparticles prepared by a sol-gel-solvothermal method. Using Eu3+ as a sensitive optical probe, three significantly different luminescence centers of Eu3+ in TiO2 nanoparticles were detected by means of site-selective spectroscopy at 10 K. Based on the crystal-field (CF) splitting of Eu3+ at each site, C2v and D2 symmetries were proposed for Eu3+ incorporated at two lattice sites. A structural model for the formation of multiple sites was proposed based on the optical behaviors of Eu3+ at different sites. Similar multi-site luminescence was observed in Sm(3+)- or Nd(3+)-doped TiO2 nanoparticles. In Eu(3+)-doped TiO2 nanoparticles, only weak energy transfer from the TiO2 host to the Eu3+ ions was observed at 10 K due to the mismatch of energy between the TiO2 band-gap and the Eu3+ excited states. On the contrary, efficient host-sensitized luminescences were realized in Sm(3+)- or Nd(3+)-doped anatase TiO2 nanoparticles due to the match of energy between TiO2 band-gap and the Sm3+ and Nd3+ excited states. The excitation spectra of both Sm(3+)- and Nd(3+)-doped samples exhibit a dominant broad peak centered at approximately 340 nm, which is associated with the band-gap of TiO2, indicating that sensitized emission is much more efficient than direct excitation of the Sm3+ and Nd3+ ions. Single lattice site emission of Er3+ in TiO2 nanocrystals can be achieved by modifying the experimental conditions. Upon excitation by a Ti: sapphire laser at 978 nm, intense green upconverted luminescence was observed. The characteristic emission of Er3+ ions was obtained both in the ultraviolet-visible (UV-vis) and

  11. TiO2 nanoparticles versus TiO2-SiO2 nanocomposites: A comparative study of photo catalysis on acid red 88

    NASA Astrophysics Data System (ADS)

    Balachandran, K.; Venckatesh, Rajendran; Sivaraj, Rajeshwari; Rajiv, P.

    2014-07-01

    A novel, simple, less time-consuming and cost-effective wet chemical technique was used to synthesis TiO2 nanoparticles and TiO2-SiO2 nanocomposites using Titanium tetra isopropoxide (TTIP) as a precursor relatively at low temperature in acidic pH. Titania sol was prepared by hydrolysis of TTIP and was mixed with silicic acid and tetrahydrofuran mixture. The reaction was carried out under vigorous stirring for 6 h and dried at room temperature. The resulting powders were characterized by UV-Visible spectroscopy, Fourier transform infrared (FT-IR), X-ray diffraction, scanning electron microscope (SEM) and transmission electron microscope (TEM). The grain size of the particles was calculated by X-ray diffraction, surface morphology and chemical composition was determined from scanning electron microscopy-energy dispersive spectroscopy, metal oxide stretching was confirmed from FT-IR spectroscopy, band gap was calculated using UV-Visible spectroscopy. Surface area of the composite as calculated by BET analyzer and it was found to be 65 and 75 m2/g for TiO2 and TiO2-SiO2 respectively. The photocatalytic experiments were performed with aqueous solution of acid red 88 with TiO2 and TiO2-SiO2 batch studies for 4 h irradiation, direct photolysis of TiO2 and TiO2-SiO2 contributed 94.2% and 96.5% decomposition in solar radiation for the optimized concentration of acid red 88.

  12. Synergistic effects between TiO2 and carbon nanotubes (CNTs) in a TiO2/CNTs system under visible light irradiation.

    PubMed

    Wu, Chung-Hsin; Kuo, Chao-Yin; Chen, Shih-Ting

    2013-01-01

    This study synthesized a TiO2/carbon nanotubes (CNTs) composite via the sol-gel method. The surface characteristics of the TiO2/CNTs composite were determined by X-ray diffraction, transmission electron microscopy, specific surface area analyser, ultraviolent (UV)-vis spectroscopy, X-ray photoelectron spectroscopy and Raman spectrometer. The photocatalytic activity ofthe TiO2/CNTs composite was evaluated by decolourizing C.I. Reactive Red 2 (RR2) under visible light irradiation. Furthermore, the effects of calcination temperature, pH, RR2 concentration, and the TiO2/CNTs composite dosage on RR2 decolourization were determined simultaneously. The optimal calcination temperature to generate TiO2 and the TiO2/CNTs composite was 673 K, as the percentage of anatase crystallization at this temperature was highest. The specific surface area of the TiO2/CNTs composite and TiO2 were 45 and 42 m2/g, respectively. The band gap of TiO2 and the TiO2/CNTs composite was 2.97 and 2.71 eV by UV-vis measurements, respectively. Experimental data indicate that the Ti-O-C bond formed in the TiO2/CNTs composite. The RR2 decolourization rates can be approximated by pseudo-first-order kinetics; moreover, only the TiO2/CNTs composite had photocatalytic activity under visible light irradiation. At pH 7, the RR2 decolourization rate constant of 0.5, 1 and 2 g/L TiO2/CNTs addition was 0.005, 0.0015, and 0.0047 min(-1), respectively. Decolourization rate increased as pH and the RR2 concentration decreased. The CNTs functioned as electron acceptors, promoting separation of photoinduced electron-hole pairs to retard their recombination; thus, photocatalytic activity of the TiO2/CNTs composite exceeded that of TiO2.

  13. Elementary photocatalytic chemistry on TiO2 surfaces.

    PubMed

    Guo, Qing; Zhou, Chuanyao; Ma, Zhibo; Ren, Zefeng; Fan, Hongjun; Yang, Xueming

    2016-07-07

    Photocatalytic hydrogen production and pollutant degradation provided both great opportunities and challenges in the field of sustainable energy and environmental science. Over the past few decades, we have witnessed fast growing interest and efforts in developing new photocatalysts, improving catalytic efficiency and exploring the reaction mechanism at the atomic and molecular levels. Owing to its relatively high efficiency, nontoxicity, low cost and high stability, TiO2 becomes one of the most extensively investigated metal oxides in semiconductor photocatalysis. Fundamental studies on well characterized single crystals using ultrahigh vacuum based surface science techniques could provide key microscopic insight into the underlying mechanism of photocatalysis. In this review, we have summarized recent progress in the photocatalytic chemistry of hydrogen, water, oxygen, carbon monoxide, alcohols, aldehydes, ketones and carboxylic acids on TiO2 surfaces. We focused this review mainly on the rutile TiO2(110) surface, but some results on the rutile TiO2(011), anatase TiO2(101) and (001) surfaces are also discussed. These studies provided fundamental insights into surface photocatalysis as well as stimulated new investigations in this exciting field. At the end of this review, we have discussed how these studies can help us to develop new photocatalysis models.

  14. Synthesis of reduced graphene oxide-anatase TiO2 nanocomposite and its improved photo-induced charge transfer properties.

    PubMed

    Wang, Ping; Zhai, Yueming; Wang, Dejun; Dong, Shaojun

    2011-04-01

    The construction of reduced graphene oxide or graphene oxide with semiconductor has gained more and more attention due to its unexpected optoelectronic and electronic properties. The synthesis of reduced graphene oxide (RGO) or graphene oxide-semiconductor nanocomposite with well-dispersed decorated particles is still a challenge now. Herein, we demonstrate a facile method for the synthesis of graphene oxide-amorphous TiO(2) and reduced graphene oxide-anatase TiO(2) nanocomposites with well-dispersed particles. The as-synthesized samples were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis absorption spectroscopy, Fourier transform infrared spectrometry, and thermogravimetric analysis. The photovoltaic properties of RGO-anatase TiO(2) were also compared with that of similar sized anatase TiO(2) by transient photovoltage technique, and it was interesting to find that the combination of reduced graphene oxide with anatase TiO(2) will significantly increase the photovoltaic response and retard the recombination of electron-hole pairs in the excited anatase TiO(2).

  15. Electronic coupling in iron oxide-modified TiO2 leads to a reduced band gap and charge separation for visible light active photocatalysis.

    PubMed

    Nolan, Michael

    2011-10-28

    In recent experiments Tada et al. have shown that TiO(2) surfaces modified with iron oxide display visible light photocatalytic activity. This paper presents first principles simulations of iron oxide clusters adsorbed at the rutile TiO(2) (110) surface to elucidate the origin of the visible light photocatalytic activity of iron oxide modified TiO(2). Small iron oxide clusters adsorb at rutile (110) surface and their presence shifts the valence band so that the band gap of the composite is narrowed towards the visible, thus confirming the origin of the visible light activity of this composite material. The presence of iron oxide at the TiO(2) surface leads to charge separation, which is the origin of enhanced photocatalytic efficiency, consistent with experimental photoluminesence and photocurrent data. Surface modification of a metal oxide is thus an interesting route in the development of visible light photocatalytic materials. This journal is © the Owner Societies 2011

  16. A Quasi-Classical Model of the Hubbard Gap in Lightly Compensated Semiconductors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Poklonski, N. A.; Vyrko, S. A.; Kovalev, A. I.

    2016-03-15

    A quasi-classical method for calculating the narrowing of the Hubbard gap between the A{sup 0} and A{sup +} acceptor bands in a hole semiconductor or the D{sup 0} and D{sup –} donor bands in an electron semiconductor is suggested. This narrowing gives rise to the phenomenon of a semiconductor transition from the insulator to metal state with an increase in doping level. The major (doping) impurity can be in one of three charge states (–1, 0, or +1), while the compensating impurity can be in states (+1) or (–1). The impurity distribution over the crystal is assumed to be randommore » and the width of Hubbard bands (levels), to be much smaller than the gap between them. It is shown that narrowing of the Hubbard gap is due to the formation of electrically neutral acceptor (donor) states of the quasicontinuous band of allowed energies for holes (electrons) from excited states. This quasicontinuous band merges with the top of the valence band (v band) for acceptors or with the bottom of the conduction band (c band) for donors. In other words, the top of the v band for a p-type semiconductor or the bottom of the c band for an n-type semiconductor is shifted into the band gap. The value of this shift is determined by the maximum radius of the Bohr orbit of the excited state of an electrically neutral major impurity atom, which is no larger than half the average distance between nearest impurity atoms. As a result of the increasing dopant concentration, the both Hubbard energy levels become shallower and the gap between them narrows. Analytical formulas are derived to describe the thermally activated hopping transition of holes (electrons) between Hubbard bands. The calculated gap narrowing with increasing doping level, which manifests itself in a reduction in the activation energy ε{sub 2} is consistent with available experimental data for lightly compensated p-Si crystals doped with boron and n-Ge crystals doped with antimony.« less

  17. TiO2 nanoparticles versus TiO2-SiO2 nanocomposites: a comparative study of photo catalysis on acid red 88.

    PubMed

    Balachandran, K; Venckatesh, Rajendran; Sivaraj, Rajeshwari; Rajiv, P

    2014-07-15

    A novel, simple, less time-consuming and cost-effective wet chemical technique was used to synthesis TiO2 nanoparticles and TiO2-SiO2 nanocomposites using Titanium tetra isopropoxide (TTIP) as a precursor relatively at low temperature in acidic pH. Titania sol was prepared by hydrolysis of TTIP and was mixed with silicic acid and tetrahydrofuran mixture. The reaction was carried out under vigorous stirring for 6h and dried at room temperature. The resulting powders were characterized by UV-Visible spectroscopy, Fourier transform infrared (FT-IR), X-ray diffraction, scanning electron microscope (SEM) and transmission electron microscope (TEM). The grain size of the particles was calculated by X-ray diffraction, surface morphology and chemical composition was determined from scanning electron microscopy-energy dispersive spectroscopy, metal oxide stretching was confirmed from FT-IR spectroscopy, band gap was calculated using UV-Visible spectroscopy. Surface area of the composite as calculated by BET analyzer and it was found to be 65 and 75 m(2)/g for TiO2 and TiO2-SiO2 respectively. The photocatalytic experiments were performed with aqueous solution of acid red 88 with TiO2 and TiO2-SiO2 batch studies for 4h irradiation, direct photolysis of TiO2 and TiO2-SiO2 contributed 94.2% and 96.5% decomposition in solar radiation for the optimized concentration of acid red 88. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Quantized conductance doubling and hard gap in a two-dimensional semiconductor-superconductor heterostructure.

    PubMed

    Kjaergaard, M; Nichele, F; Suominen, H J; Nowak, M P; Wimmer, M; Akhmerov, A R; Folk, J A; Flensberg, K; Shabani, J; Palmstrøm, C J; Marcus, C M

    2016-09-29

    Coupling a two-dimensional (2D) semiconductor heterostructure to a superconductor opens new research and technology opportunities, including fundamental problems in mesoscopic superconductivity, scalable superconducting electronics, and new topological states of matter. One route towards topological matter is by coupling a 2D electron gas with strong spin-orbit interaction to an s-wave superconductor. Previous efforts along these lines have been adversely affected by interface disorder and unstable gating. Here we show measurements on a gateable InGaAs/InAs 2DEG with patterned epitaxial Al, yielding devices with atomically pristine interfaces between semiconductor and superconductor. Using surface gates to form a quantum point contact (QPC), we find a hard superconducting gap in the tunnelling regime. When the QPC is in the open regime, we observe a first conductance plateau at 4e 2 /h, consistent with theory. The hard-gap semiconductor-superconductor system demonstrated here is amenable to top-down processing and provides a new avenue towards low-dissipation electronics and topological quantum systems.

  19. Light-controlled plasmon switching using hybrid metal-semiconductor nanostructures.

    PubMed

    Paudel, Hari P; Leuenberger, Michael N

    2012-06-13

    We present a proof of concept for the dynamic control over the plasmon resonance frequencies in a hybrid metal-semiconductor nanoshell structure with Ag core and TiO(2) coating. Our method relies on the temporary change of the dielectric function ε of TiO(2) achieved through temporarily generated electron-hole pairs by means of a pump laser pulse. This change in ε leads to a blue shift of the Ag surface plasmon frequency. We choose TiO(2) as the environment of the Ag core because the band gap energy of TiO(2) is larger than the Ag surface plasmon energy of our nanoparticles, which allows the surface plasmon being excited without generating electron-hole pairs in the environment at the same time. We calculate the magnitude of the plasmon resonance shift as a function of electron-hole pair density and obtain shifts up to 126 nm at wavelengths around 460 nm. Using our results, we develop the model of a light-controlled surface plasmon polariton switch.

  20. Multinary I-III-VI2 and I2-II-IV-VI4 Semiconductor Nanostructures for Photocatalytic Applications.

    PubMed

    Regulacio, Michelle D; Han, Ming-Yong

    2016-03-15

    Semiconductor nanostructures that can effectively serve as light-responsive photocatalysts have been of considerable interest over the past decade. This is because their use in light-induced photocatalysis can potentially address some of the most serious environmental and energy-related concerns facing the world today. One important application is photocatalytic hydrogen production from water under solar radiation. It is regarded as a clean and sustainable approach to hydrogen fuel generation because it makes use of renewable resources (i.e., sunlight and water), does not involve fossil fuel consumption, and does not result in environmental pollution or greenhouse gas emission. Another notable application is the photocatalytic degradation of nonbiodegradable dyes, which offers an effective way of ridding industrial wastewater of toxic organic pollutants prior to its release into the environment. Metal oxide semiconductors (e.g., TiO2) are the most widely studied class of semiconductor photocatalysts. Their nanostructured forms have been reported to efficiently generate hydrogen from water and effectively degrade organic dyes under ultraviolet-light irradiation. However, the wide band gap characteristic of most metal oxides precludes absorption of light in the visible region, which makes up a considerable portion of the solar radiation spectrum. Meanwhile, nanostructures of cadmium chalcogenide semiconductors (e.g., CdS), with their relatively narrow band gap that can be easily adjusted through size control and alloying, have displayed immense potential as visible-light-responsive photocatalysts, but the intrinsic toxicity of cadmium poses potential risks to human health and the environment. In developing new nanostructured semiconductors for light-driven photocatalysis, it is important to choose a semiconducting material that has a high absorption coefficient over a wide spectral range and is safe for use in real-world settings. Among the most promising candidates

  1. Data on the effect of improved TiO2/FTO interface and Ni(OH)2 cocatalyst on the photoelectrochemical performances and stability of CdS cased ZnIn2S4/TiO2 heterojunction.

    PubMed

    Mahadik, Mahadeo A; Shinde, Pravin S; Lee, Hyun Hwi; Cho, Min; Jang, Jum Suk

    2018-04-01

    This data article presents the experimental evidences of the effect of TiO 2 -fluorine doped tin oxide interface annealing and Ni(OH) 2 cocatalysts on the photoelectrochemical, structural, morphological and optical properties of Ni(OH) 2 /CdS/ZnIn 2 S 4 /TiO 2 heterojunction. The Raman spectroscopy exhibits the sharp features of the rutile phase of TiO 2 and in agreement with the X-ray diffraction data. The band gap energy of the 500 °C sample was found to be 3.12 eV, further it was increased to 3.20, 3.22 eV for samples annealed at 600 and 700 °C respectively. The decrease in the band gap energy at 500 °C related to the oxygen vacancies and was analysed by photoluminescence spectroscopy analysis. The synthesis, characterization methods and other experimental details of TiO 2 based heterostructure are also provided. The presence of CdS and ZnIn 2 S 4 coating on surface of TiO 2 electrodes providing a high surface area, extended visible absorption and helps to improve the change separation. This data article contains data related to the research article entitled "Highly efficient and stable 3D Ni(OH) 2 /CdS/ZnIn 2 S 4 /TiO 2 heterojunction under solar light: Effect of an improved TiO 2 /FTO interface and cocatalyst" (Mahadik et al., 2017) [1].

  2. The Effect of High N-DOPED Anatase TiO2 on the Band Gap Narrowing and Redshift by First-Principles

    NASA Astrophysics Data System (ADS)

    Hou, Qingyu; Jin, Yongjun; Ying, Chun; Zhao, Erjun; Zhang, Yue; Dong, Hongying

    2012-10-01

    Anatase TiO2 supercells were studied by first-principles, in which one was undoped and another three were high N-doping. Partial densities of states, band structure, population and absorption spectrum were calculated. The calculated results indicated that in the condition of TiO2-xNx (x = 0.0625, 0.125, 0.25), the higher the doping concentration is, the shorter will be the lattice parameters parallel to the direction of c-axis. The strength of covalent bond significantly varied. The formation energy increases at first, and then decreases. The doping models become less stable as N-doping concentration increases. Meanwhile, the narrower the band gap is, the more significant will be the redshift, which is in agreement with the experimental results.

  3. Variation in Optoelectronic Properties of Azo Dye-Sensitized TiO 2 Semiconductor Interfaces with Different Adsorption Anchors: Carboxylate, Sulfonate, Hydroxyl and Pyridyl Groups

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, Lei; Cole, Jacqueline M.; Dai, Chencheng

    2014-05-28

    The optoelectronic properties of four azo dye-sensitized TiO2 interfaces are systematically studied as a function of a changing dye anchoring group: carboxylate, sulfonate, hydroxyl, and pyridyl. The variation in optoelectronic properties of the free dyes and those in dye/TiO 2 nanocomposites are studied both experimentally and computationally, in the context of prospective dye-sensitized solar cell (DSSC) applications. Experimental UV/vis absorption spectroscopy, cyclic voltammetry, and DSSC device performance testing reveal a strong dependence on the nature of the anchor of the optoelectronic properties of these dyes, both in solution and as dye/TiO2 nanocomposites. First-principles calculations on both an isolated dye/TiO2 clustermore » model (using localized basis sets) and each dye modeled onto the surface of a 2D periodic TiO2 nanostructure (using plane wave basis sets) are presented. Detailed examination of these experimental and computational results, in terms of light harvesting, electron conversion and photovoltaic device performance characteristics, indicates that carboxylate is the best anchoring group, and hydroxyl is the worst, whereas sulfonate and pyridyl groups exhibit competing potential. Different sensitization solvents are found to affect critically the extent of dye adsorption achieved in the dye-sensitization of the TiO2 semiconductor, especially where the anchor is a pyridyl group.« less

  4. Transparent nanostructured Fe-doped TiO2 thin films prepared by ultrasonic assisted spray pyrolysis technique

    NASA Astrophysics Data System (ADS)

    Rasoulnezhad, Hossein; Hosseinzadeh, Ghader; Ghasemian, Naser; Hosseinzadeh, Reza; Homayoun Keihan, Amir

    2018-05-01

    Nanostructured TiO2 and Fe-doped TiO2 thin films with high transparency were deposited on glass substrate through ultrasonic-assisted spray pyrolysis technique and were used in the visible light photocatalytic degradation of MB dye. The resulting thin films were characterized by scanning electron microscopy (SEM), Raman spectroscopy, photoluminescence spectroscopy, x-ray diffraction (XRD), and UV-visible absorption spectroscopy techniques. Based on Raman spectroscopy results, both of the TiO2 and Fe-doped TiO2 films have anatase crystal structure, however, because of the insertion of Fe in the structure of TiO2 some point defects and oxygen vacancies are formed in the Fe-doped TiO2 thin film. Presence of Fe in the structure of TiO2 decreases the band gap energy of TiO2 and also reduces the electron–hole recombination rate. Decreasing of the electron–hole recombination rate and band gap energy result in the enhancement of the visible light photocatalytic activity of the Fe-doped TiO2 thin film.

  5. Interfacial band alignment and structural properties of nanoscale TiO2 thin films for integration with epitaxial crystallographic oriented germanium

    NASA Astrophysics Data System (ADS)

    Jain, N.; Zhu, Y.; Maurya, D.; Varghese, R.; Priya, S.; Hudait, M. K.

    2014-01-01

    We have investigated the structural and band alignment properties of nanoscale titanium dioxide (TiO2) thin films deposited on epitaxial crystallographic oriented Ge layers grown on (100), (110), and (111)A GaAs substrates by molecular beam epitaxy. The TiO2 thin films deposited at low temperature by physical vapor deposition were found to be amorphous in nature, and high-resolution transmission electron microscopy confirmed a sharp heterointerface between the TiO2 thin film and the epitaxially grown Ge with no traceable interfacial layer. A comprehensive assessment on the effect of substrate orientation on the band alignment at the TiO2/Ge heterointerface is presented by utilizing x-ray photoelectron spectroscopy and spectroscopic ellipsometry. A band-gap of 3.33 ± 0.02 eV was determined for the amorphous TiO2 thin film from the Tauc plot. Irrespective of the crystallographic orientation of the epitaxial Ge layer, a sufficient valence band-offset of greater than 2 eV was obtained at the TiO2/Ge heterointerface while the corresponding conduction band-offsets for the aforementioned TiO2/Ge system were found to be smaller than 1 eV. A comparative assessment on the effect of Ge substrate orientation revealed a valence band-offset relation of ΔEV(100) > ΔEV(111) > ΔEV(110) and a conduction band-offset relation of ΔEC(110) > ΔEC(111) > ΔEC(100). These band-offset parameters are of critical importance and will provide key insight for the design and performance analysis of TiO2 for potential high-κ dielectric integration and for future metal-insulator-semiconductor contact applications with next generation of Ge based metal-oxide field-effect transistors.

  6. The influence of material type and composition of TiO2- ZnO on manufacturing of paste for the application of DSSC

    NASA Astrophysics Data System (ADS)

    Retnaningsih, L.; Muliani, L.; Aggraini, P. N.; Hidayat, J.

    2016-11-01

    Research, fabrication and material selection for the application of Dye- sensitized solar cell (DSSC) has been performed on glass FTO (Flour Tin Oxide). The material is used in the form of TiO2 paste, TiO2 powder and ZnO powder. Dye-sensitized solar cell (DSSC), is a fotoelektrokimia-based solar cells where the absorption process light done by the dye molecules and the process of separation of inorganic semiconductor materials by charge of Titanium dioxide (TiO2) and Zinc oxide (ZnO). The purpose of this research is to know the exact composition of TiO2 and ZnO materials in order to produce the best efficiency with DSSC. On this research was done making prototype dye-sensitized solar cell using dye Z 907, and semiconductor nanoparticles TiO2 and ZnO powder that is made into a paste by mixing different composition in two variations of samples: A = ZnO (powder) + 40% TiO2 (powder) and B = 60% TiO2 (powder) (40%) + TiO2 (pasta) 60%. The second variation of this high efficiency is value at sample B i.e. TiO2 (powder) + 40% TiO2 (paste) of 60%.

  7. Preparation and solar-light photocatalytic activity of TiO2 composites: TiO2/kaolin, TiO2/diatomite, and TiO2/zeolite

    NASA Astrophysics Data System (ADS)

    Li, Y.; Li, S. G.; Wang, J.; Li, Y.; Ma, C. H.; Zhang, L.

    2014-12-01

    Three TiO2 loaded composites, TiO2/kaolin, TiO2/diatomite, and TiO2/zeolite, were prepared in order to improve the solar-light photocatalytic activity of TiO2. The results showed that the photocatalytic activity could obviously be enhanced by loading appropriate amount of inorganic mineral materials. Meanwhile, TiO2 content, heat-treatment temperature and heat-treatment time on the photocatalytic activity were reviewed. Otherwise, the effect of solar light irradiation time and dye concentration on the photocatalytic degradation of Acid Red B was investigated. Furthermore, the degradation mechanism and adsorption process were also discussed.

  8. Photolithographically Patterned TiO2 Films for Electrolyte-Gated Transistors.

    PubMed

    Valitova, Irina; Kumar, Prajwal; Meng, Xiang; Soavi, Francesca; Santato, Clara; Cicoira, Fabio

    2016-06-15

    Metal oxides constitute a class of materials whose properties cover the entire range from insulators to semiconductors to metals. Most metal oxides are abundant and accessible at moderate cost. Metal oxides are widely investigated as channel materials in transistors, including electrolyte-gated transistors, where the charge carrier density can be modulated by orders of magnitude upon application of relatively low electrical bias (2 V). Electrolyte gating offers the opportunity to envisage new applications in flexible and printed electronics as well as to improve our current understanding of fundamental processes in electronic materials, e.g. insulator/metal transitions. In this work, we employ photolithographically patterned TiO2 films as channels for electrolyte-gated transistors. TiO2 stands out for its biocompatibility and wide use in sensing, electrochromics, photovoltaics and photocatalysis. We fabricated TiO2 electrolyte-gated transistors using an original unconventional parylene-based patterning technique. By using a combination of electrochemical and charge carrier transport measurements we demonstrated that patterning improves the performance of electrolyte-gated TiO2 transistors with respect to their unpatterned counterparts. Patterned electrolyte-gated (EG) TiO2 transistors show threshold voltages of about 0.9 V, ON/OFF ratios as high as 1 × 10(5), and electron mobility above 1 cm(2)/(V s).

  9. Synthesis, characterization and sonocatalytic applications of nano-structured carbon based TiO2 catalysts.

    PubMed

    Choi, Jongbok; Cui, Mingcan; Lee, Yonghyeon; Kim, Jeonggwan; Yoon, Yeomin; Jang, Min; Khim, Jeehyeong

    2018-05-01

    In order to enhance sonocatalytic oxidation of a recalcitrant organic pollutant, rhodamine B (RhB), it is necessary to study the fundamental aspects of sonocatalysis. In this study, TiO 2 -incorporated nano-structured carbon (i.e., carbon nanotubes (CNTs) or graphene (GR)) composites were synthesized by coating TiO 2 on CNTs or GR of different mass percentages (0.5, 1, 5, and 10 wt%) by a facile hydrothermal method. The sonocatalytic degradation rates of RhB were examined for the effect of ultrasound (US) frequency and calcination temperature by using the prepared TiO 2 -NSC composites. Since US frequency affected the sonoluminescence (SL) intensities, it was proposed that there exists a correlation between the surface area or band-gap of the sonocatalysts and the degradation kinetic constants of RhB. In addition, the reusability of TiO 2 -GR composites was also investigated. Overall, the performance of TiO 2 -GRs prepared by the hydrothermal method was better than that of calcined TiO 2 -CNTs. Among TiO 2 -GRs, 5% GR incorporated media (TiO 2 -GR-5) showed the best performance. Interestingly, the kinetic constants of sonocatalysts prepared under hydrothermal conditions had a negative linear relationship with the band-gap energy for the corresponding media. Furthermore, the strongest SL intensity and highest degradation rates of RhB for both carbonaceous composites were observed at 500 kHz. The kinetic constants of calcined media decreased linearly as the specific area of the media decreased, while the band-gap energy could not be correlated with the kinetic constants. The GR combined TiO 2 composite might be a good sonocatalyst in wastewater treatment using ultrasound-based oxidation because of its high stability. Copyright © 2018 Elsevier B.V. All rights reserved.

  10. Increased photocatalytic activity induced by TiO2/Pt/SnO2 heterostructured films

    NASA Astrophysics Data System (ADS)

    Testoni, Glaucio O.; Amoresi, Rafael A. C.; Lustosa, Glauco M. M. M.; Costa, João P. C.; Nogueira, Marcelo V.; Ruiz, Miguel; Zaghete, Maria A.; Perazolli, Leinig A.

    2018-02-01

    In this work, a high photocatalytic activity was attained by intercalating a Pt layer between SnO2 and TiO2 semiconductors, which yielded a TiO2/Pt/SnO2 - type heterostructure used in the discoloration of blue methylene (MB) solution. The porous films and platinum layer were obtained by electrophoretic deposition and DC Sputtering, respectively, and were both characterized morphologically and structurally by FE-SEM and XRD. The films with the Pt interlayer were evaluated by photocatalytic activity through exposure to UV light. An increase in efficiency of 22% was obtained for these films compared to those without platinum deposition. Studies on the reutilization of the films pointed out high efficiency and recovery of the photocatalyst, rendering the methodology favorable for the construction of fixed bed photocatalytic reactors. A proposal associated with the mechanism is discussed in this work in terms of the difference in Schottky barrier between the semiconductors and the electrons transfer and trapping cycle. These are fundamental factors for boosting photocatalytic efficiency.

  11. Electrospun TiO2 nanofibers incorporated with graphene nanoflakes for energy conversion

    NASA Astrophysics Data System (ADS)

    Shinde, Manish A.; Alarifi, Ibrahim; Alharbi, Abdulaziz; Asmatulu, Ramazan

    2015-03-01

    Solar energy has been used in many different ways, including solar water heater, solar cooking, space heating, and electricity generation. The major drawbacks of the solar energy conversion systems are the lower conversion efficiency and higher manufacturing and replacement costs. In order to eliminate these obstacles, many studies were focused on the energy and cost efficiencies of the solar cells (particularly dye sensitized solar cells - DSSC and thin film solar cells). In the present study, TiO2 nanofibers incorporated with graphene nanoflakes (0, 2, 4, and 8wt.%) were produced using electrospinning process. The chemical utilized for the electrospinning process included poly (vinyle acetate), dimetylfomamide (DMF), titanium (IV) isopropoxide and acetic acid in the presence and absence of graphene nanoflakes. The resultant nanofibers were heat treated at 300 °C for 2 hrs in a standard oven to remove all the organic parts of the nanofibers, and then further heated up to 500 °C in an argon atmosphere for additional 12 hrs to crystalline the nanofibers. SEM, TEM and XRD studies showed that graphene and TiO2 nanofibers are well integrated in the nanofiber structures. This study may guide some of the scientists and engineers to tailor the energy bang gap structures of some of the semiconductor materials for different industrial applications, including DSSC, water splitting, catalyst, batteries, and fuel cell.

  12. Kinetic phenomena in zero-gap semiconductors CuFeS2 and CuFeTe2: Effect of pressure and heat treatment

    NASA Astrophysics Data System (ADS)

    Popov, V. V.; Konstantinov, P. P.; Rud', Yu. V.

    2011-10-01

    Electrical resistivity ρ and Hal coefficient R are measured as a function of the temperature ( T = 1.7-310 K) and the magnetic field (up to H = 28 kOe) in zero-gap semiconductor CuFeS2 samples subjected to hydrostatic compression and under various heat-treatment conditions. At low temperatures, anomalies are observed in the kinetic effects related to the presence of ferromagnetic clusters: the magnetoresistance at T = 4.2 K and T = 20.4 K acquires a hysteretic character and thermopower α changes its sign at T < 15 K. The temperature dependence of conduction-electron concentration n in CuFeS2 has a power form in the temperature range T = 14-300 K, which is characteristic of the intrinsic conductivity in zero-gap semiconductors. In CuFeS2, we have n( T) ∝ T 1.2; in isoelectron compound Cu1.13Fe1.22Te2, we have n( T) ∝ T 1.93. Heat treatment is found to affect the intrinsic conductivity of CuFeS2, as the action of hydrostatic compression (carrier concentration changes); that is, the carrier concentration changes. However, a power form of the n( T) and ρ( T) dependences is retained.

  13. Composite TiO2/clays materials for photocatalytic NOx oxidation

    NASA Astrophysics Data System (ADS)

    Todorova, N.; Giannakopoulou, T.; Karapati, S.; Petridis, D.; Vaimakis, T.; Trapalis, C.

    2014-11-01

    TiO2 photocatalyst received much attention for air purification applications especially for removal of air pollutants like NOx, VOCs etc. It has been established that the activity of the photocatalyst can be significantly enhanced by its immobilization onto suitable substrates like inorganic minerals, porous silica, hydroxyapatite, adsorbent materials like activated carbon, various co-catalysts such as semiconductors, graphene, reduced graphite oxide, etc. In the present work, photocatalytic composite materials consisted of mineral substrate and TiO2 in weight ratio 1:1 were manufactured and examined for oxidation and removal of nitric oxides NOx (NO and NO2). Commercial titania P25 (Evonik-Degussa) and urea-modified P25 were used as photocatalytically active components. Inorganic minerals, namely kunipia, talk and hydrotalcite were selected as supporting materials due to their layered structure and expected high NOx adsorption capability. Al3+ and Ca2+ intercalation was applied in order to improve the dispersion of TiO2 and its loading into the supporting matrix. The X-ray diffraction analysis and Scanning Electron Microscopy revealed the binary structure of the composites and homogeneous dispersion of the photocatalyst into the substrates. The photocatalytic behavior of the materials in NOx oxidation and removal was investigated under UV and visible light irradiation. The composite materials exhibited superior photocatalytic activity than the bare titania under both types of irradiation. Significant visible light activity was recorded for the composites containing urea-modified titania that was accredited to the N-doping of the semiconductor. Among the different substrates, the hydrotalcite caused highest increase in the NOx removal, while among the intercalation ions the Ca2+ was more efficient. The results were related to the improved dispersion of the TiO2 and the synergetic activity of the substrates as NOx adsorbers.

  14. Correlation of Photocatalytic Activity with Band Structure of Low-dimensional Semiconductor Nanostructures

    NASA Astrophysics Data System (ADS)

    Meng, Fanke

    Photocatalytic hydrogen generation by water splitting is a promising technique to produce clean and renewable solar fuel. The development of effective semiconductor photocatalysts to obtain efficient photocatalytic activity is the key objective. However, two critical reasons prevent wide applications of semiconductor photocatalysts: low light usage efficiency and high rates of charge recombination. In this dissertation, several low-dimensional semiconductors were synthesized with hydrothermal, hydrolysis, and chemical impregnation methods. The band structures of the low-dimensional semiconductor materials were engineered to overcome the above mentioned two shortcomings. In addition, the correlation between the photocatalytic activity of the low-dimensional semiconductor materials and their band structures were studied. First, we studied the effect of oxygen vacancies on the photocatalytic activity of one-dimensional anatase TiO2 nanobelts. Given that the oxygen vacancy plays a significant role in band structure and photocatalytic performance of semiconductors, oxygen vacancies were introduced into the anatase TiO2 nanobelts during reduction in H2 at high temperature. The oxygen vacancies of the TiO2 nanobelts boosted visible-light-responsive photocatalytic activity but weakened ultraviolet-light-responsive photocatalytic activity. As oxygen vacancies are commonly introduced by dopants, these results give insight into why doping is not always beneficial to the overall photocatalytic performance despite increases in absorption. Second, we improved the photocatalytic performance of two-dimensional lanthanum titanate (La2Ti2 O7) nanosheets, which are widely studied as an efficient photocatalyst due to the unique layered crystal structure. Nitrogen was doped into the La2Ti2O7 nanosheets and then Pt nanoparticles were loaded onto the La2Ti2O7 nanosheets. Doping nitrogen narrowed the band gap of the La2Ti 2O7 nanosheets by introducing a continuum of states by the valence

  15. The effect of Substrate temperature on physical and electrical properties of DC magnetron sputtered (Ta2O5)0.85(TiO2)0.15 films

    NASA Astrophysics Data System (ADS)

    Sekhar, M. Chandra; Uthanna, S.; Martins, R.; Jagadeesh Chandra, S. V.; Elangovan, E.

    2012-04-01

    Thin films of (Ta2O5)0.85(TiO2)0.15 were deposited on quartz and p-Si substrates by DC reactive magnetron sputtering at different substrate temperatures (Ts) in the range 303 - 873 K. The films deposited at 303 0K were in the amorphous and it transformed to crystalline at substrate temperatures >= 573 0K. The crystallite size was increased from 50 nm to 72 nm with the increase of substrate temperature. The surface morphology was significantly influenced with the substrate temperature. After deposition of the (Ta2O5)0.85(TiO2)0.15 films on Si, aluminium (Al) electrode was deposited to fabricate metal/oxide/semiconductor (MOS) capacitors with a configuration of Al/(Ta2O5)0.85(TiO2)0.15/Si. A low leakage current of 7.7 × 10-5 A/cm2 was obtained from the films deposited at 303 K. The leakage current was decreased to 9.3 × 10-8 A/cm2 with the increase of substrate temperature owing to structural changes. The conduction mechanism of the Al/(Ta2O5)0.85(TiO2)0.15/Si capacitors was analyzed and compared with mechanisms of Poole-Frenkel and Schottky emissions. The optical band gap (Eg) was decreased from 4.45 eV to 4.38 eV with the increase in substrate temperature.

  16. A note on anomalous band-gap variations in semiconductors with temperature

    NASA Astrophysics Data System (ADS)

    Chakraborty, P. K.; Mondal, B. N.

    2018-03-01

    An attempt is made to theoretically study the band-gap variations (ΔEg) in semiconductors with temperature following the works, did by Fan and O'Donnell et al. based on thermodynamic functions. The semiconductor band-gap reflects the bonding energy. An increase in temperature changes the chemical bondings, and electrons are promoted from valence band to conduction band. In their analyses, they made several approximations with respect to temperature and other fitting parameters leading to real values of band-gap variations with linear temperature dependences. In the present communication, we have tried to re-analyse the works, specially did by Fan, and derived an analytical model for ΔEg(T). Because, it was based on the second-order perturbation technique of thermodynamic functions. Our analyses are made without any approximations with respect to temperatures and other fitting parameters mentioned in the text, leading to a complex functions followed by an oscillating nature of the variations of ΔEg. In support of the existence of the oscillating energy band-gap variations with temperature in a semiconductor, possible physical explanations are provided to justify the experimental observation for various materials.

  17. Near-band-edge optical responses of solution-processed organic-inorganic hybrid perovskite CH3NH3PbI3 on mesoporous TiO2 electrodes

    NASA Astrophysics Data System (ADS)

    Yamada, Yasuhiro; Nakamura, Toru; Endo, Masaru; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

    2014-03-01

    We studied the near-band-edge optical responses of solution-processed CH3NH3PbI3 on mesoporous TiO2 electrodes, which is utilized in mesoscopic heterojunction solar cells. Photoluminescence (PL) and PL excitation spectra peaks appear at 1.60 and 1.64 eV, respectively. The transient absorption spectrum shows a negative peak at 1.61 eV owing to photobleaching at the band-gap energy, indicating a direct band-gap semiconductor. On the basis of the temperature-dependent PL and diffuse reflectance spectra, we clarified that the absorption tail at room temperature is explained in terms of an Urbach tail and consistently determined the band-gap energy to be ˜1.61 eV at room temperature.

  18. Electronic structures of anatase (TiO2)1-x(TaON)x solid solutions: a first-principles study.

    PubMed

    Dang, Wenqiang; Chen, Hungru; Umezawa, Naoto; Zhang, Junying

    2015-07-21

    Sensitizing wide band gap photo-functional materials under visible-light irradiation is an important task for efficient solar energy conversion. Although nitrogen doping into anatase TiO2 has been extensively studied for this purpose, it is hard to increase the nitrogen content in anatase TiO2 because of the aliovalent nitrogen substituted for oxygen, leading to the formation of secondary phases or defects that hamper the migration of photoexcited charge carriers. In this paper, electronic structures of (TiO2)1-x(TaON)x (0 ≤ x ≤ 1) solid solutions, in which the stoichiometry is satisfied with the co-substitution of Ti for Ta along with O for N, are investigated within the anatase crystal structure using first-principles calculations. Our computational results show that the solid solutions have substantially narrower band gaps than TiO2, without introducing any localized energy states in the forbidden gap. In addition, in comparison with the pristine TiO2, the solid solution has a direct band gap when the content of TaON exceeds 0.25, which is advantageous to light absorption. The valence band maximum (VBM) of the solid solutions, which is mainly composed of N 2p states hybridized with O 2p, Ti 3d or Ta 5d orbitals, is higher in energy than that of pristine anatase TiO2 consisting of non-bonding O 2p states. On the other hand, incorporating TaON into TiO2 causes the formation of d-d bonding states through π interactions and substantially lowers the conduction band minimum (CBM) because of the shortened distance between some metal atoms. As a result, the anatase (TiO2)1-x(TaON)x is expected to become a promising visible-light absorber. In addition, some atomic configurations are found to possess exceptionally narrow band gaps.

  19. Initial formation behaviour of polypyrrole on single crystal TiO2 through photo-electrochemical reaction.

    PubMed

    Kawakita, Jin; Weitzel, Matthias

    2011-04-01

    Hybrid materials of the organic and inorganic semiconductors have a potential to show the better performance in the charge separation at the junction upon the photovoltaic action by the presence of the space charge layer in the inorganic semiconductor. In this study, the photo-anodic polymerization was selected as a fabrication method for the hybrid materials composed of TiO2 and polypyrrole on the basis of some advantages of this method. For the process control of the photo-anodic polymerization, it is important to elucidate the formation and growth mechanisms of the organic polymer. In this study, a flat sheet of single-crystal TiO2 was used as a well-defined surface for preparation of the organic polymer of pyrrole. Photo-anodic polarization behaviour was clarified and polypyrrole was prepared on TiO2. The formation process, especially the initial step was revealed by observation of polypyrrole with atomic force microscope (AFM) and statistical interpretation of the morphology of polypyrrole in the nano-scopic level. The formation process of polypyrrole on the TiO2 surface was summarized; (1) adsorption of precursors, (2) localized formation and growth of polypyrrole under the photo-illumination, and (3) homogenous growth of polypyrrole with the external current application under the photo-illumination.

  20. Preparation of anatase TiO2 nanoparticles using low hydrothermal temperature for dye-sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Sofyan, N.; Ridhova, A.; Yuwono, A. H.; Udhiarto, A.

    2018-03-01

    One device being developed as an alternative source of renewable energy by utilizing solar energy source is dye-sensitized solar cells (DSSC). This device works using simple photosynthetic-electrochemical principle in the molecular level. In this device, the inorganic oxide semiconductor of titanium dioxide (TiO2) has a great potential for the absorption of the photon energy from the solar energy source, especially in the form of TiO2 nanoparticle structure. This nanoparticle structure is expected to improve the performance of DSSC because the surface area to weight ratio of this nanostructures is very large. In this study, the synthesis of TiO2 nanoparticle from its precursors has been performed along with the fabrication of the DSSC device. Effort to improve the size of nanocrystalline anatase TiO2 was accomplished by low hydrothermal treatment at various temperatures whereas the crystallinity of the anatase phase in the structure was performed by calcination process. Characterization of the materials was performed using X-ray Diffraction (XRD) and scanning electron microscope (SEM), while the DSSC performance was examined through a high precision current versus voltage (I-V) curve analyzer. The results showed that pure anatase TiO2 nanoparticles could be obtained at low hydrothermal of 100, 125, and 150 °C followed by calcination at 450 °C. The best performance of photocurrent-voltage characteristic was given by TiO2 hydrothermally synthesized at 150 °C with power conversion efficiency (PCE) of 4.40 %, whereas the standard TiO2 nanoparticles has PCE only 4.02 %. This result is very promising in terms low temperature and thus low cost of anatase TiO2 semiconductor preparation for DSSC application.

  1. Direct optical band gap measurement in polycrystalline semiconductors: A critical look at the Tauc method

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dolgonos, Alex; Mason, Thomas O.; Poeppelmeier, Kenneth R., E-mail: krp@northwestern.edu

    2016-08-15

    The direct optical band gap of semiconductors is traditionally measured by extrapolating the linear region of the square of the absorption curve to the x-axis, and a variation of this method, developed by Tauc, has also been widely used. The application of the Tauc method to crystalline materials is rooted in misconception–and traditional linear extrapolation methods are inappropriate for use on degenerate semiconductors, where the occupation of conduction band energy states cannot be ignored. A new method is proposed for extracting a direct optical band gap from absorption spectra of degenerately-doped bulk semiconductors. This method was applied to pseudo-absorption spectramore » of Sn-doped In{sub 2}O{sub 3} (ITO)—converted from diffuse-reflectance measurements on bulk specimens. The results of this analysis were corroborated by room-temperature photoluminescence excitation measurements, which yielded values of optical band gap and Burstein–Moss shift that are consistent with previous studies on In{sub 2}O{sub 3} single crystals and thin films. - Highlights: • The Tauc method of band gap measurement is re-evaluated for crystalline materials. • Graphical method proposed for extracting optical band gaps from absorption spectra. • The proposed method incorporates an energy broadening term for energy transitions. • Values for ITO were self-consistent between two different measurement methods.« less

  2. OXYGENATION OF HYDROCARBONS USING NANOSTRUCTURED TIO2 AS A PHOTOCATALYST: A GREEN ALTERNATIVE

    EPA Science Inventory

    High-value organic compounds have been synthesized successfully from linear and cyclic saturated hydrocarbons by a photocatalytic oxidation process using a semiconductor material, titanium dioxide (TiO2). Various hydrocarbons were partially oxygenated in both aqueous and gaseous...

  3. The Influence of Cr3+ on TiO2 Crystal Growth and Photoactivity Properties

    NASA Astrophysics Data System (ADS)

    Wahyuningsih, S.; Hidayatika, W. N.; Sari, P. L.; Sari, P. P.; Hidayat, R.; Munawaroh, H.; Ramelan, A. H.

    2018-03-01

    The photocatalyst technology is an integrated combination of photochemical processes and catalysis in order to carry out a chemical transformation reaction. One of the semiconductor materials that have good photocatalytic activity is TiO2 anatase. This study aim to determine the effect of the Cr3+ addition on the growth of TiO2 rutile crystal and the increasing of TiO2 photoactivity. Diffractogram X-Ray of the samples showed that the synthesized TiO2 at 400 °C has been produced 100% TiO2 anatase. Synthesis of TiO2 doped Cr3+ composite was using wet impregnation method. The TiO2 doped Cr3+ composites have beed grown by annealed at a temperature of 300, 400, 500, 600 and 700 °C, respectively Annealing process have capabled to gain to the TiO2 doped Cr3+ nanocomposite. The result product annealed at 500 °C only appear anatase phase due to the Cr3+ addition influence that was able to suppress the growth of rutile. Identification of TiO2 doped Cr3+ composite using Fourier Transform Infra-Red (FT-IR) showed O-Cr vibration at 2283.72 cm-1. The TiO2 doped Cr3+ photoactivity was studied to degrade Rhodamin B. The best result on photodegradation of Rhodamin B was performed by using TiO2 doped Cr3+ composite which was annealed at 700 °C i.e. 74.71%.

  4. Enhanced thermoelectric performance in the Rashba semiconductor BiTeI through band gap engineering.

    PubMed

    Wu, Lihua; Yang, Jiong; Zhang, Tiansong; Wang, Shanyu; Wei, Ping; Zhang, Wenqing; Chen, Lidong; Yang, Jihui

    2016-03-02

    Rashba semiconductors are of great interest in spintronics, superconducting electronics and thermoelectrics. Bulk BiTeI is a new Rashba system with a giant spin-split band structure. 2D-like thermoelectric response has been found in BiTeI. However, as optimizing the carrier concentration, the bipolar effect occurs at elevated temperature and deteriorates the thermoelectric performance of BiTeI. In this paper, band gap engineering in Rashba semiconductor BiTeI through Br-substitution successfully reduces the bipolar effect and improves the thermoelectric properties. By utilizing the optical absorption and Burstein-Moss-effect analysis, we find that the band gap in Rashba semiconductor BiTeI increases upon bromine substitution, which is consistent with theoretical predictions. Bipolar transport is mitigated due to the larger band gap, as the thermally-activated minority carriers diminish. Consequently, the Seebeck coefficient keeps increasing with a corresponding rise in temperature, and thermoelectric performance can thus be enhanced with a ZT  =  0.5 at 570 K for BiTeI0.88Br0.12.

  5. Thin film nano-photocatalyts with low band gap energy for gas phase degradation of p-xylene: TiO2 doped Cr, UiO66-NH2 and LaBO3 (B  =  Fe, Mn, and Co)

    NASA Astrophysics Data System (ADS)

    Loc Luu, Cam; Thuy Van Nguyen, Thi; Nguyen, Tri; Nguyen, Phung Anh; Hoang, Tien Cuong; Ha, Cam Anh

    2018-03-01

    By dip-coating technique the thin films of nano-photocatalysts TiO2, Cr-doped TiO2, LaBO3 perovskites (B  =  Fe, Mn, and Co) prepared by sol-gel method, and UiO66-NH2 prepared by a solvothermal were obtained and employed for gas phase degradation of p-xylene. Physicochemical characteristics of the catalysts were examined by the methods of BET, SEM, TEM, XRD, FT-IR, TGA, Raman and UV-vis spectroscopies. The thickness of film was determined by a Veeco-American Dektek 6M instrument. The activity of catalysts was evaluated in deep photooxidation of p-xylene in a microflow reactor at room temperature with the radiation sources of a UV (λ  =  365 nm) and LED lamps (λ  =  400-510 nm). The obtained results showed that TiO2 and TiO2 doped Cr thin films was featured by an anatase phase with nanoparticles of 10-100 nm. Doping TiO2 with 0.1%mol Cr2O3 led to reduce band gap energy from 3.01 down to 1.99 eV and extend the spectrum of photon absorption to the visible region (λ  =  622 nm). LaBO3 perovkite thin films were also featured by a crystal phase with average particle nanosize of 8-40 nm, a BET surface area of 17.6-32.7 m2 g-1 and band gap energy of 1.87-2.20 eV. UiO66-NH2 was obtained in the ball shape of 100-200 nm, a BET surface area of 576 m2 g-1 and a band gap energy of 2.83 eV. The low band gap energy nano-photocatalysts based on Cr-doped TiO2 and LaBO3 perovskites exhibited highly stable and active for photo-degradation of p-xylene in the gas phase under radiation of UV-vis light. Perovskite LaFeO3 and Cr-TiO2 thin films were the best photocatalysts with a decomposition yield being reached up to 1.70 g p-xylene/g cat.

  6. Optoelectronics of supported and suspended 2D semiconductors

    NASA Astrophysics Data System (ADS)

    Bolotin, Kirill

    2014-03-01

    Two-dimensional semiconductors, materials such monolayer molybdenum disulfide (MoS2) are characterized by strong spin-orbit and electron-electron interactions. However, both electronic and optoelectronic properties of these materials are dominated by disorder-related scattering. In this talk, we investigate approaches to reduce scattering and explore physical phenomena arising in intrinsic 2D semiconductors. First, we discuss fabrication of pristine suspended monolayer MoS2 and use photocurrent spectroscopy measurements to study excitons in this material. We observe band-edge and van Hove singularity excitons and estimate their binding energies. Furthermore, we study dissociation of these excitons and uncover the mechanism of their contribution to photoresponse of MoS2. Second, we study strain-induced modification of bandstructures of 2D semiconductors. With increasing strain, we find large and controllable band gap reduction of both single- and bi-layer MoS2. We also detect experimental signatures consistent with strain-induced transition from direct to indirect band gap in monolayer MoS2. Finally, we fabricate heterostructures of dissimilar 2D semiconductors and study their photoresponse. For closely spaced 2D semiconductors we detect charge transfer, while for separation larger than 10nm we observe Forster-like energy transfer between excitations in different layers.

  7. TiO2-SnS2 nanocomposites: solar-active photocatalytic materials for water treatment.

    PubMed

    Kovacic, Marin; Kusic, Hrvoje; Fanetti, Mattia; Stangar, Urska Lavrencic; Valant, Matjaz; Dionysiou, Dionysios D; Bozic, Ana Loncaric

    2017-08-01

    The study is aimed at evaluating TiO 2 -SnS 2 composites as effective solar-active photocatalysts for water treatment. Two strategies for the preparation of TiO 2 -SnS 2 composites were examined: (i) in-situ chemical synthesis followed by immobilization on glass plates and (ii) binding of two components (TiO 2 and SnS 2 ) within the immobilization step. The as-prepared TiO 2 -SnS 2 composites and their sole components (TiO 2 or SnS 2 ) were inspected for composition, crystallinity, and morphology using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analyses. Diffuse reflectance spectroscopy (DRS) was used to determine band gaps of immobilized TiO 2 -SnS 2 and to establish the changes in comparison to respective sole components. The activity of immobilized TiO 2 -SnS 2 composites was tested for the removal of diclofenac (DCF) in aqueous solution under simulated solar irradiation and compared with that of single component photocatalysts. In situ chemical synthesis yielded materials of high crystallinity, while their morphology and composition strongly depended on synthesis conditions applied. TiO 2 -SnS 2 composites exhibited higher activity toward DCF removal and conversion in comparison to their sole components at acidic pH, while only in situ synthesized TiO 2 -SnS 2 composites showed higher activity at neutral pH.

  8. Synthesis of TiO2/functionalized graphene sheets (FGSs) nanocomposites in super critical CO2

    NASA Astrophysics Data System (ADS)

    Farhangi, Nasrin; Medina-Gonzalez, Yaocihuatl; Chen, Bo; Charpentier, Paul A.

    2010-06-01

    Highly ordered TiO2 nanowire arrays were prepared on the surface of Functionalized Graphene sheets (FGSs) by solgel method using titanium isopropoxide monomer with acetic acid as the polycondensation agent in the green solvent, supercritical carbon dioxide (sc-CO2). Morphology of synthesized materials was studied by SEM and TEM. Optical properties of the nanocomposites studied by UV spectroscopy which showed high absorption in visible area as well as reduction in their band gap compared to TiO2. By high resolution XPS, chelating bidentate structure of TiO2 with carboxylic group on the surface of graphene sheets can be confirmed. Improvement in the optical properties of the synthesized composites compared to TiO2 alone was confirmed by photocurrent measurements.

  9. A TiO2/FeMnP Core/Shell Nanorod Array Photoanode for Efficient Photoelectrochemical Oxygen Evolution.

    PubMed

    Schipper, Desmond E; Zhao, Zhenhuan; Leitner, Andrew P; Xie, Lixin; Qin, Fan; Alam, Md Kamrul; Chen, Shuo; Wang, Dezhi; Ren, Zhifeng; Wang, Zhiming; Bao, Jiming; Whitmire, Kenton H

    2017-04-25

    A variety of catalysts have recently been developed for electrocatalytic oxygen evolution, but very few of them can be readily integrated with semiconducting light absorbers for photoelectrochemical or photocatalytic water splitting. Here, we demonstrate an efficient core/shell photoanode with a highly active oxygen evolution electrocatalyst shell (FeMnP) and semiconductor core (rutile TiO 2 ) for photoelectrochemical oxygen evolution reaction. Metal-organic chemical vapor deposition from a single-source precursor was used to ensure good contact between the FeMnP and the TiO 2 . The TiO 2 /FeMnP core/shell photoanode reaches the theoretical photocurrent density for rutile TiO 2 of 1.8 mA cm -2 at 1.23 V vs reversible hydrogen electrode under simulated 100 mW cm -2 (1 sun) irradiation. The dramatic enhancement is a result of the synergistic effects of the high oxygen evolution reaction activity of FeMnP (delivering an overpotential of 300 mV with a Tafel slope of 65 mV dec -1 in 1 M KOH) and the conductive interlayer between the surface active sites and semiconductor core which boosts the interfacial charge transfer and photocarrier collection. The facile fabrication of the TiO 2 /FeMnP core/shell nanorod array photoanode offers a compelling strategy for preparing highly efficient photoelectrochemical solar energy conversion devices.

  10. Structural properties and sensing performance of high-k Nd2TiO5 thin layer-based electrolyte-insulator-semiconductor for pH detection and urea biosensing.

    PubMed

    Pan, Tung-Ming; Lin, Jian-Chi; Wu, Min-Hsien; Lai, Chao-Sung

    2009-05-15

    For high sensitive pH sensing, an electrolyte-insulator-semiconductor (EIS) device with Nd(2)TiO(5) thin layers fabricated on Si substrates by means of reactive sputtering and the subsequent post-deposition annealing (PDA) treatment was proposed. In this work, the effect of thermal annealing (600, 700, 800, and 900 degrees C) on the structural characteristics of Nd(2)TiO(5) thin layer was investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and atomic force microscopy. The observed structural properties were then correlated with the resulting pH sensing performances. For enzymatic field-effect-transistors-based urea biosensing, a hybrid configuration of the proposed Nd(2)TiO(5) thin layer with urease-immobilized alginate film attached was established. Within the experimental conditions investigated, the EIS device with the Nd(2)TiO(5) thin layer annealed at 800 degrees C exhibited a higher pH detection sensitivity of 57.2 mV/pH, a lower hysteresis voltage of 2.33 mV, and a lower drift rate of 1.80 mV/h compared to those at other annealing temperatures. These results are attributed to the formation of a thinner low-k interfacial layer at the oxide/Si interface and the higher surface roughness occurred at this annealing temperature. Furthermore, the presented urea biosensor was also proved to be able to detect urea with good linearity (R(2)=0.99) and reasonable sensitivity of 9.52 mV/mM in the urea concentration range of 3-40 mM. As a whole, the present work has provided some fundamental data for the use of Nd(2)TiO(5) thin layer for EIS-based pH detection and the extended application for biosensing.

  11. Visible Light Photocatalysis via CdS/ TiO 2 Nanocomposite Materials

    DOE PAGES

    Srinivasan, Sesha S.; Wade, Jeremy; Stefanakos, Elias K.

    2006-01-01

    Nmore » anostructured colloidal semiconductors with heterogeneous photocatalytic behavior have drawn considerable attention over the past few years. This is due to their large surface area, high redox potential of the photogenerated charge carriers, and selective reduction/oxidation of different classes of organic compounds. In the present paper, we have carried out a systematic synthesis of nanostructured CdS- TiO 2 via reverse micelle process. The structural and microstructural characterizations of the as-prepared CdS- TiO 2 nanocomposites are determined using XRD and SEM-EDS techniques. The visible light assisted photocatalytic performance is monitored by means of degradation of phenol in water suspension.« less

  12. Highly efficient visible-light driven photocatalytic hydrogen production from a novel Z-scheme Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite

    NASA Astrophysics Data System (ADS)

    Wang, Guowei; Ma, Xue; Wei, Shengnan; Li, Siyi; Qiao, Jing; Wang, Jun; Song, Youtao

    2018-01-01

    In this work, the preparation of a novel Z-scheme photocatalyst, Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite, for visible-light photocatalytic hydrogen production is reported for the first time. In this photocatalyst, Au nanoparticles as conduction band co-catalyst provide more active sites to enrich electrons. Ta2O5-V5+||Fe3+-TiO2 as composite redox cycle system thoroughly separates the photo-generated electrons and holes. In addition, Er3+:YAlO3 as up-conversion luminescence agent (from visible-light to ultraviolet-light) provides enough ultraviolet-light for satisfying the energy demand of wide band-gap semiconductors (TiO2 and Ta2O5). The photocatalytic hydrogen production can be achieved from methanol as sacrificial agent (electron donor) under visible-light irradiation. The main influence factors such as initial solution pH and molar ratio of TiO2 and Ta2O5 on visible-light photocatalytic hydrogen production activity of Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite are discussed in detail. The results show that the Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite with 1.0:0.5 M ratio of TiO2 and Ta2O5 in methanol aqueous solution at pH = 6.50 displays the highest photocatalytic hydrogen production activity. Furthermore, a high level of photocatalytic activity can be still maintained within three cycles under the same conditions. It implies that the prepared Z-scheme Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite may be a promising photocatalyst utilizing solar energy for hydrogen production.

  13. Photocathodic Protection of 304 Stainless Steel by Bi2S3/TiO2 Nanotube Films Under Visible Light

    NASA Astrophysics Data System (ADS)

    Li, Hong; Wang, Xiutong; Wei, Qinyi; Hou, Baorong

    2017-01-01

    We report the preparation of TiO2 nanotubes coupled with a narrow bandgap semiconductor, i.e., Bi2S3, to improve the photocathodic protection property of TiO2 for metals under visible light. Bi2S3/TiO2 nanotube films were successfully synthesized using the successive ionic layer adsorption and reaction (SILAR) method. The morphology and structure of the composite films were studied by scanning electron microscopy and X-ray diffraction, respectively. UV-visible diffuse reflectance spectra were recorded to analyze the optical absorption property of the composite films. In addition, the influence of Bi2S3 deposition cycles on the photoelectrochemical and photocathodic protection properties of the composite films was also studied. Results revealed that the heterostructure comprised crystalline anatase TiO2 and orthorhombic Bi2S3 and exhibited a high visible light response. The photocurrent density of Bi2S3/TiO2 was significantly higher than that of pure TiO2 under visible light. The sensitization of Bi2S3 enhanced the separation efficiency of the photogenerated charges and photocathodic protection properties of TiO2. The Bi2S3/TiO2 nanotubes prepared by SILAR deposition with 20 cycles exhibited the optimal photogenerated cathodic protection performance on the 304 stainless steel under visible light.

  14. Photocathodic Protection of 304 Stainless Steel by Bi2S3/TiO2 Nanotube Films Under Visible Light.

    PubMed

    Li, Hong; Wang, Xiutong; Wei, Qinyi; Hou, Baorong

    2017-12-01

    We report the preparation of TiO 2 nanotubes coupled with a narrow bandgap semiconductor, i.e., Bi 2 S 3 , to improve the photocathodic protection property of TiO 2 for metals under visible light. Bi 2 S 3 /TiO 2 nanotube films were successfully synthesized using the successive ionic layer adsorption and reaction (SILAR) method. The morphology and structure of the composite films were studied by scanning electron microscopy and X-ray diffraction, respectively. UV-visible diffuse reflectance spectra were recorded to analyze the optical absorption property of the composite films. In addition, the influence of Bi 2 S 3 deposition cycles on the photoelectrochemical and photocathodic protection properties of the composite films was also studied. Results revealed that the heterostructure comprised crystalline anatase TiO 2 and orthorhombic Bi 2 S 3 and exhibited a high visible light response. The photocurrent density of Bi 2 S 3 /TiO 2 was significantly higher than that of pure TiO 2 under visible light. The sensitization of Bi 2 S 3 enhanced the separation efficiency of the photogenerated charges and photocathodic protection properties of TiO 2 . The Bi 2 S 3 /TiO 2 nanotubes prepared by SILAR deposition with 20 cycles exhibited the optimal photogenerated cathodic protection performance on the 304 stainless steel under visible light.

  15. Ultrafast recombination dynamics in dye-sensitized SnO 2/TiO 2 core/shell films

    DOE PAGES

    Gish, Melissa K.; Lapides, Alexander M.; Brennaman, M. Kyle; ...

    2016-12-02

    In dye-sensitized photoelectrosynthesis cells (DSPECs), molecular chromophores and catalysts are integrated on a semiconductor surface to perform water oxidation or CO 2 reduction after a series of light-induced electron transfer events. Unfortunately, recombination of the charge separated state (CSS) is competitive with productive catalysis. To overcome this major obstacle, implementation of photoanodic core/shell films within these devices improve electrochemical behavior and slow recombination through the introduction of an energetic barrier between the semiconductor core and oxidized species on the surface. In this study, interfacial dynamics are investigated in SnO 2/TiO 2 core/shell films derivatized with a Ru(II)-polypyridyl chromophore ([RuII(bpy)2(4,4'-(PO 3Hmore » 2) 2bpy)] 2+, RuP) using transient absorption methods. Electron injection from the chromophore into the TiO 2 shell occurs within a few picoseconds after photoexcitation. Loss of the oxidized dye through recombination occurs across time scales spanning 10 orders of magnitude. The majority (60%) of charge recombination events occur shortly after injection (τ = 220 ps), while a small fraction (≤20%) of the oxidized chromophores persists for milliseconds. The lifetime of long-lived CSS depends exponentially on shell thickness, suggesting that the injected electrons reside in the SnO 2 core and must tunnel through the TiO 2 shell to recombine with oxidized dyes. While the core/shell architecture extends the lifetime in a small fraction of the CSS, making water oxidation possible, the subnanosecond recombination process has profound implications for the overall efficiencies of DSPECs.« less

  16. Strain Effects in Epitaxial VO2 Thin Films on Columnar Buffer-Layer TiO2/Al2O3 Virtual Substrates.

    PubMed

    Breckenfeld, Eric; Kim, Heungsoo; Burgess, Katherine; Charipar, Nicholas; Cheng, Shu-Fan; Stroud, Rhonda; Piqué, Alberto

    2017-01-18

    Epitaxial VO 2 /TiO 2 thin film heterostructures were grown on (100) (m-cut) Al 2 O 3 substrates via pulsed laser deposition. We have demonstrated the ability to reduce the semiconductor-metal transition (SMT) temperature of VO 2 to ∼44 °C while retaining a 4 order of magnitude SMT using the TiO 2 buffer layer. A combination of electrical transport and X-ray diffraction reciprocal space mapping studies help examine the specific strain states of VO 2 /TiO 2 /Al 2 O 3 heterostructures as a function of TiO 2 film growth temperatures. Atomic force microscopy and transmission electron microscopy analyses show that the columnar microstructure present in TiO 2 buffer films is responsible for the partially strained VO 2 film behavior and subsequently favorable transport characteristics with a lower SMT temperature. Such findings are of crucial importance for both the technological implementation of the VO 2 system, where reduction of its SMT temperature is widely sought, as well as the broader complex oxide community, where greater understanding of the evolution of microstructure, strain, and functional properties is a high priority.

  17. Decomposition of banten ilmenite by caustic fusion process for TiO2 photocatalytic applications

    NASA Astrophysics Data System (ADS)

    Aristanti, Y.; Supriyatna, Y. I.; Masduki, N. P.; Soepriyanto, S.

    2018-01-01

    Decomposition of Banten ilmenite by caustic fusion process for TiO2 photocatalytic applications has been done. Caustic fusion process using NaOH to obtain sodium titanate compound which is soluble in sulfuric acid (H2SO4) to produces TiOSO4 as a precursor. Synthesis of TiO2 from TiOSO4 precursors by variations of pH hydrolysis are 1.0 (TiO2 A), 1.5 (TiO2 B) and 2.0 (TiO2 C). XRD pattern identified TiO2 structures crystals are anatase phase and traces α-Fe2O3 as an impurity. Presence of Fe2O3 as an impurities give positive effect on TiO2 photocatalytic activity that is to narrower the band gap energy thus facilitates of electrons excitation from valence band to conduction band and enlarge the specific surface area thus reaction between Rhodamin B solution and TiO2 surface can be faster. TiO2 A, TiO2 B and TiO2 C was compared to TiO2 M (commercial TiO2) in Rhodamin B solution for the photocatalytic activity where the maximum TiO2 degradation efficiency was obtained at TiO2 C 80.0 % while TiO2 M 59.8 %.

  18. Band gap enhancement of glancing angle deposited TiO2 nanowire array

    NASA Astrophysics Data System (ADS)

    Chinnamuthu, P.; Mondal, A.; Singh, N. K.; Dhar, J. C.; Chattopadhyay, K. K.; Bhattacharya, Sekhar

    2012-09-01

    Vertically oriented TiO2 nanowire (NW) arrays were fabricated by glancing angle deposition technique. Field emission-scanning electron microscopy shows the formation of two different diameters ˜80 nm and ˜40 nm TiO2 NW for 120 and 460 rpm azimuthal rotation of the substrate. The x-ray diffraction and Raman scattering depicted the presence of rutile and anatase phase TiO2. The overall Raman scattering intensity decreased with nanowire diameter. The role of phonon confinement in anatase and rutile peaks has been discussed. The red (7.9 cm-1 of anatase Eg) and blue (7.4 cm-1 of rutile Eg, 7.8 cm-1 of rutile A1g) shifts of Raman frequencies were observed. UV-vis absorption measurements show the main band absorption at 3.42 eV, 3.48 eV, and ˜3.51 eV for thin film and NW prepared at 120 and 460 rpm, respectively. Three fold enhance photon absorption and intense light emission were observed for NW assembly. The photoluminescence emission from the NW assembly revealed blue shift in main band transition due to quantum confinement in NW structures.

  19. Improving surface-enhanced Raman scattering properties of TiO(2) nanoparticles by metal Co doping.

    PubMed

    Yang, Libin; Qin, Xiaoyu; Gong, Mengdi; Jiang, Xin; Yang, Ming; Li, Xiuling; Li, Guangzhi

    2014-04-05

    In this paper, pure and different amount Co ions doped TiO2 nanoparticles were synthesized by a sol-hydrothermal method and were served as SERS-active substrate. The effect of metal Co doping on SERS properties of TiO2 nanoparticles was mostly investigated. The results indicate that abundant metal doping energy levels can be formed in the energy gap of TiO2 by an appropriate amount Co ions doping, which can promote the charge transfer from TiO2 to molecule, and subsequently enhance SERS signal of adsorbed molecule on TiO2 substrate, and improve remarkably SERS properties of TiO2 nanoparticles. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Characterization of the thin layer photocatalysts TiO2 and V2O5- and Fe2O3- doped TiO2 prepared by the sol-gel method

    NASA Astrophysics Data System (ADS)

    Loc Luu, Cam; Nguyen, Quoc Tuan; Thoang Ho, Si; Nguyen, Tri

    2013-09-01

    The catalysts TiO2 and TiO2 doped with Fe and V were prepared using the sol-gel method. TiO2-modified samples were obtained in the form of a thick film on pyrex glass sticks and tubes and were used as catalysts in the gas phase photo-oxidation of p-xylene. The physico-chemical characteristics of the catalysts were determined using the methods of Brunauer-Emmett-Teller adsorption, x-ray diffraction, and infrared, ultraviolet and visible and Raman spectroscopies. The experimental results show that the introduction of V did not expand the region of light absorption, but slightly reduced the size of the TiO2 particles, and reduced the number of OH-groups, which should decrease the photocatalytic activity and efficiency of the obtained catalysts compared to those of pure TiO2. The Fe-doped TiO2 samples, in contrast, are characterized by an extension of the spectrum of photon absorption to the visible region with wavenumbers λ up to 464 nm and the values of their band gap energy decreased to lower quantities (up to 2.67 eV), therefore they should have higher catalytic activity and conversion efficiency of p-xylene in the visible region than the original sample. For these catalysts, a combined utilization of radiation by ultraviolet (λ = 365 nm) and visible (λ = 470 nm) light increased the activity and the yield in p-xylene conversion by a factor of around 2-3, as well as making these quantities more stable in comparison with those of TiO2-P25 Degussa.

  1. Thermoelectricity in correlated narrow-gap semiconductors

    NASA Astrophysics Data System (ADS)

    Tomczak, Jan M.

    2018-05-01

    We review many-body effects, their microscopic origin, as well as their impact on thermoelectricity in correlated narrow-gap semiconductors. Members of this class—such as FeSi and FeSb2—display an unusual temperature dependence in various observables: insulating with large thermopowers at low temperatures, they turn bad metals at temperatures much smaller than the size of their gaps. This insulator-to-metal crossover is accompanied by spectral weight-transfers over large energies in the optical conductivity and by a gradual transition from activated to Curie–Weiss-like behaviour in the magnetic susceptibility. We show a retrospective of the understanding of these phenomena, discuss the relation to heavy-fermion Kondo insulators—such as Ce3Bi4Pt3 for which we present new results—and propose a general classification of paramagnetic insulators. From the latter, FeSi emerges as an orbital-selective Kondo insulator. Focussing on intermetallics such as silicides, antimonides, skutterudites, and Heusler compounds we showcase successes and challenges for the realistic simulation of transport properties in the presence of electronic correlations. Further, we explore new avenues in which electronic correlations may contribute to the improvement of thermoelectric performance.

  2. Energy Impacts of Wide Band Gap Semiconductors in U.S. Light-Duty Electric Vehicle Fleet.

    PubMed

    Warren, Joshua A; Riddle, Matthew E; Graziano, Diane J; Das, Sujit; Upadhyayula, Venkata K K; Masanet, Eric; Cresko, Joe

    2015-09-01

    Silicon carbide and gallium nitride, two leading wide band gap semiconductors with significant potential in electric vehicle power electronics, are examined from a life cycle energy perspective and compared with incumbent silicon in U.S. light-duty electric vehicle fleet. Cradle-to-gate, silicon carbide is estimated to require more than twice the energy as silicon. However, the magnitude of vehicle use phase fuel savings potential is comparatively several orders of magnitude higher than the marginal increase in cradle-to-gate energy. Gallium nitride cradle-to-gate energy requirements are estimated to be similar to silicon, with use phase savings potential similar to or exceeding that of silicon carbide. Potential energy reductions in the United States vehicle fleet are examined through several scenarios that consider the market adoption potential of electric vehicles themselves, as well as the market adoption potential of wide band gap semiconductors in electric vehicles. For the 2015-2050 time frame, cumulative energy savings associated with the deployment of wide band gap semiconductors are estimated to range from 2-20 billion GJ depending on market adoption dynamics.

  3. Effect of screen printing type on transparent TiO2 layer as the working electrode of dye sensitized solar cell (DSSC) for solar windows applications

    NASA Astrophysics Data System (ADS)

    Nurosyid, F.; Furqoni, L.; Supriyanto, A.; Suryana, R.

    2016-11-01

    The working electrode based on semiconductor TiO2 DSSC has been fabricated by screen printing method. This study aim is to determine the effect of the screen type on TiO2 layer as the working electrode of DSSC. Screen used for deposition of TiO2 has the types of; T- 49, T-55 and T-61. TiO2 layer was sintered at temperature of 500°C. DSSC structure was composed of semiconductor TiO2 adsorbed dye, an electrolyte solution and a platinum counter electrode. TiO2 layer thickness was characterized by Scanning Electron Microscopy (SEM), while the absorbance was characterized using UV-Vis spectrophotometer and the electrical properties of DSSC were characterized by Keithley I-V measurement. TiO2 layer fabricated by screen T-49 had the biggest thickness that was 3.2 ± 0.3 μm and the highest UV-Vis absorbance wave at the peak wavelength of 315 nm with the absorbance value was 1.7. The I-V characterization showed that the sample fabricated by screen T-49 obtained the greatest efficiency that was 1.0 × 10-1%

  4. Study of the highly ordered TiO2 nanotubes physical properties prepared with two-step anodization

    NASA Astrophysics Data System (ADS)

    Pishkar, Negin; Ghoranneviss, Mahmood; Ghorannevis, Zohreh; Akbari, Hossein

    2018-06-01

    Highly ordered hexagonal closely packed titanium dioxide nanotubes (TiO2 NTs) were successfully grown by a two-step anodization process. The TiO2 NTs were synthesized by electrochemical anodization of titanium foils in an ethylene glycol based electrolyte solution containing 0.3 wt% NH4F and 2 vol% deionized (DI) water at constant potential (50 V) for 1 h at room temperature. Physical properties of the TiO2 NTs, which were prepared via one and two-step anodization, were investigated. Atomic Force Microscopy (AFM) analysis revealed that anodization and subsequently peeled off the TiO2 NTs caused to the periodic pattern on the Ti surface. In order To study the nanotubes morphology, Field Emission Scanning Electron Microscopy (FESEM) was used, which was revealed that the two-step anodization resulted highly ordered hexagonal TiO2 NTs. Crystal structures of the TiO2 NTs were mainly anatase, determined by X-ray diffraction analysis. Optical studies were performed by Diffuse Reflection Spectra (DRS) and Photoluminescence (PL) analysis showed that the band gap of TiO2 NTs prepared via two-step anodization was lower than the band gap of samples prepared by one-step anodization process.

  5. Growth of Wide Band Gap II-VI Compound Semiconductors by Physical Vapor Transport

    NASA Technical Reports Server (NTRS)

    Su, Ching-Hua; Sha, Yi-Gao

    1995-01-01

    The studies on the crystal growth and characterization of II-VI wide band gap compound semiconductors, such as ZnTe, CdS, ZnSe and ZnS, have been conducted over the past three decades. The research was not quite as extensive as that on Si, III-V, or even narrow band gap II-VI semiconductors because of the high melting temperatures as well as the specialized applications associated with these wide band gap semiconductors. In the past several years, major advances in the thin film technology such as Molecular Beam Epitaxy (MBE) and Metal Organic Chemical Vapor Deposition (MOCVD) have demonstrated the applications of these materials for the important devices such as light-emitting diode, laser and ultraviolet detectors and the tunability of energy band gap by employing ternary or even quaternary systems of these compounds. At the same time, the development in the crystal growth of bulk materials has not advanced far enough to provide low price, high quality substrates needed for the thin film growth technology.

  6. Bi-component semiconductor oxide photoanodes for the photoelectrocatalytic oxidation of organic solutes and vapours: a short review with emphasis to TiO2-WO3 photoanodes.

    PubMed

    Georgieva, J; Valova, E; Armyanov, S; Philippidis, N; Poulios, I; Sotiropoulos, S

    2012-04-15

    The use of binary semiconductor oxide anodes for the photoelectrocatalytic oxidation of organic species (both in solution and gas phase) is reviewed. In the first part of the review, the principle of electrically assisted photocatalysis is presented, the preparation methods for the most common semiconductor oxide catalysts are briefly mentioned, while the advantages of appropriately chosen semiconductor combinations for efficient UV and visible (vis) light utilization are highlighted. The second part of the review focuses on the discussion of TiO(2)-WO(3) photoanodes (among the most studied bi-component semiconductor oxide systems) and in particular on coatings prepared by electrodeposition/electrosynthesis or powder mixtures (the focus of the authors' research during recent years). Studies concerning the microscopic, spectroscopic and photoelectrochemical characterization of the catalysts are presented and examples of photoanode activity towards typical dissolved organic contaminants as well as organic vapours are given. Particular emphasis is paid to: (a) The dependence of photoactivity on catalyst morphology and composition and (b) the possibility of carrying out photoelectrochemistry in all-solid cells, thus opening up the opportunity for photoelectrocatalytic air treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Interfacial charge-transfer transitions in a TiO2-benzenedithiol complex with Ti-S-C linkages.

    PubMed

    Fujisawa, Jun-ichi; Muroga, Ryuki; Hanaya, Minoru

    2015-11-28

    Interfacial charge-transfer (ICT) transitions between organic materials and inorganic semiconductors are a new mechanism for light absorption at organic-semiconductor interfaces. ICT transitions cause one-step interfacial charge separation without loss of energy. This feature is potentially useful to realize efficient organic-inorganic hybrid solar cells. ICT transitions have been examined by employing titanium dioxide (TiO2) nanoparticles chemisorbed with π-conjugated molecules via Ti-O-C linkages. Here, we report ICT transitions in a TiO2 and 1,2-benzenedithiol (BDT) complex with Ti-S-C linkages. BDT adsorbs on TiO2 by the bridging bidentate coordination of the sulfur atoms to surface titanium atoms. The TiO2-BDT complex shows ICT transitions from the BDT moiety to the conduction band of TiO2 in the visible region. The ICT transitions occur by orbital overlaps between the d orbitals of the surface titanium atoms and the π orbitals of the benzene ring. Our density-functional-theory (DFT) analysis reveals that the 3p valence orbitals of the sulfur bridging atoms contribute to more than 50% of the highest occupied molecular orbital (HOMO) and the 3d-3p(sulfur)-π interaction via the Ti-S-C linkage enhances the electronic mixing between the titanium atoms and the benzene moiety as compared to the 3d-2p(oxygen)-πvia the Ti-O-C linkage. This result indicates the important role of the heavier-atom linkers for strong organic-inorganic electronic couplings.

  8. Effect of Thermal Processes on the Electrical and Optical Properties of Fe2TiO5 Ceramics

    NASA Astrophysics Data System (ADS)

    Fajarin, R.; Widyastuti; Baqiya, M. A.; Putri, I. Y. S.

    2017-05-01

    Pseudobrookite (Fe2TiO5) is one of the Fe-Ti oxides that have been commonly studied. It is the most stable phase among the Fe-titanates. The multiferroic properties of Fe2TiO5 make the material can be used as a potential candidate for new applications due to the combination of semiconducting, magnetic, dielectric, and optical properties. In this research, Fe2TiO5 ceramics were synthesized using mechanical milling method for 7 h with various temperatures of 1100 °C, 1200 °C, and 1300 °C. Scanning electron microscopy (SEM) observation and x-ray diffraction (XRD) measurements were performed to analyze the microstructures and crystal structures of the Fe2TiO5 ceramics. In order to investigate the band gap of the Fe2TiO5, the UV-Vis Diffuse Reflectance measurements were conducted. It has been found that the Fe2TiO5 ceramic can be applied as a promising candidate for semiconducting devices in which the electrical conductivity and the band gap of the Fe2TiO5 ceramic were 1.73 × 10-7 Ω-1.cm-1 and 1.71 eV, respectively.

  9. Effect of sintering temperatures and screen printing types on TiO2 layers in DSSC applications

    NASA Astrophysics Data System (ADS)

    Supriyanto, Agus; Furqoni, Lutfi; Nurosyid, Fahru; Hidayat, Jojo; Suryana, Risa

    2016-03-01

    Dye-Sensitized Solar Cell (DSSC) is a candidate solar cell, which has a big potential in the future due to its eco-friendly material. This research is conducted to study the effect of sintering temperature and the type of screen-printing toward the characteristics of TiO2 layer as a working electrode in DSSC. TiO2 layers were fabricated using a screen-printing method with a mesh size of T-49, T-55, and T-61. TiO2 layers were sintered at temperatures of 600°C and 650°C for 60 min. DSSC structure was composed of TiO2 as semiconductors, ruthenium complex as dyes, and carbon as counter electrodes. The morphology of TiO2 layer was observed by using Nikon E2 Digital Camera Microscopy. The efficiencies of DSSC were calculated from the I-V curves. The highest efficiency is 0.015% at TiO2 layer fabricated with screen type T-61 and at a sintering temperature of 650°C.

  10. P and n-type microcrystalline semiconductor alloy material including band gap widening elements, devices utilizing same

    DOEpatents

    Guha, Subhendu; Ovshinsky, Stanford R.

    1988-10-04

    An n-type microcrystalline semiconductor alloy material including a band gap widening element; a method of fabricating p-type microcrystalline semiconductor alloy material including a band gap widening element; and electronic and photovoltaic devices incorporating said n-type and p-type materials.

  11. A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

    PubMed

    Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

    2016-08-01

    Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst.

  12. Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

    NASA Technical Reports Server (NTRS)

    Coutts, Janelle L.; Hintze, Paul E.; Clausen, Christian; Richards, Jeffrey Todd

    2014-01-01

    Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of

  13. Low-temperature electrodeposition approach leading to robust mesoscopic anatase TiO2 films

    NASA Astrophysics Data System (ADS)

    Patra, Snehangshu; Andriamiadamanana, Christian; Tulodziecki, Michal; Davoisne, Carine; Taberna, Pierre-Louis; Sauvage, Frédéric

    2016-02-01

    Anatase TiO2, a wide bandgap semiconductor, likely the most worldwide studied inorganic material for many practical applications, offers unequal characteristics for applications in photocatalysis and sun energy conversion. However, the lack of controllable, cost-effective methods for scalable fabrication of homogeneous thin films of anatase TiO2 at low temperatures (ie. < 100 °C) renders up-to-date deposition processes unsuited to flexible plastic supports or to smart textile fibres, thus limiting these wearable and easy-to-integrate emerging technologies. Here, we present a very versatile template-free method for producing robust mesoporous films of nanocrystalline anatase TiO2 at temperatures of/or below 80 °C. The individual assembly of the mesoscopic particles forming ever-demonstrated high optical quality beads of TiO2 affords, with this simple methodology, efficient light capture and confinement into the photo-anode, which in flexible dye-sensitized solar cell technology translates into a remarkable power conversion efficiency of 7.2% under A.M.1.5G conditions.

  14. Low-temperature electrodeposition approach leading to robust mesoscopic anatase TiO2 films

    PubMed Central

    Patra, Snehangshu; Andriamiadamanana, Christian; Tulodziecki, Michal; Davoisne, Carine; Taberna, Pierre-Louis; Sauvage, Frédéric

    2016-01-01

    Anatase TiO2, a wide bandgap semiconductor, likely the most worldwide studied inorganic material for many practical applications, offers unequal characteristics for applications in photocatalysis and sun energy conversion. However, the lack of controllable, cost-effective methods for scalable fabrication of homogeneous thin films of anatase TiO2 at low temperatures (ie. < 100 °C) renders up-to-date deposition processes unsuited to flexible plastic supports or to smart textile fibres, thus limiting these wearable and easy-to-integrate emerging technologies. Here, we present a very versatile template-free method for producing robust mesoporous films of nanocrystalline anatase TiO2 at temperatures of/or below 80 °C. The individual assembly of the mesoscopic particles forming ever-demonstrated high optical quality beads of TiO2 affords, with this simple methodology, efficient light capture and confinement into the photo-anode, which in flexible dye-sensitized solar cell technology translates into a remarkable power conversion efficiency of 7.2% under A.M.1.5G conditions. PMID:26911529

  15. Mechanism of strong visible light photocatalysis by Ag2O-nanoparticle-decorated monoclinic TiO2(B) porous nanorods

    NASA Astrophysics Data System (ADS)

    Paul, Kamal Kumar; Ghosh, Ramesh; Giri, P. K.

    2016-08-01

    We report on the ultra-high rate of photodegradation of organic dyes under visible light illumination on Ag2O-nanoparticle-decorated (NP) porous pure B-phase TiO2 (TiO2(B)) nanorods (NRs) grown by a solvothermal route. The as-grown TiO2(B) NRs are found to be nanoporous in nature and the Ag2O NPs are uniformly decorated over its surface, since most of the pores work as nucleation sites for the growth of Ag2O NPs. The effective band gap of the TiO2(B)/Ag2O heterostructure (HS), with a weight ratio of 1:1, has been significantly reduced to 1.68 eV from the pure TiO2(B) band gap of 2.8 eV. Steady state and time-resolved photoluminescence (PL) studies show the reduced intensity of visible PL and slower recombination dynamics in the HS samples. The photocatalytic degradation efficiency of the TiO2(B)/Ag2O HS has been investigated using aqueous methyl orange and methylene blue as reference dyes under visible light (390-800 nm) irradiation. It is found that photodegradation by the TiO2(B)/Ag2O HS is about one order of magnitude higher than that of bare TiO2(B) NRs and Ag2O NPs. The optimized TiO2(B)/Ag2O HS exhibited the highest photocatalytic efficiency, with 88.2% degradation for 30 min irradiation. The corresponding first order degradation rate constant is 0.071 min-1, which is four times higher than the reported values. Furthermore, cyclic stability studies show the high stability of the HS photocatalyst for up to four cycles of use. The major improvement in photocatalytic efficiency has been explained on the basis of enhanced visible light absorption and band-bending-induced efficient charge separation in the HS. Our results demonstrate the long-term stability and superiority of the TiO2(B)/Ag2O HS over the bare TiO2(B) NRs and other TiO2-based photocatalysts for its cutting edge application in hydrogen production and environmental cleaning driven by solar light photocatalysis.

  16. Interfacial interactions of semiconductor with graphene and reduced graphene oxide: CeO2 as a case study.

    PubMed

    Xu, Liang; Huang, Wei-Qing; Wang, Ling-Ling; Huang, Gui-Fang

    2014-11-26

    The pursuit of superb building blocks of light harvesting systems has stimulated increasing efforts to develop graphene (GR)-based semiconductor composites for solar cells and photocatalysts. One critical issue for GR-based composites is understanding the interaction between their components, a problem that remains unresolved after intense experimental investigation. Here, we use cerium dioxide (CeO2) as a model semiconductor to systematically explore the interaction of semiconductor with GR and reduced graphene oxide (RGO) with large-scale ab initio calculations. The amount of charge transferred at the interfaces increases with the concentration of O atoms, demonstrating that the interaction between CeO2 and RGO is much stronger than that between CeO2 and GR due to the decrease of the average equilibrium distance between the interfaces. The stronger interaction between semiconductor and RGO is expected to be general, as evidenced by the results of two paradigms of TiO2 and Ag3PO4 coupled with RGO. The interfacial interaction can tune the band structure: the CeO2(111)/GR interface is a type-I heterojunction, while a type-II staggered band alignment exists between the CeO2(111) surface and RGO. The smaller band gap, type-II heterojunction, and negatively charged O atoms on the RGO as active sites are responsible for the enhanced photoactivity of CeO2/RGO composite. These findings can rationalize the available experimental reports and enrich our understanding of the interaction of GR-based composites for developing high-performance photocatalysts and solar cells.

  17. Quantum dot sensitized solar cell based on TiO2/CdS/Ag2S heterostructure

    NASA Astrophysics Data System (ADS)

    Pawar, Sachin A.; Patil, Dipali S.; Kim, Jin Hyeok; Patil, Pramod S.; Shin, Jae Cheol

    2017-04-01

    Quantum dot sensitized solar cell (QDSSC) is fabricated based on a stepwise band structure of TiO2/CdS/Ag2S to improve the photoconversion efficiency of TiO2/CdS system by incorporating a low band gap Ag2S QDs. Vertically aligned TiO2 nanorods assembly is prepared by a simple hydrothermal technique. The formation of CdS and Ag2S QDs over TiO2 nanorods assembly as a photoanode is carried out by successive ionic layer adsorption and reaction (SILAR) technique. The synthesized electrode materials are characterized by XRD, XPS, field emission scanning electron microscopy (FE-SEM), Optical, solar cell and electrochemical performances. The results designate that the QDs of CdS and Ag2S have efficiently covered exterior surfaces of TiO2 nanorods assembly. A cautious evaluation between TiO2/CdS and TiO2/CdS/Ag2S sensitized cells tells that CdS and Ag2S synergetically helps to enhance the light harvesting ability. Under AM 1.5G illumination, the photoanodes show an improved power conversion efficiency of 1.87%, in an aqueous polysulfide electrolyte with short-circuit photocurrent density of 7.03 mA cm-2 which is four fold higher than that of a TiO2/CdS system.

  18. First-Principles Modeling of Polaron Formation in TiO2 Polymorphs.

    PubMed

    Elmaslmane, A R; Watkins, M B; McKenna, K P

    2018-06-21

    We present a computationally efficient and predictive methodology for modeling the formation and properties of electron and hole polarons in solids. Through a nonempirical and self-consistent optimization of the fraction of Hartree-Fock exchange (α) in a hybrid functional, we ensure the generalized Koopmans' condition is satisfied and self-interaction error is minimized. The approach is applied to model polaron formation in known stable and metastable phases of TiO 2 including anatase, rutile, brookite, TiO 2 (H), TiO 2 (R), and TiO 2 (B). Electron polarons are predicted to form in rutile, TiO 2 (H), and TiO 2 (R) (with trapping energies ranging from -0.02 eV to -0.35 eV). In rutile the electron localizes on a single Ti ion, whereas in TiO 2 (H) and TiO 2 (R) the electron is distributed across two neighboring Ti sites. Hole polarons are predicted to form in anatase, brookite, TiO 2 (H), TiO 2 (R), and TiO 2 (B) (with trapping energies ranging from -0.16 eV to -0.52 eV). In anatase, brookite, and TiO 2 (B) holes localize on a single O ion, whereas in TiO 2 (H) and TiO 2 (R) holes can also be distributed across two O sites. We find that the optimized α has a degree of transferability across the phases, with α = 0.115 describing all phases well. We also note the approach yields accurate band gaps, with anatase, rutile, and brookite within six percent of experimental values. We conclude our study with a comparison of the alignment of polaron charge transition levels across the different phases. Since the approach we describe is only two to three times more expensive than a standard density functional theory calculation, it is ideally suited to model charge trapping at complex defects (such as surfaces and interfaces) in a range of materials relevant for technological applications but previously inaccessible to predictive modeling.

  19. Alternative photocatalysts to TiO2 for the photocatalytic reduction of CO2

    NASA Astrophysics Data System (ADS)

    Nikokavoura, Aspasia; Trapalis, Christos

    2017-01-01

    The increased concentration of CO2 in the atmosphere, originating from the burning of fossil fuels in stationary and mobile sources, is referred as the "Anthropogenic Greenhouse Effect" and constitutes a major environmental concern. The scientific community is highly concerned about the resulting enhancement of the mean atmospheric temperature, so a vast diversity of methods has been applied. Thermochemical, electrochemical, photocatalytic, photoelectrochemical processes, as well as combination of solar electricity generation and water splitting processes have been performed in order to lower the CO2 atmospheric levels. Photocatalytic methods are environmental friendly and succeed in reducing the atmospheric CO2 concentration and producing fuels or/and useful organic compounds at the same time. The most common photocatalysts for the CO2 reduction are the inorganic, the carbon based semiconductors and the hybrids based on semiconductors, which combine stability, low cost and appropriate structure in order to accomplish redox reactions. In this review, inorganic semiconductors such as single-metal oxide, mixed-metal oxides, metal oxide composites, layered double hydroxides (LDHs), salt composites, carbon based semiconductors such as graphene based composites, CNT composites, g-C3N4 composites and hybrid organic-inorganic materials (ZIFs) were studied. TiO2 and Ti based photocatalysts are extensively studied and therefore in this review they are not mentioned.

  20. Studies on Nano-Engineered TiO2 Photo Catalyst for Effective Degradation of Dye

    NASA Astrophysics Data System (ADS)

    Sowmya, S. R.; Madhu, G. M.; Hashir, Mohammed

    2018-02-01

    All Heterogeneous photo catalysis employing efficient photo-catalyst is the advanced dye degradation technology for the purification of textile effluent. The present work focuses on Congo red dye degradation employing synthesized Ag doped TiO2 nanoparticles as photocatalyst which is characterized using SEM, XRD and FTIR. Studies are conducted to study the effect of various parameters such as initial dye concentration, catalyst loading and pH of solution. Ag Doped TiO2 photocatalyst improve the efficacy of TiO2 by reducing high band gap and electron hole recombination of TiO2. The reaction kinetics is analyzed and the process is found to follow pseudo first order kinetics.

  1. Morphology modulation of SrTiO3/TiO2 heterostructures for enhanced photoelectrochemical performance.

    PubMed

    Jiao, Zhengbo; Chen, Tao; Yu, Hongchao; Wang, Teng; Lu, Gongxuan; Bi, Yingpu

    2014-04-01

    Design and fabrication of nanoscale semiconductors with regulatable morphology or structure has attracted tremendous interest due to the dependency relationship between properties and architectures. Two types of SrTiO3/TiO2 nanocomposites with different morphologies and structures have been fabricated by controlling the kinetics of hydrothermal reactions. One is TiO2 nanotube arrays densely wrapped by SrTiO3 film and the other is SrTiO3 nanospheres distributed on the top region of TiO2 nanotube arrays, which has been firstly fabricated. It has been found that the photoelectrochemical performances of these heterostructures are crucially dominated by their architectures. Heterostructured SrTiO3/TiO2 nanotube arrays were fabricated by traditional method in the absence of NaOH and they exhibited higher photoelectrochemical performance than pure TiO2 nanotube arrays. However, the compact SrTiO3 coating film on the sidewalls of TiO2 nanotube arrays could inevitably destroy the tubular structures of TiO2 and thus go against the vectorial transport of electrons. Interestingly, when excess NaOH was added into the growth solution, SrTiO3 nanospheres would be rationally grafted on the top of TiO2 nanotube arrays, which could preserve the tubular structures of TiO2, and thus further improve the photoelectrochemical performance. Copyright © 2013 Elsevier Inc. All rights reserved.

  2. TiO2 nanorods thin-films embedded with gold nanoparticles for enhanced photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Raval, Dhyey; Jani, Margi; Mukhopadhyay, Indrajit; Ray, Abhijit

    2018-05-01

    This article reports on the gold nanoparticle (Au-NP) induced absorption enhancement in the hydrothermally grown titanium dioxide nanorods (TiO2-NRs). The localized surface plasmon resonance (LSPR) and transfer of electron from Au-NPs attached to the TiO2-NR have been related to their photocatalytic response. The photocurrent enhancement observed in the studies of IPCE has been explained on the basis of electrons in the conduction band of TiO2-NR. The electrons from the Au-NP to the conduction band of TiO2-NR with respect to the wavelength of the incident spectrum shows an increase in efficiency over pristine TiO2-NRs sample. Further, to investigate the role of Au-NP, an absorption spectra with its incident wavelength shows an increase in the visible spectrum in the present study. This provides an explanation for the response to the absorption of the wide bandgap semiconductor oxide which gives an opportunity to develop a hybrid structure on the transparent substrates. The better response of Au-NPs/TiO2-NRs system can be used in photocatalytic processes.

  3. Enhanced Adsorption and Photocatalytic Activities of Co-Doped TiO2 Immobilized on Silica for Paraquat

    NASA Astrophysics Data System (ADS)

    Nghia, Nguyen Manh; Negishi, Nobuaki; Hue, Nguyen Thi

    2018-01-01

    We studied the adsorption and photocatalysis of paraquat in an aqueous solution with cobalt-doped TiO2 supported on mesoporous silica gel. With Co concentration increasing from 0% to 9%, it was found that the TiO2 anatase phase remained unchanged and the Co was uniformly distributed, while the band gap energy decreased from 3.32 eV to 2.64 eV. The drop in band gap energy leads to the Co-TiO2/silica gel photocatalyst oxidation of paraquat to NH4 + and NO3 - products under visible light. Relative to TiO2, the incorporation of Co into TiO2 led to an increase in the adsorption ability against the paraquat. A possible mechanism of the paraquat degradation may be that the paraquat was selectively adsorbed onto the Co-TiO2/silica gel photocatalyst before light irradiation and after that the paraquat was continuously photodecomposed.

  4. The Application of Nano-TiO2 Photo Semiconductors in Agriculture

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Sun, Changjiao; Zhao, Xiang; Cui, Bo; Zeng, Zhanghua; Wang, Anqi; Liu, Guoqiang; Cui, Haixin

    2016-11-01

    Nanometer-sized titanium dioxide (TiO2) is an environmentally friendly optical semiconductor material. It has wide application value in many fields due to its excellent structural, optical, and chemical properties. The photocatalytic process of nano-TiO2 converts light energy into electrical or chemical energy under mild conditions. In recent years, the study and application of nano-TiO2 in the agricultural sector has gradually attracted attention. The nano-TiO2 applications of degrading pesticides, plant germination and growth, crop disease control, water purification, pesticide residue detection, etc. are good prospects. This review describes all of these applications and the research status and development, including the underlying principles, features, comprehensive applications, functional modification, and potential future directions, for TiO2 in agriculture.

  5. Effects of photocatalytic activity of metal and non-metal doped Tio2 for Hydrogen production enhancement - A Review

    NASA Astrophysics Data System (ADS)

    Nur Aqilah Sulaiman, Siti; Zaky Noh, Mohamad; Nadia Adnan, Nurul; Bidin, Noriah; Razak, Siti Noraiza Ab

    2018-05-01

    Titanium dioxide TiO2 is well-known materials that has become an efficient photocatalyst for environmental sustainability. Known as solar driven catalysis, TiO2 is considered as the most promising way to alleviate environmental issues caused by the combustion of fossil fuels and to meet worldwide demands for energy. Much effort has been concerned on TiO2 band gap modification to become a visible-light-activated photocatalysts of TiO2 because it can only be excited by UV light irradiation due to its large band gap. Modifications like metals and nonmetals doping has been proposed in the past decades. This reviews survey recent advanced preparation methods of doped-TiO2 including various types of doping methods for various types of dopants and provides general review on further modifications. The characterizations techniques used in order to determine the structural, morphological and optical properties of modified TiO2 is also discussed. Further, a new method of TiO2 modification is proposed in this mini review paper.

  6. Energy Impacts of Wide Band Gap Semiconductors in U.S. Light-Duty Electric Vehicle Fleet

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Warren, Joshua A.; Riddle, Matthew E.; Graziano, Diane J.

    2015-08-12

    Silicon carbide and gallium nitride, two leading wide band gap semiconductors with significant potential in electric vehicle power electronics, are examined from a life cycle energy perspective and compared with incumbent silicon in U.S. light-duty electric vehicle fleet. Cradle-to-gate, silicon carbide is estimated to require more than twice the energy as silicon. However, the magnitude of vehicle use phase fuel savings potential is comparatively several orders of magnitude higher than the marginal increase in cradle-to-gate energy. Gallium nitride cradle-to-gate energy requirements are estimated to be similar to silicon, with use phase savings potential similar to or exceeding that of siliconmore » carbide. Potential energy reductions in the United States vehicle fleet are examined through several scenarios that consider the market adoption potential of electric vehicles themselves, as well as the market adoption potential of wide band gap semiconductors in electric vehicles. For the 2015–2050 time frame, cumulative energy savings associated with the deployment of wide band gap semiconductors are estimated to range from 2–20 billion GJ depending on market adoption dynamics.« less

  7. Study of Sn and Mg doping effects on TiO2/Ge stack structure by combinatorial synthesis

    NASA Astrophysics Data System (ADS)

    Nagata, Takahiro; Suzuki, Yoshihisa; Yamashita, Yoshiyuki; Ogura, Atsushi; Chikyow, Toyohiro

    2018-04-01

    The effects of Sn and Mg doping of a TiO2 film on a Ge substrate were investigated to improve leakage current properties and Ge diffusion into the TiO2 film. For systematic analysis, dopant-composition-spread TiO2 samples with dopant concentrations of up to 20.0 at. % were fabricated by RF sputtering and a combinatorial method. X-ray photoelectron spectroscopy revealed that the instability of Mg doping of TiO2 at dopant concentrations above 10.5 at. %. Both Sn and Mg dopants reduced Ge diffusion into TiO2. Sn doping enhanced the crystallization of the rutile phase, which is a high-dielectric-constant phase, although the Mg-doped TiO2 film indicated an amorphous structure. Sn-doping indicated systematic leakage current reduction with increasing dopant concentration. Doping at Sn concentrations higher than 16.8 at. % improved the leakage properties (˜10-7 A/cm2 at -3.0 V) and capacitance-voltage properties of metal-insulator-semiconductor (MIS) operation. The Sn doping of TiO2 may be useful for interface control and as a dielectric material for Ge-based MIS capacitors.

  8. Effective nitrogen doping into TiO2 (N-TiO2) for visible light response photocatalysis.

    PubMed

    Yoshida, Tomoko; Niimi, Satoshi; Yamamoto, Muneaki; Nomoto, Toyokazu; Yagi, Shinya

    2015-06-01

    The thickness-controlled TiO2 thin films are fabricated by the pulsed laser deposition (PLD) method. These samples function as photocatalysts under UV light irradiation and the reaction rate depends on the TiO2 thickness, i.e., with an increase of thickness, it increases to the maximum, followed by decreasing to be constant. Such variation of the reaction rate is fundamentally explained by the competitive production and annihilation processes of photogenerated electrons and holes in TiO2 films, and the optimum TiO2 thickness is estimated to be ca. 10nm. We also tried to dope nitrogen into the effective depth region (ca. 10nm) of TiO2 by an ion implantation technique. The nitrogen doped TiO2 enhanced photocatalytic activity under visible-light irradiation. XANES and XPS analyses indicated two types of chemical state of nitrogen, one photo-catalytically active N substituting the O sites and the other inactive NOx (1⩽x⩽2) species. In the valence band XPS spectrum of the high active sample, the additional electronic states were observed just above the valence band edge of a TiO2. The electronic state would be originated from the substituting nitrogen and be responsible for the band gap narrowing, i.e., visible light response of TiO2 photocatalysts. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. Anisotropy of band gap absorption in TlGaSe2 semiconductor by ferroelectric phase transformation

    NASA Astrophysics Data System (ADS)

    Gulbinas, Karolis; Grivickas, Vytautas; Gavryushin, Vladimir

    2014-12-01

    The depth-resolved free-carrier absorption and the photo-acoustic response are used to examine the band-gap absorption in 2D-TlGaSe2 layered semiconductor after its transformation into the ferroelectric F-phase below 107 K. The absorption exhibits unusual behavior with a biaxial character in respect to the light polarization on the layer plane. A spectral analysis shows that the anisotropy is associated to the lowest Γ-direct optical transition. The Γ-absorption and the localized exciton at 2.11 eV are dipole-prohibited or partially allowed in two nearly perpendicular polarization directions. The shift of anisotropy axis in respect to crystallographic a- and b-directions demonstrates the non-equivalent zigzag rearrangement of the interlayer connecting Tl+ ions, which is responsible for occurrence of the F-phase.

  10. Antimicrobial effect of TiO2 doped with Ag and Cu on Escherichia coli and Pseudomonas putida

    NASA Astrophysics Data System (ADS)

    Angelov, O.; Stoyanova, D.; Ivanova, I.

    2016-10-01

    Antimicrobial effect of TiO2 doped with Ag and Cu on Gram-negative bacteria Escherichia coli and Pseudomonas putida is studied. The thin films are deposited on glass substrates without heating during the deposition by r.f. magnetron co-sputtering of TiO2 target and pieces of Ag and Cu. The studied films, thickness about 65 nm, were as deposited and annealed (5200C, 4h, N2+5%H2, 4Pa). The as deposited thin films TiO2:Ag:Cu have band gap energy of 3.56 eV little higher than the band gap of crystalline anatase TiO2 which can be explained with the quantum effect of the granular structure of r.f. magnetron sputtered films. The annealed samples have band gap of 2.52 eV due to formation of donor levels from Ag and Cu atoms near the bottom of the conduction band. The toxic effect was determined through the classical Koch's method and the optical density measurements at λ=610 nm. The as deposited TiO2:Ag:Cu thin films demonstrate stronger inhibition effect - bactericidal for P. putida and bacteriostatic for E. coli (up to the 6th hour) in comparison with the annealed samples. The both methods of study show the same trends of the bacterial growth independently of their different sensitivity which confirms the observed effect.

  11. A weak-light-responsive TiO2/g-C3N4 composite film: photocatalytic activity under low-intensity light irradiation.

    PubMed

    Wang, Peifang; Guo, Xiang; Rao, Lei; Wang, Chao; Guo, Yong; Zhang, Lixin

    2018-05-10

    A TiO 2 /g-C 3 N 4 composite photocatalytic film was prepared by in situ synthesis method and its photocatalytic capability under weak-visible-light condition was studied. The co-precursor with different ratio of melamine and TiO 2 sol-gel precursor were treated using ultrasonic mixing, physical deposition, and co-sintering method to form the smooth, white-yellow, and compact TiO 2 /g-C 3 N 4 composite films. The prepared TiO 2 /g-C 3 N 4 materials were characterized by SEM, TEM, EDS, XRD, BET, VBXPS, and UV-vis diffuse reflectance spectra. The results of composite showed that TiO 2 and g-C 3 N 4 have close interfacial connections which are favorable to charge transfer between these two semiconductors with suitable band structure, g-C 3 N 4 retard the anatase-to-rutile phase transition of TiO 2 significantly, the specific surface area were increased with g-C 3 N 4 ratio raised. Under weak-light irradiation, composite films photocatalytic experiments exhibited RhB removal efficiency approaching 90% after three recycles. Powders suspension degradation experiments revealed the removal efficiency of TiO 2 /g-C 3 N 4 (90.8%) was higher than pure TiO 2 (52.1%) and slightly lower than pure g-C 3 N 4 (96.6%). By control experiment, the enhanced photocatalysis is ascribed to the combination of TiO 2 and g-C 3 N 4 , which not only produced thin films with greater stability but also formed heterojunctions that can be favorable to charge transfer between these two semiconductors with suitable band structure. This study presents the potential application of photocatalytic film in the wastewater treatment under weak-light situation.

  12. Surface modification of mixed-phase hydrogenated TiO2 and corresponding photocatalytic response

    NASA Astrophysics Data System (ADS)

    Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd; Juan, Joon Ching; Basirun, Wan Jefrey; Kandjani, Ahmad Esmaielzadeh

    2015-12-01

    Preparation of highly photo-activated TiO2 is achievable by hydrogenation at constant temperature and pressure, with controlled hydrogenation duration. The formation of surface disorders and Ti3+ is responsible for the color change from white unhydrogenated TiO2 to bluish-gray hydrogenated TiO2. This color change, together with increased oxygen vacancies and Ti3+ enhanced the solar light absorption from UV to infra-red region. Interestingly, no band gap narrowing is observed. The photocatalytic activity in the UV and visible region is controlled by Ti3+ and oxygen vacancies respectively. Both Ti3+ and oxygen vacancies increases the electron density on the catalyst surface thus facilitates rad OH radicals formation. The lifespan of surface photo-excited electrons and holes are also sustained thus prevents charge carrier recombination. However, excessive amount of oxygen vacancies deteriorates the photocatalytic activity as it serves as charge traps. Hydrogenation of TiO2 also promotes the growth of active {0 0 1} facets and facilitates the photocatalytic activity by higher concentration of surface OH radicals. However, the growth of {0 0 1} facets is small and insignificant toward the overall photo-kinetics. This work also shows that larger role is played by Ti3+ and oxygen vacancies rather than the surface disorders created during the hydrogenation process. It also demonstrates the ability of hydrogenated TiO2 to absorb wider range of photons even though at a similar band gap as unhydrogenated TiO2. In addition, the photocatalytic activity is shown to be decreased for extended hydrogenation duration due to excessive catalyst growth and loss in the total surface area. Thus, a balance in the physico-chemical properties of hydrogenated TiO2 is crucial to enhance the photocatalytic activity by simply controlling the hydrogenation duration.

  13. New Material Transistor with Record-High Field-Effect Mobility among Wide-Band-Gap Semiconductors.

    PubMed

    Shih, Cheng Wei; Chin, Albert

    2016-08-03

    At an ultrathin 5 nm, we report a new high-mobility tin oxide (SnO2) metal-oxide-semiconductor field-effect transistor (MOSFET) exhibiting extremely high field-effect mobility values of 279 and 255 cm(2)/V-s at 145 and 205 °C, respectively. These values are the highest reported mobility values among all wide-band-gap semiconductors of GaN, SiC, and metal-oxide MOSFETs, and they also exceed those of silicon devices at the aforementioned elevated temperatures. For the first time among existing semiconductor transistors, a new device physical phenomenon of a higher mobility value was measured at 45-205 °C than at 25 °C, which is due to the lower optical phonon scattering by the large SnO2 phonon energy. Moreover, the high on-current/off-current of 4 × 10(6) and the positive threshold voltage of 0.14 V at 25 °C are significantly better than those of a graphene transistor. This wide-band-gap SnO2 MOSFET exhibits high mobility in a 25-205 °C temperature range, a wide operating voltage of 1.5-20 V, and the ability to form on an amorphous substrate, rendering it an ideal candidate for multifunctional low-power integrated circuit (IC), display, and brain-mimicking three-dimensional IC applications.

  14. Size Effects in Dye-Sensitized TiO2 Clusters

    NASA Astrophysics Data System (ADS)

    Marom, Noa; Körzdörfer, Thomas; Ren, Xinguo; Tkatchenko, Alexandre; Chelikowsky, James

    2014-03-01

    The development of solar cells is driven by the need for clean and sustainable energy. Organic and dye sensitized cells are considered as promising technologies, particularly for large area, low cost applications. However, the efficiency of such cells is still far from the theoretical limit. Ab initio simulations may be used for computer-aided design of new materials and nano-structures for more efficient solar cells. It is essential to obtain an accurate description of the electronic structure, including the fundamental gaps and energy level alignment at the interfaces in the device active region. This requires going beyond ground-state DFT to the GW approximation. A recently developed GW method [PRB 86, 041110R (2012)] is applied to dye-sensitized TiO2 clusters [PRB 84, 245115 (2011)]. The effect of cluster size on the energy level alignment at the dye-TiO2 interface is discussed. With the increase in the TiO2 cluster size its gap narrows. The gap of the molecule attached to the cluster subsequently narrows due to screening. As a result, the energy level alignment at the interface changes in an unexpected way [Marom, Körzdörfer, Ren, Tkatchenko, Chelikowsky, to be published].

  15. Molecular design of TiO2 for gigantic red shift via sublattice substitution.

    PubMed

    Shao, Guosheng; Deng, Quanrong; Wan, Lin; Guo, Meilan; Xia, Xiaohong; Gao, Yun

    2010-11-01

    The effects of 3d transition metal doping in TiO2 phases have been simulated in detail. The results of modelling indicate that Mn has the biggest potential among 3d transition metals, for the reduction of energy gap and the introduction of effective intermediate bands to allow multi-band optical absorption. On the basis of theoretical formulation, we have incorporated considerable amount of Mn in nano-crystalline TiO2 materials. Mn doped samples demonstrate significant red shift in the optical absorption edge, with a secondary absorption edge corresponding to theoretically predicted intermediate bands/states. The gigantic red shift achievable in Mn-doped TiO2 is expected to extend the useful TiO2 functionalities well beyond the UV threshold via the optical absorption of both visible and infrared photon irradiance.

  16. Formation of Sol Gel Dried Droplets of Carbon Doped Titanium Dioxide (TiO2) at Low Temperature via Electrospraying

    NASA Astrophysics Data System (ADS)

    Halimi, S. U.; Hashib, S. Abd; Abu Bakar, N. F.; Ismail, S. N.; Nazli Naim, M.; Rahman, N. Abd; Krishnan, J.

    2018-05-01

    The high band gap energy of TiO2 and inconsistency in particles size has imposed a significant drawback on TiO2 applications. Dried droplets of carbon-doped TiO2 fine particles were produced by using electrospraying technique. The C-doped TiO2 particles were prepared by hydrolysis of titanium isopropoxide with the addition of carbon precursor followed by electrospraying the suspension in stable Taylor cone-jet mode. Coulomb fission of charged droplets from the electrospraying technique successfully transformed dispersed liquid C-doped TiO2 particles into solid. The deposited C-doped TiO2 droplets were collected on aluminium substrates placed at working distances of 10 to 20 cm from the tip of the electrospray needle. The collected C-doped TiO2 droplets were characterized by using FESEM, UV-Vis, FTIR and XRD. By increasing the working distance, the average droplets size of the deposited C-doped TiO2 was reduced from ±163.2 nm to ±147.56 nm. UV-Vis analysis showed a strong absorption in the visible-light region and about 93 nm red shift of the onset spectrum for C-doped TiO2. The red shift indicates an increase in photocatalytic efficiency by reducing the TiO2 band gap energy from 3.0 eV to 2.46 eV and shifting its activity to the visible-light region. FTIR analysis indicated the presence of Ti-C and C-O chemical bonding in the C-doped TiO2.

  17. ALD-Developed Plasmonic Two-Dimensional Au-WO3-TiO2 Heterojunction Architectonics for Design of Photovoltaic Devices.

    PubMed

    Karbalaei Akbari, Mohammad; Hai, Zhenyin; Wei, Zihan; Detavernier, Christophe; Solano, Eduardo; Verpoort, Francis; Zhuiykov, Serge

    2018-03-28

    Electrically responsive plasmonic devices, which benefit from the privilege of surface plasmon excited hot carries, have supported fascinating applications in the visible-light-assisted technologies. The properties of plasmonic devices can be tuned by controlling charge transfer. It can be attained by intentional architecturing of the metal-semiconductor (MS) interfaces. In this study, the wafer-scaled fabrication of two-dimensional (2D) TiO 2 semiconductors on the granular Au metal substrate is achieved using the atomic layer deposition (ALD) technique. The ALD-developed 2D MS heterojunctions exhibited substantial enhancement of the photoresponsivity and demonstrated the improvement of response time for 2D Au-TiO 2 -based plasmonic devices under visible light illumination. To circumvent the undesired dark current in the plasmonic devices, a 2D WO 3 nanofilm (∼0.7 nm) was employed as the intermediate layer on the MS interface to develop the metal-insulator-semiconductor (MIS) 2D heterostructure. As a result, 13.4% improvement of the external quantum efficiency was obtained for fabricated 2D Au-WO 3 -TiO 2 heterojunctions. The impedancometry measurements confirmed the modulation of charge transfer at the 2D MS interface using MIS architectonics. Broadband photoresponsivity from the UV to the visible light region was observed for Au-TiO 2 and Au-WO 3 -TiO 2 heterostructures, whereas near-infrared responsivity was not observed. Consequently, considering the versatile nature of the ALD technique, this approach can facilitate the architecturing and design of novel 2D MS and MIS heterojunctions for efficient plasmonic devices.

  18. Effects of nano anatase-rutile TiO2 volume fraction with natural dye containing anthocyanin on the dye sensitized solar cell performance

    NASA Astrophysics Data System (ADS)

    Agustini, S.; Wahyuono, R. A.; Sawitri, D.; Risanti, D. D.

    2013-09-01

    Since its first development, efforts to improve efficiency of Dye Sensitized Solar Cell (DSSC) are continuously carried out, either through selection of dye materials, the type of semiconductor, counter electrode design or the sandwiched structure. It is widely known that anatase and rutile are phases of TiO2 that often being used for fabrication of DSSC. Rutile is thermodynamically more stable phase having band-gap suitable for absorption of sunlight spectrum. On the other hand, anatase has higher electrical conductivity, capability to adsorp dye as well as higher electron diffusion coefficient than those of rutile. Present research uses mangosteen pericarp and Rhoeo spathacea extracted in ethanol as natural dye containing anthocyanin. These dyes were characterized by using UV-Vis and FTIR, showing that the absorption maxima peaks obtained at 389 nm and 413 nm, for mangosteen and Rhoeo spathacea, respectively. The nano TiO2 was prepared by means of co-precipitation method. The particle size were 9-11 nm and 54.5 nm for anatase and rutile, respectively, according to Scherrer's equation. DSSCs were fabricated in various volume fractions of anatase and rutile TiO2. The fabricated DSSCs were tested under 17 mW/cm2 of solar irradiation. The current-voltage (I-V) characteristic of DSSCs employing 75%: 25% volume fraction of anatase and rutile TiO2 have outstanding result than others. The highest conversion efficiencies of 0.037% and 0.013% are obtained for DSSC employing natural dye extract from mangosteen pericarp and Rhoeo spathacea, respectively.

  19. Facile preparation of a TiO2 quantum dot/graphitic carbon nitride heterojunction with highly efficient photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Wang, Xing; Jiang, Subin; Huo, Xuejian; Xia, Rui; Muhire, Elisée; Gao, Meizhen

    2018-05-01

    In this article, mechanical grinding, an effortless and super-effective synthetic strategy, is used to successfully synthesize a TiO2 quantum dot (TiO2QD)/graphitic carbon nitride (g-C3N4) heterostructure. X-ray photoelectron spectroscopy results together with transmission electron microscopy reveal the formation of the TiO2QD/g-C3N4 heterostructure with strong interfacial interaction. Because of the advantages of this characteristic, the prepared heterostructure exhibits excellent properties for photocatalytic wastewater treatment. Notably, the optimum photocatalytic activity of the TiO2QD/g-C3N4 heterostructure is nearly 3.4 times higher than that of the g-C3N4 nanosheets used for the photodegradation of rhodamine B pollutant. In addition, the stability and possible degradation mechanism of the TiO2QD/g-C3N4 heterojunction are studied in detail. This method may stimulate an effective approach to synthesizing QD-sensitized semiconductor materials and facilitate their application in environmental protection.

  20. Multivalent Mn-doped TiO2 thin films

    NASA Astrophysics Data System (ADS)

    Lin, C. Y. W.; Channei, D.; Koshy, P.; Nakaruk, A.; Sorrell, C. C.

    2012-07-01

    Thin films of TiO2 doped with Mn were deposited on F-doped SnO2-coated glass using spin coating. The concentration of the dopant was in the range 0-7 wt% Mn (metal basis). The films were examined in terms of the structural, chemical, and optical properties. Glancing angle X-ray diffraction data show that the films consisted of the anatase polymorph of TiO2, without any contaminant phases. The X-ray photoelectron spectroscopy data indicate the presence of Mn3+ and Mn4+ in the doped films as well as atomic disorder and associated structural distortion. Ultraviolet-visible spectrophotometry data show that the optical indirect band gap of the films decreased significantly with increasing manganese doping, from 3.32 eV for the undoped composition to 2.90 eV for that doped with 7 wt% Mn.

  1. Self-doped Ti(3+)-TiO2 as a photocatalyst for the reduction of CO2 into a hydrocarbon fuel under visible light irradiation.

    PubMed

    Sasan, Koroush; Zuo, Fan; Wang, Yuan; Feng, Pingyun

    2015-08-28

    Self-doped TiO2 shows visible light photocatalytic activity, while commercial TiO2 (P25) is only UV responsive. The incorporation of Ti(3+) into TiO2 structures narrows the band gap (2.90 eV), leading to significantly increased photocatalytic activity for the reduction of CO2 into a renewable hydrocarbon fuel (CH4) in the presence of water vapour under visible light irradiation.

  2. Synthesis of TiO2-CNT hybrid nanocatalyst and its application in direct oxidation of H2S to S

    NASA Astrophysics Data System (ADS)

    Daraee, Maryam; Baniadam, Majid; Rashidi, Alimorad; Maghrebi, Morteza

    2018-07-01

    In this study, a TiO2-CNT hybrid catalyst has been synthesized and its catalytic activity in the oxidation of H2S to S has been investigated and compared with those of TiO2 nanoparticles and pyrolyzed TiO2-CNT hybrid (P-TiO2-CNT). The optimum catalyst amount was determined using central composite design (CCD) method. Catalysts were characterized by various analytical techniques. The H2S conversion, sulfur selectivity and yield at the optimal temperature of 200 °C and O2/H2S ratio of 0.5 were 98.3, 99.5 and 97%, respectively. TiO2-CNT16% catalyst has a higher surface area than TiO2 nanoparticles and P-TiO2-CNT. In addition, the former catalyst gives a high conversion of H2S and sulfur selectivity at 200 °C and O2/H2S ratio of 0.5 compared with the latter two catalysts. The superior conversion (over 10%) of TiO2-CNT16% hybrid compared to TiO2 nanoparticles can be attributed to the synergistic effects of TiO2 and CNT, the reduced band gap of TiO2-CNT16% hybrid and high specific surface area of the catalyst.

  3. Cobalt and Yttrium Modified TiO2 Nanotubes Based Dye-Sensitized Solar Cells for Solar-Energy Conversion

    NASA Astrophysics Data System (ADS)

    Shabanov, N. S.; Isaev, A. B.; Orudzhev, F. F.; Murliev, E. K.

    2018-01-01

    The solar-energy conversion in eosin-sensitized solar cells based on cobalt and yttrium modified TiO2 nanotubes has been studied.It is established that the doping with metal ions shifts the absorption edge for Co and Y doped titanium dioxide samples to longer and shorter wavelengths, respectively. The efficiency of solar energy conversion depends on the wide bandgap of the semiconductor anode and reaches a maximum (4.4%) for yttrium-doped TiO2 in comparison to that (4.1%) for pure titanium dioxide.

  4. Rapid detection of TiO2 (E171) in table sugar using Raman spectroscopy.

    PubMed

    Tan, Chen; Zhao, Bin; Zhang, Zhiyun; He, Lili

    2017-02-01

    The potential toxic effects of titanium dioxide (TiO 2 ) to humans remain debatable despite its broad application as a food additive. Thus, confirmation of the existence of TiO 2 particles in food matrices and subsequently quantifying them are becoming increasingly critical. This study developed a facile, rapid (< 30 min) and highly reliable method to detect and quantify TiO 2 particles (E171) from food products (e.g., table sugar) by Raman spectroscopy. To detect TiO 2 particles from sugar solution, sequential centrifugation and washing procedures were effectively applied to separate and recover 97% of TiO 2 particles from the sugar solution. The peak intensity of TiO 2 sensitively responded to the concentration of TiO 2 with a limit of detection (LOD) of 0.073 mg kg -1 . In the case of sugar granules, a mapping technique was applied to directly estimate the level of TiO 2 , which can be potentially used for rapid online monitoring. The plot of averaged intensity to TiO 2 concentration in the sugar granules exhibited a good linear relationship in the wide range of 5-2000 mg kg -1 , with an LOD of 8.46 mg kg -1 . Additionally, we applied Raman spectroscopy to prove the presence of TiO 2 in sugar-coated doughnuts. This study begins to fill in the analytical gaps that exist regarding the rapid detection and quantification of TiO 2 in food, which facilitate the risk assessment of TiO 2 through food exposure.

  5. Hydrogenated TiO2 nanotube photonic crystals for enhanced photoelectrochemical water splitting

    NASA Astrophysics Data System (ADS)

    Meng, Ming; Zhou, Sihua; Yang, Lun; Gan, Zhixing; Liu, Kuili; Tian, Fengshou; Zhu, Yu; Li, ChunYang; Liu, Weifeng; Yuan, Honglei; Zhang, Yan

    2018-04-01

    We report the design, fabrication and characterization of novel TiO2 nanotube photonic crystals with a crystalline core/disordered shell structure as well as substantial oxygen vacancies for photoelectrochemical (PEC) water splitting. The novel TiO2 nanotube photonic crystals are fabricated by annealing of anodized TiO2 nanotube photonic crystals in hydrogen atmosphere at various temperatures. The optimized novel TiO2 nanotube photonic crystals produce a maximal photocurrent density of 2.2 mA cm-2 at 0.22 V versus Ag/AgCl, which is two times higher that of the TiO2 nanotube photonic crystals annealed in air. Such significant PEC performance improvement can be ascribed to synergistic effects of the disordered surface layer and oxygen vacancies. The reduced band gap owing to the disordered surface layer and localized states induced by oxygen vacancies can enhance the efficient utilization of visible light. In addition, the disordered surface layer and substantial oxygen vacancies can promote the efficiency for separation and transport of the photogenerated carriers. This work may open up new opportunities for the design and construction of the high efficient and low-cost PEC water splitting system.

  6. Hydrogenated TiO2 nanotube photonic crystals for enhanced photoelectrochemical water splitting.

    PubMed

    Meng, Ming; Zhou, Sihua; Yang, Lun; Gan, Zhixing; Liu, Kuili; Tian, Fengshou; Zhu, Yu; Li, ChunYang; Liu, Weifeng; Yuan, Honglei; Zhang, Yan

    2018-04-02

    We report the design, fabrication and characterization of novel TiO 2 nanotube photonic crystals with a crystalline core/disordered shell structure as well as substantial oxygen vacancies for photoelectrochemical (PEC) water splitting. The novel TiO 2 nanotube photonic crystals are fabricated by annealing of anodized TiO 2 nanotube photonic crystals in hydrogen atmosphere at various temperatures. The optimized novel TiO 2 nanotube photonic crystals produce a maximal photocurrent density of 2.2 mA cm -2 at 0.22 V versus Ag/AgCl, which is two times higher that of the TiO 2 nanotube photonic crystals annealed in air. Such significant PEC performance improvement can be ascribed to synergistic effects of the disordered surface layer and oxygen vacancies. The reduced band gap owing to the disordered surface layer and localized states induced by oxygen vacancies can enhance the efficient utilization of visible light. In addition, the disordered surface layer and substantial oxygen vacancies can promote the efficiency for separation and transport of the photogenerated carriers. This work may open up new opportunities for the design and construction of the high efficient and low-cost PEC water splitting system.

  7. Optical properties of rhodamine 6G-doped TiO2 sol-gel films

    NASA Astrophysics Data System (ADS)

    Tomás, S. A.; Stolik, S.; Palomino, R.; Lozada, R.; Persson, C.; Ahuja, R.; Pepe, I.; Ferreira da Silva, A.

    2005-06-01

    The optical properties of titania (TiO2) thin films prepared by the sol-gel process and doped with rhodamine 6G were studied by Photoacoustic Spectroscopy. Rhodamine 6G-doping was achieved by adding 0.01%, 0.02%, 0.05% y 0.1% mol rhodamine to a solution that contained titanium isopropoxide as precursor. Two absorption regions were distinguished in the absorption spectrum of a typical rhodamine 6G-doped TiO2 film. A shift of these bands occured as a function of rhodamine 6G-doping concentration. In addition, the optical absorption and band gap energy for rutile-phase TiO2 films were calculated employing the full-potential linearized augmented plane wave method. A comparison of these calculations with experimental data of TiO2 films prepared by sol-gel at room temperature was performed.

  8. Photocatalytic degradation of diclofenac using TiO2-SnO2 mixed oxide catalysts.

    PubMed

    Mugunthan, E; Saidutta, M B; Jagadeeshbabu, P E

    2017-12-26

    The complex nature of diclofenac limits its biological degradation, posing a serious threat to aquatic organisms. Our present work aims to eliminate diclofenac from wastewater through photocatalytic degradation using TiO 2 -SnO 2 mixed-oxide catalysts under various operating conditions such as catalyst loading, initial diclofenac concentration and initial pH. Different molar ratios of Ti-Sn (1:1, 5:1, 10:1, 20:1 and 30:1) were prepared by the hydrothermal method and were characterized. The results indicated that addition of Sn in small quantity enhances the catalytic activity of TiO 2 . Energy Band gap of the TiO 2 -SnO 2 catalysts was found to increase with an increase in Tin content. TiO 2 -SnO 2 catalyst with a molar ratio of 20:1 was found to be the most effective when compared to other catalysts. The results suggested that initial drug concentration of 20 mg/L, catalyst loading of 0.8 g/L and pH 5 were the optimum operating conditions for complete degradation of diclofenac. Also, the TiO 2 -SnO 2 catalyst was effective in complete mineralization of diclofenac with a maximum total organic carbon removal of 90% achieved under ultraviolet irradiation. The repeatability and stability results showed that the TiO 2 -SnO 2 catalyst exhibited an excellent repeatability and better stability over the repeated reaction cycles. The photocatalytic degradation of diclofenac resulted in several photoproducts, which were identified through LC-MS.

  9. Visible light driven photocatalyst of vanadium (V3+) doped TiO2 synthesized using sonochemical method

    NASA Astrophysics Data System (ADS)

    Aini, N.; Ningsih, R.; Maulina, D.; Lami’, F. F.; Chasanah, S. N.

    2018-03-01

    TiO2 has been widely investigated due to its superior photocatalytic activity under ultraviolet irradiation among the photocatalyst materials. In this research, vanadium (V3+) was doped into TiO2 to enhance its light response under visible irradiation for wider application. Vanadium was introduced into TiO2 lattice at various concentration respectively 0.3, 0.5, 0.7 and 0.9% using simple and fast sonochemical method. X-Ray Diffraction data show that vanadium doped TiO2 crystallized in anatase phase with I41amd space group. X-Ray Diffraction pattern shifted to lower value of 2θ due to vanadium dopant. It indicated that V3+ was incorporated into anatase lattice. UV-Vis Diffuse Reflectance Spectra was revealed that the doped TiO2 has lowered reflectance and enhanced absorption coefficient in visible region than undoped TiO2 and commercial anatase TiO2. Band gap energy for undoped and doped TiO2 were respectively 3.22, 3.05, 2.93, 3.03 and 2.40 eV. Therefore vanadium doped TiO2 had potential to be applied under visible light.

  10. Two-dimensional wide-band-gap II-V semiconductors with a dilated graphene-like structure

    NASA Astrophysics Data System (ADS)

    Zhang, Xue-Jing; Liu, Bang-Gui

    2016-12-01

    Since the advent of graphene, two-dimensional (2D) materials have become very attractive and there is growing interest in exploring new 2D materials beyond graphene. Here, through density-functional theory (DFT) calculations, we predict 2D wide-band-gap II-V semiconductor materials of M3X2 (M = Zn, Cd and X = N, P, As) with a dilated graphene-like honeycomb structure. In this structure the group-V X atoms form two X-atomic planes symmetrically astride the centering group-IIB M atomic plane. Our DFT calculation shows that 2D Zn3N2, Zn3P2 and Zn3As2 have direct band gaps of 2.87, 3.81 and 3.55 eV, respectively, and 2D Cd3N2, Cd3P2 and Cd3As2 exhibit indirect band gaps of 2.74, 3.51 and 3.29 eV, respectively. Each of the six 2D materials is shown to have effective carrier (either hole or electron) masses down to 0.03m 0-0.05m 0. The structural stability and feasibility of experimental realization of these 2D materials has been shown in terms of DFT phonon spectra and total energy comparison with related existing bulk materials. On the experimental side, there already are many similar two-coordinate structures of Zn and other transition metals in various organic materials. Therefore, these 2D semiconductors can enrich the family of 2D electronic materials and may have promising potential for achieving novel transistors and optoelectronic devices.

  11. Nanostructured Gd3+-TiO2 surfaces for self-cleaning application

    NASA Astrophysics Data System (ADS)

    Saif, M.; El-Molla, S. A.; Aboul-Fotouh, S. M. K.; Ibrahim, M. M.; Ismail, L. F. M.; Dahn, Douglas C.

    2014-06-01

    Preparation of self-cleaning surfaces based on lanthanide modified titanium dioxide nanoparticles has rarely been reported. In the present work, gadolinium doped titanium dioxide thin films (x mol Gd3+-TiO2 where x = 0.000, 0.005, 0.008, 0.010, 0.020 and 0.030 mol) were synthesized by sol-gel method and deposited using doctor-blade method. These films were characterized by studying their structural, optical and electrical properties. Doping with gadolinium decreases the band gap energy and increase conductivity of thin films. The photo self-cleaning activity in term of quantitative determination of the active oxidative species (rad OH) produced on the thin film surfaces was evaluated using fluorescent probe method. The results show that, the highly active thin film is the 0.020 Gd3+-TiO2. The structural, morphology, optical, electrical and photoactivity properties of Gd3+-TiO2 thin films make it promising surfaces for self-cleaning application. Mineralization of commercial textile dye (Remazol Red RB-133, RR) and durability using 0.020Gd3+-TiO2 film surface was studied.

  12. Highly reactive {001} facets of TiO2-based composites: synthesis, formation mechanism and characterization

    NASA Astrophysics Data System (ADS)

    Ong, Wee-Jun; Tan, Lling-Lling; Chai, Siang-Piao; Yong, Siek-Ting; Mohamed, Abdul Rahman

    2014-01-01

    Titanium dioxide (TiO2) is one of the most widely investigated metal oxides due to its extraordinary surface, electronic and catalytic properties. However, the large band gap of TiO2 and massive recombination of photogenerated electron-hole pairs limit its photocatalytic and photovoltaic efficiency. Therefore, increasing research attention is now being directed towards engineering the surface structure of TiO2 at the most fundamental and atomic level namely morphological control of {001} facets in the range of microscale and nanoscale to fine-tune its physicochemical properties, which could ultimately lead to the optimization of its selectivity and reactivity. The synthesis of {001}-faceted TiO2 is currently one of the most active interdisciplinary research areas and demonstrations of catalytic enhancement are abundant. Modifications such as metal and non-metal doping have also been extensively studied to extend its band gap to the visible light region. This steady progress has demonstrated that TiO2-based composites with {001} facets are playing and will continue to play an indispensable role in the environmental remediation and in the search for clean and renewable energy technologies. This review encompasses the state-of-the-art research activities and latest advancements in the design of highly reactive {001} facet-dominated TiO2via various strategies, including hydrothermal/solvothermal, high temperature gas phase reactions and non-hydrolytic alcoholysis methods. The stabilization of {001} facets using fluorine-containing species and fluorine-free capping agents is also critically discussed in this review. To overcome the large band gap of TiO2 and rapid recombination of photogenerated charge carriers, modifications are carried out to manipulate its electronic band structure, including transition metal doping, noble metal doping, non-metal doping and incorporating graphene as a two-dimensional (2D) catalyst support. The advancements made in these aspects are

  13. Highly reactive {001} facets of TiO2-based composites: synthesis, formation mechanism and characterization.

    PubMed

    Ong, Wee-Jun; Tan, Lling-Lling; Chai, Siang-Piao; Yong, Siek-Ting; Mohamed, Abdul Rahman

    2014-02-21

    Titanium dioxide (TiO2) is one of the most widely investigated metal oxides due to its extraordinary surface, electronic and catalytic properties. However, the large band gap of TiO2 and massive recombination of photogenerated electron-hole pairs limit its photocatalytic and photovoltaic efficiency. Therefore, increasing research attention is now being directed towards engineering the surface structure of TiO2 at the most fundamental and atomic level namely morphological control of {001} facets in the range of microscale and nanoscale to fine-tune its physicochemical properties, which could ultimately lead to the optimization of its selectivity and reactivity. The synthesis of {001}-faceted TiO2 is currently one of the most active interdisciplinary research areas and demonstrations of catalytic enhancement are abundant. Modifications such as metal and non-metal doping have also been extensively studied to extend its band gap to the visible light region. This steady progress has demonstrated that TiO2-based composites with {001} facets are playing and will continue to play an indispensable role in the environmental remediation and in the search for clean and renewable energy technologies. This review encompasses the state-of-the-art research activities and latest advancements in the design of highly reactive {001} facet-dominated TiO2via various strategies, including hydrothermal/solvothermal, high temperature gas phase reactions and non-hydrolytic alcoholysis methods. The stabilization of {001} facets using fluorine-containing species and fluorine-free capping agents is also critically discussed in this review. To overcome the large band gap of TiO2 and rapid recombination of photogenerated charge carriers, modifications are carried out to manipulate its electronic band structure, including transition metal doping, noble metal doping, non-metal doping and incorporating graphene as a two-dimensional (2D) catalyst support. The advancements made in these aspects are

  14. Decoration of wide bandgap semiconducting materials for enhancing photoelectrochemical efficiency of PEC systems.

    NASA Astrophysics Data System (ADS)

    Bakranov, N.; Zhabaikhanov, A.; Kudaibergenov, S.; Ibraev, N.

    2018-03-01

    The production of photoanodes based on wide-band gap materials such as TiO2 is economically viable because of the low cost of synthesis methods. Contrary to economic aspects, wide-band gap semiconductor materials have a significant disadvantage due to low sensitivity to photons of visible light. To increase the photoactive parameters of the material of the electrodes in the visible range, the methods for decorating nanomasses of titanium dioxide by narrow-gap semiconductors are used. One of the most suitable narrow-gap semiconductor materials are CdS and Fe2O3. Controlled deposition of such materials on wide-gap semiconductors allows to regulate both the diffusion time of charge carriers and the band structure of TiO2/Fe2O3 and TiO2/CdS composites. The dimensions of the structure of the photoelectrode material of the cell have a large influence on the characteristics of the photocatalyst created. Thus, in the hematite structures of nanometre dimension, the rate of recombination of charge carriers fades away in comparison with bulk structures. Reducing the size of CdS structures also positively affects the nature of the photocatalytic reaction.

  15. Integrated titanium dioxide (TiO2) nanoparticles on interdigitated device electrodes (IDEs) for pH analysis

    NASA Astrophysics Data System (ADS)

    Azizah, N.; Hashim, U.; Arshad, M. K. Md.; Gopinath, Subash C. B.; Nadzirah, Sh.; Farehanim, M. A.; Fatin, M. F.; Ruslinda, A. R.; Ayub, R. M.

    2016-07-01

    Titanium dioxide (TiO2) nanoparticles based Interdigitated Device Electrodes (IDEs) Nanobiosensor device was developed for intracellular biochemical detection. Fabrication and characterization of pH sensors using IDE nanocoated with TiO2 was studied in this paper. In this paper, a preliminary assessment of this intracellular sensor with electrical measurement under different pH levels. 3-aminopropyltriethoxysilane (APTES) was used to enhance the sensitivity of titanium dioxide layer as well as able to provide surface modification by undergoing protonation and deprotonation process. Different types of pH solution provide different resistivity and conductivity towards the surface. Base solution has the higher current compared to an acid solution. Amine and oxide functionalized TiO2 based IDE exhibit pH-dependent could be understood in terms of the change in surface charge during protonation and deprotonation. The simple fabrication process, high sensitivity, and fast response of the TiO2 based IDEs facilitate their applications in a wide range of areas. The small size of semiconductor TiO2 based IDE for sensitive, label-free, real time detection of a wide range of biological species could be explored in vivo diagnostics and array-based screening.

  16. Effects of donor doping and acceptor doping on rutile TiO2 particles for photocatalytic O2 evolution by water oxidation

    NASA Astrophysics Data System (ADS)

    Amano, Fumiaki; Tosaki, Ryosuke; Sato, Kyosuke; Higuchi, Yamato

    2018-02-01

    Crystalline defects of photocatalyst particles may be considered to be the recombination center of photoexcited electrons and holes. In this study, we investigated the photocatalytic activity of cation-doped rutile TiO2 photocatalysts for O2 evolution from an aqueous silver nitrate solution under ultraviolet light irradiation. The photocatalytic activity of rutile TiO2 was enhanced by donor doping of Ta5+ and Nb5+ with a valence higher than that of Ti4+, regardless of increased density of electrons and Ti3+ species (an electron trapped in Ti4+ sites). Conversely, acceptor doping of lower valence cations such as In3+ and Ga3+ decreased photocatalytic activity for O2 evolution by water oxidation. The doping of equal valence cations such as Sn4+ and Ge4+ hardly changed the activity of non-doped TiO2. This study demonstrates that Ti3+ species, which is a crystalline defect, enhanced the photocatalytic activity of semiconductor oxides, for example rutile TiO2 with large crystalline size.

  17. A Study of a QCM Sensor Based on TiO2 Nanostructures for the Detection of NO2 and Explosives Vapours in Air

    PubMed Central

    Procek, Marcin; Stolarczyk, Agnieszka; Pustelny, Tadeusz; Maciak, Erwin

    2015-01-01

    The paper deals with investigations concerning the construction of sensors based on a quartz crystal microbalance (QCM) containing a TiO2 nanostructures sensor layer. A chemical method of synthesizing these nanostructures is presented. The prepared prototype of the QCM sensing system, as well as the results of tests for detecting low NO2 concentrations in an atmosphere of synthetic air have been described. The constructed NO2 sensors operate at room temperature, which is a great advantage, because resistance sensors based on wide gap semiconductors often require much higher operation temperatures, sometimes as high as 500 °C. The sensors constructed by the authors can be used, among other applications, in medical and chemical diagnostics, and also for the purpose of detecting explosive vapours. Reactions of the sensor to nitroglycerine vapours are presented as an example of its application. The influence of humidity on the operation of the sensor was studied. PMID:25912352

  18. Nanostructured TiO2 and ZnO prepared by using pressurized hot water and their eco-toxicological evaluation

    NASA Astrophysics Data System (ADS)

    Troppová, Ivana; Matějová, Lenka; Sezimová, Hana; Matěj, Zdeněk; Peikertová, Pavlína; Lang, Jaroslav

    2017-06-01

    The eco-toxicological effects of unconventionally prepared nanostructured TiO2 and ZnO were evaluated in this study, since both oxides are keenly investigated semiconductor photocatalysts in the last three decades. Unconventional processing by pressurized hot water was applied in order to crystallize oxide materials as an alternative to standard calcination. Acute biological toxicity of the synthesized oxides was evaluated using germination of Sinapis alba seed (ISO 11269-1) and growth of Lemna minor fronds (ISO 20079) and was compared to commercially available TiO2 Degussa P25. Toxicity results revealed that synthesized ZnO as well as TiO2 is toxic contrary to commercial TiO2 Degussa P25 which showled stimulation effect to L. minor and no toxicity to S. alba. ZnO was significantly more toxic than TiO2. The effect of crystallite size was considered, and it was revealed that small crystallite size and large surface area are not the toxicity-determining factors. Factors such as the rate of nanosized crystallites aggregation and concentration, shape and surface properties of TiO2 nanoparticles affect TiO2 toxicity to both plant species. Seriously, the dissolution of Ti4+ ions from TiO2 was also observed which may contribute to its toxicity. In case of ZnO, the dissolution of Zn2+ ions stays the main cause of its toxicity.

  19. Band edge movement and structural modifications in transition metal doped TiO2 nanocrystals for the application of DSSC

    NASA Astrophysics Data System (ADS)

    Patle, L. B.; Huse, V. R.; Chaudhari, A. L.

    2017-10-01

    Nanocrystalline undoped and transition metal ion doped (TM:Cu2+, Mn2+ and Fe3+) TiO2 nanoparticles, with 1 mol% were synthesized by a simple and cost effective modified co-precipitation method at room temperature and were successfully used as photoanode for dye sensitized solar cell (DSSC). The effect of transition metal ions into TiO2 nano crystalline powder has been systematically investigated using x-ray diffraction (XRD), UV-Vis spectroscope, scanning electron microscope (SEM), transmission electron microscope (TEM) and energy dispersive x-ray spectroscopy (EDX). The results of XRD confirm nanocrystalline anatase tetragonal structure of prepared undoped and TM doped TiO2 semiconductor. The influence of doping on band edge movement has been estimated using UV-visible spectroscopy. The SEM results indicate that microscopic effect of doping on morphology of the TiO2. The peaks of EDX signify incorporation of transition metal cations into TiO2 lattice. The effect of doping on flat band potential was estimated using interpolation on Mott-Schottky plot. The performances of DSSCs of undoped and doped TiO2 photoelectrodes were investigated under light illumination. In comparison with undoped and (Cu2+, Fe3+) doped TiO2 photoanodes we found that incorporation of Mn2+ into TiO2 exhibits improvement in photoconversion efficiency (η). There is increase in photoconversion efficiency of DSSCs with Mn2+ doped TiO2 by 6% as compared to that of undoped TiO2 photoanode.

  20. Inter-band optoelectronic properties in quantum dot structure of low band gap III-V semiconductors

    NASA Astrophysics Data System (ADS)

    Dey, Anup; Maiti, Biswajit; Chanda Sarkar, Debasree

    2014-04-01

    A generalized theory is developed to study inter-band optical absorption coefficient (IOAC) and material gain (MG) in quantum dot structures of narrow gap III-V compound semiconductor considering the wave-vector (k→) dependence of the optical transition matrix element. The band structures of these low band gap semiconducting materials with sufficiently separated split-off valance band are frequently described by the three energy band model of Kane. This has been adopted for analysis of the IOAC and MG taking InAs, InSb, Hg1-xCdxTe, and In1-xGaxAsyP1-y lattice matched to InP, as example of III-V compound semiconductors, having varied split-off energy band compared to their bulk band gap energy. It has been found that magnitude of the IOAC for quantum dots increases with increasing incident photon energy and the lines of absorption are more closely spaced in the three band model of Kane than those with parabolic energy band approximations reflecting the direct the influence of energy band parameters. The results show a significant deviation to the MG spectrum of narrow-gap materials having band nonparabolicity compared to the parabolic band model approximations. The results reflect the important role of valence band split-off energies in these narrow gap semiconductors.

  1. Energy level alignment in TiO2/metal sulfide/polymer interfaces for solar cell applications.

    PubMed

    Lindblad, Rebecka; Cappel, Ute B; O'Mahony, Flannan T F; Siegbahn, Hans; Johansson, Erik M J; Haque, Saif A; Rensmo, Håkan

    2014-08-28

    Semiconductor sensitized solar cell interfaces have been studied with photoelectron spectroscopy to understand the interfacial electronic structures. In particular, the experimental energy level alignment has been determined for complete TiO2/metal sulfide/polymer interfaces. For the metal sulfides CdS, Sb2S3 and Bi2S3 deposited from single source metal xanthate precursors, it was shown that both driving forces for electron injection into TiO2 and hole transfer to the polymer decrease for narrower bandgaps. The energy level alignment results were used in the discussion of the function of solar cells with the same metal sulfides as light absorbers. For example Sb2S3 showed the most favourable energy level alignment with 0.3 eV driving force for electron injection and 0.4 eV driving force for hole transfer and also the most efficient solar cells due to high photocurrent generation. The energy level alignment of the TiO2/Bi2S3 interface on the other hand showed no driving force for electron injection to TiO2, and the performance of the corresponding solar cell was very low.

  2. Nanoplasmonically Engineered Interfaces on Amorphous TiO2 for Highly Efficient Photocatalysis in Hydrogen Evolution.

    PubMed

    Liang, Huijun; Meng, Qiuxia; Wang, Xiaobing; Zhang, Hucheng; Wang, Jianji

    2018-04-25

    The nanoplasmonic metal-driven photocatalytic activity depends heavily on the spacing between metal nanoparticles (NPs) and semiconductors, and this work shows that ethylene glycol (EG) is an ideal candidate for interface spacer. Controlling the synthetic systems at pH 3, the composite of Ag NPs with EG-stabilized amorphous TiO 2 (Ag/TiO 2 -3) was synthesized by the facile light-induced reduction. It is verified that EG spacers can set up suitable geometric arrangement in the composite: the twin hydroxyls act as stabilizers to bind Ag NPs and TiO 2 together and the nonconductive alkyl chains consisting only of two CH 2 are able to separate the two building blocks completely and also provide the shortest channels for an efficient transfer of radiation energies to reach TiO 2 . Employed as photocatalysts in hydrogen evolution under visible light, amorphous TiO 2 hardly exhibits the catalytic activity due to high defect density, whereas Ag/TiO 2 -3 represents a remarkably high catalytic efficiency. The enhancement mechanism of the reaction rate is proposed by the analysis of the compositional, structural, and optical properties from a series of Ag/TiO 2 composites.

  3. 100-Fold Enhancement of Charge Transport in Uniaxially Oriented Mesoporous Anatase TiO 2 Films

    DOE PAGES

    Li, Ke; Liu, Jie; Sheng, Xia; ...

    2017-12-04

    Mesoporous semiconductor films are of considerable interest for applications in photoelectrochemical devices, however, despite intensive research till now, their charge transport properties remain significantly lower than their single-crystal counterparts. Herein, we report a novel low-temperature template-free technique for growing high surface area mesoporous anatase TiO2 films with a preferred [001] crystalline-orientation on FTO-coated glass substrate. Compared to mesoporous films that comprised of randomly oriented crystallites, the uniaxial orientation enables a 100-fold increase in the rate of electron transport. The uniaxially oriented mesoporous anatase TiO2 films exhibit should greatly facilitate the development and application of photoelectrochemical and electrochemical devices.

  4. Electrical and structural properties of TiO2-δ thin film with oxygen vacancies prepared by RF magnetron sputtering using oxygen radical

    NASA Astrophysics Data System (ADS)

    Kawamura, Kinya; Suzuki, Naoya; Tsuchiya, Takashi; Shimazu, Yuichi; Minohara, Makoto; Kobayashi, Masaki; Horiba, Koji; Kumigashira, Hiroshi; Higuchi, Tohru

    2016-06-01

    Anatase TiO2-δ thin film was prepared by RF magnetron sputtering using oxygen radical and Ti-metal target. Degrees of the TiO2-δ crystal orientation in the thin film depends of the oxygen gas pressure (P\\text{O2}) in the radical gun. The (004)- and (112)-oriented TiO2-δ thin films crystallized without postannealing have the mixed valence Ti4+/Ti3+ state. The electrical conductivities, which corresponds to n-type oxide semiconductor, is higher in the case of (004)-oriented TiO2-δ thin film containing with high concentration of oxygen vacancy. The donor band of TiO2-δ thin film is observed at ˜1.0 eV from the Fermi level (E F). The density-of-state at E F is higher in (004)-oriented TiO2-δ thin film. The above results indicate that the oxygen vacancies can control by changing the P\\text{O2} of the oxygen radical.

  5. TiO2-TiO2 composite resistive humidity sensor: ethanol crosssensitivity

    NASA Astrophysics Data System (ADS)

    Ghalamboran, Milad; Saedi, Yasin

    2016-03-01

    The fabrication method and characterization results of a TiO2-TiO2 composite bead used for humidity sensing along with its negative cross-sensitivity to ethanol vapor are reported. The bead shaped resistive sample sensors are fabricated by the drop-casting of a TiO2 slurry on two Pt wire segments. The dried bead is pre-fired at 750°C and subsequently impregnated with a Ti-based sol. The sample is ready for characterization after a thermal annealing at 600°C in air. Structurally, the bead is a composite of the micron-sized TiO2 crystallites embedded in a matrix of nanometric TiO2 particle aggregates. The performance of the beads as resistive humidity sensors is recorded at room temperature in standard humidity level chambers. Results evince the wide dynamic range of the sensors fabricated in the low relative humidity range. While the sensor conductance is not sensitive to ethanol vapor in dry air, in humid air, sensor's responses are negatively affected by the contaminant.

  6. Visible Light-Driven H 2 Production over Highly Dispersed Ruthenia on Rutile TiO 2 Nanorods

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nguyen-Phan, Thuy-Duong; Luo, Si; Vovchok, Dimitriy

    2016-01-04

    The immobilization of miniscule quantities of RuO 2 (~0.1%) onto one-dimensional (1D) TiO 2 nanorods (NRs) allows H 2 evolution from water under visible light irradiation. Rod-like rutile TiO 2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO 2 to enable photocatalytic activity in the visible region. The superior performance is rationalized on the basis of fundamental experimental studies and theoretical calculations, demonstrating that RuO 2(110) grown as 1D nanowires on rutile TiO 2(110), which occurs only at extremely low loads of RuO 2, leads to the formation of a heterointerface that efficientlymore » adsorbs visible light. The surface defects, band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers« less

  7. Visible Light-Driven H 2 Production over Highly Dispersed Ruthenia on Rutile TiO 2 Nanorods

    DOE PAGES

    Nguyen-Phan, Thuy-Duong; Luo, Si; Vovchok, Dimitriy; ...

    2015-12-02

    The immobilization of miniscule quantities of RuO 2 (~0.1%) onto one-dimensional (1D) TiO 2 nanorods (NRs) allows H 2 evolution from water under visible light irradiation. In addition, rod-like rutile TiO 2 structures, exposing preferentially (110) surfaces, are shown to be critical for the deposition of RuO 2 to enable photocatalytic activity in the visible region. The superior performance is rationalized on the basis of fundamental experimental studies and theoretical calculations, demonstrating that RuO 2(110) grown as 1D nanowires on rutile TiO 2(110), which occurs only at extremely low loads of RuO 2, leads to the formation of a heterointerfacemore » that efficiently adsorbs visible light. The surface defects, band gap narrowing, visible photoresponse, and favorable upward band bending at the heterointerface drastically facilitate the transfer and separation of photogenerated charge carriers.« less

  8. Remarkable optical red shift and extremely high optical absorption coefficient of V-Ga co-doped TiO2

    NASA Astrophysics Data System (ADS)

    Deng, Quanrong; Han, Xiaoping; Gao, Yun; Shao, Guosheng

    2012-07-01

    A first attempt has been made to study the effect of codoping of transition metal and sp metal on the electronic structure and associated optical properties of TiO2, through V-Ga codoped thin films. V-Ga codoped rutile TiO2 films were fabricated on fused quartz substrates using pulsed laser ablation, followed by heat treatment at high temperatures. Gigantic redshift in the optical absorption edge was observed in V-Ga co-doped TiO2 materials, from UV to infrared region with high absorption coefficient. Through combined structural characterization and theoretical modeling, this is attributed to the p-d hybridization between the two metals. This leads to additional energy bands to overlap with the minimum of the conduction band, leading to remarkably narrowed band gap free of mid-gap states. The direct-gap of the co-doped phase is key to the remarkably high optical absorption coefficient of the coped titania.

  9. Chalcogenide Sensitized Carbon Based TiO2 Nanomaterial For Solar Driven Applications

    NASA Astrophysics Data System (ADS)

    Pathak, Pawan

    The demand for renewable energy is growing because fossils fuels are depleting at a rapid pace. Solar energy an abundant green energy resource. Utilizing this resource in a smart manner can resolve energy-crisis related issues. Sun light can be efficiently harvested using semiconductor based materials by utilizing photo-generated charges for numerous beneficial applications. The main goal of this thesis is to synthesize different nanostructures of TiO2, develop a novel method of coupling and synthesizing chalcogenide nanocrystals with TiO2 and to study the charge transportation effects of the various carbon allotropes in the chalcogenide nanocrystal sensitized TiO2 nanostructure. We have fabricated different nanostructures of TiO2 as solar energy harvesting materials. Effects of the different phases of TiO2 have also been studied. The anatase phase of TiO2 is more photoactive than the rutile phase of TiO2, and the higher dimension of the TiO2 can increase the surface area of the material which can produce higher photocurrent. Since TiO2 only absorbs in the UV range; to increase the absorbance TiO2 should be coupled to visible light absorbing materials. This dissertation presents a simple approach to synthesize and couple chalcogenide nanocrystals with TiO2 nanostructure to form a heterostructured composite. An atmospheric pressure based, single precursor, one-pot approach has been developed and tested to assemble chalcogenide nanocrystal on the TiO2 surface. Surface characterization using microscopy, X-ray diffraction, and elemental analysis indicates the formation of nanocrystals along the nanotube walls and inter-tubular spacing. Optical measurements indicate that the chalcogenide nanocrystals absorb in the visible region and demonstrate an increase in photocurrent in comparison to bare TiO2 nanostructure. The CdS synthesized TiO2 nanostructure produced the highest photocurrent as measured in the three electrode system. We have also assembled the PbS nanocrystal

  10. Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

    PubMed Central

    Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

    2017-01-01

    Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I–V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later. PMID:28252106

  11. Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers

    NASA Astrophysics Data System (ADS)

    Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

    2017-03-01

    Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO2/nanoporous-Si and the TiO2/nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO2/nanoporous Si are lower than that of the HfO2/nanoporous Si, the former is more stable than the later.

  12. Enhanced PEC performance of nanoporous Si photoelectrodes by covering HfO2 and TiO2 passivation layers.

    PubMed

    Xing, Zhuo; Ren, Feng; Wu, Hengyi; Wu, Liang; Wang, Xuening; Wang, Jingli; Wan, Da; Zhang, Guozhen; Jiang, Changzhong

    2017-03-02

    Nanostructured Si as the high efficiency photoelectrode material is hard to keep stable in aqueous for water splitting. Capping a passivation layer on the surface of Si is an effective way of protecting from oxidation. However, it is still not clear in the different mechanisms and effects between insulating oxide materials and oxide semiconductor materials as passivation layers. Here, we compare the passivation effects, the photoelectrochemical (PEC) properties, and the corresponding mechanisms between the HfO 2 /nanoporous-Si and the TiO 2 /nanoporous-Si by I-V curves, Motte-schottky (MS) curves, and electrochemical impedance spectroscopy (EIS). Although the saturated photocurrent densities of the TiO 2 /nanoporous Si are lower than that of the HfO 2 /nanoporous Si, the former is more stable than the later.

  13. Influence of Au and TiO2 structures on hydrogen dissociation over TiO2/Au(100)

    NASA Astrophysics Data System (ADS)

    Nakamura, I.; Mantoku, H.; Furukawa, T.; Takahashi, A.; Fujitani, T.

    2012-11-01

    We performed H2-D2 exchange reactions over TiOx/Au(100) and compared the observed reaction kinetics with those reported for TiOx/Au(111) in order to clarify the influence of the Au and TiO2 structures on dissociation of H2 molecules. Low energy electron diffraction observations showed that the TiO2 produced on Au(100) was disordered, in contrast to the comparatively ordered TiO2 structure formed on Au(111). The activation energies and the turnover frequencies for HD formation over TiO2/Au(100) agreed well with those for TiO2/Au(111), clearly indicating that the hydrogen dissociation sites created over TiO2/Au(100) were the perimeter interface between stoichiometric TiO2 and Au, as was previously concluded for TiO2/Au(111). We concluded that the creation of active sites for hydrogen dissociation was independent of the Au and TiO2 structures consisting perimeter interface, and that local bonds that formed between Au and O atoms of stoichiometric TiO2 were essential for the creation of active sites.

  14. Electrical level of defects in single-layer two-dimensional TiO2

    NASA Astrophysics Data System (ADS)

    Song, X. F.; Hu, L. F.; Li, D. H.; Chen, L.; Sun, Q. Q.; Zhou, P.; Zhang, D. W.

    2015-11-01

    The remarkable properties of graphene and transition metal dichalcogenides (TMDCs) have attracted increasing attention on two-dimensional materials, but the gate oxide, one of the key components of two-dimensional electronic devices, has rarely reported. We found the single-layer oxide can be used as the two dimensional gate oxide in 2D electronic structure, such as TiO2. However, the electrical performance is seriously influenced by the defects existing in the single-layer oxide. In this paper, a nondestructive and noncontact solution based on spectroscopic ellipsometry has been used to detect the defect states and energy level of single-layer TiO2 films. By fitting the Lorentz oscillator model, the results indicate the exact position of defect energy levels depends on the estimated band gap and the charge state of the point defects of TiO2.

  15. Optical and Structural Properties of Zn2TiO4:Mn2+

    NASA Astrophysics Data System (ADS)

    Sosman, L. P.; López, A.; Camara, A. R.; Pedro, S. S.; Carvalho, I. C. S.; Cella, N.

    2017-12-01

    Polycrystalline Zn2TiO4 samples with Mn2+ doping level of 0%, 0.1%, 1.0%, and 5.0% have been produced by conventional solid-state method and their optical and structural properties investigated. Rietveld refinement of x-ray diffraction patterns revealed the formed phases and the crystallographic parameters. The chemical composition was obtained by x-ray fluorescence measurements. The optical properties were studied by photoluminescence, excitation, reflectance, and photoacoustic spectroscopy. All measurements were performed at room temperature. The photoluminescence spectrum of the pure sample (0% Mn2+) showed a band in the red region associated with Zn2TiO4, while the sample with 0.1% Mn2+ exhibited two bands, in the green and red spectral regions, assigned to Mn2+ ions at tetrahedral and octahedral sites. No emission was observed for the samples with 1.0% or 5.0% Mn2+. The excitation results for the sample with 0.1% Mn2+ ions showed characteristic peaks of Mn2+ transitions. Tanabe-Sugano theory was used to obtain the crystal field Dq, B, and C Racah parameters from the energy peak positions in the excitation spectrum of the sample with 0.1% Mn2+. Photoacoustic measurements revealed a broad band, characteristic of semiconductor materials, hiding the Mn2+ transitions.

  16. Heterogeneous activation of H2O2 by defect-engineered TiO(2-x) single crystals for refractory pollutants degradation: A Fenton-like mechanism.

    PubMed

    Zhang, Ai-Yong; Lin, Tan; He, Yuan-Yi; Mou, Yu-Xuan

    2016-07-05

    The heterogeneous catalyst plays a key role in Fenton-like reaction for advanced oxidation of refractory pollutants in water treatment. Titanium dioxide (TiO2) is a typical semiconductor with high industrial importance due to its earth abundance, low cost and no toxicity. In this work, it is found that TiO2 can heterogeneously activate hydrogen peroxide (H2O2, E°=1.78 eV), a common chemical oxidant, to efficiently generate highly-powerful hydroxyl radical, OH (E(0)=2.80 eV), for advanced water treatment, when its crystal shape, exposed facet and oxygen-stoichiometry are finely tuned. The defect-engineered TiO2 single crystals exposed by high-energy {001} facets exhibited an excellent Fenton-like activity and stability for degrading typical refractory organic pollutants such as methyl orange and p-nitrophenol. Its defect-centered Fenton-like superiority is mainly attributed to the crystal oxygen-vacancy, single-crystalline structure and exposed polar {001} facet. Our findings could provide new chance to utilize TiO2 for Fenton-like technology, and develop novel heterogeneous catalyst for advanced water treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

  17. Electron transfer dynamics and yield from gold nanoparticle to different semiconductors induced by plasmon band excitation

    NASA Astrophysics Data System (ADS)

    Du, L. C.; Xi, W. D.; Zhang, J. B.; Matsuzaki, H.; Furube, A.

    2018-06-01

    Photoinduced electron transfer from gold nanoparticles (NPs) to semiconductor under plasmon excitation is an important phenomenon in photocatalysis and solar cell applications. Femtosecond plasmon-induced electron transfer from gold NPs to the conduction band of different semiconductor like TiO2, SnO2, and ZnO was monitored at 3440 nm upon optical excitation of the surface plasmon band of gold NPs. It was found that electron injection was completed within 240 fs and the electron injection yield reached 10-30% under 570 nm excitation. It means TiO2 is not the only proper semiconductor as electron acceptors in such gold/semiconductor nanoparticle systems.

  18. Effect of Ti Substrate Ion Implantation on the Physical Properties of Anodic TiO2 Nanotubes

    NASA Astrophysics Data System (ADS)

    Jedi-Soltanabadi, Zahra; Ghoranneviss, Mahmood; Ghorannevis, Zohreh; Akbari, Hossein

    2018-03-01

    The influence of nitrogen-ion implantation on the titanium (Ti) surface is studied. The nontreated Ti and the Ti treated with ion implantation were anodized in an ethylene-glycol-based electrolyte solution containing 0.3 wt% ammonium fluoride (NH4F) and 3 vol% deionized (DI) water at a potential of 60 V for 1 h at room temperature. The current density during the growth of the TiO2 nanotubes was monitored in-situ. The surface roughnesses of the Ti substrates before and after the ion implantation were investigated with atomic force microscopy (AFM). The surface roughness was lower for the treated Ti substrate. The morphology of the anodic TiO2 nanotubes was studied by using field-emission scanning electron microscopy (FESEM). Clearly, the titanium nanotubes grown on the treated substrate were longer. In addition, some ribs were observed on their walls. The optical band gap of the anodic TiO2 nanotubes was characterized by using a diffuse reflection spectral (DRS) analysis. The anodic TiO2 nanotubes grown on the treated Ti substrate revealed a band gap energy of approximately 3.02 eV.

  19. Fe-N co-doped SiO2@TiO2 yolk-shell hollow nanospheres with enhanced visible light photocatalytic degradation

    NASA Astrophysics Data System (ADS)

    Wan, Hengcheng; Yao, Weitang; Zhu, Wenkun; Tang, Yi; Ge, Huilin; Shi, Xiaozhong; Duan, Tao

    2018-06-01

    SiO2@TiO2 yolk@shell hollow nanospheres (STNSs) is considered as an outstanding photocatalyst due to its tunable structure and composition. Based on this point, we present an unprecedentedly excellent photocatalytic property of STNSs toward tannic acid via a Fe-N co-doped strategy. Their morphologies, compositions, structure and properties are characterized. The Fe-N co-doped STNSs formed good hollow yolk@shell structure. The results show that the energy gap of the composites can be downgraded to 2.82 eV (pure TiO2 = 3.2 eV). Photocatalytic degradation of tannic acid (TA, 30 mg L-1) under visible light (380 nm < λ < 780 nm) irradiation is used to evaluate the photocatalytic activity of the composites. Compared with pure TiO2 nanospheres, non-doped STNSs and N-doped STNSs, the Fe-N co-doped STNSs exhibits the highest activity, which can degrade 99.5% TA into CO2 and H2O in 80 min. The probable degradation mechanism of the composites is simultaneously proposed, the band gap of STNSs becomes narrow by co-doping Fe-N, so that the TiO2 shell can stimulate electrons under visible light exposure, generate the ions of radOH and radO2- with a strong oxidizing property. Therefore this approach works is much desired for radioactive organic wastewater photocatalytic degradation.

  20. Surface modification of layered perovskite Sr2TiO4 for improved CO2 photoreduction with H2O to CH4.

    PubMed

    Kwak, Byeong Sub; Do, Jeong Yeon; Park, No-Kuk; Kang, Misook

    2017-11-27

    Layered perovskite Sr 2 TiO 4 photocatalyst was synthesized by using sol-gel method with citric acid. In order to increase the surface area of layered perovskite Sr 2 TiO 4 , and thus to improve its photocatalytic activity for CO 2 reduction, its surface was modified via hydrogen treatment or exfoliation. The physical and chemical properties of the prepared catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy, elemental mapping analysis, energy-dispersive X-ray spectroscopy, N 2 adsorption-desorption, UV-Vis spectroscopy, X-ray photoelectron spectroscopy, photoluminescence, and electrophoretic light scattering. CO 2 photoreduction was performed in a closed reactor under 6 W/cm 2 UV irradiation. The gaseous products were analyzed using a gas chromatograph equipped with flame ionization and thermal conductivity detectors. The exfoliated Sr 2 TiO 4 catalyst (E-Sr 2 TiO 4 ) exhibited a narrow band gap, a large surface area, and high dispersion. Owing to these advantageous properties, E-Sr 2 TiO 4 photocatalyst showed an excellent catalytic performance for CO 2 photoreduction reaction. The rate of CH 4 production from the photoreduction of CO 2 with H 2 O using E-Sr 2 TiO 4 was about 3431.77 μmol/g cat after 8 h.

  1. Synthesis and characterization of UV-treated Fe-doped bismuth lanthanum titanate-doped TiO2 layers in dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Song, Myoung Geun; Bark, Chung Wung

    2016-06-01

    Dye-sensitized solar cells (DSSCs) based on titanium dioxide (TiO2) have been extensively studied because they constitute promising low-cost alternatives to their conventional semiconductor-based counterparts. However, much of the effort aimed at achieving high conversion efficiencies has focused on dye and liquid electrolytes. In this work, we report the photovoltaic characteristics of DSSCs fabricated by mixing TiO2 with Fe-doped bismuth lanthanum titanate (Fe-BLT). These nanosized Fe-BLT powders were prepared by using a high-energy ball-milling process. In addition, we used a UV radiation-ozone (UV-O3) treatment to change the surface wettability of TiO2 from hydrophobic to hydrophilic and thereby prevented the easy separation of the Fe-BLT-mixed TiO2 from the fluorine-doped tin-oxide (FTO) coating glass.

  2. Optical, electrical and dielectric properties of TiO2-SiO2 films prepared by a cost effective sol-gel process.

    PubMed

    Vishwas, M; Rao, K Narasimha; Gowda, K V Arjuna; Chakradhar, R P S

    2011-12-01

    Titanium dioxide (TiO(2)) and silicon dioxide (SiO(2)) thin films and their mixed films were synthesized by the sol-gel spin coating method using titanium tetra isopropoxide (TTIP) and tetra ethyl ortho silicate (TEOS) as the precursor materials for TiO(2) and SiO(2) respectively. The pure and composite films of TiO(2) and SiO(2) were deposited on glass and silicon substrates. The optical properties were studied for different compositions of TiO(2) and SiO(2) sols and the refractive index and optical band gap energies were estimated. MOS capacitors were fabricated using TiO(2) films on p-silicon (100) substrates. The current-voltage (I-V) and capacitance-voltage (C-V) characteristics were studied and the electrical resistivity and dielectric constant were estimated for the films annealed at 200°C for their possible use in optoelectronic applications. Copyright © 2011 Elsevier B.V. All rights reserved.

  3. Solution-processed all-oxide bulk heterojunction solar cells based on CuO nanaorod array and TiO2 nanocrystals.

    PubMed

    Wu, Fan; Qiao, Qiquan; Bahrami, Behzad; Chen, Ke; Pathak, Rajesh; Tong, Yanhua; Li, Xiaoyi; Zhang, Tiansheng; Jian, Ronghua

    2018-05-25

    We present a method to synthesize CuO nanorod array/TiO 2 nanocrystals bulk heterojunction (BHJ) on fluorine-tin-oxide (FTO) glass, in which single-crystalline p-type semiconductor of the CuO nanorod array is grown on the FTO glass by hydrothermal reaction and the n-type semiconductor of the TiO 2 precursor is filled into the CuO nanorods to form well-organized nano-interpenetrating BHJ after air annealing. The interface charge transfer in CuO nanorod array/TiO 2 heterojunction is studied by Kelvin probe force microscopy (KPFM). KPFM results demonstrate that the CuO nanorod array/TiO 2 heterojunction can realize the transfer of photo-generated electrons from the CuO nanorod array to TiO 2 . In this work, a solar cell with the structure FTO/CuO nanoarray/TiO 2 /Al is successfully fabricated, which exhibits an open-circuit voltage (V oc ) of 0.20 V and short-circuit current density (J sc ) of 0.026 mA cm -2 under AM 1.5 illumination. KPFM studies indicate that the very low performance is caused by an undesirable interface charge transfer. The interfacial surface potential (SP) shows that the electron concentration in the CuO nanorod array changes considerably after illumination due to increased photo-generated electrons, but the change in the electron concentration in TiO 2 is much less than in CuO, which indicates that the injection efficiency of the photo-generated electrons from CuO to TiO 2 is not satisfactory, resulting in an undesirable J sc in the solar cell. The interface photovoltage from the KPFM measurement shows that the low V oc results from the small interfacial SP difference between CuO and TiO 2 because the low injected electron concentration cannot raise the Fermi level significantly in TiO 2 . This conclusion agrees with the measured work function results under illumination. Hence, improvement of the interfacial electron injection is primary for the CuO nanorod array/TiO 2 heterojunction solar cells.

  4. Solution-processed all-oxide bulk heterojunction solar cells based on CuO nanaorod array and TiO2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Wu, Fan; Qiao, Qiquan; Bahrami, Behzad; Chen, Ke; Pathak, Rajesh; Tong, Yanhua; Li, Xiaoyi; Zhang, Tiansheng; Jian, Ronghua

    2018-05-01

    We present a method to synthesize CuO nanorod array/TiO2 nanocrystals bulk heterojunction (BHJ) on fluorine-tin-oxide (FTO) glass, in which single-crystalline p-type semiconductor of the CuO nanorod array is grown on the FTO glass by hydrothermal reaction and the n-type semiconductor of the TiO2 precursor is filled into the CuO nanorods to form well-organized nano-interpenetrating BHJ after air annealing. The interface charge transfer in CuO nanorod array/TiO2 heterojunction is studied by Kelvin probe force microscopy (KPFM). KPFM results demonstrate that the CuO nanorod array/TiO2 heterojunction can realize the transfer of photo-generated electrons from the CuO nanorod array to TiO2. In this work, a solar cell with the structure FTO/CuO nanoarray/TiO2/Al is successfully fabricated, which exhibits an open-circuit voltage (V oc) of 0.20 V and short-circuit current density (J sc) of 0.026 mA cm‑2 under AM 1.5 illumination. KPFM studies indicate that the very low performance is caused by an undesirable interface charge transfer. The interfacial surface potential (SP) shows that the electron concentration in the CuO nanorod array changes considerably after illumination due to increased photo-generated electrons, but the change in the electron concentration in TiO2 is much less than in CuO, which indicates that the injection efficiency of the photo-generated electrons from CuO to TiO2 is not satisfactory, resulting in an undesirable J sc in the solar cell. The interface photovoltage from the KPFM measurement shows that the low V oc results from the small interfacial SP difference between CuO and TiO2 because the low injected electron concentration cannot raise the Fermi level significantly in TiO2. This conclusion agrees with the measured work function results under illumination. Hence, improvement of the interfacial electron injection is primary for the CuO nanorod array/TiO2 heterojunction solar cells.

  5. Structural and photocatalytic studies of hydrothermally synthesized Mn2+-TiO2 nanoparticles under UV and visible light irradiation

    NASA Astrophysics Data System (ADS)

    Kamble, Ravi; Sabale, Sandip; Chikode, Prashant; Puri, Vijaya; Mahajan, Smita

    2016-11-01

    Pure TiO2 and Mn2+-TiO2 nanoparticles have been prepared by simple hydrothermal method with different Mn2+ concentrations. Obtained samples were analysed to determine it’s structural, optical, morphological and compositional properties using x-ray diffraction, UV-DRS, Raman, photoluminescence, XPS, TEM and EDS analysis. The EDS micrograph confirms the existence of Mn2+ atoms in TiO2 matrix with 0.86, 1.60 and 1.90 wt%. The crystallite size as well as band gap decreases with increase in Mn2+ concentration. The average particle size obtained from TEM was found 8-11 nm which is in good agreement with XRD results. Raman bands at 640, 518 and 398 cm-1 further confirmed pure phase anatase in all samples. XPS shows the proper substitutions of few sites of Ti4+ ions by Mn2+ ions in the TiO2 host lattice. The intensity of PL spectra for Mn2+-TiO2 shows a gradual decrease in the peak intensity with increasing Mn2+ concentration in TiO2, it implies lower electron-hole recombination rate as Mn2+ ions increases. The obtained samples were further studied for its photocatalytic activities using malachite green dye under UV light and visible light.

  6. Structural, electronic properties and stability of metatitanic acid (H 2TiO 3) nanotubes

    NASA Astrophysics Data System (ADS)

    Enyashin, A. N.; Denisova, T. A.; Ivanovskii, A. L.

    2009-12-01

    Quite recently, metatitanic acid (H 2TiO 3) has been successfully prepared, which extended the family of known titanic acids H 2Ti nO 2n+1 ( n = 2, 3 and 4). Here the atomic models for nanotubes (NTs) of metatitanic acid are designed and their cohesive and electronic properties are considered depending on their chirality and radii by means of density-functional theory-tight-binding (DFTB) method. Our main findings are that the proposed H 2TiO 3 tubes are stable and that all these NTs will be the insulators (independently from their chirality and the diameters) with forbidden gaps at about ˜4.6 eV. We have found also that aforementioned properties of predicted H 2TiO 3 NTs are very similar with those of recently prepared fabricated nanotubes of polytitanic acids; thus, it is possible to expect that the proposed H 2TiO 3 tubular materials may be fabricated.

  7. Surface-modified TiO2 powders with phenol derivatives: A comparative DFT and experimental study

    NASA Astrophysics Data System (ADS)

    Sredojević, Dušan N.; Kovač, Tijana; Džunuzović, Enis; Ðorđević, Vesna; Grgur, Branimir N.; Nedeljković, Jovan M.

    2017-10-01

    The charge transfer complex formation between TiO2 powder and variety of phenol derivatives (phenol, 4-nitrophenol, 4-bromophenol, 4-tert-butylphenol, hydroquinone) was achieved. The red-shift of optical absorption was observed upon surface modification of TiO2 powders with phenol derivatives. The influence of substituent functional groups in para position on the optical band gap and conduction band edge of inorganic/organic hybrids was studied using reflection spectroscopy and cyclic voltammetry. The experimental findings were supported by density functional theory calculations. The measured reflection spectra of surface-modified TiO2 powders with phenol derivatives were compared with calculated electronic excitation spectra of corresponding model systems.

  8. Ultrasound assisted synthesis of iron doped TiO2 catalyst.

    PubMed

    Ambati, Rohini; Gogate, Parag R

    2018-01-01

    The present work deals with synthesis of Fe (III) doped TiO 2 catalyst using the ultrasound assisted approach and conventional sol-gel approach with an objective of establishing the process intensification benefits. Effect of operating parameters such as Fe doping, type of solvent, solvent to precursor ratio and initial temperature has been investigated to get the best catalyst with minimum particle size. Comparison of the catalysts obtained using the conventional and ultrasound assisted approach under the optimized conditions has been performed using the characterization techniques like DLS, XRD, BET, SEM, EDS, TEM, FTIR and UV-Vis band gap analysis. It was established that catalyst synthesized by ultrasound assisted approach under optimized conditions of 0.4mol% doping, irradiation time of 60min, propan-2-ol as the solvent with the solvent to precursor ratio as 10 and initial temperature of 30°C was the best one with minimum particle size as 99nm and surface area as 49.41m 2 /g. SEM analysis, XRD analysis as well as the TEM analysis also confirmed the superiority of the catalyst obtained using ultrasound assisted approach as compared to the conventional approach. EDS analysis also confirmed the presence of 4.05mol% of Fe element in the sample of 0.4mol% iron doped TiO 2 . UV-Vis band gap results showed the reduction in band gap from 3.2eV to 2.9eV. Photocatalytic experiments performed to check the activity also confirmed that ultrasonically synthesized Fe doped TiO 2 catalyst resulted in a higher degradation of Acid Blue 80 as 38% while the conventionally synthesized catalyst resulted in a degradation of 31.1%. Overall, the work has clearly established importance of ultrasound in giving better catalyst characteristics as well as activity for degradation of the Acid Blue 80 dye. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Twisted bilayer blue phosphorene: A direct band gap semiconductor

    NASA Astrophysics Data System (ADS)

    Ospina, D. A.; Duque, C. A.; Correa, J. D.; Suárez Morell, Eric

    2016-09-01

    We report that two rotated layers of blue phosphorene behave as a direct band gap semiconductor. The optical spectrum shows absorption peaks in the visible region of the spectrum and in addition the energy of these peaks can be tuned with the rotational angle. These findings makes twisted bilayer blue phosphorene a strong candidate as a solar cell or photodetection device. Our results are based on ab initio calculations of several rotated blue phosphorene layers.

  10. Preparation of rutile TiO(2) coating by thermal chemical vapor deposition for anticoking applications.

    PubMed

    Tang, Shiyun; Wang, Jianli; Zhu, Quan; Chen, Yaoqiang; Li, Xiangyuan

    2014-10-08

    To inhibit the metal catalytic coking and improve the oxidation resistance of TiN coating, rutile TiO2 coating has been directly designed as an efficient anticoking coating for n-hexane pyrolysis. TiO2 coatings were prepared on the inner surface of SS304 tubes by a thermal CVD method under varied temperatures from 650 to 900 °C. The rutile TiO2 coating was obtained by annealing the as-deposited TiO2 coating, which is an alternative route for the deposition of rutile TiO2 coating. The morphology, elemental and phase composition of TiO2 coatings were characterized by SEM, EDX and XRD, respectively. The results show that deposition temperature of TiO2 coatings has a strong effect on the morphology and thickness of as-deposited TiO2 coatings. Fe, Cr and Ni at.% of the substrate gradually changes to 0 when the temperature is increased to 800 °C. The thickness of TiO2 coating is more than 6 μm and uniform by metalloscopy, and the films have a nonstoichiometric composition of Ti3O8 when the deposition temperature is above 800 °C. The anticoking tests show that the TiO2 coating at a deposition temperature of 800 °C is sufficiently thick to cover the cracks and gaps on the surface of blank substrate and cut off the catalytic coke growth effect of the metal substrate. The anticoking ratio of TiO2 coating corresponding to each 5 cm segments is above 65% and the average anticoking ratio of TiO2 coating is up to 76%. Thus, the TiO2 coating can provide a very good protective layer to prevent the substrate from severe coking efficiently.

  11. Photocatalytic degradation of Rhodamine B dye using Fe doped TiO2 nanocomposites

    NASA Astrophysics Data System (ADS)

    Barkhade, Tejal; Banerjee, Indrani

    2018-05-01

    The unique properties of titanium dioxide (TiO2) such as high photo catalytic activity, high chemical stability and low toxicity have made it a suitable photocatalyst in recent decades. The effect of modification of TiO2 with doping of iron on its characteristics and photo catalytic efficiency was studied. The change in band gap energy of TiO2 nanoparticles after doping with Fe has been studied. Significant enhancement in photo catalytic property of TiO2 after Fe doping under light exposure conditions has been investigated. Acute exposure to non-biodegradable Rhodamine B resulted in many health problems like burning of eyes, skin irritation, nasal burning, and chest pain etc. Therefore, degradation of this dye is needed to save environment and animals. Considering the similar radius of Fe3+ and Ti4+ ions (respectively 0.64 Å and 0.68 Å), titanium position in the lattice of TiO2 can be replaced by iron cations easily. The undoped and Fe doped TiO2 nano composites were synthesized by sol-gel method, in which 1.0M% of Fe was doped with TiO2 and then the samples were characterized by using FE-SEM, UV-Visible diffuse spectroscopy, Raman Spectroscopy, and FTIR. Photo catalytic degradation of Rhodamine B dye experiment was carried out in visible light range. After 90 min time duration pink colour of dye turned colourless, indicating significant degradation rate with time.

  12. Enhanced photocatalytic degradation of dyes under sunlight using biocompatible TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Bharati, B.; Sonkar, A. K.; Singh, N.; Dash, D.; Rath, Chandana

    2017-08-01

    As TiO2 is one of the most popular photocatalysts, we have studied here the photocatalytic degradation of the most common dyestuffs like rhodamine B (RhB), congo red (CR) and methylene blue (MB), which mainly come from the textile and photographic industries using nanoparticles of TiO2. Nanoparticles of TiO2 synthesized through a simple and cost effective sol-gel technique crystallizes in the anatase phase, showing a band gap less than that of bulk value. Particles consisting of coherently scattered domains of size 33 nm are found to be agglomerated and polycrystalline in nature. While the degradation rates of MB, CR and RhB after irradiating with a renewable source of energy, i.e. sunlight, show 100% degradation, TiO2 irradiated with UV light of 4.8 eV shows a much slower degradation rate. To use the waste water after photocatalysis, we examine further the biocompatibile nature of the TiO2 nanoparticles by platelet interaction activity, hemolysis effect and MTT assay. It is worth mentioning here that TiO2 nanoparticles are found to be highly hemocompatible, show no platelet aggregation, and the level of intracellular ROS in human platelets does not show significant change in ROS level. We conclude that TiO2 nanoparticles constitute an excellent photocatalyst and biocompatible material, and that after photocatalytic degradation of dye effluents obtained from textile industries, purified water can be used in agriculture and domestic sectors.

  13. Room temperature ferromagnetism in non-magnetic doped TiO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Gómez-Polo, C.; Larumbe, S.; Pastor, J. M.

    2013-05-01

    Room-temperature ferromagnetism in non-magnetic doped TiO2 semiconductor nanoparticles is analyzed in the present work. Undoped and N-doped TiO2 nanoparticles were obtained employing sol-gel procedure using urea as the nitrogen source. The obtained gels were first dried at 70 °C and afterwards calcined in air at 300 °C. A residual carbon concentration was retained in the samples as a consequence of the organic decomposition process. Post-annealing treatments at 300 °C under air and vacuum conditions were also performed. The crystallographic structure of nanoparticles was analyzed by X-ray diffraction, obtaining a single anatase crystalline phase after the calcinations (mean nanoparticle diameters around 5-8 nm). SQUID magnetometry was employed to analyze the magnetic response of the samples. Whereas for the undoped samples synthesized with hydrolysis rate h = 6, paramagnetic like behavior is observed at room temperature, the N-doped nanoparticles (h = 3) show a weak ferromagnetic response (saturation magnetization ≈10-3 emu/g). Moreover, a clear reinforcement of the room-temperature ferromagnetism response is found with the post-annealing treatments, in particular that performed in vacuum. Thus, the results indicate the dominant role of the oxygen stoichiometry and the oxygen vacancies in the room temperature ferromagnetic response of these TiO2 nanoparticles.

  14. Three-dimensional hot electron photovoltaic device with vertically aligned TiO2 nanotubes.

    PubMed

    Goddeti, Kalyan C; Lee, Changhwan; Lee, Young Keun; Park, Jeong Young

    2018-05-09

    Titanium dioxide (TiO 2 ) nanotubes with vertically aligned array structures show substantial advantages in solar cells as an electron transport material that offers a large surface area where charges travel linearly along the nanotubes. Integrating this one-dimensional semiconductor material with plasmonic metals to create a three-dimensional plasmonic nanodiode can influence solar energy conversion by utilizing the generated hot electrons. Here, we devised plasmonic Au/TiO 2 and Ag/TiO 2 nanodiode architectures composed of TiO 2 nanotube arrays for enhanced photon absorption, and for the subsequent generation and capture of hot carriers. The photocurrents and incident photon to current conversion efficiencies (IPCE) were obtained as a function of photon energy for hot electron detection. We observed enhanced photocurrents and IPCE using the Ag/TiO 2 nanodiode. The strong plasmonic peaks of the Au and Ag from the IPCE clearly indicate an enhancement of the hot electron flux resulting from the presence of surface plasmons. The calculated electric fields and the corresponding absorbances of the nanodiode using finite-difference time-domain simulation methods are also in good agreement with the experimental results. These results show a unique strategy of combining a hot electron photovoltaic device with a three-dimensional architecture, which has the clear advantages of maximizing light absorption and a metal-semiconductor interface area.

  15. Amorphisation and recrystallisation study of lithium intercalation into TiO2 nano-architecture.

    NASA Astrophysics Data System (ADS)

    Matshaba, M. G.; Sayle, D. C.; Sayle, T. X. T.; Ngoepe, P. E.

    2017-02-01

    Titanium dioxide is playing an increasingly significant role in easing environmental and energy concerns. Its rich variety of polymorphic crystal structures has facilitated a wide range of applications such as photo-catalysis, photo-splitting of water, photoelectrochromic devices, insulators in metal oxide, semiconductors devices, dye sensitized solar cells (DSSCs) (energy conversions), rechargeable lithium batteries (electrochemical storage). The complex structural aspects in nano TiO2, are elucidated by microscopic visualization and quantification of the microstructure for electrode materials, since cell performance and various aging mechanisms depend strongly on the appearance and changes in the microstructure. Recent studies on MnO2 have demonstrated that amorphisation and recrystallisation simulation method can adequately generate various nanostructures, for Li-ion battery compounds. The method was also previously employed to produce nano-TiO2. In the current study, the approach is used to study lithiated nanoporous structure for TiO2 which have been extensively studied experimentally, as mentioned above. Molecular graphic images showing microstructural features, including voids and channels have accommodated lithium’s during lithiation and delithiation. Preliminary lithiation of TiO2 will be considered.

  16. Visible light-harvesting of TiO2 nanotubes array by pulsed laser deposited CdS

    NASA Astrophysics Data System (ADS)

    Bjelajac, Andjelika; Djokic, Veljko; Petrovic, Rada; Socol, Gabiel; Mihailescu, Ion N.; Florea, Ileana; Ersen, Ovidiu; Janackovic, Djordje

    2014-08-01

    Titanium dioxide (TiO2) nanotubes arrays, obtained by anodization technique and annealing, were decorated with CdS using pulsed laser deposition method. Their structural, morphological and chemical characterization was carried out by electron microscopy in scanning (SEM) and transmission (TEM) modes, combined with energy dispersive spectroscopy (EDS) and electron energy loss spectroscopy (EELS). It was demonstrated that the quantity of deposited CdS can be controlled by varying the number of laser pulses. The chemical mapping of the elements of interest was performed using the energy filtered mode of the electron microscope. The results showed that pulse laser deposition is an adequate technique for deposition of CdS inside and between 100 nm wide TiO2 nanotubes. The diffuse reflectance spectroscopy investigation of selected samples proved that the absorption edge of the prepared CdS/TiO2 nanocomposites is significantly extended to the visible range. The corresponding band gaps were determinated from the Tauc plot of transformed Kubelka-Munk function. The band gap reduction of TiO2 nanotubes by pulsed laser deposition of CdS was put in evidence.

  17. Sol-Gel Synthesis of Fe-Doped TiO2 Nanocrystals

    NASA Astrophysics Data System (ADS)

    Marami, Mohammad Bagher; Farahmandjou, Majid; Khoshnevisan, Bahram

    2018-03-01

    Fe-doped TiO2 powders were synthesized by the sol-gel method using titanium (IV) isopropoxide (TTIP) as the starting material, ethanol as solvent, and ethylene glycol (EG) as stabilizer. These prepared samples were characterized by x-ray diffractometer (XRD), field emission scanning electron microscope (FESEM), Fourier-transform infrared (FTIR) spectroscopy, diffuse reflection spectroscopy (DRS), energy-dispersive x-ray spectroscopy (EDX), and photoluminescence (PL) analyses to study their structure, morphology, and optical properties. The particle size of Fe-doped TiO2 was in the range of 18-39 nm and the minimum crystallite size was achieved for 4 mol.% of Fe. The XRD result of the samples that were doped with Fe showed a tetragonal structure. It also revealed the coexistence of the anatase and rutile phases, and showed that their ratio changed with various molar concentrations of Fe dopant. FTIR spectroscopy showed the presence of the Ti-O vibration band in the samples. PL analysis revealed the PL property in the UV region. Visible irradiation and the intensity of PL spectra were both reduced by doping TiO2 with 3 mol.% of Fe as compared to the pure variety. The spectra from the DRS showed a red shift and a reduction of 2.6 eV in the band gap energy for 4 mol.% Fe-doped TiO2. The optimum level of impurity (4 mol.%) for Fe-doped TiO2 nanoparticles (NPs), which improve the optical and electrical properties by using new precursors and can be used in solar cells and electronic devices, was determined. The novelty of this work consists of: the Fe/TiO2 NPs are synthesized by new precursors from sol-gel synthesis of iron and TTIP using acetic acid-catalyzed solvolysis (original idea) and the optical properties optimized with a mixture of phases (anatase/rutile) of Fe-doped TiO2 by this facile method.

  18. Sol-Gel Synthesis of Fe-Doped TiO2 Nanocrystals

    NASA Astrophysics Data System (ADS)

    Marami, Mohammad Bagher; Farahmandjou, Majid; Khoshnevisan, Bahram

    2018-07-01

    Fe-doped TiO2 powders were synthesized by the sol-gel method using titanium (IV) isopropoxide (TTIP) as the starting material, ethanol as solvent, and ethylene glycol (EG) as stabilizer. These prepared samples were characterized by x-ray diffractometer (XRD), field emission scanning electron microscope (FESEM), Fourier-transform infrared (FTIR) spectroscopy, diffuse reflection spectroscopy (DRS), energy-dispersive x-ray spectroscopy (EDX), and photoluminescence (PL) analyses to study their structure, morphology, and optical properties. The particle size of Fe-doped TiO2 was in the range of 18-39 nm and the minimum crystallite size was achieved for 4 mol.% of Fe. The XRD result of the samples that were doped with Fe showed a tetragonal structure. It also revealed the coexistence of the anatase and rutile phases, and showed that their ratio changed with various molar concentrations of Fe dopant. FTIR spectroscopy showed the presence of the Ti-O vibration band in the samples. PL analysis revealed the PL property in the UV region. Visible irradiation and the intensity of PL spectra were both reduced by doping TiO2 with 3 mol.% of Fe as compared to the pure variety. The spectra from the DRS showed a red shift and a reduction of 2.6 eV in the band gap energy for 4 mol.% Fe-doped TiO2. The optimum level of impurity (4 mol.%) for Fe-doped TiO2 nanoparticles (NPs), which improve the optical and electrical properties by using new precursors and can be used in solar cells and electronic devices, was determined. The novelty of this work consists of: the Fe/TiO2 NPs are synthesized by new precursors from sol-gel synthesis of iron and TTIP using acetic acid-catalyzed solvolysis (original idea) and the optical properties optimized with a mixture of phases (anatase /rutile) of Fe-doped TiO2 by this facile method.

  19. Hierarchical Honeycomb Br-, N-Codoped TiO2 with Enhanced Visible-Light Photocatalytic H2 Production.

    PubMed

    Zhang, Chao; Zhou, Yuming; Bao, Jiehua; Sheng, Xiaoli; Fang, Jiasheng; Zhao, Shuo; Zhang, Yiwei; Chen, Wenxia

    2018-06-06

    The halogen elements modification strategy of TiO 2 encounters a bottleneck in visible-light H 2 production. Herein, we have for the first time reported a hierarchical honeycomb Br-, N-codoped anatase TiO 2 catalyst (HM-Br,N/TiO 2 ) with enhanced visible-light photocatalytic H 2 production. During the synthesizing process, large amounts of meso-macroporous channels and TiO 2 nanosheets were fabricated in massive TiO 2 automatically, constructing the hierarchical honeycomb structure with large specific surface area (464 m 2 g -1 ). cetyl trimethylammonium bromide and melamine played a key role in constructing the meso-macroporous channels. Additionally, HM-Br,N/TiO 2 showed a high visible-light H 2 production rate of 2247 μmol h -1 g -1 , which is far more higher than single Br- or N-doped TiO 2 (0 or 63 μmol h -1 g -1 , respectively), thereby demonstrating the excellent synergistic effects of Br and N elements in H 2 evolution. In HM-Br,N/TiO 2 catalytic system, the codoped Br-N atoms could reduce the band gap of TiO 2 to 2.88 eV and the holes on acceptor levels (N acceptor) can passivate the electrons on donor levels (Br donor), thereby preventing charge carriers recombination significantly. Furthermore, the proposed HM-Br,N/TiO 2 fabrication strategy had a wide range of choices for N source (e.g., melamine, urea, and dicyandiamide) and it can be applied to other TiO 2 materials (e.g., P25) as well, thereby implying its great potential application in visible-light H 2 production. Finally, on the basis of experimental results, a possible photocatalytic H 2 production mechanism for HM-Br,N/TiO 2 was proposed.

  20. Electronic structure of the indium tin oxide/nanocrystalline anatase (TiO2)/ruthenium-dye interfaces in dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Lyon, J. E.; Rayan, M. K.; Beerbom, M. M.; Schlaf, R.

    2008-10-01

    The electronic structure of two interfaces commonly found in dye-sensitized photovoltaic cells based on nanocrystalline anatase TiO2 ("Grätzel cells") was investigated using photoemission spectroscopy (PES). X-ray photoemission spectroscopy (XPS) and ultraviolet photoemission spectroscopy (UPS) measurements were carried out on the indium tin oxide (ITO)/TiO2 and the TiO2/cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium(II)bis-tetrabutylammonium dye ("N719" or "Ruthenium 535-bisTBA") interfaces. Both contacts were investigated using a multistep deposition procedure where the entire structure was prepared in vacuum using electrospray deposition. In between deposition steps the surface was characterized with XPS and UPS resulting in a series of spectra, allowing the determination of the orbital and band lineup at the interfaces. The results of these efforts confirm previous PES measurements on TiO2/dye contacts prepared under ambient conditions, suggesting that ambient contamination might not have significant influence on the electronic structure at the dye/TiO2 interface. The results also demonstrate that there may be a significant barrier for electron injection at the sputtered ITO/TiO2 interface and that this interface should be viewed as a semiconductor heterojunction rather than as metal-semiconductor (Schottky) contact.

  1. Characterization of N3 dye adsorption on TiO2 using quartz-crystal microbalance with dissipation monitoring

    NASA Astrophysics Data System (ADS)

    Wayment-Steele, Hannah K.; Johnson, Lewis E.; Dixon, Matthew C.; Johal, Malkiat S.

    2013-09-01

    Understanding the kinetics of dye adsorption on semiconductors is crucial for designing dye-sensitized solar cells (DSSCs) with enhanced efficiency. Harms et al. recently applied the Quartz-Crystal Microbalance with Dissipation Monitoring (QCM-D) to study in situ dye adsorption on flat TiO2 surfaces. QCM-D measures adsorption in real time and therefore allows one to determine the kinetics of the process. In this work, we characterize the adsorption of N3, a commercial RuBipy dye, using the native oxide layer of a titanium sensor to simulate the TiO2 substrate of a DSSC. We report equilibrium constants that are in agreement with previous absorbance studies of N3 adsorption, and therefore demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption.

  2. BC8 Silicon (Si-III) is a Narrow-Gap Semiconductor

    NASA Astrophysics Data System (ADS)

    Zhang, Haidong; Liu, Hanyu; Wei, Kaya; Kurakevych, Oleksandr O.; Le Godec, Yann; Liu, Zhenxian; Martin, Joshua; Guerrette, Michael; Nolas, George S.; Strobel, Timothy A.

    2017-04-01

    Large-volume, phase-pure synthesis of BC8 silicon (I a 3 ¯ , c I 16 ) has enabled bulk measurements of optical, electronic, and thermal properties. Unlike previous reports that conclude BC8-Si is semimetallic, we demonstrate that this phase is a direct band gap semiconductor with a very small energy gap and moderate carrier concentration and mobility at room temperature, based on far- and midinfrared optical spectroscopy, temperature-dependent electrical conductivity, Seebeck and heat capacity measurements. Samples exhibit a plasma wavelength near 11 μ m , indicating potential for infrared plasmonic applications. Thermal conductivity is reduced by 1-2 orders of magnitude depending on temperature as compared with the diamond cubic (DC-Si) phase. The electronic structure and dielectric properties can be reproduced by first-principles calculations with hybrid functionals after adjusting the level of exact Hartree-Fock (HF) exchange mixing. These results clarify existing limited and controversial experimental data sets and ab initio calculations.

  3. Au nanostructure-decorated TiO2 nanowires exhibiting photoactivity across entire UV-visible region for photoelectrochemical water splitting.

    PubMed

    Pu, Ying-Chih; Wang, Gongming; Chang, Kao-Der; Ling, Yichuan; Lin, Yin-Kai; Fitzmorris, Bob C; Liu, Chia-Ming; Lu, Xihong; Tong, Yexiang; Zhang, Jin Z; Hsu, Yung-Jung; Li, Yat

    2013-08-14

    Here we demonstrate that the photoactivity of Au-decorated TiO2 electrodes for photoelectrochemical water oxidation can be effectively enhanced in the entire UV-visible region from 300 to 800 nm by manipulating the shape of the decorated Au nanostructures. The samples were prepared by carefully depositing Au nanoparticles (NPs), Au nanorods (NRs), and a mixture of Au NPs and NRs on the surface of TiO2 nanowire arrays. As compared with bare TiO2, Au NP-decorated TiO2 nanowire electrodes exhibited significantly enhanced photoactivity in both the UV and visible regions. For Au NR-decorated TiO2 electrodes, the photoactivity enhancement was, however, observed in the visible region only, with the largest photocurrent generation achieved at 710 nm. Significantly, TiO2 nanowires deposited with a mixture of Au NPs and NRs showed enhanced photoactivity in the entire UV-visible region. Monochromatic incident photon-to-electron conversion efficiency measurements indicated that excitation of surface plasmon resonance of Au is responsible for the enhanced photoactivity of Au nanostructure-decorated TiO2 nanowires. Photovoltage experiment showed that the enhanced photoactivity of Au NP-decorated TiO2 in the UV region was attributable to the effective surface passivation of Au NPs. Furthermore, 3D finite-difference time domain simulation was performed to investigate the electrical field amplification at the interface between Au nanostructures and TiO2 upon SPR excitation. The results suggested that the enhanced photoactivity of Au NP-decorated TiO2 in the UV region was partially due to the increased optical absorption of TiO2 associated with SPR electrical field amplification. The current study could provide a new paradigm for designing plasmonic metal/semiconductor composite systems to effectively harvest the entire UV-visible light for solar fuel production.

  4. Interaction of TiO2 nanocluster with graphene oxide: Experimental and theoretical investigations

    NASA Astrophysics Data System (ADS)

    Yadav, A.; Gangan, A. S.; Chakraborty, B.; Ramaniah, L. M.; Patel, N.; Yadav, M.; Dashora, A.; Kothari, D. C.; Press, M.

    2017-05-01

    Go-TiO2 composites are gaining importance because of their applications in various fields and also due to their stability. In this work, we have reported for the first time, interaction of Graphene Oxide (GO) with TiO2 nanocluster. To understand the interfacial interaction between GO and TiO2, we have proposed GO-TiO2 models through simulations. The calculated optical properties of theoretical models were compared with experimentally synthesized RGO-TiO2 composite. Optical absorption spectra indicated enhancement in visible region for RGO-TiO2 nanocomposite when compared to that of TiO2. The variation in optical properties of RGO-TiO2 cluster with degree of functionalization was also studied. It was observed that in GO-TiO2 model with optimum OH groups, new states were formed within the band gap which could be responsible for enhanced absorption in visible region.

  5. Calculating the optical properties of defects and surfaces in wide band gap materials

    NASA Astrophysics Data System (ADS)

    Deák, Peter

    2018-04-01

    The optical properties of a material critically depend on its defects, and understanding that requires substantial and accurate input from theory. This paper describes recent developments in the electronic structure theory of defects in wide band gap materials, where the standard local or semi-local approximations of density functional theory fail. The success of the HSE06 screened hybrid functional is analyzed in case of Group-IV semiconductors and TiO2, and shown that it is the consequence of error compensation between semi-local and non-local exchange, resulting in a proper derivative discontinuity (reproduction of the band gap) and a total energy which is a linear function of the fractional occupation numbers (removing most of the electron self-interaction). This allows the calculation of electronic transitions with accuracy unseen before, as demonstrated on the single-photon emitter NV(-) center in diamond and on polaronic states in TiO2. Having a reliable tool for electronic structure calculations, theory can contribute to the understanding of complicated cases of light-matter interaction. Two examples are considered here: surface termination effects on the blinking and bleaching of the light-emission of the NV(-) center in diamond, and on the efficiency of photocatalytic water-splitting by TiO2. Finally, an outlook is presented for the application of hybrid functionals in other materials, as, e.g., ZnO, Ga2O3 or CuGaS2.

  6. TiO2 Nanorods Decorated with Pd Nanoparticles for Enhanced Liquefied Petroleum Gas Sensing Performance.

    PubMed

    Dhawale, Dattatray S; Gujar, Tanaji P; Lokhande, Chandrakant D

    2017-08-15

    Development of highly sensitive and selective semiconductor-based metal oxide sensor devices to detect toxic, explosive, flammable, and pollutant gases is still a challenging research topic. In the present work, we systematically enhanced the liquefied petroleum gas (LPG) sensing performance of chemical bath deposited TiO 2 nanorods by decorating Pd nanoparticle catalyst. Surface morphology with elemental mapping, crystal structure, composition and oxidation states, and surface area measurements of pristine TiO 2 and Pd:TiO 2 nanorods was examined by high resolution transmission electron microscopy with energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and nitrogen adsorption-desorption characterization techniques. LPG sensing performance of pristine TiO 2 and Pd:TiO 2 nanorods was investigated in different LPG concentration and operating temperature ranges. The LPG response of 21% for pristine TiO 2 nanorods is enhanced to 49% after Pd catalyst decoration with reasonably fast response and recovery times. Further, the sensor exhibited long-term stability, which could be due to the strong metal support (Pd:TiO 2 ) interaction and catalytic properties offered by the Pd nanoparticle catalyst. The work described herein demonstrates a general and scalable approach that provides a promising route for rational design of variety of sensor devices for LPG detection.

  7. Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

    PubMed

    Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

    2016-02-01

    This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

  8. Thermoelectric properties of the 3C, 2H, 4H, and 6H polytypes of the wide-band-gap semiconductors SiC, GaN, and ZnO

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Huang, Zheng; Lü, Tie-Yu; Wang, Hui-Qiong

    We have investigated the thermoelectric properties of the 3C, 2H, 4H, and 6H polytypes of the wide-band-gap(n-type) semiconductors SiC, GaN, and ZnO based on first-principles calculations and Boltzmann transport theory. Our results show that the thermoelectric performance increases from 3C to 6H, 4H, and 2H structures with an increase of hexagonality for SiC. However, for GaN and ZnO, their power factors show a very weak dependence on the polytype. Detailed analysis of the thermoelectric properties with respect to temperature and carrier concentration of 4H-SiC, 2H-GaN, and 2H-ZnO shows that the figure of merit of these three compounds increases with temperature,more » indicating the promising potential applications of these thermoelectric materials at high temperature. The significant difference of the polytype-dependent thermoelectric properties among SiC, GaN, and ZnO might be related to the competition between covalency and ionicity in these semiconductors. Our calculations may provide a new way to enhance the thermoelectric properties of wide-band-gap semiconductors through atomic structure design, especially hexagonality design for SiC.« less

  9. Structure and lattice dynamics of the wide band gap semiconductors MgSiN2 and MgGeN2

    NASA Astrophysics Data System (ADS)

    Râsander, M.; Quirk, J. B.; Wang, T.; Mathew, S.; Davies, R.; Palgrave, R. G.; Moram, M. A.

    2017-08-01

    We have determined the structural and lattice dynamical properties of the orthorhombic, wide band gap semiconductors MgSiN2 and MgGeN2 using density functional theory. In addition, we present the structural properties and Raman spectra of MgSiN2 powder. The structural properties and lattice dynamics of the orthorhombic systems are compared to those of wurtzite AlN. We find clear differences in the lattice dynamics between MgSiN2, MgGeN2 and AlN, for example, we find that the highest phonon frequency in MgSiN2 is about 100 cm-1 higher than the highest frequency in AlN, and that MgGeN2 is much softer. We also provide the Born effective charge tensors and dielectric tensors of MgSiN2, MgGeN2 and AlN. Phonon related thermodynamic properties, such as the heat capacity and the entropy, have also been evaluated and are found to be in very good agreement with available experimental results.

  10. Removal of 4-Nitrophenol from Water Using Ag–N–P-Tridoped TiO2 by Photocatalytic Oxidation Technique

    PubMed Central

    Achamo, Temesgen; Yadav, O. P.

    2016-01-01

    Photocatalytic oxidation using semiconductor nanoparticles is an efficient, eco-friendly, and cost-effective process for the removal of organic pollutants, such as dyes, pesticides, phenols, and their derivatives in water. In the present study, nanosize Ag–N–P-tridoped titanium(IV) oxide (TiO2) was prepared by using sol–gel-synthesized Ag-doped TiO2 and soybean (Glycine max) or chickpea (Cicer arietinum) seeds as nonmetallic bioprecursors. As-synthesized photocatalysts were characterized using X-ray diffraction, Fourier transform infrared, and ultra violet (UV)–visible spectroscopic techniques. Average crystallite size of the studied photocatalysts was within 39–46 nm. Whereas doped Ag in TiO2 minimized the photogenerated electron–hole recombination, doped N and P extended its photoabsorption edge to visible region. Tridoping of Ag, N, and P in TiO2 exhibited synergetic effect toward enhancing its photocatalytic degradation of 4-nitrophenol (4-NP), separately, under UV and visible irradiations. At three hours, degradations of 4-NP over Ag–N–P-tridoped TiO2 under UV and visible radiations were 73.8 and 98.1%, respectively. PMID:27081309

  11. Effect of molarity on sol-gel routed nano TiO2 thin films

    NASA Astrophysics Data System (ADS)

    Lourduraj, Stephen; Williams, Rayar Victor

    The nanostructured titanium dioxide (TiO2) thin films have been prepared for the molar concentrations of titanium tetra isopropoxide (TTIP) 0.05M, 0.1M, 0.15M and 0.2M by sol-gel routed spin coating technique with calcination at 450∘C. The processing parameters such as, pH value (8), catalyst HCl (0.1ml), spin speed (3000rpm) and calcination temperature (450∘C) are optimized. The crystalline nature and surface morphology were analyzed by XRD, SEM and AFM analysis. The XRD results confirm that the films are crystalline with anatase phase, and are nanostructured. The SEM micrographs of the TiO2 film reveal the spherical nature of the particle. AFM analysis establishes that the uniformity of the TiO2 thin film was optimized at 0.2M. The optical measurements show that the transmittance depends on the molarity, and the optical band gap energy of TiO2 films is found to be inversely proportional to molarity. The I-V characteristics exhibit that the molarity strongly influences the electrical conductivity of the film. The results indicate that the significant effect of molarity on structural, optical and electrical properties of the nanostructured TiO2 thin films will be useful to photovoltaic application.

  12. Incorporating TiO2 nanotubes with a peptide of D-amino K122-4 (D) for enhanced mechanical and photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Guo, L. Q.; Hu, Y. W.; Yu, B.; Davis, E.; Irvin, R.; Yan, X. G.; Li, D. Y.

    2016-02-01

    Titanium dioxide (TiO2) nanotubes are promising for a wide variety of potential applications in energy, biomedical and environmental sectors. However, their low mechanical strength and wide band gap limit their widespread technological use. This article reports our recent efforts to increase the mechanical strength of TiO2 nanotubes with lowered band gap by immobilizing a peptide of D-amino K122-4 (D) onto the nanotubes. Topographies and chemical compositions of the peptide-coated and uncoated TiO2 nanotubular arrays were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy (XPS). Properties of the peptide-coated and uncoated TiO2 nanotubular arrays, including hardness, elastic modulus, electron work function and photocurrent, were evaluated using micromechanical probe, Kelvin Probe and electrochemical system. Effect of the peptide on surface conductivity was also investigated through current mapping and I-V curve analysis with conductive atomic force microscopy. It is demonstrated that the peptide coating simultaneously enhances the mechanical strength, photocatalytic and electrical properties of TiO2 nanotubes.

  13. Effect of sintering on transparent TiO2 18NR-T type thin films as the working electrode for transparent solar cells

    NASA Astrophysics Data System (ADS)

    Supriyanto, A.; Nandani; Wahyuningsih, S.; Ramelan, A. H.

    2018-03-01

    The working electrode based on semiconductor transparent TiO2 type 18NR-T for transparent solar cells have been grown by screen printing method. This study aim is to determine the effect of sintering on TiO2 thin films transparent as the working electrode of transparent solar cells. TiO2 films will be sintered at temperature 450°C, 500°C, 550°C and 600°C. TiO2 films optical properties were characterized using UV-Vis spectrophotometer, electrical properties were characterized using 4 point probemethods and the crystallization was characterized by X-Ray Diffraction (XRD). The lowest transmittance due to the treatment of annealing temperature variations is 550°C because the 550°C TiO2 layer is more absorbing. The peaks resulted from the annealing temperature treatment show that the high temperature the more anatase peaks. Characterization using four-point probe showed that the highest conductivity of TiO2 18NR-T thin film was 2.42 x 102 Ω-1m-1 at annealing temperature 550°C.

  14. Unconventionally prepared TiO2/g-C3N4 photocatalysts for photocatalytic decomposition of nitrous oxide

    NASA Astrophysics Data System (ADS)

    Troppová, Ivana; Šihor, Marcel; Reli, Martin; Ritz, Michal; Praus, Petr; Kočí, Kamila

    2018-02-01

    The TiO2/g-C3N4 nanocomposites with the various TiO2:g-C3N4 weight ratios from 1:1 to 1:3 were prepared unconventionally by pressurized hot water processing in a flow regime. The parent TiO2 and g-C3N4 was prepared by thermal hydrolysis and thermal annealing, respectively. The nanocomposites as well as parent TiO2 and g-C3N4 were characterized using several complementary characterization methods and investigated in the photocatalytic decomposition of N2O under UVA (λ = 365 nm) irradiation. All the prepared TiO2/g-C3N4 nanocomposites showed higher photocatalytic activity in comparison with the pure g-C3N4 and chiefly pure TiO2. The photocatalytic activity of TiO2/g-C3N4 nanocomposites was decreasing in the following sequence: TiO2/g-C3N4 (1:3) > TiO2/g-C3N4 (1:2) > TiO2/g-C3N4 (1:1). In comparison with the parent TiO2 or g-C3N4, the TiO2/g-C3N4 nanocomposites' photocatalytic capability was significantly enhanced by coupling TiO2 with g-C3N4. The generation of TiO2/g-C3N4 Z-scheme photocatalyst mainly benefited from the effective separation of photoinduced electron-hole pairs and the extended optical absorption range. The TiO2/g-C3N4 (1:3) nanocomposite showed the best photocatalytic behavior in a consequence of the optimal weight ratio of TiO2:g-C3N4 and the lowest band gap energy from all nanocomposites. The N2O conversion in its presence was 70.6% after 20 h of UVA irradiation.

  15. Role of Zn doping in oxidative stress mediated cytotoxicity of TiO2 nanoparticles in human breast cancer MCF-7 cells

    NASA Astrophysics Data System (ADS)

    Ahamed, Maqusood; Khan, M. A. Majeed; Akhtar, Mohd Javed; Alhadlaq, Hisham A.; Alshamsan, Aws

    2016-07-01

    We investigated the effect of Zn-doping on structural and optical properties as well as cellular response of TiO2 nanoparticles (NPs) in human breast cancer MCF-7 cells. A library of Zn-doped (1-10 at wt%) TiO2 NPs was prepared. Characterization data indicated that dopant Zn was incorporated into the lattice of host TiO2. The average particle size of TiO2 NPs was decreases (38 to 28 nm) while the band gap energy was increases (3.35 eV-3.85 eV) with increasing the amount of Zn-doping. Cellular data demonstrated that Zn-doped TiO2 NPs induced cytotoxicity (cell viability reduction, membrane damage and cell cycle arrest) and oxidative stress (reactive oxygen species generation & glutathione depletion) in MCF-7 cells and toxic intensity was increases with increasing the concentration of Zn-doping. Molecular data revealed that Zn-doped TiO2 NPs induced the down-regulation of super oxide dismutase gene while the up-regulation of heme oxygenase-1 gene in MCF-7 cells. Cytotoxicity induced by Zn-doped TiO2 NPs was efficiently prevented by N-acetyl-cysteine suggesting that oxidative stress might be the primarily cause of toxicity. In conclusion, our data indicated that Zn-doping decreases the particle size and increases the band gap energy as well the oxidative stress-mediated toxicity of TiO2 NPs in MCF-7 cells.

  16. Role of Zn doping in oxidative stress mediated cytotoxicity of TiO2 nanoparticles in human breast cancer MCF-7 cells

    PubMed Central

    Ahamed, Maqusood; Khan, M. A. Majeed; Akhtar, Mohd Javed; Alhadlaq, Hisham A.; Alshamsan, Aws

    2016-01-01

    We investigated the effect of Zn-doping on structural and optical properties as well as cellular response of TiO2 nanoparticles (NPs) in human breast cancer MCF-7 cells. A library of Zn-doped (1–10 at wt%) TiO2 NPs was prepared. Characterization data indicated that dopant Zn was incorporated into the lattice of host TiO2. The average particle size of TiO2 NPs was decreases (38 to 28 nm) while the band gap energy was increases (3.35 eV–3.85 eV) with increasing the amount of Zn-doping. Cellular data demonstrated that Zn-doped TiO2 NPs induced cytotoxicity (cell viability reduction, membrane damage and cell cycle arrest) and oxidative stress (reactive oxygen species generation & glutathione depletion) in MCF-7 cells and toxic intensity was increases with increasing the concentration of Zn-doping. Molecular data revealed that Zn-doped TiO2 NPs induced the down-regulation of super oxide dismutase gene while the up-regulation of heme oxygenase-1 gene in MCF-7 cells. Cytotoxicity induced by Zn-doped TiO2 NPs was efficiently prevented by N-acetyl-cysteine suggesting that oxidative stress might be the primarily cause of toxicity. In conclusion, our data indicated that Zn-doping decreases the particle size and increases the band gap energy as well the oxidative stress-mediated toxicity of TiO2 NPs in MCF-7 cells. PMID:27444578

  17. Sunscreens with Titanium Dioxide (TiO2) Nano-Particles: A Societal Experiment

    PubMed Central

    van de Poel, Ibo; Osseweijer, Patricia

    2010-01-01

    The risks of novel technologies, such as nano(bio)technology cannot be fully assessed due to the existing uncertainties surrounding their introduction into society. Consequently, the introduction of innovative technologies can be conceptualised as a societal experiment, which is a helpful approach to evaluate moral acceptability. This approach is illustrated with the marketing of sunscreens containing nano-sized titanium dioxide (TiO2) particles. We argue that the marketing of this TiO2 nanomaterial in UV protective cosmetics is ethically undesirable, since it violates four reasonable moral conditions for societal experimentation (absence of alternatives, controllability, limited informed consent, and continuing evaluation). To remedy the current way nano-sized TiO2 containing sunscreens are utilised, we suggest five complementing actions (closing the gap, setup monitoring tools, continuing review, designing for safety, and regulative improvements) so that its marketing can become more acceptable. PMID:20835397

  18. Efficient Solar-Induced Photoelectrochemical Response Using Coupling Semiconductor TiO2-ZnO Nanorod Film

    PubMed Central

    Abd Samad, Nur Azimah; Lai, Chin Wei; Lau, Kung Shiuh; Abd Hamid, Sharifah Bee

    2016-01-01

    Efficient solar driven photoelectrochemical (PEC) response by enhancing charge separation has attracted great interest in the hydrogen generation application. The formation of one-dimensional ZnO nanorod structure without bundling is essential for high efficiency in PEC response. In this present research work, ZnO nanorod with an average 500 nm in length and average diameter of about 75 nm was successfully formed via electrodeposition method in 0.05 mM ZnCl2 and 0.1 M KCl electrolyte at 1 V for 60 min under 70 °C condition. Continuous efforts have been exerted to further improve the solar driven PEC response by incorporating an optimum content of TiO2 into ZnO nanorod using dip-coating technique. It was found that 0.25 at % of TiO2 loaded on ZnO nanorod film demonstrated a maximum photocurrent density of 19.78 mA/cm2 (with V vs. Ag/AgCl) under UV illumination and 14.75 mA/cm2 (with V vs. Ag/AgCl) under solar illumination with photoconversion efficiency ~2.9% (UV illumination) and ~4.3% (solar illumination). This performance was approximately 3–4 times higher than ZnO film itself. An enhancement of photocurrent density and photoconversion efficiency occurred due to the sufficient Ti element within TiO2-ZnO nanorod film, which acted as an effective mediator to trap the photo-induced electrons and minimize the recombination of charge carriers. Besides, phenomenon of charge-separation effect at type-II band alignment of Zn and Ti could further enhance the charge carrier transportation during illumination. PMID:28774068

  19. Sol-gel preparation of self-cleaning SiO2-TiO2/SiO2-TiO2 double-layer antireflective coating for solar glass

    NASA Astrophysics Data System (ADS)

    Lin, Wensheng; Zheng, Jiaxian; Yan, Lianghong; Zhang, Xinxiang

    2018-03-01

    Self-cleaning SiO2-TiO2/SiO2-TiO2 double-layer antireflective (AR) coating is prepared by sol-gel process. SiO2 sol is prepared by using tetraethyl orthosilicate (TEOS) as precursor and ammonia as catalyst, while TiO2 sol was prepared by using tetrabutyl orthotitanate (TBOT) as precursor and hydrochloric acid as catalyst. The effect of TiO2 content on refractive index, abrasion-resistance and photo-catalytic activity of SiO2-TiO2 hybrid thin films or powders is systematically investigated. It is found that the refractive index of SiO2-TiO2 hybrid thin films increases gradually from 1.18 to 1.53 as the weight ratio of TiO2 to SiO2 increased from 0 to 1.0. The SiO2-TiO2 hybrid thin film and powder possesses good abrasion-resistance and photo-catalytic activity, respectively, as the weight ratio of TiO2 to SiO2 is 0.4. The degradation degree of Rhodamine B by SiO2-TiO2 hybrid powder is 88.3%. Finally, SiO2-TiO2/SiO2-TiO2 double-layer AR coating with high transmittance, abrasion-resistance and self-cleaning property is realized.

  20. First-principles study on codoping effect to enhance photocatalytic activity of anatase TiO2

    NASA Astrophysics Data System (ADS)

    Bai, Yujie; Zhang, Qinfang; Zheng, Fubao; Yang, Yun; Meng, Qiangqiang; Zhu, Lei; Wang, Baolin

    2017-03-01

    Codopant is an effective approach to modify the bandgap and band edge positions of transition metal oxide. Here, the electronic structures as well as the optical properties of pristine, mono-doped (N/P/Sb) and codoped (Sb, N/P) anatase TiO2 have been systematically investigated based on density functional theory calculations. It is found that mono-doped TiO2 exhibits either unoccupied or partially occupied intermediate state within the energy gap, which promotes the recombination of electron-hole pairs. However, the presence of (Sb, N/P) codopant not only effectively reduces the width of bandgap by introducing delocalized occupied intermediate states, but also adjusts the band edge alignment to enhance the hydrogen evolution activity of TiO2. Moreover, the optical absorption spectrum for (Sb, N/P) codoped TiO2, which is favored under oxygen-rich condition, demonstrates the improvement of its visible light absorption. These findings will promote the potential application of (Sb, N/P) codoped TiO2 photocatalysis for water splitting under visible light irradiation.

  1. Schottky Barrier Height Engineering for Electrical Contacts of Multilayered MoS2 Transistors with Reduction of Metal-Induced Gap States.

    PubMed

    Kim, Gwang-Sik; Kim, Seung-Hwan; Park, June; Han, Kyu Hyun; Kim, Jiyoung; Yu, Hyun-Yong

    2018-06-06

    The difficulty in Schottky barrier height (SBH) control arising from Fermi-level pinning (FLP) at electrical contacts is a bottleneck in designing high-performance nanoscale electronics and optoelectronics based on molybdenum disulfide (MoS 2 ). For electrical contacts of multilayered MoS 2 , the Fermi level on the metal side is strongly pinned near the conduction-band edge of MoS 2 , which makes most MoS 2 -channel field-effect transistors (MoS 2 FETs) exhibit n-type transfer characteristics regardless of their source/drain (S/D) contact metals. In this work, SBH engineering is conducted to control the SBH of electrical top contacts of multilayered MoS 2 by introducing a metal-interlayer-semiconductor (MIS) structure which induces the Fermi-level unpinning by a reduction of metal-induced gap states (MIGS). An ultrathin titanium dioxide (TiO 2 ) interlayer is inserted between the metal contact and the multilayered MoS 2 to alleviate FLP and tune the SBH at the S/D contacts of multilayered MoS 2 FETs. A significant alleviation of FLP is demonstrated as MIS structures with 1 nm thick TiO 2 interlayers are introduced into the S/D contacts. Consequently, the pinning factor ( S) increases from 0.02 for metal-semiconductor (MS) contacts to 0.24 for MIS contacts, and the controllable SBH range is widened from 37 meV (50-87 meV) to 344 meV (107-451 meV). Furthermore, the Fermi-level unpinning effect is reinforced as the interlayer becomes thicker. This work widens the scope for modifying electrical characteristics of contacts by providing a platform to control the SBH through a simple process as well as understanding of the FLP at the electrical top contacts of multilayered MoS 2 .

  2. Zirconium doped TiO2 thin films deposited by chemical spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Juma, A.; Oja Acik, I.; Oluwabi, A. T.; Mere, A.; Mikli, V.; Danilson, M.; Krunks, M.

    2016-11-01

    Chemical spray pyrolysis (CSP) is a flexible deposition technique that allows for mixing of the precursor solutions in different proportions suitable for doping thin films. The CSP method was used to dope TiO2 thin films with Zr by adding zirconium(IV) acetylacetonate into a solution of titanium(IV) isopropoxide in ethanol stabilized by acetylacetone at [Zr]/[Ti] of 0, 5, 10 and 20 at%. The Zr-doped TiO2 thin films were uniform and homogeneous showing much smaller grains than the undoped TiO2 films. Zr stabilized the anatase phase to temperatures above 800 °C depending on Zr concentration in the spray solution. The concentration of Zr determined by XPS was 6.4 at% for the thin film deposited from the 20 at% solution. According to AFM studies, Zr doping decreased the root mean square roughness of TiO2 film from 5.9 to 1.1 nm. An XRD study of samples with the highest Zr amount showed the ZrTiO4 phase started forming after annealing at 800 °C. The optical band gap for TiO2 decreased from 3.3 eV to 3.0 eV after annealing at 800 °C but for the TiO2:Zr(20) film it remained at 3.4 eV. The dielectric constant increased by more than four times with Zr-doping and this was associated with the change in the bond formations caused by substitution of Ti by Zr in the lattice.

  3. Band structures of TiO2 doped with N, C and B*

    PubMed Central

    Xu, Tian-Hua; Song, Chen-Lu; Liu, Yong; Han, Gao-Rong

    2006-01-01

    This study on the band structures and charge densities of nitrogen (N)-, carbon (C)- and boron (B)-doped titanium dioxide (TiO2) by first-principles simulation with the CASTEP code (Segall et al., 2002) showed that the three 2p bands of impurity atom are located above the valence-band maximum and below the Ti 3d bands, and that along with the decreasing of impurity atomic number, the fluctuations become more intensive. We cannot observe obvious band-gap narrowing in our result. Therefore, the cause of absorption in visible light might be the isolated impurity atom 2p states in band-gap rather than the band-gap narrowing. PMID:16532532

  4. A General Strategy to Achieve Colossal Permittivity and Low Dielectric Loss Through Constructing Insulator/Semiconductor/Insulator Multilayer Structures

    NASA Astrophysics Data System (ADS)

    Liu, Kai; Sun, Yalong; Zheng, Fengang; Tse, Mei-Yan; Sun, Qingbo; Liu, Yun; Hao, Jianhua

    2018-06-01

    In this work, we propose a route to realize high-performance colossal permittivity (CP) by creating multilayer structures of insulator/semiconductor/insulator. To prove the new concept, we made heavily reduced rutile TiO2 via annealing route in Ar/H2 atmosphere. Dielectric studies show that the maximum dielectric permittivity ( 3.0 × 104) of our prepared samples is about 100 times higher than that ( 300) of conventional TiO2. The minimum dielectric loss is 0.03 (at 104-105 Hz). Furthermore, CP is almost independent of the frequency (100-106 Hz) and the temperature (20-350 K). We suggest that the colossal permittivity is attributed to the high carrier concentration of the inner TiO2 semiconductor, while the low dielectric loss is due to the presentation of the insulator layer on the surface of TiO2. The method proposed here can be expanded to other material systems, such as semiconductor Si sandwiched by top and bottom insulator layers of Ga2O3.

  5. Rapid photo-degradation of 2-chlorophenol under visible light irradiation using cobalt oxide-loaded TiO2/reduced graphene oxide nanocomposite from aqueous media.

    PubMed

    Sharma, Ajit; Lee, Byeong-Kyu

    2016-01-01

    The photocatalytic removal of 2-chlorophenol (2-CP) from water environment was investigated by TiO2-RGO-CoO. Cobalt oxide-loaded TiO2 (TiO2-CoO) supported with reduced graphene oxide (RGO) was synthesized using a sol-gel method and then annealed at 500 °C for 5 min. The material characteristics were analyzed by UV-Vis analysis, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. Incorporation of cobalt oxide and RGO into the TiO2 system (TiO2-RGO-CoO) lowered the band gap energy to 2.83 eV, which greatly enhanced the visible light absorption. The TiO2-RGO-CoO photocatalyst showed complete removal of 20 mg/L 2-CP within 8 h with the addition of 0.01% H2O2 under 100 W visible light irradiation. The photo-degradation efficiency of 2-CP (10 mg/L) was 35.2, 48.9, 58.9 and 98.2% for TiO2, TiO2-RGO, TiO2-CoO and TiO2-RGO-CoO, respectively, in the presence of visible light irradiation at solution pH of 6.0. The TiO2-RGO-CoO photocatalyst retained its high removal efficiency even after five photocatalytic cycles. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. HfSe2 and ZrSe2: Two-dimensional semiconductors with native high-κ oxides

    PubMed Central

    Mleczko, Michal J.; Zhang, Chaofan; Lee, Hye Ryoung; Kuo, Hsueh-Hui; Magyari-Köpe, Blanka; Moore, Robert G.; Shen, Zhi-Xun; Fisher, Ian R.; Nishi, Yoshio; Pop, Eric

    2017-01-01

    The success of silicon as a dominant semiconductor technology has been enabled by its moderate band gap (1.1 eV), permitting low-voltage operation at reduced leakage current, and the existence of SiO2 as a high-quality “native” insulator. In contrast, other mainstream semiconductors lack stable oxides and must rely on deposited insulators, presenting numerous compatibility challenges. We demonstrate that layered two-dimensional (2D) semiconductors HfSe2 and ZrSe2 have band gaps of 0.9 to 1.2 eV (bulk to monolayer) and technologically desirable “high-κ” native dielectrics HfO2 and ZrO2, respectively. We use spectroscopic and computational studies to elucidate their electronic band structure and then fabricate air-stable transistors down to three-layer thickness with careful processing and dielectric encapsulation. Electronic measurements reveal promising performance (on/off ratio > 106; on current, ~30 μA/μm), with native oxides reducing the effects of interfacial traps. These are the first 2D materials to demonstrate technologically relevant properties of silicon, in addition to unique compatibility with high-κ dielectrics, and scaling benefits from their atomically thin nature. PMID:28819644

  7. Tuning the band gap in hybrid tin iodide perovskite semiconductors using structural templating.

    PubMed

    Knutson, Jeremy L; Martin, James D; Mitzi, David B

    2005-06-27

    Structural distortions within the extensive family of organic/inorganic hybrid tin iodide perovskite semiconductors are correlated with their experimental exciton energies and calculated band gaps. The extent of the in- and out-of-plane angular distortion of the SnI4(2-) perovskite sheets is largely determined by the relative charge density and steric requirements of the organic cations. Variation of the in-plane Sn-I-Sn bond angle was demonstrated to have the greatest impact on the tuning of the band gap, and the equatorial Sn-I bond distances have a significant secondary influence. Extended Hückel tight-binding band calculations are employed to decipher the crystal orbital origins of the structural effects that fine-tune the band structure. The calculations suggest that it may be possible to tune the band gap by as much as 1 eV using the templating influence of the organic cation.

  8. Growth of rutile TiO2 nanorods in Ti and Cu ion sequentially implanted SiO2 and the involved mechanisms

    NASA Astrophysics Data System (ADS)

    Mu, Xiaoyu; Liu, Xiaoyu; Wang, Xiaohu; Dai, Haitao; Liu, Changlong

    2018-01-01

    TiO2 in nanoscale exhibits unique physicochemical and optoelectronic properties and has attracted much more interest of the researchers. In this work, TiO2 nanostructures are synthesized in amorphous SiO2 slices by implanting Ti ions, or sequentially implanting Ti and Cu ions combined with annealing at high temperature. The morphology, structure, spatial distribution and optical properties of the formed nanostructures have been investigated in detail. Our results clearly show that the thermal growth of TiO2 nanostructures in SiO2 substrate is significantly enhanced by presence of post Cu ion implantation, which depends strongly on the applied Cu ion fluence, as well as the annealing atmosphere. Due to the formation of Cu2O in the substrate, rutile TiO2 nanorods of large size have been well fabricated in the Ti and Cu sequentially implanted SiO2 after annealing in N2 atmosphere, in which Cu2O plays a role as a catalyst. Moreover, the sample with well-fabricated TiO2 nanorods exhibits a narrowed band gap, an enhanced optical absorption in visible region, and catalase-/peroxidase-like catalytic characteristics. Our findings provide an effective route to fabricate functional TiO2 nanorods in SiO2 via ion implantation.

  9. Effect of photocatalytic reduction of carbon dioxide by N-Zr co-doped nano TiO2.

    PubMed

    Zhang, Ru; Wang, Li; Kang, Zhuo; Li, Qiang; Pan, Huixian

    2017-11-01

    Modified sol-gel method was adopted to prepare TiO 2 , Zr-TiO 2 and N/Zr-TiO 2 composite catalyst. The as-synthesized photocatalysts were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Brunner- Emmet- Teller measurement and UV-Vis diffuse reflectance spectroscopy. And the photocatalytic performance toward CO 2 reduction was evaluated under ultraviolet light. The catalyst particles were demonstrated in the nanometer level size. When N and Zr are co-doped, on the one hand, Ti 4+ can be replaced by Zr 4  +, which leads to lattice distortion and inhibits electron-hole recombination. On the other hand, N enters into TiO 2 lattice gap to form O-Ti-N bond structure, and partial Ti 4+ are reduced to Ti 3+ . Compared with pristine TiO 2 , the specific surface area and the band gap of N/Zr-TiO 2 were improved and reduced, respectively. The N and Zr synergistically contribute to the obviously strengthened absorption intensity in visible region, as well as significantly improved photocatalytic activity. In the gas phase reactor, when the calcination temperature was 550°C, 0.125N/0.25Zr-TiO 2 composite performed the highest photocatalytic activity UV irradiation for 8 h, and the corresponding CH 4 yield was 11.837 µmol/g, which was 87.8% higher than that of pristine TiO 2 . For the visible light, the CH 4 yield was 9.003 µmol/g after 8 h irradiation, which was 83.9% higher than that of pristine TiO 2 .

  10. Tempe Waste Water Degradation Using TiO2-N/Bentonite alginate Granule Photocatalyst with Ultraviolet Light Irradiation

    NASA Astrophysics Data System (ADS)

    Khoirun Nisaa', Aldila; Wardhani, Sri; Purwonugroho, Danar; Darjito

    2018-01-01

    Tempe waste water stew has high ammonia concentration which causes odor due to polluting by anaerobic decay. Free ammonia in the waste has exceeded the limit, thus endangering the aquatic environment. This research aims to determine the activity of photocatalyst granule TiO2-N/bentonite-alginate as decomposers of compounds in the photodegradation process. Photodegradation is the decomposition process of compounds by semiconductors with light. Results expected includes the photocatalyst activity of TiO2-N/bentonite-alginate granule produced by ultraviolet rays is known based on the effect of dopant N concentration on the catalyst and the effect of photocatalytic ratio toward tempe waste water. Methods proposed in this research are activation of bentonite using H2SO4 0.8 M, TiO2-N synthesize by sonication method with urea as the source of N, then TiO2-N impregnation into bentonite. Photocatalyst in granule form synthesized with alginate was then dripped with syringe pump into 3% (w/v) CaCl2. The photocatalyst characterization will be performed using XRD. The optimum tempe waste water degradation at the concentration of TiO2-N 0.4 (g/g) bentonite is 53.66%. The ratio of photocatalyst and tempe waste water, optimum at 150 mg of photocatalyst with 25 mL of waste equal to 53.66%.

  11. TiO2-graphene oxide nanocomposite as advanced photocatalytic materials.

    PubMed

    Stengl, Václav; Bakardjieva, Snejana; Grygar, Tomáš Matys; Bludská, Jana; Kormunda, Martin

    2013-02-27

    Graphene oxide composites with photocatalysts may exhibit better properties than pure photocatalysts via improvement of their textural and electronic properties. TiO2-Graphene Oxide (TiO2 - GO) nanocomposite was prepared by thermal hydrolysis of suspension with graphene oxide (GO) nanosheets and titania peroxo-complex. The characterization of graphene oxide nanosheets was provided by using an atomic force microscope and Raman spectroscopy. The prepared nanocomposites samples were characterized by Brunauer-Emmett-Teller surface area and Barrett-Joiner-Halenda porosity, X-ray Diffraction, Infrared Spectroscopy, Raman Spectroscopy and Transmission Electron Microscopy. UV/VIS diffuse reflectance spectroscopy was employed to estimate band-gap energies. From the TiO2 - GO samples, a 300 μm thin layer on a piece of glass 10×15 cm was created. The photocatalytic activity of the prepared layers was assessed from the kinetics of the photocatalytic degradation of butane in the gas phase. The best photocatalytic activity under UV was observed for sample denoted TiGO_100 (k = 0.03012 h-1), while sample labeled TiGO_075 (k = 0.00774 h-1) demonstrated the best activity under visible light.

  12. TiO2-graphene oxide nanocomposite as advanced photocatalytic materials

    PubMed Central

    2013-01-01

    Background Graphene oxide composites with photocatalysts may exhibit better properties than pure photocatalysts via improvement of their textural and electronic properties. Results TiO2-Graphene Oxide (TiO2 - GO) nanocomposite was prepared by thermal hydrolysis of suspension with graphene oxide (GO) nanosheets and titania peroxo-complex. The characterization of graphene oxide nanosheets was provided by using an atomic force microscope and Raman spectroscopy. The prepared nanocomposites samples were characterized by Brunauer–Emmett–Teller surface area and Barrett–Joiner–Halenda porosity, X-ray Diffraction, Infrared Spectroscopy, Raman Spectroscopy and Transmission Electron Microscopy. UV/VIS diffuse reflectance spectroscopy was employed to estimate band-gap energies. From the TiO2 - GO samples, a 300 μm thin layer on a piece of glass 10×15 cm was created. The photocatalytic activity of the prepared layers was assessed from the kinetics of the photocatalytic degradation of butane in the gas phase. Conclusions The best photocatalytic activity under UV was observed for sample denoted TiGO_100 (k = 0.03012 h-1), while sample labeled TiGO_075 (k = 0.00774 h-1) demonstrated the best activity under visible light. PMID:23445868

  13. High electron doping to a wide band gap semiconductor 12CaO•7Al2O3 thin film

    NASA Astrophysics Data System (ADS)

    Miyakawa, Masashi; Hirano, Masahiro; Kamiya, Toshio; Hosono, Hideo

    2007-04-01

    High-density electrons (˜1.9×1021cm-3) were doped into a polycrystalline film of a wide band gap (˜7eV) semiconductor 12CaO•7Al2O3 (C12A7) by an in situ postdeposition reduction treatment using an oxygen-deficient C12A7 overlayer. The resultant film exhibits metallic conduction with a Hall mobility of ˜2.5cm2V-1s-1 and a conductivity of ˜800Scm-1. Optical analyses indicate that most of the doped electrons behave as free carriers with an effective mass of 0.82me and the estimated in-grain mobility is 5.2cm2V-1s-1, which agrees reasonably with the value obtained for high-quality single crystals.

  14. TiO2 films photocatalytic activity improvements by swift heavy ions irradiation

    NASA Astrophysics Data System (ADS)

    Rafik, Hazem; Mahmoud, Izerrouken; Mohamed, Trari; Abdenacer, Benyagoub

    2014-08-01

    TiO2 thin films synthesized by sol-gel on glass substrates are irradiated by 90 MeV Xe ions at various fluences and room temperature under normal incidence. The structural, electrical, optical and surface topography properties before and after Xe ions irradiation are investigated. X-ray diffraction (XRD) reveals that the crystallinity is gradually destroyed, and the films become amorphous above 5×1012 ions/cm2. The band gap is not affected by Xe ions irradiation as evidenced from the optical measurements. By contrast, the conductivity increases with raising Xe fluence. The energy band diagram established from the electrochemical characterization shows the feasibility of TiO2 films for the photo-electrochemical chromate reduction. Xe ion irradiation results in enhanced photocatalytic activity in aquatic medium, evaluated by the reduction of Cr(VI) into trivalent state. TiO2 films irradiated at 1013 Xe/cm2 exhibit the highest photoactivity; 69% of chromate (10 ppm) is reduced at pH 3 after 4 h of exposure to sunlight (1120 mW cm-2) with a quantum yield of 0.06%.

  15. PAMAM templated N,Pt co-doped TiO2 for visible light photodegradation of brilliant black.

    PubMed

    Nzaba, Sarre Kadia Myra; Ntsendwana, Bulelwa; Mamba, Bhekie Brilliance; Kuvarega, Alex Tawanda

    2018-05-01

    This study examined the photocatalytic degradation of an azo dye brilliant black (BB) using non-metal/metal co-doped TiO 2 . N,Pt co-doped TiO 2 photocatalysts were prepared by a modified sol-gel method using amine-terminated polyamidoamine dendrimer generation 0 (PG0) as a template and source of nitrogen. Structural, morphological, and textural properties were evaluated using scanning electron microscopy coupled to energy-dispersive X-ray spectroscopy (SEM/EDX), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), Fourier transform infrared (FTIR), Raman spectroscopy (RS), photoluminescence (PL) and ultra-violet/visible spectroscopy (UV-Vis). The synthesized photocatalysts exhibited lower band gap energies as compared to the Degussa P-25, revealing a red shift in band gap towards the visible light absorption region. Photocatalytic activity of N,Pt co-doped TiO 2 was measured by the reaction of photocatalytic degradation of BB dye. Enhanced photodegradation efficiency of BB was achieved after 180-min reaction time with an initial concentration of 50 ppm. This was attributed to the rod-like shape of the materials, larger surface area, and enhanced absorption of visible light induced by N,Pt co-doping. The N,Pt co-doped TiO 2 also exhibited pseudo-first-order kinetic behavior with half-life and rate constant of 0.37 and 0.01984 min -1 , respectively. The mechanism of the photodegradation of BB under the visible light irradiation was proposed. The obtained results prove that co-doping of TiO 2 with N and Pt contributed to the enhanced photocatalytic performances of TiO 2 for visible light-induced photodegradation of organic contaminants for environmental remediation. Therefore, this work provides a new approach to the synthesis of PAMAM templated N,Pt co-doped TiO 2 for visible light photodegradation of brilliant black.

  16. Sol-gel Synthesis, Photo- and Electrocatalytic Properties of Mesoporous TiO2 Modified with Transition Metal Ions

    NASA Astrophysics Data System (ADS)

    Smirnova, N.; Petrik, I.; Vorobets, V.; Kolbasov, G.; Eremenko, A.

    2017-03-01

    Mesoporous nanosized titania films modified with Co2+, Ni2+, Mn3+, and Cu2+ ions have been produced by templated sol-gel method and characterized by optical spectroscopy, X-ray diffraction (XRD), and Brunauer, Emmett, and Teller (BET) surface area measurement. Band gap energy and the position of flat band potentials were estimated by photoelectrochemical measurements. The films doped with transition metals possessed higher photocurrent quantum yield, as well as photo- and electrochemical activity compared to undoped samples. Mn+/TiO2 (M-Co, Ni, Mn, Cu) electrodes with low dopant content demonstrate high efficiency in electrocatalytic reduction of dissolved oxygen. Polarization curves of TiO2, TiO2/Ni2+, TiO2/Co2+/3+, and TiO2/Mn3+ electrodes contain only one current wave (oxygen reduction current). It means that reaction proceeds without the formation of an intermediate product H2O2.

  17. Charge storage in oxygen deficient phases of TiO2: defect Physics without defects.

    PubMed

    Padilha, A C M; Raebiger, H; Rocha, A R; Dalpian, G M

    2016-07-01

    Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO2, known as Magnéli phases. These Magnéli phases (TinO2n-1) present well-defined crystalline structures, i.e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with an electronic quadruple donor transitions akin to interstitial Ti defect levels in rutile TiO2. Thus, the Magnéli phases behave as if they contained a very large pseudo-defect density: ½ per formula unit TinO2n-1. Depending on the Fermi Energy the whole material will become charged. These crystals are natural charge storage materials with a storage capacity that rivals the best known supercapacitors.

  18. A density functional study of the effect of hydrogen on electronic properties and band discontinuity at anatase TiO2/diamond interface

    NASA Astrophysics Data System (ADS)

    Wu, Kongping; Liao, Meiyong; Sang, Liwen; Liu, Jiangwei; Imura, Masataka; Ye, Haitao; Koide, Yasuo

    2018-04-01

    Tailoring the electronic states of the dielectric oxide/diamond interface is critical to the development of next generation semiconductor devices like high-power high-frequency field-effect transistors. In this work, we investigate the electronic states of the TiO2/diamond 2 × 1-(100) interface by using first principles total energy calculations. Based on the calculation of the chemical potentials for the TiO2/diamond interface, it is observed that the hetero-interfaces with the C-OTi configuration or with two O vacancies are the most energetically favorable structures under the O-rich condition and under Ti-rich condition, respectively. The band structure and density of states of both TiO2/diamond and TiO2/H-diamond hetero-structures are calculated. It is revealed that there are considerable interface states at the interface of the anatase TiO2/diamond hetero-structure. By introducing H on the diamond surface, the interface states are significantly suppressed. A type-II alignment band structure is disclosed at the interface of the TiO2/diamond hetero-structure. The valence band offset increases from 0.6 to 1.7 eV when H is introduced at the TiO2/diamond interface.

  19. Selective CO2 reduction conjugated with H2O oxidation utilizing semiconductor/metal-complex hybrid photocatalysts

    NASA Astrophysics Data System (ADS)

    Morikawa, T.; Sato, S.; Arai, T.; Uemura, K.; Yamanaka, K. I.; Suzuki, T. M.; Kajino, T.; Motohiro, T.

    2013-12-01

    We developed a new hybrid photocatalyst for CO2 reduction, which is composed of a semiconductor and a metal complex. In the hybrid photocatalyst, ΔG between the position of conduction band minimum (ECBM) of the semiconductor and the CO2 reduction potential of the complex is an essential factor for realizing fast electron transfer from the conduction band of semiconductor to metal complex leading to high photocatalytic activity. On the basis of this concept, the hybrid photocatalyst InP/Ru-complex, which functions in aqueous media, was developed. The photoreduction of CO2 to formate using water as an electron donor and a proton source was successfully achieved as a Z-scheme system by functionally conjugating the InP/Ru-complex photocatalyst for CO2 reduction with a TiO2 photocatalyst for water oxidation. The conversion efficiency from solar energy to chemical energy was ca. 0.04%, which approaches that for photosynthesis in a plant. Because this system can be applied to many other inorganic semiconductors and metal-complex catalysts, the efficiency and reaction selectivity can be enhanced by optimization of the electron transfer process including the energy-band configurations, conjugation conformations, and catalyst structures. This electrical-bias-free reaction is a huge leap forward for future practical applications of artificial photosynthesis under solar irradiation to produce organic species.

  20. In situ growth of lamellar ZnTiO3 nanosheets on TiO2 tubular array with enhanced photocatalytic activity.

    PubMed

    Cai, Yunyu; Ye, Yixing; Tian, Zhenfei; Liu, Jun; Liu, Yishu; Liang, Changhao

    2013-12-14

    We report a self-sacrificed in situ growth design toward preparation of ZnTiO3-TiO2 heterojunction structure. Highly reactive zinc oxide colloidal particles derived by laser ablation in liquids can react with TiO2 nanotubes to form a lamellar ZnTiO3 nanosheet structure in a hydrothermal-treatment process. Such hybrid structural product was characterized by X-ray diffraction, scanning and transmission electron microscopy, UV-vis diffuse reflection spectroscopy and X-ray photoelectron spectroscopy. The enhanced photocatalytic activity of the hybrid structure toward degradation of methyl orange (MO) and pentachlorophenol (PCP) molecules was demonstrated and compared with single phase TiO2, as a result of the efficient separation of light excited electrons and holes at the hetero-interfaces in the two semiconductors.

  1. Enhancing the photoresponse and photocatalytic properties of TiO 2 by controllably tuning defects across {101} facets

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wan, Piaopiao; Hood, Zachary D.; Oak Ridge National Lab.

    Introducing defects into semiconductors with well-controlled exposed facets offers an effective route for the development of photocatalytic materials with greatly improved properties. Here, we report a facile ethylene glycol reduction procedure to make anatase titanium dioxide (TiO 2) with different concentrations of exposed {001} and {101} facets, leading to different surficial defects. TiO 2 with increased concentrations of {101} facets shows a 5-fold improvement in photocurrent generation as well as improved photocatalytic activity towards water splitting under visible light irradiation. Thus, the improved activity is ascribed to the oxygen vacancies as well as the variable surface chemical states, which collectivelymore » induce a slower recombination rate of photo-induced electron-hole pairs. This work also highlights a feasible strategy to obtain the defective TiO 2 and explore the synergistic effect of surface defects and different concentrations of exposed {001} and {101} facets for photocurrent and photocatalytic properties under visible light irradiation.« less

  2. Unraveling the charge transfer/electron transport in mesoporous semiconductive TiO2 films by voltabsorptometry.

    PubMed

    Renault, Christophe; Nicole, Lionel; Sanchez, Clément; Costentin, Cyrille; Balland, Véronique; Limoges, Benoît

    2015-04-28

    In this work, we demonstrate that chronoabsorptometry and more specifically cyclic voltabsorptometry are particularly well suited techniques for acquiring a comprehensive understanding of the dynamics of electron transfer/charge transport within a transparent mesoporous semiconductive metal oxide film loaded with a redox-active dye. This is illustrated with the quantitative analysis of the spectroelectrochemical responses of two distinct heme-based redox probes adsorbed in highly-ordered mesoporous TiO2 thin films (prepared from evaporation-induced self-assembly, EISA). On the basis of a finite linear diffusion-reaction model as well as the establishment of the analytical expressions governing the limiting cases, it was possible to quantitatively analyse, predict and interpret the unusual voltabsorptometric responses of the adsorbed redox species as a function of the potential applied to the semiconductive film (i.e., as a function of the transition from an insulating to a conductive state or vice versa). In particular, we were able to accurately determine the interfacial charge transfer rates between the adsorbed redox species and the porous semiconductor. Another important and unexpected finding, inferred from the voltabsorptograms, is an interfacial electron transfer process predominantly governed by the extended conduction band states of the EISA TiO2 film and not by the localized traps in the bandgap. This is a significant result that contrasts those previously observed for dye-sensitized solar cells formed of randomly sintered TiO2 nanoparticles, a behaviour that was ascribed to a particularly low density of localized surface states in EISA TiO2. The present methodology also provides a unique and straightforward access to an activation-driving force relationship according to the Marcus theory, thus opening new opportunities not only to investigate the driving-force effects on electron recombination dynamics in dye-sensitized solar cells but also to study the

  3. Photocatalytic behaviour of WO3/TiO2-N for diclofenac degradation using simulated solar radiation as an activation source.

    PubMed

    Cordero-García, A; Turnes Palomino, G; Hinojosa-Reyes, L; Guzmán-Mar, J L; Maya-Teviño, L; Hernández-Ramírez, A

    2017-02-01

    In this study, the photocatalytic removal of an emerging contaminant, diclofenac (DCF) sodium, was performed using the nitrogen-doped WO 3 /TiO 2 -coupled oxide catalyst (WO 3 /TiO 2 -N). The catalyst synthesis was accomplished by a sol-gel method using tetrabutyl orthotitanate (C 16 H 36 O 4 Ti), ammonium p-tungstate [(NH 4 ) 10 H 2 W 12 O 42 ·4H 2 O] and ammonium nitrate (NH 4 NO 3 ) as the nitrogen source. For comparison, TiO 2 and WO 3 /TiO 2 were also prepared under similar conditions. Analysis by X-ray diffraction (XRD), N 2 adsorption-desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), diffuse reflectance UV-Vis spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS) were conducted to characterize the synthesized materials. The photocatalytic efficiency of the semiconductors was determined in a batch reactor irradiated with simulated solar light. Residual and mineralized DCF were quantified by high-performance liquid chromatography, total organic carbon analysis and ion exchange chromatography. The results indicated that the tungsten atoms were dispersed on the surface of TiO 2 as WO 3 . The partial substitution of oxygen by nitrogen atoms into the lattice of TiO 2 was an important factor to improve the photocatalytic efficiency of WO 3 /TiO 2 . Therefore, the best photocatalytic activity was obtained with the WO 3 /TiO 2 -N 0.18 catalyst, reaching 100% DCF transformation at 250 kJ m -2 and complete mineralization at 400 kJ m -2 of solar-accumulated energy.

  4. Non-metal doped TiO2 nanotube arrays for high efficiency photocatalytic decomposition of organic species in water

    NASA Astrophysics Data System (ADS)

    Szkoda, Mariusz; Siuzdak, Katarzyna; Lisowska-Oleksiak, Anna

    2016-10-01

    Titanium dioxide is a well-known photoactive semiconductor with a variety of possible applications. The procedure of pollutant degradation is mainly performed using TiO2 powder suspension. It can also be exploited an immobilized catalyst on a solid support. Morphology and chemical doping have a great influence on TiO2 activity under illumination. Here we compare photoactivity of titania nanotube arrays doped with non-metal atoms: nitrogen, iodine and boron applied for photodegradation of organic dye - methylene blue and terephtalic acid. The doped samples act as a much better photocatalyst in the degradation process of methylene blue and lead to the formation of much higher amount of hydroxyl radicals (•OH) than undoped TiO2 nanotube arrays. The use of a catalyst active under solar light illumination in the form of thin films on a stable substrate can be scaled up for an industrial application.

  5. Density functional theory study of atomic and electronic properties of defects in reduced anatase TiO2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Morita, Kazuki; Yasuoka, Kenji

    2018-03-01

    Anatase TiO2 nanocrystals have received considerable attention owing to their promising applications in photocatalysis, photovoltaics, and fuel cells. Although experimental evidence has shown that the performance of nanocrystals can be significantly improved through reduction, the mechanistic basis of this enhancement remains unclear. To shed a light on the chemistry of reduced anatase TiO2 nanocrystals, density functional theory were used to investigate the properties of defects and excess electrons. We demonstrated that oxygen vacancies are stable both on the surface and at the sub-surface of the nanocrystal, while titanium interstitials prefer sub-surface sites. Different defect locations possessed different excess electron structures, which contributed to deep and shallow states in the band gap of the nanocrystals. Furthermore, valence band tailing was observed, resulting in band gap narrowing. The theoretical results presented here deepen our understanding, and show the potential of defects to considerably change the macroscopic properties of anatase TiO2 nanocrystals.

  6. Photocatalytic Oxidation of Propylene on Pd-Loaded Anatase TiO2 Nanotubes Under Visible Light Irradiation

    NASA Astrophysics Data System (ADS)

    Li, Chen; Zong, Lanlan; Li, Qiuye; Zhang, Jiwei; Yang, Jianjun; Jin, Zhensheng

    2016-05-01

    TiO2 nanotubes attract much attention because of their high photoelectron-chemical and photocatalytic efficiency. But their large band gap leads to a low absorption of the solar light and limits the practical application. How to obtain TiO2 nanotubes without any dopant and possessing visible light response is a big challenge nowadays. Orthorhombic titanic acid nanotubes (TAN) are a special precursor of TiO2, which possess large Brunauer-Emmett-Teller (BET) surface areas and strong ion exchange and adsorption capacity. TAN can transform to a novel TiO2 with a large amount of single-electron-trapped oxygen vacancies (SETOV) during calcination, while their nanotubular structure would be destroyed, and a BET surface area would decrease remarkably. And interestingly, SETOV can lead to a visible light response for this kind of TiO2. Herein, glucose was penetrated into TAN by the vacuum inhalation method, and TAN would dehydrate to anatase TiO2, and glucose would undergo thermolysis completely in the calcination process. As a result, the pure TiO2 nanotubes with visible light response and large BET surface areas were obtained. For further improving the photocatalytic activity, Pd nanoparticles were loaded as the foreign electron traps on TiO2 nanotubes and the photocatalytic oxidation efficiency of propylene was as high as 71 % under visible light irradiation, and the photostability of the catalyst kept over 90 % after 4 cyclic tests.

  7. Development of high efficient visible light-driven N, S-codoped TiO2 nanowires photocatalysts

    NASA Astrophysics Data System (ADS)

    Zhang, Yanlin; Liu, Peihong; Wu, Honghai

    2015-02-01

    One-dimensional (1D) nanowire material (especially nonmetal doped 1D nanowires) synthesized by a facile way is of great significance and greatly desired as it has higher charge carrier mobility and lower carrier recombination rate. N, S-codoped TiO2 nanowires were synthesized using titanium sulfate as a precursor and isopropanol as a protective capping agent by a hydrothermal route. The obtained doped nanowires were characterized by XRD, SEM, HRTEM, SAED, XPS, BET and UV-vis absorption spectrum. The incorporation of N and S into TiO2 NWs can lead to the expansion of its lattice and remarkably lower its electron-transfer resistance. Photocatalytic activity measurement showed that the N, S-codoped TiO2 nanowires with high quantum efficiency revealed the best photocatalytic performance for atrazine degradation under visible light irradiation compared to N, S-codoped TiO2 nanoparticles and S-doped TiO2 nanowires, which was attributed to (i) the synergistic effect of N and S doping in narrowing the band gap, separating electron-hole pairs and increasing the photoinduced electrons, and (ii) extending the anatase-to-rutile transformation temperature above 600 °C.

  8. Charge disproportionation in tetragonal La2MoO5, a small band gap semiconductor influenced by direct Mo-Mo bonding.

    PubMed

    Colabello, Diane M; Camino, Fernando E; Huq, Ashfia; Hybertsen, Mark; Khalifah, Peter G

    2015-01-28

    The structure of the novel compound La2MoO5 has been solved from powder X-ray and neutron diffraction data and belongs to the tetragonal space group P4/m (no. 83) with a = 12.6847(3) Å and c = 6.0568(2) Å and with Z = 8. It consists of equal proportions of bioctahedral (Mo2O10) and square prismatic (Mo2O8) dimers, both of which contain direct Mo-Mo bonds and are arranged in 1D chains. The Mo-Mo bond length in the Mo2O10 dimers is 2.684(8) Å, while there are two types of Mo2O8 dimers with Mo-Mo bonds lengths of 2.22(2) and 2.28(2) Å. Although the average Mo oxidation state in La2MoO5 is 4+, the very different Mo-Mo distances reflect the fact that the Mo2O10 dimers contain only Mo(5+) (d(1)), while the prismatic Mo2O8 dimers only contain Mo(3+) (d(3)), a result directly confirmed by density function theory calculations. This is due to the complete disproportionation of Mo(4+), a phenomenon which has not previously been observed in solid-state compounds. La2MoO5 is diamagnetic, behavior which is not expected for a nonmetallic transition-metal oxide whose cation sites have an odd number of d-electrons. The resistivity displays the Arrhenius-type activated behavior expected for a semiconductor with a band gap of 0.5 eV, exhibiting an unusually small transport gap relative to other diamagnetic oxides. Diffuse reflectance studies indicate that La2MoO5 is a rare example of a stable oxide semiconductor with strong infrared absorbance. It is shown that the d-orbital splitting associated with the Mo2O8 and Mo2O10 dimeric units can be rationalized using simple molecular orbital bonding concepts.

  9. Charge Disproportionation in Tetragonal La 2MoO 5 , a Small Band Gap Semiconductor Influenced by Direct Mo–Mo Bonding

    DOE PAGES

    Colabello, Diane M.; Camino, Fernando E.; Huq, Ashfia; ...

    2014-12-31

    The structure of the novel compound La 2MoO 5 has been solved from powder X-ray and neutron diffraction data and belongs to the tetragonal space group P4/m (no. 83) with a = 12.6847(3) Å and c = 6.0568(2) Å and with Z = 8. It consists of equal proportions of bioctahedral (Mo 2O 10) and square prismatic (Mo 2O 8) dimers, both of which contain direct Mo-Mo bonds and are arranged in 1D chains. The Mo-Mo bond length in the Mo 2O 10dimers is 2.684(8) Å, while there are two types of Mo 2O 8 dimers with Mo-Mo bonds lengthsmore » of 2.22(2) and 2.28(2) Å. Although the average Mo oxidation state in La 2MoO 5 is 4+, the very different Mo-Mo distances reflect the fact that the Mo 2O 10 dimers contain only Mo5+ (d(1)), while the prismatic Mo2O8 dimers only contain Mo 3+ (d 3), a result directly confirmed by density function theory calculations. This is due to the complete disproportionation of Mo 4+, a phenomenon which has not previously been observed in solid-state compounds. La 2MoO 5 is diamagnetic, behavior which is not expected for a nonmetallic transition-metal oxide whose cation sites have an odd number of d-electrons. The resistivity displays the Arrhenius-type activated behavior expected for a semiconductor with a band gap of 0.5 eV, exhibiting an unusually small transport gap relative to other diamagnetic oxides. Diffuse reflectance studies indicate that La 2MoO 5 is a rare example of a stable oxide semiconductor with strong infrared absorbance. Lastly, we show that the d-orbital splitting associated with the Mo 2O 8 and Mo 2O 10 dimeric units can be rationalized using simple molecular orbital bonding concepts.« less

  10. Effect of top-down nanomachining on electrical conduction properties of TiO2 nanostructure-based chemical sensors.

    PubMed

    Francioso, L; De Pascali, C; Capone, S; Siciliano, P

    2012-03-09

    The present research was motivated by the growing interest of the scientific community towards the understanding of basic gas-surface interaction mechanisms in 1D nanostructured metal oxide semiconductors, whose significantly enhanced chemical detection sensitivity is known. In this work, impedance spectroscopy (IS) was used to evaluate how a top-down patterning of the sensitive layer can modulate the electrical properties of a gas sensor based on a fully integrated nanometric array of TiO(2) polycrystalline strips. The aim of the study was supported by comparative experimental activity carried out on different thin film gas sensors based on identical TiO(2) polycrystalline sensitive thin films. The impedance responses of the investigated devices under dry air (as the reference environment) and ethanol vapors (as the target gas) were fitted by a complex nonlinear least-squares method using LEVM software, in order to find an appropriate equivalent circuit describing the main conduction processes involved in the gas/semiconductor interactions. Two different equivalent circuit models were identified as completely representative of the TiO(2) thin film and the TiO(2) nanostructure-based gas sensors, respectively. All the circuit parameters were quantified and the related standard deviations were evaluated. The simulated results well approximated the experimental data as indicated by the small mean errors of the fits (in the range of 10(-4)) and the small standard deviations of the circuit parameters. In addition to the substrate capacitance, three different contributions to the overall conduction mechanism were identified for both equivalent circuits: bulk conductivity, intergrain contact and semiconductor-electrode contact, electrically represented by an ideal resistor R(g), a parallel R(gb)C(gb) block and a parallel R(c)-CPE(c) combination, respectively. In terms of equivalent circuit modeling, the sensitive layer patterning introduced an additional parameter in

  11. Effect of Germanium on the TiO2 Photoanode for Dye Sensitized Solar Cell Applications. A Potential Sintering Aid

    NASA Astrophysics Data System (ADS)

    Ahmad, M. S.; Pandey, AK; Rahim, N. A.

    2018-05-01

    Anatase titanium-germanium (TiO2-Ge) nanocomposite has been prepared by using colloidal suspension process and investigated for photoanode to be used in dye sensitized solar cell. Ge possesses lower band gap energy compared to TiO2 and has the capability to absorb infrared region of solar spectrum. Its remarkable absorption and good electron transfer ability due to lower band gap energy makes it a potential candidate material in the field of DSSCs to counter important disadvantages such as high probability of electron recombination reactions and absorption of small region (UV region) of solar spectrum. Another advantage is its low sintering temperature which proved to be an added advantage to increase inter-particle contact which in turn leads to improved electron transfer. Scanning electron microscopy (SEM), uv-vis spectroscopy and electron impedance spectroscopy (EIS) have been employed to evaluate the effect of Ge on TiO2photoanode.

  12. Theoretical Discussion of Electron Transport Rate Constant at TCNQ / Ge and TiO2 System

    NASA Astrophysics Data System (ADS)

    Al-agealy, Hadi J. M.; Alshafaay, B.; Hassooni, Mohsin A.; Ashwiekh, Ahmed M.; Sadoon, Abbas K.; Majeed, Raad H.; Ghadhban, Rawnaq Q.; Mahdi, Shatha H.

    2018-05-01

    We have been studying and estimation the electronic transport constant at TCNQ / Ge and Tio2 interface by means of tunneling potential (TP), transport energy reorientation (TER), driving transition energy DTE and coupling coefficient constant. A simple quantum model for the transition processes was adapted to estimation and analysis depending on the quantum state for donor state |α D > and acceptor stated |α A > and assuming continuum levels of the system. Evaluation results were performed for the surfaces of Ge and Tio2 as best as for multilayer TCNQ. The results show an electronic transfer feature for electronic TCNQ density of states and a semiconductor behavior. The electronic rate constant result for both systems shows a good tool to election system in applied devices. All these results indicate the

  13. Role of the conducting layer substrate on TiO2 nucleation when using microwave activated chemical bath deposition

    NASA Astrophysics Data System (ADS)

    Zumeta, I.; Espinosa, R.; Ayllón, J. A.; Vigil, E.

    2002-12-01

    Nanostructured TiO2 is used in novel dye sensitized solar cells. Because of their interaction with light, thin TiO2 films are also used as coatings for self-cleaning glasses and tiles. Microwave activated chemical bath deposition represents a simple and cost-effective way to obtain nanostructured TiO2 films. It is important to study, in this technique, the role of the conducting layer used as the substrate. The influence of microwave-substrate interactions on TiO2 deposition is analysed using different substrate positions, employing substrates with different conductivities, and also using different microwave radiation powers for film deposition. We prove that a common domestic microwave oven with a large cavity and inhomogeneous radiation field can be used with equally satisfactory results. The transmittance spectra of the obtained films were studied and used to analyse film thickness and to obtain gap energy values. The results, regarding different indium-tin oxide resistivities and different substrate positions in the oven cavity, show that the interaction of the microwave field with the conducting layer is determinant in layer deposition. It has also been found that film thickness increases with the power of the applied radiation while the gap energies of the TiO2 films decrease approaching the 3.2 eV value reported for bulk anatase. This indicates that these films are not crystalline and it agrees with x-ray spectra that do not reveal any peak.

  14. Bacteria Adherence Properties of Nitrogen-Doped TiO2 Coatings by Plasma Surface Alloying Technique

    NASA Astrophysics Data System (ADS)

    Wang, Hefeng; Tang, Bin; Li, Xiuyan; Fan, Ailan

    Titanium nitride coatings on 316L stainless steel (S. S) were obtained by plasma surface alloying technique. Nitrogen-doped titanium dioxide (TiO2-xNx) was synthesized by oxidative annealing the resulted TiNx coatings in air. The reference TiO2 samples were also prepared by oxidation of sputtered Ti coatings. The as-prepared coatings were characterized by X-ray diffraction, glow discharge optical emission spectrometer (GDOES), scanning electron microscopy, X-ray hotoelectron spectroscopy and UV-Vis spectrophotometry, respectively. The bacteria adherence property of the TiO2-xNx coatings on stainless steel on the oral bacteria Streptococcus Mutans was investigated and compared with that of stainless steel by fluorescence microscopy. The mechanism of the bacteria adherence was discussed. The results show that the TiO2-xNx coatings are composed of anatase crystalline structure. SEM measurement indicates a rough surface morphology with three-dimensional homogenous protuberances after annealing treatment. Optical properties reveal an extended tailing of the absorption edge toward the visible region due to nitrogen presence. The band gap of the N-doped sample is reduced from 2.29 eV to 1.90 eV compared with the pure TiO2 one. Because of the different roughness and microstructure, the TiO2-xNx coatings inhibit the bacteria adherence.

  15. Quantum chemical elucidation of the mechanism for hydrogenation of TiO2 anatase crystals

    NASA Astrophysics Data System (ADS)

    Raghunath, P.; Huang, W. F.; Lin, M. C.

    2013-04-01

    Hydrogenation of TiO2 is relevant to hydrogen storage and water splitting. We have carried out a detailed mechanistic study on TiO2 hydrogenation through H and/or H2 diffusion from the surface into subsurface layers of anatase TiO2 (101) by periodic density functional theory calculations implementing on-site Coulomb interactions (DFT + U). Both H atoms and H2 molecules can migrate from the crystal surface into TiO2 near subsurface layer with 27.8 and 46.2 kcal/mol energy barriers, respectively. The controlling step for the former process is the dissociative adsorption of H2 on the surface which requires 47.8 kcal/mol of energy barrier. Both hydrogen incorporation processes are expected to be equally favorable. The barrier energy for H2 migration from the first layer of the subsurface Osub1 to the 2nd layer of the subsurface oxygen Osub2 requires only 6.6 kcal. The presence of H atoms on the surface and inside the subsurface layer tends to promote both H and H2 penetration into the subsurface layer by reducing their energy barriers, as well as to prevent the escape of the H2 from the cage by increasing its escaping barrier energy. The H2 molecule inside a cage can readily dissociate and form 2HO-species exothermically (ΔH = -31.0 kcal/mol) with only 26.2 kcal/mol barrier. The 2HO-species within the cage may further transform into H2O with a 22.0 kcal/mol barrier and 19.3 kcal/mol exothermicity relative to the caged H2 molecule. H2O formation following the breaking of Ti-O bonds within the cage may result in the formation of O-vacancies and surface disordering as observed experimentally under a high pressure and moderately high temperature condition. According to density of states analysis, the projected density of states of the interstitial H, H2, and H2O appear prominently within the TiO2 band gap; in addition, the former induces a shift of the band gap position notably towards the conduction band. The thermochemistry for formation of the most stable sub

  16. Hydrothermal synthesis of TiO2/WO3 compositions and their photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Pyachin, Sergey A.; Karpovich, Natalia F.; Zaitsev, Alexey V.; Makarevich, Konstantin S.; Burkov, Alexander A.; Ustinov, Alexander Yu.

    2016-11-01

    Photocatalytic activity, optical properties, thermal stability, phase patterns and morphology of nano-size TiO2/WO3 compositions obtained from organic precursors through hydrothermal synthesis have been studied. It has been shown that doping of anatase nanoparticles with tungsten W+6 results in particle diameter reduction from 35 to 10 nm; decrease in width of the band gap from 3.15 eV to 2.91 eV and increase in temperature of phase transition of anatase to rutile up to 980oC. Catalytic activity of TiO2/WO3 (4 mol.%) composition under photochemical methylene blue (MB) oxidation by simulated solar light exceeds that of undoped anatase (obtained in the same way) 6-fold.

  17. First-principles real-space study of electronic and optical excitations in rutile TiO 2 nanocrystals

    DOE PAGES

    Hung, Linda; Baishya, Kopinjol; Öğüt, Serdar

    2014-10-17

    We model rutile titanium dioxide nanocrystals (NCs) up to ~1.5 nm in size to study the effects of quantum confinement on their electronic and optical properties. Ionization potentials (IPs) and electron affinities (EAs) are obtained via the perturbative GW approximation (G 0W 0) and ΔSCF method for NCs up to 24 and 64 TiO 2 formula units, respectively. These demanding GW computations are made feasible by using a real-space framework that exploits quantum confinement to reduce the number of empty states needed in GW summations. Time-dependent density functional theory (TDDFT) is used to predict the optical properties of NCs upmore » to 64 TiO 2 units. For a NC containing only 2 TiO 2 units, the offsets of the IP and the EA from the corresponding bulk limits are of similar magnitude. However, as NC size increases, the EA is found to converge more slowly to the bulk limit than the IP. The EA values computed at the G 0W 0 and ΔSCF levels of theory are found to agree fairly well with each other, while the IPs computed with ΔSCF are consistently smaller than those computed with G 0W 0 by a roughly constant amount. TDDFT optical gaps exhibit weaker size dependence than GW quasiparticle gaps, and result in exciton binding energies on the order of eV. Finally, altering the dimensions of a fixed-size NC can change electronic and optical excitations up to several tenths of an eV. The largest NCs modeled are still quantum confined and do not yet have quasiparticle levels or optical gaps at bulk values. Nevertheless, we find that classical Mie-Gans theory can quite accurately reproduce the line shape of TDDFT absorption spectra, even for (anisotropic) TiO 2 NCs of subnanometer size.« less

  18. First-principles real-space study of electronic and optical excitations in rutile TiO2 nanocrystals

    NASA Astrophysics Data System (ADS)

    Hung, Linda; Baishya, Kopinjol; Ã-ǧüt, Serdar

    2014-10-01

    We model rutile titanium dioxide nanocrystals (NCs) up to ˜1.5 nm in size to study the effects of quantum confinement on their electronic and optical properties. Ionization potentials (IPs) and electron affinities (EAs) are obtained via the perturbative GW approximation (G0W0) and ΔSCF method for NCs up to 24 and 64 TiO2 formula units, respectively. These demanding GW computations are made feasible by using a real-space framework that exploits quantum confinement to reduce the number of empty states needed in GW summations. Time-dependent density functional theory (TDDFT) is used to predict the optical properties of NCs up to 64 TiO2 units. For a NC containing only 2 TiO2 units, the offsets of the IP and the EA from the corresponding bulk limits are of similar magnitude. However, as NC size increases, the EA is found to converge more slowly to the bulk limit than the IP. The EA values computed at the G0W0 and ΔSCF levels of theory are found to agree fairly well with each other, while the IPs computed with ΔSCF are consistently smaller than those computed with G0W0 by a roughly constant amount. TDDFT optical gaps exhibit weaker size dependence than GW quasiparticle gaps, and result in exciton binding energies on the order of eV. Altering the dimensions of a fixed-size NC can change electronic and optical excitations up to several tenths of an eV. The largest NCs modeled are still quantum confined and do not yet have quasiparticle levels or optical gaps at bulk values. Nevertheless, we find that classical Mie-Gans theory can quite accurately reproduce the line shape of TDDFT absorption spectra, even for (anisotropic) TiO2 NCs of subnanometer size.

  19. Fabrication of efficient TiO2-RGO heterojunction composites for hydrogen generation via water-splitting: Comparison between RGO, Au and Pt reduction sites

    NASA Astrophysics Data System (ADS)

    El-Bery, Haitham M.; Matsushita, Yoshihisa; Abdel-moneim, Ahmed

    2017-11-01

    A facile one-step synthesis approach of M/TiO2/RGO (M = Au or Pt) ternary composite by hydrothermal treatment for hydrogen generation via water-splitting was investigated. Photocurrent response measurements revealed that TiO2 (P25) nanoparticles anchored on the reduced graphene oxide (RGO) surface exhibited a p-n heterojunction interface by changing the photocurrent direction with the applied bias from reverse to forward potential. H2 evolution rate of TiO2/RGO (5 wt.%) composite was substantially enhanced by 12-fold in comparison to bare TiO2 under simulated solar light irradiation. Cyclic volatmmetry measurements manifested, that the optimized 0.3 wt.% of platinum metal loaded on TiO2/RGO composite was the most active catalytic reduction sites for hydrogen generation reaction with an initial hydrogen rate of 670 μmol h-1. This study sheds the light on the tunable semiconductor type of TiO2/RGO composite fabricated by solution mixing pathway and its merits to improve the photocatalytic activity.

  20. CoFe2O4-TiO2 and CoFe2O4-ZnO thin film nanostructures elaborated from colloidal chemistry and atomic layer deposition.

    PubMed

    Clavel, Guylhaine; Marichy, Catherine; Willinger, Marc-Georg; Ravaine, Serge; Zitoun, David; Pinna, Nicola

    2010-12-07

    CoFe(2)O(4)-TiO(2) and CoFe(2)O(4)-ZnO nanoparticles/film composites were prepared from directed assembly of colloidal CoFe(2)O(4) in a Langmuir-Blodgett monolayer and atomic layer deposition (ALD) of an oxide (TiO(2) or ZnO). The combination of these two methods permits the use of well-defined nanoparticles from colloidal chemistry, their assembly on a large scale, and the control over the interface between a ferrimagnetic material (CoFe(2)O(4)) and a semiconductor (TiO(2) or ZnO). Using this approach, architectures can be assembled with a precise control from the Angstrom scale (ALD) to the micrometer scale (Langmuir-Blodgett film). The resulting heterostructures present well-calibrated thicknesses. Electron microscopy and magnetic measurement studies give evidence that the size of the nanoparticles and their intrinsic magnetic properties are not altered by the various steps involved in the synthesis process. Therefore, the approach is suitable to obtain a layered composite with a quasi-monodisperse layer of ferrimagnetic nanoparticles embedded in an ultrathin film of semiconducting material.

  1. Density functional theory studies of TiO2 for photocatalysis and Li storage applications

    NASA Astrophysics Data System (ADS)

    Kim, Yong-Hoon; Lee, Ji Il; Lee, Dong Ki; Lee, Gyu Heon; Kang, Jeung Ku

    We present two theory-experiment collaboration studies of anatase TiO2 for energy applications. First, we discuss a hydrogen-nitrogen co-doped TiO2 (HN-TiO2) as a photocatalyst, and show that the interstitially introduced HN contributes to the increase of solar-to-fuel conversion efficiency. We find that the variation of valence band maximum (VBM) of NH-TiO2 extends the photoactive spectrum to the visible light, and argue that created mid-gap states produce efficient electron and hole conduction channels. Next, we consider experimentally fabricated hierarchical TiO2 nanocrystals integrated with binder-free porous graphene (PG) network foam for a Li storage application. It was found that the TiO2-PG facilitated rapid ionic transfer during the Li-ion insertion/extraction process. We clarify the mechanisms by showing that Li ion migration into the TiO2-PG interface stabilize the binder-free oxide-graphene interface. Atomistic mechanism of Li ion insertion and migration is discussed by comparing cases between an isolated Li ion, when the crowding effect is included, and when the surface Li ions are present. We found that the supply of additional surface Li ions significantly reduce the Li insertion barrier, driving a spontaneous domino-like concerted Li insertion at the oxide surface region.

  2. A Novel Green TiO2 Photocatalyst with a Surface Charge-Transfer Complex of Ti and Hydrazine Groups.

    PubMed

    Tian, Lihong; Xu, Jilian; Alnafisah, Abrar; Wang, Ran; Tan, Xinyu; Oyler, Nathan A; Liu, Lei; Chen, Xiaobo

    2017-04-19

    The optical property of TiO 2 plays an important role in its various and promising photocatalytic applications. Previous efforts in improving its optical properties include doping with various metal and/or non-metal elements, coupling with other colorful semiconductors or molecules, and hydrogenating to crystalline/disordered core/shell nanostructures. Here, we report a beautiful green TiO 2 achieved by forming the charge-transfer complex of colorless hydrazine groups and surface Ti 4+ , which extends the optical absorption into the near infrared region (≈1100 nm, 1.05 eV). It shows an enhanced photocatalytic performance in hydrogen generation under simulated sunlight, and degradation of organic pollution under visible light due to an impurity state (about 0.28 eV) resulting in fast electron-hole separation and injection of electrons from the ligand to the conduction band of TiO 2 . This study demonstrates an alternative approach to tune the optical, impurity state and photocatalytic properties of TiO 2 nanoparticles and we believe this will spur a wide interest in related materials and applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. TiO2 activity enhancement through synergistic effect of photons localization of photonic crystals and the sensitization of CdS quantum dots

    NASA Astrophysics Data System (ADS)

    Li, Ping; Wang, Yuan; Wang, Ai-Jun; Chen, Sheng-Li

    2017-02-01

    In this work, the enhancement of TiO2 photocatalytic activity was studied through synergistic effect of the photons localization of photonic crystals and the sensitization of CdS quantum dots (CdS QDs). CdS QDs sensitized TiO2 membrane (denoted as CdS QDs/TiO2) was synthesized through doping the TiO2 membrane with CdS QDs by chemical bath deposition method (CBD). After TiO2 was sensitized with CdS QDs, the edge of light absorption of TiO2 was red-shifted to 470 nm and the light absorption in the range of 400 600 nm was higher than that of plain TiO2 membrane. Another type of composite membrane, CdS QDs/TiO2/SiO2 opal composite membrane was prepared by coupling SiO2 opal (a kind of photonic crystal) layer onto the CdS QDs/TiO2 membrane, and the photonic band gap of the SiO2 opal photonic crystal layer was deliberately planned at the electronic band gap of the CdS QDs. The photodegradation of gaseous CH3CHO (acetaldehyde) was used as probe reaction to test the photocatalytic activity of the as-prepared membranes, and the results showed that the CdS QDs sensitization can significantly improve the photocatalytic activity of TiO2 membrane under visible light irradiation, with the acetaldehyde degradation rate constant (k) on CdS QDs/TiO2 membranes being 1.59 times of that on plain TiO2 membranes. The acetaldehyde degradation rate constant on CdS QDs/TiO2/SiO2 opal composite membrane reached 4 times of that on plain TiO2 membrane. The photocatalytic activity of TiO2 membrane can be improved through synergistic effect of the photons localization of photonic crystals and the sensitization of CdS QDs.

  4. Structural and Visible-Near Infrared Optical Properties of Cr-Doped TiO2 for Colored Cool Pigments

    NASA Astrophysics Data System (ADS)

    Yuan, Le; Weng, Xiaolong; Zhou, Ming; Zhang, Qingyong; Deng, Longjiang

    2017-11-01

    Chromium-doped TiO2 pigments were synthesized via a solid-state reaction method and studied with X-ray diffraction, SEM, XPS, and UV-VIS-NIR reflectance spectroscopy. The incorporation of Cr3+ accelerates the transition from the anatase phase to the rutile phase and compresses the crystal lattice. Moreover, the particle morphology, energy gap, and reflectance spectrum of Cr-doped TiO2 pigments is affected by the crystal structure and doping concentration. For the rutile samples, some of the Cr3+ ions are oxidized to Cr4+ after sintering at a high temperature, which leads to a strong near-infrared absorption band due to the 3A2 → 3 T1 electric dipole-allowed transitions of Cr4+. And the decrease of the band gap causes an obvious redshift of the optical absorption edges as the doping concentration increases. Thus, the VIS and near-infrared average reflectance of the rutile Ti1 - x Cr x O2 sample decrease by 60.2 and 58%, respectively, when the Cr content increases to x = 0.0375. Meanwhile, the color changes to black brown. However, for the anatase Ti1 - x Cr x O2 pigments, only the VIS reflection spectrum is inhibited by forming some characteristic visible light absorption peaks of Cr3+. The morphology, band gap, and NIR reflectance are not significantly affected. Finally, a Cr-doped anatase TiO2 pigment with a brownish-yellow color and 90% near-infrared reflectance can be obtained.

  5. Nanospherical like reduced graphene oxide decorated TiO2 nanoparticles: an advanced catalyst for the hydrogen evolution reaction

    PubMed Central

    Chen, Dejian; Zou, Liling; Li, Shunxing; Zheng, Fengying

    2016-01-01

    Modification of titanium dioxide (TiO2) for H2 generation is a grand challenge due to its high chemical inertness, large bandgap, narrow light-response range and rapid recombination of electrons and holes. Herein, we report a simple process to prepare nanospherical like reduced graphene oxide (NS-rGO) decorated TiO2 nanoparticles (NS-rGO/TiO2) as photocatalysts. This modified TiO2 sample exhibits remarkably significant improvement on visible light absorption, narrow band gap and efficient charge collection and separation. The photocatalytic H2 production rate of NS-rGO/TiO2 is high as 13996 μmol g−1 h−1, which exceeds that obtained on TiO2 alone and TiO2 with parallel graphene sheets by 3.45 and 3.05 times, respectively. This improvement is due to the presence of NS-rGO as an electron collector and transporter. The geometry of NS-rGO should be effective in the design of a graphene/TiO2 composite for photocatalytic applications. PMID:26828853

  6. Nanospherical like reduced graphene oxide decorated TiO2 nanoparticles: an advanced catalyst for the hydrogen evolution reaction.

    PubMed

    Chen, Dejian; Zou, Liling; Li, Shunxing; Zheng, Fengying

    2016-02-01

    Modification of titanium dioxide (TiO2) for H2 generation is a grand challenge due to its high chemical inertness, large bandgap, narrow light-response range and rapid recombination of electrons and holes. Herein, we report a simple process to prepare nanospherical like reduced graphene oxide (NS-rGO) decorated TiO2 nanoparticles (NS-rGO/TiO2) as photocatalysts. This modified TiO2 sample exhibits remarkably significant improvement on visible light absorption, narrow band gap and efficient charge collection and separation. The photocatalytic H2 production rate of NS-rGO/TiO2 is high as 13996 μmol g(-1) h(-1), which exceeds that obtained on TiO2 alone and TiO2 with parallel graphene sheets by 3.45 and 3.05 times, respectively. This improvement is due to the presence of NS-rGO as an electron collector and transporter. The geometry of NS-rGO should be effective in the design of a graphene/TiO2 composite for photocatalytic applications.

  7. Nanospherical like reduced graphene oxide decorated TiO2 nanoparticles: an advanced catalyst for the hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Chen, Dejian; Zou, Liling; Li, Shunxing; Zheng, Fengying

    2016-02-01

    Modification of titanium dioxide (TiO2) for H2 generation is a grand challenge due to its high chemical inertness, large bandgap, narrow light-response range and rapid recombination of electrons and holes. Herein, we report a simple process to prepare nanospherical like reduced graphene oxide (NS-rGO) decorated TiO2 nanoparticles (NS-rGO/TiO2) as photocatalysts. This modified TiO2 sample exhibits remarkably significant improvement on visible light absorption, narrow band gap and efficient charge collection and separation. The photocatalytic H2 production rate of NS-rGO/TiO2 is high as 13996 μmol g-1 h-1, which exceeds that obtained on TiO2 alone and TiO2 with parallel graphene sheets by 3.45 and 3.05 times, respectively. This improvement is due to the presence of NS-rGO as an electron collector and transporter. The geometry of NS-rGO should be effective in the design of a graphene/TiO2 composite for photocatalytic applications.

  8. How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

    PubMed

    Bachmeier, Andreas; Wang, Vincent C C; Woolerton, Thomas W; Bell, Sophie; Fontecilla-Camps, Juan C; Can, Mehmet; Ragsdale, Stephen W; Chaudhary, Yatendra S; Armstrong, Fraser A

    2013-10-09

    The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, show that the electronic state of the electrode strongly biases the direction of electrocatalysis of CO2/CO and H(+)/H2 interconversions. Attached to graphite electrodes, these enzymes show high activities for both oxidation and reduction, but there is a marked shift in bias, in favor of CO2 or H(+) reduction, when the respective enzymes are attached instead to n-type semiconductor electrodes constructed from CdS and TiO2 nanoparticles. This catalytic rectification effect can arise for a reversible electrocatalyst attached to a semiconductor electrode if the electrode transforms between semiconductor- and metallic-like behavior across the same narrow potential range (<0.25 V) that the electrocatalytic current switches between oxidation and reduction.

  9. Facile synthesis of hierarchical Ag3PO4/TiO2 nanofiber heterostructures with highly enhanced visible light photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Xie, Jinlei; Yang, Yefeng; He, Haiping; Cheng, Ding; Mao, Minmin; Jiang, Qinxu; Song, Lixin; Xiong, Jie

    2015-11-01

    Heterostructured semiconductor nanostructures have provoked great interest in the areas of energy, environment and catalysis. Herein, we report a novel hierarchical Ag3PO4/TiO2 heterostructure consisting of nearly spherical Ag3PO4 particles firmly coupled on the surface of TiO2 nanofibers (NFs). The construction of Ag3PO4/TiO2 heterostructure with tailored morphologies, compositions and optical properties was simply achieved via a facile and green synthetic strategy involving the electrospinning and solution-based processes. Owing to the synergetic effects of the components, the resulting hybrid heterostructures exhibited much improved visible light photocatalytic performance, which could degrade the RhB dye completely in 7.5 min. In addition, the coupling of Ag3PO4 particles with UV-light-sensitive TiO2 NFs enabled full utilization of solar energy and less consumption of noble metals, significantly appealing for their practical use in new energy sources and environmental issues. The developed synthetic strategy was considered to be applicable for the rational design and construction of other heterostructured catalysts.

  10. Self assembled sulfur induced interconnected nanostructure TiO2 electrode for visible light photoresponse and photocatalytic application

    NASA Astrophysics Data System (ADS)

    Anitha, B.; Ravidhas, C.; Venkatesh, R.; Raj, A. Moses Ezhil; Ravichandran, K.; Subramanian, B.; Sanjeeviraja, C.

    2017-07-01

    Pristine TiO2 and sulfur doped TiO2 (S-TiO2) thin films were coated over the glass substrates by varying the concentration of sulfur source (thiourea - 2, 4, 6, 8 and 10 at%) using a cost-effective Jet nebulizer spray technique. The deposited thin films were in anatase phase with the tetragonal structure analyzed from the XRD pattern. The chemical state of the elements was determined from XPS analysis. Pristine TiO2 and S-TiO2 thin films depict the presence of spherical particles embedded over 3-D interconnected wire-like structure from SEM analysis. Optical studies revealed reduction in band gap of S-TiO2 films on increasing the sulfur concentration (3.2-2.8 eV). The sulfur incorporation in TiO2 lattice confirmed by the fall in intensity of near band edge emission as observed from room temperature PL spectra. The charge carrier dynamics of the prepared thin films were studied by means of steady state and transient photoconduction measurements. The photocatalytic performance of pristine TiO2 and S-TiO2 thin films for the degradation of malachite green dye was investigated under visible light.

  11. Stability and rheology of dilute TiO2-water nanofluids

    PubMed Central

    2011-01-01

    The apparent wall slip (AWS) effect, accompanying the flow of colloidal dispersions in confined geometries, can be an important factor for the applications of nanofluids in heat transfer and microfluidics. In this study, a series of dilute TiO2 aqueous dispersions were prepared and tested for the possible presence of the AWS effect by means of a novel viscometric technique. The nanofluids, prepared from TiO2 rutile or anatase nanopowders by ultrasonic dispersing in water, were stabilized by adjusting the pH to the maximum zeta potential. The resulting stable nanofluid samples were dilute, below 0.7 vol.%. All the samples manifest Newtonian behavior with the fluidities almost unaffected by the presence of the dispersed phase. No case of important slip contribution was detected: the Navier slip coefficient of approximately 2 mm Pa-1 s-1 would affect the apparent fluidity data in a 100-μm gap by less than 1%. PMID:21711783

  12. Properties of Structurally Excellent N-doped TiO2 Rutile

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chambers, Scott A.; Cheung, Sau H.; Shutthanandan, V.

    2007-10-15

    We have used plasma-assisted molecular beam epitaxy to synthesize structurally near-perfect crystalline films of TiO2-xNx rutile for the first time. These materials allow the properties of TiO2-xNx to be elucidated without the interfering effects of oxygen vacancy defects. In the absence of such defects, the extent of N incorporation in the lattice is limited to 2 ± 1 at. % of the anions. Substitutional N (NO) exhibits a -3 formal charge due to charge transfer from shallow-donor interstitial Ti(III), which forms during epitaxial growth. Hybridization between NO and adjacent lattice Ti ions occurs, resulting in new states off the topmore » of the rutile valence band and an apparent band gap reduction of ~ 0.5 eV. It is not yet known if these new states result in mobile electron-hole pair creation upon irradiation, but experiments are planned to answer this important question.« less

  13. GeAs and SiAs monolayers: Novel 2D semiconductors with suitable band structures

    NASA Astrophysics Data System (ADS)

    Zhou, Liqin; Guo, Yu; Zhao, Jijun

    2018-01-01

    Two dimensional (2D) materials provide a versatile platform for nanoelectronics, optoelectronics and clean energy conversion. Based on first-principles calculations, we propose a novel kind of 2D materials - GeAs and SiAs monolayers and investigate their atomic structure, thermodynamic stability, and electronic properties. The calculations show that monolayer GeAs and SiAs sheets are energetically and dynamically stable. Their small interlayer cohesion energies (0.191 eV/atom for GeAs and 0.178 eV/atom for SiAs) suggest easy exfoliation from the bulk solids that exist in nature. As 2D semiconductors, GeAs and SiAs monolayers possess band gap of 2.06 eV and 2.50 eV from HSE06 calculations, respectively, while their band gap can be further engineered by the number of layers. The relatively small and anisotropic carrier effective masses imply fast electric transport in these 2D semiconductors. In particular, monolayer SiAs is a direct gap semiconductor and a potential photocatalyst for water splitting. These theoretical results shine light on utilization of monolayer or few-layer GeAs and SiAs materials for the next-generation 2D electronics and optoelectronics with high performance and satisfactory stability.

  14. Photocatalytic activity of TiO2/Nb2O5/PANI and TiO2/Nb2O5/RGO as new nanocomposites for degradation of organic pollutants.

    PubMed

    Zarrin, Saviz; Heshmatpour, Felora

    2018-06-05

    In this study, highly active titanium dioxide modified by niobium oxide (Nb 2 O 5 ), polymer (PANI) and reduced graphene oxide (RGO) were successfully prepared. The morphology, structure, surface area and light absorption properties of the present nanocomposites for removal of methylene blue (MB) and methyl orange (MO) were investigated and compared with those of TiO 2 /Nb 2 O 5 and TiO 2 nanoparticles. The characterization techniques such as XRD, FT-IR, UV-vis, SEM, EDX, BET and TEM were employed in order to identify the nanocomposites. Also, photocatalytic properties of TiO 2 /Nb 2 O 5 /PANI and TiO 2 /Nb 2 O 5 /RGO nanocomposites under visible light irradiation were studied. In this way, the obtained results were compared to each other and also compared to TiO 2 /Nb 2 O 5 and TiO 2 nanoparticles. In this context, the chemical oxygen demand (COD) removal follows the photodegradation in observed performance. The results indicate that reduced TiO 2 /Nb 2 O 5 nanocomposite is effectively modified by graphene oxide to give TiO 2 /Nb 2 O 5 /RGO composite. The TiO 2 /Nb 2 O 5 /RGO exhibits significantly higher photocatalytic activity in degradation of organic dyes under visible light rather than that of TiO 2 /Nb 2 O 5 /PANI, TiO 2 /Nb 2 O 5 and pure TiO 2 . Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Electric field changes on Au nanoparticles on semiconductor supports--the molecular voltmeter and other methods to observe adsorbate-induced charge-transfer effects in Au/TiO2 nanocatalysts.

    PubMed

    McEntee, Monica; Stevanovic, Ana; Tang, Wenjie; Neurock, Matthew; Yates, John T

    2015-02-11

    Infrared (IR) studies of Au/TiO2 catalyst particles indicate that charge transfer from van der Waals-bound donor or acceptor molecules on TiO2 to or from Au occurs via transport of charge carriers in the semiconductor TiO2 support. The ΔνCO on Au is shown to be proportional to the polarizability of the TiO2 support fully covered with donor or acceptor molecules, producing a proportional frequency shift in νCO. Charge transfer through TiO2 is associated with the population of electron trap sites in the bandgap of TiO2 and can be independently followed by changes in photoluminescence intensity and by shifts in the broad IR absorbance region for electron trap sites, which is also proportional to the polarizability of donors by IR excitation. Density functional theory calculations show that electron transfer from the donor molecules to TiO2 and to supported Au particles produces a negative charge on the Au, whereas the transfer from the Au particles to the TiO2 support into acceptor molecules results in a positive charge on the Au. These changes along with the magnitudes of the shifts are consistent with the Stark effect. A number of experiments show that the ∼3 nm Au particles act as "molecular voltmeters" in influencing ΔνCO. Insulator particles, such as SiO2, do not display electron-transfer effects to Au particles on their surface. These studies are preliminary to doping studies of semiconductor-oxide particles by metal ions which modify Lewis acid/base oxide properties and possibly strongly modify the electron-transfer and catalytic activity of supported metal catalyst particles.

  16. Study of concentration-dependent cobalt ion doping of TiO2 and TiO(2-x)Nx at the nanoscale.

    PubMed

    Gole, James L; Prokes, Sharka M; Glembocki, O J; Wang, Junwei; Qiu, Xiaofeng; Burda, Clemens

    2010-07-01

    Experiments with a porous sol-gel generated TiO(2) nanocolloid and its corresponding oxynitride TiO(2-x)N(x) are carried out to evaluate those transformations which accompany additional doping with transition metals. In this study, doping with cobalt (Co(ii)) ions is evaluated using a combination of core level and VB-photoelectron and optical spectroscopy, complementing data obtained from Raman spectroscopy. Raman spectroscopy suggests that cobalt doping of porous sol-gel generated anatase TiO(2) and nitridated TiO(2-x)N(x) introduces a spinel-like structure into the TiO(2) and TiO(2-x)N(x) lattices. TEM and XPS data complemented by valence band-photoelectron spectra demonstrate that metallic cobalt clusters are not formed even at high doping levels. As evidenced by Raman spectroscopy, the creation of a spinel-like structure is commensurate with the room temperature conversion of the oxide and its oxynitride from the anatase to the rutile form. The onset of this kinetically driven process correlates with the formation of spinel sites within the TiO(2) and TiO(2-x)N(x) particles. Despite their visible light absorption, the photocatalytic activity of these cobalt seeded systems is diminished relative to the oxynitride TiO(2-x)N(x).

  17. Acidic Peptizing Agent Effect on Anatase-Rutile Ratio and Photocatalytic Performance of TiO2 Nanoparticles

    NASA Astrophysics Data System (ADS)

    Mahmoud, Hatem A.; Narasimharao, Katabathini; Ali, Tarek T.; Khalil, Kamal M. S.

    2018-02-01

    TiO2 nanoparticles were synthesized from titanium isopropoxide by a simple peptization method using sulfuric, nitric, and acetic acids. The effect of peptizing acid on physicochemical and photocatalytic properties of TiO2 powders was studied. The structural properties of synthesized TiO2 powders were analyzed by using XRD, TEM, N2-physisorption, Raman, DR UV- vis, FTIR, and X-ray photoelectron spectroscopy techniques. The characterization results showed that acetic acid peptization facilitated the formation of pure anatase phase after thermal treatment at 500 °C; in contrast, nitric acid peptization led to a major rutile phase formation (67%). Interestingly, the sample peptized using sulfuric acid yielded 95% anatase and 5% rutile phases. The photocatalytic activity of synthesized TiO2 nanoparticles was evaluated for degradation of selected organic dyes (crystal violet, methylene blue, and p-nitrophenol) in aqueous solution. The results confirmed that the TiO2 sample peptized using nitric acid (with rutile and anatase phases in 3:1 ratio) offered the highest activity for degradation of organic dyes, although, TiO2 samples peptized using sulfuric acid and acetic acid possessed smaller particle size, higher band gap energy, and high surface area. Interestingly, TiO2 sample peptized with nitric acid possessed relatively high theoretical photocurrent density (0.545 mAcm-2) and pore diameter (150 Å), which are responsible for high electron-hole separation efficiency and diffusion and mass transportation of organic reactants during the photochemical degradation process. The superior activity of TiO2 sample peptized with nitric acid is due to the effective transfer of photogenerated electrons between rutile and anatase phases.

  18. Magnetic, electronic, optical, and photocatalytic properties of nonmetal- and halogen-doped anatase TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Fadlallah, M. M.

    2017-05-01

    The structure stability, magnetic, electronic, optical, and photocatalytic properties of nonmetal (B, C, N, P, and S), and halogen (F, Cl, Br, and I)-doped anatase TiO2 nanotubes (TNTs) have been investigated using spin polarized density functional theory. The N- and F-doped TNTs are the most stable among other doped TNTs. It is found that the magnetic moment of doped TNT is the difference between the number of the valence electrons of the dopant and host anion. All dopants decrease the band gap of TNT. The decrease in the band gap of nonmetal (C, N, P, and S)-doped TNTs, in particular N and P, is larger than that of halogen-doped TNTs due to the created states of the nonmetal dopant in the band gap. There is a good agreement between the calculation results and the experimental observations. Even though C-, N-, and P-doped TNTs have the lowest band gap, they cannot be used as a photocatalysis for water splitting. The B-, S-, and I-doped TiO2 nanotubes are of great potential as candidates for water splitting in the visible light range.

  19. Optical phonon effect in quasi-one-dimensional semiconductor quantum wires: Band-gap renormalization

    NASA Astrophysics Data System (ADS)

    Dan, Nguyen Trung; Bechstedt, F.

    1996-02-01

    We present theoretical studies of dynamical screening in quasi-one-dimensional semiconductor quantum wires including electron-electron and electron-LO-phonon interactions. Within the random-phase approximation we obtain analytical expressions for screened interaction potentials. These expressions can be used to calculate the band-gap renormalization of quantum wires, which depends on the free-carrier density and temperature. We find that the optical phonon interaction effect plays a significant role in band-gap renormalization of quantum wires. The numerical results are compared with some recent experiment measurements as well as available theories.

  20. Single-step One-pot Synthesis of TiO2 Nanosheets Doped with Sulfur on Reduced Graphene Oxide with Enhanced Photocatalytic Activity

    PubMed Central

    Wang, Weilin; Wang, Zhaofeng; Liu, Jingjing; Luo, Zhu; Suib, Steven L.; He, Peng; Ding, Guqiao; Zhang, Zhengguo; Sun, Luyi

    2017-01-01

    A hybrid photocatalyst based on anatase TiO2 was designed by doping TiO2 with sulfur and incorporating reduced graphene oxide (TiO2-S/rGO hybrid), with an aim to narrow the band gap to potentially make use of visible light and decrease the recombination of excitons, respectively. This TiO2-S/rGO hybrid was successfully synthesized using a one-pot hydrothermal method via single-step reaction. The structure and morphology of the TiO2-S/rGO hybrid catalyst was carefully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Its photocatalytic reactivity was evaluated by the degradation of methyl blue. The results showed that both the doping of sulfur and the introduction of rGO worked as designed, and the TiO2-S/rGO hybrid exhibited high photocatalytic activity under simulated sunlight. Considering both the facile and scalable reaction to synthesize TiO2-S/rGO hybrid, and its excellent photocatalytic performance, such TiO2-S/rGO hybrids are expect to find practical applications in environmental and energy sectors. PMID:28429736

  1. Single-step One-pot Synthesis of TiO2 Nanosheets Doped with Sulfur on Reduced Graphene Oxide with Enhanced Photocatalytic Activity.

    PubMed

    Wang, Weilin; Wang, Zhaofeng; Liu, Jingjing; Luo, Zhu; Suib, Steven L; He, Peng; Ding, Guqiao; Zhang, Zhengguo; Sun, Luyi

    2017-04-21

    A hybrid photocatalyst based on anatase TiO 2 was designed by doping TiO 2 with sulfur and incorporating reduced graphene oxide (TiO 2 -S/rGO hybrid), with an aim to narrow the band gap to potentially make use of visible light and decrease the recombination of excitons, respectively. This TiO 2 -S/rGO hybrid was successfully synthesized using a one-pot hydrothermal method via single-step reaction. The structure and morphology of the TiO 2 -S/rGO hybrid catalyst was carefully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Its photocatalytic reactivity was evaluated by the degradation of methyl blue. The results showed that both the doping of sulfur and the introduction of rGO worked as designed, and the TiO 2 -S/rGO hybrid exhibited high photocatalytic activity under simulated sunlight. Considering both the facile and scalable reaction to synthesize TiO 2 -S/rGO hybrid, and its excellent photocatalytic performance, such TiO 2 -S/rGO hybrids are expect to find practical applications in environmental and energy sectors.

  2. Single-step One-pot Synthesis of TiO2 Nanosheets Doped with Sulfur on Reduced Graphene Oxide with Enhanced Photocatalytic Activity

    NASA Astrophysics Data System (ADS)

    Wang, Weilin; Wang, Zhaofeng; Liu, Jingjing; Luo, Zhu; Suib, Steven L.; He, Peng; Ding, Guqiao; Zhang, Zhengguo; Sun, Luyi

    2017-04-01

    A hybrid photocatalyst based on anatase TiO2 was designed by doping TiO2 with sulfur and incorporating reduced graphene oxide (TiO2-S/rGO hybrid), with an aim to narrow the band gap to potentially make use of visible light and decrease the recombination of excitons, respectively. This TiO2-S/rGO hybrid was successfully synthesized using a one-pot hydrothermal method via single-step reaction. The structure and morphology of the TiO2-S/rGO hybrid catalyst was carefully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Its photocatalytic reactivity was evaluated by the degradation of methyl blue. The results showed that both the doping of sulfur and the introduction of rGO worked as designed, and the TiO2-S/rGO hybrid exhibited high photocatalytic activity under simulated sunlight. Considering both the facile and scalable reaction to synthesize TiO2-S/rGO hybrid, and its excellent photocatalytic performance, such TiO2-S/rGO hybrids are expect to find practical applications in environmental and energy sectors.

  3. Photo-electrochemical properties of graphene wrapped hierarchically branched nanostructures obtained through hydrothermally transformed TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Rambabu, Y.; Jaiswal, Manu; Roy, Somnath C.

    2017-10-01

    Hierarchically structured nanomaterials play an important role in both light absorption and separation of photo-generated charges. In the present study, hierarchically branched TiO2 nanostructures (HB-MLNTs) are obtained through hydrothermal transformation of electrochemically anodized TiO2 multi-leg nanotubes (MLNT) arrays. Photo-anodes based on HB-MLNTs demonstrated 5 fold increase in applied bias to photo-conversion efficiency (%ABPE) over that of TiO2 MLNTs without branches. Further, such nanostructures are wrapped with reduced graphene oxide (rGO) films to enhance the charge separation, which resulted in ∼6.5 times enhancement in %ABPE over that of bare MLNTs. We estimated charge transport (η tr) and charge transfer (η ct) efficiencies by analyzing the photo-current data. The ultra-fine nano branches grown on the MLNTs are effective in increasing light absorption through multiple scattering and improving charge transport/transfer efficiencies by enlarging semiconductor/electrolyte interface area. The charge transfer resistance, interfacial capacitance and electron decay time have been estimated through electrochemical impedance measurements which correlate with the results obtained from photocurrent measurements.

  4. Floating growth of large-scale freestanding TiO2 nanorod films at the gas-liquid interface for additive-free Li-ion battery applications.

    PubMed

    Xia, Hua-Rong; Li, Jia; Peng, Chen; Sun, Wen-Tao; Li, Long-Wei; Peng, Lian-Mao

    2014-10-22

    The floating growth process of large-scale freestanding TiO2 nanorod films at the gas-liquid interface was investigated. On the basis of the experiments, a self-templated growth scenario was developed to account for the self-assembly process. In the scenario, titanium complexes function not only as the Ti source for the growth of TiO2 but also as a soft template provider for the floating growth. According to the scenario, several new recipes of preparing freestanding TiO2 nanorod films at the gas-liquid interface were developed. The freestanding film was applied to a lithium ion battery as a binder-free and conducting agent-free anode, and good cyclability was obtained. This work may pave a new way to floating and freestanding TiO2 and other semiconductor materials, which has great potential not only in basic science but also in the applications such as materials engineering, Li-ion battery, photocatalyst, dye-sensitized solar cell, and flexible electronics.

  5. Fe doped TiO2 nanofibers on the surface of graphene sheets for photovoltaics applications

    NASA Astrophysics Data System (ADS)

    Farhangi, Nasrin; Medina-Gonzalez, Yaocihuatl; Charpentier, Paul A.

    2011-08-01

    Highly ordered, visible light driven TiO2 nanowire arrays doped with Fe photocatalysts were grown on the surface of functionalized graphene sheets (FGSs) using a sol-gel method with titanium isopropoxide (TIP) monomer, acetic acid (HAc) as the polycondensation agent and iron chloride in the green solvent, supercritical carbon dioxide (scCO2). The morphology of the synthesized materials was studied by SEM and TEM, which showed uniform formation of Fe doped TiO2 nanofibers on the surface of graphene sheets, which acted as a template for nanowire growth through surface -COOH functionalities. Increasing Fe content in the nanowires did not change the morphology significantly. Optical properties of the synthesized composites were examined by UV spectroscopy which showed a significant reduction in band gap with increasing Fe content, i.e. 2.25 eV at 0.6% Fe. The enhancement of the optical properties of synthesized materials was confirmed by photocurrent measurement. The optimum sample containing 0.6% Fe doped TiO2 on the graphene sheets increased the power conversation efficiency by 6-fold in comparison to TiO2 alone.

  6. Photocatalysis effect of nanometer TiO2 and TiO2-coated ceramic plate on Hepatitis B virus.

    PubMed

    Zan, Ling; Fa, Wenjun; Peng, Tianyou; Gong, Zhen-Kui

    2007-02-01

    The photocatalysis effect of nanometer TiO2 particles and TiO2-coated ceramic plate on Hepatitis B virus surface antigen (HBsAg) was investigated. The ELISA (enzyme-linked immunosorbent assay) standard method was used to assess the efficiency of TiO2 material to destroy the HBsAg. The research has shown that the suspension of TiO2 (0.5g/L) can destroy most of the HBsAg under the irradiation of mercury lamp, with the light intensity of 0.6mW/cm(2) at 365nm wavelength, or under the sunlight irradiation for a few hours. TiO2-coated ceramic plates can also destroy the HBsAg under the irradiation of mercury lamp, with the light intensity of 0.05mW/cm(2) at 365nm wavelength or under the room daylight for a few hours.

  7. Effect of annealing on the structural and optical properties of TiO2 powder prepared by sol-gel route

    NASA Astrophysics Data System (ADS)

    Halder, Nilanjan; Misra, Kamakhya Prakash

    2016-05-01

    Using titanium isopropoxide as the precursor, Titanium dioxide (TiO2) powder was synthesized via sol-gel method, a promising low temperature route for preparing nanosized metal oxide semiconductors with good homogeneity at low cost. The as-prepared nano powder was thermally treated in air at 550, 650, 750, 900 and 1100°C for 1hr after drying at room temperature and used for further characterization. X-ray diffraction measurements showed that the annealing treatment has a strong impact on the crystal phase of TiO2 samples. The crystallite size as calculated from Debye Scherer formula lies in the range 29-69 nm and is found to increase with increase in annealing temperature. Photoluminescence studies exhibit an improvement in the optical efficiency of the samples with post synthesis heat treatment. Annealing at temperature above 900°C results in a degradation of the structural and optical quality of the TiO2 nano powder samples.

  8. FOREWORD: Focus on Superconductivity in Semiconductors Focus on Superconductivity in Semiconductors

    NASA Astrophysics Data System (ADS)

    Takano, Yoshihiko

    2008-12-01

    Since the discovery of superconductivity in diamond, much attention has been given to the issue of superconductivity in semiconductors. Because diamond has a large band gap of 5.5 eV, it is called a wide-gap semiconductor. Upon heavy boron doping over 3×1020 cm-3, diamond becomes metallic and demonstrates superconductivity at temperatures below 11.4 K. This discovery implies that a semiconductor can become a superconductor upon carrier doping. Recently, superconductivity was also discovered in boron-doped silicon and SiC semiconductors. The number of superconducting semiconductors has increased. In 2008 an Fe-based superconductor was discovered in a research project on carrier doping in a LaCuSeO wide-gap semiconductor. This discovery enhanced research activities in the field of superconductivity, where many scientists place particular importance on superconductivity in semiconductors. This focus issue features a variety of topics on superconductivity in semiconductors selected from the 2nd International Workshop on Superconductivity in Diamond and Related Materials (IWSDRM2008), which was held at the National Institute for Materials Science (NIMS), Tsukuba, Japan in July 2008. The 1st workshop was held in 2005 and was published as a special issue in Science and Technology of Advanced Materials (STAM) in 2006 (Takano 2006 Sci. Technol. Adv. Mater. 7 S1). The selection of papers describe many important experimental and theoretical studies on superconductivity in semiconductors. Topics on boron-doped diamond include isotope effects (Ekimov et al) and the detailed structure of boron sites, and the relation between superconductivity and disorder induced by boron doping. Regarding other semiconductors, the superconducting properties of silicon and SiC (Kriener et al, Muranaka et al and Yanase et al) are discussed, and In2O3 (Makise et al) is presented as a new superconducting semiconductor. Iron-based superconductors are presented as a new series of high

  9. Enhanced photo-catalytic activity of Sr and Ag co-doped TiO2 nanoparticles for the degradation of Direct Green-6 and Reactive Blue-160 under UV & visible light.

    PubMed

    Naraginti, Saraschandra; Thejaswini, T V L; Prabhakaran, D; Sivakumar, A; Satyanarayana, V S V; Arun Prasad, A S

    2015-10-05

    This work is focused on sol-gel synthesis of silver and strontium co-doped TiO2 nanoparticles and their utilization as photo-catalysts in degradation of two textile dyes. Effect of pH, intensity of light, amount of photo-catalyst, concentration of dye, sensitizers, etc., were studied to optimize conditions for obtaining enhanced photo-catalytic activity of synthesized nanoparticles. XRD, BET, HR-TEM, EDAX and UV-Vis (diffused reflectance mode) techniques were used to characterize the nanoparticles. Interestingly, band gap of Sr and Ag co-doped TiO2 nanoparticles showed considerable narrowing (2.6 eV) when compared to Ag doped TiO2 (2.7 eV) and undoped TiO2 (3.17 eV) nanoparticles. Incorporation of Ag and Sr in the lattice of TiO2 could bring isolated energy levels near conduction and valence bands thus narrowing band gap. The XRD analysis shows that both Ag and Sr nanoparticles are finely dispersed on the surface of titania framework, without disturbing its crystalline structure. TEM images indicate that representative grain sizes of Ag-doped TiO2 & Sr and Ag co-doped TiO2 nanoparticles are in the range of 8-20 nm and 11-25 nm, respectively. Effective degradation of Direct Green-6 (DG-6) and Reactive Blue-160 (RB-160) under UV and visible light has been achieved using the photo-catalysts. Sr and Ag co-doped TiO2 photo-catalysts showed higher catalytic activity during degradation process in visible region when compared to Ag-doped and undoped TiO2 nanoparticles which could be attributed to the interactive effect caused by band gap narrowing and enhancement in charge separation. For confirming degradation of the dyes, total organic carbon (TOC) content was monitored periodically. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. The electrical conductivity and energy band gap of ‘bunga belimbing buluh’/tio2 nanocrystals as hybrid solar cell

    NASA Astrophysics Data System (ADS)

    Kamarulzaman, N. H.; Salleh, H.; Ghazali, M. S. M.; Ghazali, S. M.; Ahmad, Z.

    2018-05-01

    This research intends to explore the effect of thickness of inorganic titania nanocrystals (TiO2 NCs) materials and Averrhoe bilimbi’s flower towards the electrical conductivity. Averrhoe bilimbi’s flower or also known as ‘bunga belimbing buluh’ was used for the first time as a natural dye in hybrid solar cells. The performance of electrical conductivity can be improved in bilayer heterojunction hybrid solar cell (HCS). The TiO2 NCs was deposited on the ITO substrate using Electrochemistry method at room temperature. The dye extracted from Averrhoe bilimbi’s flower was deposited on the top of TiO2 NCs layered using the same method. The electrical conductivity can be recorded using Four Point Probe (FPP) under dark and light radiation (range of 0 Wm-2 to 200Wm-2). From the results, electrical conductivity was increased by the increment light intensity and suitable for further solar cell fabrications.

  11. Red shifts of the Eg(1) Raman mode of nanocrystalline TiO2:Er monoliths grown by sol-gel process

    NASA Astrophysics Data System (ADS)

    Palomino-Merino, R.; Trejo-Garcia, P.; Portillo-Moreno, O.; Jiménez-Sandoval, S.; Tomás, S. A.; Zelaya-Angel, O.; Lozada-Morales, R.; Castaño, V. M.

    2015-08-01

    Nanocrystalline monoliths of Er doped TiO2 were prepared by the sol-gel technique, by controlling the Er-doping levels into the TiO2 precursor solution. As-prepared and annealed in air samples showed the anatase TiO2 phase. The average diameter of the nanoparticles ranged from 19 to 2.6 nm as the nominal concentration of Er varies from 0% to 7%, as revealed by EDS analysis in an electron microscope. Photo Acoustic Spectroscopy (PAS) allowed calculate the forbidden band gap, evidencing an absorption edge at around 300 nm, attributed to TiO2 and evidence of electronic transitions or Er3+. The Raman spectra, corresponding to the anatase phase, show the main phonon mode Eg(1) band position at 144 cm-1 with a red shift for the annealing samples.

  12. Optical and structural properties of carbon dots/TiO2 nanostructures prepared via DC arc discharge in liquid

    NASA Astrophysics Data System (ADS)

    Biazar, Nooshin; Poursalehi, Reza; Delavari, Hamid

    2018-01-01

    Synthesis and development of visible active catalysts is an important issue in photocatalytic applications of nanomaterials. TiO2 nanostructures coupled with carbon dots demonstrate a considerable photocatalytic activity in visible wavelengths. Extending optical absorption of a wide band gap semiconductor such as TiO2 with carbon dots is the origin of the visible activity of carbon dots modified semiconductor nanostructures. In addition, carbon dots exhibit high photostability, appropriate electron transport and chemical stability without considerable toxicity or environmental footprints. In this study, optical and structural properties of carbon dots/TiO2 nanostructures prepared via (direct current) DC arc discharge in liquid were investigated. Crystal structure, morphology and optical properties of the samples were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-visible spectroscopy respectively. SEM images show formation of spherical nanoparticles with an average size of 27 nm. In comparison with pristine TiO2, optical transmission spectrum of carbon dots/TiO2 nanostructures demonstrates an absorption edge at longer wavelengths as well a high optical absorption in visible wavelengths which is significant for visible activity of nanostructures as a photocatalyst. Finally, these results can provide a flexible and versatile pathway for synthesis of carbon dots/oxide semiconductor nanostructures with an appropriate activity under visible light.

  13. Incorporation of indium in TiO2-based photoanodes for enhancing the photovoltaic conversion efficiency of dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Beula, R. Jeba; Devadason, Suganthi; Vidhya, B.

    2018-06-01

    Sol-gel-assisted spin-coating method was used to prepare TiO2 photoelectrodes doped with four different concentrations of indium 0.025, 0.05, 0.075 and 0.1 M. The crystalline phase and average crystallite size of the pure- and indium-doped TiO2 films were found using X-ray diffractometer. Raman analysis was performed for the pure- and In-doped TiO2 films to confirm the structure of anatase phase. UV-visible and photoluminescence spectrophotometer were used to analyze the optical properties of the films. A shift towards a lower wavelength in the absorption spectrum and widening of band gap were noted for the doped TiO2 films. Reduction in the peak intensity was observed in the PL spectra to indicate the inhibiting action of electron-hole recombination. A maximum (2.71%) light to current efficiency is noted for the dye-sensitized solar cells (DSSC) fabricated based on 0.025M In-doped TiO2 electrode.

  14. Niobium Doping Effects on TiO2 Mesoscopic Electron Transport Layer-Based Perovskite Solar Cells.

    PubMed

    Kim, Dong Hoe; Han, Gill Sang; Seong, Won Mo; Lee, Jin-Wook; Kim, Byeong Jo; Park, Nam-Gyu; Hong, Kug Sun; Lee, Sangwook; Jung, Hyun Suk

    2015-07-20

    Perovskite solar cells (PSCs) are the most promising candidates as next-generation solar energy conversion systems. To design a highly efficient PSC, understanding electronic properties of mesoporous metal oxides is essential. Herein, we explore the effect of Nb doping of TiO2 on electronic structure and photovoltaic properties of PSCs. Light Nb doping (0.5 and 1.0 at %) increased the optical band gap slightly, but heavy doping (5.0 at %) distinctively decreased it. The relative Fermi level position of the conduction band is similar for the lightly Nb-doped TiO2 (NTO) and the undoped TiO2 whereas that of the heavy doped NTO decreased by as much as ∼0.3 eV. The lightly doped NTO-based PSCs exhibit 10 % higher efficiency than PSCs based on undoped TiO2 (from 12.2 % to 13.4 %) and 52 % higher than the PSCs utilizing heavy doped NTO (from 8.8 % to 13.4 %), which is attributed to fast electron injection/transport and preserved electron lifetime, verified by transient photocurrent decay and impedance studies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Investigation of energy band alignments and interfacial properties of rutile NMO2/TiO2 (NM = Ru, Rh, Os, and Ir) by first-principles calculations.

    PubMed

    Yang, Chen; Zhao, Zong-Yan

    2017-11-08

    In the field of photocatalysis, constructing hetero-structures is an efficient strategy to improve quantum efficiency. However, a lattice mismatch often induces unfavorable interfacial states that can act as recombination centers for photo-generated electron-hole pairs. If the hetero-structure's components have the same crystal structure, this disadvantage can be easily avoided. Conversely, in the process of loading a noble metal co-catalyst onto the TiO 2 surface, a transition layer of noble metal oxides is often formed between the TiO 2 layer and the noble metal layer. In this article, interfacial properties of hetero-structures composed of a noble metal dioxide and TiO 2 with a rutile crystal structure have been systematically investigated using first-principles calculations. In particular, the Schottky barrier height, band bending, and energy band alignments are studied to provide evidence for practical applications. In all cases, no interfacial states exist in the forbidden band of TiO 2 , and the interfacial formation energy is very small. A strong internal electric field generated by interfacial electron transfer leads to an efficient separation of photo-generated carriers and band bending. Because of the differences in the atomic properties of the components, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures demonstrate band dividing, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures have a pseudo-gap near the Fermi energy level. Furthermore, NMO 2 /TiO 2 hetero-structures show upward band bending. Conversely, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures present a relatively strong infrared light absorption, while RhO 2 /TiO 2 and IrO 2 /TiO 2 hetero-structures show an obvious absorption edge in the visible light region. Overall, considering all aspects of their properties, RuO 2 /TiO 2 and OsO 2 /TiO 2 hetero-structures are more suitable than others for improving the photocatalytic performance of TiO 2 . These findings will provide useful information

  16. Raman study of TiO2 coatings modified by UV pulsed laser

    NASA Astrophysics Data System (ADS)

    Belka, Radosław; Keczkowska, Justyna; Sek, Piotr

    2016-12-01

    The TiO2 coatings were prepared by simple sol-gel method and modified by UV pulsed laser. TiO2, also know as titania, is a ceramic compound, existing in numerous polymorphic forms, mainly as tetragonal rutile and anatase, and rhomboidal brookite. Rutile is the most stable form of titanium dioxide, whereas anatase is a metastable form, created in lower temperatures than rutile. Anatase is marked with higher specific surface area, porosity and a higher number of surface hydroxyl groups as compared to rutile. The unique optical and electronic properties of TiO2 results in its use as semiconductors dielectric mirrors, sunscreen and UV-blocking pigments and especially as photocatalyst. In this paper, the tetraisopropoxide was used as Ti precursor according to sol-gel method. An organic base was applied during sol preparation. Prepared gel was coated on glass substrates and calcined in low temperature to obtain amorphous phase of titania. Prepared coatings were modified by UV picosecond pulse laser with different pulse repetition rate and pulse power. Physical modification of the coatings using laser pulses was intended in order change the phase content of the produced material. Raman spectroscopy (RS) method was applied to studies of modified coatings as it is one of the basic analytical techniques, supporting the identification of compounds and obtaining information about the structure. Especially, RS is a useful method for distinguishing the anatase and rutile phases. In these studies, anatase to rutile transformation was observed, depending on laser parameters.

  17. Preparation of TiO2-SiO2 via sol-gel method: Effect of Silica precursor on Catalytic and Photocatalytic properties

    NASA Astrophysics Data System (ADS)

    Fatimah, I.

    2017-02-01

    TiO2-SiO2have been synthesized by the sol-gel method from titanium isopropoxide and varied silica precursors: tetraethyl orthosilicate and tetra methyl ortho silicate. To study the effect of the precursor, prepared materials were characterized by X-ray diffraction, scanning electron microscopy, Diffuse Reflectance UV-vis optical absorption, and also gas sorption analysis. XRD patterns showed the formation of TiO2 anatase in the TiO2-SiO2 composite with different crystallite size from different silica precursor as well as the different surface morphology. The DRUV-vis absorption spectra exhibit similar band gap energy correspond to 3.21eV value while the surface area, pore volume and pore radius of the materials seems to be affected by the precursor. The higher specific surface area contributes to give the enhanced activity in phenol hydroxylation and methylene blue photodegradation.

  18. Solvothermal synthesis of hierarchical TiO2 nanostructures with tunable morphology and enhanced photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Fan, Zhenghua; Meng, Fanming; Zhang, Miao; Wu, Zhenyu; Sun, Zhaoqi; Li, Aixia

    2016-01-01

    This paper presents controllable growth and photocatalytic activity of TiO2 hierarchical nanostructures by solvothermal method at different temperatures. It is revealed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) that the morphology of TiO2 can be effectively controlled as rose-like, chrysanthemum-like and sea-urchin-like only changing solvothermal temperature. BET surface area analysis confirms the presence of a mesoporous network in all the nanostructures, and shows high surface area at relatively high temperature. The photocatalytic activities of the photocatalysts are evaluated by the photodegradation of RhB under UV light irradiation. The TiO2 samples exhibit high activity on the photodegradation of RhB, which is higher than that of the commercial P25. The enhancement in photocatalytic performance can be attributed to the synergetic effect of the surface area, crystallinity, band gap and crystalline size.

  19. Charge-transfer complex formation between TiO2 nanoparticles and thiosalicylic acid: A comprehensive experimental and DFT study

    NASA Astrophysics Data System (ADS)

    Milićević, Bojana; Đorđević, Vesna; Lončarević, Davor; Dostanić, Jasmina M.; Ahrenkiel, S. Phillip; Dramićanin, Miroslav D.; Sredojević, Dušan; Švrakić, Nenad M.; Nedeljković, Jovan M.

    2017-11-01

    Under normal conditions, titanium dioxide does not absorb visible light photons due to large band gap. Nevertheless, when titanium dioxide nanoparticles (TiO2 NPs) are surface-modified with thiosalicylic acid (TSA), their optical properties are altered owing to the formation of charge transfer complex that initiates absorption in the visible spectral range. Colloidal and sol-gel techniques were used to synthesize uniform TiO2 NPs of different sizes (average diameters in the range 4-15 nm), and effects of their subsequent modification by TSA molecules were compared with effect of modification of commercial Degussa TiO2 powder. Thorough microstructural characterization of TiO2 nanoparticulates was performed including transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis, as well as nitrogen adsorption-desorption isotherms. Optical measurements revealed that all surface-modified TiO2 samples with TSA have similar spectral features independent of their morphological differences, and, more importantly, absorption onset of modified TiO2 samples was found to be red-shifted by 1.0 eV compared to the unmodified ones. The mode of binding between TSA and surface Ti atoms was analyzed by infrared spectroscopy. Finally, the quantum chemical calculations, based on density functional theory, were performed to support optical characterization of surface-modified TiO2 with TSA.

  20. Anisotropic Metal Deposition on TiO2 Particles by Electric-Field-Induced Charge Separation.

    PubMed

    Tiewcharoen, Supakit; Warakulwit, Chompunuch; Lapeyre, Veronique; Garrigue, Patrick; Fourier, Lucas; Elissalde, Catherine; Buffière, Sonia; Legros, Philippe; Gayot, Marion; Limtrakul, Jumras; Kuhn, Alexander

    2017-09-11

    Deposition of metals on TiO 2 semiconductor particles (M-TiO 2 ) results in hybrid Janus objects combining the properties of both materials. One of the techniques proposed to generate Janus particles is bipolar electrochemistry (BPE). The concept can be applied in a straightforward way for the site-selective modification of conducting particles, but is much less obvious to use for semiconductors. Herein we report the bulk synthesis of anisotropic M-TiO 2 particles based on the synergy of BPE and photochemistry, allowing the intrinsic limitations, when they are used separately, to be overcome. When applying electric fields during irradiation, electrons and holes can be efficiently separated, thus breaking the symmetry of particles by modifying them selectively and in a wireless way on one side with either gold or platinum. Such hybrid materials are an important first step towards high-performance designer catalyst particles, for example for photosplitting of water. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Chemical modification of semiconductor surfaces

    NASA Technical Reports Server (NTRS)

    Finklea, H. O.

    1981-01-01

    Results of research on the chemical modification of TiO2 powders in the gas phase and the examination of the modified powders by infrared absorption spectroscopy are comprehensively summarized. The range of information obtainable by IR spectroscopy of chemically modified semiconductors, and a definition of the optimum reaction conditions for synthesizing a monolayer of methylsilanes using vapor phase reaction conditions were considered.

  2. Reduced TiO2-Graphene Oxide Heterostructure As Broad Spectrum-Driven Efficient Water-Splitting Photocatalysts.

    PubMed

    Li, Lihua; Yu, Lili; Lin, Zhaoyong; Yang, Guowei

    2016-04-06

    The reduced TiO2-graphene oxide heterostructure as an alternative broad spectrum-driven efficient water splitting photocatalyst has become a really interesting topic, however, its syntheses has many flaws, e.g., tedious experimental steps, time-consuming, small scale production, and requirement of various additives, for example, hydrazine hydrate is widely used as reductant to the reduction of graphene oxide, which is high toxicity and easy to cause the second pollution. For these issues, herein, we reported the synthesis of the reduced TiO2-graphene oxide heterostructure by a facile chemical reduction agent-free one-step laser ablation in liquid (LAL) method, which achieves extended optical response range from ultraviolet to visible and composites TiO(2-x) (reduced TiO2) nanoparticle and graphene oxide for promoting charge conducting. 30.64% Ti(3+) content in the reduced TiO2 nanoparticles induces the electronic reconstruction of TiO2, which results in 0.87 eV decrease of the band gap for the visible light absorption. TiO(2-x)-graphene oxide heterostructure achieved drastically increased photocatalytic H2 production rate, up to 23 times with respect to the blank experiment. Furthermore, a maximum H2 production rate was measured to be 16 mmol/h/g using Pt as a cocatalyst under the simulated sunlight irradiation (AM 1.5G, 135 mW/cm(2)), the quantum efficiencies were measured to be 5.15% for wavelength λ = 365 ± 10 nm and 1.84% for λ = 405 ± 10 nm, and overall solar energy conversion efficiency was measured to be 14.3%. These findings provided new insights into the broad applicability of this methodology for accessing fascinate photocatalysts.

  3. Photocatalytic activity of self-assembled porous TiO2 nano-columns array fabricated by oblique angle sputter deposition

    NASA Astrophysics Data System (ADS)

    Shi, Pengjun; Li, Xibo; Zhang, Qiuju; Yi, Zao; Luo, Jiangshan

    2018-04-01

    A well-separated and oriented TiO2 nano-columns arrays with porous structure were fabricated by the oblique angle sputter deposition technique and subsequently annealing at 450 °C in Ar/O2 mixed atmosphere. The deposited substrate was firstly modified by a template of self-assembled close-packed arrays of 500 nm-diameter silica (SiO2) spheres. Scanning electronic microscopic (SEM) images show that the porous columnar nanostructure is formed as a result of the geometric shadowing effect and surface diffusion of the adatoms in oblique angle deposition (OAD). X-ray diffraction (XRD) measurements reveal that the physically OAD film with annealing treatment are generally mixed phase of rutile and anatase TiO2 polymorphic forms. The morphology induced absorbance and band gap tuning by different substrates was demonstrated by the UV–vis spectroscopy. The well-separated one-dimensional (1D) nano-columns array with specific large porous surface area is beneficial for charge separation in photocatalytic degradation. Compared with compact thin film, such self-assembled porous TiO2 nano-columns array fabricated by oblique angle sputter deposition performed an enhanced visible light induced photocatalytic activity by decomposing methyl orange (MO) solution. The well-designed periodic array-structured porous TiO2 films by using modified patterned substrates has been demonstrated significantly increased absorption edge in the UV-visible light region with a narrower optical band gap, which are expected to be favorable for application in photovoltaic, lithium-ion insertion and photocatalytic, etc.

  4. Effects of various applied voltages on physical properties of TiO2 nanotubes by anodization method

    NASA Astrophysics Data System (ADS)

    Hoseinzadeh, T.; Ghorannevis, Z.; Ghoranneviss, M.; Sari, A. H.; Salem, M. K.

    2017-09-01

    Three steps anodization process is used to synthesize highly ordered and uniform multilayered titanium oxide (TiO2) nanotubes and effect of different anodization voltages are studied on their physical properties such as structural, morphological and optical. The crystalized structure of the synthesized tubes is investigated by X-ray diffractometer analysis. To study the morphology of the tubes, field emission scanning electron microscopy is used, which showed that the wall thicknesses and the diameters of the tubes are affected by the different anodization voltages. Moreover, optical studies performed by diffuse reflection spectra suggested that band gap of the TiO2 nanotubes are also changed by applying different anodization voltages. In this study using physical investigations, an optimum anodization voltage is obtained to synthesize the uniform crystalized TiO2 nanotubes with suitable diameter, wall thickness and optical properties.

  5. Engineering of band gap states of amorphous SiZnSnO semiconductor as a function of Si doping concentration.

    PubMed

    Choi, Jun Young; Heo, Keun; Cho, Kyung-Sang; Hwang, Sung Woo; Kim, Sangsig; Lee, Sang Yeol

    2016-11-04

    We investigated the band gap of SiZnSnO (SZTO) with different Si contents. Band gap engineering of SZTO is explained by the evolution of the electronic structure, such as changes in the band edge states and band gap. Using ultraviolet photoelectron spectroscopy (UPS), it was verified that Si atoms can modify the band gap of SZTO thin films. Carrier generation originating from oxygen vacancies can modify the band-gap states of oxide films with the addition of Si. Since it is not easy to directly derive changes in the band gap states of amorphous oxide semiconductors, no reports of the relationship between the Fermi energy level of oxide semiconductor and the device stability of oxide thin film transistors (TFTs) have been presented. The addition of Si can reduce the total density of trap states and change the band-gap properties. When 0.5 wt% Si was used to fabricate SZTO TFTs, they showed superior stability under negative bias temperature stress. We derived the band gap and Fermi energy level directly using data from UPS, Kelvin probe, and high-resolution electron energy loss spectroscopy analyses.

  6. Engineering of band gap states of amorphous SiZnSnO semiconductor as a function of Si doping concentration

    PubMed Central

    Choi, Jun Young; Heo, Keun; Cho, Kyung-Sang; Hwang, Sung Woo; Kim, Sangsig; Lee, Sang Yeol

    2016-01-01

    We investigated the band gap of SiZnSnO (SZTO) with different Si contents. Band gap engineering of SZTO is explained by the evolution of the electronic structure, such as changes in the band edge states and band gap. Using ultraviolet photoelectron spectroscopy (UPS), it was verified that Si atoms can modify the band gap of SZTO thin films. Carrier generation originating from oxygen vacancies can modify the band-gap states of oxide films with the addition of Si. Since it is not easy to directly derive changes in the band gap states of amorphous oxide semiconductors, no reports of the relationship between the Fermi energy level of oxide semiconductor and the device stability of oxide thin film transistors (TFTs) have been presented. The addition of Si can reduce the total density of trap states and change the band-gap properties. When 0.5 wt% Si was used to fabricate SZTO TFTs, they showed superior stability under negative bias temperature stress. We derived the band gap and Fermi energy level directly using data from UPS, Kelvin probe, and high-resolution electron energy loss spectroscopy analyses. PMID:27812035

  7. The Effect of the Electron Tunneling on the Photoelectric Hot Electrons Generation in Metallic-Semiconductor Nanostructures

    NASA Astrophysics Data System (ADS)

    Elsharif, Asma M.

    2018-01-01

    Semiconductor photonic crystals (MSPhC) were used to convert solar energy into hot electrons. An experimental model was designed by using metallic semiconductor photonic crystals (MSPhC). The designed MSPhC is based on TiO2/Au schottky contact. The model has similar nanocavity structure for broad gold absorption, but the materials on top of the cavity were changed to a metal and a semiconductor in order to collect the hot electrons. Detailed design steps and characterization have shown a broadband sub-bandgap photoresponse at a wavelength of 590 nm. This is due to the surface plasmon absorption by the wafer-scale Au/TiO2 metallic-semiconductor photonic crystal. Analytical calculation of the hot electron transport from the Au thin layer to the TiO2 conduction band is discussed. This theoretical study is based on the quantum tunneling effect. The photo generation of the hot electrons was undertaken at different wavelengths in Au absorber followed by tunneling through a schottky barrier into a TiO2 collector. The presence of a tunnel current from the absorber to the collector under illumination, offers a method to extract carriers from a hot-electron distribution at few bias voltages is presented in this study. The effects of doping different concentrations of the semiconductor on the evolution of the current characteristics were also investigated and discussed. The electrical characteristics were found to be sensitive to any change in the thickness of the barrier.

  8. Pure rotational spectra of TiO and TiO2 in VY Canis Majoris

    NASA Astrophysics Data System (ADS)

    Kamiński, T.; Gottlieb, C. A.; Menten, K. M.; Patel, N. A.; Young, K. H.; Brünken, S.; Müller, H. S. P.; McCarthy, M. C.; Winters, J. M.; Decin, L.

    2013-03-01

    We report the first detection of pure rotational transitions of TiO and TiO2 at (sub-)millimeter wavelengths towards the red supergiant VY CMa. A rotational temperature, Trot, of about 250 K was derived for TiO2. Although Trot was not well constrained for TiO, it is likely somewhat higher than that of TiO2. The detection of the Ti oxides confirms that they are formed in the circumstellar envelopes of cool oxygen-rich stars and may be the "seeds" of inorganic-dust formation, but alternative explanations for our observation of TiO and TiO2 in the cooler regions of the envelope cannot be ruled out at this time. The observations suggest that a significant fraction of the oxides is not converted to dust, but instead remains in the gas phase throughout the outflow. Based on observations carried out with the Submillimeter Array and IRAM Plateau de Bure Interferometer.Plateau de Bure data (FITS file) is only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/551/A113

  9. Penta-SiC5 monolayer: A novel quasi-planar indirect semiconductor with a tunable wide band gap

    NASA Astrophysics Data System (ADS)

    Naseri, Mosayeb

    2018-03-01

    In this paper, by using of the first principles calculations in the framework of the density functional theory, we systematically investigated the structure, stability, electronic and optical properties of a novel two-dimensional pentagonal monolayer semiconductors namely penta-SiC5 monolayer. Comparing elemental silicon, diamond, and previously reported 2D carbon allotropes, our calculation shows that the predicted penta-SiC5 monolayer has a metastable nature. The calculated results indicate that the predicted monolayer is an indirect semiconductor with a wide band gap of about 2.82 eV by using Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional level of theory which can be effectively tuned by external biaxial strains. The obtained exceptional electronic properties suggest penta-SiC5 monolayer as promising candidates for application in new electronic devices in nano scale.

  10. Development of a TiO2 modified optical fiber electrode and its incorporation into a photoelectrochemical reactor for wastewater treatment.

    PubMed

    Esquivel, K; Arriaga, L G; Rodríguez, F J; Martínez, L; Godínez, Luis A

    2009-08-01

    Electrochemical advanced oxidation processes (EAOPs) are used to chemically burn non biodegradable complex organic compounds that are present in polluted effluents. A common approach involves the use of TiO2 semiconductor substrates as either photocatalytic or photoelectrocatalytic materials in reactors that produce a powerful oxidant (hydroxyl radical) that reacts with pollutant species. In this context, the purpose of this work is to develop a new TiO2 based photoanode using an optic fiber support. The novel arrangement of a TiO2 layer positioned on top of a surface modified optical fiber substrate, allowed the construction of a photoelectrochemical reactor that works on the basis of an internally illuminated approach. In this way, a semi-conductive optical fiber modified surface was prepared using 30 microm thickness SnO2:Sb films on which the photoactive TiO2 layer was electrophoretically deposited. UV light transmission experiments were conducted to evaluate the transmittance along the optical fiber covered with SnO2:Sb and TiO2 showing that 43% of UV light reached the optical fiber tip. With different illumination configurations (external or internal), it was possible to get an increase in the amount of photo-generated H(2)O(2) close to 50% as compared to different types of TiO2 films. Finally, the electro-Fenton photoelectrocatalytic Oxidation process studied in this work was able to achieve total color removal of Azo orange II dye (15 mg L(-1)) and a 57% removal of total organic carbon (TOC) within 60 min of degradation time.

  11. High-resolution photoelectron spectroscopy of TiO3H2-: Probing the TiO2- + H2O dissociative adduct

    NASA Astrophysics Data System (ADS)

    DeVine, Jessalyn A.; Abou Taka, Ali; Babin, Mark C.; Weichman, Marissa L.; Hratchian, Hrant P.; Neumark, Daniel M.

    2018-06-01

    Slow electron velocity-map imaging spectroscopy of cryogenically cooled TiO3H2- anions is used to probe the simplest titania/water reaction, TiO20/- + H2O. The resultant spectra show vibrationally resolved structure assigned to detachment from the cis-dihydroxide TiO(OH)2- geometry based on density functional theory calculations, demonstrating that for the reaction of the anionic TiO2- monomer with a single water molecule, the dissociative adduct (where the water is split) is energetically preferred over a molecularly adsorbed geometry. This work represents a significant improvement in resolution over previous measurements, yielding an electron affinity of 1.2529(4) eV as well as several vibrational frequencies for neutral TiO(OH)2. The energy resolution of the current results combined with photoelectron angular distributions reveals Herzberg-Teller coupling-induced transitions to Franck-Condon forbidden vibrational levels of the neutral ground state. A comparison to the previously measured spectrum of bare TiO2- indicates that reaction with water stabilizes neutral TiO2 more than the anion, providing insight into the fundamental chemical interactions between titania and water.

  12. Phosphorous-doped TiO2 nanoparticles: synthesis, characterization, and visible photocatalytic evaluation on sulfamethazine degradation.

    PubMed

    Mendiola-Alvarez, Sandra Yadira; Hernández-Ramírez, Ma Aracely; Guzmán-Mar, Jorge Luis; Garza-Tovar, Lorena Leticia; Hinojosa-Reyes, Laura

    2018-05-24

    Mesoporous phosphorous-doped TiO 2 (TP) with different wt% of P (0.5, 1.0, and 1.5) was synthetized by microwave-assisted sol-gel method. The obtained materials were characterized by XRD with cell parameters refinement approach, Raman, BET-specific surface area analysis, SEM, ICP-OES, UV-Vis with diffuse reflectance, photoluminescence, FTIR, and XPS. The photocatalytic activity under visible light was evaluated on the degradation of sulfamethazine (SMTZ) at pH 8. The characterization of the phosphorous materials (TP) showed that incorporation of P in the lattice of TiO 2 stabilizes the anatase crystalline phase, even increasing the annealing temperature. The mesoporous P-doped materials showed higher surface area and lower average crystallite size, band gap, and particle size; besides, more intense bands attributed to O-H bond were observed by FTIR analysis compared with bare TiO 2 . The P was substitutionally incorporated in the TiO 2 lattice network as P 5+ replacing Ti 4+ to form Ti-O-P bonds and additionally present as PO 4 3-  on the TiO 2 surface. All these characteristics explain the observed superior photocatalytic activity on degradation (100%) and mineralization (32%) of SMTZ under visible radiation by TP catalysts, especially for P-doped TiO 2 1.0 wt% calcined at 450 °C (TP1.0-450). Ammonium, nitrate, and sulfate ions released during the photocatalytic degradation were quantified by ion chromatography; the nitrogen and sulfur mass balance evidenced the partial mineralization of this recalcitrant molecule.

  13. Single-step One-pot Synthesis of TiO 2 Nanosheets Doped with Sulfur on Reduced Graphene Oxide with Enhanced Photocatalytic Activity

    DOE PAGES

    Wang, Weilin; Wang, Zhaofeng; Liu, Jingjing; ...

    2017-04-21

    A hybrid photocatalyst based on anatase TiO 2 was designed by doping TiO 2 with sulfur and incorporating reduced graphene oxide (TiO 2-S/rGO hybrid), with an aim to narrow the band gap to potentially make use of visible light and decrease the recombination of excitons, respectively. This TiO 2-S/rGO hybrid was successfully synthesized using a one-pot hydrothermal method via single-step reaction. The structure and morphology of the TiO 2-S/rGO hybrid catalyst was carefully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Its photocatalytic reactivity was evaluated by the degradation ofmore » methyl blue. The results showed that both the doping of sulfur and the introduction of rGO worked as designed, and the TiO 2-S/rGO hybrid exhibited high photocatalytic activity under simulated sunlight. Finally, considering both the facile and scalable reaction to synthesize TiO 2-S/rGO hybrid, and its excellent photocatalytic performance, such TiO 2-S/rGO hybrids are expect to find practical applications in environmental and energy sectors.« less

  14. Thermal characteristics, Raman spectra, optical and structural properties of TiO2-Bi2O3-B2O3-TeO2 glasses

    NASA Astrophysics Data System (ADS)

    Gupta, Nupur; Khanna, Atul; Gonzàlez, Fernando; Iordanova, Reni

    2017-05-01

    Tellurite and borotellurite glasses containing Bi2O3 and TiO2 were prepared and structure-property correlations were carried out by density measurements, X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Raman and UV-visible spectroscopy. Titanium tellurite glasses require high melt-cooling rates and were fabricated by splat quenching. On adding B2O3, the glass forming ability (GFA) enhances, and glasses could be synthesized at lower quenching rates. The density of glasses shows a direct correlation with molecular mass of the constituents. UV-visible studies were used to determine the optical band gap and refractive index. Raman studies found that the co-ordination number of tellurium ions with oxygen (NTe-O) decreases with the increase in B2O3 as well as Bi2O3 content while, TiO2 produce only a small decrease in NTe-O, which explains the lower GFA of titanium tellurite glasses that do not contain Bi2O3 and B2O3. DSC studies show that the glass transition temperature (Tg) increases with B2O3 and TiO2 concentrations and that Tg correlates well with bond enthalpy of the metal oxides.

  15. Enhancement of Perovskite Solar Cells Efficiency using N-Doped TiO2 Nanorod Arrays as Electron Transfer Layer.

    PubMed

    Zhang, Zhen-Long; Li, Jun-Feng; Wang, Xiao-Li; Qin, Jian-Qiang; Shi, Wen-Jia; Liu, Yue-Feng; Gao, Hui-Ping; Mao, Yan-Li

    2017-12-01

    In this paper, N-doped TiO 2 (N-TiO 2 ) nanorod arrays were synthesized with hydrothermal method, and perovskite solar cells were fabricated using them as electron transfer layer. The solar cell performance was optimized by changing the N doping contents. The power conversion efficiency of solar cells based on N-TiO 2 with the N doping content of 1% (N/Ti, atomic ratio) has been achieved 11.1%, which was 14.7% higher than that of solar cells based on un-doped TiO 2 . To get an insight into the improvement, some investigations were performed. The structure was examined with X-ray powder diffraction (XRD), and morphology was examined by scanning electron microscopy (SEM). Energy dispersive spectrometer (EDS) and Tauc plot spectra indicated the incorporation of N in TiO 2 nanorods. Absorption spectra showed higher absorption of visible light for N-TiO 2 than un-doped TiO 2 . The N doping reduced the energy band gap from 3.03 to 2.74 eV. The photoluminescence (PL) and time-resolved photoluminescence (TRPL) spectra displayed the faster electron transfer from perovskite layer to N-TiO 2 than to un-doped TiO 2 . Electrochemical impedance spectroscopy (EIS) showed the smaller resistance of device based on N-TiO 2 than that on un-doped TiO 2 .

  16. Influence of immersion cycles during n-β-Bi2O3 sensitization on the photoelectrochemical behaviour of N-F-codoped TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Hoyos, Lina J.; Rivera, Diego F.; Gualdrón-Reyes, Andrés F.; Ospina, Rogelio; Rodríguez-Pereira, Jhonatan; Ropero-Vega, Jose L.; Niño-Gómez, Martha E.

    2017-11-01

    Sensitization of TiO2 nanotube (TNT)-based photoanodes with narrow-band gap semiconductors is an important alternative to improving the photoelectrochemical properties of the material. However, the interaction between the sensitizer and TNT is not understood deeply enough to relate charge carrier transport into the composite photoanode with its photoactivity. In this contribution, we studied the photoelectrochemical behaviour of N-F-self codoped TiO2 nanotubes (N-F-TNTs) that were grown by anodization of titanium plates and sensitized with β-Bi2O3 by immersing the TNTs into a Bi2O3 sol solution by dip-coating. The number of immersion cycles was varied. The as-fabricated photoanodes were characterized by FESEM, GIXRD, DRS and XPS, while their photoelectrochemical and semiconducting properties were investigated by photovoltammetry, electrochemical impedance spectroscopy and Mott-Schottky analysis in 0.1 M HClO4. The photoelectrocatalytic activity of the composite photoanodes was evaluated for glycerol oxidation under acidic and alkaline conditions. The N-F-TNTs exhibit a well-oriented structure after β-Bi2O3 deposition. The presence of substitutions of both N and F, identified by XPS, indicates the self-doping of the TNTs during anodization. The visible-light harvesting of the N-F-TNT photoanode was enhanced after three -immersion cycles during β-Bi2O3 sensitization, establishing an adequate n-n heterojunction at the N-F-TNT/Bi2O3 interface. In addition, bismuth migration from the sensitizer to the TNT lattice was promoted during thermal treatment, forming Bi-N-F-tridoping of TNT (Bi-N-F-TNT). The suitable band alignment between TNT and β-Bi2O3 and incorporation of the Bi3+ energy levels into TiO2 facilitate charge carrier separation and electron transport throughout the cell. Nevertheless, increasing the number of immersion cycles over three creates an excess of Bi3+ species at the N-F-TNT/β-Bi2O3 interface, producing an energetic barrier that hinders electron

  17. Structural, Electrical and Optical Properties of TiO2 Thin Film Deposited on the Nano Porous Silicon Template

    NASA Astrophysics Data System (ADS)

    Bahar, Mahmood; Dermani, Ensieh Khalili

    The porous silicon (PSi), which is produced by the electrochemical etching, has been used as a substrate for the growth of the titanium oxide (TiO2) thin films. By using the EBPVD method, TiO2 thin films have been deposited on the surface of the PSi substrate. TiO2/PSi layers were annealed at the temperature of 400∘C, 500∘C and 600∘C for different tests. The morphology and structures of layers were investigated by the scanning electron microscopy (SEM) and X-ray diffraction (XRD). The current-voltage characteristic curves of samples and the ideality factor of heterojunction were studied. The results showed that the electrical properties of the samples change with increase in the annealing temperature. The optical properties of the prepared samples were investigated by using UV-Vis and photoluminescence (PL) spectroscopy. Green light emission of the PSi combined with the blue light and violet-blue emission obtained from the TiO2/PSi PL spectra. The results showed that the optical band gap energy of the PSi has increased from 1.86eV to 2.93eV due to the deposition of TiO2 thin film.

  18. Investigation of the photocatalytic transformation of acesulfame K in the presence of different TiO2-based materials.

    PubMed

    López-Muňoz, M J; Daniele, A; Zorzi, M; Medana, C; Calza, P

    2018-02-01

    The photocatalytic transformation of acesulfame K - an artificial sweetener that has gained popularity over the last decades for being a calorie-free additive in food, beverages and several pharmaceutical products - was studied using three different photocatalysts, the benchmark TiO 2 -P25 and two other forms of synthetized titanium oxides named TiO 2 -SG1 and TiO 2 -SG2. The two latter materials were synthesized by a sol gel process in which the hydrolysis rate of titanium n-butoxide was controlled by the water formed in situ through an esterification reaction between ethanol and acetic acid. The investigation included monitoring the sweetener disappearance, identifying its intermediate compounds, assessing mineralization and evaluating toxicity. The analyses were carried out using high-performance liquid chromatography (HPLC) coupled with a LTQ-Orbitrap analyzer via an electrospray ionization (ESI) in the negative ion mode. This is a powerful tool for the identification, characterization and measurement of the transformation products (TPs); overall 13 species were identified. The use of several semiconductors has pointed out differences in terms of both photocatalytic efficiency and mechanism: the assessment of the evolution kinetics of each species (TPs, total organic carbon and inorganic ions) has brought to the elaboration of a general transformation pathway of acesulfame K. TiO 2 -SG2 proved to be the most efficient material in degrading the artificial sweetener and leads to the complete mineralization within 6 h of irradiation, while up to 16 h are required for TiO 2 -P25. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. TiO2 Nanoparticles Are Phototoxic to Marine Phytoplankton

    PubMed Central

    Miller, Robert J.; Bennett, Samuel; Keller, Arturo A.; Pease, Scott; Lenihan, Hunter S.

    2012-01-01

    Nanoparticulate titanium dioxide (TiO2) is highly photoactive, and its function as a photocatalyst drives much of the application demand for TiO2. Because TiO2 generates reactive oxygen species (ROS) when exposed to ultraviolet radiation (UVR), nanoparticulate TiO2 has been used in antibacterial coatings and wastewater disinfection, and has been investigated as an anti-cancer agent. Oxidative stress mediated by photoactive TiO2 is the likely mechanism of its toxicity, and experiments demonstrating cytotoxicity of TiO2 have used exposure to strong artificial sources of ultraviolet radiation (UVR). In vivo tests of TiO2 toxicity with aquatic organisms have typically shown low toxicity, and results across studies have been variable. No work has demonstrated that photoactivity causes environmental toxicity of TiO2 under natural levels of UVR. Here we show that relatively low levels of ultraviolet light, consistent with those found in nature, can induce toxicity of TiO2 nanoparticles to marine phytoplankton, the most important primary producers on Earth. No effect of TiO2 on phytoplankton was found in treatments where UV light was blocked. Under low intensity UVR, ROS in seawater increased with increasing nano-TiO2 concentration. These increases may lead to increased overall oxidative stress in seawater contaminated by TiO2, and cause decreased resiliency of marine ecosystems. Phototoxicity must be considered when evaluating environmental impacts of nanomaterials, many of which are photoactive. PMID:22276179

  20. Enhanced Dispersion of TiO2 Nanoparticles in a TiO2/PEDOT:PSS Hybrid Nanocomposite via Plasma-Liquid Interactions

    NASA Astrophysics Data System (ADS)

    Liu, Yazi; Sun, Dan; Askari, Sadegh; Patel, Jenish; Macias-Montero, Manuel; Mitra, Somak; Zhang, Richao; Lin, Wen-Feng; Mariotti, Davide; Maguire, Paul

    2015-10-01

    A facile method to synthesize a TiO2/PEDOT:PSS hybrid nanocomposite material in aqueous solution through direct current (DC) plasma processing at atmospheric pressure and room temperature has been demonstrated. The dispersion of the TiO2 nanoparticles is enhanced and TiO2/polymer hybrid nanoparticles with a distinct core shell structure have been obtained. Increased electrical conductivity was observed for the plasma treated TiO2/PEDOT:PSS nanocomposite. The improvement in nanocomposite properties is due to the enhanced dispersion and stability in liquid polymer of microplasma treated TiO2 nanoparticles. Both plasma induced surface charge and nanoparticle surface termination with specific plasma chemical species are proposed to provide an enhanced barrier to nanoparticle agglomeration and promote nanoparticle-polymer binding.

  1. Photo-Catalytic Properties of TiO2 Supported on MWCNTs, SBA-15 and Silica-Coated MWCNTs Nanocomposites.

    PubMed

    Ramoraswi, Nteseng O; Ndungu, Patrick G

    2015-12-01

    Mesoporous silica, specifically SBA-15, acid-treated multi-walled carbon nanotubes and a hybrid nanocomposite of SBA-15 coated onto the sidewalls acid-treated multi-walled carbon nanotubes (CNTs) were prepared and used as supports for anatase TiO2. Sol-gel methods were adapted for the synthesis of selected supports and for coating the materials with selected wt% loading of titania. Physical and chemical properties of the supports and catalyst composite materials were investigated by powder X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis, scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), UV-vis diffuse reflectance spectroscopy and fluorescence spectroscopy. The photo-activity of the catalyst composites were evaluated on the decolorisation of methylene blue as a model pollutant. Coating CNTs with SBA-15 improved the thermal stability and textural properties of the nanotubes. All supported titania composites had high surface areas (207-301 m(2)/g), altered band gap energies and reduced TiO2 crystallite sizes. The TiO2/SBA-CNT composite showed enhanced photo-catalytic properties and activity than the TiO2/SBA-15 and TiO2/CNT composites. In addition, an interesting observation was noted with the TiO2/SBA-15 nanocomposites, which had a significantly greater photo-catalytic activity than the TiO2/CNT nanocomposites in spite of the high electron-hole recombination phenomena observed with the photoluminescence results. Discussions in terms of morphological, textural and physical-chemical aspects to account for the result are presented.

  2. Photo-Catalytic Properties of TiO2 Supported on MWCNTs, SBA-15 and Silica-Coated MWCNTs Nanocomposites

    NASA Astrophysics Data System (ADS)

    Ramoraswi, Nteseng O.; Ndungu, Patrick G.

    2015-10-01

    Mesoporous silica, specifically SBA-15, acid-treated multi-walled carbon nanotubes and a hybrid nanocomposite of SBA-15 coated onto the sidewalls acid-treated multi-walled carbon nanotubes (CNTs) were prepared and used as supports for anatase TiO2. Sol-gel methods were adapted for the synthesis of selected supports and for coating the materials with selected wt% loading of titania. Physical and chemical properties of the supports and catalyst composite materials were investigated by powder X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis, scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM), UV-vis diffuse reflectance spectroscopy and fluorescence spectroscopy. The photo-activity of the catalyst composites were evaluated on the decolorisation of methylene blue as a model pollutant. Coating CNTs with SBA-15 improved the thermal stability and textural properties of the nanotubes. All supported titania composites had high surface areas (207-301 m2/g), altered band gap energies and reduced TiO2 crystallite sizes. The TiO2/SBA-CNT composite showed enhanced photo-catalytic properties and activity than the TiO2/SBA-15 and TiO2/CNT composites. In addition, an interesting observation was noted with the TiO2/SBA-15 nanocomposites, which had a significantly greater photo-catalytic activity than the TiO2/CNT nanocomposites in spite of the high electron-hole recombination phenomena observed with the photoluminescence results. Discussions in terms of morphological, textural and physical-chemical aspects to account for the result are presented.

  3. Atomic layer deposition TiO 2-Al 2O 3 stack: An improved gate dielectric on Ga-polar GaN metal oxide semiconductor capacitors

    DOE PAGES

    Wei, Daming; Edgar, James H.; Briggs, Dayrl P.; ...

    2014-10-15

    This research focuses on the benefits and properties of TiO 2-Al 2O 3 nano-stack thin films deposited on Ga 2O 3/GaN by plasma-assisted atomic layer deposition (PA-ALD) for gate dielectric development. This combination of materials achieved a high dielectric constant, a low leakage current, and a low interface trap density. Correlations were sought between the films’ structure, composition, and electrical properties. The gate dielectrics were approximately 15 nm thick and contained 5.1 nm TiO 2, 7.1 nm Al 2O 3 and 2 nm Ga 2O 3 as determined by spectroscopic ellipsometry. The interface carbon concentration, as measured by x-ray photoelectronmore » spectroscopy (XPS) depth profile, was negligible for GaN pretreated by thermal oxidation in O 2 for 30 minutes at 850°C. The RMS roughness slightly increased after thermal oxidation and remained the same after ALD of the nano-stack, as determined by atomic force microscopy. The dielectric constant of TiO 2-Al 2O 3 on Ga2O3/GaN was increased to 12.5 compared to that of pure Al 2O 3 (8~9) on GaN. In addition, the nano-stack's capacitance-voltage (C-V) hysteresis was small, with a total trap density of 8.74 × 10 11 cm -2. The gate leakage current density (J=2.81× 10 -8 A/cm 2) was low at +1 V gate bias. These results demonstrate the promising potential of plasma ALD deposited TiO 2/Al 2O 3 for serving as the gate oxide on Ga 2O 3/GaN based MOS devices.« less

  4. Atomic layer deposition TiO 2-Al 2O 3 stack: An improved gate dielectric on Ga-polar GaN metal oxide semiconductor capacitors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wei, Daming; Edgar, James H.; Briggs, Dayrl P.

    This research focuses on the benefits and properties of TiO 2-Al 2O 3 nano-stack thin films deposited on Ga 2O 3/GaN by plasma-assisted atomic layer deposition (PA-ALD) for gate dielectric development. This combination of materials achieved a high dielectric constant, a low leakage current, and a low interface trap density. Correlations were sought between the films’ structure, composition, and electrical properties. The gate dielectrics were approximately 15 nm thick and contained 5.1 nm TiO 2, 7.1 nm Al 2O 3 and 2 nm Ga 2O 3 as determined by spectroscopic ellipsometry. The interface carbon concentration, as measured by x-ray photoelectronmore » spectroscopy (XPS) depth profile, was negligible for GaN pretreated by thermal oxidation in O 2 for 30 minutes at 850°C. The RMS roughness slightly increased after thermal oxidation and remained the same after ALD of the nano-stack, as determined by atomic force microscopy. The dielectric constant of TiO 2-Al 2O 3 on Ga2O3/GaN was increased to 12.5 compared to that of pure Al 2O 3 (8~9) on GaN. In addition, the nano-stack's capacitance-voltage (C-V) hysteresis was small, with a total trap density of 8.74 × 10 11 cm -2. The gate leakage current density (J=2.81× 10 -8 A/cm 2) was low at +1 V gate bias. These results demonstrate the promising potential of plasma ALD deposited TiO 2/Al 2O 3 for serving as the gate oxide on Ga 2O 3/GaN based MOS devices.« less

  5. Hetero-Orientation Epitaxial Growth of TiO2 Splats on Polycrystalline TiO2 Substrate

    NASA Astrophysics Data System (ADS)

    Chen, Lin; Yang, Guan-Jun

    2018-05-01

    In the present study, the effect of titania (TiO2) substrate grain size and orientation on the epitaxial growth of TiO2 splat was investigated. Interestingly, the splat presented comparable grain size with that of substrate, indicating the hereditary feature of grain size. In addition, hetero- and homo-orientation epitaxial growth was observed at deposition temperatures below 400 °C and above 500 °C, respectively. The preferential growth of high-energy (001) face was also observed at low deposition temperatures (≤ 400 °C), which was found to result from dynamic nonequilibrium effect during the thermal spray deposition. Moreover, thermal spray deposition paves the way for a new approach to prepare high-energy (001) facets of TiO2 crystals.

  6. Effect of Cr3+ concentration on structural and optical properties of TiO2:Cr3+ anatase and rutile phases

    NASA Astrophysics Data System (ADS)

    Loan, Trinh Thi; Bang, Ngac An; Huong, Vu Hoang; Long, Nguyen Ngoc

    2017-07-01

    TiO2 powders doped with different amounts of Cr3+ions (from 0 to 10 mol%) have been prepared by hydrothermal technique. TiO2:Cr3+ powders were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, diffuse reflection, absorption, photoluminescence and photoluminescence excitation spectra. The results showed that the Cr3+ dopant concentrations did not affect on the lattice constants of TiO2 crystal, but affected on shift and broadening of the Raman modes for both anatase and rutile phases. The band gap of both the anatase and rutile TiO2 host lattice was strongly decreased with increasing Cr3+ dopant concentration. The photoluminescence spectra of TiO2:Cr3+ anatase phase exhibited a weak narrow peak (the so-called R-line) at 698 nm, meanwhile those of TiO2:Cr3+ rutile phase consisted of a very intense narrow zero-phonon R-line at 695 nm assigned to the 2E(2G) → 4A2(4F) transition of Cr3+ ions in strong octahedral field and its phonon-sidebands. In particular, in the PL spectrum of TiO2:Cr3+ rutile phase is also observed an abroad emission band centered at 813 nm assigned to the 4T2(4F) → 4A2(4F) transition of ions Cr3+ in weak octahedral field.

  7. Development of inorganic composite material based TiO2 for environmental application

    NASA Astrophysics Data System (ADS)

    Wahyuningsih, Sayekti; Handono Ramelan, Ari; Pramono, Edi; Purnawan, Candra; Anjani, Velina; Estianingsih, Puji; Rinawati, Ludfiaastu; Fadli, Khusnan

    2016-02-01

    Syntheses of various materials, for green energy nanotechnology applications have special attention to develop emerging areas, such as environmental as well as energy materials. Various approaches for preparing nanostructured photocatalysts, such as titanium dioxide, nickel oxide, lead oxide and their composites, was introduced. The use of nanomaterials as photocatalysts water detoxification by visible light photocatalyst of an inorganic composite as well as dye-sensitized photoreduction was also discussed. The enhancement of selective photocatalyst system was gain by the use of photocatalyst composite materials and applied potential bias on the system. The photoelectrocatalytic degradation of rhodamine B (RB) and Remazol Yellow FG (RY) as water contaminant using the thin film of modified TiO2 as the electrode was investigated via a series of potentials, and various pH. The result showed that the anodic potential bias influenced the degradation rate of water contaminant and exhibited better performance by the positive anodic bias was applied. The pH conditions influence the active dye structure whereas it will interact with inorganic semiconductor photocatalyst. Using dye- sensitized TiO2 system (DSTs), we have applied this system to build water decolorization as a novelty environmental remediation system.

  8. Gold nanoparticles-immobilized, hierarchically ordered, porous TiO2 nanotubes for biosensing of glutathione

    PubMed Central

    Mers, SV Sheen; Kumar, Elumalai Thambuswamy Deva; Ganesh, V

    2015-01-01

    Glutathione (GSH) is vital for several functions of our human body such as neutralization of free radicals and reactive oxygen compounds, maintaining the active forms of vitamin C and E, regulation of nitric oxide cycle, iron metabolism, etc. It is also an endogenous antioxidant in most of the biological reactions. Given the importance of GSH, a simple strategy is proposed in this work to develop a biosensor for quantitative detection of GSH. This particular biosensor comprises of gold nanoparticles (Au NPs)-immobilized, hierarchically ordered titanium dioxide (TiO2) porous nanotubes. Hexagonally arranged, honeycomb-like nanoporous tubular TiO2 electrodes are prepared by using a simple electrochemical anodization process by applying a constant potential of 30 V for 24 hours using ethylene glycol consisting of ammonium fluoride as an electrolytic medium. Structural morphology and crystalline nature of such TiO2 nanotubes are analyzed using field emission scanning electron microscope (FESEM) and X-ray diffraction (XRD). Interestingly, nanocomposites of TiO2 with Au NPs is prepared in an effort to alter the intrinsic properties of TiO2, especially tuning of its band gap. Au NPs are prepared by a well-known Brust and Schiffrin method and are immobilized onto TiO2 electrodes which act as a perfect electrochemical sensing platform for GSH detection. Structural characterization and analysis of these modified electrodes are performed using FESEM, XRD, and UV-visible spectroscopic studies. GSH binding events on Au NPs-immobilized porous TiO2 electrodes are monitored by electrochemical techniques, namely, cyclic voltammetry (CV) and chronoamperometry (CA). Several parameters such as sensitivity, selectivity, stability, limit of detection, etc are investigated. In addition, Au NPs dispersed in aqueous medium are also explored for naked-eye detection of GSH using UV-visible spectroscopy in order to compare the performance of the proposed sensor. Our studies clearly indicate

  9. Sandwich-like TiO2@ZnO-based noble metal (Ag, Au, Pt, or Pd) for better photo-oxidation performance: Synergistic effect between noble metal and metal oxide phases

    NASA Astrophysics Data System (ADS)

    Li, Shunxing; Cai, Jiabai; Wu, Xueqing; Zheng, Fengying

    2018-06-01

    The performance of different noble metals (NMs) with controllable size (5 nm) as co-catalyst on the photocatalytic oxidation of TiO2@ZnO hollow spheres was tested with benzyl alcohol in the presence of water under ambient conditions. A new type of solar-light-driven TiO2@NMs@ZnO nanocomposite was fabricated by using a template (surface functionalized polystyrene balls), hydrothermal reaction, and calcination. Under simulated sunlight irradiation, the photo-oxidation rate of benzyl alcohol was in the following of TiO2@Ag@ZnO > TiO2@Au@ZnO > TiO2@Pt@ZnO > TiO2@Pd@ZnO > TiO2@ZnO. This result was due to the combination of TiO2 and ZnO, as well as the sandwiched Ag NPs as electron trap site, which can store and shuttle photo-generated electrons, and then enhance photo-generation of active radicals. Electron paramagnetic resonance (EPR) spectroscopy, as well as photo-luminescence (PL), photo-reduction of Cr(VI) and electrochemical measurements were taken to verify this conclusion. Taking into account the multi-functional combination of precious metals and semiconductor materials, this work could provide new insights for the design of high-performance photocatalysts.

  10. Exchange of TiO2 nanoparticles between streams and streambeds.

    PubMed

    Boncagni, Natalia Ticiana; Otaegui, Justo Manuel; Warner, Evelyn; Curran, Trisha; Ren, Jianhong; de Cortalezzi, Maria Marta Fidalgo

    2009-10-15

    The expanding use of manufactured nanoparticles has increased the potential for their release into the natural environment. Particularly, TiO2 nanoparticles pose significant exposure risk to humans and other living species due to their extensive use in a wide range of fields. To better understand the environmental and health risks associated with the release of TiO2 nanoparticles, knowledge on their fate and transport is needed. This study evaluates the transport of two different TiO2 nanoparticles: one commercially available (P25 TiO2 and the other synthesized at a lab scale (synthesized TiO2). Laboratory flume, column, and batch experiments were conducted to investigate the processes dominating the transport of TiO2 nanoparticles between streams and streambeds and to characterize the properties of these nanoparticles under different physicochemical conditions. Results show that the synthesized TiO2 was more stable compared to the P25 TiO2, which underwent significant aggregation under the same experimental conditions. As a result, P25 TiO2 deposited at a faster rate than the synthesized TiO2 in the streambed. Both types of TiO2 nanoparticles deposited in the streambed were easily released when the stream velocity was increased. The aggregation and deposition of P25 TiO2 were highly dependent on pH. A process-based colloid exchange model was applied to interpret the observed transport behavior of the TiO2 nanoparticles.

  11. Influence of Iron Doping on Structural, Optical and Magnetic Properties of TiO2 Nanoparticles

    NASA Astrophysics Data System (ADS)

    Zahid, R.; Manzoor, M.; Rafiq, A.; Ikram, M.; Nafees, M.; Butt, A. R.; Hussain, S. G.; Ali, S.

    2018-05-01

    In this study, various concentrations of Fe doped TiO2 nanoparticles have been successfully synthesized using the sol-gel method. A variety of characterization techniques as ultra-violet visible (UV-Vis) spectroscopy, X-ray diffractometer (XRD), vibrating sample magnetometry (VSM) and field emission scanning electron microscopy (FESEM) were employed to analyze the prepared nanopowders. XRD measurement confirmed the substitution of Fe ion without disturbing the tetragonal crystal system of TiO2. The crystallite size was found to decrease and lattice strain increases upon doping estimated by Williamson Hall plot. Furthermore, the average grain size calculated by FESEM found was between 10 and 30 nm for pure and doped TiO2. UV-Vis spectroscopy showed an increase in absorption accompanied red shift and increase in band gap energies from 3.36 to 3.62 eV with the addition of Fe. The FTIR spectroscopy was employed to confirm the presence of functional groups in the fabricated nanopowders. Upon mixing the saturation magnetization (Ms) varying from (2.12 to 1.51)10-2 emu/g was observed.

  12. Photodecolorisation of melanoidins in vinasse with illuminated TiO2-ZnO/activated carbon composite.

    PubMed

    Otieno, Benton O; Apollo, Seth O; Naidoo, Bobby E; Ochieng, Aoyi

    2017-06-07

    A hybrid photo-catalyst, TiO 2 -ZnO, was synthesized by immobilizing ZnO on commercial TiO 2 (aeroxide P25). Activated carbon (AC) was subsequently used to support the hybrid, thus forming a TiO 2 -ZnO/AC composite catalyst. Fourier transform infrared (FTIR) analysis and scanning electron microscopy integrated with energy-dispersive X-ray spectroscopy (SEM-EDX) investigations revealed successful catalyst synthesis. Optical properties of the hybrid determined from photoluminescence (PL) and Ultraviolet-visible (UV-vis) spectroscopy confirmed a restrained recombination of electron-hole pairs and reduced energy band gap due to a successful heterojunction formation. The prepared catalysts were used to photodecolorise vinasse in a 12-W UVC batch photoreactor. TiO 2 -ZnO had improved photocatalytic activity compared with TiO 2 and ZnO separately. On supporting the hybrid onto AC, both adsorption and photocatalytic activities were further enhanced with improved overall color removal of 86% from 68%. Photodecolorisation followed the pseudo-first-order reaction model with the rate constant ([Formula: see text]) observed decreasing from 0.0701 to 0.0436 min -1 on increasing the initial concentration from 5,000 to 14,000 ppm. The UV process was found to be 33-fold less energy intensive for color reduction as compared to total organic carbon (TOC) reduction. Formation of nitrates during the photodecolorisation process was attributed to the mineralization of nitrogen heteroatoms in the color-causing melanoidin compounds.

  13. Computational study of TiO2 Brookite (100), (010) and (210) surface doped with Ruthenium for application in Dye Sensitised Solar Cells

    NASA Astrophysics Data System (ADS)

    Dima, R. S.; Maluta, N. E.; Maphanga, R. R.; Sankaran, V.

    2017-10-01

    Titanium dioxide (TiO2) polymorphs are widely used in many energy-related applications due to their peculiar electronic and physicochemical properties. The electronic structures of brookite TiO2 surfaces doped with transition metal ruthenium have been investigated by ab initio band calculations based on the density functional theory with the planewave ultrasoft pseudopotential method. The generalized gradient approximation (GGA) was used in the scheme of Perdew-Burke-Ernzerhof (PBE) to describe the exchange-correlation functional. All calculations were carried out with CASTEP (Cambridge Sequential Total EnergyPackage) code in Materials Studio of Accelrys Inc. The surface structures of Ru doped TiO2 were constructed by cleaving the 1 × 1 × 1 optimized bulk structure of brookite TiO2. The results indicate that Ru doping can narrow the band gap of TiO2, leading to the improvement in the photoreactivity of TiO2, and simultaneously maintain strong redox potential. The theoretical calculations could provide meaningful guide to develop more active photocatalysts with visible light response.

  14. Evidence for Itinerant Carriers in an Anisotropic Narrow-Gap Semiconductor by Angle-Resolved Photoemission Spectroscopy.

    PubMed

    Ju, Sailong; Bai, Wei; Wu, Liming; Lin, Hua; Xiao, Chong; Cui, Shengtao; Li, Zhou; Kong, Shuai; Liu, Yi; Liu, Dayong; Zhang, Guobin; Sun, Zhe; Xie, Yi

    2018-01-01

    The ability to accurately determine the electronic structure of solids has become a key prerequisite for modern functional materials. For example, the precise determination of the electronic structure helps to balance the three thermoelectric parameters, which is the biggest challenge to design high-performance thermoelectric materials. Herein, by high-resolution, angle-resolved photoemission spectroscopy (ARPES), the itinerant carriers in CsBi 4 Te 6 (CBT) are revealed for the first time. CBT is a typical anisotropic, narrow-gap semiconductor used as a practical candidate for low-temperature thermoelectric applications, and p-doped CBT series show superconductivity at relatively low carrier concentrations. The ARPES results show a significantly larger bandwidth near the Fermi surface than calculations, which means the carriers transport anisotropically and itinerantly in CBT. It is reasonable to believe that these newly discovered features of carriers in narrow-gap semiconductors are promising for designing optimal thermoelectric materials and superconductors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Enhanced performance of perovskite solar cells by ultraviolet-ozone treatment of mesoporous TiO2

    NASA Astrophysics Data System (ADS)

    Wang, Zengze; Fang, Jin; Mi, Yang; Zhu, Xiaoyang; Ren, He; Liu, Xinfeng; Yan, Yong

    2018-04-01

    The performance of a semiconductor electronic or photonic device depends greatly on the properties of the interface. In a typical perovskite solar cell (PSC), the interface between electron transport layer (ETL) and perovskites is found to significantly influence the power conversion efficiency (PCE). Herein, Ultraviolet-ozone (UVO) treatment, a technique commonly used to clean a device substrate, is applied on ETL, specially, mesoporous/compact TiO2 layer. This treatment increases the conductivity of ETL and removes the residual organics at the surface. Consequently, an improved interface between mesoporous TiO2 and perovskite is achieved to enhance the performance of PSC. For example, the fill factor (FF) increases by ∼13%, the short-circuit current density (Jsc) and open-circuit voltage (Voc) increase by ∼2%, and the PCE finally enhances by ∼20% with 15 min of UVO treatment. With this method, the PCE of the best cell reaches to 20.43% under the illumination of AM 1.5 (100 mW cm-2) simulated sunlight.

  16. Preparation and Use of Photocatalytically Active Segmented Ag|ZnO and Coaxial TiO2-Ag Nanowires Made by Templated Electrodeposition

    PubMed Central

    Maijenburg, A. Wouter; Rodijk, Eddy J.B.; Maas, Michiel G.; ten Elshof, Johan E.

    2014-01-01

    Photocatalytically active nanostructures require a large specific surface area with the presence of many catalytically active sites for the oxidation and reduction half reactions, and fast electron (hole) diffusion and charge separation. Nanowires present suitable architectures to meet these requirements. Axially segmented Ag|ZnO and radially segmented (coaxial) TiO2-Ag nanowires with a diameter of 200 nm and a length of 6-20 µm were made by templated electrodeposition within the pores of polycarbonate track-etched (PCTE) or anodized aluminum oxide (AAO) membranes, respectively. In the photocatalytic experiments, the ZnO and TiO2 phases acted as photoanodes, and Ag as cathode. No external circuit is needed to connect both electrodes, which is a key advantage over conventional photo-electrochemical cells. For making segmented Ag|ZnO nanowires, the Ag salt electrolyte was replaced after formation of the Ag segment to form a ZnO segment attached to the Ag segment. For making coaxial TiO2-Ag nanowires, a TiO2 gel was first formed by the electrochemically induced sol-gel method. Drying and thermal annealing of the as-formed TiO2 gel resulted in the formation of crystalline TiO2 nanotubes. A subsequent Ag electrodeposition step inside the TiO2 nanotubes resulted in formation of coaxial TiO2-Ag nanowires. Due to the combination of an n-type semiconductor (ZnO or TiO2) and a metal (Ag) within the same nanowire, a Schottky barrier was created at the interface between the phases. To demonstrate the photocatalytic activity of these nanowires, the Ag|ZnO nanowires were used in a photocatalytic experiment in which H2 gas was detected upon UV illumination of the nanowires dispersed in a methanol/water mixture. After 17 min of illumination, approximately 0.2 vol% H2 gas was detected from a suspension of ~0.1 g of Ag|ZnO nanowires in a 50 ml 80 vol% aqueous methanol solution. PMID:24837535

  17. Dry-spray deposition of TiO2 for a flexible dye-sensitized solar cell (DSSC) using a nanoparticle deposition system (NPDS).

    PubMed

    Kim, Min-Saeng; Chun, Doo-Man; Choi, Jung-Oh; Lee, Jong-Cheon; Kim, Yang Hee; Kim, Kwang-Su; Lee, Caroline Sunyong; Ahn, Sung-Hoon

    2012-04-01

    TiO2 powders were deposited on indium tin oxide (ITO) coated polyethylene terephthalate (PET) substrates for application to the photoelectrode of a dye-sensitized solar cell (DSSC). In the conventional DSSC manufacturing process, a semiconductor oxide such as TiO2 powder requires a sintering process at higher temperature than the glass transition temperature (T(g)) of polymers, and thus utilization of flexible polymer substrates in DSSC research has been constrained. To overcome this restriction related to sintering, we used a nanoparticle deposition system (NPDS) that could produce a thin coating layer through a dry-spray method under atmospheric pressure at room temperature. The powder was sprayed through a slit-type nozzle having a 0.4 x 10 mm2 rectangular outlet. In order to determine the deposited TiO2 thickness, five kinds of TiO2 layered specimens were prepared, where the specimens have single and double layer structures. Deposited powders on the ITO coated PET substrates were observed using FE-SEM and a scan profiler The thicker TiO2 photoelectrode with a DSSC having a double layer structure showed higher energy efficiency than the single layer case. The highest fabricated flexible DSSC displayed a short circuit current density J(sc) = 1.99 mA cm(-2), open circuit voltage V(oc) = 0.71 V, and energy efficiency eta = 0.94%. These results demonstrate the possibility of utilizing the dry-spray method to fabricate a TiO2 layer on flexible polymer substrates at room temperature under atmospheric pressure.

  18. Electronic properties of Cr-N codoped rutile TiO2(110) thin films

    NASA Astrophysics Data System (ADS)

    Cheng, Zhengwang; Zhang, Lili; Dong, Shihui; Ma, Xiaochuan; Ju, Huanxin; Zhu, Junfa; Cui, Xuefeng; Zhao, Jin; Wang, Bing

    2017-12-01

    We report our investigation on the electronic properties of Cr-N codoped rutile TiO2(110) single crystal thin films, homoepitaxially grown by pulsed-laser-deposition method, and characterized using scanning tunneling microscopy and spectroscopy (STM/STS), X-ray/ultraviolet photoemission spectroscopy (XPS/UPS), in combination with first-principles calculations. Our results show that the bandgap reduction of the TiO2(110) surface is mainly contributed by the delocalized states whose position is at 2.0 eV below the Fermi level, introduced by the substitutional codoped Cr-2N pair, which is evidenced by the accordance of the results between the STS spectra and the calculated DOS. The codoped Cr-N pair contributes the gap state at about 0.8 eV below the Fermi level, in consistent with the theoretical calculations. While, the monodoped Cr contributes the states either close to the valence band maximum or the conduction band minimum, which should not contribute to the bandgap reduction too much. Our experimental results joint with theoretical calculations provide an atomic view of the bandgap reduction of the rutile TiO2(110) surface, which indicates that the excess substitutional N atoms should be important to efficiently narrow the bandgap by introducing the Cr-2N pairs.

  19. Universal features underlying the magnetism in diluted magnetic semiconductors

    NASA Astrophysics Data System (ADS)

    Andriotis, Antonis N.; Menon, Madhu

    2018-04-01

    Investigation of a diverse variety of wide band gap semiconductors and metal oxides that exhibit magnetism on substitutional doping has revealed the existence of universal features that relate the magnetic moment of the dopant to a number of physical properties inherent to the dopants and the hosts. The investigated materials consist of ZnO, GaN, GaP, TiO2, SnO2, Sn3N4, MoS2, ZnS and CdS doped with 3d-transition metal atoms. The primary physical properties contributing to magnetism include the orbital hybridization and charge distribution, the d-band filling, d-band center, crystal field splitting, electron pairing energy and electronegativity. These features specify the strength of the spin-polarization induced by the dopants on their first nearest neighboring anions which in turn specify the long range magnetic coupling among the dopants through successively induced spin polarizations (SSP) on neighboring dopants. The proposed local SSP process for the establishment of the magnetic coupling among the TM-dopants appears as a competitor to other classical processes (superexchange, double exchange, etc). Furthermore, these properties can be used as a set of descriptors suitable for developing statistical predictive theories for a much larger class of magnetic materials.

  20. Labeling TiO2 nanoparticles with dyes for optical fluorescence microscopy and determination of TiO2-DNA nanoconjugate stability.

    PubMed

    Thurn, Kenneth T; Paunesku, Tatjana; Wu, Aiguo; Brown, Eric M B; Lai, Barry; Vogt, Stefan; Maser, Jörg; Aslam, Mohammed; Dravid, Vinayak; Bergan, Raymond; Woloschak, Gayle E

    2009-06-01

    Visualization of nanoparticles without intrinsic optical fluorescence properties is a significant problem when performing intracellular studies. Such is the case with titanium dioxide (TiO2) nanoparticles. These nanoparticles, when electronically linked to single-stranded DNA oligonucleotides, have been proposed to be used both as gene knockout devices and as possible tumor imaging agents. By interacting with complementary target sequences in living cells, these photoinducible TiO2-DNA nanoconjugates have the potential to cleave intracellular genomic DNA in a sequence specific and inducible manner. The nanoconjugates also become detectable by magnetic resonance imaging with the addition of gadolinium Gd(III) contrast agents. Herein two approaches for labeling TiO2 nanoparticles and TiO2-DNA nanoconjugates with optically fluorescent agents are described. This permits direct quantification of fluorescently labeled TiO2 nanoparticle uptake in a large population of living cells (>10(4) cells). X-ray fluorescence microscopy (XFM) is combined with fluorescent microscopy to determine the relative intracellular stability of the nanoconjugates and used to quantify intracellular nanoparticles. Imaging the DNA component of the TiO2-DNA nanoconjugate by fluorescent confocal microscopy within the same cell shows an overlap with the titanium signal as mapped by XFM. This strongly implies the intracellular integrity of the TiO2-DNA nanoconjugates in malignant cells.

  1. Structural and elastic properties of AIBIIIC 2 VI semiconductors

    NASA Astrophysics Data System (ADS)

    Kumar, V.; Singh, Bhanu P.

    2018-01-01

    The plane wave pseudo-potential method within density functional theory has been used to calculate the structural and elastic properties of AIBIIIC 2 VI semiconductors. The electronic band structure, density of states, lattice constants (a and c), internal parameter (u), tetragonal distortion (η), energy gap (Eg), and bond lengths of the A-C (dAC) and B-C (dBC) bonds in AIBIIIC 2 VI semiconductors have been calculated. The values of elastic constants (Cij), bulk modulus (B), shear modulus (G), Young's modulus (Y), Poisson's ratio (υ), Zener anisotropy factor (A), Debye temperature (ϴD) and G/B ratio have also been calculated. The values of all 15 parameters of CuTlS2 and CuTlSe2 compounds, and 8 parameters of 20 compounds of AIBIIIC 2 VI family, except AgInS2 and AgInSe2, have been calculated for the first time. Reasonably good agreement has been obtained between the calculated, reported and available experimental values.

  2. Charge transfer between biogenic jarosite derived Fe3+and TiO2 enhances visible light photocatalytic activity of TiO2.

    PubMed

    Chowdhury, Mahabubur; Shoko, Sipiwe; Cummings, Fransciuos; Fester, Veruscha; Ojumu, Tunde Victor

    2017-04-01

    In this work, we have shown that mining waste derived Fe 3+ can be used to enhance the photocatalytic activity of TiO 2 . This will allow us to harness a waste product from the mines, and utilize it to enhance TiO 2 photocatalytic waste water treatment efficiency. An organic linker mediated route was utilized to create a composite of TiO 2 and biogenic jarosite. Evidence of FeOTi bonding in the TiO 2 /jarosite composite was apparent from the FTIR, EFTEM, EELS and ELNEFS analysis. The as prepared material showed enhanced photocatalytic activity compared to pristine TiO 2 , biogenic jarosite and mechanically mixed sample of jarosite and TiO 2 under both simulated and natural solar irradiation. The prepared material can reduce the electrical energy consumption by 4 times compared to pristine P25 for degradation of organic pollutant in water. The material also showed good recyclability. Results obtained from sedimentation experiments showed that the larger sized jarosite material provided the surface to TiO 2 nanoparticles, which increases the settling rate of the materials. This allowed simple and efficient recovery of the catalyst from the reaction system after completion of photocatalysis. Enhanced photocatalytic activity of the composite material was due to effective charge transfer between TiO 2 and jarosite derived Fe 3+ as was shown from the EELS and ELNEFS. Generation of OH was supported by photoluminesence (PL) experiments. Copyright © 2016. Published by Elsevier B.V.

  3. Cationic (V, Y)-codoped TiO2 with enhanced visible light induced photocatalytic activity: A combined experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Khan, Matiullah; Cao, Wenbin

    2013-11-01

    To employ TiO2 as an efficient photocatalyst, high reactivity under visible light and improved separation of photoexcited carriers are required. An effective co-doping approach is applied to modify the photocatalytic properties of TiO2 by doping vanadium (transition metal) and yttrium (rare earth element). V and/or Y codoped TiO2 was prepared using hydrothermal method without any post calcination for crystallization. Based on density functional theory, compensated and noncompensated V, Y codoped TiO2 models were constructed and their structural, electronic, and optical properties were calculated. Through combined experimental characterization and theoretical modeling, V, Y codoped TiO2 exhibited high absorption coefficient with enhanced visible light absorption. All the prepared samples showed pure anatase phase and spherical morphology with uniform particle distribution. Electronic band structure demonstrates that V, Y codoping drastically reduced the band gap of TiO2. It is found that both the doped V and Y exist in the form of substitutional point defects replacing Ti atom in the lattice. The photocatalytic activity, evaluated by the degradation of methyl orange, displays that the codoped TiO2 sample exhibits enhanced visible light photocatalytic activity. The synergistic effects of V and Y drastically improved the Brunauer-Emmett-Teller specific surface area, visible light absorption, and electron-hole pair's separation leading to the enhanced visible light catalytic activity.

  4. Highly Visible Light Responsive, Narrow Band gap TiO2 Nanoparticles Modified by Elemental Red Phosphorus for Photocatalysis and Photoelectrochemical Applications

    PubMed Central

    Ansari, Sajid Ali; Cho, Moo Hwan

    2016-01-01

    This paper reports that the introduction of elemental red phosphorus (RP) into TiO2 can shift the light absorption ability from the UV to the visible region, and confirmed that the optimal RP loading and milling time can effectively improve the visible light driven-photocatalytic activity of TiO2. The resulting RP-TiO2 nanohybrids were characterized systematically by a range of techniques and the photocatalytic ability of the RP-TiO2 photocatalysts was assessed further by the photodegradation of a model Rhodamine B pollutant under visible light irradiation. The results suggest that the RP-TiO2 has superior photodegradation ability for model contaminant decomposition compared to other well-known photocatalysts, such as TiO2 and other reference materials. Furthermore, as a photoelectrode, electrochemical impedance spectroscopy, differential pulse voltammetry, and linear scan voltammetry were also performed in the dark and under visible light irradiation. These photoelectrochemical performances of RP-TiO2 under visible light irradiation revealed more efficient photoexcited electron-hole separation and rapid charge transfer than under the dark condition, and thus improved photocatalytic activity. These findings show that the use of earth abundant and inexpensive red phosphorus instead of expensive plasmonic metals for inducing visible light responsive characteristics in TiO2 is an effective strategy for the efficient energy conversion of visible light. PMID:27146098

  5. A simple and low temperature process for super-hydrophilic rutile TiO 2 thin films growth

    NASA Astrophysics Data System (ADS)

    Mane, R. S.; Joo, Oh-Shim; Min, Sun-Ki; Lokhande, C. D.; Han, Sung-Hwan

    2006-11-01

    We investigate an environmentally friendly aqueous solution system for rutile TiO2 violet color nanocrystalline thin films growth on ITO substrate at room temperature. Film shows considerable absorption in visible region with excitonic maxima at 434 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), UV-vis, water surface contact angle and energy dispersive X-ray analysis (EDX) techniques in addition to actual photo-image that shows purely rutile phase of TiO2 with violet color, super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 3.15 ± 0.4 nm, characterize the films. Band gap energy of 4.61 eV for direct transition was obtained for the rutile TiO2 films. Film surface shows super-hydrophilic behavior, as exhibited water contact angle was 7°. Strong visible absorption (not due to chlorine) leaves future challenge to use these films in extremely thin absorber (ETA) solar cells.

  6. Porous immobilized C coated N doped TiO2 containing in-situ generated polyenes for enhanced visible light photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Sabri, N. A.; Nawi, M. A.; Nawawi, W. I.

    2015-10-01

    Carbon coated nitrogen-doped Degussa P25TiO2 (or C,N-P25TiO2) was successfully immobilized on a glass plate using epoxidized natural rubber (ENR-50) and polyvinyl chloride (PVC) as the organic binders. Photo-etching of the fabricated system for 10 h oxidized its PVC binder into polyenes as well as forming a highly porous surface. The band gap energy (Eg) of the photo-etched immobilized photocatalyst system (C,N-P25TiO2/ENR/PVC-10 h) was reduced from 2.91 to 2.86 eV. Its photocatalytic activity was studied via photocatalytic degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) under a 45 W visible light fluorescent lamp. C,N-P25TiO2/ENR/PVC-10 h with polyenes performed better than its slurry counterpart under visible light irradiation where the conjugated double bonds acted as photo sensitizers. The immobilized C,N-P25TiO2/ENR/PVC-10 h has excellent reusability and sustainable with an average k value of 0.056 ± 0.011 min-1 and average percent removal of 99.18 ± 0.54%.

  7. Improved performance of Ag-doped TiO2 synthesized by modified sol-gel method as photoanode of dye-sensitized solar cell

    NASA Astrophysics Data System (ADS)

    Gupta, Arun Kumar; Srivastava, Pankaj; Bahadur, Lal

    2016-08-01

    Ag-doped TiO2 with Ag content ranging from 1 to 7 mol% was synthesized by a modified sol-gel route, and its performance as the photoanode of dye-sensitized solar cells (DSSCs) was compared with undoped TiO2 photoanode. Titanium(IV)isopropoxide was used as precursor and hexamethylenetetramine as the capping agent. XRD results show the formation of TiO2 nanoparticles with an average crystallite size of 5 nm (1 % Ag-doped TiO2) and 9 nm (undoped TiO2), respectively. The TiO2 nanopowder was used to prepare its thin film photoelectrode using doctor's blade method. Significant improvement in light-to-energy conversion efficiency was achieved when thin films of 1 % Ag-doped TiO2 were applied as photoanode in DSSC taking N719 as the sensitizer dye. As evidenced by EIS measurements, the electron lifetime of DSSC with Ag-doped TiO2 increased from 1.33 (for undoped TiO2) to 2.05 ms. The short-circuit current density ( J sc), open-circuit voltage ( V oc), fill factor (FF) and the overall energy conversion efficiency ( η) were 1.07 mA cm-2, 0.72 V, 0.73 and 0.40 %, respectively, with the use of 1 % Ag-doped TiO2 photoanode, whereas with undoped TiO2 under similar conditions, J sc = 0.63 mA cm-2, V oc = 0.70 V, fill factor 0.45 and conversion efficiency 0.14 % could be obtained. Therefore, compared with the reference DSSC containing an undoped TiO2 photoanode, the power conversion efficiency of the cell based on Ag-doped TiO2 has been remarkably enhanced by ~70 %. The substantial improvement in the device performance is attributed to the reduced band-gap energy, retarded charge recombination and greater surface coverage of the sensitizing dye over Ag-doped TiO2, which ultimately resulted in improved IPCE, J SC and η values.

  8. Ultrasonic spray pyrolysis synthesis of reduced graphene oxide/anatase TiO2 composite and its application in the photocatalytic degradation of methylene blue in water.

    PubMed

    Park, Jeong-Ann; Yang, Boram; Lee, Joongki; Kim, In Gyeom; Kim, Jae-Hyun; Choi, Jae-Woo; Park, Hee-Deung; Nah, In Wook; Lee, Sang-Hyup

    2018-01-01

    Reduced graphene oxide (RGO)/anatase TiO 2 composite was prepared using a simple one-step technique-ultrasonic spray pyrolysis-in order to inhibit the aggregation of TiO 2 nanoparticles and to improve the photocatalytic performance for degradation of methylene blue (MB). Different proportions (0-5 wt%) of RGO/TiO 2 composites were characterized by scanning electronic microscopy (SEM), dispersive X-ray spectrometry (EDS), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) surface area, X-ray photoelectron spectroscopy (XPS), X-ray diffractometry (XRD), Raman spectroscopy, UV-vis spectroscopy, and electrochemical impedance spectroscopy (EIS) to verify mechanism. From these analysis, TiO 2 nanoparticles are distributed uniformly on the RGO sheets with crumpled shape during ultrasonic spray pyrolysis and surface area is increasing by increasing portion of RGO. Band gap of RGO 5 /TiO 2 (5 wt% of RGO) composite is 2.72 eV and band gap was reduced by increasing portion of RGO in RGO/TiO 2 composites. The RGO 5 /TiO 2 composite was superior to other lower content of RGO/TiO 2 composites with a rapid transport of charge carriers and an effective charge separation. The highest removal efficiency of MB was obtained at the RGO 5 /TiO 2 composite under UVC irradiation, which coincided with the EIS, and the optimal dose of the composite was determined to be 0.5 g/L. The RGO 5 /TiO 2 composite improve the photocatalytic degradation rate of MB over the TiO 2 due to a retardation of electron-hole recombination. The MB adsorption capacity and photocatalytic degradation efficiency were greatly affected by pH changes and increased with increasing pH due to electrostatic interactions and generation of more hydroxyl radicals. The reusability of RGO 5 /TiO 2 composite was examined during 3 cycles. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Zr-doped TiO2 supported on delaminated clay materials for solar photocatalytic treatment of emerging pollutants.

    PubMed

    Belver, C; Bedia, J; Rodriguez, J J

    2017-01-15

    Solar light-active Zr-doped TiO 2 nanoparticles were successfully immobilized on delaminated clay materials by a one-step sol-gel route. Fixing the amount of TiO 2 at 65wt.%, this work studies the influence of Zr loading (up to 2%) on the photocatalytic activity of the resulting Zr-doped TiO 2 /clay materials. The structural characterization demonstrates that all samples were formed by a delaminated clay with nanostructured anatase assembled on its surface. The Zr dopant was successfully incorporated into the anatase lattice, resulting in a slight deformation of the anatase crystal and the reduction of the band gap. These materials exhibit high surface area with a disordered mesoporous structure formed by TiO 2 particles (15-20nm) supported on a delaminated clay. They were tested in the solar photodegradation of antipyrine, usually used as an analgesic drug and selected as an example of emerging pollutant. High degradation rates have been obtained at low antipyrine concentrations and high solar irradiation intensities with the Zr-doped TiO 2 /clay catalyst, more effective than the undoped one. This work demonstrates the potential application of the synthesis method for preparing novel and efficient solar-light photocatalysts based on metal-doped anatase and a delaminated clay. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. The presence of Ti(II) centers in doped nanoscale TiO2 and TiO2-xNx

    NASA Astrophysics Data System (ADS)

    Mikulas, Tanya; Fang, Zongtang; Gole, James L.; White, Mark G.; Dixon, David A.

    2012-06-01

    Unusual trends are observed in the Ti (2s, 2p) XPS spectra of Fe(II) doped TiO2 and TiO2-xNx. The binding energy of Ti (2s, 2p) initially decreases with increasing Fe(II) concentration, as expected, but increases at higher Fe(II) doping levels. Density functional theory is used to analyze the results. The observed VB-XPS and core level XPS spectra are consistent with the facile charge transfer sequence Ti(IV) + Fe(II) → Ti(III) + Fe(III) followed by Ti(III) + Fe(II) → Ti(II) + Fe(III). The formed Ti(II) sites may be relevant to nanoparticle catalysis on TiO2 surfaces.

  11. Solution-combustion synthesis of doped TiO2 compounds and its potential antileishmanial activity mediated by photodynamic therapy.

    PubMed

    Lopera, A A; Velásquez, A M A; Clementino, L C; Robledo, S; Montoya, A; de Freitas, L M; Bezzon, V D N; Fontana, C R; Garcia, C; Graminha, M A S

    2018-06-01

    Photodynamic therapy has emerged as an alternative treatment for cutaneous leishmaniasis, and compounds with photocatalytic behavior are promising candidates to develop new therapeutic strategies for the treatment of this parasitic disease. Titanium dioxide TiO 2 is a semiconductor ceramic material that shows excellent photocatalytic and antimicrobial activity under Ultraviolet irradiation. Due to the harmful effects of UV radiation, many efforts have been made in order to enhance both photocatalytic and antimicrobial properties of TiO 2 in the visible region of the spectrum by doping or through modifications in the route of synthesis. Herein, Fe-, Zn-, or Pt- doped TiO 2 nanostructures were synthesized by solution-combustion route. The obtained compounds presented aggregates of 100 nm, formed by particles smaller than 20 nm. Doping compounds shift the absorption spectrum towards the visible region, allowing production of reactive oxygen species in the presence of oxygen and molecular water when the system is irradiated in the visible spectrum. The Pt (EC 50  = 18.2 ± 0.8 μg/mL) and Zn (EC 50  = 16.4 ± 0.3 μg/mL) -doped TiO 2 presented the higher antileishmanial activities under visible irradiation and their application as photosensitizers in photodynamic therapy (PDT) strategies for the treatment of cutaneous leishmaniasis should be considered. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. Improving the Optoelectronic Properties of Mesoporous TiO2 by Cobalt Doping for High-Performance Hysteresis-free Perovskite Solar Cells.

    PubMed

    Sidhik, Siraj; Cerdan Pasarán, Andrea; Esparza, Diego; López Luke, Tzarara; Carriles, Ramón; De la Rosa, Elder

    2018-01-31

    We for the first time report the incorporation of cobalt into a mesoporous TiO 2 electrode for application in perovskite solar cells (PSCs). The Co-doped PSC exhibits excellent optoelectronic properties; we explain the improvements by passivation of electronic trap or sub-band-gap states arising due to the oxygen vacancies in pristine TiO 2 , enabling faster electron transport and collection. A simple postannealing treatment is used to prepare the cobalt-doped mesoporous electrode; UV-visible spectroscopy, X-ray photoemission spectroscopy, space charge-limited current, photoluminescence, and electrochemical impedance measurements confirm the incorporation of cobalt, enhanced conductivity, and the passivation effect induced in the TiO 2 . An optimized doping concentration of 0.3 mol % results in the maximum power conversion efficiency of 18.16%, 21.7% higher than that of a similar cell with an undoped TiO 2 electrode. Also, the device shows negligible hysteresis and higher stability, retaining 80.54% of the initial efficiency after 200 h.

  13. Photocatalytic TiO2 nanoparticles enhanced polymer antimicrobial coating

    NASA Astrophysics Data System (ADS)

    Wei, Xiaojin; Yang, Zhendi; Tay, See Leng; Gao, Wei

    2014-01-01

    Copper (Cu) containing coatings can provide sustainable protection against microbial contamination. However, metallic Cu coatings have not been widely used due to the relatively high cost, poor corrosion resistance, and low compatibility with non-metal substrates. Titanium dioxide (TiO2) possesses antibacterial functions by its photocatalytic properties which can destroy bacteria or suppress their reproduction. TiO2 also has the function of improving the mechanical properties through particle dispersion strengthening. We have recently developed an innovative polymer based coating system containing fine particles of Cu and TiO2 nanoparticles. These polymer based coatings simultaneously display excellent antimicrobial and good mechanical properties. The results showed that the addition of TiO2 has improved the antimicrobial property under sunlight, which provides extended applications in outdoor environment. The elimination of 106 bacterial by contacting the coatings without TiO2 needs 5 h, while contacting with the Cu/TiO2- 1 wt.% TiO2 took only 2 h to kill the same amount of bacteria. The coatings also presented enhanced hardness and wear resistance after adding TiO2. The width of wear track decreased from 270 μm of the Cu-polymer coating to 206 μm of Cu/TiO2-polymer coatings with 10 wt.% TiO2. Synchrotron Infrared Microscopy was used to in-situ and in-vivo study the bacteria killing process at the molecular level. The real-time chemical images of bacterial activities showed that the bacterial cell membranes were damaged by the Cu and TiO2 containing coatings

  14. Influence of the surface chemistry on TiO2 - TiO2 nanocontact forces as measured by an UHV-AFM

    NASA Astrophysics Data System (ADS)

    Kunze, Christian; Giner, Ignacio; Torun, Boray; Grundmeier, Guido

    2014-03-01

    Particle-wall contact forces between a TiO2 film coated AFM tip and TiO2(1 1 0) single crystal surfaces were analyzed by means of UHV-AFM. As a reference system an octadecylphosphonic acid monolayer covered TiO2(1 1 0) surface was studied. The defect chemistry of the TiO2 substrate was modified by Ar ion bombardment, water dosing at 3 × 10-6 Pa and an annealing step at 473 K which resulted in a varying density of Ti(III) states. The observed contact forces are correlated to the surface defect density and are discussed in terms of the change in the electronic structure and its influence on the Hamaker constant.

  15. In situ Fenton reagent generated from TiO2/Cu2O composite film: a new way to utilize TiO2 under visible light irradiation.

    PubMed

    Zhang, Yong-Gang; Ma, Li-Li; Li, Jia-Lin; Yu, Ying

    2007-09-01

    TiO2/Cu2O composite is prepared by a simple electrochemical method and coated on glass matrix through a spraying method. The obtained composite is characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effect of TiO2/Cu2O composite films with different ratio of TiO2 and Cu2O on photodegradation of the dye methylene blue under visible light is investigated in detail. It is found that the photocatalytic activity of TiO2/Cu2O composite film with the presence of FeSO4 and EDTA is much higher than that for the similar system with only TiO2 and Cu2O film respectively. Without the presence of FeSO4 and EDTA, there is no degradation for methylene blue. The exploration of the optimized parameters for the degradation of methylene blue by using TiO2/Cu2O composite film as catalyst under visible light was also carried out. The most significant factor is the amount of Ti02 in the composite, and the second significant factor is the concentration of FeSO4. During the degradation of methylene blue under visible light, TiO2/Cu2O composite film generates H202, and Fenton regent is formed with Fe2+ and EDTA, which is detected in this study. The mechanism for the great improvement of photocatalytic activity of TiO2/Cu2O composite film under visible light is proposed by the valence band theory. Electrons excitated from TiO2/Cu2O composite under visible light are transferred from the conduction band of Cu2O to that of Ti02. The formed intermediate state of Ti 3+ ion is observed by X-ray photoelectron spectroscopy (XPS) on the TiO/Cu2O composite film. Additionally, the accumulated electrons in the conduction band of TiO2 are transferred to oxygen on the TiO2 surface for the formation of O2- or O2(2-), which combines with H+ to form H2O2. The evolved H202 with FeSO4 and EDTA forms Fenton reagentto degrade methylene blue. Compared to the traditional Fenton reagent, this new kind of in situ Fenton reagent generated from TiO2/Cu2O composite film does not need to

  16. Semiconductor sensors

    NASA Technical Reports Server (NTRS)

    Gatos, Harry C. (Inventor); Lagowski, Jacek (Inventor)

    1977-01-01

    A semiconductor sensor adapted to detect with a high degree of sensitivity small magnitudes of a mechanical force, presence of traces of a gas or light. The sensor includes a high energy gap (i.e., .about. 1.0 electron volts) semiconductor wafer. Mechanical force is measured by employing a non-centrosymmetric material for the semiconductor. Distortion of the semiconductor by the force creates a contact potential difference (cpd) at the semiconductor surface, and this cpd is determined to give a measure of the force. When such a semiconductor is subjected to illumination with an energy less than the energy gap of the semiconductors, such illumination also creates a cpd at the surface. Detection of this cpd is employed to sense the illumination itself or, in a variation of the system, to detect a gas. When either a gas or light is to be detected and a crystal of a non-centrosymmetric material is employed, the presence of gas or light, in appropriate circumstances, results in a strain within the crystal which distorts the same and the distortion provides a mechanism for qualitative and quantitative evaluation of the gas or the light, as the case may be.

  17. Tailoring optical properties of TiO2-Cr co-sputtered films using swift heavy ions

    NASA Astrophysics Data System (ADS)

    Gupta, Ratnesh; Sen, Sagar; Phase, D. M.; Avasthi, D. K.; Gupta, Ajay

    2018-05-01

    Effect of 100 MeV Au7+ ion irradiation on structure and optical properties of Cr-doped TiO2 films has been studied using X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, UV-Visible spectroscopy, X-ray reflectivity, and atomic force microscopy. X-ray reflectivity measurement implied that film thickness reduces as a function of ion fluence while surface roughness increases. The variation in surface roughness is well correlated with AFM results. Ion irradiation decreases the band gap energy of the film. Swift heavy ion irradiation enhances the oxygen vacancies in the film, and the extra electrons in the vacancies act as donor-like states. In valence band spectrum, there is a shift in the Ti3d peak towards lower energies and the shift is equivalent to the band gap energy obtained from UV spectrum. Evidence for band bending is also provided by the corresponding Ti XPS peak which exhibits a shift towards lower energy due to the downward band bending. X-ray absorption studies on O Kand Cr L3,2 edges clearly indicate that swift heavy ion irradiation induces formation of Cr-clusters in TiO2 matrix.

  18. Stereospecific growth of densely populated rutile mesoporous TiO2 nanoplate films: a facile low temperature chemical synthesis approach

    NASA Astrophysics Data System (ADS)

    Lee, Go-Woon; Ambade, Swapnil B.; Cho, Young-Jin; Mane, Rajaram S.; Shashikala, V.; Yadav, Jyotiprakash; Gaikwad, Rajendra S.; Lee, Soo-Hyoung; Jung, Kwang-Deog; Han, Sung-Hwan; Joo, Oh-Shim

    2010-03-01

    We report for the first time, using a simple and environmentally benign chemical method, the low temperature synthesis of densely populated upright-standing rutile TiO2 nanoplate films onto a glass substrate from a mixture of titanium trichloride, hydrogen peroxide and thiourea in triply distilled water. The rutile TiO2 nanoplate films (the phase is confirmed from x-ray diffraction analysis, selected area electron diffraction, energy-dispersive x-ray analysis, and Raman shift) are 20-35 nm wide and 100-120 nm long. The chemical reaction kinetics for the growth of these upright-standing TiO2 nanoplate films is also interpreted. Films of TiO2 nanoplates are optically transparent in the visible region with a sharp absorption edge close to 350 nm, confirming an indirect band gap energy of 3.12 eV. The Brunauer-Emmet-Teller surface area, Barret-Joyner-Halenda pore volume and pore diameter, obtained from N2 physisorption studies, are 82 m2 g - 1, 0.0964 cm3 g - 1 and 3.5 nm, respectively, confirming the mesoporosity of scratched rutile TiO2 nanoplate powder that would be ideal for the direct fabrication of nanoscaled devices including upcoming dye-sensitized solar cells and gas sensors.

  19. Effect of p–d hybridization, structural distortion and cation electronegativity on electronic properties of ZnSnX{sub 2} (X=P, As, Sb) chalcopyrite semiconductors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mishra, S.; Ganguli, B., E-mail: biplabg@nitrkl.ac.in

    2013-04-15

    Significant effects of p–d hybridization, structural distortion and cation-electro-negativity are found on band gap in ZnSnX{sub 2} (X=P, As, Sb). Our study suggests these compounds to be direct band gap semiconductors with band gaps of 1.23, 0.68 and 0.19 eV respectively. Lattice constants, tetragonal distortion (η), anion displacement, bond lengths and bulk moduli are calculated by Density Functional Theory based on Tight binding Linear Muffin-Tin orbital method. Our result of structural properties is in good agreement with the available experimental and other theoretical results. Calculated band gaps also agree well with the experimental works within LDA limitation. Unlike other semiconductorsmore » in the group II–IV–V{sub 2}, there is a reduction in the band gap of 0.22, 0.20 and 0.24 eV respectively in ZnSnX{sub 2} (X=P, As, Sb) due to p–d hybridization. Structural distortion decreases band gap by 0.20, 0.12 and 0.10 eV respectively. We find that cation electronegativity effect is responsible for increasing the band gap relative to their binary analogs GaInP{sub 2}, InGaAs{sub 2} and GaInSb{sub 2} respectively and increment are 0.13, 0.04 and 0.13 eV respectively. - Graphical abstract: One unit cell of ZnSnX{sub 2} (X=P, As, Sb) chalcopyrite semiconductor. Semiconductors ZnSnX{sub 2} (X=P, As, Sb) are found to be direct band gap semiconductors with band gaps 1.23, 0.68 and 0.19 eV respectively. The quantitative estimate of effects of p–d hybridization, structural distortion and cation electronegativity shows band gaps change significantly due to these effects. Highlights: ► ZnSnX{sub 2} (X=P, As, Sb) are direct band gap semiconductors. ► These have band gaps of 1.23 eV, 0.68 eV and 0.19 eV respectively. ► The band gap reduction due to p–d hybridization is 13.41%, 18.51% and 40% respectively. ► Band gap reduction due to structural distortion is 12.12%, 11.11% and 16.66% respectively. ► Band gap increases 8.38%, 3.70% and 21

  20. Density functional theory study on the metal-support interaction between a Au9 cluster and an anatase TiO2(001) surface.

    PubMed

    Jiang, Zong-You; Zhao, Zong-Yan

    2017-08-23

    Noble metals supported on TiO 2 surfaces have shown extraordinary photocatalytic properties in many important processes such as hydrogenation, water splitting, degradation of hazards, and so on. Using density functional theory calculations, this work has systematically investigated the microstructure and electronic structure of three different Au 9 isomers loaded on anatase TiO 2 (001) surface. The calculated results show that the interaction between the Au 9 cluster and the TiO 2 support is closely related to the adsorption site and the stability of the Au 9 cluster in the gas phase. The adsorption energy of the 2D configuration is larger than that of the 3D configuration of the Au 9 cluster, owing to the stronger interactions between more adsorption sites. The stable adsorption site for Au 9 clusters deposited on the anatase TiO 2 (001) surface tends to be the O 2c -O 2c hollow site. The presentation of the MIGS of the Au 9 cluster, the disappearance of surface states of the TiO 2 (001) surface, and the shifting of the Fermi level from the top of the valence band to the bottom of the conduction band suggest strong interactions between the Au 9 clusters and the TiO 2 (001) surface. Importantly, the electron transfer from the Au 9 clusters to the TiO 2 support occurs mainly through Au-O 2c interactions, which are mainly localized at the contact layer of the Au 9 clusters. These conclusions are useful to understand various physical and chemical properties of noble metal clusters loaded onto an oxide surface, and helpful to design novel metal/semiconductor functional composite materials and devices.

  1. Sol-gel TiO2 films as NO2 gas sensors

    NASA Astrophysics Data System (ADS)

    Georgieva, V.; Gadjanova, V.; Grechnikov, A.; Donkov, N.; Sendova-Vassileva, M.; Stefanov, P.; Kirilov, R.

    2014-05-01

    TiO2 films were prepared by a sol-gel technique with commercial TiO2 powder as a source material (P25 Degussa AG). After a special treatment, printing paste was prepared. The TiO2 layers were formed by means of drop-coating on Si-control wafers and on the Au-electrodes of quartz resonators. The surface morphology of the films was examined by scanning electron microscopy (SEM). Their structure was studied by Raman spectroscopy and the surface composition was determined by X-ray photoelectron spectroscopy (XPS). The layers had a grain-like surface morphology and consisted mainly of anatase TiO2 phase. The sensitivity of the TiO2 films to NO2 was assessed by the quartz crystal microbalance (QCM) technique. To this end, the films were deposited on both sides of a 16-MHz QCM. The sensing characteristic of the TiO2-QCM structure was investigated by measuring the resonant frequency shift (ΔF) of the QCM due to the mass loading caused by NO2 adsorption. The Sauerbrey equation was applied to establish the correlation between the QCM frequency changes measured after exposure to different NO2 concentrations and the mass-loading of the QCM. The experiments were carried out in a dynamic mode on a special laboratory setup with complete control of the process parameters. The TiO2 films were tested in the NO2 concentration interval from 10 ppm to 5000 ppm. It was found that a TiO2 loading of the QCM by 5.76 kHz corresponded to a system sensitive to NO2 concentrations above 250 ppm. On the basis of the frequency-time characteristics (FTCs) measured, AF at different NO2 concentrations was defined, the adsorption/desorption cycles were studied and the response and recovery times were estimated. The results obtained show that the process is reversible in the NO2 interval investigated. The results further suggested that TiO2 films prepared by a sol-gel method on a QCM can be used as a sensor element for NO2 detection.

  2. Donor defects and small polarons on the TiO2(110) surface

    NASA Astrophysics Data System (ADS)

    Moses, P. G.; Janotti, A.; Franchini, C.; Kresse, G.; Van de Walle, C. G.

    2016-05-01

    The role of defects in the chemical activity of the rutile TiO2(110) surface remains a rich topic of research, despite the rutile (110) being one of the most studied surfaces of transition-metal oxides. Here, we present results from hybrid functional calculations that reconcile apparently disparate views on the impact of donor defects, such as oxygen vacancies and hydrogen impurities, on the electronic structure of the (110) rutile surface. We find that the bridging oxygen vacancy and adsorbed or substitutional hydrogen are actually shallow donors, which do not induce gap states. The excess electrons from these donor centers tend to localize in the form of small polarons, which are the factual cause of the deep states ˜1 eV below the conduction band, often observed in photoelectron spectroscopy measurements. Our results offer a new framework for understanding the surface electronic structure of TiO2 and related oxides.

  3. A TiO2 abundance map for the northern maria

    NASA Technical Reports Server (NTRS)

    Johnson, T. V.; Saunders, R. S.; Matson, D. L.; Mosher, J. A.

    1977-01-01

    A map of TiO2 abundance for most of the northern maria is presented. The telescopic data base used is the 0.38/0.56-micron ratio mosaic from Johnson et at. (1977). The titanium content has been estimated using the correlation established by Charette et al. (1974). The combination of observational, processing, and calibration errors indicates that the TiO2 map is accurate to + or - 2% (wt% TiO2) for high TiO2 content (more than 5%) and + or - 1% for low values of TiO2. Analysis of the lunar sample and telescopic data suggests strongly that the spectral parameter mapped is sensitive primarily to TiO2 abundance in the range 3-9% and does not correlate directly with iron content. It is suggested, however, that for the low TiO2 mare regions (less than 2-3% TiO2) there may be a relation between the spectral ratio and iron content and that some of the reddest mare areas in the Imbrium region may have low iron contents as well as low titanium abundances.

  4. Facet-dependent photocatalytic properties of TiO(2) -based composites for energy conversion and environmental remediation.

    PubMed

    Ong, Wee-Jun; Tan, Lling-Lling; Chai, Siang-Piao; Yong, Siek-Ting; Mohamed, Abdul Rahman

    2014-03-01

    Titanium dioxide (TiO2 ) is one of the most widely investigated metal oxides because of its extraordinary surface, electronic, and photocatalytic properties. However, the large band gap of TiO2 and the considerable recombination of photogenerated electron-hole pairs limit its photocatalytic efficiency. Therefore, research attention is being increasingly directed towards engineering the surface structure of TiO2 on the atomic level (namely morphological control of {001} facets on the micro- and nanoscale) to fine-tune its physicochemical properties; this could ultimately lead to the optimization of selectivity and reactivity. This Review encompasses the fundamental principles to enhance the photocatalytic activity by using highly reactive {001}-faceted TiO2 -based composites. The current progress of such composites, with particular emphasis on the photodegradation of pollutants and photocatalytic water splitting for hydrogen generation, is also discussed. The progresses made are thoroughly examined for achieving remarkable photocatalytic performances, with additional insights with regard to charge transfer. Finally, a summary and some perspectives on the challenges and new research directions for future exploitation in this emerging frontier are provided, which hopefully would allow for harnessing the outstanding structural and electronic properties of {001} facets for various energy- and environmental-related applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Synthesis of Nano-Ilmenite (FeTiO3) doped TiO2/Ti Electrode for Photoelectrocatalytic System

    NASA Astrophysics Data System (ADS)

    Hikmawati; Watoni, A. H.; Wibowo, D.; Maulidiyah; Nurdin, M.

    2017-11-01

    Ilmenite (FeTiO3) doped on Ti and TiO2/Ti electrodes were successfully prepared by using the sol-gel method. The structure, morphology, and optical properties of FeTiO3 are characterized by XRD, UV-Vis DRS, and SEM. The FeTiO3 and TiO2 greatly affect the photoelectrocatalysis performance characterized by Linear Sweep Voltammetry (LSV) and Cyclic Voltammetry (CV). The characterization result shows a band gap of FeTiO3 is 2.94 eV. XRD data showed that FeTiO3 formed at 2θ were 35.1° (110), 49.9° (024), and 61.2° (214). The morphology of FeTiO3/Ti and FeTiO3.TiO2/Ti using SEM shows that the formation of FeTiO3 thin layer signifies the Liquid Phase Deposition method effectively in the coating process. Photoelectrochemical (PEC) test showed that FeTiO3.TiO2/Ti electrode was highly oxidation responsive under visible light compared to the FeTiO3/Ti electrodes i.e. 7.87×10-4 A and 9.87×10-5 A. Degradation test of FeTiO3/Ti and FeTiO3.TiO2/Ti electrodes on titan yellow showed that the percentages of degradation with photoelectrocatalysis at 0.5 mg/L were 41% and 43%, respectively.

  6. Properties of the ferroelectric visible light absorbing semiconductors: Sn 2 P 2 S 6 and Sn 2 P 2 Se 6

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Li, Yuwei; Singh, David J.

    Ferroelectrics with suitable band gaps have recently attracted attention as candidate solar absorbing materials for photovoltaics. The inversion symmetry breaking may promote the separation of photoexcited carriers and allow voltages higher than the band gap. However, these effects are not fully understood, in part because of a lack of suitable model systems for studying these effects in detail. Here, we report properties of ferroelectric Sn 2P 2S 6 and Sn 2P 2Se 6 using first principles calculations. Results are given for the electronic structure, carrier pocket shapes, optical absorption, and transport.We find indirect band gaps of 2.20 eV and 1.55more » eV, respectively, and favorable band structures for carrier transport, including both holes and electrons. Strong absorption is found above the direct gaps of 2.43 eV and 1.76 eV. Furthermore these compounds may serve as useful model systems for understanding photovoltaic effects in ferroelectric semiconductors.« less

  7. Properties of the ferroelectric visible light absorbing semiconductors: Sn 2 P 2 S 6 and Sn 2 P 2 Se 6

    DOE PAGES

    Li, Yuwei; Singh, David J.

    2017-12-05

    Ferroelectrics with suitable band gaps have recently attracted attention as candidate solar absorbing materials for photovoltaics. The inversion symmetry breaking may promote the separation of photoexcited carriers and allow voltages higher than the band gap. However, these effects are not fully understood, in part because of a lack of suitable model systems for studying these effects in detail. Here, we report properties of ferroelectric Sn 2P 2S 6 and Sn 2P 2Se 6 using first principles calculations. Results are given for the electronic structure, carrier pocket shapes, optical absorption, and transport.We find indirect band gaps of 2.20 eV and 1.55more » eV, respectively, and favorable band structures for carrier transport, including both holes and electrons. Strong absorption is found above the direct gaps of 2.43 eV and 1.76 eV. Furthermore these compounds may serve as useful model systems for understanding photovoltaic effects in ferroelectric semiconductors.« less

  8. Hybrid TiO2/ZnO and TiO2/Al plasmon impregnated ZnO nanocomposite photoanodes for DSSCs: synthesis and characterisation

    NASA Astrophysics Data System (ADS)

    Pugazhendhi, K.; D’Almeida, Steven; Naveen Kumar, P.; Sahaya Selva Mary, J.; Tenkyong, Tenzin; Sharmila, D. J.; J, Madhavan; Merline Shyla, J.

    2018-04-01

    The proposed work reports the synthesis and characterisation of novel and hybrid nanocomposites TiO2/ZnO and TiO2/Al plasmon impregnated ZnO, prepared using sol-gel method. X-Ray Diffraction analysis confirmed the crystalline nature of the nanocomposites with high degree of purity and the crystallite size was found to be 22 nm (TiO2/ZnO) and 21 nm (TiO2/Al-ZnO) using Scherrer’s formula. The surface chemistry, elemental compositions and purity were investigated and established using Energy Dispersive X-ray Analysis. The specific surface area of TiO2/ZnO was observed to be 23 m2 g‑1 whereas on comparison, a slight decrease was observed in the case of TiO2/Al-ZnO to 19 m2 g‑1 from Brunauer–Emmett–Teller analysis and in addition, both the samples were identified to be mesoporous in nature. The vibrational assignments were observed using Fourier Transform Infra-Red spectroscopy and results confirmed the existence of TiO2, ZnO and Al groups. The electrical response of the nanocomposites to the incident radiation with applied electric field was examined using Field Dependent Dark and Photo conductivity studies. The observed measurements revealed that the photocurrent values are greater than the dark currents which confirmed the photoconductive nature of the nanocomposites. While both the prepared nanocomposites qualify as good candidates for usage as efficient photoanodes for DSSCs, TiO2/Al-ZnO indicates a slight edge over the other.

  9. Interface engineering of CsPbBr3/TiO2 heterostructure with enhanced optoelectronic properties for all-inorganic perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Qian, Chong-Xin; Deng, Zun-Yi; Yang, Kang; Feng, Jiangshan; Wang, Ming-Zi; Yang, Zhou; Liu, Shengzhong Frank; Feng, Hong-Jian

    2018-02-01

    Interface engineering has become a vital method in accelerating the development of perovskite solar cells in the past few years. To investigate the effect of different contacted surfaces of a light absorber with an electron transporting layer, TiO2, we synthesize CsPbBr3/TiO2 thin films with two different interfaces (CsBr/TiO2 and PbBr2/TiO2). Both interfacial heterostructures exhibit enhanced visible light absorption, and the CsBr/TiO2 thin film presents higher absorption than the PbBr2/TiO2 interface, which is attributed to the formation of interface states and the decreased interface bandgap. Furthermore, compared with the PbBr2/TiO2 interface, CsBr/TiO2 solar devices present larger output short circuit current and shorter photoluminescence decay time, which indicates that the CsBr contacting layer with TiO2 can better extract and separate the photo-induced carriers. The first-principles calculations confirm that, due to the existence of staggered gap (type II) offset junction and the interface states, the CsBr/TiO2 interface can more effectively separate the photo-induced carriers and thus drive the electron transfer from the CsPbBr3 perovskite layer to the TiO2 layer. These results may be beneficial to exploit the potential application of all-inorganic perovskite CsPbBr3-based solar cells through the interface engineering route.

  10. Ternary composite of TiO2 nanotubes/Ti plates modified by g-C3N4 and SnO2 with enhanced photocatalytic activity for enhancing antibacterial and photocatalytic activity.

    PubMed

    Faraji, Masoud; Mohaghegh, Neda; Abedini, Amir

    2018-01-01

    A series of g-C 3 N 4 -SnO 2 /TiO 2 nanotubes/Ti plates were fabricated via simple dipping of TiO 2 nanotubes/Ti in a solution containing SnCl 2 and g-C 3 N 4 nanosheets and finally annealing of the plates. Synthesized plates were characterized by various techniques. The SEM analysis revealed that the g-C 3 N 4 -SnO 2 nanosheets with high physical stability have been successfully deposited onto the surface of TiO 2 nanotubes/Ti plate. Photocatalytic activity was investigated using two probe chemical reactions: oxidative decomposition of acetic acid and oxidation of 2-propanol under irradiation. Antibacterial activities for Escherichia coli (E. coli) bacteria were also investigated in dark and under UV/Vis illuminations. Detailed characterization and results of photocatalytic and antibacterial activity tests revealed that semiconductor coupling significantly affected the photocatalyst properties synthesized and hence their photocatalytic and antibacterial activities. Modification of TiO 2 nanotubes/Ti plates with g-C 3 N 4 -SnO 2 deposits resulted in enhanced photocatalytic activities in both chemical and microbial systems. The g-C 3 N 4 -SnO 2 /TiO 2 nanotubes/Ti plate exhibited the highest photocatalytic and antibacterial activity, probably due to the heterojunction between g-C 3 N 4 -SnO 2 and TiO 2 nanotubes/Ti in the ternary composite plate and thus lower electron/hole recombination rate. Based on the obtained results, a photocatalytic and an antibacterial mechanism for the degradation of E. coli bacteria and chemical pollutants over g-C 3 N 4 -SnO 2 /TiO 2 nanotubes/Ti plate were proposed and discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Coloration of tyrosine by organic-semiconductor interfacial charge-transfer transitions

    NASA Astrophysics Data System (ADS)

    Fujisawa, Jun-ichi; Kikuchi, Natsumi; Hanaya, Minoru

    2016-11-01

    L-tyrosine (Tyr) plays a crucial role as a proteinogenic amino acid and also as a precursor to several neurotransmitters and hormones. Here we demonstrate coloration of Tyr based on organic-semiconductor interfacial charge-transfer (ICT) transitions. The ICT transitions from Tyr to TiO2 are induced by the chemisorption of Tyr on TiO2 surfaces via the hydroxy group of the phenol moiety. Because other amino acids possess no chemical group to induce ICT transitions, this coloration method enables to detect Tyr selectively without drastic structural change in contrast to the conventional coloration methods.

  12. Laser Cooling of 2-6 Semiconductors

    DTIC Science & Technology

    2016-08-12

    practical optical refrigeration . The challenge is the stoichiometric defect in bulk crystal which introduces mid-gap states that manifest as broad-band...cooling in semiconductor has stimulated strong interest in further scaling up towards practical optical refrigeration . The challenge is the...energy. The upconversion process is facilitated by the annihilation of phonons and leads to cooling of the matter. The concept of optical refrigeration

  13. Optical properties of titanium-di-oxide (TiO2) prepared by hydrothermal method

    NASA Astrophysics Data System (ADS)

    Rahman, Kazi Hasibur; Biswas, Sayari; Kar, Asit Kumar

    2018-05-01

    Research on titanate and its derived TiO2 nanostructures with large specific surface area have received great attention due to their enhanced efficiency in photocatalysis, DSSC etc. Here, in this communication TiO2 powder has been prepared by hydrothermal method at 180 °C. In this work we have shown the changes in optical properties of the powder with two different sintering temperatures ‒ 500 °C and 800 °C. The as prepared powder was also studied. FESEM images show spherical particles for the as prepared samples which look more like agglomeration after sintering. Band gaps of the prepared samples were calculated from UV-Vis spectroscopy which lies in the range 2.85 eV ‒ 3.13 eV. The photoluminescence (PL) spectra of the prepared samples were recorded at room temperature in the range of 300‒700 nm. It shows two distinct peaks at 412 nm and 425 nm.

  14. Influence of transition metal doping on the structural, optical, and magnetic properties of TiO2 films deposited on Si substrates by a sol–gel process

    PubMed Central

    2013-01-01

    Transition metal (TM)-doped TiO2 films (TM = Co, Ni, and Fe) were deposited on Si(100) substrates by a sol–gel method. With the same dopant content, Co dopants catalyze the anatase-to-rutile transformation (ART) more obviously than Ni and Fe doping. This is attributed to the different strain energy induced by the different dopants. The optical properties of TM-doped TiO2 films were studied with spectroscopic ellipsometry data. With increasing dopant content, the optical band gap (EOBG) shifts to lower energy. With the same dopant content, the EOBG of Co-doped TiO2 film is the smallest and that of Fe-doped TiO2 film is the largest. The results are related to electric disorder due to the ART. Ferromagnetic behaviors were clearly observed for TM-doped TiO2 films except the undoped TiO2 film which is weakly magnetic. Additionally, it is found that the magnetizations of the TM-doped TiO2 films decrease with increasing dopant content. PMID:24350904

  15. SnO2/TiO2 bilayer thin films exhibiting superhydrophilic properties

    NASA Astrophysics Data System (ADS)

    Talinungsang, Nibedita Paul; Purkayastha, Debarun Dhar

    2017-05-01

    Nanostructured thin films of TiO2, SnO2, and SnO2/TiO2 have been deposited by sol-gel method. The films are characterized by X-ray diffraction, wettability and optical properties. In the present work, we have achieved a way of converting hydrophilic to super-hydrophilic state by incorporating TiO2 buffer layer in between substrate and SnO2 film, which has its utility in anti-fogging surfaces. The decrease in contact angle of water over SnO2/TiO2 bilayer is attributed to the increase in roughness of the film as well as surface energy of the substrate.

  16. Hydrogenated TiO2 nanotube arrays for supercapacitors.

    PubMed

    Lu, Xihong; Wang, Gongming; Zhai, Teng; Yu, Minghao; Gan, Jiayong; Tong, Yexiang; Li, Yat

    2012-03-14

    We report a new and general strategy for improving the capacitive properties of TiO(2) materials for supercapacitors, involving the synthesis of hydrogenated TiO(2) nanotube arrays (NTAs). The hydrogenated TiO(2) (denoted as H-TiO(2)) were obtained by calcination of anodized TiO(2) NTAs in hydrogen atmosphere in a range of temperatures between 300 to 600 °C. The H-TiO(2) NTAs prepared at 400 °C yields the largest specific capacitance of 3.24 mF cm(-2) at a scan rate of 100 mV s(-1), which is 40 times higher than the capacitance obtained from air-annealed TiO(2) NTAs at the same conditions. Importantly, H-TiO(2) NTAs also show remarkable rate capability with 68% areal capacitance retained when the scan rate increase from 10 to 1000 mV s(-1), as well as outstanding long-term cycling stability with only 3.1% reduction of initial specific capacitance after 10,000 cycles. The prominent electrochemical capacitive properties of H-TiO(2) are attributed to the enhanced carrier density and increased density of hydroxyl group on TiO(2) surface, as a result of hydrogenation. Furthermore, we demonstrate that H-TiO(2) NTAs is a good scaffold to support MnO(2) nanoparticles. The capacitor electrodes made by electrochemical deposition of MnO(2) nanoparticles on H-TiO(2) NTAs achieve a remarkable specific capacitance of 912 F g(-1) at a scan rate of 10 mV s(-1) (based on the mass of MnO(2)). The ability to improve the capacitive properties of TiO(2) electrode materials should open up new opportunities for high-performance supercapacitors. © 2012 American Chemical Society

  17. An Unusual Strong Visible-Light Absorption Band in Red Anatase TiO2 Photocatalyst Induced by Atomic Hydrogen-Occupied Oxygen Vacancies.

    PubMed

    Yang, Yongqiang; Yin, Li-Chang; Gong, Yue; Niu, Ping; Wang, Jian-Qiang; Gu, Lin; Chen, Xingqiu; Liu, Gang; Wang, Lianzhou; Cheng, Hui-Ming

    2018-02-01

    Increasing visible light absorption of classic wide-bandgap photocatalysts like TiO 2 has long been pursued in order to promote solar energy conversion. Modulating the composition and/or stoichiometry of these photocatalysts is essential to narrow their bandgap for a strong visible-light absorption band. However, the bands obtained so far normally suffer from a low absorbance and/or narrow range. Herein, in contrast to the common tail-like absorption band in hydrogen-free oxygen-deficient TiO 2 , an unusual strong absorption band spanning the full spectrum of visible light is achieved in anatase TiO 2 by intentionally introducing atomic hydrogen-mediated oxygen vacancies. Combining experimental characterizations with theoretical calculations reveals the excitation of a new subvalence band associated with atomic hydrogen filled oxygen vacancies as the origin of such band, which subsequently leads to active photo-electrochemical water oxidation under visible light. These findings could provide a powerful way of tailoring wide-bandgap semiconductors to fully capture solar light. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Interface actions between TiO2 and porous diatomite on the structure and photocatalytic activity of TiO2-diatomite

    NASA Astrophysics Data System (ADS)

    Xia, Yue; Li, Fangfei; Jiang, Yinshan; Xia, Maosheng; Xue, Bing; Li, Yanjuan

    2014-06-01

    TiO2-diatomite photocatalysts were prepared by sol-gel process with various pre-modified diatomite. In order to obtain diatomite with different surface characteristics, two modification approaches including calcination and phosphoric acid treatment on the micro-structure of diatomite are introduced. The photocatalysts were characterized by XRD, XPS, nitrogen adsorption-desorption isotherms and micromorphology analysis. The results indicate that, compared with pure TiO2, the anatase-to-rutile phase transition temperature of TiO2 loaded on diatomite carrier is significantly increased to nearly 900 °C, depending on the different pretreatment method of diatomite. The photocatalytic activities of different samples were evaluated by their degradation rate of methyl orange (MO) dye under UV and visible-light irradiation. The samples prepared by phosphoric acid pretreatment method exhibit the highest photocatalytic activity. After 90 min of UV irradiation, about 90% of MO is decomposed by the best effective photocatalyst. And after 8 h visible-light irradiation, nearly 60% of MO is decomposed by the same sample. Further mechanism investigation reveals that the H3PO4 pretreatment process can obviously change the surface features of diatomite carrier, cause the formation of Si-O-Ti bond, increase the binding strength between TiO2 and diatomite, restrain crystal growth of loaded TiO2, and thus form thermal-stable mesoporous structure at the granular spaces. It helps to build micro-, meso- and macro-porous hierarchical porous structure in TiO2-diatomite, and improves the charge and mass transfer efficiency during catalyzing process, resulting in the significantly increased photocatalytic activity of TiO2-diatomite pretreated by phosphoric acid.

  19. Study the target effect on the structural, surface and optical properties of TiO2 thin film fabricated by RF sputtering method

    NASA Astrophysics Data System (ADS)

    Vyas, Sumit; Tiwary, Rohit; Shubham, Kumar; Chakrabarti, P.

    2015-04-01

    The effect of target (Ti metal target and TiO2 target) on Titanium Dioxide (TiO2) thin films grown on ITO coated glass substrate by RF magnetron sputtering has been investigated. A comparative study of both the films was done in respect of crystalline structure, surface morphology and optical properties by using X-ray diffractometer (XRD), Atomic Force Microscopy (AFM) studies and ellipsometric measurements. The XRD results confirmed the crystalline structure and indicated that the deposited films have the intensities of anatase phase. The surface morphology and roughness values indicated that the film using Ti metal target has a smoother surface and densely packed with grains as compared to films obtained using TiO2 target. A high transmission in the visible region, and direct band gap of 3.67 eV and 3.75 eV for films derived by using Ti metal and TiO2 target respectively and indirect bandgap of 3.39 eV for the films derived from both the targets (Ti metal and TiO2 target) were observed by the ellipsometric measurements.

  20. The Electronic Structure and Optical Properties of Anatase TiO2 with Rare Earth Metal Dopants from First-Principles Calculations

    PubMed Central

    Xie, Kefeng; Jia, Qiangqiang; Wang, Yizhe; Zhang, Wenxue; Xu, Jingcheng

    2018-01-01

    The electronic and optical properties of the rare earth metal atom-doped anatase TiO2 have been investigated systematically via density functional theory calculations. The results show that TiO2 doped by Ce or Pr is the optimal choice because of its small band gap and strong optical absorption. Rare earth metal atom doping induces several impurity states that tune the location of valence and conduction bands and an obvious lattice distortion that should reduce the probability of electron–hole recombination. This effect of band change originates from the 4f electrons of the rare earth metal atoms, which leads to an improved visible light absorption. This finding indicates that the electronic structure of anatase TiO2 is tuned by the introduction of impurity atoms. PMID:29364161

  1. Stacking orders induced direct band gap in bilayer MoSe2-WSe2 lateral heterostructures.

    PubMed

    Hu, Xiaohui; Kou, Liangzhi; Sun, Litao

    2016-08-16

    The direct band gap of monolayer semiconducting transition-metal dichalcogenides (STMDs) enables a host of new optical and electrical properties. However, bilayer STMDs are indirect band gap semiconductors, which limits its applicability for high-efficiency optoelectronic devices. Here, we report that the direct band gap can be achieved in bilayer MoSe2-WSe2 lateral heterostructures by alternating stacking orders. Specifically, when Se atoms from opposite layers are stacked directly on top of each other, AA and A'B stacked heterostructures show weaker interlayer coupling, larger interlayer distance and direct band gap. Whereas, when Se atoms from opposite layers are staggered, AA', AB and AB' stacked heterostructures exhibit stronger interlayer coupling, shorter interlayer distance and indirect band gap. Thus, the direct/indirect band gap can be controllable in bilayer MoSe2-WSe2 lateral heterostructures. In addition, the calculated sliding barriers indicate that the stacking orders of bilayer MoSe2-WSe2 lateral heterostructures can be easily formed by sliding one layer with respect to the other. The novel direct band gap in bilayer MoSe2-WSe2 lateral heterostructures provides possible application for high-efficiency optoelectronic devices. The results also show that the stacking order is an effective strategy to induce and tune the band gap of layered STMDs.

  2. Tuning band alignment by CdS layers using a SILAR method to enhance TiO2/CdS/CdSe quantum-dot solar-cell performance.

    PubMed

    Zhang, Bingkai; Zheng, Jiaxin; Li, Xiaoning; Fang, Yanyan; Wang, Lin-Wang; Lin, Yuan; Pan, Feng

    2016-04-28

    We report tuning band alignment by optimized CdS layers using a SILAR method to achieve the recorded best performance with about 6% PCE in TiO2/CdS/CdSe QDSSCs. Combining experimental and theoretical studies, we find that a better lattices match between CdS and TiO2 assists the growth of CdSe, and the combined effect of charge transfer and surface dipole moment at the TiO2/CdS/CdSe interface shifts the energy levels of TiO2 upward and increases Voc of the solar cells. More importantly, the band gap of CdS buffer layers is sensitive to the distortion induced by lattice mismatch and numbers of CdS layers. For example, the barrier for charge transfer disappears when there are more than 4 layers of CdS, facilitating the charge injection from CdSe to TiO2.

  3. Visible light photocatalytic antibacterial activity of Ni-doped and N-doped TiO2 on Staphylococcus aureus and Escherichia coli bacteria.

    PubMed

    Ananpattarachai, Jirapat; Boonto, Yuphada; Kajitvichyanukul, Puangrat

    2016-03-01

    The Ni-doped and N-doped TiO2 nanoparticles were investigated for their antibacterial activities on Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) bacteria. Their morphological features and characteristics such as particle size, surface area, and visible light absorbing capacity were compared and discussed. Scanning electron microscopy, X-ray diffraction, and UV-visible spectrophotometry were used to characterize both materials. The inactivation of E. coli (as an example of Gram-negative bacteria) and S. aureus (as an example of Gram-positive bacteria) with Ni-doped and N-doped TiO2 was investigated in the absence and presence of visible light. Antibacterial activity tests were conducted using undoped, Ni-doped, and N-doped TiO2. The N-doped TiO2 nanoparticles show higher antibacterial activity than Ni-doped TiO2. The band gap narrowing of N-doped TiO2 can induce more visible light absorption and leads to the superb antibacterial properties of this material. The complete inactivation time for E. coli at an initial cell concentration of 2.7 × 10(4) CFU/mL was 420 min which is longer than the 360 min required for S. aureus inactivation. The rate of inactivation of S. aureus using the doped TiO2 nanoparticles in the presence of visible light is greater than that of E. coli. The median lethal dose (LD50) values of S. aureus and E. coli by antibacterial activity under an 18-W visible light intensity were 80 and 350 mg/ml for N-doped TiO2, respectively.

  4. Studies on the Fe3+ Doping Effect on Structural, Optical and Catalytic Properties of Hydrothermally Synthesized TiO2 Photocatalyst

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kamble, Ravi; Sabale, Sandip; Chikode, Prashant

    2017-08-01

    Pure TiO2 and Fe3+-TiO2 nanoparticles have been prepared by simple hydrothermal method with different Fe3+ concentrations. The synthesized nanoparticles are analysed to determine its structural, optical, morphological and compositional properties using X-ray diffraction, Raman, UV-DRS, photoluminescence, Mossbauer, XPS, TEM and SEM/EDS. The EDS micrograph confirms the existence of Fe3+ atoms in the TiO2 matrix with 0.85, 1.52 and 1.87 weight percent. The crystallite size and band gap decrease with increase in Fe3+concentration. The average particle size obtained from TEM is 7-11 nm which is in good agreement with XRD results. Raman bands at 640 cm-1, 517 cm-1 and 398 cm-1more » further confirm pure phase anatase in all samples. XPS shows the proper substitutions of few sites of Ti4+ ions by Fe3+ ions in the TiO2 host lattice. The intensity of PL spectra for Fe3+-TiO2 shows a gradual decrease in the peak intensity with increasing Fe3+ concentration in TiO2, and it indicates lower recombination rate as Fe3+ ions increases. These nanoparticles are further studied for its photocatalytic activities using malachite green dye under UV light, visible light and sunlight.« less

  5. Thermoelectric Properties of Self Assembled TiO2/SnO2 Nanocomposites

    NASA Technical Reports Server (NTRS)

    Dynys, Fred; Sayir, Ali; Sehirlioglu, Alp

    2008-01-01

    Recent advances in improving efficiency of thermoelectric materials are linked to nanotechnology. Thermodynamically driven spinodal decomposition was utilized to synthesize bulk nanocomposites. TiO2/SnO2 system exhibits a large spinodal region, ranging from 15 to 85 mole % TiO2. The phase separated microstructures are stable up to 1400 C. Semiconducting TiO2/SnO2 powders were synthesized by solid state reaction between TiO2 and SnO2. High density samples were fabricated by pressureless sintering. Self assemble nanocomposites were achieved by annealing at 1000 to 1350 C. X-ray diffraction reveal phase separation of (Ti(x)Sn(1-x))O2 type phases. The TiO2/SnO2 nanocomposites exhibit n-type behavior; a power factor of 70 W/mK2 at 1000 C has been achieved with penta-valent doping. Seebeck, thermal conductivity, electrical resistivity and microstructure will be discussed in relation to composition and doping.

  6. Targeted sonodynamic therapy using protein-modified TiO2 nanoparticles.

    PubMed

    Ninomiya, Kazuaki; Ogino, Chiaki; Oshima, Shuhei; Sonoke, Shiro; Kuroda, Shun-ichi; Shimizu, Nobuaki

    2012-05-01

    Our previous study suggested new sonodynamic therapy for cancer cells based on the delivery of titanium dioxide (TiO(2)) nanoparticles (NPs) modified with a protein specifically recognizing target cells and subsequent generation of hydroxyl radicals from TiO(2) NPs activated by external ultrasound irradiation (called TiO(2)/US treatment). The present study first examined the uptake behavior of TiO(2) NPs modified with pre-S1/S2 (model protein-recognizing hepatocytes) by HepG2 cells for 24h. It took 6h for sufficient uptake of the TiO(2) NPs by the cells. Next, the effect of the TiO(2)/US treatment on HepG2 cell growth was examined for 96 h after the 1 MHz ultrasound was irradiated (0.1 W/cm(2), 30s) to the cells which incorporated the TiO(2) NPs. Apoptosis was observed at 6h after the TiO(2)/US treatment. Although no apparent cell-injury was observed until 24h after the treatment, the viable cell concentration had deteriorated to 46% of the control at 96 h. Finally, the TiO(2)/US treatment was applied to a mouse xenograft model. The pre-S1/S2-immobilized TiO(2) (0.1mg) was directly injected into tumors, followed by 1 MHz ultrasound irradiation at 1.0 W/cm(2) for 60s. As a result of the treatment repeated five times within 13 days, tumor growth could be hampered up to 28 days compared with the control conditions. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Thermoelectric Properties of Self Assemble TiO2/SnO2 Nanocomposites

    NASA Technical Reports Server (NTRS)

    Dynys, Fred; Sayir, Ali; Sehirlioglu, Alp

    2008-01-01

    Recent advances in improving efficiency of thermoelectric materials are linked to nanotechnology. Thermodynamically driven spinodal decomposition was utilized to synthesize bulk nanocomposites. TiO2/SnO2 system exhibits a large spinodal region, ranging from 15 to 85 mole % TiO2. The phase separated microstructures are stable up to 1400 C. Semiconducting TiO2/SnO2 powders were synthesized by solid state reaction between TiO2 and SnO2. High density samples were fabricated by pressureless sintering. Self assemble nanocomposites were achieved by annealing at 1000 to 1350 C. X-ray diffraction reveal phase separation of (Ti(x)Sn(1-x))O2 type phases. The TiO2/SnO2 nanocomposites exhibit n-type behavior; a power factor of 70 (mu)W/m sq K at 1000 C has been achieved with penta-valent doping. Seebeck, thermal conductivity, electrical resistivity and microstructure will be discussed in relation to composition and doping.

  8. Photocatalytic performance of Cu-doped TiO2 nanofibers treated by the hydrothermal synthesis and air-thermal treatment

    NASA Astrophysics Data System (ADS)

    Wu, Ming-Chung; Wu, Po-Yeh; Lin, Ting-Han; Lin, Tz-Feng

    2018-02-01

    Series of transition metal-doped TiO2 (metal/TiO2) is prepared by combining the hydrothermal synthesis and air-thermal treatment without any reduction process. The selected transition metal precursors, including Ag, Au, Co, Cr, Cu, Fe, Ni, Pd, Pt, Y, and Zn, were individually doped into TiO2 nanofibers to evaluate the photocatalytic degradation activity and photocatalytic hydrogen generation. Consider the photocatalytic performance of these synthesized metal/TiO2 under UV-A irradiation, copper doped TiO2 nanofibers (Cu/TiO2 NFs) was chosen for further study due to its extraordinary reactivity. Systematical studies were spread to optimize the doping concentration and the calcination condition for much higher photocatalytic activity Cu/TiO2 NFs. In the photocatalytic degradation test, 0.5 mol%-Cu/TiO2 NFs calcined at 650 °C exhibits the highest activity, which is even higher than commercial TiO2-AEROXIDE® TiO2 P25 under UV-A irradiation. The synthesized 0.5 mol%-Cu/TiO2-650 NFs also have the capability in the photocatalytic hydrogen production. The hydrogen evolution rates are 200 μmol/g·h under UV-A irradiation and 280 μmol/g·h under UV-B irradiation. The density of state calculated by CASTEP for Cu/TiO2 indicates that Cu doping contributes to the states near valence band edge and narrows the band gap. The disclosed process in this study is industrial safe, convenient and cost-effective. We further produce a significant amount of TiO2-based catalysts without any hydrogen reduction treatment.

  9. A novel theoretical model for the temperature dependence of band gap energy in semiconductors

    NASA Astrophysics Data System (ADS)

    Geng, Peiji; Li, Weiguo; Zhang, Xianhe; Zhang, Xuyao; Deng, Yong; Kou, Haibo

    2017-10-01

    We report a novel theoretical model without any fitting parameters for the temperature dependence of band gap energy in semiconductors. This model relates the band gap energy at the elevated temperature to that at the arbitrary reference temperature. As examples, the band gap energies of Si, Ge, AlN, GaN, InP, InAs, ZnO, ZnS, ZnSe and GaAs at temperatures below 400 K are calculated and are in good agreement with the experimental results. Meanwhile, the band gap energies at high temperatures (T  >  400 K) are predicted, which are greater than the experimental results, and the reasonable analysis is carried out as well. Under low temperatures, the effect of lattice expansion on the band gap energy is very small, but it has much influence on the band gap energy at high temperatures. Therefore, it is necessary to consider the effect of lattice expansion at high temperatures, and the method considering the effect of lattice expansion has also been given. The model has distinct advantages compared with the widely quoted Varshni’s semi-empirical equation from the aspect of modeling, physical meaning and application. The study provides a convenient method to determine the band gap energy under different temperatures.

  10. Nano sulfide and oxide semiconductors as promising materials for studies by positron annihilation

    NASA Astrophysics Data System (ADS)

    Nambissan, P. M. G.

    2013-06-01

    A number of wide band gap sulfide and oxide semiconducting nanomaterial systems were investigated using the experimental techniques of positron lifetime and coincidence Doppler broadening measurements. The results indicated several features of the nanomaterial systems, which were found strongly related to the presence of vacancy-type defects and their clusters. Quantum confinement effects were displayed in these studies as remarkable changes in the positron lifetimes and the lineshape parameters around the same grain sizes below which characteristic blue shifts were observed in the optical absorption spectra. Considerable enhancement in the band gap and significant rise of the positron lifetimes were found occurring when the particle sizes were reduced to very low sizes. The results of doping or substitutions by other cations in semiconductor nanosystems were also interesting. Variously heat-treated TiO2 nanoparticles were studied recently and change of positron annihilation parameters across the anatase to rutile structural transition are carefully analyzed. Preliminary results of positron annihilation studies on Eu-doped CeO nanoparticles are also presented.

  11. Photodecomposition of volatile organic compounds using TiO2 nanoparticles.

    PubMed

    Jwo, Ching-Song; Chang, Ho; Kao, Mu-Jnug; Lin, Chi-Hsiang

    2007-06-01

    This study examined the photodecomposition of volatile organic compounds (VOCs) using TiO2 catalyst fabricated by the Submerged Arc Nanoparticle Synthesis System (SANSS). TiO2 catalyst was employed to decompose volatile organic compounds and compare with Degussa-P25 TiO2 in terms of decomposition efficiency. In the electric discharge manufacturing process, a Ti bar, applied as the electrode, was melted and vaporized under high temperature. The vaporized Ti powders were then rapidly quenched under low-temperature and low-pressure conditions in deionized water, thus nucleating and forming nanocrystalline powders uniformly dispersed in the base solvent. The average diameter of the TiO2 nanoparticles was 20 nm. X-ray diffraction analysis confirmed that the nanoparticles in the deionized water were Anatase type TiO2. It was found that gaseous toluene exposed to UV irradiation produced intermediates that were even harder to decompose. After 60-min photocomposition, Degussa-P25 TiO2 reduced the concentration of gaseous toluene to 8.18% while the concentration after decomposition by SANSS TiO2 catalyst dropped to 0.35%. Under UV irradiation at 253.7 +/- 184.9 nm, TiO2 prepared by SANSS can produce strong chemical debonding energy, thus showing great efficiency, superior to that of Degussa-P25 TiO2, in decomposing gaseous toluene and its intermediates.

  12. SiO2 and TiO2 nanoparticles synergistically trigger macrophage inflammatory responses.

    PubMed

    Tsugita, Misato; Morimoto, Nobuyuki; Nakayama, Masafumi

    2017-04-11

    Silicon dioxide (SiO 2 ) nanoparticles (NPs) and titanium dioxide (TiO 2 ) NPs are the most widely used inorganic nanomaterials. Although the individual toxicities of SiO 2 and TiO 2 NPs have been extensively studied, the combined toxicity of these NPs is much less understood. In this study, we observed unexpected and drastic activation of the caspase-1 inflammasome and production of IL-1β in mouse bone marrow-derived macrophages stimulated simultaneously with SiO 2 and TiO 2 NPs at concentrations at which these NPs individually do not cause macrophage activation. Consistent with this, marked lung inflammation was observed in mice treated intratracheally with both SiO 2 and TiO 2 NPs. In macrophages, SiO 2 NPs localized in lysosomes and TiO 2 NPs did not; while only TiO 2 NPs produced ROS, suggesting that these NPs induce distinct cellular damage leading to caspase-1 inflammasome activation. Intriguingly, dynamic light scattering measurements revealed that, although individual SiO 2 and TiO 2 NPs immediately aggregated to be micrometer size, the mixture of these NPs formed a stable and relatively monodisperse complex with a size of ~250 nm in the presence of divalent cations. Taken together, these results suggest that SiO 2 and TiO 2 NPs synergistically induce macrophage inflammatory responses and subsequent lung inflammation. Thus, we propose that it is important to assess the synergistic toxicity of various combinations of nanomaterials.

  13. Synthesis of nanodimensional TiO2 thin films.

    PubMed

    Thakurdesai, Madhavi; Mohanty, T; John, J; Rao, T K Gundu; Raychaudhuri, Pratap; Bhattacharyya, V; Kanjilal, D

    2008-08-01

    Nanodimensional TiO2 has wide application in the field of photocatalysis, photovoltaic and photochromic devices. In present investigation TiO2 thin films deposited by pulsed laser deposition method are irradiated by 100 MeV Ag ion beam to achieve growth of nanophases. The nanostructure evolution is characterized by atomic force microscopy (AFM). The phases of TiO2 formed after irradiation are identified by glancing angle X-ray diffraction and Raman spectroscopy. The particle radius estimated by AFM varies from 10-13 nm. Anatase phase of TiO2 is formed after irradiation. The blue shift observed in UV-VIS absorption spectra indicates the nanostructure formation. The shape and size of nanoparticles formed due to high electronic excitation depend upon thickness of the film.

  14. High band gap 2-6 and 3-5 tunneling junctions for silicon multijunction solar cells

    NASA Technical Reports Server (NTRS)

    Daud, Taher (Inventor); Kachare, Akaram H. (Inventor)

    1986-01-01

    A multijunction silicon solar cell of high efficiency is provided by providing a tunnel junction between the solar cell junctions to connect them in series. The tunnel junction is comprised of p+ and n+ layers of high band gap 3-5 or 2-6 semiconductor materials that match the lattice structure of silicon, such as GaP (band gap 2.24 eV) or ZnS (band gap 3.6 eV). Each of which has a perfect lattice match with silicon to avoid defects normally associated with lattice mismatch.

  15. One-pot engineering TiO2/graphene interface for enhanced adsorption and photocatalytic degradation of multiple organics.

    PubMed

    Song, Jianhua; Ling, Yun; Xie, Yu; Liu, Lianjun; Zhu, Huihua

    2018-06-13

    It is challenging to design a multifunctional structure or composite for simultaneously adsorb and photocatalytic degrade organic pollutants in water. Towards this goal, this work innovatively engineered interfacial sites between TiO2 particles and reduced graphene oxide (RGO) sheets by employing in situ one-pot one-step solvothermal method. The interface was associated with the content of RGO, solvothermal time and solvent ratio of n-pentanol to n-hexane. It was found that when at a moderate amount of RGO (25%), TiO2 nanoparticles were well dispersed on the surface of RGO or wrapped by RGO, thus leading to a fully contact and strong interaction to form Ti - O - C interfacial structure. But when at a low content of RGO (6%), TiO2 aggregates were mixture of nanosheets, nanoparticles and nanorods. 25%RGO/TiO2 also had 175% higher surface area (146m2/g), 95% larger volume (0.339 cm3/g) and smaller band gap than 6%RGO/TiO2. More importantly, 25%RGO/TiO2 demonstrated higher adsorption efficiency (25%) and 4 times faster degradation rate than TiO2 (0%). It also exhibited good capability to eliminate multiple organics and stable long-term cycle performance (up to 93% retention after 30 cycles). Its superiority was attributed to the large surface area and unique interface between TiO2 and RGO, which not only provided more active sites to capture pollutants but also enhanced charge transfer (3 µA/cm2, 5 times higher than TiO2). This work offered a promising way to purify water through engineering new materials structure and integrating adsorption and photodegradation technologies. © 2018 IOP Publishing Ltd.

  16. Main regularities of SERS on semiconductors and dielectrics

    NASA Astrophysics Data System (ADS)

    Chelibanov, V. P.; Polubotko, A. M.

    2018-04-01

    The paper demonstrates that the reason of SERS on dielectrics and semiconductors is the enhancement of the electric field in the regions of the tops of the surface roughness with a very large positive curvature. The enhancement in many ways depends on the dielectric constant of the substrate and is stronger for a larger dielectric constant. The theoretical result points out that on dielectrics and semiconductors it is weaker than on metals. Experimentally it is demonstrated that there are forbidden lines on hydroquinone, adsorbed on TiO2 , which indicate on the existence of strong quadrupole light-molecule interaction in such systems.

  17. Interplay of dopant, defects and electronic structure in driving ferromagnetism in Co-doped oxides: TiO(2), CeO(2) and ZnO.

    PubMed

    Ali, Bakhtyar; Shah, Lubna R; Ni, C; Xiao, J Q; Shah, S Ismat

    2009-11-11

    A comprehensive study of the defects and impurity (Co)-driven ferromagnetism is undertaken in the oxide semiconductors: TiO(2), ZnO and CeO(2). The effect of magnetic (Co(2+)) and non-magnetic (Cu(2+)) impurities in conjunction with defects, such as oxygen vacancies (V(o)), have been thoroughly investigated. Analyses of the x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) data reveal the incorporation of cobalt in the lattice, with no signature of cobalt segregation. It is shown that oxygen vacancies are necessary for the ferromagnetic coupling in the Co-doped oxides mentioned above. The possible exchange mechanisms responsible for the ferromagnetism are discussed in light of the energy levels of dopants in the host oxides. In addition, Co and Cu co-doped TiO(2) samples are studied in order to understand the role of point defects in establishing room temperature ferromagnetism. The parameters calculated from the bound magnetic polaron (BMP) and Jorgensen's optical electronegativity models offer a satisfactory explanation of the defect-driven ferromagnetism in the doped/co-doped samples.

  18. Graphene-insulator-semiconductor capacitors as superior test structures for photoelectric determination of semiconductor devices band diagrams

    NASA Astrophysics Data System (ADS)

    Piskorski, K.; Passi, V.; Ruhkopf, J.; Lemme, M. C.; Przewlocki, H. M.

    2018-05-01

    We report on the advantages of using Graphene-Insulator-Semiconductor (GIS) instead of Metal-Insulator-Semiconductor (MIS) structures in reliable and precise photoelectric determination of the band alignment at the semiconductor-insulator interface and of the insulator band gap determination. Due to the high transparency to light of the graphene gate in GIS structures large photocurrents due to emission of both electrons and holes from the substrate and negligible photocurrents due to emission of carriers from the gate can be obtained, which allows reliable determination of barrier heights for both electrons, Ee and holes, Eh from the semiconductor substrate. Knowing the values of both Ee and Eh allows direct determination of the insulator band gap EG(I). Photoelectric measurements were made of a series of Graphene-SiO2-Si structures and an example is shown of the results obtained in sequential measurements of the same structure giving the following barrier height values: Ee = 4.34 ± 0.01 eV and Eh = 4.70 ± 0.03 eV. Based on this result and results obtained for other structures in the series we conservatively estimate the maximum uncertainty of both barrier heights estimations at ± 0.05 eV. This sets the SiO2 band gap estimation at EG(I) = 7.92 ± 0.1 eV. It is shown that widely different SiO2 band gap values were found by research groups using various determination methods. We hypothesize that these differences are due to different sensitivities of measurement methods used to the existence of the SiO2 valence band tail.

  19. Improved hydrogen storage properties of MgH2 catalyzed with TiO2

    NASA Astrophysics Data System (ADS)

    Jangir, Mukesh; Meena, Priyanka; Jain, I. P.

    2018-05-01

    In order to improve the hydrogenation properties of the MgH2, various concentration of rutile Titanium Oxide (TiO2) (X wt%= 5, 10, 15 wt %) is added to MgH2 by ball milling and the catalytic effect of TiO2 on hydriding/dehydriding properties of MgH2 has been investigated. Result shows that the TiO2 significantly reduced onset temperature of desorption. Onset temperature as low as 190 °C were observed for the MgH2-15 wt% TiO2 sample which is 60 °C and 160 °C lower than the as-milled and as-received MgH2. Fromm the Kissinger plot the activation energy of 15 wt% TiO2 added sample is calculated to be -75.48 KJ/mol. These results indicate that the hydrogenation properties of MgH2-TiO2 have been improved compared to the as-milled and as-received MgH2. Furthermore, XRD and XPS were performed to characterize the structural evolution upon milling and dehydrogenation.

  20. Photo degradation of methyl orange by attapulgite-SnO2-TiO2 nanocomposites.

    PubMed

    Zhang, Lili; Lv, Fujian; Zhang, Weiguang; Li, Rongqing; Zhong, Hui; Zhao, Yijiang; Zhang, Yu; Wang, Xin

    2009-11-15

    Photocatalytic removal of methyl orange under ultraviolet radiation has been studied using attapulgite (ATT) composites, which were synthesized by depositing SnO(2)-TiO(2) hybrid oxides on the surface of ATT to form a composite photocatalyst (denoted ATT-SnO(2)-TiO(2)) using an in situ sol-gel technique. Results showed that SnO(2)-TiO(2) nanocomposite particles with average size of about 10nm were loaded successfully on to the surface of ATT fibers and were widely dispersed. Correspondingly, the photocatalytic activity of ATT was improved significantly by loading SnO(2)-TiO(2). The photoactivity of the composite photocatalyst decreased in the sequence ATT-SnO(2)-TiO(2)>ATT-SnO(2)>ATT-TiO(2)>ATT. In order to achieve the best photocatalyst, the molar ratio of SnO(2) and TiO(2) in the ATT-SnO(2)-TiO(2) composites was adjusted to give a series with proportions r=n(Ti)/(n(Ti)+n(Sn))=0.0, 0.25, 0.33, 0.50, 0.67, 0.75, 0.80, 0.82, 0.86, 1.0. Results indicated that the proportion of SnO(2) and TiO(2) had a critical effect on the photocatalytic activity, which increased as the content of TiO(2) increased to r0.82. The highest degradation rate of methyl orange was 99% within 30 min obtained by using ATT-SnO(2)-TiO(2) with r=0.82. The repeated use of the composite photocatalyst was also confirmed.

  1. Oriented epitaxial TiO2 nanowires for water splitting

    NASA Astrophysics Data System (ADS)

    Hou, Wenting; Cortez, Pablo; Wuhrer, Richard; Macartney, Sam; Bozhilov, Krassimir N.; Liu, Rong; Sheppard, Leigh R.; Kisailus, David

    2017-06-01

    Highly oriented epitaxial rutile titanium dioxide (TiO2) nanowire arrays have been hydrothermally grown on polycrystalline TiO2 templates with their orientation dependent on the underlying TiO2 grain. Both the diameter and areal density of the nanowires were tuned by controlling the precursor concentration, and the template surface energy and roughness. Nanowire tip sharpness was influenced by precursor solubility and diffusivity. A new secondary ion mass spectrometer technique has been developed to install additional nucleation sites in single crystal TiO2 templates and the effect on nanowire growth was probed. Using the acquired TiO2 nanowire synthesis knowhow, an assortment of nanowire arrays were installed upon the surface of undoped TiO2 photo-electrodes and assessed for their photo-electrochemical water splitting performance. The key result obtained was that the presence of short and dispersed nanowire arrays significantly improved the photocurrent when the illumination intensity was increased from 100 to 200 mW cm-2. This is attributed to the alignment of the homoepitaxially grown nanowires to the [001] direction, which provides the fastest charge transport in TiO2 and an improved pathway for photo-holes to find water molecules and undertake oxidation. This result lays a foundation for achieving efficient water splitting under conditions of concentrated solar illumination.

  2. Photodegradation of Orange II by mesoporous TiO2.

    PubMed

    Kuang, Liyuan; Zhao, Yaping; Liu, Lu

    2011-09-01

    Mesoporous TiO(2) microspheres were prepared by a hydrothermal reaction and are characterized in this paper. Decoloration and mineralization during photodegradation of Orange II by mesoporous TiO(2) at different pH values, formation of sulfate, relative luminosity to luminous bacteria and recycling experiments of the catalyst were studied. The FTIR results further suggested that the novel mesoporous TiO(2) can not only decolor and mineralize dyes completely but also can be effectively reused several times. On the basis of the research, mesoporous TiO(2) would be a promising photocatalyst for practical use.

  3. Feasibility of applying the LED-UV-induced TiO2/ZnO-supported H3PMo12O40 nanoparticles in photocatalytic degradation of aniline.

    PubMed

    Taghavi, Mahmoud; Ghaneian, Mohammad Taghi; Ehrampoush, Mohammad Hasan; Tabatabaee, Masoumeh; Afsharnia, Mojtaba; Alami, Ali; Mardaneh, Jalal

    2018-03-03

    In the present study, TiO 2 /ZnO-supported phosphomolybdic acid nanoparticles are investigated by the impregnation method, followed by analyzing their photocatalytic activity under UV-LED light and degradation kinetics degrading aniline as an organic pollutant model. Nanoparticle characteristics and the remaining Keggin structure in the nanocomposites were confirmed by means of FESEM, FTIR, and XRD analyses. Heterogenization of phosphomolybdic acid on TiO 2 and ZnO nanoparticles resulted in the improved light absorption intensity and decreased band gap of nanocomposites. Photocatalytic degradation of aniline was also improved for composite nanoparticles and reached to 25.62, 43.48, and 38.25% for TiO 2 /HPMo, ZnO/HPMo, and TiO 2 /ZnO/HPMo, respectively. Overall, the results showed a good fit to the Langmuir-Hinshelwood kinetic model.

  4. Hierarchical TiO2/C nanocomposite monoliths with a robust scaffolding architecture, mesopore-macropore network and TiO2-C heterostructure for high-performance lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Huang, Hai-Bo; Yang, Yue; Chen, Li-Hua; Wang, Yun; Huang, Shao-Zhuan; Tao, Jia-Wei; Ma, Xiao-Ting; Hasan, Tawfique; Li, Yu; Xu, Yan; Su, Bao-Lian

    2016-05-01

    Engineering hierarchical structures of electrode materials is a powerful strategy for optimizing the electrochemical performance of an anode material for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical TiO2/C nanocomposite monoliths by mediated mineralization and carbonization using bacterial cellulose (BC) as a scaffolding template as well as a carbon source. TiO2/C has a robust scaffolding architecture, a mesopore-macropore network and TiO2-C heterostructure. TiO2/C-500, obtained by calcination at 500 °C in nitrogen, contains an anatase TiO2-C heterostructure with a specific surface area of 66.5 m2 g-1. When evaluated as an anode material at 0.5 C, TiO2/C-500 exhibits a high and reversible lithium storage capacity of 188 mA h g-1, an excellent initial capacity of 283 mA h g-1, a long cycle life with a 94% coulombic efficiency preserved after 200 cycles, and a very low charge transfer resistance. The superior electrochemical performance of TiO2/C-500 is attributed to the synergistic effect of high electrical conductivity, anatase TiO2-C heterostructure, mesopore-macropore network and robust scaffolding architecture. The current material strategy affords a general approach for the design of complex inorganic nanocomposites with structural stability, and tunable and interconnected hierarchical porosity that may lead to the next generation of electrochemical supercapacitors with high energy efficiency and superior power density.Engineering hierarchical structures of electrode materials is a powerful strategy for optimizing the electrochemical performance of an anode material for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical TiO2/C nanocomposite monoliths by mediated mineralization and carbonization using bacterial cellulose (BC) as a scaffolding template as well as a carbon source. TiO2/C has a robust scaffolding architecture, a mesopore-macropore network and TiO2-C heterostructure. TiO2/C-500

  5. Characterization and application of the hetero-junction ZnFe2O4/TiO2 for Cr(VI) reduction under visible light

    NASA Astrophysics Data System (ADS)

    Rekhila, G.; Trari, M.; Bessekhouad, Y.

    2017-06-01

    The spinel ZnFe2O4 prepared by nitrate route is used as dispersed photons collector capable to sensitize TiO2 under visible light and to reduce Cr(VI) into trivalent state. The transport properties, optical and photo-electrochemical characterizations are correlated, to build the energetic diagram of the hetero-system ZnFe2O4/TiO2/CrO4 - solution. A gap of 1.97 eV is obtained for the spinel from the diffuse reflectance. The conduction band of ZnFe2O4 (-1.47 V SCE) favors the electrons injection into TiO2, permitting a physical separation of the charge carriers. The oxidation of oxalic acid by photoholes prevents the corrosion of the spinel. The best configuration ZnFe2O4 (75 %)/TiO2 (25 %) is used to catalyze the downhill reaction (2HCrO4 - + 3C2H4O4 + 1.5O2 + 8H+ → 2Cr3+ + 6CO2 + 11 H2O, Δ G° = -557 kcal mol-1). 60 % of Cr(VI) are reduced after 3 h of visible light illumination and the photoactivity follows a first-order kinetic with a half-life of 70 min. The water reduction competes with the HCrO4 - reduction which is the reason in the regression of the photoactivity; a hydrogen evolution rate of 24 µmol mg-1 h-1 is obtained.

  6. Green synthesis of highly crystalline and visible-light sensitive C-, N- and S- codoped with Ag TiO2 nanocatalyst

    EPA Science Inventory

    Titanium dioxide (TiO2) has been a focus of attention as chemically stable, relatively nontoxic, inexpensive and highly efficient photocatalyst applicable for a wide array of uses. However, main disadvantage that severely limits its wider use is the large band gap, 3.0 eV and 3.2...

  7. High pressure synthesis of amorphous TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Li, Quanjun; Liu, Ran; Wang, Tianyi; Xu, Ke; Dong, Qing; Liu, Bo; Liu, Jing; Liu, Bingbing

    2015-09-01

    Amorphous TiO2 nanotubes with diameters of 8-10 nm and length of several nanometers were synthesized by high pressure treatment of anatase TiO2 nanotubes. The structural phase transitions of anatase TiO2 nanotubes were investigated by using in-situ high-pressure synchrotron X-ray diffraction (XRD) method. The starting anatase structure is stable up to ˜20GPa, and transforms into a high-density amorphous (HDA) form at higher pressure. Pressure-modified high- to low-density transition was observed in the amorphous form upon decompression. The pressure-induced amorphization and polyamorphism are in good agreement with the previous results in ultrafine TiO2 nanoparticles and nanoribbons. The relationship between the LDA form and α-PbO2 phase was revealed by high-resolution transmission electron microscopy (HRTEM) study. In addition, the bulk modulus (B0 = 158 GPa) of the anatase TiO2 nanotubes is smaller than those of the corresponding bulks and nanoparticles (180-240 GPa). We suggest that the unique open-ended nanotube morphology and nanosize play important roles in the high pressure phase transition of TiO2 nanotubes.

  8. [Preparation and Photocatalytic Properties of Supported TiO2 Photocatalytic Material].

    PubMed

    Guo, Yu; Jin, Yu-jia; Wu, Hong-mei; Li, Dong-xin

    2015-06-01

    Titanium dioxide (TiO2) supported on spherical alumina substrate was prepared by using sol-gel method combined with dip-coating process. The surface morphology and structure of the synthesized samples were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) pattern. The results show that the morphology of the supported TiO2 composite material was obviously different from that of the original support. It reveals a layer formed by anatase TiO2 nanoparticles of 10-20 nm was deposited on the alumina substrate. Energy dispersive X-ray spectroscopy (EDX) analyses on the spherical alumina substrate and the resulting TiO2 composite catalyst were performed to determine the TiO2 loading content in the samples. It indicates that the TiO2 loading content on alumina substrate could be effectively increased by increasing the times of dip-coating alumina support in TiO2 sol. When dip-coating times increased to 5, the TiO2 loading content increased from 3.8 Wt. % to 15.7 Wt. %. In addition, the photocatalytic performances of the supported TiO2 materials prepared by different dip-coating times have been investigated by degrading methylene blue. It was found that the surface morphology of the supported TiO2 material was not only improved, but also the photocatalytic activity could be promoted significantly by increasing the dip-coating times. When the alumina substrate was dip-coated in TiO2 sol from 1 to 4 times, the degradation rate of methylene blue increased from 40% to 83.1%. However, after dip-coating the alumina support in TiO2 sol for 5 times, the degradation of methylene blue was only up to 85.6%. This indicates that the photocatalytic activity increased slowly when the TiO2 content in the supported catalyst was up to some extent. It is attributed to the continuous dip-coating resulted in less opportunities and weak intensity of illumination for the TiO2 nano-particles that under lower layer. The photocatalytic activity was relatively stable

  9. Newtype single-layer magnetic semiconductor in transition-metal dichalcogenides VX2 (X = S, Se and Te)

    NASA Astrophysics Data System (ADS)

    Fuh, Huei-Ru; Chang, Ching-Ray; Wang, Yin-Kuo; Evans, Richard F. L.; Chantrell, Roy W.; Jeng, Horng-Tay

    2016-09-01

    We present a newtype 2-dimensional (2D) magnetic semiconductor based on transition-metal dichalcogenides VX2 (X = S, Se and Te) via first-principles calculations. The obtained indirect band gaps of monolayer VS2, VSe2, and VTe2 given from the generalized gradient approximation (GGA) are respectively 0.05, 0.22, and 0.20 eV, all with integer magnetic moments of 1.0 μB. The GGA plus on-site Coulomb interaction U (GGA + U) enhances the exchange splittings and raises the energy gap up to 0.38~0.65 eV. By adopting the GW approximation, we obtain converged G0W0 gaps of 1.3, 1.2, and 0.7 eV for VS2, VSe2, and VTe2 monolayers, respectively. They agree very well with our calculated HSE gaps of 1.1, 1.2, and 0.6 eV, respectively. The gap sizes as well as the metal-insulator transitions are tunable by applying the in-plane strain and/or changing the number of stacking layers. The Monte Carlo simulations illustrate very high Curie-temperatures of 292, 472, and 553 K for VS2, VSe2, and VTe2 monolayers, respectively. They are nearly or well beyond the room temperature. Combining the semiconducting energy gap, the 100% spin polarized valence and conduction bands, the room temperature TC, and the in-plane magnetic anisotropy together in a single layer VX2, this newtype 2D magnetic semiconductor shows great potential in future spintronics.

  10. Electrospinning processed nanofibrous TiO2 membranes for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Onozuka, Katsuhiro; Ding, Bin; Tsuge, Yosuke; Naka, Takayuki; Yamazaki, Michiyo; Sugi, Shinichiro; Ohno, Shingo; Yoshikawa, Masato; Shiratori, Seimei

    2006-02-01

    We have recently fabricated dye-sensitized solar cells (DSSCs) comprising nanofibrous TiO2 membranes as electrode materials. A thin TiO2 film was pre-deposited on fluorine doped tin oxide (FTO) coated conducting glass substrate by immersion in TiF4 aqueous solution to reduce the electron back-transfer from FTO to the electrolyte. The composite polyvinyl acetate (PVac)/titania nanofibrous membranes can be deposited on the pre-deposited thin TiO2 film coated FTO by electrospinning of a mixture of PVac and titanium isopropoxide in N,N-dimethylformamide (DMF). The nanofibrous TiO2 membranes were obtained by calcining the electrospun composite nanofibres of PVac/titania as the precursor. Spectral sensitization of the nanofibrous TiO2 membranes was carried out with a ruthenium (II) complex, cis-dithiocyanate-N,N'-bis(2,2'-bipyridyl-4,4'-dicarboxylic acid) ruthenium (II) dihydrate. The results indicated that the photocurrent and conversion efficiency of electrodes can be increased with the addition of the pre-deposited TiO2 film and the adhesion treatment using DMF. Additionally, the dye loading, photocurrent, and efficiency of the electrodes were gradually increased by increasing the average thickness of the nanofibrous TiO2 membranes. The efficiency of the fibrous TiO2 photoelectrode with the average membrane thickness of 3.9 µm has a maximum value of 4.14%.

  11. A Ag synchronously deposited and doped TiO2 hybrid as an ultrasensitive SERS substrate: a multifunctional platform for SERS detection and photocatalytic degradation.

    PubMed

    Yang, Libin; Sang, Qinqin; Du, Juan; Yang, Ming; Li, Xiuling; Shen, Yu; Han, Xiaoxia; Jiang, Xin; Zhao, Bing

    2018-06-06

    Ag simultaneously deposited and doped TiO2 (Ag-TiO2) hybrid nanoparticles (NPs) were prepared via a sol-hydrothermal method, as both a sensitive surface-enhanced Raman scattering (SERS) substrate and a superior photocatalyst for the first time. Ag-TiO2 hybrid NPs exhibit excellent SERS performance for several probe molecules and the enhancement factor is calculated to be 1.86 × 105. The detection limit of the 4-mercaptobenzoic acid (4-MBA) probe on the Ag-TiO2 substrate is 1 × 10-9 mol L-1, which is four orders of magnitude lower than that on pure TiO2 as a consequence of the synergistic effects of TiO2 and Ag. This is the highest SERS sensitivity among the reported semiconductor substrates and even comparable to noble metal substrates, and a SERS enhancement mechanism from the synergistic contribution of the semiconductor and noble metal was proposed. And importantly, the Ag-TiO2 hybrid shows excellent photocatalytic degradation activity for the detected species under UV light irradiation at lower concentration conditions, even for the hard to degrade 4-MBA molecule. This makes the Ag-TiO2 hybrid promising as a dual-function platform for both highly sensitive SERS detection and photocatalytic degradation of a pollutant system. Moreover, it also proves that the Ag-TiO2 hybrid can serve as a promising recyclable SERS-active substrate by virtue of its photocatalytic self-cleaning properties for some specific applications, for instance comparative studies of different species on the same SERS platform, in addition to the economic benefit.

  12. Impact of bimetal electrodes on dielectric properties of TiO2 and Al-doped TiO2 films.

    PubMed

    Kim, Seong Keun; Han, Sora; Jeon, Woojin; Yoon, Jung Ho; Han, Jeong Hwan; Lee, Woongkyu; Hwang, Cheol Seong

    2012-09-26

    Rutile structured Al-doped TiO(2) (ATO) and TiO(2) films were grown on bimetal electrodes (thin Ru/thick TiN, Pt, and Ir) for high-performance capacitors. The work function of the top Ru layer decreased on TiN and increased on Pt and Ir when it was thinner than ~2 nm, suggesting that the lower metal within the electrodes influences the work function of the very thin Ru layer. The use of the lower electrode with a high work function for bottom electrode eventually improves the leakage current properties of the capacitor at a very thin Ru top layer (≤2 nm) because of the increased Schottky barrier height at the interface between the dielectric and the bottom electrode. The thin Ru layer was necessary to achieve the rutile structured ATO and TiO(2) dielectric films.

  13. Improved photoelectrical performance of graphene supported highly crystallized anatase TiO2

    NASA Astrophysics Data System (ADS)

    Zhang, Min; Sun, Qiong; Zhao, Mei; Li, Yang; Liu, Qiuhong; Dong, Lifeng

    2015-08-01

    In this study, titanium oxysulfate (TiOSO4) and graphene were used as titanium source and supporter, respectively, to synthesize anatase TiO2-graphene (TiO2-G) composite. Crystal structure, morphology, and composition of TiO2-G were investigated by X-ray diffraction, scanning electron microscope, transmission electron microscope, and thermogravimetric analysis. Both TiO2-G and blank TiO2 powders exhibit spindle-shaped structure with the long axis along [001]. Compared to unsupported TiO2, TiO2 nanoparticles uniformly formed on graphene surface. When fabricated into dye-sensitized solar cells, photoelectrical conversion efficiency of TiO2-G (2.3 %) was much higher than that of blank TiO2 (0.89 %) prepared at the same conditions. Moreover, high sintering temperature enhanced photoelectrical performance of the composite. When the temperature was increased from 450 to 600 °C, the efficiency was improved from 1.5 to 2.6 %. The findings above demonstrate that TiO2-G has great potential for applications in dye-sensitized solar cells.

  14. The double peaks and symmetric path phenomena in the catalytic activity of Pd/Al2O3-TiO2 catalysts with different TiO2 contents

    NASA Astrophysics Data System (ADS)

    Zhang, Shen; Guo, Yuyu; Li, Xingying; Wu, Xu; Li, Zhe

    2018-06-01

    Physicochemical properties of Pd/Al2O3-TiO2 catalysts with different amounts of TiO2 contents were investigated by XRD, nitrogen adsorption-desorption, FTIR, NH3-TPD, H2-TPR and XPS techniques. Catalysts of different compositions were tested in the ethanol oxidation reaction to study the effects of TiO2 contents. Double peaks and symmetric path phenomena were observed at certain temperatures with the increase in TiO2 contents. The symmetric peak phenomena and the diverse activity fluctuations have been ascribed to the controlling factors such as temperature and compositions. With the increase in TiO2 content, the surface area, adsorbed oxygen contents and surface acid quantity decreased gradually. The large surface area and adsorbed oxygen contents were conducive to the performance, while increased acid amounts were not beneficial for ethanol oxidation. At 150 and 175 °C, Pd/AT(X1

  15. Effect of TiO2, ZrO2, and TiO2-ZrO2 on the performance of CuO-ZnO catalyst for CO2 hydrogenation to methanol

    NASA Astrophysics Data System (ADS)

    Xiao, Jie; Mao, Dongsen; Guo, Xiaoming; Yu, Jun

    2015-05-01

    The influence of TiO2, ZrO2, and TiO2-ZrO2 mixed oxide on the catalytic performance of CuO-ZnO catalyst in the methanol synthesis from CO2 hydrogenation was studied. The catalysts were prepared by oxalate co-precipitation method and characterized by TGA, N2 adsorption, XRD, reactive N2O adsorption, XPS, H2-TPR, H2-TPD, and CO2-TPD techniques. Characterization results reveal that all the additives improve the CuO dispersion in the catalyst body and increase the Cu surface area and adsorption capacities of CO2 and H2. The results of catalytic test reveal that the additives increase both the CO2 conversion and methanol selectivity, and TiO2-ZrO2 mixed oxide is more effective than single components of TiO2 or ZrO2. Moreover, the activity of methanol synthesis is correlated directly with CO2 adsorption capacity over the catalysts.

  16. The structural and optical constants of Ag2S semiconductor nanostructure in the Far-Infrared.

    PubMed

    Zamiri, Reza; Abbastabar Ahangar, Hossein; Zakaria, Azmi; Zamiri, Golnoosh; Shabani, Mehdi; Singh, Budhendra; Ferreira, J M F

    2015-01-01

    In this paper a template-free precipitation method was used as an easy and low cost way to synthesize Ag2S semiconductor nanoparticles. The Kramers-Kronig method (K-K) and classical dispersion theory was applied to calculate the optical constants of the prepared samples, such as the reflective index n(ω) and dielectric constant ε(ω) in Far-infrared regime. Nanocrystalline Ag2S was synthesized by a wet chemical precipitation method. Ag2S nanoparticle was characterized by X-ray diffraction, Scanning Electron Microscopy, UV-visible, and FT-IR spectrometry. The refinement of the monoclinic β-Ag2S phase yielded a structure solution similar to the structure reported by Sadanaga and Sueno. The band gap of Ag2S nanoparticles is around 0.96 eV, which is in good agreement with previous reports for the band gap energy of Ag2S nanoparticles (0.9-1.1 eV). The crystallite size of the synthesized particles was obtained by Hall-Williamson plot for the synthesized Ag2S nanoparticles and it was found to be 217 nm. The Far-infrared optical constants of the prepared Ag2S semiconductor nanoparticles were evaluated by means of FTIR transmittance spectra data and K-K method. Graphical abstractThe Far-infrared optical constants of Ag2S semiconductor nanoparticles.

  17. Iron insertion and hematite segregation on Fe-doped TiO2 nanoparticles obtained from sol-gel and hydrothermal methods.

    PubMed

    Santos, Reginaldo da S; Faria, Guilherme A; Giles, Carlos; Leite, Carlos A P; Barbosa, Herbert de S; Arruda, Marco A Z; Longo, Claudia

    2012-10-24

    Iron-doped TiO(2) (Fe:TiO(2)) nanoparticles were synthesized by the sol-gel method (with Fe/Ti molar ratio corresponding to 1, 3, and 5%), followed by hydrothermal treatment, drying, and annealing. A similar methodology was used to synthesize TiO(2) and α-Fe(2)O(3) nanoparticles. For comparison, a mixture hematite/titania, with Fe/Ti = 4% was also investigated. Characterization of the samples using Rietveld refinement of X-ray diffraction data revealed that TiO(2) consisted of 82% anatase and 18% brookite; for Fe:TiO(2), brookite increased to 30% and hematite was also identified (0.5, 1.0, and 1.2 wt % for samples prepared with 1, 3, and 5% of Fe/Ti). For hematite/titania mixture, Fe/Ti was estimated as 4.4%, indicating the Rietveld method reliability for estimation of phase composition. Because the band gap energy, estimated as 3.2 eV for TiO(2), gradually ranged from 3.0 to 2.7 eV with increasing Fe content at Fe:TiO(2), it can be assumed that a Fe fraction was also inserted as dopant in the TiO(2) lattice. Extended X-ray absorption fine structure spectra obtained for the Ti K-edge and Fe K-edge indicated that absorbing Fe occupied a Ti site in the TiO(2) lattice, but hematite features were not observed. Hematite particles also could not be identified in the images obtained by transmission electron microscopy, in spite of iron identification by elemental mapping, suggesting that hematite can be segregated at the grain boundaries of Fe:TiO(2).

  18. Enhancement in photo-electrochemical efficiency by reducing recombination rate in branched TiO2 nanotube array on functionalizing with ZnO micro crystals

    NASA Astrophysics Data System (ADS)

    Boda, Muzaffar Ahmad; Ashraf Shah, Mohammad

    2018-06-01

    In this study, branched TiO2 nanotube array were fabricated through electrochemical anodization process at constant voltage using third generation electrolyte. On account of morphological advantage, these nanotubes shows significant enhancement in photo-electrochemical property than compact or conventional titania nanotube array. However, their photo-electrochemical efficiency intensifies on coating with ZnO micro-crystals. ZnO coated branched TiO2 nanotube array shows a photocurrent density of 27.8 mA cm‑2 which is 1.55 times the photocurrent density (17.2 mA cm‑2) shown by bare branched titania nanotubes. The significant enhancement in photocurrent density shown by the resulting ZnO/TiO2 hybrid structure is attributed to suppression in electron–hole recombination phenomenon by offering smooth pathway to photo generated excitons on account of staggered band edge positions in individual semiconductors.

  19. Photochemical quenching of aqueous methylene blue by N, Nb co-doped TiO2 nanomaterials under visible light: a confirmatory UV/LC-MS study

    NASA Astrophysics Data System (ADS)

    Gupta, Kamini; Pandey, Ashutosh; Singh, R. P.

    2017-12-01

    Nanodimensional un-doped, Nb doped, N doped and N,Nb co-doped TiO2 particles have been prepared by the sol-gel procedure. Phase identification of the anatase particles was done by X-ray powder diffraction and Deby-Scherrer calculations revealed their particle sizes to range from 20 to 30 nm. The band gap energies of the samples were measured by UV-Vis-diffuse reflectance (UV-DRS) spectra. While un-doped TiO2 showed wide optical absorption in the UV region. The co-doped TiO2 particles exhibited narrow band gaps of ~2.7 eV, which showed absorption in the visible region. A decline in charge carrier recombination rates in the prepared samples was confirmed through photoluminescence (PL). The morphological appearances of the particles have been examined by scanning electron microscopy. X-ray photoelectron spectroscopy (XPS) of the samples confirmed the incorporations of N and Nb into the TiO2 matrices. The photocatalytic efficiencies of the prepared particles have been determined by the degradation of the non-biodegradable dye methylene blue (MB) under electromagnetic radiation. The co-doped sample showed superior photocatalytic activity under the visible light (λ  >  400) over the other samples. Photochemical quenching of aqueous MB was further analysed by UV/LC-MS which confirmed the attenuation of methylene blue.

  20. Assessing the performance of self-consistent hybrid functional for band gap calculation in oxide semiconductors

    NASA Astrophysics Data System (ADS)

    He, Jiangang; Franchini, Cesare

    2017-11-01

    In this paper we assess the predictive power of the self-consistent hybrid functional scPBE0 in calculating the band gap of oxide semiconductors. The computational procedure is based on the self-consistent evaluation of the mixing parameter α by means of an iterative calculation of the static dielectric constant using the perturbation expansion after discretization method and making use of the relation \

  1. TiO2-BASED Composite Films for the Photodegradation of Oxytetracycline

    NASA Astrophysics Data System (ADS)

    Li, Hui; Guan, Ling-Xiao; Feng, Ji-Jun; Li, Fang; Yao, Ming-Ming

    2015-02-01

    The spread of the antibiotic oxytetracycline (OTC) has been thought as a threat to the safety of drinking water. In this paper, the photocatalytic activity of the nanocrystalline Fe/Ca co-doped TiO2-SiO2 composite film for the degradation of OTC was studied. The films were characterized by field emission scanning electron microscopy (FE-SEM) equipped with energy-dispersive spectroscopy (EDS), N2 adsorption/desorption isotherms, photoluminescence (PL) spectra, and UV-Vis diffraction reflectance absorption spectra (DRS). The FE-SEM results indicated that the Fe/Ca co-doped TiO2-SiO2 film was composed of smaller nanoparticles compared to pure TiO2 or TiO2-SiO2 film. The BET surface area results showed that the specific surface area of the pure TiO2, TiO2-SiO2 and Ca2+/Fe3+ co-doped TiO2-SiO2 is 118.3 m2g-1, 294.3 m2g-1 and 393.7 m2g-1, respectively. The DRS and PL spectra revealed that the Fe/Ca co-doped TiO2-SiO2 film had strong visible light adsorption and diminished electrons/holes recombination. Experimental results showed that the Fe/Ca co-doped TiO2-SiO2 film is effective in the degradation of OTC under both UV and visible light irradiation.

  2. Tuning the Phase and Microstructural Properties of TiO2 Films Through Pulsed Laser Deposition and Exploring Their Role as Buffer Layers for Conductive Films

    NASA Astrophysics Data System (ADS)

    Agarwal, S.; Haseman, M. S.; Leedy, K. D.; Winarski, D. J.; Saadatkia, P.; Doyle, E.; Zhang, L.; Dang, T.; Vasilyev, V. S.; Selim, F. A.

    2018-04-01

    Titanium oxide (TiO2) is a semiconducting oxide of increasing interest due to its chemical and thermal stability and broad applicability. In this study, thin films of TiO2 were deposited by pulsed laser deposition on sapphire and silicon substrates under various growth conditions, and characterized by x-ray diffraction (XRD), atomic force microscopy (AFM), optical absorption spectroscopy and Hall-effect measurements. XRD patterns revealed that a sapphire substrate is more suitable for the formation of the rutile phase in TiO2, while a silicon substrate yields a pure anatase phase, even at high-temperature growth. AFM images showed that the rutile TiO2 films grown at 805°C on a sapphire substrate have a smoother surface than anatase films grown at 620°C. Optical absorption spectra confirmed the band gap energy of 3.08 eV for the rutile phase and 3.29 eV for the anatase phase. All the deposited films exhibited the usual high resistivity of TiO2; however, when employed as a buffer layer, anatase TiO2 deposited on sapphire significantly improves the conductivity of indium gallium zinc oxide thin films. The study illustrates how to control the formation of TiO2 phases and reveals another interesting application for TiO2 as a buffer layer for transparent conducting oxides.

  3. SnO 2 nanowires decorated with forsythia-like TiO 2 for photoenergy conversion

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Park, Ik Jae; Park, Sangbaek; Kim, Dong Hoe

    Here, we report forsythia-like TiO 2-decorated SnO 2 nanowires on fluorine-doped SnO 2 electrode as a photoelectrode of dye-sensitized solar cells. When SnO 2 nanowires grown via vapor-liquid-solid reaction were soaked in TiCl 4 solution, leaf-shaped rutile TiO 2 was grown onto the surface of the nanowires. The TiO 2 decoration increases the short circuit current (J sc), open circuit voltage (V oc) and fill factor (FF) of dye-sensitized solar cells. Further, electron lifetime increased by employing an atomic-layer-deposited TiO 2 nanoshell between the TiO 2 leaves and the SnO 2 nanowire, due to preventing charge recombination at the nanowire/electrolytemore » interface.« less

  4. SnO 2 nanowires decorated with forsythia-like TiO 2 for photoenergy conversion

    DOE PAGES

    Park, Ik Jae; Park, Sangbaek; Kim, Dong Hoe; ...

    2017-05-17

    Here, we report forsythia-like TiO 2-decorated SnO 2 nanowires on fluorine-doped SnO 2 electrode as a photoelectrode of dye-sensitized solar cells. When SnO 2 nanowires grown via vapor-liquid-solid reaction were soaked in TiCl 4 solution, leaf-shaped rutile TiO 2 was grown onto the surface of the nanowires. The TiO 2 decoration increases the short circuit current (J sc), open circuit voltage (V oc) and fill factor (FF) of dye-sensitized solar cells. Further, electron lifetime increased by employing an atomic-layer-deposited TiO 2 nanoshell between the TiO 2 leaves and the SnO 2 nanowire, due to preventing charge recombination at the nanowire/electrolytemore » interface.« less

  5. Eco-friendly synthesis of TiO2, Au and Pt doped TiO2 nanoparticles for dye sensitized solar cell applications and evaluation of toxicity

    NASA Astrophysics Data System (ADS)

    Gopinath, K.; Kumaraguru, S.; Bhakyaraj, K.; Thirumal, S.; Arumugam, A.

    2016-04-01

    Driven by the demand of pure TiO2, Au and Pt doped TiO2 NPs were successfully synthesized using Terminalia arjuna bark extract. The eco-friendly synthesized NPs were characterized by UV-Vis-DRS, ATR-FT-IR, PL, XRD, Raman, SEM with EDX and TEM analysis. The synthesized NPs were investigation for dye sensitized solar cell applications. UV-Vis-Diffused Reflectance Spectra clearly showed that the expected TiO2 inter band absorption below 306 nm, incorporation of gold shows surface plasma resonant (SPR) near 555 nm and platinum incorporated TiO2 NPs shows absorbance at 460 nm. The energy conversion efficiency for Au doped TiO2 NPs when compared to pure and Pt doped TiO2 NPs. In addition to that, Au noble metal present TiO2 matrix and an improve open-circuit voltage (Voc) of DSSC. Synthesized NPs was evaluated into antibacterial and antifungal activities by disk diffusion method. It is observed that NPs have not shown any activities in all tested bacterial and fungal strains. In this eco-friendly synthesis method to provide non toxic and environmental friendly nanomaterials can be used for solar energy device application.

  6. Bipolar doping and band-gap anomalies in delafossite transparent conductive oxides.

    PubMed

    Nie, Xiliang; Wei, Su-Huai; Zhang, S B

    2002-02-11

    Doping wide-gap materials p type is highly desirable but often difficult. This makes the recent discovery of p-type delafossite oxides, CuM(III)O2, very attractive. The CuM(III)O2 also show unique and unexplained physical properties: Increasing band gap from M(III) = Al,Ga, to In, not seen in conventional semiconductors. The largest gap CuInO2 can be mysteriously doped both n and p type but not the smaller gaps CuAlO2 and CuGaO2. Here, we show that both properties are results of a large disparity between the fundamental gap and the apparent optical gap, a finding that could lead to a breakthrough in the study of bipolarly dopable wide-gap semiconductor oxides.

  7. Nanoparticle size and combined toxicity of TiO2 and DSLS (surfactant) contribute to lysosomal responses in digestive cells of mussels exposed to TiO2 nanoparticles.

    PubMed

    Jimeno-Romero, A; Oron, M; Cajaraville, M P; Soto, M; Marigómez, I

    2016-10-01

    The aim of this investigation was to understand the bioaccumulation, cell and tissue distribution and biological effects of disodium laureth sulfosuccinate (DSLS)-stabilised TiO2 nanoparticles (NPs) in marine mussels, Mytilus galloprovincialis. Mussels were exposed in vivo to 0.1, 1 and 10 mg Ti/L either as TiO2 NPs (60 and 180 nm) or bulk TiO2, as well as to DSLS alone. A significant Ti accumulation was observed in mussels exposed to TiO2 NPs, which were localised in endosomes, lysosomes and residual bodies of digestive cells, and in the lumen of digestive tubules, as demonstrated by ultrastructural observations and electron probe X-ray microanalysis. TiO2 NPs of 60 nm were internalised within digestive cell lysosomes to a higher extent than TiO2 NPs of 180 nm, as confirmed by the quantification of black silver deposits after autometallography. The latter were localised mainly forming large aggregates in the lumen of the gut. Consequently, lysosomal membrane stability (LMS) was significantly reduced upon exposure to both TiO2 NPs although more markedly after exposure to TiO2-60 NPs. Exposure to bulk TiO2 and to DSLS also affected the stability of the lysosomal membrane. Thus, effects on the lysosomal membrane depended on the nanoparticle size and on the combined biological effects of TiO2 and DSLS.

  8. ZrO2-modified mesoporous nanocrystalline TiO2-xNx as efficient visible light photocatalysts.

    PubMed

    Wang, Xinchen; Yu, Jimmy C; Chen, Yilin; Wu, Ling; Fu, Xianzhi

    2006-04-01

    Mesoporous nanocrystalline TiO2-xNx and TiO2-xNx/ZrO2 visible-light photocatalysts have been prepared by a sol-gel method. The photocatalysts were characterized by XRD, N2 adsorption-desorption, TEM, XPS, UV/Vis, and IR spectroscopy. The photocatalytic activity of the samples was evaluated by the decomposition of ethylene in air under visible light (lambda > 450 nm) illumination. Results revealed that nitrogen was doped into the lattice of TiO2 by the thermal treatment of NH3-adsorbed TiO2 hydrous gels, converting the TiO2 into a visible-light responsive catalyst. The introduction of ZrO2 into TiO2-xNx considerably inhibits the undesirable crystal growth during calcination. Consequently, the ZrO2-modified TiO2-xNx displays higher porosity, higher specific surface area, and an improved thermal stability over the corresponding unmodified TiO2-xNx samples.

  9. Low temperature perovskite solar cells with an evaporated TiO 2 compact layer for perovskite silicon tandem solar cells

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bett, Alexander J.; Schulze, Patricia S. C.; Winkler, Kristina

    Silicon-based tandem solar cells can overcome the efficiency limit of single junction silicon solar cells. Perovskite solar cells are particularly promising as a top cell in monolithic tandem devices due to their rapid development towards high efficiencies, a tunable band gap with a sharp optical absorption edge and a simple production process. In monolithic tandem devices, the perovskite solar cell is deposited directly on the silicon cell, requiring low-temperature processes (< 200 °C) to maintain functionality of under-lying layers of the silicon cell in case of highly efficient silicon hetero-junction (SHJ) bottom solar cell. In this work, we present amore » complete low-temperature process for perovskite solar cells including a mesoporous titanium oxide (TiO 2) scaffold - a structure yielding the highest efficiencies for single-junction perovskite solar cells. We show that evaporation of the compact TiO 2 hole blocking layer and ultra-violet (UV) curing for the mesoporous TiO 2 layer allows for good performance, comparable to high-temperature (> 500 °C) processes. With both manufacturing routes, we obtain short-circuit current densities (J SC) of about 20 mA/cm 2, open-circuit voltages (V OC) over 1 V, fill factors (FF) between 0.7 and 0.8 and efficiencies (n) of more than 15%. We further show that the evaporated TiO 2 layer is suitable for the application in tandem devices. The series resistance of the layer itself and the contact resistance to an indium doped tin oxide (ITO) interconnection layer between the two sub-cells are low. Additionally, the low parasitic absorption for wavelengths above the perovskite band gap allow a higher absorption in the silicon bottom solar cell, which is essential to achieve high tandem efficiencies.« less

  10. Low temperature perovskite solar cells with an evaporated TiO 2 compact layer for perovskite silicon tandem solar cells

    DOE PAGES

    Bett, Alexander J.; Schulze, Patricia S. C.; Winkler, Kristina; ...

    2017-09-21

    Silicon-based tandem solar cells can overcome the efficiency limit of single junction silicon solar cells. Perovskite solar cells are particularly promising as a top cell in monolithic tandem devices due to their rapid development towards high efficiencies, a tunable band gap with a sharp optical absorption edge and a simple production process. In monolithic tandem devices, the perovskite solar cell is deposited directly on the silicon cell, requiring low-temperature processes (< 200 °C) to maintain functionality of under-lying layers of the silicon cell in case of highly efficient silicon hetero-junction (SHJ) bottom solar cell. In this work, we present amore » complete low-temperature process for perovskite solar cells including a mesoporous titanium oxide (TiO 2) scaffold - a structure yielding the highest efficiencies for single-junction perovskite solar cells. We show that evaporation of the compact TiO 2 hole blocking layer and ultra-violet (UV) curing for the mesoporous TiO 2 layer allows for good performance, comparable to high-temperature (> 500 °C) processes. With both manufacturing routes, we obtain short-circuit current densities (J SC) of about 20 mA/cm 2, open-circuit voltages (V OC) over 1 V, fill factors (FF) between 0.7 and 0.8 and efficiencies (n) of more than 15%. We further show that the evaporated TiO 2 layer is suitable for the application in tandem devices. The series resistance of the layer itself and the contact resistance to an indium doped tin oxide (ITO) interconnection layer between the two sub-cells are low. Additionally, the low parasitic absorption for wavelengths above the perovskite band gap allow a higher absorption in the silicon bottom solar cell, which is essential to achieve high tandem efficiencies.« less

  11. Instability of Hydrogenated TiO2

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Nandasiri, Manjula I.; Shutthanandan, V.; Manandhar, Sandeep

    2015-11-06

    Hydrogenated TiO2 (H-TiO2) is toted as a viable visible light photocatalyst. We report a systematic study on the thermal stability of H-implanted TiO2 using X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA). Protons (40 keV) implanted at a ~2 atom % level within a ~120 nm wide profile of rutile TiO2(110) were situated ~300 nm below the surface. NRA revealed that this H-profile broadened preferentially toward the surface after annealing at 373 K, dissipated out of the crystal into vacuum at 473 K, and was absent within the beam sampling depthmore » (~800 nm) at 523 K. Photoemission showed that the surface was reduced in concert with these changes. Similar anneals had no effect on pristine TiO2(110). The facile bulk diffusivity of H in rutile, as well as its activity toward interfacial reduction, significantly limits the utilization of H-TiO2 as a photocatalyst. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.« less

  12. A self-cleaning coating based on commercial grade polyacrylic latex modified by TiO2/Ag-exchanged-zeolite-A nanocomposite

    NASA Astrophysics Data System (ADS)

    Nosrati, Rahimeh; Olad, Ali; Nofouzi, Katayoon

    2015-08-01

    The commercial grade polyacrylic latex was modified in order to prepare a self-cleaning coating. TiO2/Ag-exchanged-zeolite-A nanocomposite was prepared and used as additive in the matrix of polyacrylic latex to achieve a hydrophilic and photocatalytic coating. FTIR and UV-visible spectroscopy, X-ray diffraction patterns and FESEM were used to characterize the composition and structure of the nanocomposites and coatings. The acrylic coatings, were prepared by using of TiO2/Ag-exchanged-zeolite-A additive, had better UV and visible light absorption, hydrophilic, degradation of organic pollutants, stability in water and antimicrobial properties than pristine commercial grade polyacrylic latex coating. According to the results, the modified polyacrylic based coating containing 0.5 wt% of TiO2/Ag-exchanged-zeolite-A nanocomposite additive with TiO2 to Ag-exchanged-zeolite-A ratio of 1:2 was the best coating considering most of useful properties such as small band gap and low water contact angle. The water contact angle for unmodified polyacrylic latex coating was 68° which was decreased to less than 10° in modified coating after 24 h LED lamp illumination.

  13. Er3+ -doped anatase TiO2 nanocrystals: crystal-field levels, excited-state dynamics, upconversion, and defect luminescence.

    PubMed

    Luo, Wenqin; Fu, Chengyu; Li, Renfu; Liu, Yongsheng; Zhu, Haomiao; Chen, Xueyuan

    2011-11-04

    A comprehensive survey of electronic structure and optical properties of rare-earth ions embedded in semiconductor nanocrystals (NCs) is of vital importance for their potential applications in areas as diverse as luminescent bioprobes, lighting, and displays. Er3+ -doped anatase TiO2 NCs, synthesized via a facile sol-gel solvothermal method, exhibit intense and well-resolved intra-4f emissions of Er3+ . Crystal-field (CF) spectra of Er3+ in TiO2 NCs are systematically studied by means of high-resolution emission and excitation spectra at 10-300 K. The CF analysis of Er3+ assuming a site symmetry of C(2v) yields a small root-mean-square deviation of 25.1 cm(-1) and reveals the relatively large CF strength (549 cm(-1) ) of Er3+, thus verifying the rationality of the C(2v) symmetry assignment of Er3+ in anatase TiO2 NCs. Based on a simplified thermalization model for the temperature-dependent photoluminescence (PL) dynamics from (4) S(3/2) , the intrinsic radiative luminescence lifetimes of (4) S(3/2) and (2) H(11/2) are experimentally determined to be 3.70 and 1.73 μs, respectively. Green and red upconversion (UC) luminescence of Er3+ can be achieved upon laser excitation at 974.5 nm. The UC intensity of Er3+ in Yb/Er-codoped NCs is found to be about five times higher than that of Er-singly-doped counterparts as a result of efficient Yb3+ sensitization and energy transfer upconversion (ETU) evidenced by its distinct UC luminescence dynamics. Furthermore, the origin of defect luminescence is revealed based on the temperature-dependent PL spectra upon excitation above the TiO2 bandgap at 325 nm. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Electronic characterization of defects in narrow gap semiconductors

    NASA Technical Reports Server (NTRS)

    Patterson, James D.

    1994-01-01

    We use a Green's function technique to calculate the position of deep defects in narrow gap semiconductors. We consider substitutional (including antisite), vacancy, and interstitial (self and foreign) deep defects. We also use perturbation theory to look at the effect of nonparabolic bands on shallow defect energies and find nonparabolicity can increase the binding by 10 percent or so. We consider mercury cadmium telluride (MCT), mercury zinc telluride (MZT), and mercury zinc selenide (MZS). For substitutional and interstitial defects we look at the situation with and without relaxation. For substitutional impurities in MCT, MZT, and MZS, we consider x (the concentration of Cd or Zn) in the range 0.1 less than x less than 0.3 and also consider appropriate x so E(sub g) = 0.1 eV for each of the three compounds. We consider several cation site s-like deep levels and anion site p-like levels. For E(sub g) = 0.1 eV, we also consider the effects of relaxation. Similar comments apply to the interstitial deep levels whereas no relaxation is considered for the ideal vacancy model. Relaxation effects can be greater for the interstitial than the substitutional cases. Specific results are given in figures and tables and comparison to experiment is made in a limited number of cases. We find, for example, that I, Se, S, Rn, and N are possible cation site, s-like deep levels in MCT and Zn and Mg are for anion site, p-like levels (both levels for substitutional cases). The corresponding cation and anion site levels for interstitial deep defects are (Au, Ag, Hg, Cd, Cu, Zn) and (N, Ar, O, F). For the substitutional cases we have some examples of relaxation moving the levels into the band gap, whereas for the interstitial case we have examples where relaxation moves it out of the band gap. Future work involves calculating the effects of charge state interaction and seeing the effect of relaxation on vacancy levels.

  15. Preparation and photocatalytic properties of nanometer-sized magnetic TiO2/SiO2/CoFe2O4 composites.

    PubMed

    Li, Hansheng; Zhang, Yaping; Wu, Qin; Wang, Xitao; Liu, Changhao

    2011-11-01

    Magnetic TiO2/SiO2/CoFe2O4 nanoparticles (TiO2/SCFs) were prepared by a sol-gel process in a reverse microemulsion combined with solvent-thermal technique. TiO2/SCFs were characterized by Fourier transform infrared spectrometry, thermogravimetric analysis-differential scanning calorimetry, X-ray diffraction, Raman spectrometry, TEM, BET specific surface area measurement, and magnetic analysis. Structure analyses indicated that TiO2/SCFs presented a core-shell structure with TiO2 uniformly coating on SiO2/CoFe2O4 nanomagnets (SCFs) and typical ferromagnetic hysteresis. TiO2/SCFs showed larger specific surface area and better photocatalytic activities than TiO2 and TiO2/CoFe2O4 photocatalysts prepared by the same method. The doping interaction between TiO2 and CoFe2O4 reduced thanks to the inert SiO2 mesosphere.

  16. Tunable growth of TiO2 nanostructures on Ti substrates

    NASA Astrophysics Data System (ADS)

    Peng, Xinsheng; Wang, Jingpeng; Thomas, Dan F.; Chen, Aicheng

    2005-10-01

    A simple and facile method is described to directly synthesize TiO2 nanostructures on titanium substrates by oxidizing Ti foil using small organic molecules as the oxygen source. The effect of reaction temperature and oxygen source on the formation of the TiO2 nanostructures has been studied using scanning electron microscopy, x-ray diffraction, transmission electron microscopy, Raman spectroscopy and water contact angle measurement. Polycrystalline grains are formed when pure oxygen and formic acid are used as the oxygen source; elongated micro-crystals are produced when water vapour is used as the oxygen source; oriented and aligned TiO2 nanorod arrays are synthesized when ethanol, acetaldehyde or acetone are used as the oxygen source. The growth mechanism of the TiO2 nanostructures is discussed. The diffusion of Ti atoms to the oxide/gas interface via the network of the grain boundaries of the thin oxide layer is the determining factor for the formation of well-aligned TiO2 nanorod arrays. The wetting properties of the TiO2 nanostructured surfaces formed are dictated by their structure, varying from a hydrophilic surface to a strongly hydrophobic surface as the surface structure changes from polycrystalline grains to well-aligned nanorod arrays. This tunable growth of TiO2 nanostructures is desirable for promising applications of TiO2 nanostructures in the development of optical devices, sensors, photo-catalysts and self-cleaning coatings.

  17. Photocatalytic degradation properties of V-doped TiO2 to automobile exhaust.

    PubMed

    Wang, Tong; Shen, Dongya; Xu, Tao; Jiang, Ruiling

    2017-05-15

    To improve the photocatalytic degradation properties of titanium dioxide (TiO 2 ) used as raw materials for purifying automobile exhaust (AE), the vanadium (V)-doped TiO 2 samples were prepared. The photocatalytic degradation efficiencies of V-doped TiO 2 to each component in AE were evaluated under ultraviolet (UV) and visible light irradiation, respectively. Results indicated that the photocatalytic activity of V-doped TiO 2 to AE was higher than that of pure TiO 2 , and the optimal V dopant content of TiO 2 was 1.0% under UV light irradiation. The degradation efficiencies of V-doped TiO 2 to NOx and HC were higher than those to CO 2 and CO in AE because of the reversible reaction between CO 2 and CO. In addition, it was found that the photocatalytic degradation efficiencies of V-doped TiO 2 to each component in AE were also increased under visible light irradiation. The V-doped TiO 2 also showed higher degradation efficiencies to NOx and HC than those to CO 2 and CO under visible light irradiation. The V doped TiO 2 presented higher photocatalytic activity to CO 2 than that to CO, but the reversible reaction between CO and CO 2 was not found under visible light irradiation. The photocatalytic reactions of pure and V-doped TiO 2 samples to each component in AE followed the first order kinetic pathway under the two light irradiations. It is concluded that the V doping is a feasible method to improve the photocatalytic degradation properties of TiO 2 to AE for air purification, developing a sustainable environmental purification technology based on TiO 2 materials. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. A study on native defects and magnetic properties in undoped rutile TiO2 using LDA and LDA+UO p+UTi d methods

    NASA Astrophysics Data System (ADS)

    Shi, Li-Bin; Wang, Yong Ping

    2016-05-01

    The native defects and magnetic properties in undoped rutile TiO2 are studied using local density approximation (LDA) and LDA adding Hubbard parameters (U) schemes. The band gap is adjusted to experimental value of 3.0 eV by combination of UTi d=4.2 eV and UO p=4.8 eV. This LDA+U methodology overcomes the band-gap problem and renders the approach more predictive. The formation energies of oxygen vacancy (VO), oxygen interstitial (Oi), titanium vacancy (VTi), titanium interstitial (Tii), oxygen anti-sites (OTi), and titanium anti-sites (TiO) are investigated by the LDA and LDA+U methods. In addition, some ground state configurations can be obtained by optimization of total spin. It is found that native defects can induce spin polarization and produce magnetic moment.

  19. Titanium mesh supported TiO2 nanowire arrays/upconversion luminescence Er3+-Yb3+ codoped TiO2 nanoparticles novel composites for flexible dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Liu, Wenwu; Zhang, Huanyu; Wang, Hui-gang; Zhang, Mei; Guo, Min

    2017-11-01

    Ti-mesh supported TiO2 nanowire arrays (NWAs)/upconversion luminescence Er3+-Yb3+ codoped TiO2 nanoparticles (UC-EY-TiO2 NPs) composite structured photoanodes for fully flexible dye sensitized solar cells (DSSCs) were firstly constructed via a hydrothermal and spin coating process. UV-vis-NIR absorption spectra of the TiO2 NWAs/UC-EY-TiO2 NPs composites exhibited strong absorption around near infrared (NIR) 980 nm. The composites excited by 980 nm NIR laser could emit upconversion fluorescence at 489, 526, 549 and 658 nm, which expanded the spectral response range and sunlight capturing capability of formed flexible DSSCs. Moreover, the TiO2 NWAs/UC-EY-TiO2 NPs was coated with an Nb2O5 thin layer to further suppress electron recombination losses. The complete flexible DSSCs based on Nb2O5 coated TiO2 NWAs/2.0 mol% Er3+-1.0 mol% Yb3+ codoped TiO2 NPs photoanode and Pt/ITO-PEN counter electrode exhibited an enhanced photon to current conversion efficiency of 8.10%, a 68% improvement compared to TiO2 NWAs/undoped TiO2 NPs based DSSCs (4.82%).

  20. Protein Corona Prevents TiO2 Phototoxicity.

    PubMed

    Garvas, Maja; Testen, Anze; Umek, Polona; Gloter, Alexandre; Koklic, Tilen; Strancar, Janez

    2015-01-01

    TiO2 nanoparticles have generally low toxicity in the in vitro systems although some toxicity is expected to originate in the TiO2-associated photo-generated radical production, which can however be modulated by the radical trapping ability of the serum proteins. To explore the role of serum proteins in the phototoxicity of the TiO2 nanoparticles we measure viability of the exposed cells depending on the nanoparticle and serum protein concentrations. Fluorescence and spin trapping EPR spectroscopy reveal that the ratio between the nanoparticle and protein concentrations determines the amount of the nanoparticles' surface which is not covered by the serum proteins and is proportional to the amount of photo-induced radicals. Phototoxicity thus becomes substantial only at the protein concentration being too low to completely coat the nanotubes' surface. These results imply that TiO2 nanoparticles should be applied with ligands such as proteins when phototoxic effects are not desired - for example in cosmetics industry. On the other hand, the nanoparticles should be used in serum free medium or any other ligand free medium, when phototoxic effects are desired - as for efficient photodynamic cancer therapy.

  1. Protein Corona Prevents TiO2 Phototoxicity

    PubMed Central

    Garvas, Maja; Testen, Anze; Umek, Polona; Gloter, Alexandre; Koklic, Tilen; Strancar, Janez

    2015-01-01

    Background & Aim TiO2 nanoparticles have generally low toxicity in the in vitro systems although some toxicity is expected to originate in the TiO2-associated photo-generated radical production, which can however be modulated by the radical trapping ability of the serum proteins. To explore the role of serum proteins in the phototoxicity of the TiO2 nanoparticles we measure viability of the exposed cells depending on the nanoparticle and serum protein concentrations. Methods & Results Fluorescence and spin trapping EPR spectroscopy reveal that the ratio between the nanoparticle and protein concentrations determines the amount of the nanoparticles’ surface which is not covered by the serum proteins and is proportional to the amount of photo-induced radicals. Phototoxicity thus becomes substantial only at the protein concentration being too low to completely coat the nanotubes’ surface. Conclusion These results imply that TiO2 nanoparticles should be applied with ligands such as proteins when phototoxic effects are not desired - for example in cosmetics industry. On the other hand, the nanoparticles should be used in serum free medium or any other ligand free medium, when phototoxic effects are desired – as for efficient photodynamic cancer therapy. PMID:26083725

  2. Dye-sensitized solar cells with vertically aligned TiO2 nanowire arrays grown on carbon fibers.

    PubMed

    Cai, Xin; Wu, Hongwei; Hou, Shaocong; Peng, Ming; Yu, Xiao; Zou, Dechun

    2014-02-01

    One-dimensional semiconductor TiO2 nanowires (TNWs) have received widespread attention from solar cell and related optoelectronics scientists. The controllable synthesis of ordered TNW arrays on arbitrary substrates would benefit both fundamental research and practical applications. Herein, vertically aligned TNW arrays in situ grown on carbon fiber (CF) substrates through a facile, controllable, and seed-assisted thermal process is presented. Also, hierarchical TiO2 -nanoparticle/TNW arrays were prepared that favor both the dye loading and depressed charge recombination of the CF/TNW photoanode. An impressive conversion efficiency of 2.48 % (under air mass 1.5 global illumination) and an apparent efficiency of 4.18 % (with a diffuse board) due to the 3D light harvesting of the wire solar cell were achieved. Moreover, efficient and inexpensive wire solar cells made from all-CF electrodes and completely flexible CF-based wire solar cells were demonstrated, taking into account actual application requirements. This work may provide an intriguing avenue for the pursuit of lightweight, cost-effective, and high-performance flexible/wearable solar cells. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Apatite-forming PEEK with TiO2 surface layer coating.

    PubMed

    Kizuki, Takashi; Matsushita, Tomiharu; Kokubo, Tadashi

    2015-01-01

    Polyetheretherketone (PEEK) is widely used in orthopedic implants, such as spinal fusion devices, because of its moderate elastic modulus, as well as relatively high mechanical strength. However, it does not bond to living bone, and hence it needs autograft to be fixed to the bone. In this study, we attempted to add bone-bonding properties to PEEK by coating with TiO2 synthesized by the sol-gel process. When a TiO2 sol solution consisting of titanium isopropoxide, water, ethanol, and nitric acid was deposited on a PEEK substrate without any pretreatment, the formed TiO2 gel layer was easily peeled off after subsequent treatments. However, when the same solution was deposited on PEEK that was preliminarily subjected to UV or O2 plasma treatment, the deposited TiO2 gel layer strongly adhered to the substrate even after subsequent treatments. The strong adhesion was attributed to the interaction among the C-O, C=O, and O-C=O groups on the PEEK owing to the UV or O2 plasma treatment and the Ti-O bond of the TiO2 gel. Apatite did not form on the as-formed TiO2 gel layer in a simulated body fluid (SBF) even within 3 days; however, apatite formed after soaking in 0.1 M HCl solution at 80 °C for 24 h. This apatite formation was attributed to positive surface charge of the TiO2 gel layer induced by the acid treatment. The PEEK with the TiO2 gel layer coating formed by the proposed process is expected to bond to living bone, because a positively charged titanium oxide which facilitates the formation of apatite in SBF within a short period is known to bond to living bone.

  4. Pressure-induced structural and semiconductor-semiconductor transitions in C o0.5M g0.5C r2O4

    NASA Astrophysics Data System (ADS)

    Rahman, S.; Saqib, Hajra; Zhang, Jinbo; Errandonea, D.; Menéndez, C.; Cazorla, C.; Samanta, Sudeshna; Li, Xiaodong; Lu, Junling; Wang, Lin

    2018-05-01

    The effect of pressure on the structural, vibrational, and electronic properties of Mg-doped Cr bearing spinel C o0.5M g0.5C r2O4 was studied up to 55 GPa at room-temperature using x-ray diffraction, Raman spectroscopy, electrical transport measurements, and ab initio calculations. We found that the ambient-pressure phase is cubic (spinel-type, F d 3 ¯m ) and underwent a pressure-induced structural transition to a tetragonal phase (space group I 4 ¯m 2 ) above 28 GPa. The ab initio calculation confirmed this first-order phase transition. The resistivity of the sample decreased at low pressures with the existence of a low-pressure (LP) phase and started to increase with the emergence of a high-pressure (HP) phase. The temperature dependent resistivity experiments at different pressures illustrated the wide band gap semiconducting nature of both the LP and HP phases with different activation energies, suggesting a semiconductor-semiconductor transition at HP. No evidence of chemical decomposition or a semiconductor-metal transition was observed in our studies.

  5. Efficient photodecomposition of herbicide imazapyr over mesoporous Ga2O3-TiO2 nanocomposites.

    PubMed

    Ismail, Adel A; Abdelfattah, Ibrahim; Faisal, M; Helal, Ahmed

    2018-01-15

    The unabated release of herbicide imazapyr into the soil and groundwater led to crop destruction and several pollution-related concerns. In this contribution, heterogeneous photocatalytic technique was employed utilizing mesoporous Ga 2 O 3 -TiO 2 nanocomposites for degrading imazapyr herbicide as a model pollutant molecule. Mesoporous Ga 2 O 3 -TiO 2 nanocomposites with varied Ga 2 O 3 contents (0-5wt%) were synthesized through sol-gel process. XRD and Raman spectra exhibited extremely crystalline anatase TiO 2 phase at low Ga 2 O 3 content which gradually reduced with the increase of Ga 2 O 3 content. TEM images display uniform TiO 2 particles (10±2nm) with mesoporous structure. The mesoporous TiO 2 exhibits large surface areas of 167m 2 g -1 , diminished to 108m 2 g -1 upon 5% Ga 2 O 3 incorporation, with tunable mesopore diameter in the range of 3-9nm. The photocatalytic efficiency of synthesized Ga 2 O 3 -TiO 2 nanocomposites was assessed by degrading imazapyr herbicide and comparing with commercial photocatalyst UV-100 and mesoporous Ga 2 O 3 under UV illumination. 0.1% Ga 2 O 3 -TiO 2 nanocomposite is considered the optimum photocatalyst, which degrades 98% of imazapyr herbicide within 180min. Also, the photodegradation rate of imazapyr using 0.1% Ga 2 O 3 -TiO 2 nanocomposite is nearly 10 and 3-fold higher than that of mesoporous Ga 2 O 3 and UV-100, respectively. The high photonic efficiency and long-term stability of the mesoporous Ga 2 O 3 -TiO 2 nanocomposites are ascribed to its stronger oxidative capability in comparison with either mesoporous TiO 2 , Ga 2 O 3 or commercial UV-100. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Strain-induced optical band gap variation of SnO 2 films

    DOE PAGES

    Rus, Stefania Florina; Ward, Thomas Zac; Herklotz, Andreas

    2016-06-29

    In this paper, thickness dependent strain relaxation effects are utilized to study the impact of crystal anisotropy on the optical band gap of epitaxial SnO 2 films grown by pulsed laser deposition on (0001)-oriented sapphire substrates. An X-ray diffraction analysis reveals that all films are under tensile biaxial in-plane strain and that strain relaxation occurs with increasing thickness. Variable angle spectroscopic ellipsometry shows that the optical band gap of the SnO 2 films continuously increases with increasing film thickness. This increase in the band gap is linearly related to the strain state of the films, which indicates that the mainmore » origin of the band gap change is strain relaxation. The experimental observation is in excellent agreement with results from density functional theory for biaxial in-plane strain. Our research demonstrates that strain is an effective way to tune the band gap of SnO 2 films and suggests that strain engineering is an appealing route to tailor the optical properties of oxide semiconductors.« less

  7. TiO2--a prototypical memristive material.

    PubMed

    Szot, K; Rogala, M; Speier, W; Klusek, Z; Besmehn, A; Waser, R

    2011-06-24

    Redox-based memristive switching has been observed in many binary transition metal oxides and related compounds. Since, on the one hand, many recent reports utilize TiO(2) for their studies of the memristive phenomenon and, on the other hand, there is a long history of the electronic structure and the crystallographic structure of TiO(2) under the impact of reduction and oxidation processes, we selected this material as a prototypical material to provide deeper insight into the mechanisms behind memristive switching. In part I, we briefly outline the results of the historical and recent studies of electroforming and resistive switching of TiO(2)-based cells. We describe the (tiny) stoichiometrical range for TiO(2 - x) as a homogeneous compound, the aggregation of point defects (oxygen vacancies) into extended defects, and the formation of the various Magnéli phases. Furthermore, we discuss the driving forces for these solid-state reactions from the thermodynamical point of view. In part II, we provide new experimental details about the hierarchical transformation of TiO(2) single crystals into Magnéli phases, and vice versa, under the influence of chemical, electrical and thermal gradients, on the basis of the macroscopic and nanoscopic measurements. Those include thermogravimetry, high-temperature x-ray diffraction (XRD), high-temperature conductivity measurements, as well as low-energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), and LC-AFM (atomic force microscope equipped with a conducting tip) studies. Conclusions are drawn concerning the relevant parameters that need to be controlled in order to tailor the memristive properties.

  8. Method of fabricating n-type and p-type microcrystalline semiconductor alloy material including band gap widening elements

    DOEpatents

    Guha, Subhendu; Ovshinsky, Stanford R.

    1990-02-02

    A method of fabricating doped microcrystalline semiconductor alloy material which includes a band gap widening element through a glow discharge deposition process by subjecting a precursor mixture which includes a diluent gas to an a.c. glow discharge in the absence of a magnetic field of sufficient strength to induce electron cyclotron resonance.

  9. Electron-plasmon and electron-phonon satellites in the angle-resolved photoelectron spectra of n -doped anatase TiO2

    NASA Astrophysics Data System (ADS)

    Caruso, Fabio; Verdi, Carla; Poncé, Samuel; Giustino, Feliciano

    2018-04-01

    We develop a first-principles approach based on many-body perturbation theory to investigate the effects of the interaction between electrons and carrier plasmons on the electronic properties of highly doped semiconductors and oxides. Through the evaluation of the electron self-energy, we account simultaneously for electron-plasmon and electron-phonon coupling in theoretical calculations of angle-resolved photoemission spectra, electron linewidths, and relaxation times. We apply this methodology to electron-doped anatase TiO2 as an illustrative example. The simulated spectra indicate that electron-plasmon coupling in TiO2 underpins the formation of satellites at energies comparable to those of polaronic spectral features. At variance with phonons, however, the energy of plasmons and their spectral fingerprints depends strongly on the carrier concentration, revealing a complex interplay between plasmon and phonon satellites. The electron-plasmon interaction accounts for approximately 40% of the total electron-boson interaction strength, and it is key to improve the agreement with measured quasiparticle spectra.

  10. Antibacterial activity of DLC films containing TiO2 nanoparticles.

    PubMed

    Marciano, F R; Lima-Oliveira, D A; Da-Silva, N S; Diniz, A V; Corat, E J; Trava-Airoldi, V J

    2009-12-01

    Diamond-like carbon (DLC) films have been the focus of extensive research in recent years due to their potential applications as surface coatings on biomedical devices. Titanium dioxide (TiO2) in the anatase crystalline form is a strong bactericidal agent when exposed to near-UV light. In this work we investigate the bactericidal activity of DLC films containing TiO2 nanoparticles. The films were grown on 316L stainless-steel substrates from a dispersion of TiO2 in hexane using plasma-enhanced chemical vapor deposition. The composition, bonding structure, surface energy, stress, and surface roughness of these films were also evaluated. The antibacterial tests were performed against Escherichia coli (E. coli) and the results were compared to the bacterial adhesion force to the studied surfaces. The presence of TiO2 in DLC bulk was confirmed by Raman spectroscopy. As TiO2 content increased, I(D)/I(G) ratio, hydrogen content, and roughness also increased; the films became more hydrophilic, with higher surface free energy and the interfacial energy of bacteria adhesion decreased. Experimental results show that TiO2 increased DLC bactericidal activity. Pure DLC films were thermodynamically unfavorable to bacterial adhesion. However, the chemical interaction between the E. coli and the studied films increased for the films with higher TiO2 concentration. As TiO2 bactericidal activity starts its action by oxidative damage to the bacteria wall, a decrease in the interfacial energy of bacteria adhesion causes an increase in the chemical interaction between E. coli and the films, which is an additional factor for the increasing bactericidal activity. From these results, DLC with TiO2 nanoparticles can be useful for producing coatings with antibacterial properties.

  11. Fast diffusion of silver in TiO2 nanotube arrays

    PubMed Central

    Zhang, Wanggang; Liu, Yiming; Zhou, Diaoyu; Wang, Hui

    2016-01-01

    Summary Using magnetron sputtering and heat treatment, Ag@TiO2 nanotubes are prepared. The effects of heat-treatment temperature and heating time on the evolution of Ag nanofilms on the surface of TiO2 nanotubes and microstructure of Ag nanofilms are investigated by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. Ag atoms migrate mainly on the outmost surface of the TiO2 nanotubes, and fast diffusion of Ag atoms is observed. The diffusivity for the diffusion of Ag atoms on the outmost surface of the TiO2 nanotubes at 400 °C is 6.87 × 10−18 m2/s, which is three orders of magnitude larger than the diffusivities for the diffusion of Ag through amorphous TiO2 films. The activation energy for the diffusion of Ag atoms on the outmost surface of the TiO2 nanotubes in the temperature range of 300 to 500 °C is 157 kJ/mol, which is less than that for the lattice diffusion of Ag and larger than that for the grain boundary diffusion. The diffusion of Ag atoms leads to the formation of Ag nanocrystals on the outmost surface of TiO2 nanotubes. Probably there are hardly any Ag nanocrystals formed inside the TiO2 nanotubes through the migration of Ag. PMID:27547630

  12. Single-walled carbon nanotube-facilitated dispersion of particulate TiO2 on ZrO2 ceramic membrane filters.

    PubMed

    Yao, Yuan; Li, Gonghu; Gray, Kimberly A; Lueptow, Richard M

    2008-07-15

    We report that SWCNTs substantially improve the uniformity and coverage of TiO2 coatings on porous ZrO2 ceramic membrane filters. The ZrO2 filters were dip coated with 100 nm anatase TiO2, TiO2/SWCNT composites, a TiO2+SWCNT mixture, and a TiO2/MWCNT composite at pH 3, 5, and 8. Whereas the TiO2+SWCNT mixture and the TiO2/MWCNT composite promote better coverage and less clumping than TiO2 alone, the TiO2/SWCNT composite forms a complete uniform coating without cracking at pH 5 ( approximately 100% coverage). A combination of chemical and electrostatic effects between TiO2 and SWCNTs forming the composite as well as between the composite and the ZrO2 surface explains these observations.

  13. Fabrication of predominantly Mn4+ -doped TiO2 nanoparticles under equilibrium conditions and their application as visible-light photocatalyts.

    PubMed

    Wang, Lijie; Fan, Jiajie; Cao, Zetan; Zheng, Yichao; Yao, Zhiqiang; Shao, Guosheng; Hu, Junhua

    2014-07-01

    The chemical state of a transition-metal dopant in TiO(2) can intrinsically determine the performance of the doped material in applications such as photocatalysis and photovoltaics. In this study, manganese-doped TiO2 is fabricated by a near-equilibrium process, in which the TiO(2) precursor powder precipitates from a hydrothermally obtained transparent mother solution. The doping level and subsequent thermal treatment influence the morphology and crystallization of the TiO(2) samples. FTIR spectroscopy and X-ray photoelectron spectroscopy analyses indicate that the manganese dopant is substitutionally incorporated by replacing Ti(4+) cations. The absorption band edge can be gradually shifted to 1.8 eV by increasing the nominal manganese content to 10 at %. Manganese atoms doped into the titanium lattice are associated with the dominant 4+ valence oxidation state, which introduces two curved, intermediate bands within the band gap and results in a significant enhancement in photoabsorption and the quantity of photogenerated hydroxyl radicals. Additionally, the high photocatalytic performance of manganese-doped TiO(2) is also attributed to the low oxygen content, owing to the equilibrium fabrication conditions. This work provides an important strategy to control the chemical and defect states of dopants by using an equilibrium fabrication process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. An innovative approach to synthesize highly-ordered TiO2 nanotubes.

    PubMed

    Isimjan, Tayirjan T; Yang, D Q; Rohani, Sohrab; Ray, Ajay K

    2011-02-01

    An innovative route to prepare highly-ordered and dimensionally controlled TiO2 nanotubes has been proposed using a mild sonication method. The nanotube arrays were prepared by the anodization of titanium in an electrolyte containing 3% NH4F and 5% H2O in glycerol. It is demonstrated that the TiO2 nanostructures has two layers: the top layer is TiO2 nanowire and underneath is well-ordered TiO2 nanotubes. The top layer can easily fall off and form nanowires bundles by implementing a mild sonication after a short annealing time. We found that the dimensions of the TiO2 nanotubes were only dependent on the anodizing condition. The proposed technique may be extended to fabricate reproducible well-ordered TiO2 nanotubes with large area on other metals.

  15. Hybridization gap in the semiconducting compound SrIr 4In 2Ge 4

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Calta, Nicholas P.; Im, Jino; Fang, Lei

    Here, large single crystals of SrIr 4In 2Ge 4 were synthesized using the In flux method. This compound is a hybridization gap semiconductor with an experimental optical band gap of E g = 0.25(3) eV. It crystallizes in the tetragonal EuIr 4In 2Ge 4 structure type with space group 1more » $$\\overline{4}$$2m and unit cell parameters a = 6.9004(5) Å and c = 8.7120(9) Å. The electronic structure is very similar to both EuIr 4In 2Ge 4 and the parent structure Ca 3Ir 4Ge 4, suggesting that these compounds comprise a new family of hybridization gap materials that exhibit indirect gap, semiconducting behavior at a valence electron count of 60 per formula unit, similar to the Heusler alloys.« less

  16. Hybridization gap in the semiconducting compound SrIr 4In 2Ge 4

    DOE PAGES

    Calta, Nicholas P.; Im, Jino; Fang, Lei; ...

    2016-11-18

    Here, large single crystals of SrIr 4In 2Ge 4 were synthesized using the In flux method. This compound is a hybridization gap semiconductor with an experimental optical band gap of E g = 0.25(3) eV. It crystallizes in the tetragonal EuIr 4In 2Ge 4 structure type with space group 1more » $$\\overline{4}$$2m and unit cell parameters a = 6.9004(5) Å and c = 8.7120(9) Å. The electronic structure is very similar to both EuIr 4In 2Ge 4 and the parent structure Ca 3Ir 4Ge 4, suggesting that these compounds comprise a new family of hybridization gap materials that exhibit indirect gap, semiconducting behavior at a valence electron count of 60 per formula unit, similar to the Heusler alloys.« less

  17. Thermo-selective Tm(x)Ti(1-x)O(2-x/2) nanoparticles: from Tm-doped anatase TiO2 to a rutile/pyrochlore Tm2Ti2O7 mixture. An experimental and theoretical study with a photocatalytic application.

    PubMed

    Navas, Javier; Sánchez-Coronilla, Antonio; Aguilar, Teresa; De los Santos, Desireé M; Hernández, Norge C; Alcántara, Rodrigo; Fernández-Lorenzo, Concha; Martín-Calleja, Joaquín

    2014-11-07

    This is an experimental and theoretical study of thulium doped TiO2 nanoparticles. From an experimental perspective, a method was used to synthesize thulium-doped TiO2 nanoparticles in which Tm(3+) replaces Ti(4+) in the lattice, which to our knowledge has neither been reported nor studied theoretically so far. Different proportions of anatase and rutile phases were obtained at different annealing temperatures, and XRD and Raman spectroscopy also revealed the presence of a pyrochlore phase (Tm2Ti2O7) at 1173 K. Thus, the structure of the Tm-doped nanoparticles was thermally-controlled. Furthermore, XPS showed the presence of Tm(3+) in the samples synthesized, which produces oxygen vacancies to maintain the local neutrality in the lattice. The presence of Tm(3+) in the samples led to changes in the UV-Vis absorption spectra, so they showed photoluminescence properties and new states in the band gap, which produce a new lower energy electronic transition than the main TiO2 one. Periodic DFT calculations were performed to understand the experimentally produced structures. The production of oxygen vacancies was analysed and the changes generated in the structure were fully detailed. The DOS and PDOS analyses confirmed the experimental results obtained using UV-Vis spectroscopy, and showed that the new electronic states in the band gap are due to interactions of the f state of Tm and the p state of O. Likewise, the charge study and the ELF analysis indicate that when Tm is introduced into the TiO2 structure, the Ti-O bond around the oxygen vacancy is strengthened. Finally, an example of a photocatalytic application was developed to show the high efficiency of the samples due to the heterojunction in the interfaces of the phases in the samples, which improved the charge separation and the good charge carrier mobility due to the presence of the pyrochlore phase, as was also shown theoretically.

  18. Preparation and photocatalytic activity of nitrogen-doped TiO2 hollow nanospheres

    NASA Astrophysics Data System (ADS)

    Cho, Hyung-Joon; Hwang, Poong-Gok; Jung, Dongwoon

    2011-12-01

    TiO2 hollow nanospheres were prepared using silicon oxide as a template. N-doped titanium oxide hollow spheres, TiO2-xNx were synthesized by reacting TiO2 hollow spheres with thiourea at 500 °C. XRD and XPS data showed that oxygen was successfully substituted by nitrogen through the nitrogen-doping reaction, and finally N-doped TiO2 hollow spheres were formed. The N-doped TiO2 hollow spheres showed new absorption shoulder in visible light region so that they were expected to exhibit photocatalytic activity in the visible light. The photocatalytic activity of N-doped TiO2 hollow spheres under visible light was similar to that of normal spherical TiO2-xNx in spite of the structural difference.

  19. VO2/TiO2 Nanosponges as Binder-Free Electrodes for High-Performance Supercapacitors

    NASA Astrophysics Data System (ADS)

    Hu, Chenchen; Xu, Henghui; Liu, Xiaoxiao; Zou, Feng; Qie, Long; Huang, Yunhui; Hu, Xianluo

    2015-11-01

    VO2/TiO2 nanosponges with easily tailored nanoarchitectures and composition were synthesized by electrostatic spray deposition as binder-free electrodes for supercapacitors. Benefiting from the unique interconnected pore network of the VO2/TiO2 electrodes and the synergistic effect of high-capacity VO2 and stable TiO2, the as-formed binder-free VO2/TiO2 electrode exhibits a high capacity of 86.2 mF cm-2 (~548 F g-1) and satisfactory cyclability with 84.3% retention after 1000 cycles. This work offers an effective and facile strategy for fabricating additive-free composites as high-performance electrodes for supercapacitors.

  20. VO2/TiO2 Nanosponges as Binder-Free Electrodes for High-Performance Supercapacitors.

    PubMed

    Hu, Chenchen; Xu, Henghui; Liu, Xiaoxiao; Zou, Feng; Qie, Long; Huang, Yunhui; Hu, Xianluo

    2015-11-04

    VO2/TiO2 nanosponges with easily tailored nanoarchitectures and composition were synthesized by electrostatic spray deposition as binder-free electrodes for supercapacitors. Benefiting from the unique interconnected pore network of the VO2/TiO2 electrodes and the synergistic effect of high-capacity VO2 and stable TiO2, the as-formed binder-free VO2/TiO2 electrode exhibits a high capacity of 86.2 mF cm(-2) (~548 F g(-1)) and satisfactory cyclability with 84.3% retention after 1000 cycles. This work offers an effective and facile strategy for fabricating additive-free composites as high-performance electrodes for supercapacitors.