Low temperature destruction of PCDD/Fs over V2O5-CeO2/TiO2 catalyst with ozone.

PubMed

Yu, Ming-Feng; Lin, Xiao-Qing; Yan, Mi; Li, Xiao-Dong; Chen, Tong; Yan, Jian-Hua

2016-09-01

Catalytic destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans) over V2O5-CeO2/TiO2 catalyst was investigated at a low temperature range of 140-180 °C, in the absence and presence of ozone (200 ppm). Nano-TiO2 support was used to prepare the catalyst by step impregnation method. A stable PCDD/Fs-generating system was established to support the catalytic destruction tests. In the presence of ozone alone, destruction efficiencies of PCDD/Fs are between 32.2 and 43.1 % with temperature increasing from 140 to 180 °C. The activity of V2O5-CeO2/TiO2 catalyst alone on PCDD/Fs destruction is also studied. The increase of temperature from 140 to 180 °C enhances the activity of catalyst with destruction efficiencies increasing from 54.7 to 73.4 %. However, ozone addition greatly enhances the catalytic activity of V2O5-CeO2/TiO2 catalyst on PCDD/Fs decomposition. At 180 °C, the destruction efficiency of PCDD/Fs achieved with V2O5-CeO2/TiO2 catalyst and ozone is above 86.0 %. It indicates that the combined use of ozone and catalyst reduces the reaction temperature of PCDD/Fs oxidation and offers a new method to destroy PCDD/Fs with high destruction efficiency at a low temperature. Furthermore, the destruction efficiencies of 17 toxic PCDD/F congeners, achieved with ozone alone, catalyst alone, and catalyst/ozone are analyzed.

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

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.

Interplay between the spin-selection rule and frontier orbital theory in O2 activation and CO oxidation by single-atom-sized catalysts on TiO2(110).

PubMed

Li, Shunfang; Zhao, Xingju; Shi, Jinlei; Jia, Yu; Guo, Zhengxiao; Cho, Jun-Hyung; Gao, Yanfei; Zhang, Zhenyu

2016-09-28

Exploration of the catalytic activity of low-dimensional transition metal (TM) or noble metal catalysts is a vital subject of modern materials science because of their instrumental role in numerous industrial applications. Recent experimental advances have demonstrated the utilization of single atoms on different substrates as effective catalysts, which exhibit amazing catalytic properties such as more efficient catalytic performance and higher selectivity in chemical reactions as compared to their nanostructured counterparts; however, the underlying microscopic mechanisms operative in these single atom catalysts still remain elusive. Based on first-principles calculations, herein, we present a comparative study of the key kinetic rate processes involved in CO oxidation using a monomer or dimer of two representative TMs (Pd and Ni) on defective TiO2(110) substrates (TMn@TiO2(110), n = 1, 2) to elucidate the underlying mechanism of single-atom catalysis. We reveal that the O2 activation rates of the single atom TM catalysts deposited on TiO2(110) are governed cooperatively by the classic spin-selection rule and the well-known frontier orbital theory (or generalized d-band picture) that emphasizes the energy gap between the frontier orbitals of the TM catalysts and O2 molecule. We further illuminate that the subsequent CO oxidation reactions proceed via the Langmuir-Hinshelwood mechanism with contrasting reaction barriers for the Pd monomer and dimer catalysts. These findings not only provide an explanation for existing observations of distinctly different catalytic activities of Pd@TiO2(110) and Pd2@TiO2(110) [Kaden et al., Science, 2009, 326, 826-829] but also shed new insights into future utilization and optimization of single-atom catalysis.

Preparation and characterization of mesoporous TiO2-sphere-supported Au-nanoparticle catalysts with high activity for CO oxidation at ambient temperature

NASA Astrophysics Data System (ADS)

Wang, Lili; Huang, Shouying; Zhu, Baolin; Zhang, Shoumin; Huang, Weiping

2016-11-01

Mesoporous TiO2-sphere-supported Au-nanoparticles (Au/m-TiO2-spheres) catalysts have been synthesized by a simple method using tetrabutyl titanate as TiO2 precursor and characterized with XRD, BET, ICP, SEM, TEM, UV-Vis DRS, XPS, as well as FT-IR. The samples with the size in the range of 200-400 nm were almost perfectly spherical. The average diameter of pores was about 3.6 nm, and the mesopore size distribution was in the range of 2-6 nm with a narrow distribution. When the catalyst was calcined at 300 °C, the Au NPs with the size ca. 5 nm were highly dispersed on the surfaces of m-TiO2 spheres and partially embedded in the supports. Remarkably, the specific surface area of the Au/m-TiO2-spheres was as high as 117 m2 g-1. The CO-adsorbed catalyst showed an apparent IR adsorption peak at 1714 cm-1 that matched with bridging model CO. It means the catalysts should be of high catalytic activity for the CO oxidation due to they could adsorb and activate CO commendably. When Au-content was 0.48 wt.%, the Au/m-TiO2-spheres could convert CO completely into CO2 at ambient temperature.

Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst.

PubMed

Gu, Jing; Yan, Yong; Young, James L; Steirer, K Xerxes; Neale, Nathan R; Turner, John A

2016-04-01

Producing hydrogen through solar water splitting requires the coverage of large land areas. Abundant metal-based molecular catalysts offer scalability, but only if they match noble metal activities. We report on a highly active p-GaInP2 photocathode protected through a 35-nm TiO2 layer functionalized by a cobaloxime molecular catalyst (GaInP2-TiO2-cobaloxime). This photoelectrode mediates H2 production with a current density of ∼9 mA cm(-2) at a potential of 0 V versus RHE under 1-sun illumination at pH 13. The calculated turnover number for the catalyst during a 20-h period is 139,000, with an average turnover frequency of 1.9 s(-1). Bare GaInP2 shows a rapid current decay, whereas the GaInP2-TiO2-cobaloxime electrode shows ≤5% loss over 20 min, comparable to a GaInP2-TiO2-Pt catalyst particle-modified interface. The activity and corrosion resistance of the GaInP2-TiO2-cobaloxime photocathode in basic solution is made possible by an atomic layer-deposited TiO2 and an attached cobaloxime catalyst.

Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen

NASA Astrophysics Data System (ADS)

Luo, Si

Abstract of the Dissertation. Investigation of TiO2 based Mixed-metal Oxide Catalysts for the Production of Hydrogen. by. Si Luo. Doctor of Philosophy. in. Chemistry. Stony Brook University. 2017. The environmental impacts of fossil fuel consumption and the resulting global warming have attracted increasing attention to technologies and fuels that are both sustainable and renewable in the 21st century. To date, hydrogen has been proposed as an encouraging candidate of the next generation of chemical fuels, which meets all demands for carbon free and efficient chemistries that could be produced from a variety of sources. However, despite tremendous efforts, there is a clear need to develop new catalysts for the production of hydrogen through catalytic processes that are sustainable, such as in the photocatalytic splitting of water (PCS: H2O → H2 + 0.5O2) and the water-gas shift process (WGS: CO + H2O → H2 + CO2). This thesis is primarily motivated by this challenge and has focused on the photochemical and thermal production of H2 by the employment of novel TiO2 based catalysts. TiO2 is one of the most widely studied photocatalysts in all history, due to its relatively high activity, robust stability, safety and low cost. In this thesis, several TiO2-based mixed metal oxide nano catalysts (CeOx-TiO2, Ru-TiO2, Ga-TiO2) have been synthesized with carefully controlled morphology/structure and with inclusion of co-catalysts (Pt). These novel materials were comprehensively characterized to better understand their morphology, crystal structure, and electronic properties in an attempt to unravel phenomena responsible for high catalytic performance for the production of H2 from H2O. We have discovered the importance of low-dimensional metal oxide and interfacial stabilized nano-scaled mixed metal oxides for H2 production, while learning how best to tune such structure to optimize both thermal and photochemical conversion. Optimized structure and/or composition have been

Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH 3 with V 2O 5-WO 3/TiO 2 catalysts

DOE PAGES

He, Yuanyuan; Ford, Michael E.; Zhu, Minghui; ...

2016-04-14

We compared the molecular structures, surface acidity and catalytic activity for NO/NH 3/O 2 SCR of V 2O 5-WO 3/TiO 2 catalysts for two different synthesis methods: co-precipitation of aqueous vanadium and tungsten oxide precursors with TiO(OH) 2 and by incipient wetness impregnation of the aqueous precursors on a reference crystalline TiO 2 support (P25; primarily anatase phase). Bulk analysis by XRD showed that co-precipitation results in small and/or poorly ordered TiO 2(anatase) particles and that VO x and WO x do not form solid solutions with the bulk titania lattice. Surface analysis of the co-precipitated catalyst by High Sensitivity-Lowmore » Energy Ion Scattering (HS-LEIS) confirms that the VO x and WO x are surface segregated for the co-precipitated catalysts. In situ Raman and IR spectroscopy revealed that the vanadium and tungsten oxide components are present as surface mono-oxo O = VO 3 and O = WO 4 sites on the TiO 2 supports. Co-precipitation was shown for the first time to also form new mono-oxo surface VO 4 and WO 4 sites that appear to be anchored at surface defects of the TiO 2 support. IR analysis of chemisorbed ammonia showed the presence of both surface NH 3 * on Lewis acid sites and surface NH 4 +* on Brønsted acid sites. TPSR spectroscopy demonstrated that the specific SCR kinetics was controlled by the redox surface VO 4 species and that the surface kinetics was independent of TiO 2 synthesis method or presence of surface WO 5 sites. SCR reaction studies revealed that the surface WO5 sites possess minimal activity below ~325 °C and their primary function is to increase the adsorption capacity of ammonia. A relationship between the SCR activity and surface acidity was not found. The SCR reaction is controlled by the surface VO 4 sites that initiate the reaction at ~200 °C. The co-precipitated catalysts were always more active than the corresponding impregnated catalysts. Finally, we ascribe the higher activity of the co

Highly stable CuO incorporated TiO(2) catalyst for photo-catalytic hydrogen production from H(2)O.

PubMed

Bandara, J; Udawatta, C P K; Rajapakse, C S K

2005-11-01

A CuO incorporated TiO(2) catalyst was found to be an active photo-catalyst for the reduction of H(2)O under sacrificial conditions. The catalytic activity originates from the photogeneration of excited electrons in the conduction bands of both TiO(2) and CuO resulting in a build-up of excess electrons in the conduction band of CuO. Consequently, the accumulation of excess electrons in CuO causes a negative shift in the Fermi level of CuO. The efficient inter-particle charge transfer leads to a higher catalytic activity and the formation of highly reduced states of TiO(2)/CuO, which are stable even under oxygen saturated condition. Negative shift in the Fermi level of CuO of the catalyst TiO(2)/CuO gains the required over-voltage necessary for efficient water reduction reaction. The function of CuO is to help the charge separation and to act as a water reduction site. The amount of CuO and crystalline structure were found to be crucial for the catalytic activity and the optimum CuO loading was ca. approximately 5-10%(w/w).

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.

Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

NASA Technical Reports Server (NTRS)

Klettlinger, Jennifer Lindsey Suder

2012-01-01

The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the

Synthesis of Highly Active Sub-Nanometer Pt@Rh Core-Shell Nanocatalyst via a Photochemical Route: Porous Titania Nanoplates as a Superior Photoactive Support.

PubMed

Zhan, Wen-Wen; Zhu, Qi-Long; Dang, Song; Liu, Zheng; Kitta, Mitsunori; Suenaga, Kazutomo; Zheng, Lan-Sun; Xu, Qiang

2017-04-01

Sub-nanometer Pt@Rh nanoparticles highly dispersed on MIL-125-derived porous TiO 2 nanoplates are successfully prepared for the first time by a photochemical route, where the porous TiO 2 nanoplates with a relatively high specific surface area play a dual role as both effective photoreductant and catalyst support. The resulting Pt@Rh/p-TiO 2 can be utilized as a highly active catalyst. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

AN INVESTIGATION OF CFC12 (CCI2F2) DECOMPOSITION ON TIO2 CATALYST

EPA Science Inventory

The catalytic oxidation of CFC12 was studied over a titania (TiO2) catalyst in a fixed-bed reactor at temperatures ranging from 200 to 400 degrees C and space velocity of 10,500 h-1. Results showed substantially complete conversion of CFC12 (>90%) to CO2 and halogen acids at and...

Hydrophilic TiO2 porous spheres anchored on hydrophobic polypropylene membrane for wettability induced high photodegrading activities.

PubMed

Niu, Fang; Zhang, Le-Sheng; Chen, Chao-Qiu; Li, Wei; Li, Lin; Song, Wei-Guo; Jiang, Lei

2010-08-01

TiO(2) porous nanospheres on polypropylene (PP) films (TiO(2)/PP composite) are produced at ambient temperature. Particle/pore size match up is the key anchoring point to overcome the low affinity between hydrophilic materials and hydrophobic materials. With the hydrophilic TiO(2) catalyst evenly dispersed on a hydrophobic surface, the aqueous solution will selectively skip the substrate and wet the catalysts. Such a wettability-induced smart system maximizes the degrading activity of the TiO(2) catalyst. In photodegrading reactions, the resulting TiO(2)/PP composite film exhibits a 10 times higher activity in flow-type setup than the same TiO(2) catalyst in a traditional batch-type setup.

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 .

Size-Selective Synthesis and Stabilization of Small Silver Nanoparticles on TiO 2 Partially Masked by SiO 2

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

Bo, Zhenyu; Eaton, Todd R.; Gallagher, James R.

Controlling metal nanoparticle size is one of the principle challenges in developing new supported catalysts. Typical methods where a metal salt is deposited and reduced can result in a polydisperse mixture of metal nanoparticles, especially at higher loading. Polydispersity can exacerbate the already significant challenge of controlling sintering at high temperatures, which decreases catalytic surface area. Here, we demonstrate the size-selective photoreduction of Ag nanoparticles on TiO2 whose surface has been partially masked with a thin SiO2 layer. To synthesize this layered oxide material, TiO2 particles are grafted with tert-butylcalix[4]arene molecular templates (~2 nm in diameter) at surface densities ofmore » 0.05–0.17 templates.nm–2, overcoated with ~2 nm of SiO2 through repeated condensation cycles of limiting amounts of tetraethoxysilane (TEOS), and the templates are removed oxidatively. Ag photodeposition results in uniform nanoparticle diameters ≤ 3.5 nm (by transmission electron microscopy (TEM)) on the partially masked TiO2, whereas Ag nanoparticles deposited on the unmodified TiO2 are larger and more polydisperse (4.7 ± 2.7 nm by TEM). Furthermore, Ag nanoparticles on the partially masked TiO2 do not sinter after heating at 450 °C for 3 h, while nanoparticles on the control surfaces sinter and grow by at least 30%, as is typical. Overall, this new synthesis approach controls metal nanoparticle dispersion and enhances thermal stability, and this facile synthesis procedure is generalizable to other TiO2-supported nanoparticles and sizes and may find use in the synthesis of new catalytic materials.« less

Study of TiO2 particles size, dyes, and catalyst to improve the performance of DSSC

NASA Astrophysics Data System (ADS)

Saehana, Sahrul; Darsikin, Muslimin

2016-02-01

This study reports effort to improve performance of solar cells by using various natural dyes in dye-sensitized solar cell (DSSC). We applied three kind of natural dye, i.e, black rice dye, cactus dye and dragon fruit dye. We found that performance of DSSC which employ black rice dye was higher than other natural dyes. It is because the wider spectrum wavelength of black rice dyes. Its performance also compared with rhutenium dye (N719). Effect of TiO2 particle to DSSC performance was also investigated. It was concluded that smaller TiO2 particle size will increase the performance of DSSC solar cells. It was because the smaller particle size (high surface area) will load more dye. In addition, we also demonstrated the use of graphite from lead pencil as counter electrode.

Color and COD degradation in photocatalytic process of procion red by using TiO2 catalyst under solar irradiation

NASA Astrophysics Data System (ADS)

Sari, Melati Ireng; Agustina, Tuty Emilia; Melwita, Elda; Aprianti, Tine

2017-11-01

Increasing textile industries in Indonesia resulted in increasing the utilization of dyes. The use of synthetic dyes are still dominating because they have many advantages. But, synthetic dyes are difficult to decompose in nature so they can cause potential pollution if discharged directly into the environment. In this study, Procion Red was used as a model of synthetic dye wastewater. The objective of this research is to study the effect of TiO2 catalyst concentration and irradiation time on the degradation of Procion Red under solar irradiation. Photo degradation takes place by using TiO2 catalyst powder in the various concentration of Procion Red of 150-300 ppm. The various concentrations of TiO2 catalyst of 0.5-8 g/l were used. The color and COD degradation of Procion Red for 12 hours of solar irradiation were investigated. Color degradation was measured by using a spectrophotometer. While COD degradation was measured by using Ferrous Ammonium Sulfate (FAS) analysis method. The result showed when using Procion Red of 150 ppm, the highest color degradation of 100% was achieved by using TiO2 catalyst of 6 g/l and the highest COD degradation of 62% was obtained by using TiO2 catalyst of 8 g/l, under 12 hours of solar irradiation

New Insight into SO2 Poisoning and Regeneration of CeO2-WO3/TiO2 and V2O5-WO3/TiO2 Catalysts for Low-Temperature NH3-SCR.

PubMed

Xu, Liwen; Wang, Chizhong; Chang, Huazhen; Wu, Qingru; Zhang, Tao; Li, Junhua

2018-06-19

In this study, the poisoning effects of SO 2 on the V 2 O 5 -WO 3 /TiO 2 (1%VWTi) and CeO 2 -WO 3 /TiO 2 (5%CeWTi) selective catalytic reduction (SCR) catalysts were investigated in the presence of steam, and also the regeneration of deactivated catalysts was studied. After pretreating the catalysts in a flow of NH 3 + SO 2 + H 2 O + O 2 at 200 °C for 24 h, it was observed that the low-temperature SCR (LT-SCR) activity decreased significantly over the 1%VWTi and 5%CeWTi catalysts. For 1%VWTi, NH 4 HSO 4 (ABS) was the main product detected after the poisoning process. Both of NH 4 HSO 4 and cerium sulfate species were formed on the poisoned 5%CeWTi catalyst, indicating that SO 2 reacted with Ce 3+ /Ce 4+ , even in the presence of high concentration of NH 3 . The decrease of BET specific surface area, NO x adsorption capacity, the ratio of chemisorbed oxygen, and reducibility were responsible for the irreversible deactivation of the poisoned 5%CeWTi catalyst. Meanwhile, the LT-SCR activity could be recovered over the poisoned 1%VWTi after regeneration at 400 °C, but not for the 5%CeWTi catalyst. For industrial application, it is suggested that the regeneration process can be utilized for 1%VWTi catalysts after a period of time after NH 4 HSO 4 accumulated on the catalysts.

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

Bimetallic Ag-Pt Sub-nanometer Supported Clusters as Highly Efficient and Robust Oxidation Catalysts

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

Negreiros, Fabio R.; Halder, Avik; Yin, Chunrong

A combined experimental and theoretical investigation of Ag-Pt sub-nanometer clusters as heterogeneous catalysts in the CO -> CO2 reaction (COox) is presented. Ag9Pt2 and Ag9Pt3 clusters are size-selected in the gas phase, deposited on an ultrathin amorphous alumina support, and tested as catalysts experimentally under realistic conditions and by first-principles simulations at realistic coverage. Insitu GISAXS/TPRx demonstrates that the clusters do not sinter or deactivate even after prolonged exposure to reactants at high temperature, and present comparable, extremely high COox catalytic efficiency. Such high activity and stability are ascribed to a synergic role of Ag and Pt in ultranano-aggregates, inmore » which Pt anchors the clusters to the support and binds and activates two CO molecules, while Ag binds and activates O-2, and Ag/Pt surface proximity disfavors poisoning by CO or oxidized species.« less

Critical current densities of powder-in-tube MgB2 tapes fabricated with nanometer-size Mg powder

NASA Astrophysics Data System (ADS)

Yamada, H.; Hirakawa, M.; Kumakura, H.; Matsumoto, A.; Kitaguchi, H.

2004-03-01

We fabricated powder-in-tube MgB2/Fe tapes using a powder mixture of nanometer-size Mg and commercial amorphous B and investigated the transport properties. High-purity nanometer-size Mg powder was fabricated by applying the thermal plasma method. 5-10 mol % SiC powder doping was tried to enhance the Jc properties. We found that the use of nanometer-size Mg powder was effective to increase the Jc values. The transport Jc values of the nondoped and 10 mol % SiC-doped tapes prepared with nanometer-size Mg powder reached 90 and 250 A/mm2 at 4.2 K and 10 T, respectively. These values were about five times higher than those of the tapes prepared with commercial Mg powder.

Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst

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

Gu, Jing; Yan, Yong; Young, James L.

2015-12-21

Producing hydrogen through solar water splitting requires the coverage of large land areas. Abundant metal-based molecular catalysts offer scalability, but only if they match noble metal activities. We report on a highly active p-GaInP2 photocathode protected through a 35-nm TiO2 layer functionalized by a cobaloxime molecular catalyst (GaInP2-TiO2-cobaloxime). This photoelectrode mediates H2 production with a current density of ~9"0mA"0cm-2 at a potential of 0"0V versus RHE under 1-sun illumination at pH"013. The calculated turnover number for the catalyst during a 20-h period is 139,000, with an average turnover frequency of 1.9"0s-1. Bare GaInP2 shows a rapid current decay, whereas themore » GaInP2-TiO2-cobaloxime electrode shows« less

Photoassist-phosphorylated TiO2 as a catalyst for direct formation of 5-(hydroxymethyl)furfural from glucose.

PubMed

Hattori, Masashi; Kamata, Keigo; Hara, Michikazu

2017-02-01

Photo-assisted phosphorylation of an anatase TiO 2 catalyst was examined to improve its catalytic performance for the direct production of 5-(hydroxymethyl)furfural (HMF), a versatile chemical platform, from glucose. In phosphorylation based on simple esterification between phosphoric acid and surface OH groups on anatase TiO 2 with water-tolerant Lewis acid sites, the density of phosphates immobilized on TiO 2 is limited to 2 phosphates nm -2 , which limits selective HMF production. Phosphorylation of the TiO 2 surface under fluorescent light irradiation increases the surface phosphate density to 50%, which is higher than the conventional limit, thus preventing the adsorption of hydrophilic glucose molecules on TiO 2 and resulting in a more selective HMF production over photoassist-phosphorylated TiO 2 .

Thermally Stable TiO2 - and SiO2 -Shell-Isolated Au Nanoparticles for In Situ Plasmon-Enhanced Raman Spectroscopy of Hydrogenation Catalysts.

PubMed

Hartman, Thomas; Weckhuysen, Bert M

2018-03-12

Raman spectroscopy is known as a powerful technique for solid catalyst characterization as it provides vibrational fingerprints of (metal) oxides, reactants, and products. It can even become a strong surface-sensitive technique by implementing shell-isolated surface-enhanced Raman spectroscopy (SHINERS). Au@TiO 2 and Au@SiO 2 shell-isolated nanoparticles (SHINs) of various sizes were therefore prepared for the purpose of studying heterogeneous catalysis and the effect of metal oxide coating. Both SiO 2 - and TiO 2 -SHINs are effective SHINERS substrates and thermally stable up to 400 °C. Nano-sized Ru and Rh hydrogenation catalysts were assembled over the SHINs by wet impregnation of aqueous RuCl 3 and RhCl 3 . The substrates were implemented to study CO adsorption and hydrogenation under in situ conditions at various temperatures to illustrate the differences between catalysts and shell materials with SHINERS. This work demonstrates the potential of SHINS for in situ characterization studies in a wide range of catalytic reactions. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Highly branched RuO2 Nanorods on Electrospun TiO2 Nanofibers toward Electrochemical Catalysts

NASA Astrophysics Data System (ADS)

Cho, Yukyung; Kim, Su-Jin; Lee, Nam-Suk; Kim, Myung Hwa; Lee, Youngmi

2014-03-01

We report a facile growth route to synthesize hierarchically grown single crystalline metallic RuO2 nanorods on electrospun TiO2 nanofibers via a combination of a simple vapour phase transport process with an electrospinning process. This synthetic strategy could be very useful to design a variety of highly branched network architectures of the functional hetero-nanostructures for electrochemical applications. Particularly, Ruthenium oxide (RuO2) 1-dimensional nanostructures can be used as the effective catalysts or electrochemical electrode materials. Thus, we first synthesize TiO2 nanofibers from mixture of titanium isopropoxide precursor and polymer and then ruthenium hydroxide precursor on TiO2 nanofibers are transformed into RuO2 nanorods by thermal treatment at 250oC in air. The crystalline structures of products are confirmed using scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) spectrum, Raman spectroscopy, and high resolution electron microscopy (HRTEM). The fundamental electrochemical performances are examined using cyclic voltammetry (CV).

The Reactivity and Structure of Size Selected VxO y Clusters on a TiO2 (110)-(1 X 1) Surface of Variable Oxidation State

NASA Astrophysics Data System (ADS)

Neilson, Hunter L.

The Reactivity and Structure of Size Selected VxOy Clusters on a TiO2 (110) Surface of Variable Oxidation State by Hunter L Neilson The selective oxidative dehydrogenation of methanol by vanadium oxide/TiO2 model systems has received a great deal of interest in the surface science community. Previous studies using temperature programmed desorption and reaction (TPD/R) to probe the oxidation of methanol to formaldehyde by vanadia/TiO2 model catalysts have shown that the activity of these systems vary considerably based on the way in which the model system is prepared with formaldehyde desorption temperatures observed anywhere from room temperature to 660 K. The principle reason for this variation is that the preparation of sub-monolayer films of vanadia on TiO2 produces clusters with a multitude of VxOy structures and a mixture of vanadium oxidation states. As a result the stoichiometry of the active vanadium oxide catalyst as well as the oxidation state of vanadium in the active catalyst remain unknown. To better understand this system, our group has probed the reactivity and structure of size-selected Vx, VOy and VxOy clusters on a reduced TiO2 (110) support in ultra-high vacuum (UHV) via TPD/R and scanning tunneling microscopy (STM). Ex situ preparation of these clusters in the gas phase prior to deposition has allowed us to systematically vary the stoichiometry of the vanadia clusters; a layer of control not available via the usual routes to vanadium oxide. The most active catalysts are shown to have (VO3)n stoichiometry in agreement with the theoretical models of the Metiu group. We have shown that both the activity and selectivity of V2O6 and V3O9 cluster catalysts depend sensitively on the oxidation state of the TiO2 (110) support. For example, V2O6 on a reduced surface is selective for the oxidation of methanol to formaldehyde while the selectivity shifts to favor methyl formate as the surface becomes increasingly oxidized. STM studies show that the

Photo-reduced Cu/CuO nanoclusters on TiO2 nanotube arrays as highly efficient and reusable catalyst

NASA Astrophysics Data System (ADS)

Jin, Zhao; Liu, Chang; Qi, Kun; Cui, Xiaoqiang

2017-01-01

Non-noble metal nanoparticles are becoming more and more important in catalysis recently. Cu/CuO nanoclusters on highly ordered TiO2 nanotube arrays are successfully developed by a surfactant-free photoreduction method. This non-noble metal Cu/CuO-TiO2 catalyst exhibits excellent catalytic activity and stability for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with the presence of sodium borohydride (NaBH4). The rate constant of this low-cost Cu/CuO based catalyst is even higher than that of the noble metal nanoparticles decorated on the same TiO2 substrate. The conversion efficiency remains almost unchanged after 7 cycles of recycling. The recycle process of this Cu/CuO-TiO2 catalyst supported by Ti foil is very simple and convenient compared with that of the common powder catalysts. This catalyst also exhibited great catalytic activity to other organic dyes, such as methylene blue (MB), rhodamine B (RhB) and methyl orange (MO). This highly efficient, low-cost and easily reusable Cu/CuO-TiO2 catalyst is expected to be of great potential in catalysis in the future.

Excited-state dynamics of size-dependent colloidal TiO2-Au nanocomposites

NASA Astrophysics Data System (ADS)

Karam, Tony E.; Khoury, Rami A.; Haber, Louis H.

2016-03-01

The ultrafast excited-state dynamics of size-dependent TiO2-Au nanocomposites synthesized by reducing gold nanoclusters to the surface of colloidal TiO2 nanoparticles are studied using pump-probe transient absorption spectroscopy with 400 nm excitation pulses. The results show that the relaxation processes of the plasmon depletion band, which are described by electron-phonon and phonon-phonon scattering lifetimes, are independent of the gold nanocluster shell size surrounding the TiO2 nanoparticle core. The dynamics corresponding to interfacial electron transfer between the gold nanoclusters and the TiO2 bandgap are observed to spectrally overlap with the gold interband transition signal, and the electron transfer lifetimes are shown to significantly decrease as the nanocluster shell size increases. Additionally, size-dependent periodic oscillations are observed and are attributed to acoustic phonons of a porous shell composed of aggregated gold nanoclusters around the TiO2 core, with frequencies that decrease and damping times that remain constant as the nanocluster shell size increases. These results are important for the development of improved catalytic nanomaterial applications.

Leaching of vanadium from waste V2O5-WO3/TiO2 catalyst catalyzed by functional microorganisms.

PubMed

Wang, Shuhua; Xie, Yaling; Yan, Weifu; Wu, Xuee; Wang, Chin-Tsan; Zhao, Feng

2018-05-22

Solid wastes are currently produced in large amounts. Although bioleaching of metals from solid wastes is an economical and sustainable technology, it has seldom been used to recycle metals from abandoned catalyst. In this study, the bioleaching of vanadium from V 2 O 5 -WO 3 /TiO 2 catalyst were comprehensively investigated through five methods: Oligotrophic way, Eutrophic way, S-mediated way, Fe-mediated way and Mixed way of S-mediated and Fe-mediated. The observed vanadium bioleaching effectiveness of the assayed methods was follows: S-mediated > Mixed > Oligotrophic > Eutrophic > Fe-mediated, which yielded the maximum bioleaching efficiencies of approximately 90%, 35%, 33%, 20% and 7%, respectively. The microbial community analysis suggested that the predominant genera Acidithiobacillus and Sulfobacillus from the S-mediated bioleaching way effectively catalyzed the vanadium leaching, which could have occurred through the indirect mechanism from the microbial oxidation of S 0 . In addition, the direct mechanism, involving direct electron transfer between the catalyst and the microorganisms that attached to the catalyst surface, should also help the vanadium to be leached more effectively. Therefore, this work provides guidance for future research and practical application on the treatment of waste V 2 O 5 -WO 3 /TiO 2 catalyst. Copyright © 2018 Elsevier B.V. All rights reserved.

TiO2 effect on crystallization mechanism and physical properties of nano glass-ceramics of MgO-Al2O3-SiO2 glass system.

PubMed

Jo, Sinae; Kang, Seunggu

2013-05-01

The effect of TiO2 on the degree of crystallization, thermal properties and microstructure for MgO-Al2O3-SiO2 glass-ceramics system containing 0-13 wt% TiO2 and 0-1.5 wt% B2O3 in which the cordierite is the main phase was studied. Using Kissinger and Augis-Bennett equations, the activation energy, 510 kJ/mol and Avrami constant, 1.8 were calculated showing the surface-oriented crystallization would be preferred. The alpha-cordierite phase was generated in the glass-ceramics of containing TiO2 of 0-5.6 wt%. However, for the glass-ceramics of TiO2 content above 7 wt%, an alpha-cordierite disappeared and micro-cordierite phase was formed. The glass-ceramics of no TiO2 added had spherical crystals of few tens nanometer size spread in the matrix. As TiO2 content increased up to 5.6 wt%, a lump of dendrite was formed. In the glass-ceramics containing TiO2 7-13 wt%, in which the main phase is micro-cordierite, the dendrite crystal disappeared and a few hundred nanometer sized crystal particles hold tightly each other were generated. The thermal conductivity of glass-ceramics of both a-cordierite and micro-cordierite base decreased with TiO2 contend added. The thermal conductivity of glass-ceramics of 1.5 wt% TiO2 added was 3.4 W/mK which is 36% higher than that of glass-ceramics of no TiO2 added. The sintering temperature for 1.5 wt% TiO2 glass-ceramics was 965 degrees C which could be concluded as to apply to LTCC process for LED packaging.

UV and visible activation of Cr(III)-doped TiO2 catalyst prepared by a microwave-assisted sol-gel method during MCPA degradation.

PubMed

Mendiola-Alvarez, S Y; Guzmán-Mar, J L; Turnes-Palomino, G; Maya-Alejandro, F; Hernández-Ramírez, A; Hinojosa-Reyes, L

2017-05-01

Photocatalytic degradation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in aqueous solution using Cr(III)-doped TiO 2 under UV and visible light was investigated. The semiconductor material was synthesized by a microwave-assisted sol-gel method with Cr(III) doping contents of 0.02, 0.04, and 0.06 wt%. The catalyst was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), nitrogen physisorption, UV-Vis diffuse reflectance spectroscopy (DRS), and atomic absorption spectroscopy (AAS). The photocatalytic activity for the photodegradation of MCPA was followed by reversed-phase high-performance liquid chromatography (HPLC) and total organic carbon (TOC) analysis. The intermediates formed during degradation were identified using gas chromatography-mass spectrometry (GC-MS). Chloride ion evolution was measured by ion chromatography. Characterization results showed that Cr(III)-doped TiO 2 materials possessed a small crystalline size, high surface area, and mesoporous structure. UV-Vis DRS showed enhanced absorption in the visible region as a function of the Cr(III) concentration. The Cr(III)-doped TiO 2 catalyst with 0.04 wt% of Cr(III) was more active than bare TiO 2 for the degradation of MCPA under both UV and visible light. The intermediates identified during MCPA degradation were 4-chloro-2-methylphenol (CMP), 2-(4-hydroxy-2-methylphenoxy) acetic acid (HMPA), and 2-hydroxybuta-1,3-diene-1,4-diyl-bis (oxy)dimethanol (HBDM); the formation of these intermediates depended on the radiation source.

Radiation-induced synthesis of Fe-doped TiO 2: Characterization and catalytic properties

NASA Astrophysics Data System (ADS)

Bzdon, Sylwia; Góralski, Jacek; Maniukiewicz, Waldemar; Perkowski, Jan; Rogowski, Jacek; Szadkowska-Nicze, Magdalena

2012-03-01

Fe-doped TiO 2 catalyst was prepared by wet impregnation, using TiO 2 P25 Degussa as a precursor and Fe(NO 3) 3 as a dopant, followed by irradiation with an electron beam or γ-rays. Surface properties of Fe/TiO 2 samples were examined by BET, XRD, ToF-SIMS, and TPR methods. The photocatalytic activity towards destruction of the anionic surfactant, sodium dodecylbenzenesulfonate (SDBS), in aqueous solutions was higher for the irradiated Fe/TiO 2 catalysts than for bare TiO 2 P25 or that calcined at 500 °C. The results show that irradiated catalysts exhibit a more uniform texture with high dispersion of iron species. An enhancement of the activity of irradiated Fe/TiO 2 systems can be attributed to the synergetic effects of small crystallite size and homogenous distribution of iron species including FeTiO 3 phase.

Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural with ALD overcoating (II) – Comparison between TiO2 and Al2O3 overcoatings

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

Zhang, Hongbo; Canlas, Christian; Kropf, A. Jeremy

2015-01-01

TiO2 atomic layer deposition (ALD) overcoatings were applied to copper chromite catalysts to increase the stability for 2-furfuraldehyde (“furfural”) hydrogenation. After overcoating, about 75% activity was preserved compared to neat copper chromite: much higher activity than an alumina ALD overcoated catalyst with a similar number of ALD cycles. The effects of ALD TiO2 on the active Cu nanoparticles were studied extensively using both in-situ TPR/isothermal-oxidation and in-situ furfural hydrogenation via Cu XAFS. The redox properties of Cu were modified only slightly by the TiO2 ALD overcoat. However, a subtle electronic interaction was observed between the TiO2 ALD layers and themore » Cu nanoparticles. With calcination at 500 °C the interaction between the TiO2 overcoat and the underlying catalyst is strong enough to inhibit migration and site blocking by chromite, but is sufficiently weaker than the interaction between the Al2O3 overcoat and copper chromite that it does not strongly inhibit the catalytic activity of the copper nanoparticles.« less

MnTiO3-driven low-temperature oxidative coupling of methane over TiO2-doped Mn2O3-Na2WO4/SiO2 catalyst

PubMed Central

Wang, Pengwei; Zhao, Guofeng; Wang, Yu; Lu, Yong

2017-01-01

Oxidative coupling of methane (OCM) is a promising method for the direct conversion of methane to ethene and ethane (C2 products). Among the catalysts reported previously, Mn2O3-Na2WO4/SiO2 showed the highest conversion and selectivity, but only at 800° to 900°C, which represents a substantial challenge for commercialization. We report a TiO2-doped Mn2O3-Na2WO4/SiO2 catalyst by using Ti-MWW zeolite as TiO2 dopant as well as SiO2 support, enabling OCM with 26% conversion and 76% C2-C3 selectivity at 720°C because of MnTiO3 formation. MnTiO3 triggers the low-temperature Mn2+↔Mn3+ cycle for O2 activation while working synergistically with Na2WO4 to selectively convert methane to C2-C3. We also prepared a practical Mn2O3-TiO2-Na2WO4/SiO2 catalyst in a ball mill. This catalyst can be transformed in situ into MnTiO3-Na2WO4/SiO2, yielding 22% conversion and 62% selectivity at 650°C. Our results will stimulate attempts to understand more fully the chemistry of MnTiO3-governed low-temperature activity, which might lead to commercial exploitation of a low-temperature OCM process. PMID:28630917

Electrochemical characterization of nano-sized Pd-based catalysts as cathode materials in direct methanol fuel cells.

PubMed

Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

2011-01-01

To improve the catalytic activity of palladium (Pd) as a cathode catalyst in direct methanol fuel cells (DMFCs), we prepared palladium-titanium oxide (Pd-TiO2) catalysts which the Pd and TiO2 nanoparticles were simultaneously impregnated on carbon. We selected Pd and TiO2 as catalytic materials because of their electrochemical stability in acid solution. The crystal structure and the loading amount of Pd and TiO2 on carbon were characterized by X-ray diffraction (XRD) and energy dispersive X-ray microanalysis (EDX). The electrochemical characterization of Pd-TiO2/C catalysts for the oxygen reduction reaction was carried out in half and single cell systems. The catalytic activities of the Pd-TiO2 catalysts were strongly influenced by the TiO2 content. In the single cell test, the Pd-TiO2 catalysts showed very comparable performance to the Pt catalyst.

Progress of studies on preparation of TiO2 photocatalysts with sol-gel auto igniting synthesis

NASA Astrophysics Data System (ADS)

Wu, Di; Shi, Zaifeng; Zhang, Xiaopeng; Xinghui, Wu

2017-11-01

In this article, influencing factors on the kinetics of the process of Sol-gel Auto igniting Synthesis (SAS) which is an advanced technology for preparing nanometer particles of inorganic materials were reviewed. The studies on preparing of nanometer TiO2 photocatalysts with SAS were focused. It was concluded that SAS will play an important role in practical preparing of high-pure nanometer TiO2 powder, and as a technical support, preparation of titania TiO2 from titanic iron ore with SAS is feasible and practicable.

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.

One-step formation of TiO2 hollow spheres via a facile microwave-assisted process for photocatalytic activity

NASA Astrophysics Data System (ADS)

Mohamad Alosfur, Firas K.; Ridha, Noor J.; Hafizuddin Haji Jumali, Mohammad; Radiman, S.

2018-04-01

Mesoporous TiO2 hollow spherical nanostructures with high surface areas were successfully prepared using a microwave method. The prepared hollow spheres had a size range between 200 and 500 nm. The spheres consisted of numerous smaller TiO2 nanoparticles with an average diameter of 8 nm. The particles had an essentially mesoporous structure, with a pore size in the range of 2-50 nm. The results confirmed that the synthesised of anatase TiO2 nanoparticles with specific surface area approximately 172.3 m2 g-1. The effect of ultraviolet and visible light irradiation and catalyst dosage on the TiO2 photocatalytic activity was studied by measuring the degradation rate of methylene blue. The maximum dye degradation performances with low catalyst loading (30 mg) were 99% and 63.4% using the same duration of ultraviolet and visible light irradiation, respectively (120 min).

High performance and durability of order-structured cathode catalyst layer based on TiO2@PANI core-shell nanowire arrays

NASA Astrophysics Data System (ADS)

Chen, Ming; Wang, Meng; Yang, Zhaoyi; Wang, Xindong

2017-06-01

In this paper, an order-structured cathode catalyst layer consisting of Pt-TiO2@PANI core-shell nanowire arrays that in situ grown on commercial gas diffusion layer (GDL) are prepared and applied to membrane electrode assembly (MEA) of proton exchange membrane fuel cell (PEMFC). In order to prepare the TiO2@PANI core-shell nanowire arrays with suitable porosity and prominent conductivity, the morphologies of the TiO2 nanoarray and electrochemical polymerization process of aniline are schematically investigated. The MEA with order-structured cathode catalyst layer is assembled in the single cell to evaluate the electrochemical performance and durability of PEMFC. As a result, the PEMFC with order-structured cathode catalyst layer shows higher peak power density (773.54 mW cm-2) than conventional PEMFC (699.30 mW cm-2). Electrochemically active surface area (ECSA) and charge transfer impedance (Rct) are measured before and after accelerated degradation test (ADT), and the corresponding experimental results indicate the novel cathode structure exhibits a better stability with respect to conventional cathode. The enhanced electrochemical performance and durability toward PEMFC can be ascribed to the order-structured cathode nanoarray structure with high specific surface area increases the utilization of catalyst and reduces the tortuosity of transport pathways, and the synergistic effect between TiO2@PANI support and Pt nanoparticles promotes the high efficiency of electrochemical reaction and improves the stability of catalyst. This research provides a facile and controllable method to prepare order-structured membrane electrode with lower Pt loading for PEMFC in the future.

A Perspective on the Selective Catalytic Reduction (SCR) of NO with NH 3 by Supported V 2O 5 –WO 3/TiO 2 Catalysts

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

Lai, Jun-Kun; Wachs, Israel E.

We report the selective catalytic reduction (SCR) of NO x with NH 3 to harmless N 2 and H 2O plays a crucial role in reducing highly undesirable NO x acid gas emissions from large utility boilers, industrial boilers, municipal waste plants, and incinerators. The supported V 2O 5 –WO 3/TiO 2 catalysts have become the most widely used industrial catalysts for these SCR applications since introduction of this technology in the early 1970s. Lastly, this Perspective examines the current fundamental understanding and recent advances of the supported V 2O 5 –WO 3/TiO 2 catalyst system: (i) catalyst synthesis, (ii)more » molecular structures of titaniasupported vanadium and tungsten oxide species, (iii) surface acidity, (iv) catalytic active sites, (v) surface reaction intermediates, (vi) reaction mechanism, (vii) ratedetermining- step, and (viii) reaction kinetics.« less

A Perspective on the Selective Catalytic Reduction (SCR) of NO with NH 3 by Supported V 2O 5 –WO 3/TiO 2 Catalysts

DOE PAGES

Lai, Jun-Kun; Wachs, Israel E.

2018-06-04

We report the selective catalytic reduction (SCR) of NO x with NH 3 to harmless N 2 and H 2O plays a crucial role in reducing highly undesirable NO x acid gas emissions from large utility boilers, industrial boilers, municipal waste plants, and incinerators. The supported V 2O 5 –WO 3/TiO 2 catalysts have become the most widely used industrial catalysts for these SCR applications since introduction of this technology in the early 1970s. Lastly, this Perspective examines the current fundamental understanding and recent advances of the supported V 2O 5 –WO 3/TiO 2 catalyst system: (i) catalyst synthesis, (ii)more » molecular structures of titaniasupported vanadium and tungsten oxide species, (iii) surface acidity, (iv) catalytic active sites, (v) surface reaction intermediates, (vi) reaction mechanism, (vii) ratedetermining- step, and (viii) reaction kinetics.« less

Plasma-induced synthesis of Pt nanoparticles supported on TiO2 nanotubes for enhanced methanol electro-oxidation

NASA Astrophysics Data System (ADS)

Su, Nan; Hu, Xiulan; Zhang, Jianbo; Huang, Huihong; Cheng, Jiexu; Yu, Jinchen; Ge, Chao

2017-03-01

A Pt/C/TiO2 nanotube composite catalyst was successfully prepared for enhanced methanol electro-oxidation. Pt nanoparticles with a particle size of 2 nm were synthesized by plasma sputtering in water, and anatase TiO2 nanotubes with an inner diameter of approximately 100 nm were prepared by a simple two-step anodization method and annealing process. Field-emission scanning electron microscopy images indicated that the different morphologies of TiO2 synthesized on the surface of Ti foils were dependent on the different anodization parameters. The electrochemical performance of Pt/C/TiO2 catalysts for methanol oxidation showed that TiO2 nanotubes were more suitable for use as Pt nanoparticle support materials than irregular TiO2 short nanorods due to their tubular morphology and better electronic conductivity. X-ray photoelectron spectroscopy characterization showed that the binding energies of the Pt 4f of the Pt/C/TiO2 nanotubes exhibited a slightly positive shift caused by the relatively strong interaction between Pt and the TiO2 nanotubes, which could mitigate the poisoning of the Pt catalyst by COads, and further enhance the electrocatalytic performance. Thus, the as-obtained Pt/C/TiO2 nanotubes composites may become a promising catalyst for methanol electro-oxidation.

Synthesis of nanometer-size inorganic materials for the examination of particle size effects on heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Emerson, Sean Christian

The effect of acoustic and hydrodynamic cavitation on the precipitation of inorganic catalytic materials, specifically titania supported gold, was investigated. The overall objective was to understand the fundamental factors involved in synthesizing nanometer-size catalytic materials in the 1--10 nm range in a cavitating field. Materials with grain sizes in this range have been associated with enhanced catalytic activity compared to larger grain size materials. A new chemical approach was used to produce titania supported gold by co-precipitation with higher gold yields compared to other synthesis methods. Using this approach, it was determined that acoustic cavitation was unable to influence the gold mean crystallite size compared to non-sonicated catalysts. However, gold concentration on the catalysts was found to be very important for CO oxidation activity. By decreasing the gold concentration from a weight loading of 0.50% down to approximately 0.05%, the rate of reaction per mole of gold was found to increase by a factor of 19. Hydrodynamic cavitation at low pressures (6.9--48 bar) was determined to have no effect on gold crystallite size at a fixed gold content for the same precipitation technique used in the acoustic cavitation studies. By changing the chemistry of the precipitation system, however, it was found that a synergy existed between the dilution of the gold precursor solution, the orifice diameter, and the reducing agent addition rate. Individually, these factors were found to have little effect and only their interaction allowed gold grain size control in the range of 8--80 nm. Further modification of the system chemistry and the use of hydrodynamic cavitation at pressures in excess of 690 bar allowed the systematic control of gold crystallite size in the range of 2--9 nm for catalysts containing 2.27 +/- 0.17% gold. In addition, it was shown that the enhanced mixing due to cavitation led to larger gold yields compared to classical syntheses. The

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.

Synthesis of Cr3+-doped TiO2 nanoparticles: characterization and evaluation of their visible photocatalytic performance and stability.

PubMed

Mendiola-Alvarez, Sandra Yadira; Guzmán-Mar, Jorge Luis; Turnes-Palomino, Gemma; Maya-Alejandro, Fernando; Caballero-Quintero, Adolfo; Hernández-Ramírez, Aracely; Hinojosa-Reyes, Laura

2017-09-28

Cr 3+ -doped TiO 2 nanoparticles (Ti-Cr) were synthesized by microwave-assisted sol-gel method. The Ti-Cr catalyst was characterized by X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, N 2 adsorption-desorption analysis, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy (XPS) and zetametry. The anatase mesoporous Ti-Cr material exhibited a specific surface area of 54.5 m 2 /g. XPS analysis confirmed the proper substitution of Ti 4+ cations by Cr 3+ cations in the TiO 2 matrix. The particle size was of average size of 17 nm for the undoped TiO 2 but only 9.5 nm for Ti-Cr. The Cr atoms promoted the formation of hydroxyl radicals and modified the surface adsorptive properties of TiO 2 due to the increase in surface acidity of the material. The photocatalytic evaluation demonstrated that the Ti-Cr catalyst completely degraded (4-chloro-2-methylphenoxy) acetic acid under visible light irradiation, while undoped TiO 2 and P25 allowed 45.7% and 31.1%, respectively. The rate of degradation remained 52% after three cycles of catalyst reuse. The higher visible light photocatalytic activity of Ti-Cr was attributed to the beneficial effect of Cr 3+ ions on the TiO 2 surface creating defects within the TiO 2 crystal lattice, which can act as charge-trapping sites, reducing the electron-hole recombination process.

Pilot-scale evaluation of a novel TiO2-supported V2O5 catalyst for DeNOx at low temperatures at a waste incinerator.

PubMed

Jung, Hyounduk; Park, Eunseuk; Kim, Minsu; Jurng, Jongsoo

2017-03-01

The removal of NOx by catalytic technology at low temperatures is significant for treatment of flue gas in waste incineration plants, especially at temperatures below 200°C. A novel highly active TiO 2 -supported vanadium oxide catalyst at low temperatures (200-250°C) has been developed for the selective catalytic reduction (SCR) de-NOx process with ammonia. The catalyst was evaluated in a pilot-scale equipment, and the results were compared with those obtained in our previous work using laboratory scale (small volume test) equipment as well as bench-scale laboratory equipment. In the present work, we have performed our experiments in pilot scale equipment using a part of effluent flue gas that was obtained from flue gas cleaning equipment in a full-scale waste incineration plant in South Korea. Based on our previous work, we have prepared a TiO 2 -supported V 2 O 5 catalyst coated (with a loading of 7wt% of impregnated V 2 O 5 ) on a honeycomb cordierite monolith to remove NOx from a waste incinerator flue gas at low temperatures. The NOx (nitrogen oxides) removal efficiency of the SCR catalyst bed was measured in a catalyst fixed-bed reactor (flow rate: 100m 3 h -1 ) using real exhaust gas from the waste incinerator. The experimental results showed that the V 2 O 5 /TiO 2 SCR catalyst exhibited good DeNOx performance (over 98% conversion at an operating temperature of 300°C, 95% at 250°C, and 70% at 200°C), and was much better than the performance of commercial SCR catalysts (as low as 55% conversion at 250°C) under the same operating conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Synthesis and visible light photoactivity of anatase Ag, and garlic loaded TiO2 nanocrystalline catalyst

EPA Science Inventory

An excellent visible light activated Ag and S doped TiO2 nanocatalyst was prepared by using AgNO3 and garlic (Allium sativum) as Ag+ and sulfur sources, respectively. The catalyst resisted the change from anatase to rutile phase even at calcination at 700 oC. The photocatalytic e...

Nanoscale effects of silica particle supports on the formation and properties of TiO2 nanocatalysts

NASA Astrophysics Data System (ADS)

Li, Aize; Jin, Yuhui; Muggli, Darrin; Pierce, David T.; Aranwela, Hemantha; Marasinghe, Gaya K.; Knutson, Theodore; Brockman, Greg; Zhao, Julia Xiaojun

2013-06-01

Small TiO2 crystals in the anatase phase are in high demand as photocatalysts. Stable TiO2 crystals in the anatase phase were obtained using a silica nanoparticle as a support. The focus of this study was to investigate the nanoscale effect of the silica support on the formation and properties of small anatase crystals. The experiments were carried out using powder X-ray diffraction, differential thermal analysis, transmission electron microscopy, and energy dispersion spectroscopy. The results showed that the size of the silica support played a crucial role in crystallization of TiO2 and regulation of TiO2 properties, including phase transition, crystal size, thermodynamic property and catalytic activity. A nanoscale curvature model of the spherical silica support was proposed to explain these size effects. Finally, the developed TiO2 catalysts were applied to the oxidation of methanol using a high-throughput photochemical reactor. The size effect of the silica supports on the TiO2 catalytic efficiency was demonstrated using this system.

Forming a Highly Active, Homogeneously Alloyed AuPt Co-catalyst Decoration on TiO2 Nanotubes Directly During Anodic Growth.

PubMed

Bian, Haidong; Nguyen, Nhat Truong; Yoo, JeongEun; Hejazi, Seyedsina; Mohajernia, Shiva; Müller, Julian; Spiecker, Erdmann; Tsuchiya, Hiroaki; Tomanec, Ondrej; Sanabria-Arenas, Beatriz E; Zboril, Radek; Li, Yang Yang; Schmuki, Patrik

2018-05-30

Au and Pt do not form homogeneous bulk alloys as they are thermodynamically not miscible. However, we show that anodic TiO 2 nanotubes (NTs) can in situ be uniformly decorated with homogeneous AuPt alloy nanoparticles (NPs) during their anodic growth. For this, a metallic Ti substrate containing low amounts of dissolved Au (0.1 atom %) and Pt (0.1 atom %) is used for anodizing. The matrix metal (Ti) is converted to oxide, whereas at the oxide/metal interface direct noble metal particle formation and alloying of Au and Pt takes place; continuously these particles are then picked up by the growing nanotube wall. In our experiments, the AuPt alloy NPs have an average size of 4.2 nm, and at the end of the anodic process, these are regularly dispersed over the TiO 2 nanotubes. These alloyed AuPt particles act as excellent co-catalyst in photocatalytic H 2 generation, with a H 2 production rate of 12.04 μL h -1 under solar light. This represents a strongly enhanced activity as compared to TiO 2 NTs decorated with monometallic particles of Au (7 μL h -1 ) or Pt (9.96 μL h -1 ).

Characterization and photocatalytic performance evaluation of various metal ion-doped microstructured TiO2 under UV and visible light.

PubMed

Sahoo, Chittaranjan; Gupta, Ashok K

2015-01-01

Commercially available microcrystalline TiO2 was doped with silver, ferrous and ferric ion (1.0 mol %) using silver nitrate, ferrous sulfate and ferric nitrate solutions following the liquid impregnation technology. The catalysts prepared were characterised by FESEM, XRD, FTIR, DRS, particle size and micropore analysis. The photocatalytic activity of the prepared catalysts was tested on the degradation of two model dyes, methylene blue (3,7-bis (Dimethylamino)-phenothiazin-5-ium chloride, a cationic thiazine dye) and methyl blue (disodium;4-[4-[[4-(4-sulfonatoanilino)phenyl]-[4-(4-sulfonatophenyl)azaniumylidenecyclohexa-2,5-dien-1-ylidene]methyl]anilino]benzene sulfonate, an anionic triphenyl methane dye) under irradiation by UV and visible light in a batch reactor. The efficiency of the photocatalysts under UV and visible light was compared to ascertain the light range for effective utilization. The catalysts were found to have the anatase crystalline structure and their particle size is in a range of 140-250 nm. In the case of Fe(2+) doped TiO2 and Fe(3+) doped TiO2, there was a greater shift in the optical absorption towards the visible range. Under UV light, Ag(+) doped TiO2 was the most efficient catalyst and the corresponding decolorization was more than 99% for both the dyes. Under visible light, Fe(3+) doped TiO2 was the most efficient photocatalyst with more than 96% and 90% decolorization for methylene blue and methyl blue, respectively. The kinetics of the reaction under both UV and visible light was investigated using the Langmuir-Hinshelwood pseudo-first-order kinetic model. Kinetic measurements confirmed that, Ag(+) doped TiO2 was most efficient in the UV range, while Fe(3+) doped TiO2 was most efficient in the visible range.

Hydrogenation of p-chloronitrobenzene on Ni-B Nanometal Catalysts

NASA Astrophysics Data System (ADS)

Liu, Yu-Chang; Huang, Chung-Yin; Chen, Yu-Wen

2006-04-01

A series of Ni-B catalysts were prepared by mixing nickel acetate in 50% ethanol/water or methanol/water solution. The solution of sodium borohydride (1 M) in excess amount to nickel was then added dropwise into the mixture to ensure full reduction of nickel cations. The mol ratio of boron to nickel in mother solution was 3 to 1. The effects of preparation conditions such as temperature, stirring speed, and sheltering gas on the particle size, surface compositions, electronic states of surface atoms and catalytic activities of the Ni-B catalysts were studied. Ranel nickel catalyst was included for comparison. These catalysts were characterized by N2 sorption, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalysts were tested for liquid phase hydrogenation of p-chloronitrobenzene. All of the catalysts prepared in this study had nanosized particles. The preparation condition has significant influence on the particle size and surface compositions of the catalyst. The Ni-B catalyst was passivated by boron; therefore it was more stable than Raney nickel and did not catch fire after exposure to air. The catalysts prepared under N2 flow could suppress the oxidation of Ni by the dissolved oxygen in water and had metallic state of nickel. The catalyst prepared with vigorous stirring at 25°C under N2 stream yielded the smallest particles and resulted in the highest activity. It was much more active than the Raney nickel catalyst. The reaction condition also has pronounced effect on the hydrogenation activity. Using methanol as the reaction solvent increased p-chloronitrobenzene conversion to a large extent, compared to that using ethanol as the reaction medium. The selectivity of main product ( p-chloroaniline) was greater than 99% on all of the Ni-B catalysts.

Growth of rutile TiO2 on the convex surface of nanocylinders: from nanoneedles to nanorods and their electrochemical properties

NASA Astrophysics Data System (ADS)

Kong, Junhua; Wei, Yuefan; Zhao, Chenyang; Toh, Meng Yew; Yee, Wu Aik; Zhou, Dan; Phua, Si Lei; Dong, Yuliang; Lu, Xuehong

2014-03-01

In this work, bundles of rutile TiO2 nanoneedles/nanorods are hydrothermally grown on carbon nanofibers (CNFs), forming free-standing mats consisting of three dimensional hierarchical nanostructures (TiO2-on-CNFs). Morphologies and structures of the TiO2-on-CNFs are studied using a field-emission scanning electron microscope (FESEM), transmission electron microscope (TEM), X-ray diffractometer (XRD) and thermogravimetric analyzer (TGA). Their electrochemical properties as electrodes in lithium ion batteries (LIBs) are investigated and correlated with the morphologies and structures. It is shown that the lateral size of the TiO2 nanoneedles/nanorods ranges from a few nanometers to tens of nanometers, and increases with the hydrothermal temperature. Small interspaces are observed between individual nanoneedles/nanorods, which are due to the diverging arrangement of nanoneedles/nanorods induced by growing on the convex surface of nanocylinders. It is found that the growth process can be divided into two stages: initial growth on the CNF surface and further growth upon re-nucleation on the TiO2 bundles formed in the initial growth stage. In order to achieve good electrochemical performance in LIBs, the size of the TiO2 nanostructures needs to be small enough to ensure complete alloying and fast charge transport, while the further growth stage has to be avoided to realize direct attachment of TiO2 nanostructures on the CNFs, facilitating electron transport. The sample obtained after hydrothermal treatment at 130 °C for 2 h (TiO2-130-2) shows the above features and hence exhibits the best cyclability and rate capacity among all samples; the cyclability and rate capacity of TiO2-130-2 are also superior to those of other rutile TiO2-based LIB electrodes.In this work, bundles of rutile TiO2 nanoneedles/nanorods are hydrothermally grown on carbon nanofibers (CNFs), forming free-standing mats consisting of three dimensional hierarchical nanostructures (TiO2-on

Synthesis of TiO2 nanoparticles by hydrolysis and peptization of titanium isopropoxide solution

NASA Astrophysics Data System (ADS)

Mahata, S.; Mahato, S. S.; Nandi, M. M.; Mondal, B.

2012-07-01

Here we report the synthesis and characterization of a stable suspension of modified titania nanoparticles. Phase-pure TiO2 nanocrystallites with narrow particle-size distributions were selectively prepared by hydrolysis-peptization of modified alkoxide followed by hydrothermal treatment. Autoclaving modified TiO2 in the presence of HNO3 as cooperative catalysts led to the formation of crystalline TiO2 with narrow-sized distribution. Following the hydrothermal treatment at 150°C, X-ray diffraction shows the particles to be exclusively anatase. Synthesized powder is characterized by FT-IR, scanning electron microscopy (FESEM) and transmission electron microscopy (HRTEM). The photocatalytic activity in the degradation of orange-II is quite comparable to good anatase and rutile nanocrystallites.

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.

Optical density and photonic efficiency of silica-supported TiO2 photocatalysts.

PubMed

Marugán, J; Hufschmidt, D; Sagawe, G; Selzer, V; Bahnemann, D

2006-02-01

Over the last years, many research groups have developed supported TiO2-based materials in order to improve the engineering applications of photocatalytic technologies. However, not many attempts have been made to evaluate the optical behavior of these materials. This work focuses on the study of the photonic efficiencies of silica-supported TiO2 photocatalysts following the photodegradation of dichloroacetic acid (DCA) as model compound. Catalysts with different types of silica support and titania loadings were tested and their activity was found to be in correlation with the results of the clusters size distribution of the TiO2 nanocrystals. The photonic efficiency of the supported photocatalysts depends extremely on the optical density of the solid suspensions. Influence of the textural properties of the support and the titania loading on the optical density as well as on the photonic efficiency of the materials are discussed. The dependence of the absorption of radiation by the suspension on the catalyst concentration is also analyzed.

Synthesis of TiO2-poly(3-hexylthiophene) hybrid particles through surface-initiated Kumada catalyst-transfer polycondensation.

PubMed

Boon, Florian; Moerman, David; Laurencin, Danielle; Richeter, Sébastien; Guari, Yannick; Mehdi, Ahmad; Dubois, Philippe; Lazzaroni, Roberto; Clément, Sébastien

2014-09-30

TiO2/conjugated polymers are promising materials in solar energy conversion where efficient photoinduced charge transfers are required. Here, a "grafting-from" approach for the synthesis of TiO2 nanoparticles supported with conjugated polymer brushes is presented. Poly(3-hexylthiophene) (P3HT), a benchmark material for organic electronics, was selectively grown from TiO2 nanoparticles by surface-initiated Kumada catalyst-transfer polycondensation. The grafting of the polymer onto the surface of the TiO2 nanoparticles by this method was demonstrated by (1)H and (13)C solid-state NMR, X-ray photoelectron spectrometry, thermogravimetric analysis, transmission electron microscopy, and UV-visible spectroscopy. Sedimentation tests in tetrahydrofuran revealed improved dispersion stability for the TiO2@P3HT hybrid material. Films were produced by solvent casting, and the quality of the dispersion of the modified TiO2 nanoparticles was evaluated by atomic force microscopy. The dispersion of the P3HT-coated TiO2 NPs in the P3HT matrix was found to be homogeneous, and the fibrillar structure of the P3HT matrix was maintained which is favorable for charge transport. Fluorescence quenching measurements on these hybrid materials in CHCl3 indicated improved photoinduced electron-transfer efficiency. All in all, better physicochemical properties for P3HT/TiO2 hybrid material were reached via the surface-initiated "grafted-from" approach compared to the "grafting-onto" approach.

Assessing the concept of structure sensitivity or insensitivity for sub-nanometer catalyst materials

NASA Astrophysics Data System (ADS)

Crampton, Andrew S.; Rötzer, Marian D.; Ridge, Claron J.; Yoon, Bokwon; Schweinberger, Florian F.; Landman, Uzi; Heiz, Ueli

2016-10-01

The nature of the nano-catalyzed hydrogenation of ethylene, yielding benchmark information pertaining to the concept of structure sensitivity/insensitivity and its applicability at the bottom of the catalyst particle size-range, is explored with experiments on size-selected Ptn (n = 7-40) clusters soft-landed on MgO, in conjunction with first-principles simulations. As in the case of larger particles both the direct ethylene hydrogenation channel and the parallel hydrogenation-dehydrogenation ethylidyne-producing route must be considered, with the fundamental uncovering that at the < 1 nm size-scale the reaction exhibits characteristics consistent with structure sensitivity, in contrast to the structure insensitivity found for larger particles. In this size-regime, the chemical properties can be modulated and tuned by a single atom, reflected by the onset of low temperature hydrogenation at T > 150 K catalyzed by Ptn (n ≥ 10) clusters, with maximum room temperature reactivity observed for Pt13 using a pulsed molecular beam technique. Structure insensitive behavior, inherent for specific cluster sizes at ambient temperatures, can be induced in the more active sizes, e.g. Pt13, by a temperature increase, up to 400 K, which opens dehydrogenation channels leading to ethylidyne formation. This reaction channel was, however found to be attenuated on Pt20, as catalyst activity remained elevated after the 400 K step. Pt30 displayed behavior which can be understood from extrapolating bulk properties to this size range; in particular the calculated d-band center. In the non-scalable sub-nanometer size regime, however, precise control of particle size may be used for atom-by-atom tuning and manipulation of catalyzed hydrogenation activity and selectivity.

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 A.; Richards, Jeffrey T.

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.

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.

Influence of TiO2 hollow sphere size on its photo-reduction activity for toxic Cr(VI) removal.

PubMed

Cai, Jiabai; Wu, Xueqing; Zheng, Fengying; Li, Shunxing; Wu, Yaling; Lin, Yanping; Lin, Liting; Liu, Biwen; Chen, Qiaoying; Lin, Luxiu

2017-03-15

After polystyrene@titanium dioxide (PS@TiO 2 ) composite with different size was calcined at designated temperature, TiO 2 hollow sphere with controllable size was obtained for high efficient photo-reduction of Cr(VI). The feature of the TiO 2 hollow sphere was investigated by SEM, TEM, XRD, UV-Vis, and photoluminescence. The photo-reduction of Cr(VI) were measured for the performance assessment of the TiO 2 hollow sphere, Cr(VI) was used as an electron acceptor. After irradiation for 2h, the photo-reduction rate of Cr(VI) (pH=2.82) for TiO 2 (450nm) was 96%, which exhibited an increase of 5% and 8% compared with TiO 2 (370nm) and TiO 2 (600nm). The absorption edges of TiO 2 hollow sphere (450nm) was largest with the increasing of hollow sphere size from 370 to 600nm. The optimal hollow sphere size of TiO 2 was 450nm for the photo-reduction of Cr(VI), because the light-harvesting efficiency (the best of absorption edge) and photo-generated electron-hole separation rate (the best of photo-reduction rate) of TiO 2 hollow sphere were controlled by its hollow sphere size. In addition, we find that the behavior of the hydrogen production was inhibited by the coexistence Cr(VI) solution. This study can improve our understanding of the mechanism for the activity enhancement by the optimal hollow sphere size of TiO 2 . Copyright © 2016 Elsevier Inc. All rights reserved.

Zirconium and silver co-doped TiO2 nanoparticles as visible light catalyst for reduction of 4-nitrophenol, degradation of methyl orange and methylene blue

NASA Astrophysics Data System (ADS)

Naraginti, Saraschandra; Stephen, Finian Bernard; Radhakrishnan, Adhithya; Sivakumar, A.

2015-01-01

Catalytic activity of Zr and Ag co-doped TiO2 nanoparticles on the reduction of 4-nitrophenol, degradation of methylene blue and methyl orange was studied using sodium borohydride as reducing agent. The nanoparticles were characterized using X-ray diffraction, energy dispersive X-ray, high resolution transmission electron microscopy, selected area electron diffraction and UV-Vis spectroscopy. The rate of the reduction/degradation was found to increase with increasing amount of the photocatalyst which could be attributed to higher dispersity and small size of the nanoparticles. The catalytic activity of Zr and Ag co-doped TiO2 nanoparticles showed no significant difference even after recycling the catalyst four times indicating a promising potential for industrial application of the prepared photocatalyst.

Highly Efficient Low-Temperature N-Doped TiO2 Catalysts for Visible Light Photocatalytic Applications

PubMed Central

Mahy, Julien G.; Cerfontaine, Vincent; Devred, François; Gaigneaux, Eric M.; Heinrichs, Benoît; Lambert, Stéphanie D.

2018-01-01

In this paper, TiO2 prepared with an aqueous sol-gel synthesis by peptization process is doped with nitrogen precursor to extend its activity towards the visible region. Three N-precursors are used: urea, ethylenediamine and triethylamine. Different molar N/Ti ratios are tested and the synthesis is adapted for each dopant. For urea- and trimethylamine-doped samples, anatase-brookite TiO2 nanoparticles of 6–8 nm are formed, with a specific surface area between 200 and 275 m2·g−1. In ethylenediamine-doped samples, the formation of rutile phase is observed, and TiO2 nanoparticles of 6–8 nm with a specific surface area between 185 and 240 m2·g−1 are obtained. X-ray photoelectron spectroscopy (XPS) and diffuse reflectance measurements show the incorporation of nitrogen in TiO2 materials through Ti–O–N bonds allowing light absorption in the visible region. Photocatalytic tests on the remediation of water polluted with p-nitrophenol show a marked improvement for all doped catalysts under visible light. The optimum doping, taking into account cost, activity and ease of synthesis, is up-scaled to a volume of 5 L and compared to commercial Degussa P25 material. This up-scaled sample shows similar properties compared to the lab-scale sample, i.e., a photoactivity 4 times higher than commercial P25. PMID:29642626

Generating Color from Polydisperse, Near Micron-Sized TiO2 Particles.

PubMed

Alam, Al-Mahmnur; Baek, Kyungnae; Son, Jieun; Pei, Yi-Rong; Kim, Dong Ha; Choy, Jin-Ho; Hyun, Jerome K

2017-07-19

Single particle Mie calculations of near micron-sized TiO 2 particles predict strong light scattering dominating the visible range that would give rise to a white appearance. We demonstrate that a polydisperse collection of these "white" particles can result in the generation of visible colors through ensemble scattering. The weighted averaging of the scattering over the particle size distribution modifies the sharp, multiple, high order scattering modes from individual particles into broad variations in the collective extinction. These extinction variations are apparent as visible colors for particles suspended in organic solvent at low concentration, or for a monolayer of particles supported on a transparent substrate viewed in front of a white light source. We further exploit the color variations on optical sensitivity to the surrounding environment to promote micron-sized TiO 2 particles as stable and robust agents for detecting the optical index of homogeneous media with high contrast sensitivities. Such distribution-modulated scattering properties provide TiO 2 particles an intriguing opportunity to impart color and optical sensitivity to their widespread electronic and chemical platforms such as antibacterial windows, catalysis, photocatalysis, optical sensors, and photovoltaics.

XANES study of elemental mercury oxidation over RuO 2/TiO 2 and selective catalytic reduction catalysts for mercury emissions control

DOE PAGES

Liu, Zhouyang; Li, Can; Sriram, Vishnu; ...

2016-07-25

Linear combination fitting of the X-ray Absorption Near Edge Spectroscopy (XANES) was used to quantify oxidized mercury species over RuO 2/TiO 2 and Selective Catalytic Reduction (SCR) catalysts under different simulated flue gas conditions. Halogen gases play a major role in mercury oxidation. In the absence of halogen gas, elemental mercury can react with sulfur that is contained in both the RuO2/TiO2 and SCR catalysts to form HgS and HgSO 4. In the presence of HCl or HBr gas, HgCl 2 or HgBr 2 is the main oxidized mercury species. When both HCl and HBr gases are present, HgBr2 ismore » the preferred oxidation product and no HgCl 2 can be found. The formation of HgO and HgS cannot be neglected with or without halogen gas. Other simulated flue gas components such as NO, NH 3, SO 2 and CO 2 do not have significant effect on oxidized mercury speciation when halogen gas is present.« less

The Role of Lewis and Brønsted Acid Sites in NO Reduction with NH3 on Sulfur Modified TiO2-Supported V2O5 Catalyst

NASA Astrophysics Data System (ADS)

Zhao, Wei; Dou, Shengping; Zhong, Qin; Wu, Licheng; Wang, Qian; Wang, Aijian

2017-12-01

V2O5/S-doped TiO2 was prepared by the sol-gel and impregnation methods. The adsorption of NO, NH3, and O2 over the catalyst was studied by in situ DRIFTS spectroscopy to elucidate the reaction mechanism of the low-temperature selective catalytic reduction of NO with NH3. Exposing the catalyst to O2 and NO, three types of nitrates species appeared on the surface. The introduction of S to TiO2 could generate large amounts of acid sites for ammonia adsorption on the catalyst, which was believed to be an important role in the SCR reaction and hereby improved the catalytic activity. The results indicated two possible SCR reaction pathways for catalyst. One was that NO was absorbed to form nitrite species, which could react with NH3 on Lewis acid sites, producing N2 and H2O. Another way was that NH3 was adsorbed, then reacted with gas phase NO (E-R) and nitrite intermediates on the surface (L-H).

Synthesis of Copper-Based Nanostructured Catalysts on SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 Supports for NO Reduction.

PubMed

Namkhang, Pornpan; Kongkachuichay, Paisan

2015-07-01

The selective catalytic reduction of NO over a series of Cu-based catalysts supported on modified silica including SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 prepared via a sol-gel process and a flame spray pyrolysis (FSP) was studied. The prepared catalysts were characterized by means of TEM, XRD, XRF, TPR, and nitrogen physisorption measurement techniques, to determine particle diameter, morphology, crystallinity, phase composition, copper reducibility, surface area, and pore size of catalysts. The particles obtained from sol-gel method were almost spherical while the particles obtained from the FSP were clearly spherical and non-porous nanosized particles. The effects of Si:Al, Si:Ti, and Si:Zr molar ratio of precursor were identified as the domain for different crystalline phase of materials. It was clearly seen that a high SiO2 content inhibited the crystallization of materials. The BET surface area of catalysts obtained from sol-gel method was higher than that from the FSP and it shows that surface area increased with increasing SiO2 molar ratio due to high surface area from SiO2. The catalyst performances were tested for the selective catalytic reduction of NO with H2. It was found that the catalyst prepared over 7 wt% Cu on Si02-Al2O3 support was the most active compared with the others which converted NO as more than 70%. Moreover, the excess copper decreased the performance of NO reduction, due to the formation of CuO agglomeration covered on the porous silica as well as the alumina surface, preventing the direct contact of CO2 and AL2O3.

Study on the decomposition of trace benzene over V2O5-WO3/TiO2-based catalysts in simulated flue gas

EPA Science Inventory

Commercial and laboratory-prepared V2O5–WO3/TiO2-based catalysts with different compositions were tested for catalytic decomposition of chlorobenzene （ClBz） in simulated flue gas. Resonance enhanced multiphoton ionization-time of flight mass spectrometry (REMPI-TOFMS) was employe...

Size-dependent effects in supported highly dispersed Fe2O3 catalysts, doped with Pt and Pd

NASA Astrophysics Data System (ADS)

Cherkezova-Zheleva, Zara; Shopska, Maya; Mitov, Ivan; Kadinov, Georgi

2010-06-01

Series of Fe and Fe-Me (Me = Pt or Pd) catalyst supported on γ-Al2O3, TiO2 (anatase) or diatomite were prepared by the incipient wetness impregnation method. The metal loading was 8 wt.% Fe and 0.7 wt.% noble metal. The preparation and pretreatment conditions of all studied samples were kept to be the same. X-ray diffraction, Moessbauer spectroscopy, X-ray photoelectron spectroscopy and temperature-programmed reduction are used for characterization of the supports and the samples at different steps during their treatment and catalytic tests. The catalytic activity of the samples was tested in the reaction of total benzene oxidation. The physicochemical and catalytic properties of the obtained materials are compared with respect of the different chemical composition, dispersion of used carriers and of the supported phases. Samples with the same composition prepared by mechanical mixing are studied as catalysts for comparison and for clearing up the presence of size-dependent effect, also.

Preparation of Fe3O4/TiO2 magnetic mesoporous composites for photocatalytic degradation of organic pollutants.

PubMed

Zhang, Hongfeng; He, Xiu; Zhao, Weiwei; Peng, Yu; Sun, Donglan; Li, Hao; Wang, Xiaocong

2017-04-01

Fe 3 O 4 /TiO 2 magnetic mesoporous composites were synthesized through a sol-gel method with tetra-n-butyl titanate as precursor and surfactant P123 as template. The as-prepared Fe 3 O 4 /TiO 2 composites were characterized by X-ray diffraction, diffuse reflectance spectroscopy, nitrogen adsorption-desorption isotherm and pore size distribution. The as-synthesized products were applied as photocatalysis for the degradation of Acid Black ATT and tannery wastewater under UV lamp irradiation. Fe 3 O 4 /TiO 2 -8 composites containing Fe 3 O 4 of 8 wt% were selected as model catalysts. The optimal catalyst dosage was 3 g/L in this photocalytic system. The magnetic Fe 3 O 4 /TiO 2 composites possessed good photocatalytic stability and durability. This approach may provide a platform to prepare a magnetic composite to optimize the catalytic ability.

Study of the photocatalytic activity of Fe 3+, Cr 3+, La 3+ and Eu 3+ single-doped and co-doped TiO 2 catalysts produced by aqueous sol-gel processing

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

Malengreaux, Charline M.; Pirard, Sophie L.; Léonard, Géraldine

An aqueous sol-gel process, previously developed for producing undoped and Cu 2+, Ni 2+, Zn 2+ or Pb 2+ doped TiO 2 photocatalysts with remarkably high photocatalytic activity without requiring any calcination step, has been adapted to produce Fe 3+, Cr 3+, La 3+ or Eu 3+ single-doped TiO 2 photocatalysts as well as La3+-Fe3+ and Eu3+-Fe3+ co-doped TiO 2 catalysts. The physicochemical properties of the obtained catalysts have been characterized using a suite of complementary techniques, including ICP-AES, XRD, UV-Vis spectroscopy, nitrogen adsorption-desorption and Fe-57 M ssbauer. The active crystalline phase is obtained without requiring any calcination step andmore » all the different catalysts are composed of nanocrystallites of anatase with a size of 6-7 nm and a high specific surface area varying from 181 to 298 m 2 g -1. In this study, the effect of the NO 3:Ti(IV) mole ratio used to induce the peptisation reaction during the synthesis has been studied and the results revealed that this ratio can influence significantly the textural properties of the resulting catalyst. A screening of the photocatalytic activity of the undoped and Fe 3+, Cr 3+, La 3+ or Eu 3+ single-doped and co-doped photocatalysts has been performed by evaluating the degradation of 4-nitrophenol under UV-Visible light (330 nm < < 800 nm). This study suggests that the photocatalytic activity is significantly influenced by the dopant nature and content with an optimal dopant content being observed in the case of Fe 3+ or La 3+ single-doped as well as in the case of La 3+-Fe 3+ and Eu 3+-Fe 3+ co-doped catalysts. In the case of Cr 3+ single-doped catalysts, a detrimental effect of the dopant on the photocatalytic degradation of 4-nitrophenol has been observed while no significant influence of the dopant has been detected in the case of Eu 3+ single-doped catalysts. In conclusion, the role of the different dopants in modulating the photocatalytic activity is discussed.« less

Study of the photocatalytic activity of Fe 3+, Cr 3+, La 3+ and Eu 3+ single-doped and co-doped TiO 2 catalysts produced by aqueous sol-gel processing

DOE PAGES

Malengreaux, Charline M.; Pirard, Sophie L.; Léonard, Géraldine; ...

2016-08-30

An aqueous sol-gel process, previously developed for producing undoped and Cu 2+, Ni 2+, Zn 2+ or Pb 2+ doped TiO 2 photocatalysts with remarkably high photocatalytic activity without requiring any calcination step, has been adapted to produce Fe 3+, Cr 3+, La 3+ or Eu 3+ single-doped TiO 2 photocatalysts as well as La3+-Fe3+ and Eu3+-Fe3+ co-doped TiO 2 catalysts. The physicochemical properties of the obtained catalysts have been characterized using a suite of complementary techniques, including ICP-AES, XRD, UV-Vis spectroscopy, nitrogen adsorption-desorption and Fe-57 M ssbauer. The active crystalline phase is obtained without requiring any calcination step andmore » all the different catalysts are composed of nanocrystallites of anatase with a size of 6-7 nm and a high specific surface area varying from 181 to 298 m 2 g -1. In this study, the effect of the NO 3:Ti(IV) mole ratio used to induce the peptisation reaction during the synthesis has been studied and the results revealed that this ratio can influence significantly the textural properties of the resulting catalyst. A screening of the photocatalytic activity of the undoped and Fe 3+, Cr 3+, La 3+ or Eu 3+ single-doped and co-doped photocatalysts has been performed by evaluating the degradation of 4-nitrophenol under UV-Visible light (330 nm < < 800 nm). This study suggests that the photocatalytic activity is significantly influenced by the dopant nature and content with an optimal dopant content being observed in the case of Fe 3+ or La 3+ single-doped as well as in the case of La 3+-Fe 3+ and Eu 3+-Fe 3+ co-doped catalysts. In the case of Cr 3+ single-doped catalysts, a detrimental effect of the dopant on the photocatalytic degradation of 4-nitrophenol has been observed while no significant influence of the dopant has been detected in the case of Eu 3+ single-doped catalysts. In conclusion, the role of the different dopants in modulating the photocatalytic activity is discussed.« less

Interrelationship between TiO2 nanoparticle size and kind/size of dyes in the mechanism and conversion efficiency of dye sensitized solar cells.

PubMed

Tahay, Pooya; Babapour Gol Afshani, Meisam; Alavi, Ali; Parsa, Zahra; Safari, Nasser

2017-05-10

In order to provide a comprehensive investigation of TiO 2 nanoparticle size in relation with different dye types in DSSCs, three sizes of TiO 2 nanoparticles and two different dye types including a porphyrin dye (T2) and a ruthenium dye (N3) were synthesized. Steady state current-voltage (J-V) characteristics were investigated for the fabricated DSSCs and the results demonstrated that the optimum TiO 2 nanoparticle size changed with the dye type. The obtained J-V data were interpreted by cyclic voltammetry, UV-visible absorption spectroscopy, BET measurement, DFT calculation, IPCE measurement and impedance spectroscopy. The results for the N3 dye show that the surface area of the TiO 2 nanoparticles is a key factor for the N3 cells, which is restricted by TiO 2 pore diameter and surface state traps. In contrast, the density of localized states of the TiO 2 film under the LUMO state of the porphyrin dyes is the dominating factor for the performance of the solar cells, which is restricted by the surface area of the TiO 2 nanoparticles. These obtained results represent a significant advance in the development of porphyrin, ruthenium and even solid electrolyte DSSCs.

Toxicity of TiO2 Nanoparticles to Escherichia coli: Effects of Particle Size, Crystal Phase and Water Chemistry

PubMed Central

Lin, Xiuchun; Li, Jingyi; Ma, Si; Liu, Gesheng; Yang, Kun; Tong, Meiping; Lin, Daohui

2014-01-01

Controversial and inconsistent results on the eco-toxicity of TiO2 nanoparticles (NPs) are commonly found in recorded studies and more experimental works are therefore warranted to elucidate the nanotoxicity and its underlying precise mechanisms. Toxicities of five types of TiO2 NPs with different particle sizes (10∼50 nm) and crystal phases were investigated using Escherichia coli as a test organism. The effect of water chemistry on the nanotoxicity was also examined. The antibacterial effects of TiO2 NPs as revealed by dose-effect experiments decreased with increasing particle size and rutile content of the TiO2 NPs. More bacteria could survive at higher solution pH (5.0–10.0) and ionic strength (50–200 mg L−1 NaCl) as affected by the anatase TiO2 NPs. The TiO2 NPs with anatase crystal structure and smaller particle size produced higher content of intracellular reactive oxygen species and malondialdehyde, in line with their greater antibacterial effect. Transmission electron microscopic observations showed the concentration buildup of the anatase TiO2 NPs especially those with smaller particle sizes on the cell surfaces, leading to membrane damage and internalization. These research results will shed new light on the understanding of ecological effects of TiO2 NPs. PMID:25310452

Solar-assisted photodegradation of isoproturon over easily recoverable titania catalysts.

PubMed

Tolosana-Moranchel, A; Carbajo, J; Faraldos, M; Bahamonde, A

2017-03-01

An easily recoverable homemade TiO 2 catalyst (GICA-1) has been evaluated during the overall photodegradation process, understood as photocatalytic efficiency and catalyst recovery step, in the solar light-assisted photodegradation of isoproturon and its reuse in two consecutive cycles. The global feasibility has been compared to the commercial TiO 2 P25. The homemade GICA-1 catalyst presented better sedimentation efficiency than TiO 2 P25 at all studied pHs, which could be explained by its higher average hydrodynamic particle size (3 μm) and other physicochemical surface properties. The evaluation of the overall process (isoproturon photo-oxidation + catalyst recovery) revealed GICA-1 homemade titania catalyst strengths: total removal of isoproturon in less than 60 min, easy recovery by sedimentation, and reusability in two consecutive cycles, without any loss of photocatalytic efficiency. Therefore, considering the whole photocatalytic cycle (good performance in photodegradation plus catalyst recovery step), the homemade GICA-1 photocatalyst resulted in more affordability than commercial TiO 2 P25. Graphical abstract.

The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

DOE PAGES

An, Wei; Liu, Ping

2016-09-07

When using the TiO 2(110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd 7-3D/TiO 2(110) at low coverage to Pd 7-2D/TiO 2(110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO 2(110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O 2 dissociation and CO oxidation via bifunctional synergy.

SCR atmosphere induced reduction of oxidized mercury over CuO-CeO2/TiO2 catalyst.

PubMed

Li, Hailong; Wu, Shaokang; Wu, Chang-Yu; Wang, Jun; Li, Liqing; Shih, Kaimin

2015-06-16

CuO-CeO2/TiO2 (CuCeTi) catalyst synthesized by a sol-gel method was employed to investigate mercury conversion under a selective catalytic reduction (SCR) atmosphere (NO, NH3 plus O2). Neither NO nor NH3 individually exhibited an inhibitive effect on elemental mercury (Hg(0)) conversion in the presence of O2. However, Hg(0) conversion over the CuCeTi catalyst was greatly inhibited under SCR atmosphere. Systematic experiments were designed to investigate the inconsistency and explore the in-depth mechanisms. The results show that the copresence of NO and NH3 induced reduction of oxidized mercury (Hg(2+), HgO in this study), which offset the effect of catalytic Hg(0) oxidation, and hence resulted in deactivation of Hg(0) conversion. High NO and NH3 concentrations with a NO/NH3 ratio of 1.0 facilitated Hg(2+) reduction and therefore lowered Hg(0) conversion. Hg(2+) reduction over the CuCeTi catalyst was proposed to follow two possible mechanisms: (1) direct reaction, in which NO and NH3 react directly with HgO to form N2 and Hg(0); (2) indirect reaction, in which the SCR reaction consumed active surface oxygen on the CuCeTi catalyst, and reduced species on the CuCeTi catalyst surface such as Cu2O and Ce2O3 robbed oxygen from adjacent HgO. Different from the conventionally considered mechanisms, that is, competitive adsorption responsible for deactivation of Hg(0) conversion, this study reveals that oxidized mercury can transform into Hg(0) under SCR atmosphere. Such knowledge is of fundamental importance in developing efficient and economical mercury control technologies for coal-fired power plants.

V-doped TiO2 supported Pt as a promising oxygen reduction reaction catalyst: Synthesis, characterization and in-situ evaluation in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-09-01

This study deals with the synthesis and characterization of V-doped, TiO2 supported Pt catalyst (Pt/V-TiO2) for oxygen reduction reaction (ORR) and its in-situ performance investigation in proton exchange membrane (PEM) fuel cell. Pt/V-TiO2 nanocomposite catalyst is prepared via a facile sol-gel and microwave assisted, modified chemical reduction route and its performance is compared with the undoped TiO2 supported catalyst, Pt/TiO2 prepared in an identical way. The prepared Pt/V-TiO2 and Pt/TiO2 catalysts are employed as cathode catalyst in PEM fuel cell and compared with standard Pt/C catalyst. Their comparative studies are conducted with physical and electrochemical techniques. In-situ electrochemical characterization studies show improved ORR catalytic activity of Pt/V-TiO2 compared to Pt/TiO2. Furthermore, both Pt/TiO2 and Pt/V-TiO2 are more stable than Pt/C when subjected to 6000 voltammetric cycles in the range of 0.2-1.2 V vs. standard hydrogen electrode in operating fuel cell conditions, losing only <20% of its electrochemical surface area as compared to 50% loss exhibited by Pt/C. This study thus demonstrates Pt/V-TiO2 nanocomposite material as a potential cathode catalyst for PEM fuel cell with immense scope for further investigation.

Effect of TiO 2 particle size and layer thickness on mesoscopic perovskite solar cells

DOE PAGES

Lee, Dong Geon; Kim, Min-cheol; Kim, Byeong Jo; ...

2017-11-16

Mesoporous TiO 2 (mp-TiO 2) layers are commonly used as electron transport layers in perovskite solar cells, which help to extract electrons from the perovskite light-absorbing layer and transport them to the electrodes. We investigated the effects of the layer thickness of mp-TiO 2 and particle size of TiO 2 on photovoltaic properties, in terms of the surface area of the mp-layer and the interfacial areas of the TiO 2 nanoparticles in the mp-layer. Various mp-TiO 2 layers with thicknesses of 150, 250, and 400 nm and particle sizes of 25 nm and 41 nm were prepared to compare themore » photovoltaic properties of such layer-containing perovskite solar cells. Time-resolved photoluminescence decay and impedance studies showed that interfacial resistance as well as perovskite-to-TiO 2 charge injection are important factors affecting photovoltaic performance. The deterioration of the photovoltaic parameters with increasing TiO 2/TiO 2 interfacial area also confirms that the interfacial series resistance that arises from these connections should be reduced to enhance the performance of mesoscopic perovskite solar cells.« less

Effect of TiO 2 particle size and layer thickness on mesoscopic perovskite solar cells

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

Lee, Dong Geon; Kim, Min-cheol; Kim, Byeong Jo

Mesoporous TiO 2 (mp-TiO 2) layers are commonly used as electron transport layers in perovskite solar cells, which help to extract electrons from the perovskite light-absorbing layer and transport them to the electrodes. We investigated the effects of the layer thickness of mp-TiO 2 and particle size of TiO 2 on photovoltaic properties, in terms of the surface area of the mp-layer and the interfacial areas of the TiO 2 nanoparticles in the mp-layer. Various mp-TiO 2 layers with thicknesses of 150, 250, and 400 nm and particle sizes of 25 nm and 41 nm were prepared to compare themore » photovoltaic properties of such layer-containing perovskite solar cells. Time-resolved photoluminescence decay and impedance studies showed that interfacial resistance as well as perovskite-to-TiO 2 charge injection are important factors affecting photovoltaic performance. The deterioration of the photovoltaic parameters with increasing TiO 2/TiO 2 interfacial area also confirms that the interfacial series resistance that arises from these connections should be reduced to enhance the performance of mesoscopic perovskite solar cells.« less

Fabrication of Ce/N co-doped TiO2/diatomite granule catalyst and its improved visible-light-driven photoactivity.

PubMed

Chen, Yan; Liu, Kuiren

2017-02-15

Eliminating antibiotic remnants in aquatic environment has become one of the hottest topics among current research works. Thus, we prepared Ce, N co-doped TiO 2 /diatomite granule (CNTD-G) catalyst to provide a new method. As one typical antibiotics, oxytetracycline (OTC) was selected as the target pollutant to be degradated under visible light irradiation. The carrier diatomite helped the spread of TiO 2 nanoparticles onto its surface, and inhibited their agglomeration. The synergy of Ce and N dopants highly improved the visible-light-driven photoactivity of TiO 2 . The optimal doping amount and degradation conditions were determined. Besides, the effects of impurity ions were also investigated, including cations: Ca 2+ , Mg 2+ ; or anions: NO 3 - , SO 4 2- and PO 4 3- . The intermediates generated during degradation process were studied, and the mechanism of the photodegradation process was proposed. CNTD-G could be easily collected from the reactor, and showed excellent recyclability. Copyright © 2016 Elsevier B.V. All rights reserved.

Study on the decomposition of trace benzene over V2O5–WO3/TiO2-based catalysts in simulated flue gas

EPA Science Inventory

Trace levels (1 and 10 ppm) of gaseous benzene were catalytically decomposed in a fixed-bed catalytic reactor with monolithic oxides of vanadium and tungsten supported on titanium oxide (V2O5–WO3/TiO2) catalysts under conditions simulating the cooling of waste incineration flue g...

Impact of nano and bulk ZrO2, TiO2 particles on soil nutrient contents and PGPR.

PubMed

Karunakaran, Gopalu; Suriyaprabha, Rangaraj; Manivasakan, Palanisamy; Yuvakkumar, Rathinam; Rajendran, Venkatachalam; Kannan, Narayanasamy

2013-01-01

Currently, nanometal oxides are used extensively in different industries such as medicine, cosmetics and food. The increased consumption of nanoparticles (NPs) leads the necessity to understand the fate of the nanoparticles in the environment. The present study focused on the ecotoxicological behaviour of bulk and nano ZrO2 (Zirconia) and TiO2 (Titania) particles on PGPR (plant growth promoting rhizobacteria), soil and its nutrient contents. The microbial susceptibility study showed that nano TiO2 had 13 +/- 0.9 mm (B. megaterium), 15 +/- 0.2 mm (P. fluorescens), 16 +/- 0.2 mm (A. vinelandii) and 12 +/- 0.3 mm (B. brevis) zones of inhibition. However, nano and bulk ZrO2 particles were non-toxic to PGPR. In addition, it was found that toxicity varied depends on the medium of reaction. The soil study showed that nano TiO2 was found to be highly toxic, whereas bulk TiO2 was less toxic towards soil bacterial populations at 1000 mg L(-1). In contrast, nano and bulk ZrO2 were found to be inert at 1000 mg L(-1). The observed zeta potential and hydrophobicity of TiO2 particles causes more toxic than ZrO2 in parallel with particle size. However, nano TiO2 decreases the microbial population as well as nutrient level of the soil but not zirconia. Our finding shows that the mechanism of toxicity depends on size, hydrophobic potential and zeta potential of the metal oxide particles. Thus, it is necessary to take safety measures during the disposal and use of such toxic nanoparticles in the soil to prevent their hazardous effects.

Study on physicochemical properties of functionalized-MWNTs with 3-aminopropyltriethoxysilane loaded TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Ahmad, Amirah; Razali, Mohd Hasmizam; Amin, Khairul Anuar Mat

2017-09-01

One of the exciting developments in science today is the design and synthesis of carbon nanotubes (CNTs) that possess novel properties and not exhibited by other individual organic and inorganic materials. CNTs are prepared using a chemical vapor deposition method with acetylene and synthesized mesoporous Ni-MCM41 as the carbon source and catalyst, respectively, and are then functionalized using 3-aminopropyltriethoxysilane (APTES) through the co-condensation method and loaded with commercial TiO2. Mesoporous Ni-MCM41 catalyst is first synthesized by hydrothermal method using sodium metasilicate as silica source and cetyltrimethylammonium bromide (CTABr) as a template. Results of Raman spectroscopy confirm that the synthesized carbon nanotubes are multi-walled. The type IV nitrogen adsorption-desorption isotherm and narrow pore size distribution proved that the functionalized-MWNTs loaded TiO2 is in mesopore range. Field Emission Scanning Electron Microscopy reveals that good dispersions of TiO2 nanoparticles onto functionalized-MWNTs with hair-like structure in between 3-8 nm. BET results indicate that functionalized-MWNTs loaded TiO2 possessed high surface area thus has considerable potential as an adsorbent and photocatalyst in environmental applications.

Plasma-assisted adsorption of elemental mercury on CeO2/TiO2 at low temperatures

NASA Astrophysics Data System (ADS)

Liu, Lu; Zheng, Chenghang; Gao, Xiang

2017-11-01

Mercury is a kind of pollutants contained in flue gas which is hazardous for human beings. In this work, CeO2 was packed in the discharge zone of a plasma reactor to adsorb elemental mercury at low temperatures. Plasma-catalyst reactor can remove Hg0 efficiently with CeO2/TiO2 catalysts packed in the discharge zone. The Hg0 concentration continued to decrease gradually when the plasma was turned on, but not sank rapidly. This tendency was different with other catalysts. The treatment of plasma to CeO2/TiO2 catalysts has a promotion effect on the adsorption of Hg0. Plasma has the effect of changing the surface properties of the catalysts and the changes would restitute if the condition changed. The long-running test demonstrated that this method is an effective way to remove Hg0. The removal efficiency remained at above 99% throughout 12 hours when plasma had been turned on (15kV, 0.5 g packed CeO2/TiO2).

Synthesis of Pt@TiO2@CNTs Hierarchical Structure Catalyst by Atomic Layer Deposition and Their Photocatalytic and Photoelectrochemical Activity.

PubMed

Liao, Shih-Yun; Yang, Ya-Chu; Huang, Sheng-Hsin; Gan, Jon-Yiew

2017-04-29

Pt@TiO2@CNTs hierarchical structures were prepared by first functionalizing carbon nanotubes (CNTs) with nitric acid at 140 °C. Coating of TiO2 particles on the CNTs at 300 °C was then conducted by atomic layer deposition (ALD). After the TiO2@CNTs structure was fabricated, Pt particles were deposited on the TiO2 surface as co-catalyst by plasma-enhanced ALD. The saturated deposition rates of TiO2 on a-CNTs were 1.5 Å/cycle and 0.4 Å/cycle for substrate-enhanced process and linear process, respectively. The saturated deposition rate of Pt on TiO2 was 0.39 Å/cycle. The photocatalytic activities of Pt@TiO2@CNTs hierarchical structures were higher than those without Pt co-catalyst. The particle size of Pt on TiO2@CNTs was a key factor to determine the efficiency of methylene blue (MB) degradation. The Pt@TiO2@CNTs of 2.41 ± 0.27 nm exhibited the best efficiency of MB degradation.

Synthesis of Pt@TiO2@CNTs Hierarchical Structure Catalyst by Atomic Layer Deposition and Their Photocatalytic and Photoelectrochemical Activity

PubMed Central

Liao, Shih-Yun; Yang, Ya-Chu; Huang, Sheng-Hsin; Gan, Jon-Yiew

2017-01-01

Pt@TiO2@CNTs hierarchical structures were prepared by first functionalizing carbon nanotubes (CNTs) with nitric acid at 140 °C. Coating of TiO2 particles on the CNTs at 300 °C was then conducted by atomic layer deposition (ALD). After the TiO2@CNTs structure was fabricated, Pt particles were deposited on the TiO2 surface as co-catalyst by plasma-enhanced ALD. The saturated deposition rates of TiO2 on a-CNTs were 1.5 Å/cycle and 0.4 Å/cycle for substrate-enhanced process and linear process, respectively. The saturated deposition rate of Pt on TiO2 was 0.39 Å/cycle. The photocatalytic activities of Pt@TiO2@CNTs hierarchical structures were higher than those without Pt co-catalyst. The particle size of Pt on TiO2@CNTs was a key factor to determine the efficiency of methylene blue (MB) degradation. The Pt@TiO2@CNTs of 2.41 ± 0.27 nm exhibited the best efficiency of MB degradation. PMID:28468248

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.

Effect of low Fe3+ doping on characteristics, sonocatalytic activity and reusability of TiO2 nanotubes catalysts for removal of Rhodamine B from water.

PubMed

Pang, Yean Ling; Abdullah, Ahmad Zuhairi

2012-10-15

Fe-doped titanium dioxide (TiO(2)) nanotubes were prepared using sol-gel followed by hydrothermal methods and characterized using various methods. The sonocatalytic activity was evaluated based on oxidation of Rhodamine B under ultrasonic irradiation. Iron ions (Fe(3+)) might incorporate into the lattice and intercalated in the interlayer spaces of TiO(2) nanotubes. The catalysts showed narrower band gap energies, higher specific surface areas, more active surface oxygen vacancies and significantly improved sonocatalytic activity. The optimum Fe doping at Fe:Ti=0.005 showed the highest sonocatalytic activity and exceeded that of un-doped TiO(2) nanotubes by a factor of 2.3 times. It was believed that Fe(3+) doping induced the formation of new states close to the valence band and conduction bands and accelerated the separation of charge carriers. Leached Fe(3+) could catalyze Fenton-like reaction and led to an increase in the hydroxyl radical (OH) generation. Fe-doped TiO(2) nanotubes could retain high degradation efficiency even after being reused for 4 cycles with minimal loss of Fe from the surface of the catalyst. Copyright © 2012 Elsevier B.V. All rights reserved.

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].

Surface-enhanced Raman scattering of amorphous TiO2 thin films by gold nanostructures: Revealing first layer effect with thickness variation

NASA Astrophysics Data System (ADS)

Degioanni, S.; Jurdyc, A.-M.; Bessueille, F.; Coulm, J.; Champagnon, B.; Vouagner, D.

2013-12-01

In this paper, amorphous titanium dioxide (TiO2) thin films have been deposited on a commercially available Klarite substrate using the sol-gel process to produce surface-enhanced Raman scattering (SERS). The substrate consists of square arrays of micrometer-sized pyramidal pits in silicon with a gold coating. Several thin TiO2 layers have been deposited on the surface to study the influence of film thickness. Ultimately, we obtained information on SERS of an amorphous TiO2 layer by gold nanostructures, whose range is less than a few nanometers. Mechanisms responsible for the enhancement are the product of concomitant chemical and electromagnetic effects with an important contribution from plasmon-induced charge transfer.

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.

Size-Controlled TiO(2) nanocrystals with exposed {001} and {101} facets strongly linking to graphene oxide via p-Phenylenediamine for efficient photocatalytic degradation of fulvic acids.

PubMed

Yan, Wen-Yuan; Zhou, Qi; Chen, Xing; Yang, Yong; Zhang, Yong; Huang, Xing-Jiu; Wu, Yu-Cheng

2016-08-15

Photocatalytic degradation is one of the most promising methods for removal of fulvic acids (FA), which is a typical category of natural organic contamination in groundwater. In this paper, TiO2/graphene nanocomposites (N-RGO/TiO2) were prepared via simple chemical functionalization and one-step hydrothermal method for efficient photodegradation of FA under illumination of a xenon lamp as light source. Here, p-phenylenediamine was used as not only the linkage chemical agent between TiO2 nanocrystals and graphene, but also the nitrogen dopant for TiO2 nanocrystals and graphene. During the hydrothermal process, facets of TiO2 nanocrystals were modulated with addition of HF, and sizes of TiO2 nanocrystals were controlled by the contents of graphene oxide functionalized with p-phenylenediamine (RGO-NH2). The obtained N-RGO/TiO2 nanocomposites exhibited a much higher photocatalytic activity and stability for degradation of methyl blue (MB) and FA compared with other TiO2 samples under xenon lamp irradiation. For the third cycle, the 10wt%N-RGO/TiO2 catalyst maintains high photoactivity (87%) for the degradation of FA, which is much better than the TiO2-N/F (61%) in 3h. This approach supplies a new strategy to design and synthesize metal oxide and graphene oxide nanocomposites with highly efficient photocatalytic performance. Copyright © 2016 Elsevier B.V. All rights reserved.

A Green Synthesis of Xanthenone Derivatives in Aqueous Media Using TiO2-CNTs Nanocomposite as an Eco-Friendly and Re-Usable Catalyst.

PubMed

Samani, Amir; Abdolmohammadi, Shahrzad; Otaredi-Kashani, Asieh

2018-01-01

The xanthene (dibenzopyran) framework constitutes the core structure of many biologically active compounds, that they have been of interest because of their pharmacological activities like antiviral, antibacterial, anti-inflammatory, and CCR1 antagonist. As heterogeneous catalysts offer several advantages over homogeneous catalysts, the performance of reactions on the surface of nanosized heterogeneous salts has received a great deal of interest in recent years. In the area of nanosized heterogeneous catalysts there is a noticeable range of reactions that are catalyzed efficiently by TiO2 NPs. Moreover, carbon nanotubes (CNTs) as a support can be used to obtain nanoparticles with modified morphology, structural, chemical, electrical, and optical properties. The catalytic activity of titanium dioxide supported on carbon nanotubes has been greatly improved. The present methodology focus on the synthesis of 7,7-dimethyl-10-aryl- 6,7,8,10-tetrahydro-9H-[1,3]dioxolo[4,5-b]xanthen-9-ones, through a condensation reaction of dimedone, aromatic aldehydes and 3,4-methylenedioxyphenol, using a catalytic amount of TiO2- CNTs nanocomposite (15 mol%) at 80 ˚C in aqueous media, within 60-90 min. The TiO2-CNTs nanocomposite was also prepared by a known simple sonochemical method. A series of 7,7-dimethyl-10-aryl-6,7,8,10-tetrahydro-9H-[1,3]dioxolo[4,5-b]xanthen-9-ones were successfully synthesized in high yields (92-98%). All synthesized compounds were well characterized by their satisfactory elemental analyses, IR, 1H and 13C NMR spectroscopy. The synthesized catalyst was fully characterized by SEM, TEM, XRD, and EDX techniques. In summary, this investigation constitutes a novel and efficient route for the synthesis of 7,7-dimethyl-10-aryl-6,7,8,10-tetrahydro-9H-[1,3]dioxolo[4,5-b]xanthen-9-ones in high yields, by a three-component reaction of dimedone, aromatic aldehydes and 3,4-methylenedioxyphenol in water and in the presence of the TiO2-CNTs nanocomposite as a green

One-pot deposition of palladium on hybrid TiO2 nanoparticles and catalytic applications in hydrogenation.

PubMed

Mehri, Afef; Kochkar, Hafedh; Daniele, Stéphane; Mendez, Violaine; Ghorbel, Abdelhamid; Berhault, Gilles

2012-03-01

One-pot deposition of Pd onto TiO(2) has been achieved through directly contacting palladium(II) salt with nanosized functionalized TiO(2) support initially obtained by sol-gel process using titanium isopropoxide and citric acid. Citrate groups act as functional moieties able to directly reduce the Pd salt avoiding any further reducing treatment. Various palladium salts (Na(2)PdCl(4) and Pd(NH(3))(4)Cl(2)·H(2)O) and titanium to citrate (Ti/CA) ratios (20, 50, and 100) were used in order to study the effect of the nature of the precursor and of the citrate content on the final Pd particle size and catalytic properties of the as-obtained Pd/TiO(2) systems. Characterization was performed using N(2) adsorption-desorption isotherms, ICP-AES, FTIR, XRD, XPS, and TEM. The as-obtained hybrid Pd/TiO(2) catalysts were tested in the selective hydrogenation (HYD) of an α,β-unsaturated aldehyde, i.e. cinnamaldehyde. Citrate-free Pd/TiO(2)-based catalysts present lower selectivity into saturated alcohol. However, citrate-functionalized Pd/TiO(2) catalyst seems to control the selectivity, the particle size and dispersion of Pd NPs leading to high intrinsic activity. Copyright © 2011 Elsevier Inc. All rights reserved.

Role of structural H 2O in TiO 2 nanotubes in enhancing Pt/C direct ethanol fuel cell anode electro-catalysts

NASA Astrophysics Data System (ADS)

Song, Huanqiao; Qiu, Xinping; Guo, Daojun; Li, Fushen

TiO 2 nanotubes (TNTs) with different structural water were obtained by heat treatment under different temperatures. The role of the structural water in TNTs co-catalyzing ethanol oxidation with Pt/C catalyst was studied systematically. Electrochemical studies using cyclic voltammetry and CO stripping voltammetry indicated that more structural water in TNTs was favorable for improving the tolerance of Pt/C to poisoning species; while chronoamperometry curves and repeated cyclic voltammograms showed that slightly less structural water in TNTs actually led to higher catalytic activity and better stability of Pt/C catalysts for ethanol oxidation. This strange result has been analyzed and was ascribed to the appropriate balance of bi-functional mechanism and ethanol transfer in the catalyst layer with less structural water.

High catalytic activity of Au/CeOx/TiO2(110) controlled by the nature of the mixed-metal oxide at the nanometer level.

PubMed

Park, Joon B; Graciani, Jesus; Evans, Jaime; Stacchiola, Dario; Ma, Shuguo; Liu, Ping; Nambu, Akira; Sanz, Javier Fernández; Hrbek, Jan; Rodriguez, José A

2009-03-31

Mixed-metal oxides play a very important role in many areas of chemistry, physics, materials science, and geochemistry. Recently, there has been a strong interest in understanding phenomena associated with the deposition of oxide nanoparticles on the surface of a second (host) oxide. Here, scanning tunneling microscopy, photoemission, and density-functional calculations are used to study the behavior of ceria nanoparticles deposited on a TiO(2)(110) surface. The titania substrate imposes nontypical coordination modes on the ceria nanoparticles. In the CeO(x)/TiO(2)(110) systems, the Ce cations adopt an structural geometry and an oxidation state (+3) that are quite different from those seen in bulk ceria or for ceria nanoparticles deposited on metal substrates. The increase in the stability of the Ce(3+) oxidation state leads to an enhancement in the chemical and catalytic activity of the ceria nanoparticles. The codeposition of ceria and gold nanoparticles on a TiO(2)(110) substrate generates catalysts with an extremely high activity for the production of hydrogen through the water-gas shift reaction (H(2)O + CO --> H(2) + CO(2)) or for the oxidation of carbon monoxide (2CO + O(2) --> 2CO(2)). The enhanced stability of the Ce(3+) state is an example of structural promotion in catalysis described here on the atomic level. The exploration of mixed-metal oxides at the nanometer level may open avenues for optimizing catalysts through stabilization of unconventional surface structures with special chemical activity.

Visible-Light-Responsive Photocatalysis: Ag-Doped TiO2 Catalyst Development and Reactor Design Testing

NASA Technical Reports Server (NTRS)

Coutts, Janelle L.; Hintze, Paul E.; Meier, Anne; Shah, Malay G.; Devor, Robert W.; Surma, Jan M.; Maloney, Phillip R.; Bauer, Brint M.; Mazyck, David W.

2016-01-01

In recent years, the alteration of titanium dioxide to become visible-light-responsive (VLR) has been a major focus in the field of photocatalysis. Currently, bare titanium dioxide requires ultraviolet light for activation due to its band gap energy of 3.2 eV. Hg-vapor fluorescent light sources are used in photocatalytic oxidation (PCO) reactors to provide adequate levels of ultraviolet light for catalyst activation; these mercury-containing lamps, however, hinder the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. VLR-TiO2 would allow for use of ambient visible solar radiation or highly efficient visible wavelength LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Over the past three years, Kennedy Space Center has developed a VLR Ag-doped TiO2 catalyst with a band gap of 2.72 eV and promising photocatalytic activity. Catalyst immobilization techniques, including incorporation of the catalyst into a sorbent material, were examined. Extensive modeling of a reactor test bed mimicking air duct work with throughput similar to that seen on the International Space Station was completed to determine optimal reactor design. A bench-scale reactor with the novel catalyst and high-efficiency blue LEDs was challenged with several common volatile organic compounds (VOCs) found in ISS cabin air to evaluate the system's ability to perform high-throughput trace contaminant removal. The ultimate goal for this testing was to determine if the unit would be useful in pre-heat exchanger operations to lessen condensed VOCs in recovered water thus lowering the burden of VOC removal for water purification systems.

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

NASA Astrophysics Data System (ADS)

Kim, Minjoong; Kwon, Chorong; Eom, Kwangsup; Kim, Jihyun; Cho, Eunae

2017-03-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2.

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability.

PubMed

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-03-14

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO 2 (Nb-TiO 2 ) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO 2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb 0.25 Ti 0.75 O 2 ). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO 2 -nanofibers (Pt/Nb-TiO 2 ) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO 2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO 2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO 2 nanofiber catalyst can be attributed to high corrosion resistance of TiO 2 and strong interaction between Pt and TiO 2 .

Electrospun Nb-doped TiO2 nanofiber support for Pt nanoparticles with high electrocatalytic activity and durability

PubMed Central

Kim, MinJoong; Kwon, ChoRong; Eom, KwangSup; Kim, JiHyun; Cho, EunAe

2017-01-01

This study explores a facile method to prepare an efficient and durable support for Pt catalyst of polymer electrolyte membrane fuel cell (PEMFC). As a candidate, Nb-doped TiO2 (Nb-TiO2) nanofibers are simply fabricated using an electrospinning technique, followed by a heat treatment. Doping Nb into the TiO2 nanofibers leads to a drastic increase in electrical conductivity with doping level of up to 25 at. % (Nb0.25Ti0.75O2). Pt nanoparticles are synthesized on the prepared 25 at. % Nb-doped TiO2-nanofibers (Pt/Nb-TiO2) as well as on a commercial powdered carbon black (Pt/C). The Pt/Nb-TiO2 nanofiber catalyst exhibits similar oxygen reaction reduction (ORR) activity to that of the Pt/C catalyst. However, during an accelerated stress test (AST), the Pt/Nb-TiO2 nanofiber catalyst retained more than 60% of the initial ORR activity while the Pt/C catalyst lost 65% of the initial activity. The excellent durability of the Pt/Nb-TiO2 nanofiber catalyst can be attributed to high corrosion resistance of TiO2 and strong interaction between Pt and TiO2. PMID:28290503

One-step solvothermal synthesis of TiO2-reduced graphene oxide nanocomposites with enhanced visible light photoreduction of Cr(VI)

NASA Astrophysics Data System (ADS)

Shaikh, Aasiya; Mishra, Shailendra Prasad; Mohapatra, Priyabrata; Parida, Smrutiranjan

2017-06-01

Hexavalent chromium, Cr(VI), is a mutagenic and carcinogenic heavy metal environmental pollutant. Photoreduction is one of the remediation methods of the hexavalent chromium Cr(VI), which necessitates design of an efficient catalyst for visible light performance. Here, we report a one-step solvothermal synthesis of TiO2-reduced graphene oxide (TiO2- xRGO) composite catalysts using a mild reducing agent, dimethylformamide (DMF). Nanoscale TiO2 particles in the size range of 4-9 nm were formed on the reduced graphene sheets. The formation of the composite catalysts was accompanied by the appearance of a large fluorescence quenching, which indicates an efficient separation of photogenerated electrons and holes. The composites displayed excellent photoreduction of Cr(VI) in the visible light, which was found to be a function of the weight percentage of RGO in the composite. At the optimum composition of TiO2- xRGO, a maximum removal rate of 96% was recorded, which was higher than that of the pristine TiO2, which showed no appreciable catalytic activity under the same condition. The performance degraded with increasing RGO content in the composite, which can be attributed to the higher electron-hole recombination on the RGO surface. The Cr(VI) photoreduction also exhibited a pH dependence. The highest removal rate was observed in the acidic medium.

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.

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.

Sono-synthesis of solar light responsive S-N-C-tri doped TiO2 photo-catalyst under optimized conditions for degradation and mineralization of Diclofenac.

PubMed

Ramandi, Sara; Entezari, Mohammad H; Ghows, Narjes

2017-09-01

C-N-S-tri doped TiO 2 anatase phase was synthesized using a facile, effective and novel sonochemical method at low frequency (20kHz) and at room temperature. Titanium butoxide as the titanium precursor and thiourea as the dopant source were used in the synthesis of the photo-catalyst. The effects of important parameters such as thiourea/Ti molar ratio, ultrasound intensity, sonication time and temperature were studied on the synthesis of tri-doped TiO 2 . The XPS results confirmed the presence of N, S, and C in the photo-catalyst. The photo-catalytic efficiency of the synthesized catalyst was studied toward the removal of Diclofenac as a model pharmaceutical organic pollutant. The results confirmed that the photo-catalyst synthesized with narrower band gap energy, shorter sonication time and higher ultrasound intensity leads to a rapid removal of Diclofenac. The effect of operational variables on the photo-catalytic activity of C-N-S tri doped TiO 2 nanoparticles was studied and optimized using the Taguchi method as a statistical technique. Additionally, the degradation process followed the pseudo-first-order kinetics model and the highest apparent rate constant of 0.0632min -1 achieved in 90min. Chemical oxygen demand (COD) analysis confirmed that the mineralization took place completely (100%) under the optimized conditions in 180min. Different scavengers were applied during the degradation process and active species such as OH and O 2 - had key roles in the photo-catalytic process. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

TiO2 fotokatalyse in de gasfase van morfologisch ontwerp tot plasmoneffecten

NASA Astrophysics Data System (ADS)

Verbruggen, Sammy

. Surface plasmon resonance can be regarded as a collective oscillation of free electrons in a metal. This way incident (visible) light energy can be 'captured' in the resonance and subsequently transferred to T1O2. First, a theoretical model is established that enables to predict the plasmon resonance wavelength of such alloy nanoparticles, based on the combined effect of particle size and alloy composition. It is shown that the feature of alloying presents high wavelength tunability of the visible light response. Next, alloy nanoparticles are deposited on TiO2. Thus obtained plasmonic photocatalysts are tested towards their self-cleaning performance in the degradation of stearic acid located at the catalyst-air interface. The highest quantum efficiency is obtained when the resonance wavelength of the plasmonic catalyst exactly matches that of the incident light. This is demonstrated for the case of Au 0.3Ag0.7, nanoparticles on TiO2 under 490 nm illumination, provided by LEDs.

Effect of Catalyst Loading on Photocatalytic Degradation of Phenol by Using N, S Co-doped TiO2

NASA Astrophysics Data System (ADS)

Yunus, N. N.; Hamzah, F.; So'aib, M. S.; Krishnan, J.

2017-06-01

The study on the effect of catalyst loading of photocatalytic degradation of phenol by using N, S co-doped TiO2 was investigated. The precursor of titania was Titanium (IV) isopropoxide (TTIP), while the sources of Nitrogen and Sulfur were ammonium nitrate and thiourea respectively. The photocatalyst were prepared by using dopant concentration at 1% of both Nitrogen and Sulphur that were prepared via sol-gel method. The photocatalyst were tested by different catalyst loading which were 1 g/L, 2g/L and 3 g/L. The gel obtained from the mixing process was dried and calcined at 600°C. The performance of the photocatalyst were tested by using phenol as a model pollutant. The mixture of photocatalyst and pollutant was left under visible light for five hours for irradiation time. The experiment showed that catalyst loading of 3 g/L able to fully degrade phenol while 1 g/L and 2 g/L of photocatalyst degraded phenol at 69.9% and 96.2% respectively.

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.

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.

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.

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.

TiO2 Nanotube Arrays: Fabricated by Soft-Hard Template and the Grain Size Dependence of Field Emission Performance

NASA Astrophysics Data System (ADS)

Yang, Xuxin; Ma, Pei; Qi, Hui; Zhao, Jingxin; Wu, Qiang; You, Jichun; Li, Yongjin

2017-11-01

Highly ordered TiO2 nanotube (TNT) arrays were successfully synthesized by the combination of soft and hard templates. In the fabrication of them, anodic aluminum oxide membranes act as the hard template while the self-assembly of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) complexed with titanium-tetraisopropoxide (TTIP, the precursor of TiO2) provides the soft template to control the grain size of TiO2 nanotubes. Our results indicate that the field emission (FE) performance depends crucially on the grain size of the calcinated TiO2 which is dominated by the PS-b-PEO and its blending ratio with TTIP. The optimized sample (with the TTIP/PEO ratio of 3.87) exhibits excellent FE performances involving both a low turn-on field of 3.3 V/um and a high current density of 7.6 mA/cm2 at 12.7 V/μm. The enhanced FE properties can be attributed to the low effective work function (1.2 eV) resulted from the smaller grain size of TiO2.

Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2.

PubMed

DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly; Pham, Nicholas; Graham, George W; Pan, Xiaoqing; Christopher, Phillip

2017-10-11

Oxide-supported precious metal nanoparticles are widely used industrial catalysts. Due to expense and rarity, developing synthetic protocols that reduce precious metal nanoparticle size and stabilize dispersed species is essential. Supported atomically dispersed, single precious metal atoms represent the most efficient metal utilization geometry, although debate regarding the catalytic activity of supported single precious atom species has arisen from difficulty in synthesizing homogeneous and stable single atom dispersions, and a lack of site-specific characterization approaches. We propose a catalyst architecture and characterization approach to overcome these limitations, by depositing ∼1 precious metal atom per support particle and characterizing structures by correlating scanning transmission electron microscopy imaging and CO probe molecule infrared spectroscopy. This is demonstrated for Pt supported on anatase TiO 2 . In these structures, isolated Pt atoms, Pt iso , remain stable through various conditions, and spectroscopic evidence suggests Pt iso species exist in homogeneous local environments. Comparing Pt iso to ∼1 nm preoxidized (Pt ox ) and prereduced (Pt metal ) Pt clusters on TiO 2 , we identify unique spectroscopic signatures of CO bound to each site and find CO adsorption energy is ordered: Pt iso ≪ Pt metal < Pt ox . Pt iso species exhibited a 2-fold greater turnover frequency for CO oxidation than 1 nm Pt metal clusters but share an identical reaction mechanism. We propose the active catalytic sites are cationic interfacial Pt atoms bonded to TiO 2 and that Pt iso exhibits optimal reactivity because every atom is exposed for catalysis and forms an interfacial site with TiO 2 . This approach should be generally useful for studying the behavior of supported precious metal atoms.

Modelling studies for photocatalytic degradation of organic dyes using TiO2 nanofibers.

PubMed

Singh, Narendra; Rana, Mohit Singh; Gupta, Raju Kumar

2017-09-05

In this work, modelling of the photocatalytic degradation of para-nitrophenol (PNP) using synthesized electrospun TiO 2 nanofibers under UV light illumination is reported. A dynamic model was developed in order to understand the behaviour of operating parameters, i.e. light intensity and catalyst loading on the photocatalytic activity. This model was simulated and analysed for both TiO 2 solid nanofibers and TiO 2 hollow nanofibers, applied as photocatalysts in the Langmuir-Hinshelwood kinetic framework. The entire photocatalytic degradation rate follows pseudo-first-order kinetics. The simulated results obtained from the developed model are in good agreement with the experimental results. At a catalyst loading of 1.0 mg mL -1 , better respective degradation rates were achieved at UV light irradiance of 4 mW cm -2 , for both the TiO 2 solid and hollow nanofibers. However, it was also observed that TiO 2 hollow nanofibers have a higher adsorption rate than that of TiO 2 solid nanofibers resulting in a higher photocatalytic degradation rate of PNP.

[Study on anti-coagulant property of radio frequency sputtering nano-sized TiO2 thin films].

PubMed

Tang, Xiaoshan; Li, Da

2010-12-01

Nano-TiO2 thin films were prepared by Radio frequency (RF) sputtering on pyrolytic carbon substrates. The influences of sputtering power on the structure and the surface morphology of TiO2 thin films were investigated by X-ray diffraction (XRD), and by scanning electron microscopy (SEM). The results show that the TiO2 films change to anatase through the optimum of sputtering power. The mean diameter of nano-particle is about 30 nm. The anti-coagulant property of TiO2 thin films was observed through platelet adhesion in vitro. The result of experiment reveals the amount of thrombus on the TiO2 thin films being much less than that on the pyrolytic carbon. It also indicates that the RF sputtering Nano-sized TiO2 thin films will be a new kind of promising materials applied to artificial heart valve and endovascular stent.

Pulsed Laser Ablation-Induced Green Synthesis of TiO2 Nanoparticles and Application of Novel Small Angle X-Ray Scattering Technique for Nanoparticle Size and Size Distribution Analysis.

PubMed

Singh, Amandeep; Vihinen, Jorma; Frankberg, Erkka; Hyvärinen, Leo; Honkanen, Mari; Levänen, Erkki

2016-12-01

This paper aims to introduce small angle X-ray scattering (SAXS) as a promising technique for measuring size and size distribution of TiO 2 nanoparticles. In this manuscript, pulsed laser ablation in liquids (PLAL) has been demonstrated as a quick and simple technique for synthesizing TiO 2 nanoparticles directly into deionized water as a suspension from titanium targets. Spherical TiO 2 nanoparticles with diameters in the range 4-35 nm were observed with transmission electron microscopy (TEM). X-ray diffraction (XRD) showed highly crystalline nanoparticles that comprised of two main photoactive phases of TiO 2 : anatase and rutile. However, presence of minor amounts of brookite was also reported. The traditional methods for nanoparticle size and size distribution analysis such as electron microscopy-based methods are time-consuming. In this study, we have proposed and validated SAXS as a promising method for characterization of laser-ablated TiO 2 nanoparticles for their size and size distribution by comparing SAXS- and TEM-measured nanoparticle size and size distribution. SAXS- and TEM-measured size distributions closely followed each other for each sample, and size distributions in both showed maxima at the same nanoparticle size. The SAXS-measured nanoparticle diameters were slightly larger than the respective diameters measured by TEM. This was because SAXS measures an agglomerate consisting of several particles as one big particle which slightly increased the mean diameter. TEM- and SAXS-measured mean diameters when plotted together showed similar trend in the variation in the size as the laser power was changed which along with extremely similar size distributions for TEM and SAXS validated the application of SAXS for size distribution measurement of the synthesized TiO 2 nanoparticles.

Kinetics of Valeric Acid Ketonization and Ketenization in Catalytic Pyrolysis on Nanosized SiO2 , γ-Al2 O3 , CeO2 /SiO2 , Al2 O3 /SiO2 and TiO2 /SiO2.

PubMed

Kulyk, Kostiantyn; Palianytsia, Borys; Alexander, John D; Azizova, Liana; Borysenko, Mykola; Kartel, Mykola; Larsson, Mats; Kulik, Tetiana

2017-07-19

Valeric acid is an important renewable platform chemical that can be produced efficiently from lignocellulosic biomass. Upgrading of valeric acid by catalytic pyrolysis has the potential to produce value added biofuels and chemicals on an industrial scale. Understanding the different mechanisms involved in the thermal transformations of valeric acid on the surface of nanometer-sized oxides is important for the development of efficient heterogeneously catalyzed pyrolytic conversion techniques. In this work, the thermal decomposition of valeric acid on the surface of nanoscale SiO 2 , γ-Al 2 O 3 , CeO 2 /SiO 2 , Al 2 O 3 /SiO 2 and TiO 2 /SiO 2 has been investigated by temperature-programmed desorption mass spectrometry (TPD MS). Fourier transform infrared spectroscopy (FTIR) has also been used to investigate the structure of valeric acid complexes on the oxide surfaces. Two main products of pyrolytic conversion were observed to be formed depending on the nano-catalyst used-dibutylketone and propylketene. Mechanisms of ketene and ketone formation from chemisorbed fragments of valeric acid are proposed and the kinetic parameters of the corresponding reactions were calculated. It was found that the activation energy of ketenization decreases in the order SiO 2 >γ-Al 2 O 3 >TiO 2 /SiO 2 >Al 2 O 3 /SiO 2 , and the activation energy of ketonization decreases in the order γ-Al 2 O 3 >CeO 2 /SiO 2 . Nano-oxide CeO 2 /SiO 2 was found to selectively catalyze the ketonization reaction. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective defunctionalization by TiO2 of monomeric phenolics from lignin pyrolysis into simple phenols.

PubMed

Mante, Ofei D; Rodriguez, Jose A; Babu, Suresh P

2013-11-01

This study is focused on defunctionalizing monomeric phenolics from lignin into simple phenols for applications such as phenol/formaldehyde resins, epoxidized novolacs, adhesives and binders. Towards this goal, Titanium dioxide (TiO2) was used to selectively remove hydroxyl, methoxy, carbonyl and carboxyl functionalities from the monomeric phenolic compounds from lignin to produce mainly phenol, cresols and xylenols. The results showed that anatase TiO2 was more selective and active compared to rutile TiO2. Catechols were found to be the most reactive phenolics and 4-ethylguaiacol the least reactive with anatase TiO2. An overall conversion of about 87% of the phenolics was achieved at 550°C with a catalyst-to-feed ratio of 5 w/w. Over 97% conversion of phenolics is achievable at moderate temperatures (550°C or ≤ 600°C) and a moderate catalyst-to-feed ratio of 6.5:1. The reactivity of catechols on TiO2 suggests that titania is a promising catalyst in the removal of hydroxyl moiety. Published by Elsevier Ltd.

Effects of acid catalyst type on structural, morphological, and optoelectrical properties of spin-coated TiO2 thin film

NASA Astrophysics Data System (ADS)

Golobostanfard, Mohammad Reza; Abdizadeh, Hossein

2013-03-01

The effects of different acid catalysts of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, acetic acid, and citric acid on structural, morphological, and optoelectrical properties of nanocrystalline spin-coated TiO2 thin films synthesized via alkoxide sol-gel route were investigated. It was found that only the sols with HNO3 and HCl are suitable for film preparation. The X-ray diffractometry and Raman analysis showed that crystalline phases could be controlled by the type of acid catalyst. Although the H2SO4 sol shows good stability, it causes extremely different morphology to form due to its different sol nature and high contact angle. Fourier transformed infrared spectra confirmed the presence of acid anion species in all samples even after calcination. Furthermore, it was inferred from UV-visable absorption spectra that although the band gap and thickness of the films are independent of acid catalyst type, the refractive index and porosity of the films are strongly affected by the type of acids.

Degradation of organic dyes using spray deposited nanocrystalline stratified WO3/TiO2 photoelectrodes under sunlight illumination

NASA Astrophysics Data System (ADS)

Hunge, Y. M.; Yadav, A. A.; Mahadik, M. A.; Bulakhe, R. N.; Shim, J. J.; Mathe, V. L.; Bhosale, C. H.

2018-02-01

The need to utilize TiO2 based metal oxide hetero nanostructures for the degradation of environmental pollutants like Rhodamine B and reactive red 152 from the wastewater using stratified WO3/TiO2 catalyst under sunlight illumination. WO3, TiO2 and stratified WO3/TiO2 catalysts were prepared by a spray pyrolysis method. It was found that the stratified WO3/TiO2 heterostructure has high crystallinity, no mixed phase formation occurs, strong optical absorption in the visible region of the solar spectrum, and large surface area. The photocatalytic activity was tested for degradation of Rhodamine B (Rh B) and reactive red 152 in an aqueous medium. TiO2 layer in stratified WO3/TiO2 catalyst helps to extend its absorption spectrum in the solar light region. Rh B and Reactive red 152is eliminated up to 98 and 94% within the 30 and 40 min respectively at optimum experimental condition by stratified WO3/TiO2. Moreover, stratified WO3/TiO2 photoelectrode has good stability and reusability than individual TiO2 and WO3 thin film in the degradation of Rh B and reactive red 152. The photoelectrocatalytic experimental results indicate that stratified WO3/TiO2 photoelectrode is a promising material for dye removal.

A polymer solution technique for the synthesis of nano-sized Li 2TiO 3 ceramic breeder powders

NASA Astrophysics Data System (ADS)

Jung, Choong-Hwan; Lee, Sang Jin; Kriven, Waltraud M.; Park, Ji-Yeon; Ryu, Woo-Seog

2008-02-01

Nano-sized Li 2TiO 3 powder was fabricated by an organic-inorganic solution route. A steric entrapment route employing ethylene glycol was used for the preparation of the nano-sized Li 2TiO 3 particles. Titanium isopropoxide and lithium nitrate were dissolved in liquid-type ethylene glycol without any precipitation. With the optimum amount of the polymer, the metal cations (Li and Ti) were dispersed in the solution and a homogeneous polymeric network was formed. The organic-inorganic precursor gels were turned to crystalline powders through an oxidation reaction during a calcination process. The dried precursor gel showed the carbon-free Li 2TiO 3 crystalline form which was observed above 400 °C. The primary particle size of the carbon-free Li 2TiO 3 was about 70 nm, and the structure of the crystallized powder was porous and agglomerated. The powder compact was densified to 92% of TD at a relatively low sintering temperature of 1100 °C for 2 h.

Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst

NASA Astrophysics Data System (ADS)

Tahir, Muhammad; Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar

2016-12-01

Photocatalytic CO2 reduction by H2O and/or H2 reductant to selective fuels over Cu-promoted In2O3/TiO2 photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N2 adsorption-desorption, UV-vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO2, oxidized as Cu2+ and In3+, promoted efficient separation of photo-generated electron/hole pairs (e-/h+). The results indicate that the reduction rate of CO2 by H2O to CH4 approached to 181 μmol g-1 h-1 using 0.5% Cu-3% In2O3/TiO2 catalyst, a 1.53 fold higher than the production rate over the 3% In2O3/TiO2 and 5 times the amount produced over the pure TiO2. In addition, Cu was found to promote efficient production of CH3OH and yield rate reached to 68 μmol g-1 h-1 over 1% Cu-3% In2O3/TiO2 catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H2 reductant was less favorable for CH4 production, yet a significant amount of CH4 and CH3OH were obtained using a mixture of H2O/H2 reductant. Therefore, Cu-loaded In2O3/TiO2 catalyst has shown to be capable for methanol production, whereas product selectivity was greatly depending on the amount of Cu-loading and the type of reductant. A photocatalytic reaction mechanism was proposed to understand the experimental results over the Cu-loaded In2O3/TiO2 catalyst.

Probing properties of the interfacial perimeter sites in TiO x /Au/SiO 2 with 2-propanol decomposition

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

Wu, Yi Y.; Kung, Harold H.

The decomposition of 2-propanol was studied over SiO2, SiO2 with an overlayer of TiO2 (Ti/SiO2), Au/SiO2, and Au/SiO2 with an overlayer of TiO2 (Ti/[Au/SiO2]) at 170–190 °C. There was no reaction on SiO2. Propene was the only product on Ti/SiO2, and its rate of formation increased proportionally with the Ti content. Acetone was the major product (selectivity 65–99%) on all Au-containing catalysts. Its rate of formation also increased with Ti loading. In addition, small amounts of propene were also formed on Ti/[Au/SiO2] the rate of which increased with Ti loading. Characterization of the catalysts with N2 adsorption, STEM, DR-UV-vis spectroscopy,more » XPS, XANES and EXAFS suggested that the Ti formed an amorphous TiO2 overlayer on the catalyst. At high Ti loadings (4–5 wt.%), there were patches of thick porous TiO2 layer, and some microdomains of crystalline TiO2 could be detected. Au was present as 1–3 nm nanoparticles on all catalysts, before and after used in reaction. Only Lewis acid sites were detected based on results from pyridine adsorption, and their quantities increased with Ti loading. Based on the comparison of reaction rates, the dependence of the kinetics on 2-propanol partial pressure, the apparent activation energies, and the effect of co-feeding O2 among different catalysts, it was concluded that propene was formed on the TiO2 overlayer, acetone was formed primarily at the Au-TiO2 interfacial perimeter sites, and α-C-H bond breaking preceding acetone formation was more facile on Au at the interfacial site than other surface Au atoms. Implication of these results to the selective acetone formation in the oxidation of propane in the presence of a O2/H2 mixture was discussed.« less

On the preparation of TiO2-sepiolite hybrid materials for the photocatalytic degradation of TCE: influence of TiO2 distribution in the mineralization.

PubMed

Suárez, Silvia; Coronado, Juan M; Portela, Raquel; Martín, Juan Carlos; Yates, Malcolm; Avila, Pedro; Sánchez, Benigno

2008-08-15

Hybrid structured photocatalysts based on sepiolite, an adsorbent, and TiO2 were prepared by extrusion of ceramic dough and conformed as plates. The influence of the photocatalyst configuration was studied either by including TiO2 in the extrusion process (incorporated materials) or by coating the sepiolite plates with a TiO2 film (coated materials). The influence of the OH- surface concentration in the photocatalytic performance was studied by treating the ceramic plates at different temperatures. The samples were characterized by N2 adsorption-desorption, MIP, SEM, XRD, and UV-vis-NIR spectroscopy and tested in the photocatalytic degradation of trichloroethylene (TCE) as a target VOC molecule. Most of the catalysts presented high photoactivity, but considerable differences were observed when the CO2 selectivity was analyzed. The results demonstrate that there is a significant effect of the catalyst configuration on the selectivity of the process. An intimate contact between the sepiolite fibers and TiO2 particles for incorporated materials with a corncob-like structure favored the migration of nondesirable reaction products such as COCl2 and dichloroacetyl chloride (DCAC) to the adsorbent, reacting with OH- groups of the adsorbent and favoring the TCE mimeralization.

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.

Titanium Dioxide as a Catalyst Support in Heterogeneous Catalysis

PubMed Central

Bagheri, Samira; Muhd Julkapli, Nurhidayatullaili; Bee Abd Hamid, Sharifah

2014-01-01

The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications. PMID:25383380

Optimization of Al2O3/TiO2/Al 2O3 Multilayer Antireflection Coating With X-Ray Scattering Techniques

NASA Astrophysics Data System (ADS)

Li, Chao

Broadband multilayer antireflection coatings (ARCs) are keys to improving solar cell efficiencies. The goal of this dissertation is to optimize the multilayer Al2O3/TiO2/Al2O 3 ARC designed for a III-V space multi-junction solar cell with understanding influences of post-annealing and varying deposition parameters on the optical properties. Accurately measuring optical properties is important in accessing optical performances of ARCs. The multilayer Al2O3/TiO 2/Al2O3 ARC and individual Al2O 3 and TiO2 layers were characterized by a novel X-ray reflectivity (XRR) method and a combined method of grazing-incidence small angle X-ray scattering (GISAXS), atomic force microscopy (AFM), and XRR developed in this study. The novel XRR method combining an enhanced Fourier analysis with specular XRR simulation effectively determines layer thicknesses and surface and interface roughnesses and/or grading with sub-nanometer precision, and densities less than three percent uncertainty. Also, the combined method of GISAXS, AFM, and XRR characterizes the distribution of pore size with one-nanometer uncertainty. Unique to this method, the diffuse scattering from surface and interface roughnesses is estimated with surface parameters (root mean square roughness sigma, lateral correlation length ξ, and Hurst parameter h) obtained from AFM, and layer densities, surface grading and interface roughness/grading obtained from specular XRR. It is then separated from pore scattering. These X-ray scattering techniques obtained consistent results and were validated by other techniques including optical reflectance, spectroscopic ellipsometry (SE), glancing incidence X-ray diffraction, transmission electron microscopy and energy dispersive X-ray spectroscopy. The ARCs were deposited by atomic layer deposition with standard parameters at 200 °C. The as-deposited individual Al2O3 layer on Si is porous and amorphous as indicated by the combined methods of GISAXS, AFM, and XRR. Both post

Sol-gel-Derived nano-sized double layer anti-reflection coatings (SiO2/TiO2) for low-cost solar cell fabrication.

PubMed

Lee, Seung Jun; Hur, Man Gyu; Yoon, Dae Ho

2013-11-01

We investigate nano-sized double layer anti-reflection coatings (ARCs) using a TiO2 and SiO2 sol-gel solution process for mono-crystalline silicon solar cells. The process can be easily adapted for spraying sol-gel coatings to reduce manufacturing cost. The spray-coated SiO2/TiO2 nano-sized double layer ARCs were deposited on mono-crystalline silicon solar cells, and they showed good optical properties. The spray coating process is a lower-cost fabrication process for large-scale coating than vacuum deposition processes such as PECVD. The measured average optical reflectance (300-1200 nm) was about approximately 8% for SiO2/TiO2 nano-sized double layer ARCs. The electrical parameters of a mono-crystalline silicon solar cell and reflection losses show that the SiO2/TiO2 stacks can improve cell efficiency by 0.2% compared to a non-coated mono-crystalline silicon solar cell. In the results, good correlation between theoretical and experimental data was obtained. We expect that the sol-gel spray-coated mono-crystalline silicon solar cells have high potential for low-cost solar cell fabrication.

Mechanism of Hg(0) oxidation in the presence of HCl over a commercial V2O5-WO3/TiO2 SCR catalyst.

PubMed

Liu, Ruihui; Xu, Wenqing; Tong, Li; Zhu, Tingyu

2015-10-01

Experiments were conducted in a fixed-bed reactor containing a commercial V2O5/WO3/TiO2 catalyst to investigate mercury oxidation in the presence of HCl and O2. Mercury oxidation was improved significantly in the presence of HCl and O2, and the Hg(0) oxidation efficiencies decreased slowly as the temperature increased from 200 to 400°C. Upon pretreatment with HCl and O2 at 350°C, the catalyst demonstrated higher catalytic activity for Hg(0) oxidation. Notably, the effect of pretreatment with HCl alone was not obvious. For the catalyst treated with HCl and O2, better performance was observed with lower reaction temperatures. The results showed that both HCl and Hg(0) were first adsorbed onto the catalyst and then reacted with O2 following its adsorption, which indicates that the oxidation of Hg(0) over the commercial catalyst followed the Langmuir-Hinshelwood mechanism. Several characterization techniques, including Hg(0) temperature-programmed desorption (Hg-TPD) and X-ray photoelectron spectroscopy (XPS), were employed in this work. Hg-TPD profiles showed that weakly adsorbed mercury species were converted to strongly bound species in the presence of HCl and O2. XPS patterns indicated that new chemisorbed oxygen species were formed by the adsorption of HCl, which consequently facilitated the oxidation of mercury. Copyright © 2015. Published by Elsevier B.V.

[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

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.

Size-selective reactivity of subnanometer Ag 4 and Ag 16 clusters on a TiO 2 surface

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

Chen, Po-Tuan; Tyo, Eric C.; Hayashi, Michitoshi

Size-selected Ag 4 and Ag 16 clusters on a titania surface have been studied for their potential in CO oxidation using theoretical calculations and X-ray absorption near edge spectroscopy. The first peak at the measured Ag K-edge of Ag 16@TiO 2 is more prominent in air than in carbon monoxide environment, but no variation was found between the spectra of Ag 4@TiO 2 in air and in carbon monoxide environments. Density functional theory calculations show a preference for molecular oxygen adsorption for Ag 4@TiO 2 and that for a dissociative one on Ag 16@TiO 2, while carbon monoxide reactions withmore » adsorbed oxygen reduced the Ag 16@TiO 2 cluster. The dissociated oxygen atoms increased the oxidation state of Ag 16 cluster and resulted in the prominent first peak in Ag K-edge spectrum in quasi-particle theory calculations, with the subsequent carbon monoxide oxidation reversing the character of Ag K-edge spectrum associated with the reduction of the cluster. Finally, the results provide insight into the size selectivity of supported subnanometer silver clusters in their interactions with oxygen and carbon monoxide, with implications on the cluster catalytic properties in oxidative reactions.« less

Size-selective reactivity of subnanometer Ag 4 and Ag 16 clusters on a TiO 2 surface

DOE PAGES

Chen, Po-Tuan; Tyo, Eric C.; Hayashi, Michitoshi; ...

2017-03-08

Size-selected Ag 4 and Ag 16 clusters on a titania surface have been studied for their potential in CO oxidation using theoretical calculations and X-ray absorption near edge spectroscopy. The first peak at the measured Ag K-edge of Ag 16@TiO 2 is more prominent in air than in carbon monoxide environment, but no variation was found between the spectra of Ag 4@TiO 2 in air and in carbon monoxide environments. Density functional theory calculations show a preference for molecular oxygen adsorption for Ag 4@TiO 2 and that for a dissociative one on Ag 16@TiO 2, while carbon monoxide reactions withmore » adsorbed oxygen reduced the Ag 16@TiO 2 cluster. The dissociated oxygen atoms increased the oxidation state of Ag 16 cluster and resulted in the prominent first peak in Ag K-edge spectrum in quasi-particle theory calculations, with the subsequent carbon monoxide oxidation reversing the character of Ag K-edge spectrum associated with the reduction of the cluster. Finally, the results provide insight into the size selectivity of supported subnanometer silver clusters in their interactions with oxygen and carbon monoxide, with implications on the cluster catalytic properties in oxidative reactions.« less

Photocatalytic Activity of W-Doped TiO2 Nanofibers for Methylene Blue Dye Degradation.

PubMed

Song, Yo-Seung; Cho, Nam-Ihn; Lee, Myung-Hyun; Kim, Bae-Yeon; Lee, Deuk Yong

2016-02-01

Photocatalytic degradation of methylene blue (MB) in water was examined using W-doped TiO2 nanofibers prepared by a sol-gel derived electrospinning and subsequent calcination for 4 h at 550 degrees C. Different concentrations of W dopant in the range of 0 to 8 mol% were synthesized to evaluate the effect of W concentration on the photocatalytic activity of TiO2. XRD results indicated that the undoped TiO2 is composed of anatase and rutile phases. The rutile phase was transformed to anatase phase completely with the W doping. Among W-TiO2 catalysts, the 2 mol% W-TiO2 catalyst showed the highest MB degradation rate. The degradation kinetic constant increased from 1.04 x 10(-3) min(-1) to 3.54 x 10(-3) min(-1) with the increase of W doping from 0 to 2 mol%, but decreased down to 1.77 x 10(-3) min(-1) when the W content was 8 mol%. It can be concluded that the degradation of MB under UV radiation was more efficient with W-TiO2 catalysts than with pure TiO2-

Evaluating photo-degradation of COD and TOC in petroleum refinery wastewater by using TiO2/ZnO photo-catalyst.

PubMed

Aljuboury, Dheeaa Al Deen Atallah; Palaniandy, Puganeshwary; Abdul Aziz, Hamidi Bin; Feroz, Shaik; Abu Amr, Salem S

2016-09-01

The aim of this study is to investigate the performance of combined solar photo-catalyst of titanium oxide/zinc oxide (TiO 2 /ZnO) with aeration processes to treat petroleum wastewater. Central composite design with response surface methodology was used to evaluate the relationships between operating variables for TiO 2 dosage, ZnO dosage, air flow, pH, and reaction time to identify the optimum operating conditions. Quadratic models for chemical oxygen demand (COD) and total organic carbon (TOC) removals prove to be significant with low probabilities (<0.0001). The obtained optimum conditions included a reaction time of 170 min, TiO 2 dosage (0.5 g/L), ZnO dosage (0.54 g/L), air flow (4.3 L/min), and pH 6.8 COD and TOC removal rates of 99% and 74%, respectively. The TOC and COD removal rates correspond well with the predicted models. The maximum removal rate for TOC and COD was 99.3% and 76%, respectively at optimum operational conditions of TiO 2 dosage (0.5 g/L), ZnO dosage (0.54 g/L), air flow (4.3 L/min), reaction time (170 min) and pH (6.8). The new treatment process achieved higher degradation efficiencies for TOC and COD and reduced the treatment time comparing with other related processes.

Effect of Particle Size Upon Pt/SiO 2 Catalytic Cracking of n-Dodecane Under Supercritical Conditions: in situ SAXS and XANES Studies

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

Lee, Sungwon; Lee, Sungsik; Kumbhalkar, Mrunmayi

The endothermic cracking and dehydrogenation of n-dodecane is investigated over well-defined nanometer size platinum catalysts supported on SiO 2 to study the particle size effects in the catalytic cracking reaction, with simultaneous in situ monitoring of the particle size and oxidation state of the working catalysts by in situ SAXS (small angle X-ray scattering) and XAS (X-ray absorption spectroscopy). The selectivity toward olefins products was found dominant in the 1 nm size platinum catalysts, whereas paraffins are dominant in the 2 nm catalysts. This reveals a strong correlation between catalytic performance and catalyst size as well as the stability ofmore » the nanoparticles in supercritical condition of n-dodecane. The presented results suggest that controlling the size and geometric structure of platinum nanocatalysts could lead to a fundamentally new level of understanding of nanoscale materials by monitoring the catalysts in realistic reaction conditions.« less

Effect of particle size of TiO2 and additive materials to improve dye sensitized solar cells efficiency

NASA Astrophysics Data System (ADS)

Ali, Falah H.; Alwan, Dheyaa B.

2018-05-01

It became a great interest Dye-sensitized solar cells (DSSC) as a successful alternative to silicon solar cells in terms of cost and simplicity. These cells rely on a semi-conductive material of electricity TiO2 nanocrystalline which encapsulates glass electrodes from the connected side at a temperature 450°C. In this work, the effect of nanoparticle size shows the size of atoms. The smaller the size of the atoms, the greater the surface area and thus the sufficient absorption of the dye and the stimulation of electrons, where increasing surface area increases efficiency. Then a limited amount was added and at a certain concentration, which led to a reasonable improvement in efficiency. According to this procedure commercially available TiO2 (10 nm,25 nm,33 nm, 50 nm) standard. A TiO2 paste was prepared by mixing commercial TiO2, ethanol, distilled water, F:SnO2 (FTO film thickness 14 μm) conductive glasses. By using Dr. Blade method we got films with appropriate thicknesses, then by using several particle sizes (10 nm, 25 nm, 33 nm, 50 nm),many efficiencies were founded (2.39 %, 2.1 %,1.85 %,1.65%) respectively. Improved solar cell efficiency after addition of several chemical materials and the best that got is Cu (NO3)2. Efficiency became for (10 nm) (2.61 %, 2.34 %,2.1%,1.85%) respectively under 40 mW/cm2.

Tuning Phase Composition of TiO2 by Sn(4+) Doping for Efficient Photocatalytic Hydrogen Generation.

PubMed

Wang, Fenglong; Ho, Jie Hui; Jiang, Yijiao; Amal, Rose

2015-11-04

The anatase-rutile mixed-phase photocatalysts have attracted extensive research interest because of the superior activity compared to their single phase counterparts. In this study, doping of Sn(4+) ions into the lattice of TiO2 facilitates the phase transformation from anatase to rutile at a lower temperature while maintaining the same crystal sizes compared to the conventional annealling approach. The mass ratios between anatase and rutile phases can be easily manipulated by varying the Sn-dopant content. Characterization results reveal that the Sn(4+) ions entered into the lattice of TiO2 by substituting some of the Ti(4+) ions and distributed evenly in the matrix of TiO2. The substitution induced the distortion of the lattice structure, which realized the phase transformation from anatase to rutile at a lower temperature and the close-contact phase junctions were consequently formed between anatase and rutile, accounting for the efficient charge separations. The mixed-phase catalysts prepared by doping Sn(4+) ions into the TiO2 exhibit superior activity for photocatalytic hydrogen generation in the presence of Au nanoparticles, relatively to their counterparts prepared by the conventional annealling at higher temperatures. The band allignment between anatase and rutile phases is established based on the valence band X-ray photoelectron spectra and diffuse reflectance spectra to understand the spatial charge separation process at the heterojunction between the two phases. The study provides a new route for the synthesis of mixed-phase TiO2 catalysts for photocatalytic applications and advances the understanding on the enhanced photocatalytic properties of anatase-rutile mixtures.

Solar photocatalytic degradation of isoproturon over TiO2/H-MOR composite systems.

PubMed

Sharma, Mangalampalli V Phanikrishna; Durgakumari, Valluri; Subrahmanyam, Machiraju

2008-12-30

The photocatalytic degradation and mineralization of isoproturon herbicide was investigated in aqueous solution containing TiO2 over H-mordenite (H-MOR) photocatalysts under solar light. The catalysts are characterized by X-ray diffraction (XRD), UV-Vis diffused reflectance spectra (UV-Vis DRS), Fourier transform-infra red spectra (FT-IR) and scanning electron microscopy (SEM) techniques. The effect of TiO2, H-MOR support and different wt% of TiO2 over the support on the photocatalytic degradation and influence of parameters such as TiO2 loading, catalyst amount, pH and initial concentration of isoproturon on degradation are evaluated. 15wt% TiO2/H-MOR composite is found to be optimum. The degradation reaction follows pseudo-first order kinetics and is discussed in terms of Langmuir-Hinshelwood (L-H) kinetic model. The extent of isoproturon mineralization studied with chemical oxygen demand (COD) and total organic carbon (TOC) measurements and approximately 80% mineralization occurred in 5h. A plausible mechanism is proposed based on the intermediates identified by liquid chromatography-mass spectroscopy (LC-MS).

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.

A magnetically separable and recyclable Ag-supported magnetic TiO2 composite catalyst: Fabrication, characterization, and photocatalytic activity.

PubMed

Chung, Woo Jin; Nguyen, Dinh Duc; Bui, Xuan Thanh; An, Sang Woo; Banu, J Rajesh; Lee, Sang Moon; Kim, Sung Su; Moon, Dea Hyun; Jeon, Byong Hun; Chang, Soon Woong

2018-05-01

In this study, a magnetically separable, highly active, and recyclable photocatalyst was synthesized by physico-chemical incorporation of Ag, TiO 2 , and Fe 3 O 4 into one structure. The physical and chemical properties of the catalysts were evaluated by X-ray diffraction, X-ray fluorescence spectrometry, scanning electron microscopy, field emission transmission electron microscopy, energy dispersive X-ray spectroscopy, and diffuse reflectance spectroscopy. The Ag-supported magnetic TiO 2 composite demonstrated desirable properties and features such as a narrow band gap of 1.163 eV, modifiable structure, and high degradation efficiency. The activity and durability of the synthesized photocatalyst in the degradation of methyl orange (MO) in aqueous solutions under visible light irradiation and different experimental conditions were evaluated and compared to those of commercial TiO 2 and Ag/TiO 2 composites. It was found that the synthesized composite showed a much higher MO photodegradation efficiency than the other composites under visible light irradiation. Moreover, it exhibited a high photocatalytic activity and was recoverable and durable; its photocatalytic efficiency in MO removal was consistently higher than 93.1% after five reuses without any evident signs of deactivation. Thus, the developed photocatalyst is a very promising material for practical applications in environmental pollution remediation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Transesterification of diethyl oxalate with phenol over sol-gel MoO(3)/TiO(2) catalysts.

PubMed

Kotbagi, Trupti; Nguyen, Duy Luan; Lancelot, Christine; Lamonier, Carole; Thavornprasert, Kaew-Arpha; Wenli, Zhu; Capron, Mickaël; Jalowiecki-Duhamel, Louise; Umbarkar, Shubhangi; Dongare, Mohan; Dumeignil, Franck

2012-08-01

The transesterification of diethyl oxalate (DEO) with phenol to form diphenyl oxalate (DPO) has been carried out in the liquid phase over very efficient MoO(3)/TiO(2) solid-acid sol-gel catalysts. A selectivity of 100 % with a remarkable maximum yield of 88 % were obtained, which opens the route to downstream phosgene-free processes for the synthesis of polycarbonates. Interpretation of the results of various acidity measurements (NH(3) and pyridine desorption, methanol oxidation as a probe reaction) allowed us to identify the catalytic sites as Lewis acid sites. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Micrometer- and nanometer-sized platinum group nuggets in micrometeorites from deep-sea sediments of the Indian Ocean

NASA Astrophysics Data System (ADS)

Rudraswami, N. G.; Parashar, K.; Shyam Prasad, M.

2011-03-01

We examined 378 micrometeorites collected from deep-sea sediments of the Indian Ocean of which 175, 180, and 23 are I-type, S-type, and G-type, respectively. Of the 175 I-type spherules, 13 contained platinum group element nuggets (PGNs). The nuggets occur in two distinct sizes and have distinctly different elemental compositions: micrometer (μm)-sized nuggets that are >3 μm contain dominantly Ir, Os, and Ru (iridium-platinum group element or IPGE) and sub-μm (or nanometer)-sized (<1 μm) nuggets, which contain dominantly Pt, Rh, and Pd (palladium—PGE or PPGE). The μm-sized nuggets are found only one per spherule in the cross section observed and are usually found at the edge of the spherule. By contrast, there are hundreds of nanometer-sized nuggets distributed dominantly in the magnetite phases of the spherules, and rarely in the wüstite phases. Both the nugget types are found as separate entities in the same spherule and apparently, nugget formation is a common phenomenon among I-type micrometeorites. However, the μm-sized nuggets are seen in fewer specimens (˜2.5% of the observed I-type spherules). In all, we analyzed four nuggets of μm size and 213 nanometer-sized nuggets from 13 I-type spherules for platinum group elements. Chemically, the μm-sized PGNs contain chondritic ratios of Os/Ir, but are depleted in the more volatile PGE (Pt, Rh, and Pd) relative to chondritic ratios. On the other hand, the nanometer-sized nuggets contain dominantly Pt and Rh. Importantly, the refractory PGEs are conspicuous by their absence in these nanometer nuggets. Palladium, the most volatile PGE is highly depleted (<1.1%) with respect to chondritic ratios in the μm-sized PGNs, and is observed in only 17 of 213 nanometer nuggets with concentrations that are just above the detection limit (≥0.2%). Distinct fractionation of the PGE into IPGE (Ir, Os, Ru) and PPGE seems to take place during the short span of atmospheric entry. These observations suggest several

Bare TiO2 and graphene oxide TiO2 photocatalysts on the degradation of selected pesticides and influence of the water matrix

NASA Astrophysics Data System (ADS)

Cruz, Marta; Gomez, Cristina; Duran-Valle, Carlos J.; Pastrana-Martínez, Luisa M.; Faria, Joaquim L.; Silva, Adrián M. T.; Faraldos, Marisol; Bahamonde, Ana

2017-09-01

The photocatalytic activity of a home-made titanium dioxide (TiO2) and its corresponding composite based on graphene oxide (GO), the GO-TiO2 catalyst, has been investigated under UV-vis in the photodegradation of a mixture of four pesticides classified by the European Union as priority pollutants: diuron, alachlor, isoproturon and atrazine. The influence of two water matrices (ultrapure or natural water) was also studied. Natural water led to a decrease on the degradation of the studied pollutants when the bare TiO2 photocatalyst was employed, since this water contains both inorganic and organic species that are dissolved and commonly restrain the photocatalytic process. On the contrary, the photo-efficiency of the GO-TiO2 composite seems to be less affected by water matrix variation, with very good initial pesticide photodegradation rates under both natural and ultrapure water matrices. A comparative study between GO-TiO2 and the commercial Evonik TiO2 P25 catalyst was also carried out to analyze the photocatalytic degradation of these pesticides under visible light illumination conditions. Once again, a higher photocatalytic activity was found for the GO-TiO2 composite.

Enhanced TiO2 Photocatalytic Processing of Organic Wastes for Green Space Exploration

NASA Technical Reports Server (NTRS)

Udom, I.; Goswami, D. Y.; Ram, M. K.; Stefanakos, E. K.; Heep, A. F.; Kulis, M. J.; McNatt, J. S.; Jaworske, D. A.; Jones, C. A.

2013-01-01

The effect of transition metal co-catalysts on the photocatalytic properties of TiO2 was investigated. Ruthenium (Ru), palladium, platinum, copper, silver, and gold, were loaded onto TiO2 powders (anatase and mixed-phase P25) and screened for the decomposition of rhodamine B (RhB) under broad-band irradiation. The morphology and estimated chemical composition of photocatalysts were determined by scanning electron microscopy and energy dispersive spectroscopy, respectively. Brunhauer, Emmett and Teller (BET) analysis measured mass-specific surface area(s). X-ray diffraction analysis was performed to confirm the identity of titania phase(s) present. The BET surface area of anatase TiO2/Ru 1% (9.2 sq m/gm) was one of the highest measured of all photocatalysts prepared in our laboratory. Photolyses conducted under air-saturated and nitrogen-saturated conditions revealed photodegradation efficiencies of 85 and 2 percent, respectively, after 60 min compared to 58 percent with no catalyst. The cause of low photocatalytic activity under an inert atmosphere is discussed. TiO2/Ru 1% showed a superior photocatalytic activity relative to P25-TiO2 under broad-band irradiation. A potential deployment of photocatalytic technologies on a mission could be a reactor with modest enhancement in solar intensity brought about by a trough-style reactor, with reactants and catalyst flowing along the axis of the trough and therefore being illuminated for a controlled duration based on the flow rate.

Photocatalytic degradation of isoproturon herbicide over TiO2/Al-MCM-41 composite systems using solar light.

PubMed

Phanikrishna Sharma, M V; Durga Kumari, V; Subrahmanyam, M

2008-06-01

The present investigation covers immobilization of TiO2 using a simple solid state dispersion technique over mesoporous Al-MCM-41 support for the treatment of isoproturon herbicide. Catalysts are characterized by XRD, X-ray photo electron spectroscopy (XPS), surface area, UV-Vis diffused reflectance spectra (DRS), SEM and TEM. A detailed photocatalytic degradation study of isoproturon under solar light in aqueous suspensions is reported. The 10 wt% TiO2/Al-MCM-41 composite system found to be optimum with high degradation activity. The reaction follows pseudo-first order kinetics. The parameters like TiO2 loading over Al-MCM-41, amount of catalyst, concentration of substrate, pH effect, durability of the catalyst, activity comparison of TiO2 and Al-MCM-41 supported system are studied. The mineralization of isoproturon is monitored by TOC. Based on the degradation products detected through LC-MS, a plausible degradation mechanism is proposed. The data indicates that TiO2/Al-MCM-41 composite system is an effective photocatalyst for treatment of isoproturon in contaminated water.

Photocatalytic oxidation of organic dyes with visible-light-driven codoped TiO2 photocatalysts

NASA Astrophysics Data System (ADS)

Zhang, Dongfang; Zeng, Fanbin

2011-06-01

A novel copper (II) and zinc (II) codoped TiO2 photocatalyst was synthesized by a modified sol-gel method using titanium (IV) isopropoxide, Zn(NO3)2 · 6H2O and copper(Il) nitrate as precursors. The samples were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS) and photo-luminescence spectra (PL). The XRD results showed undoped and Zn, Cu-codoped TiO2 nanoparticles mainly including anatase phase and a tiny amount of Zn- and Cu-oxides exist in the mixed system, which is attributed to the decomposition of copper and zinc nitrates in the TiO2 gel to form CuO and ZnO and randomly dispersed on the TiO2 surface. On the basis of the optical characterization results, we found that the codoping of copper (II) and zinc (II) resulted a red shift of adsorption and lower recombination probability between electrons and holes, which were the reasons for high photocatalytic activity of Zn, Cu-codoped TiO2 nanoparticles under visible light (λ > 400 nm). The photocatalytic activity of samples was tested for degradation of methyl orange (MO) in solutions. The results indicated that the visible-light driven capability of the codoped catalyst were much higher than that of the pure TiO2 catalyst under visible irradiation. Because of the synergetic effect of copper (II) and zinc (II) element, the Zn, Cu-codoped TiO2 catalyst will show higher quantum yield and enhance absorption of visible light. In the end, a key mechanism was proposed in order to account for the enhanced activity.

Fabrication and Characterization of New Composite Tio2 Carbon Nanofiber Anodic Catalyst Support for Direct Methanol Fuel Cell via Electrospinning Method.

PubMed

Abdullah, N; Kamarudin, S K; Shyuan, L K; Karim, N A

2017-12-06

Platinum (Pt) is the common catalyst used in a direct methanol fuel cell (DMFC). However, Pt can lead towards catalyst poisoning by carbonaceous species, thus reduces the performance of DMFC. Thus, this study focuses on the fabrication of a new composite TiO 2 carbon nanofiber anodic catalyst support for direct methanol fuel cells (DMFCs) via electrospinning technique. The distance between the tip and the collector (DTC) and the flow rate were examined as influencing parameters in the electrospinning technique. To ensure that the best catalytic material is fabricated, the nanofiber underwent several characterizations and electrochemical tests, including FTIR, XRD, FESEM, TEM, and cyclic voltammetry. The results show that D18, fabricated with a flow rate of 0.1 mLhr -1 and DTC of 18 cm, is an ultrafine nanofiber with the smallest average diameter, 136.73 ± 39.56 nm. It presented the highest catalyst activity and electrochemical active surface area value as 274.72 mAmg -1 and 226.75m 2  g -1 PtRu , respectively, compared with the other samples.

Fabrication and Characterization of New Composite Tio2 Carbon Nanofiber Anodic Catalyst Support for Direct Methanol Fuel Cell via Electrospinning Method

NASA Astrophysics Data System (ADS)

Abdullah, N.; Kamarudin, S. K.; Shyuan, L. K.; Karim, N. A.

2017-12-01

Platinum (Pt) is the common catalyst used in a direct methanol fuel cell (DMFC). However, Pt can lead towards catalyst poisoning by carbonaceous species, thus reduces the performance of DMFC. Thus, this study focuses on the fabrication of a new composite TiO2 carbon nanofiber anodic catalyst support for direct methanol fuel cells (DMFCs) via electrospinning technique. The distance between the tip and the collector (DTC) and the flow rate were examined as influencing parameters in the electrospinning technique. To ensure that the best catalytic material is fabricated, the nanofiber underwent several characterizations and electrochemical tests, including FTIR, XRD, FESEM, TEM, and cyclic voltammetry. The results show that D18, fabricated with a flow rate of 0.1 mLhr-1 and DTC of 18 cm, is an ultrafine nanofiber with the smallest average diameter, 136.73 ± 39.56 nm. It presented the highest catalyst activity and electrochemical active surface area value as 274.72 mAmg-1 and 226.75m2 g-1 PtRu, respectively, compared with the other samples.

Performance of Bi2O3/TiO2 prepared by sol-gel on p-Cresol degradation under solar and visible light.

PubMed

Vigil-Castillo, Héctor H; Hernández-Ramírez, Aracely; Guzmán-Mar, Jorge L; Ramos-Delgado, Norma A; Villanueva-Rodríguez, Minerva

2018-05-21

Photocatalytic degradation of p-Cresol was evaluated using the mixed oxide Bi 2 O 3 /TiO 2 (containing 2 and 20% wt. Bi 2 O 3 referred as TB2 and TB20) and was compared with bare TiO 2 under simulated solar radiation. Materials were prepared by the classic sol-gel method. All solids exhibited the anatase phase by X-ray diffraction (XRD) and Raman spectroscopy. The synthesized materials presented lower crystallite size and Eg value, and also higher surface area as Bi 2 O 3 amount was increased. Bi content was quantified showing near to 70% of theoretical values in TB2 and TB20. Bi 2 O 3 incorporation also was demonstrated by X-ray photoelectron spectroscopy (XPS). Characterization of mixed oxides suggests a homogeneous distribution of Bi 2 O 3 on TiO 2 surface. Photocatalytic tests were carried out using a catalyst loading of 1 g L -1 under simulated solar light and visible light. The incorporation of Bi 2 O 3 in TiO 2 improved the photocatalytic properties of the synthesized materials obtaining better results with TB20 than the unmodified TiO 2 under both radiation sources.

Photocatalytic Applications of Electrospun TiO2 Nanofibres Embedded with Bimodal Sized and Prismatic Gold Nanoparticles.

PubMed

Gopika, G; Asha, A M; Sivakumar, N; Balakrishnan, A; Nair, S V; Subramanian, K R V

2015-09-01

In this paper, we have synthesized electrospun TiO2 nanofibers embedded with bimodal sized and prismatic gold nanoparticles. The surface plasmons generated in the gold nanoparticles were used to enhance the performance of photocatalysis. The photocatalytic conversion efficiencies of these bimodal sized/prismatic gold nanoparticles when embedded in electrospun TiO2 fibres showed an enhancement of upto 60% over bare fiber systems and also show higher efficiencies than electrospun fibrous systems embedded with unimodal sized gold nanoparticles. Anisotropic bimodal gold nanoparticles show the highest degree of photocatalytic activity. This may be attributed to greater density/concentration of nanoparticles with higher effective surface area and formation of a junction between the smaller and larger nanoparticles. Such a bimodally distributed range of nanoparticles could also lead to greater trapping of charge carriers at the TiO2 conduction band edge and promoting catalytic reactions on account of these trapped charges. This enhanced photocatalytic activity is explained by invoking different operating mechanisms such as improved surface area, greater trapping, coarse plasmon resonance and band effects. Thus, a useful applicability of the gold nanoparticles is shown in the area of photocatalysis.

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.

Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy.

PubMed

Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A

2017-07-14

Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.

Solar photocatalytic disinfection with immobilised TiO(2) at pilot-plant scale.

PubMed

Sordo, Carlos; Van Grieken, Rafael; Marugán, Javier; Fernández-Ibáñez, Pilar

2010-01-01

The photocatalytic disinfection efficiency has been investigated for two immobilized TiO(2) catalytic systems (wall reactor and fixed-bed reactor) in a solar pilot plant. Their performances have been compared with the use of a slurry reactor and the solar disinfection without catalyst. The use of photocatalytic TiO(2) wall reactors does no show clear benefits over the solar disinfection process in the absence of catalyst. The reason is that the efficiency of the solar disinfection is so high that the presence of titania in the reactor wall reduces the global efficiency due to the competition for the absorption of photons. As expected, the maximum efficiency was shown by the slurry TiO(2) reactor, due to the optimum contact between bacteria and catalyst. However, it is noticeable that the use of the fixed-bed reactor leads to inactivation rate quite close to that of the slurry, requiring comparable accumulated solar energy of about 6 kJ L(-1) to achieve a 6-log decrease in the concentration of viable bacteria and allowing a total disinfection of the water (below the detection limit of 1 CFU mL(-1)). Not only the high titania surface area of this configuration is responsible for the bacteria inactivation but the important contribution of the mechanical stress has to be considered. The main advantage of the fixed-bed TiO(2) catalyst is the outstanding stability, without deactivation effects after ten reaction cycles, being readily applicable for continuous water treatment systems.

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.

Enhancement of Glycerol Steam Reforming Activity and Thermal Stability by Incorporating CeO2 and TiO2 in Ni- and Co-MCM-41 Catalysts

NASA Astrophysics Data System (ADS)

Dade, William N.

Hydrogen (H2) has many applications in industry with current focus shifted to production of hydrocarbon fuels and valuable oxygenates using the Fischer-Tropsch technology and direct use in proton exchange membrane fuel cell (PEMFC). Hydrogen is generally produced via steam reforming of natural gas or alcohols like methanol and ethanol. Glycerol, a by-product of biodiesel production process, is currently considered to be one of the most attractive sources of sustainable H2 due to its high H/C ratio and bio-based origin. Ni and Co based catalysts have been reported to be active in glycerol steam reforming (GSR); however, deactivation of the catalysts by carbon deposition and sintering under GSR operating conditions is a major challenge. In this study, a series of catalysts containing Ni and Co nanoparticles incorporated in CeO2 and TiO2 modified high surface area MCM-41 have been synthesized using one-pot method. The catalysts are tested for GSR (at H2O/Glycerol mole ratio of 12 and GHSV of 2200 h-1) to study the effect of support modification and reaction temperature (450 - 700 °C) on the product selectivity and long term stability. GSR results revealed that all the catalysts performed significantly well exhibiting over 85% glycerol conversion at 650 °C except Ni catalysts that showed better low temperature activities. Deactivation studies of the catalysts conducted at 650 °C indicated that the Ni-TiO2-MCM-41 and Ni-CeO 2-MCM-41 were resistant to deactivation with ˜100% glycerol conversion for 40 h. In contrast, Co-TiO2-MCM-41 perform poorly as the catalyst rapidly deactivated after 12 h to yield ˜20% glycerol conversion after 40 h. The WAXRD and TGA-DSC analyses of spent catalysts showed a significant amount of coke deposition that might explain catalysts deactivation. The flattening shape of the original BET type IV isotherm with drastic reduction of catalyst surface area can also be responsible for observed drop in catalysts activities.

Thermostable photocatalytically active TiO2 anatase nanoparticles

NASA Astrophysics Data System (ADS)

Qi, Fei; Moiseev, Anna; Deubener, Joachim; Weber, Alfred

2011-03-01

Anatase is the low-temperature (300-550 °C) crystalline polymorph of TiO2 and it transforms to rutile upon heating. For applications utilizing the photocatalytic properties of nanoscale anatase at elevated temperatures (over 600 °C) the issue of phase stabilisation is of major interest. In this study, binary TiO2/SiO2 particles were synthesized by a flame aerosol process with TiCl4 and SiCl4 as precursors. The theoretical Si/Ti ratio was varied in the range of 0.7-1.3 mol/mol. The synthesized TiO2/SiO2 samples were heat treated at 900 and 1,000 °C for 3 h to determine the thermostability of anatase. Pyrogenic TiO2 P25 (from Evonik/Degussa, Germany) widely applied as photocatalyst was used as non-thermostabilized reference material for comparison of photocatalytic activity of powders. Both the non-calcinated and calcinated powders were characterized by means of XRD, TEM and BET. Photocatalytic activity was examined with dichloroacetic acid (DCA) chosen as a model compound. It was found that SiO2 stabilized the material retarding the collapse of catalyst surface area during calcination. The weighted anatase content of 85% remains completely unchanged even after calcination at 1,000 °C. The presence of SiO2 layer/bridge as spacer between TiO2 particles freezes the grain growth: the average crystallite size increased negligibly from 17 to 18 nm even during the calcination at 1,000 °C. Due to the stabilizing effect of SiO2 the titania nanoparticles calcinated at 900 and 1,000 °C show significant photocatalytic activity. Furthermore, the increase in photocatalytic activity with calcination temperature indicates that the titania surface becomes more accessible either due to intensified cracking of the SiO2 layer or due to enhanced transport of SiO2 into the necks thus releasing additional titania surface.

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.

Preparation, stabilization and characterization of TiO(2) on thin polyethylene films (LDPE). Photocatalytic applications.

PubMed

Zhiyong, Yu; Mielczarski, E; Mielczarski, J; Laub, D; Buffat, Ph; Klehm, U; Albers, P; Lee, K; Kulik, A; Kiwi-Minsker, L; Renken, A; Kiwi, J

2007-02-01

An innovative way to fix preformed nanocrystalline TiO(2) on low-density polyethylene film (LDPE-TiO(2)) is presented. The LDPE-TiO(2) film was able to mediate the complete photodiscoloration of Orange II using about seven times less catalyst than a TiO(2) suspension and proceeded with a photonic efficiency of approximately 0.02. The catalyst shows photostability over long operational periods during the photodiscoloration of the azo dye Orange II. The LDPE-TiO(2) catalyst leads to full dye discoloration under simulated solar light but only to a 30% TOC reduction since long-lived intermediates generated in solution seem to preclude full mineralization of the dye. Physical insight is provided into the mechanism of stabilization of the LDPE-TiO(2) composite during the photocatalytic process by X-ray photoelectron spectroscopy (XPS). The adherence of TiO(2) on LDPE is investigated by electron microscopy (EM) and atomic force microscopy (AFM). The thickness of the TiO(2) film is seen to vary between 1.25 and 1.69 microm for an unused LDPE-TiO(2) film and between 1.31 and 1.50 microm for a sample irradiated 10h during Orange II discoloration pointing out to a higher compactness of the TiO(2) film after the photocatalysis.

Photocatalytic degradation of malathion using Zn2+-doped TiO2 nanoparticles: statistical analysis and optimization of operating parameters

NASA Astrophysics Data System (ADS)

Nasseri, Simin; Omidvar Borna, Mohammad; Esrafili, Ali; Rezaei Kalantary, Roshanak; Kakavandi, Babak; Sillanpää, Mika; Asadi, Anvar

2018-02-01

A Zn2+-doped TiO2 is successfully synthesized by a facile photodeposition method and used in the catalytic photo-degradation of organophosphorus pesticide, malathion. The obtained photocatalysts are characterized in detail by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). XRD results confirm the formation of the anatase and rutile phases for the Zn2+-doped TiO2 nanoparticles, with crystallite sizes of 12.9 nm. Zn2+-doped TiO2 that was synthesized by 3.0%wt Zn doping at 200 °C exhibited the best photocatalytic activity. 60 sets of experiments were conducted using response surface methodology (RSM) by adjusting five operating parameters, i.e. initial malathion concentration, catalyst dose, pH, reaction time at five levels and presence or absence of UV light. The analysis revealed that all considered parameters are significant in the degradation process in their linear terms. The optimum values of the variables were found to be 177.59 mg/L, 0.99 g/L, 10.99 and 81.04 min for initial malathion concentration, catalyst dose, pH and reaction time, respectively, under UV irradiation (UV ON). Under the optimized conditions, the experimental values of degradation and mineralization were 98 and 74%, respectively. Moreover, the effects of competing anions and H2O2 on photocatalyst process were also investigated.

Magnetic diatomite(Kieselguhr)/Fe2O3/TiO2 composite as an efficient photo-Fenton system for dye degradation

NASA Astrophysics Data System (ADS)

Barbosa, Isaltino A.; Zanatta, Lucas D.; Espimpolo, Daniela M.; da Silva, Douglas L.; Nascimento, Leandro F.; Zanardi, Fabrício B.; de Sousa Filho, Paulo C.; Serra, Osvaldo A.; Iamamoto, Yassuko

2017-10-01

We explored the potential use of diatomite/Fe2O3/TiO2 composites as catalysts for heterogeneous photo-Fenton degradation of methylene blue under neutral pH. Such system consists in magnetic solids synthesized by co-precipitation with Fe2+/Fe3+ in the presence of diatomite, followed by impregnation of TiO2. The results showed that the optimal amount of the catalyst was 2.0 g L-1, since aggregation phenomena become significant above this concentration, which decreases the photodegradation activity. The catalyst is highly efficient in the degradation of methylene blue and shows an easy recovery by an external magnetic field. This allows for an effective catalyst reuse without significant loss of activity in catalytic cycles, which is a highly interesting prospect for recyclable dye degradation systems.

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.

TiO2 Nanotube-Carbon (TNT-C) as Support for Pt-based Catalyst for High Methanol Oxidation Reaction in Direct Methanol Fuel Cell.

PubMed

Abdullah, M; Kamarudin, S K; Shyuan, L K

2016-12-01

In this study, TiO 2 nanotubes (TNTs) were synthesized via a hydrothermal method using highly concentrated NaOH solutions varying from 6 to 12 M at 180 °C for 48 h. The effects of the NaOH concentration and the TNT crystal structure on the performance for methanol oxidation were investigated to determine the best catalyst support for Pt-based catalysts. The results showed that TNTs produced with 10 M NaOH exhibited a length and a diameter of 550 and 70 nm, respectively; these TNTs showed the best nanotube structure and were further used as catalyst supports for a Pt-based catalyst in a direct methanol fuel cell. The synthesized TNT and Pt-based catalysts were analysed by FESEM, TEM, BET, EDX, XRD and FTIR. The electrochemical performance of the catalysts was investigated using cyclic voltammetry (CV) and chronoamperometric (CA) analysis to further understand the methanol oxidation in the direct methanol fuel cell (DMFC). Finally, the result proves that Pt-Ru/TNT-C catalyst shows high performance in methanol oxidation as the highest current density achieved at 3.3 mA/cm 2 (normalised by electrochemically active surface area) and high catalyst tolerance towards poisoning species was established.

Catalytic oxidation of 1,2-DCBz over V2O5/TiO2-CNTs: effect of CNT diameter and surface functional groups.

PubMed

Du, Cuicui; Wang, Qiulin; Peng, Yaqi; Lu, Shengyong; Ji, Longjie; Ni, Mingjiang

2017-02-01

A series of V 2 O 5 /TiO 2 -carbon nanotube (CNT) catalysts were prepared and tested to decompose gaseous 1,2-dichlorobenzene (1,2-DCBz). Several physicochemical methods, including nitrogen adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and H 2 temperature-programmed reduction (TPR) were employed to characterise their physicochemical properties. To better understand the effect of CNT properties on the reactivity of V 2 O 5 /TiO 2 -CNT catalysts, the 1,2-DCBz residue remaining in the off-gas and on the catalyst surface were both collected and analysed. The results indicate that the outer diameter and the surface functional groups (hydroxide radical and carboxyl) of CNTs significantly influence upon the catalytic activity of CNT-containing V 2 O 5 /TiO 2 catalysts: the CNT outer diameter mainly affects the aggregation of CNTs and the π-π interaction between the benzene ring and CNTs, while the introduction of -OH and -COOH groups by acid treatment can further enlarge specific surface area (SSA) and contribute to a higher average oxidation state of vanadium (V aos ) and supplemental surface chemisorbed oxygen (O ads ). In addition, the enhanced mobility of lattice oxygen (O latt) also improves the oxidation ability of the catalysts.

Toxicity assessment of metoprolol and its photodegradation mixtures obtained by using different type of TiO2 catalysts in the mammalian cell lines.

PubMed

Četojević-Simin, Dragana D; Armaković, Sanja J; Šojić, Daniela V; Abramović, Biljana F

2013-10-01

Toxicity of metoprolol (MET) alone and in mixtures with its photocatalytic degradation intermediates obtained by using TiO2 Wackherr and Degussa P25 under UV irradiation in the presence of O2 was evaluated in vitro in a panel of three histologically different cell lines: rat hepatoma (H-4-II-E), human colon adenocarcinoma (HT-29) and human fetal lung (MRC-5). Both catalysts promoted a time-dependent increase in the toxicity of the photodegradation products, and those obtained using Degussa P25 photocatalyst were more toxic. The most pronounced and selective toxic action of MET and products of its photodegradation was observed in the hepatic cell line. The higher toxicity of the mixtures obtained using Degussa P25 catalyst could be explained by a different mechanism of MET degradation, i.e. by the presence or higher concentrations of some intermediates. Although the concentrations of intermediates obtained using TiO2 Wackherr catalyst were higher, they did not affect significantly the growth of the examined cell lines, indicating their lower toxicity. This suggests that a treatment aiming at complete mineralization should be performed bearing in mind that the type of catalyst, the concentration of target molecule, and the duration of the process are significant factors that determine the nature and toxicity of the resulting mixtures. Although the EC50 values of MET obtained in mammalian cell lines were higher compared to the bioassays for lower trophic levels, the time-dependent promotion of toxicity of degradation mixtures should be attributed to the higher sensitivity of mammalian cell bioassays. © 2013 Elsevier B.V. All rights reserved.

Marine environmental protection: An application of the nanometer photo catalyst method on decomposition of benzene.

PubMed

Lin, Mu-Chien; Kao, Jui-Chung

2016-04-15

Bioremediation is currently extensively employed in the elimination of coastal oil pollution, but it is not very effective as the process takes several months to degrade oil. Among the components of oil, benzene degradation is difficult due to its stable characteristics. This paper describes an experimental study on the decomposition of benzene by titanium dioxide (TiO2) nanometer photocatalysis. The photocatalyst is illuminated with 360-nm ultraviolet light for generation of peroxide ions. This results in complete decomposition of benzene, thus yielding CO2 and H2O. In this study, a nonwoven fabric is coated with the photocatalyst and benzene. Using the Double-Shot Py-GC system on the residual component, complete decomposition of the benzene was verified by 4h of exposure to ultraviolet light. The method proposed in this study can be directly applied to elimination of marine oil pollution. Further studies will be conducted on coastal oil pollution in situ. Copyright © 2016 Elsevier Ltd. All rights reserved.

Micro-size spherical TiO2(B) secondary particles as anode materials for high-power and long-life lithium-ion batteries

NASA Astrophysics Data System (ADS)

Takami, Norio; Harada, Yasuhiro; Iwasaki, Takuya; Hoshina, Keigo; Yoshida, Yorikazu

2015-01-01

Electrochemical properties of micro-size spherical TiO2(B) secondary particles have been investigated in order to develop TiO2(B) anodes for lithium-ion batteries with high-power and long-life performance. The spherical TiO2(B) electrodes with a small amount of a carbon conductor additive had a high electrode density of 2.2 g cm-3 and a volumetric reversible capacity of 475 mAh cm-3 comparable to that of graphite electrodes. Compared with nano-size needle-like TiO2(B) electrodes, the spherical TiO2(B) electrodes exhibited higher-rate discharge capability and longer-cycle life performance. The impedance of the TiO2(B)/electrolyte interface model indicated that the charge transfer resistance Rc and the passivating film resistance Rf of the spherical TiO2(B) were much smaller than those of the needle-like one. The high-rate discharge and the long-cycle performance of the spherical TiO2(B) electrode are attributed to the superior electronic connective property and Rc and Rf values smaller than those of the needle-like one. Lithium-ion cells using the spherical TiO2(B) anodes and LiNi0.8Co0.1Mn0.1O2 cathode with a capacity of 2.8 Ah exhibited a high energy density of 100 Wh kg-1, a high output power density of 1800 W kg-1 for 10 s pulse, and a long cycle life of more than 3000 cycles.

Synthesis, characterization and effect of calcination temperature on phase transformation and photocatalytic activity of Cu,S-codoped TiO 2 nanoparticles

NASA Astrophysics Data System (ADS)

Hamadanian, M.; Reisi-Vanani, A.; Majedi, A.

2010-01-01

A novel copper and sulfur codoped TiO 2 photocatalyst was synthesized by modified sol-gel method using titanium(IV) isopropoxide, CuCl 2·2H 2O and thiourea as precursors. The samples were characterized by X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), scanning electron microscopy equipped with energy dispersive X-ray micro-analysis (SEM-EDX), transmission electron microscopy (TEM) and Fourier transform infrared (FT-IR) analysis. The XRD results showed undoped and Cu,S-codoped TiO 2 nanoparticles only include anatase phase. Effect of calcination temperature showed rutile phase appears in 650 and 700 °C for undoped and 0.1% Cu,S-codoped TiO 2, respectively. The SEM analysis revealed the doping of Cu and S does not leave any change in morphology of the catalyst surface. The increase of copper doping enhanced "red-shift" in the UV-vis absorption spectra. The TEM images confirmed the dopants suppressed the growth of TiO 2 grains. The photocatalytic activity of samples was tested for degradation of methyl orange (MO) solutions. The results showed photocatalytic activity of the catalysts with 0.05% Cu,0.05% S and 0.1% Cu,0.05% S were higher than that of other catalysts under ultraviolet (UV) and visible irradiation, respectively. Because of synergetic effect of S and Cu, the Cu,S-codoped TiO 2 catalyst has higher activity than undoped and Cu or S doped TiO 2 catalysts.

A theoretical consideration of ion size effects on the electric double layer and voltammetry of nanometer-sized disk electrodes.

PubMed

Gao, Yu; Liu, Yuwen; Chen, Shengli

2016-12-12

Considering that an electric-double-layer (EDL) structure may significantly impact on the mass transport and charge transfer kinetics at the interfaces of nanometer-sized electrodes, while EDL structures could be altered by the finite sizes of electrolyte and redox ions, the possible effects of ion sizes on EDL structures and voltammetric responses of nanometer-sized disk (nanodisk) electrodes are investigated. Modified Boltzmann and Nernst-Planck (NP) equations, which include the influence of the finite ion volumes, are combined with the Poisson equation and modified Butler-Volmer equation to gain knowledge on how the finite sizes of ions and the nanometer sizes of electrodes may couple with each other to affect the structures and reactivities of a nanoscale electrochemical interface. Two typical ion radii, 0.38 nm and 0.68 nm, which could represent the sizes of the commonly used aqueous electrolyte ions (e.g., the solvated K + ) and the organic electrolyte ions (e.g., the solvated TEA + ) respectively, are considered. The finite size of ions can result in decreased screening of electrode charges, therefore magnifying EDL effects on the ion transport and the electron transfer at electrochemical interfaces. This finite size effect of ions becomes more pronounced for larger ions and at smaller electrodes as the electrode radii is larger than 10 nm. For electrodes with radii smaller than 10 nm, however, the ion size effect may be less pronounced with decreasing the electrode size. This can be explained in terms of the increased edge effect of disk electrodes at nanometer scales, which could relax the ion crowding at/near the outer Helmholtz plane. The conditions and situations under which the ion sizes may have a significant effect on the voltammetry of electrodes are discussed.

Non-noble metal Cu-loaded TiO2 for enhanced photocatalytic H2 production.

PubMed

Foo, Wei Jian; Zhang, Chun; Ho, Ghim Wei

2013-01-21

Here we have demonstrated the preparation of high-quality, monodispersed and tunable phases of Cu nanoparticles. Structural and chemical composition studies depict the evolution of Cu-Cu(2)O-CuO nanoparticles at various process stages. The loading of Cu and Cu oxide nanoparticles on TiO(2) catalyst has enhanced the photocatalytic H(2) production. Comparatively, H(2) treatment produces well-dispersed Cu nanoparticles with thin oxide shells that show the highest H(2) production amongst the samples. The relatively higher photocatalytic performance is deemed to result from reduced structural defects, higher surface area and dispersivity as well as favorable charge transfer, which inhibits recombination. The Cu nanoparticles are shown to be a promising alternative to noble metal-loaded TiO(2) catalyst systems due to their low cost and high performance in photocatalytic applications.

Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

DOE PAGES

Boyle, David T.; Wilke, Jeremy A.; Palomino, Robert M.; ...

2017-03-17

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H 2 from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO 2 nanoparticles, and TiO 2/Au interfacial surface sites on the catalyticmore » properties of TiO 2/Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO 2/Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH 3CH 2O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO 2(110), indicating both Au and TiO 2 play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO 2/Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO 2/Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.« less

Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

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

Boyle, David T.; Wilke, Jeremy A.; Palomino, Robert M.

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H 2 from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO 2 nanoparticles, and TiO 2/Au interfacial surface sites on the catalyticmore » properties of TiO 2/Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO 2/Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH 3CH 2O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO 2(110), indicating both Au and TiO 2 play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO 2/Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO 2/Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.« less

Negative surface streamers propagating on TiO2 and γ-Al2O3-supported Ag catalysts: ICCD imaging and modeling study

NASA Astrophysics Data System (ADS)

Kim, Hyun-Ha; Teramoto, Yoshiyuki; Ogata, Atsushi; Kang, Woo Seok; Hur, Min; Song, Young-Hoon

2018-06-01

Surface streamers propagating on the surface of titanium dioxide (TiO2) and alumina (γ-Al2O3) were studied in negative polarity using intensified charge coupled device (ICCD) imaging and numerical simulation. Detailed time-resolved ICCD images of cathode-directed streamers (CDSs) emanating from a ground electrode are first presented in this report. Instead of primary streamers in positive polarity, only a glow-like discharge appeared in the early stage at the cathode under negative polarity. After this discharge disappeared, a counter-propagating CDS initiated from the ground electrode (anode). Numerical simulation indicated that strong electric fields at the pellet-anode and the formation of positive ion rich local spots were the main reason for the CDS formation near the ground electrode. The maximum velocity was 750 km s‑1 for Ag-supported γ-Al2O3 and 550 km s‑1 for Ag-supported TiO2, respectively. In contrast to the CDS in the gas-phase with a positive polarity, the CDS in a catalyst packed-bed under negative polarity showed more branching and a larger number of streamers in the presence of oxygen than in pure N2.

Oxidation-induced structural changes in sub-nanometer platinum supported on alumina

DOE PAGES

DeBusk, Melanie Moses; Allard, Jr, Lawrence Frederick; Blom, Douglas Allen; ...

2015-06-26

Platinum supported on alumina is an essential component of emission treatment catalysts used in transportation. Theoretical, experimental, and mechanistic aspects of platinum particles supported on a variety of supports have been extensively studied; however, available experimental information on the behavior of single vs. sub-nanometer platinum is extremely limited. To bridge the knowledge gap between single supported platinum and well-formed supported platinum nanoparticles, we have carried out synthesis, characterization, and CO and NO oxidation studies of sub-nanometer platinum supported on α, θ, and γ-Al 2O 3 and monitored changes in structure upon exposure to CO and NO oxidation conditions. Furthermore, wemore » find that sub-nanometer Pt is highly effective for CO oxidation due to high platinum dispersion but is not very efficient as NO oxidation catalyst. Lastly, sub-nanometer platinum agglomerates rapidly under CO or NO oxidation conditions to form nanoparticles.« less

Preparation and UV-Vis photodegradation of gaseous benzene by TiO2 nanotube arrays supporting V2O5 nanoparticles

NASA Astrophysics Data System (ADS)

Zhao, Chunxia; Song, Yanbao; Yang, Yunxia; Chen, Wen; Li, Xiaoyu; Wang, Zongsheng

2015-07-01

TiO2-based catalysts effective in visible radiation for eliminating organic pollutants have attracted intense research activity as a future generation photocatalytic material. However, recombination of electron-hole pairs through trapping/de-trapping as well as the disadvantages of recycling and separation/filtration of powders lead to the limitation of powder TiO2 materials. TiO2 nanotube array films supporting vanadium pentoxide nanoparticles (VTNTs) were synthesized by electrophoresis deposition method with the prepared TiO2 nanotube arrays as the cathode and V2O5 sol as the electrolyte. The results indicate that the formation of Ti-O-V bonds and intimate interaction between host-guest interfaces help to enhance the hybrids’ photodegradation activity of gaseous benzene. Importantly, hybrid film catalysts prepared with 0.05 mol/L V2O5 sol for 10 min electrophoresis deposition perform a 98% conversion rate of benzene and 1028.8 mg/m3CO2 production in 80 min under UV-Vis irradiation.

Metal-Organic Framework Photosensitized TiO2 Co-catalyst: A Facile Strategy to Achieve a High Efficiency Photocatalytic System.

PubMed

Xie, Ming-Hua; Shao, Rong; Xi, Xin-Guo; Hou, Gui-Hua; Guan, Rong-Feng; Dong, Peng-Yu; Zhang, Qin-Fang; Yang, Xiu-Li

2017-03-17

A 3D metal-organic framework (ADA-Cd=[Cd 2 L 2 (DMF) 2 ]⋅3 H 2 O where H 2 L is (2E,2'E)-3,3'-(anthracene-9,10-diyl)diacrylic acid) constructed from diacrylate substituted anthracene, sharing structural characteristics with some frequently employed anthraquinone-type dye sensitizers, was introduced as an effective sensitizer for anatase TiO 2 to achieve enhanced visible light photocatalytic performance. A facile mechanical mixing procedure was adopted to prepare the co-catalyst denoted as ADA-Cd/TiO 2 , which showed enhanced photodegradation ability, as well as sustainability, towards several dyes under visible light irradiation. Mechanistic studies revealed that ADA-Cd acted as the antenna to harvest visible light energy, generating excited electrons, which were injected to the conduction band (CB) of TiO 2 , facilitating the separation efficiency of charge carriers. As suggested by the results of control experiments, combined with the corresponding redox potential of possible oxidative species, . O 2 - , generated from the oxygen of ambient air at the CB of TiO 2 was believed to play a dominant role over . OH and h + . UV/Vis and photoluminescence technologies were adopted to monitor the generation of . O 2 - and . OH, respectively. This work presents a facile strategy to achieve a visible light photocatalyst with enhanced catalytic activity and sustainability; the simplicity, efficiency, and stability of this strategy may provide a promising way to achieve environmental remediation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Investigation of TiO2 photocatalyst performance for decolorization in the presence of hydrodynamic cavitation as hybrid AOP.

PubMed

Bethi, Bhaskar; Sonawane, S H; Rohit, G S; Holkar, C R; Pinjari, D V; Bhanvase, B A; Pandit, A B

2016-01-01

In this article, an acoustic cavitation engineered novel approach for the synthesis of TiO2, cerium and Fe doped TiO2 nanophotocatalysts is reported. The prepared TiO2, cerium and Fe doped TiO2 nanophotocatalysts were characterized by XRD and TEM analysis to evaluate its structure and morphology. Photo catalytic performance of undoped TiO2 catalyst was investigated for the decolorization of crystal violet dye in aqueous solution at pH of 6.5 in the presence of hydro dynamic cavitation. Effect of catalyst doping with Fe and Ce was also studied for the decolorization of crystal violet dye. The results shows that, 0.8% of Fe-doped TiO2 exhibits maximum photocatalytic activity in the decolorization study of crystal violet dye due to the presence of Fe in the TiO2 and it may acts as a fenton reagent. Kinetic studies have also been reported for the hybrid AOP (HAOP) that followed the pseudo first-order reaction kinetics. Copyright © 2015 Elsevier B.V. All rights reserved.

In-situ X-ray diffraction activation study on an Fe/TiO2 pre-catalyst.

PubMed

Rayner, Matthew K; Billing, David G; Coville, Neil J

2014-06-01

This study focuses on the use of in situ powder X-ray diffraction (PXRD) and quantitative phase analysis using the Rietveld method to monitor the structural properties of a titania-supported iron (10% Fe/TiO2) pre-catalyst during calcination (oxidation) and activation (reduction) in the temperature range 25-900°C. The TiO2 oxidation study revealed an increase in anatase particle size before the anatase to rutile phase transformation, lending credibility to the bridging mechanism proposed by Kim et al. [(2007), Mater. Sci. Forum, 534-536, 65-68]. Pre-catalyst oxidation experiments allowed for the determination of a suitable calcination temperature (450°C) of the pre-catalyst in terms of maximum hematite concentration and appropriate particle size. These experiments also confirmed that the anatase to rutile phase transformation occurred at higher temperatures after Fe addition and that anatase was the sole donor of Ti(4+) ions, which are known to migrate into hematite (Gennari et al., 1998), during the formation of pseudobrookite (Fe2TiO5) at temperatures above 690°C. Using the results from the oxidation experiments, two pre-catalyst samples were calcined at different temperatures; one to represent the preferred case and one to represent a case where the pre-catalyst had been excessively heated. Samples of the excessively heated catalysts were exposed to different reducing gas atmospheres (5, 10 and 100% H2/N2) and heated in the in situ PXRD reactor, so that diffraction data could be collected during the activation process. The results show that reduction with gases containing low concentrations of H2 (5 and 10%) led to the formation of ilmenite (FeTiO3) and we were able to show that both anatase and rutile are consumed in the reaction. Higher concentrations of H2 led to the formation of magnetite (Fe3O4) and metallic iron (Fe(0)). We also noted a decrease in the anatase to rutile transformation temperature under reducing atmospheres when compared with the pre-catalyst

CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO2 Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al2O3

PubMed Central

Goto, Tomoyo; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

2015-01-01

The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO2 and Pt/α-Al2O3 catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO2, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H2, while H2 combustion was activated by repeated exposure to H2 gas during the periodic gas test. Selective CO sensing of the micro-TGS against H2 was attempted using a double catalyst structure with 0.3–30 wt% Pt/α-Al2O3 as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al2O3 catalyst, by cancelling out the combustion heat from the AuPtPd/SnO2 catalyst. In addition, the AuPtPd/SnO2 and 0.3 wt% Pt/α-Al2O3 double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H2. PMID:26694397

Biodiesel synthesis by TiO2-ZnO mixed oxide nanocatalyst catalyzed palm oil transesterification process.

PubMed

Madhuvilakku, Rajesh; Piraman, Shakkthivel

2013-12-01

Biodiesel is a promising alternating environmentally benign fuel to mineral diesel. For the development of easier transesterification process, stable and active heterogeneous mixed metal oxide of TiO2-ZnO and ZnO nanocatalysts were synthesized and exploited for the palm oil transesterification process. The synthesized catalysts were characterized by XRD, FT-IR, and FE-SEM studies for their structural and morphological characteristics. It was found that TiO2-ZnO nanocatalyst exhibits good catalytic activity and the catalytic performance was greatly depends on (i) catalyst concentration (ii) methanol to oil molar ratio (iii) reaction temperature and (iv) reaction time. A highest 98% of conversion was obtained at the optimum reaction parameters with 200 mg of catalyst loading and the biodiesel was analyzed by TLC and (1)H NMR techniques. The TiO2-ZnO nanocatalyst shows good catalytic performance over the ZnO catalyst, which could be a potential candidate for the large-scale biodiesel production from palm oil at the reduced temperature and time. Copyright © 2013. Published by Elsevier Ltd.

Influence of size and shape of sub-micrometer light scattering centers in ZnO-assisted TiO2 photoanode for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Pham, Trang T. T.; Mathews, Nripan; Lam, Yeng-Ming; Mhaisalkar, Subodh

2018-03-01

Sub-micrometer cavities have been incorporated in the TiO2 photoanode of dye-sensitized solar cell to enhance its optical property with light scattering effect. These are large pores of several hundred nanometers in size and scatter incident light due to the difference refraction index between the scattering center and the surrounding materials, according to Mie theory. The pores are created using polystyrene (PS) or zinc oxide (ZnO) templates reported previously which resulted in ellipsoidal and spherical shapes, respectively. The effect of size and shape of scattering center was modeled using a numerical analysis finite-difference time-domain (FDTD). The scattering cross-section was not affected significantly with different shapes if the total displacement volume of the scattering center is comparable. Experiments were carried out to evaluate the optical property with varying size of ZnO templates. Photovoltaic effect of dye-sensitized solar cells made from these ZnO-assisted films were investigated with incident-photon-to-current efficiency to understand the effect of scattering center size on the enhancement of absorption. With 380 nm macropores incorporated, the power conversion efficiency has increased by 11% mostly thanks to the improved current density, while 170 nm and 500 nm macropores samples did not have increment in sufficiently wide range of absorbing wavelengths.

The enhancement of CuO modified V2O5-WO3/TiO2 based SCR catalyst for Hg° oxidation in simulated flue gas

NASA Astrophysics Data System (ADS)

Chen, Chuanmin; Jia, Wenbo; Liu, Songtao; Cao, Yue

2018-04-01

CuO modified V2O5-WO3/TiO2 based SCR catalysts prepared by improved impregnation method were investigated to evaluate the catalytic activity for elemental mercury (Hg°) oxidation in simulated flue gas at 150-400 °C. Nitrogen adsorption, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts. It was found that V0.8WTi-Cu3 catalyst exhibited the superior Hg° oxidation activity and wide operating temperature window at the gas hourly space velocity (GHSV) of 3 × 105 h-1. The BET and XRD results showed that CuO was well loaded and highly dispersed on the catalysts surface. The XPS results suggested that the addition of CuO generated abundant chemisorbed oxygen, which was due to the synergistic effect between CuO and V2O5. The existence of the redox cycle of V4+ + Cu2+ ↔ V5+ + Cu+ in V0.8WTi-Cu3 catalyst enhanced Hg° oxidation activity. The effects of flue gas components (O2, NO, SO2 and H2O) on Hg° oxidation over V0.8WTi-Cu3 catalyst were also explored. Moreover, the co-presence of NO and NH3 remarkably inhibited Hg° oxidation, which was due to the competitive adsorption and reduction effect of NH3 at SCR condition. Fortunately, this inhibiting effect was gradually scavenged with the decrease of GHSV. The mechanism of Hg° oxidation was also investigated.

Effects of exposure to nano and bulk sized TiO2 and CuO in Lemna minor.

PubMed

Dolenc Koce, Jasna

2017-10-01

Nanoparticles of TiO 2 and CuO are among most commonly used nanoparticles, and elevated concentrations of them are expected to be found in all environments, including aquatic. A standard growth inhibition test ISO/CD 20079 was used to determine the toxicity of nano sized and larger micro sized (bulk) particles in the concentrations of 0.1, 1, 10, 100 and 1000 μM CuO and TiO 2 on common duckweed (Lemna minor L.). Both nano and bulk CuO particles caused changes in the structure and function of treated plants. The number of fronds and colonies decreased by as much as 78%, the length of roots and fronds decreased by 99% and 14%, respectively. Furthermore, photochemical efficiency was reduced by up to 35%, and the activities of antioxidative enzymes guaiacol peroxidase, ascorbate peroxidase and glutathione reductase increased by more than 240%. The altered physiological state of the CuO exposed plants was also reflected in the elevated occurrence of necrosis and bleaching in the duckweed colonies. Nano sized particles of CuO proved more phytotoxic than bulk particles, and the effects of both studied CuO sizes were concentration dependent. On the other hand, both bulk and nano sized particles of TiO 2 caused no severe phytotoxic effects, there was no concentration dependence and they could be considered as non-harmful to common duckweed. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

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.

The preparation of TiO2@rGO nanocomposite efficiently activated with UVA/LED and H2O2 for high rate oxidation of acetaminophen: Catalyst characterization and acetaminophen degradation and mineralization

NASA Astrophysics Data System (ADS)

Cheshme Khavar, Amir Hossein; Moussavi, Gholamreza; Mahjoub, Ali Reza

2018-05-01

The present work was focused on the preparation of TiO2@rGO nanocomposite using an innovative facile synthesis method and the investigation of its photocatalytic activity in a UVA/LED photoreactor. The XRD patterns indicated anatase structure for all samples. Presence of rGO in nanocomposites was confirmed by FT-IR and Raman spectra. Also, mono-dispersed TiO2 nanoparticles on rGO sheet were shown in the SEM and HRTEM images. The prepared TiO2@rGO nanocomposite was used as the photocatalyst for degradation of acetaminophen (ACT) in the photoreactor illuminated with UVA/LEDs having the intensity of 95 μW/cm2. The complete degradation of 50 mg/L ACT was attained within 50 min in the LED/TiO2@rGO process while P25/LED process only showed 17% ACT degradation under similar experimental conditions. The photocatalytic activity was strongly affected by the rGO to TiO2 ratio in the nanocomposites and the highest photocatalytic activity was observed at 3.0 wt.% of rGO. Reaction with free radOH was the main mechanism involved in the ACT photodegradation in the TiO2@rGO/LED process under the selected conditions. The performance of LED/TiO2@rGO process improved by four and three times in ACT degradation and mineralization, respectively, at the presence of H2O2. As made TiO2@rGO nanocompsite could preserve its catalytic activity during five consecutive recycles in the process. Accordingly, TiO2@rGO nanocomposite is an active and stable catalyst in the UVA/LED photoreactor for high rate degradation of pharmaceuticals in the contaminated water.

Toxicological aspects of photocatalytic degradation of selected xenobiotics with nano-sized Mn-doped TiO2.

PubMed

Ozmen, Murat; Güngördü, Abbas; Erdemoglu, Sema; Ozmen, Nesrin; Asilturk, Meltem

2015-08-01

The toxic effects of two selected xenobiotics, bisphenol A (BPA) and atrazine (ATZ), were evaluated after photocatalytic degradation using nano-sized, Mn-doped TiO2. Undoped and Mn-doped TiO2 nanoparticles were synthesized. The samples were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), UV-vis-diffuse reflectance spectra (DRS), X-ray fluorescence spectroscopy (XRF), and BET surface area. The photocatalytic efficiency of the undoped and Mn-doped TiO2 was evaluated for BPA and ATZ. The toxicity of the synthesized photocatalysts and photocatalytic by-products of BPA and ATZ was determined using frog embryos and tadpoles, zebrafish embryos, and bioluminescent bacteria. Possible toxic effects were also evaluated using selected enzyme biomarkers. The results showed that Mn-doped TiO2 nanoparticles did not cause significant lethality in Xenopus laevis embryos and tadpoles, but nonfiltered samples caused lethality in zebrafish. Furthermore, Mn-doping of TiO2 increased the photocatalytic degradation capability of nanoparticles, and it successfully degraded BPA and AZT, but degradation of AZT caused an increase of the lethal effects on both tadpoles and fish embryos. Degradation of BPA caused a significant reduction of lethal effects, especially after 2-4h of degradation. However, biochemical assays showed that both Mn-doped TiO2 and the degradation by-products caused a significant change of selected biomarkers on X. laevis tadpoles; thus, the ecological risks of Mn-doped TiO2 should be considered due to nanomaterial applications and for spilled nanoparticles in an aquatic ecosystem. Also, the risk of nanoparticles should be considered using indicator reference biochemical markers to verify the environmental health impacts. Copyright © 2015 Elsevier B.V. All rights reserved.

Highly crystallized nanometer-sized zeolite a with large Cs adsorption capability for the decontamination of water.

PubMed

Torad, Nagy L; Naito, Masanobu; Tatami, Junichi; Endo, Akira; Leo, Sin-Yen; Ishihara, Shinsuke; Wu, Kevin C-W; Wakihara, Toru; Yamauchi, Yusuke

2014-03-01

Nanometer-sized zeolite A with a large cesium (Cs) uptake capability is prepared through a simple post-milling recrystallization method. This method is suitable for producing nanometer-sized zeolite in large scale, as additional organic compounds are not needed to control zeolite nucleation and crystal growth. Herein, we perform a quartz crystal microbalance (QCM) study to evaluate the uptake ability of Cs ions by zeolite, to the best of our knowledge, for the first time. In comparison to micrometer-sized zeolite A, nanometer-sized zeolite A can rapidly accommodate a larger amount of Cs ions into the zeolite crystal structure, owing to its high external surface area. Nanometer-sized zeolite is a promising candidate for the removal of radioactive Cs ions from polluted water. Our QCM study on Cs adsorption uptake behavior provides the information of adsorption kinetics (e.g., adsorption amounts and rates). This technique is applicable to other zeolites, which will be highly valuable for further consideration of radioactive Cs removal in the future. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced photocatalytic activity towards degradation and H2 evolution over one dimensional TiO2@MWCNTs heterojunction

NASA Astrophysics Data System (ADS)

Zhang, Xiao; Cao, Shuang; Wu, Zhijiao; Zhao, Suling; Piao, Lingyu

2017-04-01

With the distinct electronic and optical properties, multiwall carbon nanotubes (MWCNTs) are identified as an outstanding catalyst support, which can effectively improve the performance of the TiO2 photocatalysts. Herein, the unique one dimensional TiO2@MWCNTs nanocomposites have been prepared by a facile hydrothermal method. The TiO2 coating layers are extremely uniform and the thickness is adjustable for different nanocomposites. XPS measurements confirm that intimate electronic interactions are existed between MWCNTs and TiO2 via interfacial Tisbnd Osbnd C bond and the photoluminescence intensity of the TiO2@MWCNTs nanocomposites are effectively quenched compared with pure TiO2, suggesting the fast electron transfer rates. The thickness of TiO2 coating layers of the TiO2@MWCNTs nanocomposites plays a significant role in the photocatalytic degradation of organic pollutants, such as methylene blue (MB) and Rhodamine B (RhB), and photocatalytic H2 evolution from water. Due to the formation of one dimensional heterojunction of TiO2@MWCNTs nanocomposites and the positive synergistic effect between TiO2 and carbon nanotubes, it is found that the photocatalytic activity of the system is significantly improved.

Photochemical degradation of an anionic surfactant by TiO2 nanoparticle doped with C, N in aqueous solution

NASA Astrophysics Data System (ADS)

Zamiri, M.; Giahi, M.

2016-12-01

Novel C,N-doped TiO2 nanoparticles were prepared by a solid phase reaction. The catalyst was characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). The results showed that crystallite size of synthesized C,N-doped TiO2 particles were in nanoscale. UV light photocatalytic studies were carried out using sodium naphthalenesulfonate formaldehyde condensate (SNF) as a model pollutant. The effects of initial concentration of surfactant, catalyst amount, pH, addition of oxidant on the reaction rate were ascertained and optimum conditions for maximum degradation was determined. The results indicated that for a solution of 20 mg/L of SNF, almost 98.7% of the substance were removed at pH 4.0 and 0.44 g/L photocatalyst load, with addition of 1 mM K2S2O8 and irradiation time of 90 min. The kinetics of the process was studied, and the photodegradation rate of SNF was found to obey pseudo-first-order kinetics equation represented by the Langmuir-Hinshelwood model.

Green synthesis of α-aminophosphonate derivatives on a solid supported TiO2 -SiO2 catalyst and their anticancer activity.

PubMed

Chinthaparthi, Radha Rani; Bhatnagar, Ira; Gangireddy, Chandra Sekhar Reddy; Syama, Sundar Chereddy; Cirandur, Suresh Reddy

2013-09-01

Syntheses of a new series of biologically potent α-aminophosphonates were accomplished by one-pot Kabachnik-Fields reaction using TiO2-SiO2 as solid supported catalyst under microwave irradiation conditions. The chemical structures of all the newly synthesized compounds were confirmed by analytical and spectral (IR, 1H, 13C, 31P NMR, and mass) data. Their anticancer nature was evaluated by screening the in vitro activity on two human cancer cell lines, HeLa and SK-BR-3. Compounds 4i and 4o showed the best activity on these cancer cells even though the majority of the compounds, and particularly 4l and 4p, have good cytotoxic activity against them. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of high surface area TiO 2/SiO 2 mesostructured nanocomposite

NASA Astrophysics Data System (ADS)

Bonne, Magali; Pronier, Stéphane; Can, Fabien; Courtois, Xavier; Valange, Sabine; Tatibouët, Jean-Michel; Royer, Sébastien; Marécot, Patrice; Duprez, Daniel

2010-06-01

Recently titania synthesis was reported using various structuration procedures, leading to the production of solid presenting high surface area but exhibiting moderate thermal stability. The study presents the synthesis of TiO 2/SiO 2 nanocomposites, a solid that can advantageously replace bulk titania samples as catalyst support. The silica host support used for the synthesis of the nanocomposite is a SBA-15 type silica, having a well-defined 2D hexagonal pore structure and a large pore size. The control of the impregnation media is important to obtain dispersed titania crystals into the porosity, the best results have been obtained using an impregnation in an excess of solvent. After calcination at low temperature (400 °C), nanocomposites having titania nanodomains (˜2-3 nm) located inside the pores and no external aggregates visible are obtained. This nanocomposite exhibits high specific surface area (close to that of the silica host support, even with a titania loading of 55 wt.%) and a narrow pore size distribution. Surprisingly, the increase in calcination temperature up to 800 °C does not allow to detect the anatase to rutile transition. Even at 800 °C, the hexagonal mesoporous structure of the silica support is maintained, and the anatase crystal domain size is evaluated at ˜10 nm, a size close to that of the silica host support porosity (8.4 nm). Comparison of their physical properties with the results presented in literature for bulk samples evidenced that these TiO 2/SiO 2 solids are promising in term of thermal stability.

Study of phase development and thermal stability in as synthesized TiO2 nanoparticles by laser pyrolysis: ethylene uptake and oxygen enrichment

NASA Astrophysics Data System (ADS)

Ilie, Alina Georgiana; Scarisoreanu, Monica; Dutu, Elena; Dumitrache, Florian; Banici, Ana-Maria; Fleaca, Claudiu Teodor; Vasile, Eugenia; Mihailescu, Ion

2018-01-01

Laser pyrolysis has proven a viable and trustworthy method of TiO2 nanoparticles fabrication, ensuring good quality and wide variety of nanoparticle morphologies and sizes. This work is aimed to phase control, experimentally studied, by parameter modulation, during one step laser pyrolysis synthesis or in combination with thermal annealing. High phase purity anatase and rutile TiO2 nanoparticles, oxygen abundant, are synthesized from TiCl4 and C2H4 gas mixtures, in the presence of air as oxygen donor, under CO2 laser radiation. The nano-titania samples are analyzed by X-ray Diffraction, EDAX, TEM and Raman spectroscopy and reveal good phase stability and distinct morphology. This study extends the method applicability onto rutile majoritarian TiO2 synthesis and generation of thermally stable anatase titania, a well-known catalyst.

Enhanced photocatalytic activity of Fe-doped TiO2 coated on N-doped activated carbon composites for photocatalytic degradation of dyeing wastewater

NASA Astrophysics Data System (ADS)

Zhou, Jie; Zhu, Beibei; Wang, Lu; Li, Ya; Qiao, Qichen

2017-10-01

Fe-doped TiO2 coated on N-doped activated carbon (Fe-TiO2/N-AC, FTNA) composites were synthesized simply by a straightforward two-step procedure. The obtained materials were characterized by X-ray diffractometry (XRD), N2 adsorption-desorption, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and FT-IR spectroscopies. Through the degradation of dyeing wastewater, the photocatalytic activity of FTNA was investigated under ultraviolet light irradiation. The results showed that containing N functional groups were successfully introduced onto the surface of the activated carbon. Compared with Fe-TiO2/AC (FTA), FTNA with average particle size of TiO2 13.6 nm and surface area 1007.89 m2/g showed a higher photoactivity. Additionally, for the photocatalytic degradation of dyeing wastewater, the optimum N content and catalyst content were 0.8% and 5g/L, respectively. Moreover, the photoactivity and photo stability of the catalyst after many runs was also evaluated.

Fabrication and application of mesoporous TiO2 film coated on Al wire by sol-gel method with EISA

NASA Astrophysics Data System (ADS)

Zhao, Linkang; Lu, Jianjun

2017-04-01

Mesoporous TiO2 film on Al wire was fabricated by sol-gel method with evaporation induced self assembly (EISA) process using F127 as templating agent in the mixed solution of ethanol and Tetra-n-butyl Titanate. The Ni/TiO2 film catalyst supported on Al wire was prepared by impregnation and the catalytic performance on methanation was carried out in a titanium alloy micro-reactor tube. It was shown that anatase mesoporous TiO2 film was prepared in this conditions (1 g F127,calcined at 400 °C and aged for 24 h), which has specific surface area of 127 m2 g-1 and narrow pore size distribution of 5.3 nm. Low calcined temperature (300 °C) cannot transfer film to anatase and decompose F127 completely. Ni/TiO2 film on Al wire catalyst was proved to be active in CO methanation reaction. And the CO conversion reaches 99% and CH4 selectivity close is to 80% when the reaction temperature is higher 360 °C.

Effect of deposition of Ag on TiO2 nanoparticles on the photodegradation of Reactive Yellow-17.

PubMed

Rupa, A Valentine; Manikandan, D; Divakar, D; Sivakumar, T

2007-08-25

Nanoparticles of TiO(2) were synthesized by sol-gel technique and the photodeposition of about 1% Ag on TiO(2) particles was carried out. Ag-deposited TiO(2) catalyst was characterised by XRD, TEM and UV-vis spectroscopy. The Ag-TiO(2) catalyst was evaluated for their photocatalytic activity towards the degradation of Reactive Yellow-17 (RY-17) under UV and visible light irradiations. Then the results were compared with synthesized nano-TiO(2) sol and P-25 Degussa and the enhanced degradation was obtained with Ag-deposited TiO(2). This enhanced activity of Ag-TiO(2) may be attributed to the trapping of conduction band electrons. The effect of initial dye concentration, pH and electron acceptors such as H(2)O(2), K(2)S(2)O(8) on the photocatalytic activity were studied and the results obtained were fitted with Langmuir-Hinshelwood model to study the degradation kinetics and discussed in detail.

Parameters affecting the photocatalytic degradation of dyes using TiO2: a review

NASA Astrophysics Data System (ADS)

Reza, Khan Mamun; Kurny, ASW; Gulshan, Fahmida

2017-07-01

Traditional chemical, physical and biological processes for treating wastewater containing textile dye have such disadvantages as high cost, high energy requirement and generation of secondary pollution during treatment process. The advanced oxidation processes technology has been attracting growing attention for the decomposition of organic dyes. Such processes are based on the light-enhanced generation of highly reactive hydroxyl radicals, which oxidize the organic matter in solution and convert it completely into water, CO2 and inorganic compounds. In this presentation, the photocatalytic degradation of dyes in aqueous solution using TiO2 as photocatalyst under solar and UV irradiation has been reviewed. It is observed that the degradation of dyes depends on several parameters such as pH, catalyst concentration, substrate concentration and the presence of oxidants. Reaction temperature and the intensity of light also affect the degradation of dyes. Particle size, BET-surface area and different mineral forms of TiO2 also have influence on the degradation rate.

Melting behavior of nanometer sized gold isomers

NASA Astrophysics Data System (ADS)

Liu, H. B.; Ascencio, J. A.; Perez-Alvarez, M.; Yacaman, M. J.

2001-09-01

In the present work, the melting behavior of nanometer sized gold isomers was studied using a tight-binding potential with a second momentum approximation. The cases of cuboctahedra, icosahedra, Bagley decahedra, Marks decahedra and star-like decahedra were considered. We calculated the temperature dependence of the total energy and volume during melting and the melting point for different types and sizes of clusters. In addition, the structural evolutions of the nanosized clusters during the melting transition were monitored and revealed. It is found that the melting process has three characteristic time periods for the intermediate nanosized clusters. The whole process includes surface disordering and reordering, followed by surface melting and a final rapid overall melting. This is a new observation, which it is in contrast with previous reports where surface melting is the dominant step.

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.

Microwave absorption properties of polypyrrole-SrFe12O19-TiO2-epoxy resin nanocomposites: Optimization using response surface methodology

NASA Astrophysics Data System (ADS)

Seyed Dorraji, M. S.; Rasoulifard, M. H.; Amani-Ghadim, A. R.; Khodabandeloo, M. H.; Felekari, M.; Khoshrou, M. R.; hajimiri, I.

2016-10-01

At a few works are discussed about formation of heterogeneous composites with different distribution of particle shape and size that are used for electromagnetic absorption purposes. In this study a novel heterogeneous nanocpmposites is investigated. The nanocomposite has been successfully prepared based on epoxy resin including various nano-metal oxides (TiO2, SrFe12O19) and polypyrrole (PPy) by sol-gel and the solution chemistry method, respectively. The performance of prepared nanocomposite in absorption of microwave in X-band range was investigated and transmission line method by X-band waveguide straight was used to measure EM parameters of nanocomposites. The Response surface methodology (RSM) with central composite design (CCD) was utilized to study the effects of the wt.% TiO2 in SrFe12O19, wt.% Tio2-SrFe12O19 in PPy and wt.% TiO2-SrFe12O19-PPy in epoxy resin, on the microwave absorption properties with the absorber thickness of only 2 mm. The proposed quadratic model was in accordance with the experimental results with correlation coefficient of 96.5%. The optimum condition for maximum microwave absorption efficiency were wt.% TiO2 in SrFe12O19 of 70, wt.% TiO2-SrFe12O19 in PPy of 10 and wt.% TiO2-SrFe12O19-PPy in epoxy of 25. The sample prepared in optimal conditions indicated reflection loss of -15 dB corresponding to 97% absorption, at the range of 9.2-10.8 GHz.

Heterogeneous UV/Fenton degradation of bisphenol A catalyzed by synergistic effects of FeCo2O4/TiO2/GO.

PubMed

Bai, Xue; Lyu, Lingling; Ma, Wenqiang; Ye, Zhengfang

2016-11-01

A new method for bisphenol A (BPA) degradation in aqueous solution was developed. The characteristics of BPA degradation in a heterogeneous ultraviolet (UV)/Fenton reaction catalyzed by FeCo 2 O 4 /TiO 2 /graphite oxide (GO) were studied. The properties of the synthesized catalysts were characterized using scanning electron microscopy, X-ray diffraction, and vibrating sample magnetometry. FeCo 2 O 4 and TiO 2 were grown as spherical shape, rough surface, and relatively uniform on the surface of GO (FeCo 2 O 4 /TiO 2 /GO). Batch tests were conducted to evaluate the effects of the initial pH, FeCo 2 O 4 /TiO 2 /GO dosage, and H 2 O 2 concentration on BPA degradation. In a system with 0.5 g L -1 of FeCo 2 O 4 /TiO 2 /GO and 10 mmol L -1 of H 2 O 2 , approximately 90 % of BPA (20 mg L -1 ) was degraded within 240 min of UV irradiation at pH 6.0. The reused FeCo 2 O 4 /TiO 2 /GO catalyst retained its activity after three cycles, which indicates that it is stable and reusable. The heterogeneous UV/Fenton reaction catalyzed by FeCo 2 O 4 /TiO 2 /GO is a promising advanced oxidation technology for treating wastewater that contains BPA.

Experimental elaboration and analysis of dye-sensitized TiO2 solar cells (DSSC) dyed by natural dyes and conductive polymers

NASA Astrophysics Data System (ADS)

KałuŻyński, P.; Maciak, E.; Herzog, T.; Wójcik, M.

2016-09-01

In this paper we propose low cost and easy in development fully working dye-sensitized solar cell module made with use of a different sensitizing dyes (various anthocyanins and P3HT) for increasing the absorption spectrum, transparent conducting substrates (vaccum spattered chromium and gold), nanometer sized TiO2 film, iodide and methyl viologen dichloride based electrolyte, and a counter electrode (vaccum spattered platinum or carbon). Moreover, some of the different technologies and optimization manufacturing processes were elaborated for energy efficiency increase and were presented in this paper.

Characterization of N,C-codoped TiO 2 films prepared by reactive DC magnetron sputtering

NASA Astrophysics Data System (ADS)

Wu, Kee-Rong; Hung, Chung-Hsuang

2009-12-01

Titanium dioxide (TiO 2) films are deposited by codoping nitrogen and carbon on indium tin oxide-coated substrates as visible light (Vis)-enabled catalysts. The X-ray diffraction peak intensity of the preferential orientation in (2 1 1) plane declines when the topmost 1.0 μm layer of the film is ground off. The decrease in the crystallite size and the crystallinity of anatase TiO 2 film is also evidenced by a shift towards the high wave number and broadening of the Raman spectra. Low doping concentrations of N (1.3%) and C (1.8%) are estimated by X-ray photoelectron spectroscopy (XPS) which displays an N 1 s peak at 396.8 eV and a C 1 s peak at 282.1 eV, respectively. This is attributed to the substitution of the oxygen sites with nitrogen and carbon, which is believed to be responsible for the Vis photocatalytic activity into a wavelength of >500 nm. The cross-sectional transmission electron microscopy images show larger pores at the grain boundaries and in larger columnar crystals than in the undoped TiO 2 film. All of these results indicate that porosity, crystallinity and shift in the preferential orientation are more pronounced close to the surface than close to the bottom of the sample. Wettability upon measurement of the water contact angle, methylene blue degradation and radical formation tests under both ultraviolet and Vis irradiation demonstrate that the topmost surface renders not only a larger reactive surface area but also a better carrier transport route than the rest of the film, improving its photocatalytic activity. These results show that surface porosity of the film is dominant than the tailoring of the photocatalytic activities of N,C-codoped TiO 2 catalysts.

Diatom-templated TiO2 with enhanced photocatalytic activity: biomimetics of photonic crystals

NASA Astrophysics Data System (ADS)

He, Jiao; Chen, Daomei; Li, Yongli; Shao, Junlong; Xie, Jiao; Sun, Yuejuan; Yan, Zhiying; Wang, Jiaqiang

2013-11-01

The siliceous frustules with sophisticated optical structure endow diatoms with superior solar light-harvesting abilities for effective photosynthesis. The preserved frustules of diatom ( Cocconeis placentula) cells, as biophotonic crystals, were thus employed as both hard templates and silicon resources to synthesize TiO2 photocatalyst. Characterizations by a combination of physicochemical techniques proved that the bio-inspired sample is TiO2-coated SiO2 with biogenic C self-doped in. It was found that the synthesized composites exhibited similar morphologies to the original diatom templates. In comparison with commercial Degussa P25 TiO2, the C-doped TiO2/SiO2 catalyst exhibited more light absorption in the visible region and higher photocatalytic efficiency for photodegradation of rhodamine B under visible light due to the biomorphic hierarchical structures, TiO2 coating and C-doping.

Characterization and improved solar light activity of vanadium doped TiO2/diatomite hybrid catalysts.

PubMed

Wang, Bin; Zhang, Guangxin; Leng, Xue; Sun, Zhiming; Zheng, Shuilin

2015-03-21

V-doped TiO2/diatomite composite photocatalysts with different vanadium concentrations were synthesized by a modified sol-gel method. The diatomite was responsible for the well dispersion of TiO2 nanoparticles on the matrix and consequently inhibited the agglomeration. V-TiO2/diatomite hybrids showed red shift in TiO2 absorption edge with enhanced absorption intensity. Most importantly, the dopant energy levels were formed in the TiO2 bandgap due to V(4+) ions substituted to Ti(4+) sites. The 0.5% V-TiO2/diatomite photocatalyst displayed narrower bandgap (2.95 eV) compared to undoped sample (3.13 eV) and other doped samples (3.05 eV) with higher doping concentration. The photocatalytic activities of V doped TiO2/diatomite samples for the degradation of Rhodamine B under stimulated solar light illumination were significantly improved compared with the undoped sample. In our case, V(4+) ions incorporated in TiO2 lattice were responsible for increased visible-light absorption and electron transfer to oxygen molecules adsorbed on the surface of TiO2 to produce superoxide radicals ˙O2(-), while V(5+) species presented on the surface of TiO2 particles in the form of V2O5 contributed to e(-)-h(+) separation. In addition, due to the combination of diatomite as support, this hybrid photocatalyst could be separated from solution quickly by natural settlement and exhibited good reusability. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Unravelling Site-Specific Photo-Reactions of Ethanol on Rutile TiO2(110)

PubMed Central

Hansen, Jonas Ø.; Bebensee, Regine; Martinez, Umberto; Porsgaard, Soeren; Lira, Estephania; Wei, Yinying; Lammich, Lutz; Li, Zheshen; Idriss, Hicham; Besenbacher, Flemming; Hammer, Bjørk; Wendt, Stefan

2016-01-01

Finding the active sites of catalysts and photo-catalysts is crucial for an improved fundamental understanding and the development of efficient catalytic systems. Here we have studied the photo-activated dehydrogenation of ethanol on reduced and oxidized rutile TiO2(110) in ultrahigh vacuum conditions. Utilizing scanning tunnelling microscopy, various spectroscopic techniques and theoretical calculations we found that the photo-reaction proceeds most efficiently when the reactants are adsorbed on regular Ti surface sites, whereas species that are strongly adsorbed at surface defects such as O vacancies and step edges show little reaction under reducing conditions. We propose that regular Ti surface sites are the most active sites in photo-reactions on TiO2. PMID:26915303

Efficient photodegradation of organic dye using anatase TiO2 plants as catalyst

NASA Astrophysics Data System (ADS)

Bahadur, Jitendra; Pal, Kaushik

2017-11-01

Anatase TiO2 hierarchical nanostructures with higher photocatalytic activity are of special importance in various applications. We have reported the synthesis of TiO2 as water chestnut plants like morphology via facile hydrothermal method, by using Titanium (IV) butoxide (TBOT) as a precursor solution. It is found that TiO2 nanoparticles work as seed and completely convert into water chestnut plants like structure or morphology, which are composed of crystallized anatase nanocrystals. X-ray diffraction spectra confirmed the presence of anatase phase of crystallized TiO2 plants (TPs). The average life time delay for generated charge carriers in TPs was calculated to be around 2.45 ns, which reflects slow recombination of charge carriers. The prepared TPs show excellent photocatalytic performance when applied in photo degradation of Rhodamine B organic dye. The unique features exhibited by TPs make them a promising candidate for vast potential applications in field such as solar cells, photocatalysis, supercapacitor, lithium ion batteries and some related fields.[Figure not available: see fulltext.

Characterization and activity of Pd-modified TiO2 catalysts for photocatalytic oxidation of NO in gas phase.

PubMed

Wu, Zhongbiao; Sheng, Zhongyi; Liu, Yue; Wang, Haiqiang; Tang, Nian; Wang, Jie

2009-05-30

Pd-modified TiO(2) prepared by thermal impregnation method was used in this study for photocatalytic oxidation of NO in gas phase. The physico-chemical properties of Pd/TiO(2) catalysts were characterized by X-ray diffraction analysis (XRD), Brunauer-Emmett-Teller measurements (BET), X-ray photoelectron spectrum analysis (XPS), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), UV-vis diffuse reflectance spectra (UV-vis DRS) and photoluminescence spectra (PL). It was found that Pd dopant existed as PdO particles in as-prepared photocatalysts. The results of PL spectra indicated that the photogenerated electrons and holes were efficiently separated after Pd doping. During in situ XPS study, it was found that the content of hydroxyl groups on the surface of Pd/TiO(2) increased when the catalyst was irradiated by UV light, which could result in the improvement of photocatalytic activity. The activity test showed that the optimum Pd dopant content was 0.05 wt.%. And the maximum conversion of NO was about 72% higher than that of P25 when the initial concentration of NO was 200 ppm, which showed that Pd/TiO(2) photocatalysts could be potentially applied to oxidize higher concentration of NO.

A hybridization approach to efficient TiO2 photodegradation of aqueous benzalkonium chloride.

PubMed

Suchithra, Padmajan Sasikala; Carleer, Robert; Ananthakumar, Solaippan; Yperman, Jan

2015-08-15

TiO2 get positively charged upon UV-irradiation and repel the cationic pollutants away from the surface. Hybridization of AC onto TiO2 (ACT) tends catalyst surface negatively charged besides providing highly favorable adsorptions sites for cationic pollutants. The photodegradation of benzalkonium chloride (BKC), a quaternary ammonium surfactant and a pharmaceutical, is investigated with ACT. The surface charge of the catalyst in surfactant and non-surfactant aqueous dispersion under UV-irradiation is investigated and explained. The anomalous increase in COD values at the beginning of BKC-photodegradation is explained. The intermediate products formed are identified in both solution and solid phase. Trace amount of dodecane remained adsorbed on the catalyst surface after 1h UV-irradiation, but complete mineralization of BKC is achieved with 2h UV-irradiation. We propose that BKC photodegradation starts by central fission of benzyl CN bond followed by dealkylation, and demethylation steps. Copyright © 2015 Elsevier B.V. All rights reserved.

TiO2-based (Fe3O4, SiO2, reduced graphene oxide) magnetically recoverable photocatalysts for imazalil degradation in a synthetic wastewater.

PubMed

Santiago, Dunia E; Pastrana-Martínez, Luisa M; Pulido-Melián, Elisenda; Araña, Javier; Faria, Joaquim L; Silva, Adrián M T; González-Díaz, Óscar; Doña-Rodríguez, José M

2018-03-02

Magnetite (Fe 3 O 4 ), a core-shell material (SiO 2 @Fe 3 O 4 ), and reduced graphene oxide-Fe 3 O 4 (referred as rGO-MN) were used as supports of a specific highly active TiO 2 photocatalyst. Thermal treatments at 200 or 450 °C, different atmospheres (air or N 2 ), and TiO 2 :support weight ratios (1.0, 1.5, or 2.0) were investigated. X-ray diffractograms revealed that magnetite is not oxidized to hematite when the core-shell SiO 2 @Fe 3 O 4 material-or a N 2 atmosphere (instead of air) in the thermal treatment-was employed to prepare the TiO 2 -based catalysts (the magnetic properties being preserved). The materials treated with N 2 were first tested for degradation of imazalil (a well-known fungicide) in deionized water. The best compromise between the photocatalytic activity, magnetic separation, and Fe leached (1.61 mg L -1 , i.e., below the threshold for water reuse in irrigation) was found for the magnetic catalyst prepared with SiO 2 @Fe 3 O 4 , an intermediate TiO 2 :support ratio (1.5), and treated at 200 °C under N 2 atmosphere (i.e., SiO 2 @Fe 3 O 4 -EST-1.5-200-N 2 ). This material was then tested for the treatment of imazalil in a synthetic wastewater, SW (with a chemical composition simulating an effluent resulting from fruit postharvest activity). This SW has a pH of 4.2 and the experiments were carried out at this natural pH 0 and at neutral conditions (keeping pH at 7 along the reaction). The magnetic catalyst was more active than bare TiO 2 for the treatment of imazalil in SW at natural pH. Since Fe leaching was observed (3.53 mg L -1 ), added H 2 O 2 enhanced both imazalil degradation and mineralization. Conveniently, these catalysts can be readily recovered by using a conventional magnetic field, as demonstrated over three consecutive recycling runs. Graphical abstract % Imazalil conversion using different magnetic catalysts and comparison with bare TiO 2 .

Liquid phase catalytic hydrodebromination of tetrabromobisphenol A on supported Pd catalysts

NASA Astrophysics Data System (ADS)

Wu, Ke; Zheng, Mengjia; Han, Yuxiang; Xu, Zhaoyi; Zheng, Shourong

2016-07-01

Tetrabromobisphenol A (TBBPA) is a widely used brominated flame retardant and reductive debromination is an effective method for the abatement of TBBPA pollution. In this study, Pd catalysts supported on TiO2, CeO2, Al2O3 and SiO2 were prepared by the impregnation (the resulting catalyst denoted as im-Pd/support), deposition-precipitation (the resulting catalyst denoted as dp-Pd/support), and photo-deposition (the resulting catalyst denoted as pd-Pd/support) methods. The catalysts were characterized by N2 adsorption-desorption isotherm, X-ray diffraction, transmission electron microscopy, measurement of zeta potential, CO chemisorption, and X-ray photoelectron spectroscopy. The results showed that at an identical Pd loading amount (2.0 wt.%) Pd particle size in dp-Pd/TiO2 was much smaller than those in im-Pd/TiO2 and pd-Pd/TiO2. Pd particle size of the dp-Pd/TiO2 catalyst increased with Pd loading amount. Additionally, Pd particles in the dp-Pd/TiO2 catalysts were positively charged due to the strong metal-support interaction, whereas the cationization effect was gradually attenuated with the increase of Pd loading amount. For the liquid phase catalytic hydrodebromination (HDB) of TBBPA, tri-bromobisphenol A (tri-BBPA), di-bromobisphenol A (di-BBPA), and mono-bromobisphenol A (mono-BBPA) were identified as the intermediate products, indicative of a stepwise debromination process. The catalytic HDB of TBBPA followed the Langmuir-Hinshelwood model, reflecting an adsorption enhanced catalysis mechanism. At an identical Pd loading amount, the Pd catalyst supported on TiO2 exhibited a much higher catalytic activity than those on other supports. Furthermore, dp-Pd/TiO2 was found to be more active than im-Pd/TiO2 and pd-Pd/TiO2.

Synthesis of double-shelled sea urchin-like yolk-shell Fe3O4/TiO2/Au microspheres and their catalytic applications

NASA Astrophysics Data System (ADS)

Li, Jie; Tan, Li; Wang, Ge; Yang, Mu

2015-03-01

Double-shelled sea urchin-like yolk-shell Fe3O4/TiO2/Au microspheres were successfully synthesized through loading Au nanoparticles on the Fe3O4/TiO2 support by a in situ reduction of HAuCl4 with NaBH4 aqueous solution. These microspheres possess tunable cavity size, adjustable shell layers, high structural stability and large specific surface area. The Au nanoparticles of approximately 5 nm in diameter were loaded both on the TiO2 nanofibers and inside the cavities of sea urchin-like yolk-shell Fe3O4/TiO2 microspheres. The sea urchin-like structure composed of TiO2 nanofibers ensure the good distribution of the Au nanoparticles, while the novel double-shelled yolk-shell structure guarantees the high stability of the Au nanoparticles. Furthermore, the Fe3O4 magnetic core facilitates the convenient recovery of the catalyst by applying an external magnetic field. The Fe3O4/TiO2/Au microspheres display excellent activities and recycling properties in the catalytic reduction of 4-nitrophenol (4-NP): the rate constant is 1.84 min-1 and turnover frequency is 5457 h-1.

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.

Nb doped TiO2 as a Cathode Catalyst Support Material for Polymer Electrolyte Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

O'Toole, Alexander W.

In order to reduce the emissions of greenhouse gases and reduce dependence on the use of fossil fuels, it is necessary to pursue alternative sources of energy. Transportation is a major contributor to the emission of greenhouse gases due to the use of fossil fuels in the internal combustion engine. To reduce emission of these pollutants into the atmosphere, research is needed to produce alternative solutions for vehicle transportation. Low temperature polymer electrolyte membrane fuel cells are energy conversion devices that provide an alternative to the internal combustion engine, however, they still have obstacles to overcome to achieve large scale implementation. T he following work presents original research with regards to the development of Nb doped TiO2 as a cathode catalyst support material for low temperature polymer electrolyte membrane fuel cells. The development of a new process to synthesize nanoparticles of Nb doped TiO2 with controlled compositions is presented as well as methods to scale up the process and optimize the synthesis for the aforementioned application. In addition to this, comparison of both electrochemical activity and durability with current state of the art Pt on high surface area carbon black (Vulcan XC-72) is investigated. Effects of the strong metal-support interaction on the electrochemical behavior of these materials is also observed and discussed.

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.

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.

Ru-bis(pyridine)pyrazolate (bpp)-Based Water-Oxidation Catalysts Anchored on TiO2: The Importance of the Nature and Position of the Anchoring Group.

PubMed

Francàs, Laia; Richmond, Craig; Garrido-Barros, Pablo; Planas, Nora; Roeser, Stephan; Benet-Buchholz, Jordi; Escriche, Lluís; Sala, Xavier; Llobet, Antoni

2016-04-04

Three distinct functionalisation strategies have been applied to the in,in-[{Ru(II)(trpy)}2(μ-bpp)(H2O)2](3+) (trpy=2,2':6',2''-terpyridine, bpp=bis(pyridine)pyrazolate) water-oxidation catalyst framework to form new derivatives that can adsorb onto titania substrates. Modifications included the addition of sulfonate, carboxylate, and phosphonate anchoring groups to the terpyridine and bis(pyridyl)pyrazolate ligands. The complexes were characterised in solution by using 1D NMR, 2D NMR, and UV/Vis spectroscopic analysis and electrochemical techniques. The complexes were then anchored on TiO2-coated fluorinated tin oxide (FTO) films, and the reactivity of these new materials as water-oxidation catalysts was tested electrochemically through controlled-potential electrolysis (CPE) with oxygen evolution detected by headspace analysis with a Clark electrode. The results obtained highlight the importance of the catalyst orientation with respect to the titania surface in regard to its capacity to catalytically oxidize water to dioxygen. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

TiO2-nanowire/MWCNT composite with enhanced performance and durability for polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Selvaganesh, S. Vinod; Dhanasekaran, P.; Bhat, Santoshkumar D.

2017-12-01

Durability is a major issue and has been the growing focus of research for the commercialization of polymer electrolyte fuel cells (PEFCs). Corrosion of carbon support is a key parameter as it triggers the Pt catalyst degradation and affects cell performance, which in turn affects the longevity of the cells. Herein, we describe a hybrid composite support of TiO2-nanowires and Multiwalled carbon nanotubes (MWCNTs) that offers resistance to corrosion under stressful operating conditions. Titania nanowireswhich have been shown to be more efficient and catalytically active than spherically shaped TiO2. TiO2-MWCNT composites are prepared through a hydrothermal method, followed by Pt deposition using a polyol method. Crystal structure, morphology, and oxidation state are examined through various characterization techniques. Electrochemical performance of TiO2-nanowire/MWCNT composite-supported Pt at various ratios of TiO2/MWCNT is assessed in PEFCs. Pt on support with optimum composition of TiO2-nanowires to MWCNTs exhibits fuel cell performance superior to Pt onMWCNTs. Accelerated stress testing (AST) between 1 and 1.5 V reveals that the designed catalyst on nanocomposite support possesses superior electrochemical activity and shows only 16% loss in catalytic activity in relation to 35% for Pt/MWCNTs even after 6000 potential cycles. Subsequently, the samples were characterized after AST to correlate the loss in fuel cell performance

C-C Coupling on Single-Atom-Based Heterogeneous Catalyst.

PubMed

Zhang, Xiaoyan; Sun, Zaicheng; Wang, Bin; Tang, Yu; Nguyen, Luan; Li, Yuting; Tao, Franklin Feng

2018-01-24

Compared to homogeneous catalysis, heterogeneous catalysis allows for ready separation of products from the catalyst and thus reuse of the catalyst. C-C coupling is typically performed on a molecular catalyst which is mixed with reactants in liquid phase during catalysis. This homogeneous mixing at a molecular level in the same phase makes separation of the molecular catalyst extremely challenging and costly. Here we demonstrated that a TiO 2 -based nanoparticle catalyst anchoring singly dispersed Pd atoms (Pd 1 /TiO 2 ) is selective and highly active for more than 10 Sonogashira C-C coupling reactions (R≡CH + R'X → R≡R'; X = Br, I; R' = aryl or vinyl). The coupling between iodobenzene and phenylacetylene on Pd 1 /TiO 2 exhibits a turnover rate of 51.0 diphenylacetylene molecules per anchored Pd atom per minute at 60 °C, with a low apparent activation barrier of 28.9 kJ/mol and no cost of catalyst separation. DFT calculations suggest that the single Pd atom bonded to surface lattice oxygen atoms of TiO 2 acts as a site to dissociatively chemisorb iodobenzene to generate an intermediate phenyl, which then couples with phenylacetylenyl bound to a surface oxygen atom. This coupling of phenyl adsorbed on Pd 1 and phenylacetylenyl bound to O ad of TiO 2 forms the product molecule, diphenylacetylene.

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.

Photocatalytic degradation of methyl orange and bromophenol blue dyes in water using sol-gel synthesized TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Dhanalakshmi, J.; Pathinettam Padiyan, D.

2017-09-01

TiO2 nanoparticles were prepared by a sol-gel method using titanium tetra isopropoxide as a precursor. The structural, optical, morphological and electrical properties were studied by x-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), a high resolution scanning electron microscope (HR-SEM), a transmission electron microscope (TEM), Raman analysis, Photoluminescence (PL) and impedance spectroscopy. The XRD and Raman spectra revealed that the synthesized samples are in pure anatase phase with an average crystallite size of 18 nm. Photocatalytic activity of the TiO2 nanoparticles was investigated for the degradation of 10 ppm methyl orange (MO) and bromophenol blue (BPB) dye using 10 mg of catalyst. Anatase TiO2 exhibited the removal of 67.12% and 85.51% of MO and BPB, respectively, within 240 min. The photocatalytic degradation process is explained using pseudo second order kinetics and fits well with the higher correlation coefficient.

Synthesis and characterization of a mixed phase of anatase TiO2 and TiO2(B) by low pressure chemical vapour deposition (LPCVD) for high photocatalytic activity

NASA Astrophysics Data System (ADS)

Chimupala, Y.; Hyett, G.; Simpson, R.; Brydson, R.

2014-06-01

This project is concerned with enhancing photocatalytic activity by preparing a mixed phase of nano-sized TiO2. TiO2 thin films were synthesized by using Low Pressure Chemical Vapour Deposition (LPCVD). Titanium isopropoxide and N2 gas were used as the precursor and carrier gas respectively. The effects of reaction temperature, carrier gas flow rate and deposited area were studied. TiO2 thin films with nano-sized TiO2 particles were obtained under suitable conditions and SEM, TEM, powder XRD and Raman spectroscopy were employed to characterize the phase and physical appearance of synthesized materials. Preliminary results show that a dual phase (TiO2(B) and anatase) thin film nanopowder was successfully prepared by LPCVD with needle- and polygonal plate-shape crystallites respectively. This thin film deposit produced a preferred orientation of TiO2(B) needles in the [001] direction of average crystallite size 50-80 nm in length and 5-10 nm in width, whilst the crystallite size of anatase polygonal-plates was around 200 nm. The optimal LPCVD condition for preparing this mixed phase of TiO2 was 600°C with a 1 mL/s N2 flow rate.

Inherent size effects on XANES of nanometer metal clusters: Size-selected platinum clusters on silica

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

Dai, Yang; Gorey, Timothy J.; Anderson, Scott L.

2016-12-12

X-ray absorption near-edge structure (XANES) is commonly used to probe the oxidation state of metal-containing nanomaterials, however, as the particle size in the material drops below a few nanometers, it becomes important to consider inherent size effects on the electronic structure of the materials. In this paper, we analyze a series of size-selected Pt n/SiO 2 samples, using X-ray photoelectron spectroscopy (XPS), low energy ion scattering, grazing-incidence small angle X-ray scattering, and XANES. The oxidation state and morphology are characterized both as-deposited in UHV, and after air/O 2 exposure and annealing in H 2. Here, the clusters are found tomore » be stable during deposition and upon air exposure, but sinter if heated above ~150 °C. XANES shows shifts in the Pt L 3 edge, relative to bulk Pt, that increase with decreasing cluster size, and the cluster samples show high white line intensity. Reference to bulk standards would suggest that the clusters are oxidized, however, XPS shows that they are not. Instead, the XANES effects are attributable to development of a band gap and localization of empty state wavefunctions in small clusters.« less

CO 2 hydrogenation over oxide-supported PtCo catalysts: The role of the oxide support in determining the product selectivity

DOE PAGES

Kattel, Shyam; Yu, Weiting; Yang, Xiaofang; ...

2016-05-09

By simply changing the oxide support, the selectivity of a metal–oxide catalysts can be tuned. For the CO 2 hydrogenation over PtCo bimetallic catalysts supported on different reducible oxides (CeO 2, ZrO 2, and TiO 2), replacing a TiO 2 support by CeO 2 or ZrO 2 selectively strengthens the binding of C,O-bound and O-bound species at the PtCo–oxide interface, leading to a different product selectivity. Lastly, these results reveal mechanistic insights into how the catalytic performance of metal–oxide catalysts can be fine-tuned.

Preparation and Characterization of TiO2-Based Photocatalysts by Chemical Vapour Deposition

NASA Astrophysics Data System (ADS)

Nacevski, Goran; Marinkovski, Mirko; Tomovska, Radmila; Fajgar, Radek

In the present work, a novel technique for the preparation of TiO2-based photocatalysts modified with SiO2 is presented, using a pulsed ArF laser to induce a chemical vapor deposition process. The irradiated gas mixture was composed of TiCl4/SiCl4 precursors in excess of oxygen. Laser irradiation at 193 nm with a repetition frequency of 10 Hz induced the deposition of thin nano-sized mixed oxide films. In order to improve the photocatalytic activity of the catalysts and to expand the activity from the UV to the visible part of the spectrum, doping of the catalysts with chromium oxides was performed. For that aim, the same technique of catalyst preparation was used, irradiating the same gas mixture with the addition of chromyl chloride as Cr precursor. The thin films prepared were annealed up to 500°C in order to remove crystal defects, which could be responsible for poor photocatalytic activity. The dependence of structure and properties on reaction process and irradiation conditions (laser energy and fluence, precursors pressure) were examined. The main aim was to find the best conditions for the production of highly photoactive catalysts and to decrease deactivation processes during the photo-oxidation. The composition, structure and morphology of the oxide catalysts prepared were studied by various spectroscopies, electron microscopy and diffraction techniques.

The Nanometer-Sized Eutectic Structure of Si/CrSi2 Thermoelectric Materials Fabricated by Rapid Solidification

NASA Astrophysics Data System (ADS)

Norizan, Mohd Natashah; Miyazaki, Yoshinobu; Ohishi, Yuji; Muta, Hiroaki; Kurosaki, Ken; Yamanaka, Shinsuke

2018-04-01

Nanostructuring is known to be an effective method to improve thermoelectric performance but, generally, it requires complex procedures and much labor. In the present study, self-assembled nanometer-sized composite structures of silicon (Si) and chromium disilicide (CrSi2) were easily fabricated by the rapid solidification of a melt with a eutectic composition. Ribbon-like samples were obtained with a dominant nanostructure of fine aligned lamellae with a spacing range of 20-35 nm. The thermoelectric power factor of the ribbon was observed to be 1.2 mW/mK2 at room temperature and reached 3.0 mW/mK2 at 773 K. The thermal conductivity was 65% lower than that of a bulk eutectic sample. The results suggest that this method is promising for fabricating an effective nanostructure for thermoelectric performance.

Surface Properties and Catalytic Performance of Activated Carbon Fibers Supported TiO2 Photocatalyst

NASA Astrophysics Data System (ADS)

Yang, Huifen; Fu, Pingfeng

Activated carbon fibers supported TiO2 photocatalyst (TiO2/ACF) in felt-form was successfully prepared with a dip-coating process using organic silicon modified acrylate copolymer as a binder followed by calcination at 500°C in a stream of Ar gas. The photocatalyst was characterized by SEM, XRD, XPS, FTIR, and BET surface area. Most of carbon fibers were coated with uniformly distributed TiO2 clusters of nearly 100 nm. The loaded TiO2 layer was particulate for the organic binder in the compact film was carbonized. According to XPS and FTIR analysis, amorphous silica in carbon grains was synthesized after carbonizing organic silicon groups, and the Ti-O-Si bond was formed between the interface of loaded TiO2 and silica. Additionally, the space between adjacent carbon fibers still remained unfilled after TiO2 coating, into which both UV light and polluted solutions could penetrate to form a three-dimensional environment for photocatalytic reactions. While loaded TiO2 amount increased to 456 mg TiO2/1 g ACF, the TiO2/ACF catalyst showed its highest photocatalytic activity, and this activity only dropped about 10% after 12 successive runs, exhibiting its high fixing stability of coated TiO2.

Effect of TiO2 calcination temperature on the photocatalytic oxidation of gaseous NH3.

PubMed

Wu, Hongmin; Ma, Jinzhu; Zhang, Changbin; He, Hong

2014-03-01

Carbon-modified titanium dioxide (TiO2) was prepared by a sol-gel method using tetrabutyl titanate as precursor, with calcination at various temperatures, and tested for the photocatalytic oxidation (PCO) of gaseous NH3 under visible and UV light. The test results showed that no samples had visible light activity, while the TiO2 calcined at 400°C had the best UV light activity among the series of catalysts, and was even much better than the commercial catalyst P25. The catalysts were then characterized by X-ray diffractometry, Brunauer-Emmett-Teller adsorption analysis, Raman spectroscopy, thermogravimetry/differential scanning calorimetry coupled with mass spectrometry, ultraviolet-visible diffuse reflectance spectra, photoluminescence spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy. It was shown that the carbon species residuals on the catalyst surfaces induced the visible light adsorption of the samples calcined in the low temperature range (< 300°C). However, the surface acid sites played a determining role in the PCO of NH3 under visible and UV light over the series of catalysts. Although the samples calcined at low temperatures had very high SSA, good crystallinity, strong visible light absorption and also low PL emission intensity, they showed very low PCO activity due to their very low number of acid sites for NH3 adsorption and activation. The TiO2 sample calcined at 400°C contained the highest number of acid sites among the series of catalysts, therefore showing the highest performance for the PCO of NH3 under UV light. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

A Nanometer Aerosol Size Analyzer (nASA) for Rapid Measurement of High-concentration Size Distributions

NASA Astrophysics Data System (ADS)

Han, Hee-Siew; Chen, Da-Ren; Pui, David Y. H.; Anderson, Bruce E.

2000-03-01

We have developed a fast-response nanometer aerosol size analyzer (nASA) that is capable of scanning 30 size channels between 3 and 100 nm in a total time of 3 s. The analyzer includes a bipolar charger (Po210), an extended-length nanometer differential mobility analyzer (Nano-DMA), and an electrometer (TSI 3068). This combination of components provides particle size spectra at a scan rate of 0.1 s per channel free of uncertainties caused by response-time-induced smearing. The nASA thus offers a fast response for aerosol size distribution measurements in high-concentration conditions and also eliminates the need for applying a de-smearing algorithm to resulting data. In addition, because of its thermodynamically stable means of particle detection, the nASA is useful for applications requiring measurements over a broad range of sample pressures and temperatures. Indeed, experimental transfer functions determined for the extended-length Nano-DMA using the tandem differential mobility analyzer (TDMA) technique indicate the nASA provides good size resolution at pressures as low as 200 Torr. Also, as was demonstrated in tests to characterize the soot emissions from the J85-GE engine of a T-38 aircraft, the broad dynamic concentration range of the nASA makes it particularly suitable for studies of combustion or particle formation processes. Further details of the nASA performance as well as results from calibrations, laboratory tests and field applications are presented below.

A Nanometer Aerosol Size Analyzer (nASA) for Rapid Measurement of High-Concentration Size Distributions

NASA Technical Reports Server (NTRS)

Han, Hee-Siew; Chen, Da-Ren; Pui, David Y. H.; Anderson, Bruce E.

2001-01-01

We have developed a fast-response Nanometer Aerosol Size Analyzer (nASA) that is capable of scanning 30 size channels between 3 and 100 nm in a total time of 3 seconds. The analyzer includes a bipolar charger (P0210), an extended-length Nanometer Differential Mobility Analyzer (Nano-DMA), and an electrometer (TSI 3068). This combination of components provides particle size spectra at a scan rate of 0.1 second per channel free of uncertainties caused by response-time-induced smearing. The nASA thus offers a fast response for aerosol size distribution measurements in high-concentration conditions and also eliminates the need for applying a de-smearing algorithm to resulting data. In addition, because of its thermodynamically stable means of particle detection, the nASA is useful for applications requiring measurements over a broad range of sample pressures and temperatures. Indeed, experimental transfer functions determined for the extended-length Nano-DMA using the Tandem Differential Mobility Analyzer (TDMA) technique indicate the nASA provides good size resolution at pressures as low as 200 Torr. Also, as was demonstrated in tests to characterize the soot emissions from the J85-GE engine of a T38 aircraft, the broad dynamic concentration range of the nASA makes it particularly suitable for studies of combustion or particle formation processes. Further details of the nASA performance as well as results from calibrations, laboratory tests and field applications are presented.

Constrained Geometry Organotitanium Catalysts Supported on Nanosized Silica for Ethylene (co)Polymerization.

PubMed

Li, Kuo-Tseng; Wu, Ling-Huey

2017-05-05

Supported olefin polymerization catalysts can prevent reactor-fouling problems and produce uniform polymer particles. Constrained geometry complexes (CGCs) have less sterically hindered active sites than bis-cyclopentadienyl metallocene catalysts. In the literature, micrometer-sized silica particles were used for supporting CGC catalysts, which might have strong mass transfer limitations. This study aims to improve the activity of supported CGC catalysts by using nanometer-sized silica. Ti[(C₅Me₄)SiMe₂(N t Bu)]Cl₂, a "constrained-geometry" titanium catalyst, was supported on MAO-treated silicas (nano-sized and micro-sized) by an impregnation method. Ethylene homo-polymerization and co-polymerization with 1-octene were carried out in a temperature range of 80-120 °C using toluene as the solvent. Catalysts prepared and polymers produced were characterized. For both catalysts and for both reactions, the maximum activities occurred at 100 °C, which is significantly higher than that (60 °C) reported before for supported bis-cyclopentadienyl metallocene catalysts containing zirconium, and is lower than that (≥140 °C) used for unsupported Ti[(C₅Me₄)SiMe₂(N t Bu)]Me₂ catalyst. Activities of nano-sized catalyst were 2.6 and 1.6 times those of micro-sized catalyst for homopolymerization and copolymerization, respectively. The former produced polymers with higher crystallinity and melting point than the latter. In addition, copolymer produced with nanosized catalyst contained more 1-octene than that produced with microsized catalyst.

Observation of nanometer-sized electro-active defects in insulating layers by fluorescence microscopy and electrochemistry.

PubMed

Renault, Christophe; Marchuk, Kyle; Ahn, Hyun S; Titus, Eric J; Kim, Jiyeon; Willets, Katherine A; Bard, Allen J

2015-06-02

We report a method to study electro-active defects in passivated electrodes. This method couples fluorescence microscopy and electrochemistry to localize and size electro-active defects. The method was validated by comparison with a scanning probe technique, scanning electrochemical microscopy. We used our method for studying electro-active defects in thin TiO2 layers electrodeposited on 25 μm diameter Pt ultramicroelectrodes (UMEs). The permeability of the TiO2 layer was estimated by measuring the oxidation of ferrocenemethanol at the UME. Blocking of current ranging from 91.4 to 99.8% was achieved. Electro-active defects with an average radius ranging between 9 and 90 nm were observed in these TiO2 blocking layers. The distribution of electro-active defects over the TiO2 layer is highly inhomogeneous and the number of electro-active defect increases for lower degree of current blocking. The interest of the proposed technique is the possibility to quickly (less than 15 min) image samples as large as several hundreds of μm(2) while being able to detect electro-active defects of only a few tens of nm in radius.

Alkali- and Sulfur-Resistant Tungsten-Based Catalysts for NOx Emissions Control.

PubMed

Huang, Zhiwei; Li, Hao; Gao, Jiayi; Gu, Xiao; Zheng, Li; Hu, Pingping; Xin, Ying; Chen, Junxiao; Chen, Yaxin; Zhang, Zhaoliang; Chen, Jianmin; Tang, Xingfu

2015-12-15

The development of catalysts with simultaneous resistance to alkalis and sulfur poisoning is of great importance for efficiently controlling NOx emissions using the selective catalytic reduction of NOx with NH3 (SCR), because the conventional V2O5/WO3-TiO2 catalysts often suffer severe deactivation by alkalis. Here, we support V2O5 on a hexagonal WO3 (HWO) to develop a V2O5/HWO catalyst, which has exceptional resistance to alkali and sulfur poisoning in the SCR reactions. A 350 μmol g(-1) K(+) loading and the presence of 1,300 mg m(-3) SO2 do not almost influence the SCR activity of the V2O5/HWO catalyst, and under the same conditions, the conventional V2O5/WO3-TiO2 catalysts completely lost the SCR activity within 4 h. The strong resistance to alkali and sulfur poisoning of the V2O5/HWO catalysts mainly originates from the hexagonal structure of the HWO. The HWO allows the V2O5 to be highly dispersed on the external surfaces for catalyzing the SCR reactions and has the relatively smooth surfaces and the size-suitable tunnels specifically for alkalis' diffusion and trapping. This work provides a useful strategy to develop SCR catalysts with exceptional resistance to alkali and sulfur poisoning for controlling NOx emissions from the stationary source and the mobile source.

Preparation of TiO2-Decorated Boron Particles by Wet Ball Milling and their Photoelectrochemical Hydrogen and Oxygen Evolution Reactions

PubMed Central

Jung, Hye Jin; Nam, Kyusuk; Sung, Hong-Gye; Hyun, Hyung Soo; Sohn, Youngku; Shin, Weon Gyu

2016-01-01

TiO2-coated boron particles were prepared by a wet ball milling method, with the particle size distribution and average particle size being easily controlled by varying the milling operation time. Based on the results from X-ray photoelectron spectroscopy, transmission electron microscopy, energy dispersive X-ray analysis, and Fourier transform infrared spectroscopy, it was confirmed that the initial oxide layer on the boron particles surface was removed by the wet milling process, and that a new B–O–Ti bond was formed on the boron surface. The uniform TiO2 layer on the 150 nm boron particles was estimated to be 10 nm thick. Based on linear sweep voltammetry, cyclic voltammetry, current-time amperometry, and electrochemical impedance analyses, the potential for the application of TiO2-coated boron particles as a photoelectrochemical catalyst was demonstrated. A current of 250 μA was obtained at a potential of 0.5 V for hydrogen evolution, with an onset potential near to 0.0 V. Finally, a current of 220 μA was obtained at a potential of 1.0 V for oxygen evolution. PMID:28774132

Reactivation and reuse of TiO2-SnS2 composite catalyst for solar-driven water treatment.

PubMed

Kovacic, Marin; Kopcic, Nina; Kusic, Hrvoje; Stangar, Urska Lavrencic; Dionysiou, Dionysios D; Bozic, Ana Loncaric

2018-01-01

One of the most important features of photocatalytic materials intended to be used for water treatment is their long-term stability. The study is focused on the application of thermal and chemical treatments for the reactivation of TiO 2 -SnS 2 composite photocatalyst, prepared by hydrothermal synthesis and immobilized on the glass support using titania/silica binder. Such a catalytic system was applied in solar-driven treatment, solar/TiO 2 -SnS 2 /H 2 O 2 , for the purification of water contaminated with diclofenac (DCF). The effectiveness of studied reactivation methods for retaining TiO 2 -SnS 2 activity in consecutive cycles was evaluated on basis of DCF removal and conversion, and TOC removal and mineralization of organic content. Besides these water quality parameters, biodegradability changes in DCF aqueous solution treated by solar/TiO 2 -SnS 2 /H 2 O 2 process using simply reused (air-dried) and thermally and chemically reactivated composite photocatalyst through six consecutive cycles were monitored. It was established that both thermal and chemical reactivation retain TiO 2 -SnS 2 activity in the second cycle of its reuse. However, both treatments caused the alteration in the TiO 2 -SnS 2 morphology due to the partial transformation of visible-active SnS 2 into non-active SnO 2 . Such alteration, repeated through consecutive reactivation and reuse, was reflected through gradual activity loss of TiO 2 -SnS 2 composite in applied solar-driven water treatment.

Parametric studies of diethyl phosphoramidate photocatalytic decomposition over TiO2.

PubMed

Sun, Bo; Vorontsov, Alexander V; Smirniotis, Panagiotis G

2011-02-28

The present study is focused on influences of parameters including pH, temperature, TiO(2) catalyst concentration, and reactant concentration on the rate of photocatalytic diethyl phosphoramidate (DEPA) decomposition with Hombikat UV 100 (HK) and Degussa P25 (P25) TiO(2). Total mineralization of DEPA is observed. Two regimes of pH, namely in acid and near-neutral environments were found where maximum total carbon (TC) decomposition was observed. The electrostatic effects on adsorption over the TiO(2) surface explain the above phenomena. The maximum rate is observed for P25 at DEPA concentration 1.3 mM whereas the rate grows continuously with DEPA concentration rise for HK. The temperature dependence of TC decomposition rate in the range of 15-63°C with both HK and P25 follows the Arrhenius equation. The activation energy for total carbon decomposition with HK and P25 are 29.5±1.0 and 24.3±3.1 kJ/mol, respectively. The decomposition rate of DEPA is larger over P25 than over HK. The rate over P25 increases faster than that with HK for each unit of the titania added when the TiO(2) concentration is less than 375 mg/l. The higher light absorption and particles aggregation of P25 are responsible for the decrease of reaction rate we observed at catalyst concentration above a certain level. In contrast, the rate over HK increases monotonically with the concentration of the photocatalyst used. Copyright © 2010 Elsevier B.V. All rights reserved.

TiO2/WO3 photoactive bilayers in the UV-Vis light region

NASA Astrophysics Data System (ADS)

Vasilaki, E.; Vernardou, D.; Kenanakis, G.; Vamvakaki, M.; Katsarakis, N.

2017-04-01

In this work, photoactive bilayered films consisting of anatase TiO2 and monoclinic WO3 were synthesized by a sol-gel route. Titanium isopropoxide and tungsten hexachloride were used as metal precursors and deposition was achieved by spin-coating on Corning glass substrates. The samples were characterized by X-ray diffraction, photoluminescence, UV-Vis, and Raman spectroscopy, as well as field emission scanning electron microscopy. The prepared immobilized catalysts were tested for their photocatalytic performance by the decolorization of methylene blue in aqueous matrices, under UV-Vis light irradiation. The annealing process influenced the crystallinity of the bilayered films, while the concentration of the tungsten precursor solution and the position of the tungsten trioxide layer further affected their photocatalytic performance. In particular, the photocatalytic performance of the bilayered films was optimized at a concentration of 0.1 M of the WO3 precursor solution, when deposited as an overlying layer on TiO2 by two annealing steps ( 76% methylene blue decolorization in 300 min of irradiation versus 59% in the case of a bare TiO2 film). In general, the coupled layer catalysts exhibited superior photoactivity compared to that of bare TiO2 films with WO3 acting as an electron trap, resulting, therefore, in a more efficient electron-hole separation and inhibiting their recombination.

The Comparative Photodegradation Activities of Pentachlorophenol (PCP) and Polychlorinated Biphenyls (PCBs) Using UV Alone and TiO2-Derived Photocatalysts in Methanol Soil Washing Solution

PubMed Central

Zhou, Zeyu; Zhang, Yaxin; Wang, Hongtao; Chen, Tan; Lu, Wenjing

2014-01-01

Photochemical treatment is increasingly being applied to remedy environmental problems. TiO2-derived catalysts are efficiently and widely used in photodegradation applications. The efficiency of various photochemical treatments, namely, the use of UV irradiation without catalyst or with TiO2/graphene-TiO2 photodegradation methods was determined by comparing the photodegadation of two main types of hydrophobic chlorinated aromatic pollutants, namely, pentachlorophenol (PCP) and polychlorinated biphenyls (PCBs). Results show that photodegradation in methanol solution under pure UV irradiation was more efficient than that with either one of the catalysts tested, contrary to previous results in which photodegradation rates were enhanced using TiO2-derived catalysts. The effects of various factors, such as UV light illumination, addition of methanol to the solution, catalyst dosage, and the pH of the reaction mixture, were examined. The degradation pathway was deduced. The photochemical treatment in methanol soil washing solution did not benefit from the use of the catalysts tested. Pure UV irradiation was sufficient for the dechlorination and degradation of the PCP and PCBs. PMID:25254664

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.

Photoinactivation and Toxicity of Nano-sized TiO2 on Paint Microflora Using Visible Lights

NASA Astrophysics Data System (ADS)

Obidi, Olayide; Halverson, Larry

2016-04-01

Traditional TiO2 has been used as an antimicrobial additive to paints, but more recently the use of TiO2 nanoparticles (NPs) has been proposed as an alternative because of its ability to induce oxidative damage to the cell membrane of bacteria. This study focused on how photoinactivation of TiO2 NPs by fluorescent and halogen lights (400-700 nm) influenced survival of Bacillus sphaericus (Gram-positive bacterium) and Klebsiella pneumoniae (Gram-negative bacterium) isolated from spoiled paints. The loss of viability of the test organisms in the presence of TiO2 NPs determined by culturable (plate) count technique indicated a decrease in viable bacteria that was predominant after 24-h exposure. The TiO2 NPs showed higher antibacterial performance under fluorescent light than halogen light with increasing irradiation time and confirms the photokilling effect of TiO2 NPs. TiO2 NPs were also bactericidal under dark conditions, suggesting potential antibacterial applications in the paint industry.

Optimized photodegradation of Bisphenol A in water using ZnO, TiO2 and SnO2 photocatalysts under UV radiation as a decontamination procedure

NASA Astrophysics Data System (ADS)

Abo, Rudy; Kummer, Nicolai-Alexeji; Merkel, Broder J.

2016-09-01

Experiments on photodegradation of Bisphenol A (BPA) were carried out in water samples by means photocatalytic and photo-oxidation methods in the presence of ZnO, TiO2 and SnO2 catalysts. The objective of this study was to develop an improved technique that can be used as a remediation procedure for a BPA-contaminated surface water and groundwater based on the UV solar radiation. The photodegradation of BPA in water performed under a low-intensity UV source mimics the UVC and UVA spectrum of solar radiation between 254 and 365 nm. The archived results reveal higher degradation rates observed in the presence of ZnO than with TiO2 and SnO2 catalysts during 20 h of irradiation. The intervention of the advanced photocatalytic oxidation (PCO) reduces the time of degradation to less than 1 h to reach a degradation rate of 90 % for BPA in water. The study proposes the use of ZnO as a competitor catalyst to the traditional TiO2, providing the most effective treatment of contaminated water with phenolic products.

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.

Innovative PCDD/F-containing gas stream generating system applied in catalytic decomposition of gaseous dioxins over V2O5-WO3/TiO2-based catalysts.

PubMed

Yang, Chia Cheng; Chang, Shu Hao; Hong, Bao Zhen; Chi, Kai Hsien; Chang, Moo Been

2008-10-01

Development of effective PCDD/F (polychlorinated dibenzo-p-dioxin and dibenzofuran) control technologies is essential for environmental engineers and researchers. In this study, a PCDD/F-containing gas stream generating system was developed to investigate the efficiency and effectiveness of innovative PCDD/F control technologies. The system designed and constructed can stably generate the gas stream with the PCDD/F concentration ranging from 1.0 to 100ng TEQ Nm(-3) while reproducibility test indicates that the PCDD/F recovery efficiencies are between 93% and 112%. This new PCDD/F-containing gas stream generating device is first applied in the investigation of the catalytic PCDD/F control technology. The catalytic decomposition of PCDD/Fs was evaluated with two types of commercial V(2)O(5)-WO(3)/TiO(2)-based catalysts (catalyst A and catalyst B) at controlled temperature, water vapor content, and space velocity. 84% and 91% PCDD/F destruction efficiencies are achieved with catalysts A and B, respectively, at 280 degrees C with the space velocity of 5000h(-1). The results also indicate that the presence of water vapor inhibits PCDD/F decomposition due to its competition with PCDD/F molecules for adsorption on the active vanadia sites for both catalysts. In addition, this study combined integral reaction and Mars-Van Krevelen model to calculate the activation energies of OCDD and OCDF decomposition. The activation energies of OCDD and OCDF decomposition via catalysis are calculated as 24.8kJmol(-1) and 25.2kJmol(-1), respectively.

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

Effect of TiO, nanoparticles on the interface in the PET-rubber composites.

PubMed

Vladuta, Cristina; Andronic, Luminita; Duta, Anca

2010-04-01

Usually, ceramic powders (SiO2, ZnO) are used as fillers for enhancing rubber mechanical strength. Poly-ethylene terephthalate (PET)-rubber nanocomposites were prepared by compression molding using titanium oxide (TiO2) nanoparticles as low content fillers (<2% wt). The interface properties of PET-rubber nanocomposites were studied before and after keeping the samples under UV-radiation for a week. UV-radiation has interesting potential for the photochemical modification of polymers and TiO2. The influence of UV radiation on the properties of the interface polymer-TiO2 nanoparticles was evaluated. The impact of nanoparticle aggregates on the nanometer to micrometer organization of PET-rubber composites was studied with Atomic Force Microscopy (AFM). The interface properties were explained by measuring the contact angles and surface tensions. The interactions between components of nanocomposites were investigated with Fourier Transform-Infrared (FTIR) and the effects of TiO2 nanoparticle on the interfaces and composites crystalline structure were evaluated by X-ray diffraction (XRD). The results proved that the TiO2 nanoparticles, in different weight percentages, did not alter the nanocomposites crystallinity or the average crystallites size, but improve the interface properties.

Preparation of 13X from Waste Quartz and Photocatalytic Reaction of Methyl Orange on TiO2/ZSM-5, 13X and Y-Zeolite.

PubMed

Wang, Jia-Jie; Jing, You-Hai; Ouyang, Tong; Chang, Chang-Tang

2015-08-01

TiO2 photocatalytic reactions not only remove a variety of organic pollutants via complete mineralization, but also destroy the bacterial cell wall and cell membrane, thus playing an important bactericidal role. However, the post-filtration procedures to separate nanometer-levels of TiO2 and the gradual inactivity of photocatalyst during continuous use are defects that limit its application. In this case, we propose loading TiO2 on zeolite for easy separation and 13X is considered as a promising one. In our study, 13X-zeolite was prepared by a hydrothermal method and the source of Si was extracted from waste quartz sand. For comparison, commercial zeolite with different microporous and mesoporous diameters (ZSM-5 and Y-zeolites) were also used as TiO2 supports. The pore size of the three kinds of zeolites are as follows: Y-zeolite > 13X > ZSM-5. Different TiO2 loading content over ZSM-5, 13X and Y-zeolite were prepared by the sol-gel method. XRD, FTIR, BET, UV-vis, TGA and SEM were used for investigation of material characteristics. In addition, the efficiencies of mineralization and photodegradation were studied in this paper. The effects of the loading ratio of TiO2 over zeolites, initial pH, and concentration on photocatalytic performance are investigated. The relationship between best loading content of TiO2 and pore size of the zeolite was studied. The possible roles of the ZSM-5, 13X-zeolites and Y-zeolites support on the reactions and the possible mechanisms of effects were also explored. The best loading content of TiO2 over ZSM-5, 13X and Y-zeolite was found to be 50 wt%, 12.5 wt% and 7 wt%, respectively. The optimum pH condition is 3 with TiO2 over ZSM-5, 13X-zeolites and Y-zeolites. The results showed that the degradation and mineralization efficiency of 12.5 wt%GT13X (TiO2 over 13X) after 90 min irradiation reached 57.9% and 22.0%, which was better than that of 7 wt%GTYZ (TiO2 over Y-zeolites) while much lower than that of 50 wt%GTZ (TiO2 over ZSM-5

Effect of Silica Particle Size on Texture, Structure, and Catalytic Performance of Cu/SiO2 Catalysts for Glycerol Hydrogenolysis

NASA Astrophysics Data System (ADS)

Qi, Ye Tong; Zhe, Chen Hong; Ning, Xiang

2018-03-01

The influences of carrier particle sizes of Cu/SiO2 catalysts for hydrogenolysis of glycerol were studied use mono-dispersed silica as models. Catalysts were prepared by precipitation method with the average size of the mono-dispersed silica supports varying of 10, 20, and 90 nm. Characterization of the catalysts show that the physical properties such as pore volume and BET surface area of the catalysts were largely affected by the carrier particle size of silica. However, the copper dispersion of the three samples were similar. XPS patterns show a difference in the chemical states of copper species, small carrier particle size induced formation of copper phyllosilicate, which benefits on the stability of copper species in reaction. The overall activity in the reaction of glycerol hydrogenolysis shows a correlation with the carrier particle size. The small carrier particles prevent the copper species from aggregation thus such catalysts exhibit good catalytic activity and stability.

ZnO nanoparticle catalysts for use in biodiesel production and method of making

DOEpatents

Yan, Shuli; Salley, Steven O; Ng, K. Y. Simon

2014-11-25

A method of forming a biodiesel product and a heterogeneous catalyst system used to form said product that has a high tolerance for the presence of water and free fatty acids (FFA) in the oil feedstock is disclosed. This catalyst system may simultaneously catalyze both the esterification of FAA and the transesterification of triglycerides present in the oil feedstock. The catalyst system is comprised of a mixture of zinc oxide and a second metal oxide. The zinc oxide includes a mixture of amorphous zinc oxide and zinc oxide nanocrystals, the zinc nanocrystals having a mean grain size between about 20 and 80 nanometers with at least one of the nanocrystals including a mesopore having a diameter of about 5 to 15 nanometers. Preferably, the second metal oxide is a lanthanum oxide, the lanthanum oxide being selected as one from the group of La.sub.2CO.sub.5, LaOOH, and combinations or mixtures thereof.

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.