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Sample records for dot cl hydrogen

  1. Effects of temperature and hydrogen-like impurity on the coherence time of RbCl parabolic quantum dot qubit

    NASA Astrophysics Data System (ADS)

    Xiao, Jing-Lin

    2016-02-01

    By using a variational method of Pekar type, the Fermi Golden Rule and the quantum statistics theory (VMPTFGRQST), we investigate the effects of the hydrogen-like impurity and temperature on the coherence time of a parabolic quantum dot (PQD) qubit with a hydrogen-like impurity at the center. We then derive the ground and the first excited states' (GFES) eigenenergies and the eigenfunctions in a PQD. A single qubit can be realized in this two-level quantum system. The phonon spontaneous emission causes the decoherence of the qubit. The numerical results show that the coherence time is a decreasing function of the temperature, the strength of the Coulombic impurity potential (CIP) and the polaron radius (PR).

  2. Decoherence time, hydrogenic-like impurity effect and Shannon entropy on polaron in RbCl triangular quantum dot qubit

    NASA Astrophysics Data System (ADS)

    Tiotsop, M.; Fotue, A. J.; Fautso, G. K.; Kenfack, C. S.; Fotsin, H. B.; Fai, L. C.

    2017-03-01

    Using Pekar variational method, Eigen energies of the ground and first excited states of the polaron in triangular bound and Coulomb potential quantum dot are derived in view of investigating the density of probability, the decoherence time and the Shannon entropy. Numerical analysis show that the decoherence time is decreasing function of polaron radius and the strength of the Coulombic impurity and the increase function of dispersion coefficient. These results suggest that the decrease of polaron radius and Coulombic impurity lead to the increase of coherence time. Also the entropy shows the oscillatory periodic evolution as function of the time due to the triangular form of the confinement. It's also seen that entropy is periodic for the lower value of Coulomb impurity parameter and for the higher value of the polaronic radius.

  3. Photoluminescent C-dots@RGO for sensitive detection of hydrogen peroxide and glucose.

    PubMed

    Yeh, Ting-Yin; Wang, Chen-I; Chang, Huan-Tsung

    2013-10-15

    We have demonstrated sensitive detections of hydrogen peroxide (H2O2) and glucose using reduced graphene oxide decorated with carbon dots (C-dots@RGO). The C-dots@RGO prepared from catechin (reducing agent and carbon source) and graphene oxide via hydrothermal routes possesses excitation-wavelength-dependence photoluminescence (PL) characteristics, with maximum excitation and emission wavelengths of 365 and 440 nm, respectively. The C-dots@RGO is stable in solution containing NaCl up to 350 mM, but is quenched by reactive oxygen species (ROS). ROS reacts with H2O2 and thus its PL quenching toward the C-dots@RGO is minimized. When using C-dots@RGO and glucose oxidase (GOx), the PL assay allows detection of glucose in the presence of 10 µM of bovine serum albumin, with linearity over a concentration range from 1 to 60 µM (r=0.99) and a limit of detection (at a signal-to-noise ratio of 3) of 140 nM. The practicality of this assay has been validated by determining the concentrations of glucose in serum and saliva samples, with results of 5.1 ± 0.6mM (n=3) and 117.9 ± 8.1 μM (n=3), respectively. Our simple and sensitive assay opens a new avenue of developing assays for various analytes using C-dots@RGO in conjunction with different enzymes.

  4. Effects of Shannon entropy and electric field on polaron in RbCl triangular quantum dot

    NASA Astrophysics Data System (ADS)

    M, Tiotsop; A, J. Fotue; S, C. Kenfack; N, Issofa; H, Fotsin; L, C. Fai

    2016-04-01

    In this paper, the time evolution of the quantum mechanical state of a polaron is examined using the Pekar type variational method on the condition of the electric-LO-phonon strong-coupling and polar angle in RbCl triangular quantum dot. We obtain the eigenenergies, and the eigenfunctions of the ground state, and the first excited state respectively. This system in a quantum dot can be treated as a two-level quantum system qubit and the numerical calculations are performed. The effects of Shannon entropy and electric field on the polaron in the RbCl triangular quantum dot are also studied.

  5. Computation of energy states of hydrogenic quantum dot with two-electrons

    SciTech Connect

    Yakar, Y.; Özmen, A. Çakır, B.

    2016-03-25

    In this study we have investigated the electronic structure of the hydrogenic quantum dot with two electrons inside an impenetrable potential surface. The energy eigenvalues and wavefunctions of the ground and excited states of spherical quantum dot have been calculated by using the Quantum Genetic Algorithm (QGA) and Hartree-Fock Roothaan (HFR) method, and the energies are investigated as a function of dot radius. The results show that as dot radius increases, the energy of quantum dot decreases.

  6. AgCl-doped CdSe quantum dots with near-IR photoluminescence.

    PubMed

    Kotin, Pavel Aleksandrovich; Bubenov, Sergey Sergeevich; Mordvinova, Natalia Evgenievna; Dorofeev, Sergey Gennadievich

    2017-01-01

    We report the synthesis of colloidal CdSe quantum dots doped with a novel Ag precursor: AgCl. The addition of AgCl causes dramatic changes in the morphology of synthesized nanocrystals from spherical nanoparticles to tetrapods and finally to large ellipsoidal nanoparticles. Ellipsoidal nanoparticles possess an intensive near-IR photoluminescence ranging up to 0.9 eV (ca. 1400 nm). In this article, we explain the reasons for the formation of the ellipsoidal nanoparticles as well as the peculiarities of the process. The structure, Ag content, and optical properties of quantum dots are also investigated. The optimal conditions for maximizing both the reaction yield and IR photoluminescence quantum yield are found.

  7. AgCl-doped CdSe quantum dots with near-IR photoluminescence

    PubMed Central

    Bubenov, Sergey Sergeevich; Mordvinova, Natalia Evgenievna; Dorofeev, Sergey Gennadievich

    2017-01-01

    We report the synthesis of colloidal CdSe quantum dots doped with a novel Ag precursor: AgCl. The addition of AgCl causes dramatic changes in the morphology of synthesized nanocrystals from spherical nanoparticles to tetrapods and finally to large ellipsoidal nanoparticles. Ellipsoidal nanoparticles possess an intensive near-IR photoluminescence ranging up to 0.9 eV (ca. 1400 nm). In this article, we explain the reasons for the formation of the ellipsoidal nanoparticles as well as the peculiarities of the process. The structure, Ag content, and optical properties of quantum dots are also investigated. The optimal conditions for maximizing both the reaction yield and IR photoluminescence quantum yield are found. PMID:28685116

  8. Solvothermal method to prepare graphene quantum dots by hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Tian, Renbing; Zhong, Suting; Wu, Juan; Jiang, Wei; Shen, Yewen; Jiang, Wei; Wang, Tianhe

    2016-10-01

    Graphene quantum dots (GQDs) have been synthesized by different chemical methods in recent years. For conventional chemical methods, it is inevitable to introduce a large amount of impurities in the preparation process. Long time of dialysis process increases the time cost extremely. Herein, we report a one-step solvothermal method for synthesizing GQDs with the application of hydrogen peroxide in N, N-Dimethylformamide (DMF) environment, which completely avoids the use of concentrated sulphuric acid and nitric acid to treat raw material and introduces no impurity in whole preparation process simultaneously for the first time. Pure GQDs can be obtained after evaporation/redissolution and filtration process with a strong blue emission at 15% quantum yield. This solvothermal method, not requiring dialysis process and complicated equipments, exhibits simple, eco-friendly and low time-cost properties. Besides high quantum yields, the as-prepared GQDs also show good photoluminescence stability in different pH conditions. The optical properties, morphology and structure of GQDs were studied by various equipments, implying potential application in biomedical fields and electronic device.

  9. Solar-Driven Hydrogen Peroxide Production Using Polymer-Supported Carbon Dots as Heterogeneous Catalyst

    NASA Astrophysics Data System (ADS)

    Gogoi, Satyabrat; Karak, Niranjan

    2017-10-01

    Safe, sustainable, and green production of hydrogen peroxide is an exciting proposition due to the role of hydrogen peroxide as a green oxidant and energy carrier for fuel cells. The current work reports the development of carbon dot-impregnated waterborne hyperbranched polyurethane as a heterogeneous photo-catalyst for solar-driven production of hydrogen peroxide. The results reveal that the carbon dots possess a suitable band-gap of 2.98 eV, which facilitates effective splitting of both water and ethanol under solar irradiation. Inclusion of the carbon dots within the eco-friendly polymeric material ensures their catalytic activity and also provides a facile route for easy catalyst separation, especially from a solubilizing medium. The overall process was performed in accordance with the principles of green chemistry using bio-based precursors and aqueous medium. This work highlights the potential of carbon dots as an effective photo-catalyst.

  10. Dynamic [Cl(-)](i) measurement with chloride sensing quantum dots nanosensor in epithelial cells.

    PubMed

    Wang, Yuchi; Mao, Hua; Wong, Lid B

    2010-02-05

    We have synthesized a chloride sensing quantum dots (QD) nanosensor, Cl-QD, for the dynamic measurements of chloride ion concentration in the millimolar range, a sensitivity that is applicable to most physiological intracellular chloride ion concentration ([Cl(-)](i)) measurements in epithelial cells. The Cl-QD is synthesized by conjugating an anion receptor, 1-(2-mercapto-ethyl)-3-phenyl-thiourea (MEPTU) to a water soluble CdSe/ZnS QD at an emission wavelength of 620 nm. Upon binding of chloride ions to the Cl-QD, a photo-induced electron transfer mechanism caused the fluorescence of the QD to quench. This resulted in an inversely proportional relationship between the chloride ion concentration and the fluorescence intensity of the Cl-QD. We have utilized this Cl-QD to measure [Cl(-)](i) in T84 and CF-PAC cultured cells, with either the C1C-2 or CFTR chloride channels being manipulated by pharmacological chloride channel activators and inhibitors. Activations of C1C-2 and CFTR chloride channels in T84 by the respective lubiprostone and genistein caused predictive increases in the fluorescence of the Cl-QD, i.e., a decrease of [Cl(-)](i). Conversely, glibenclamide, a chloride channel inhibitor, applied to the CF-PAC cells caused a predictable decrease in the fluorescence of Cl-QD due to the increase of [Cl(-)](i). These are the first data in using QD-based chloride ion sensors for dynamic measurements of intracellular chloride ion concentrations in epithelial cells.

  11. Dynamic [Cl-]i measurement with chloride sensing quantum dots nanosensor in epithelial cells

    NASA Astrophysics Data System (ADS)

    Wang, Yuchi; Mao, Hua; Wong, Lid B.

    2010-02-01

    We have synthesized a chloride sensing quantum dots (QD) nanosensor, Cl-QD, for the dynamic measurements of chloride ion concentration in the millimolar range, a sensitivity that is applicable to most physiological intracellular chloride ion concentration ([Cl-]i) measurements in epithelial cells. The Cl-QD is synthesized by conjugating an anion receptor, 1-(2-mercapto-ethyl)-3-phenyl-thiourea (MEPTU) to a water soluble CdSe/ZnS QD at an emission wavelength of 620 nm. Upon binding of chloride ions to the Cl-QD, a photo-induced electron transfer mechanism caused the fluorescence of the QD to quench. This resulted in an inversely proportional relationship between the chloride ion concentration and the fluorescence intensity of the Cl-QD. We have utilized this Cl-QD to measure [Cl-]i in T84 and CF-PAC cultured cells, with either the C1C-2 or CFTR chloride channels being manipulated by pharmacological chloride channel activators and inhibitors. Activations of C1C-2 and CFTR chloride channels in T84 by the respective lubiprostone and genistein caused predictive increases in the fluorescence of the Cl-QD, i.e., a decrease of [Cl-]i. Conversely, glibenclamide, a chloride channel inhibitor, applied to the CF-PAC cells caused a predictable decrease in the fluorescence of Cl-QD due to the increase of [Cl-]i. These are the first data in using QD-based chloride ion sensors for dynamic measurements of intracellular chloride ion concentrations in epithelial cells.

  12. Green synthesis of near infrared core/shell quantum dots for photocatalytic hydrogen production

    NASA Astrophysics Data System (ADS)

    Zhao, Haiguang; Jin, Lei; Zhou, Yufeng; Bandar, AlOtaibi; Fan, Zhiyuan; Govorov, Alexander O.; Mi, Zetian; Sun, Shuhui; Rosei, Federico; Vomiero, Alberto

    2016-12-01

    Quantum dots (QDs) are attractive systems for potential applications in future solar energy technologies, due to their optical properties which are tunable as a function of size and composition. In this study, we synthesized PbS QDs with first excitonic peak in the range 1060 to 1300 nm using a PbCl2/sulfur molar ratio of 10:1. The first excitonic absorption peak from 1300 to 950 nm of the PbS/CdS core/shell QDs can be further synthesized via the cation exchange approach. Our method resulted in high quantum yield, good stability, monodisperse QD solutions with a full surface coverage by excess Cd cations. In addition, we used our core/shell QDs in a photoelectrochemical cell for hydrogen generation. This heterostructure exhibited a saturated photocurrent as high as 3.3 mA cm-2, leading to ˜29 ml cm-2 d-1 hydrogen generation, indicating the strong potential of our core/shell QDs for applications in water splitting.

  13. Quantum Dot Superlattice Enabled Rational Design in Optoelectronics and Hydrogen Generation

    DTIC Science & Technology

    2014-11-25

    in Optoelectronics and Hydrogen Generation 5a. CONTRACT NUMBER FA2386-13-1-4074 5b. GRANT NUMBER Grant AOARD-134074 5c. PROGRAM ELEMENT...FA2386-13-1-4074 “Quantum Dot Superlattice Enabled Rational Design in Optoelectronics and Hydrogen Generation” April 21, 2014 PI and Co-PI...impacts on optoelectronic devices, and hydrogen generation under sunlight. Introduction: Intensive research works have been made on inorganic

  14. Evidence for formation of multi-quantum dots in hydrogenated graphene

    PubMed Central

    2012-01-01

    We report the experimental evidence for the formation of multi-quantum dots in a hydrogenated single-layer graphene flake. The existence of multi-quantum dots is supported by the low-temperature measurements on a field effect transistor structure device. The resulting Coulomb blockade diamonds shown in the color scale plot together with the number of Coulomb peaks exhibit the characteristics of the so-called ‘stochastic Coulomb blockade’. A possible explanation for the formation of the multi-quantum dots, which is not observed in pristine graphene to date, was attributed to the impurities and defects unintentionally decorated on a single-layer graphene flake which was not treated with the thermal annealing process. Graphene multi-quantum dots developed around impurities and defect sites during the hydrogen plasma exposure process. PMID:22898058

  15. Luminescent manganese-doped CsPbCl3 perovskite quantum dots

    NASA Astrophysics Data System (ADS)

    Lin, Chun Che; Xu, Kun Yuan; Wang, Da; Meijerink, Andries

    2017-04-01

    Nanocrystalline cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I) form an exciting new class of semiconductor materials showing quantum confinement. The emission color can be tuned over the full visible spectral region making them promising for light‒emitting applications. Further control over the optical and magnetic properties of quantum dots (QDs) can be achieved through doping of transition metal (TM) ions such as Mn2+ or Co2+. Here we demonstrate how, following QD synthesis in the presence of a Mn‒precursor, dropwise addition of silicon tetrachloride (SiCl4) to the QDs in toluene results in the formation of Mn‒doped CsPbCl3 QDs showing bright orange Mn2+ emission around 600 nm. Evidence for successful doping is provided by excitation spectra of the Mn2+ emission, with all features of the CsPbCl3 QD absorption spectrum and a decrease of the 410 nm excitonic emission life time with increasing Mn‒concentration, giving evidence for enhanced exciton to Mn2+ energy transfer. As a doping mechanism we propose a combination of surface etching and reconstruction and diffusion doping. The presently reported approach provides a promising avenue for doping TM ions into perovskites QDs enabling a wider control over optical and magnetic properties for this new class of QDs.

  16. Quantum-dot-sensitized TiO2 inverse opals for photoelectrochemical hydrogen generation.

    PubMed

    Cheng, Chuanwei; Karuturi, Siva Krishna; Liu, Lijun; Liu, Jinping; Li, Hongxing; Su, Liap Tat; Tok, Alfred Iing Yoong; Fan, Hong Jin

    2012-01-09

    A new nanoarchitecture photoelectrode design comprising CdS quantum-dot-sensitized, optically and electrically active TiO(2) inverse opals is developed for photoelectrochemical water splitting. The photoelectrochemical performance shows high photocurrent density (4.84 mA cm(-2) at 0 V vs. Ag/AgCl) under simulated solar-light illumination.

  17. Cooperatively enhanced ionic hydrogen bonds in Cl-(CH3OH)(1-3)Ar clusters.

    PubMed

    Beck, Jordan P; Lisy, James M

    2010-09-23

    Infrared predissociation (IRPD) spectra of Cl−(CH3OH)1-3Ar and Cl-(CH3OD)1-3Ar were obtained in the OH and CH stretching regions. The use of methanol-d1 was necessary to distinguish between CH stretches and hydrogen-bonded OH features. The spectra of Cl-(CH3OH)2-3Ar show intense features at frequencies lower than the CH stretches, indicating structures with very strong hydrogen bonds. These strong hydrogen bonds arise from structures in which a Cl-···methanol ionic hydrogen bond is cooperatively enhanced by the presence of a second shell and, in the case of Cl-(CH3OH)3Ar, a third shell methanol. The strongest hydrogen bond is observed in the Cl-(CH3OH)3Ar spectrum at 2733 cm-1, shifted a remarkable -948 cm-1 from the neutral, gas-phase methanol value. Harmonic, ab initio frequency calculations are not adequate in describing these strong hydrogen bonds. Therefore, we describe a simple computational approach to better approximate the hydrogen bond frequencies. Overall, the results of this study indicate that high-energy isomers are very efficiently trapped using our experimental method of introducing Cl- into neutral, cold methanol-argon clusters.

  18. Enhancement of electrochemical hydrogen storage in NiCl2-FeCl3-PdCl2-graphite intercalation compound effected by chemical exfoliation

    NASA Astrophysics Data System (ADS)

    Skowroński, J. M.; Rozmanowski, T.; Krawczyk, P.

    2013-06-01

    In the present work, a quaternary NiCl2-FeCl3-PdCl2-graphite intercalation compound (NiCl2-FeCl3-PdCl2-GIC) was successfully synthesized by molten salts method. A part of this compound was subsequently subjected to chemical exfoliation to obtain expanded compound (NiCl2-FeCl3-PdCl2-EGIC). The changes created in crystalline structure, morphology and chemical composition of GIC due to exfoliation were examined by XRD, SEM and EDS techniques and then related to electrochemical behaviour of electrodes made of the original and exfoliated compound. The results of electrochemical studies carried out by the cyclic voltammetry (CV) method in 6 M KOH solution showed that current charges of all the cathodic and anodic peaks recorded for NiCl2-FeCl3-PdCl2-EGIC are considerably higher already in the first two cycles as compared to those observed for the original NiCl2-FeCl3-PdCl2-GIC. This improvement is ascribed to chemical exfoliation leading to a tremendous development of surface area of the compound due to the splitting and wrinkling of graphite flakes followed by easier access of hydroxyl ions of the electrolyte to active species of intercalates preserved between the graphene interspaces as well as expelled from the graphite interspacing. A large anodic peak was recorded on CV curves after the potentiostatic polarization of electrodes at the potential of -1.2 V where the reaction of hydrogen sorption/evolution occurs and intercalates highly dispersed in the graphite matrix are reduced to a metal form. This peak mainly corresponding to the recovery of hydrogen stored in the electrode appeared to be over five times higher for electrode made of exfoliated compound. This significant enhancement of the hydrogen storage capacity is attributed to electrochemically active Pd nanoparticles highly dispersed in porous structure of exfoliated compound and likely functioning in synergy with Ni/Fe clusters.

  19. EVALUATION OF RADIOLYSIS INDUCED HYDROGEN GENERATION IN DOT 6M DRUMS FROM INTEC

    SciTech Connect

    Vinson, D

    2007-06-18

    Three DOT 6M 30-gallon drums are scheduled to be shipped from the Idaho Nuclear Technology Engineering Center (INTEC) at the Idaho National Laboratory (INL) to L-Area at the Savannah River Site (SRS). These three drums contain radioactive materials that resulted from the material recovery effort following a small explosion that had occurred in the Idaho Chemical Processing Plant (ICPP) hot chemistry laboratory (HCL). In support of the shipment and subsequent storage of the three DOT 6M drums, an evaluation of the potential for molecular hydrogen production in the drums has been completed and documented herein. The potential sources of hydrogen evaluated in the current report include radiolytic decomposition of polymeric materials in the DOT 6M drums No.3031 and No.3598 and the radiolytic decomposition of water in drum No.20102. No other potential sources have been identified based upon reported drum contents and packaging configuration. A parametric approach was used to evaluate the maximum quantity of molecular hydrogen that can be expected to evolve in two DOT 6M 30-gallon drums in support of receipt and subsequent interim storage prior to canyon processing. These drums are two of three drums scheduled for shipment from INTEC to SRS as part of the decommissioning effort of the INTEC facility. The three DOT 6M drums will be received at L-Area in SRS and stored for up to 13-years prior to final disposition at HB-Line in 2020. Results of the current analysis do not include parametric analysis of drum No.20102 containing 114/133 SAL (salvage) which contains UO{sub 3} powder. This drum has not been identified as containing polymeric materials and a conservative calculation indicates that the maximum gross molecular hydrogen production due to the radiolysis of adsorbed moisture would yield a production rate of 5.1-cm{sup 3}/yr, driven primarily by the large surface are to volume ratio of the oxide powder. The remaining two drums, No.3031 and No.3598 contain polymer

  20. Nonlinear optical rectification of a hydrogenic impurity in asymmetric lens-shaped quantum dots

    NASA Astrophysics Data System (ADS)

    Ahadi, M. A.; Vahdani, M. R. K.; Alipour, E.

    2012-09-01

    The compact density matrix approach and an iterative method are used to calculate the nonlinear optical rectification coefficient (ORC) of a hydrogenic impurity in an asymmetric lens-shaped quantum dot (LSQD). Numerical results are presented for a typical GaAs LSQD. The effects of the size of LSQD, incident photon energy and asymmetry of QDs on the ORC are investigated. The results show that the ORC increases with decreasing the mirror symmetry of the QD. In addition, the ORC increases and its peak shifts to lower energies when the dot size is increased.

  1. Double-sided CdS and CdSe quantum dot co-sensitized ZnO nanowire arrays for photoelectrochemical hydrogen generation.

    PubMed

    Wang, Gongming; Yang, Xunyu; Qian, Fang; Zhang, Jin Z; Li, Yat

    2010-03-10

    We report the design and characterization of a novel double-sided CdS and CdSe quantum dot cosensitized ZnO nanowire arrayed photoanode for photoelectrochemical (PEC) hydrogen generation. The double-sided design represents a simple analogue of tandem cell structure, in which the dense ZnO nanowire arrays were grown on an indium-tin oxide substrate followed by respective sensitization of CdS and CdSe quantum dots on each side. As-fabricated photoanode exhibited strong absorption in nearly the entire visible spectrum up to 650 nm, with a high incident-photon-to-current-conversion efficiency (IPCE) of approximately 45% at 0 V vs Ag/AgCl. On the basis on a single white light illumination of 100 mW/cm(2), the photoanode yielded a significant photocurrent density of approximately 12 mA/cm(2) at 0.4 V vs Ag/AgCl. The photocurrent and IPCE were enhanced compared to single quantum dot sensitized structures as a result of the band alignment of CdS and CdSe in electrolyte. Moreover, in comparison to single-sided cosensitized layered structures, this double-sided architecture that enables direct interaction between quantum dot and nanowire showed improved charge collection efficiency. Our result represents the first double-sided nanowire photoanode that integrates uniquely two semiconductor quantum dots of distinct band gaps for PEC hydrogen generation and can be possibly applied to other applications such as nanostructured tandem photovoltaic cells.

  2. Carbon quantum dots coated BiVO{sub 4} inverse opals for enhanced photoelectrochemical hydrogen generation

    SciTech Connect

    Nan, Feng; Shen, Mingrong; Fang, Liang E-mail: lfang@suda.edu.cn; Kang, Zhenhui E-mail: lfang@suda.edu.cn; Wang, Junling

    2015-04-13

    Carbon quantum dots (CQDs) coated BiVO{sub 4} inverse opal (io-BiVO{sub 4}) structure that shows dramatic improvement of photoelectrochemical hydrogen generation has been fabricated using electrodeposition with a template. The io-BiVO{sub 4} maximizes photon trapping through slow light effect, while maintaining adequate surface area for effective redox reactions. CQDs are then incorporated to the io-BiVO{sub 4} to further improve the photoconversion efficiency. Due to the strong visible light absorption property of CQDs and enhanced separation of the photoexcited electrons, the CQDs coated io-BiVO{sub 4} exhibit a maximum photo-to-hydrogen conversion efficiency of 0.35%, which is 6 times higher than that of the pure BiVO{sub 4} thin films. This work is a good example of designing composite photoelectrode by combining quantum dots and photonic crystal.

  3. Carbon quantum dots coated BiVO4 inverse opals for enhanced photoelectrochemical hydrogen generation

    NASA Astrophysics Data System (ADS)

    Nan, Feng; Kang, Zhenhui; Wang, Junling; Shen, Mingrong; Fang, Liang

    2015-04-01

    Carbon quantum dots (CQDs) coated BiVO4 inverse opal (io-BiVO4) structure that shows dramatic improvement of photoelectrochemical hydrogen generation has been fabricated using electrodeposition with a template. The io-BiVO4 maximizes photon trapping through slow light effect, while maintaining adequate surface area for effective redox reactions. CQDs are then incorporated to the io-BiVO4 to further improve the photoconversion efficiency. Due to the strong visible light absorption property of CQDs and enhanced separation of the photoexcited electrons, the CQDs coated io-BiVO4 exhibit a maximum photo-to-hydrogen conversion efficiency of 0.35%, which is 6 times higher than that of the pure BiVO4 thin films. This work is a good example of designing composite photoelectrode by combining quantum dots and photonic crystal.

  4. Non-extensive entropy and properties of polaron in RbCl delta quantum dot under an applied electric field and Coulombic impurity

    NASA Astrophysics Data System (ADS)

    Tiotsop, M.; Fotue, A. J.; Fotsin, H. B.; Fai, L. C.

    2017-08-01

    Bound polaron in RbCl delta quantum dot under electric field and Coulombic impurity were considered. The ground and first excited state energy were derived by employing Pekar variational and unitary transformation methods. Applying Fermi golden rule, the expression of temperature and polaron lifetime were derived. The decoherence was studied trough the Tsallis entropy. Results shows that decreasing (or increasing) the lifetime increases (or decreases) the temperature and delta parameter (electric field strength and hydrogenic impurity). This suggests that to accelerate quantum transition in nanostructure, temperature and delta have to be enhanced. The improvement of electric field and coulomb parameter, increases the lifetime of the delta quantum dot qubit. Energy spectrum of polaron increases with increase in temperature, electric field strength, Coulomb parameter, delta parameter, and polaronic radius. The control of the delta quantum dot energies can be done via the electric field, coulomb impurity, and delta parameter. Results also show that the non-extensive entropy is an oscillatory function of time. With the enhancement of delta parameter, non-extensive parameter, Coulombic parameter, and electric field strength, the entropy has a sinusoidal increase behavior with time. With the study of decoherence through the Tsallis entropy, it may be advised that to have a quantum system with efficient transmission of information, the non-extensive and delta parameters need to be significant. The study of the probability density showed an increase from the boundary to the center of the dot where it has its maximum value and oscillates with period T0 = ℏ / ΔE with the tunneling of the delta parameter, electric field strength, and Coulombic parameter. The results may be very helpful in the transmission of information in nanostructures and control of decoherence

  5. Investigation of the hydrogenation of SiCl4

    NASA Technical Reports Server (NTRS)

    Mui, J. Y. P.; Seyferth, D.

    1981-01-01

    A laboratory scale pressure reactor was constructed to study the 3 SiCl + 2H2 + Si yields 4 SiHCl3 reaction at pressures up to 500 psig. Reaction kinetic measurements were carried out as a function of reactor pressure, reaction temperature and H2/SiCl4 feed ratio. Based on the reaction kinetic data, the hydroclorination of SiCl4 and m.g. silicon metal is found to be an efficient process to produce SiHCl3 in good conversions and in high yields. Copper is an effective catalyst. Results of the corrosion study show that conventional nickel chromium alloys are suitable material of construction for the hydrochlorination reactor. The hydrochlorination reaction is relatively insensitive to external process parameters such as silicon particle size distribution and the impurities in the m.g. silicon metal.

  6. Atmospheric chemistry of the reaction ClO + O2 reversible reaction ClO (center dot) O2: Where it stands, what needs to be done, and why?

    NASA Technical Reports Server (NTRS)

    Prasad, Sheo S.; Lee, Timothy J.

    1994-01-01

    Possible existence and chemistry of ClO (center dot) O2 was originally proposed to explain the Norrish-Neville effect that O2 suppresses chlorine photosensitized loss of ozone. It was also thought that ClO (center dot) O2 might have some atmospheric chemistry significance. Recently, doubts have been cast on this proposal, because certain laboratory data seem to imply that the equilibrium constant of the title reaction is so small that ClO (center dot) O2 may be too unstable to matter. However, those data create only a superficial illusion to that effect, because on a closer analysis they do not disprove a moderately stable and chemically significant ClO (center dot) O2. Furthermore, our state-of-the-science accurate computational chemistry calculations also suggest that ClO (center dot) O2 may be a weakly bound ClOOO radical with a reactive (2)A ground electronic state. There is therefore a need to design and perform definitive experimental tests of the existence and chemistry of the ClO (center dot) O2 species, which we discuss and which have the potential to mediate the chlorine-catalyzed stratospheric ozone depletion.

  7. Atmospheric chemistry of the reaction ClO + O2 reversible reaction ClO (center dot) O2: Where it stands, what needs to be done, and why?

    NASA Technical Reports Server (NTRS)

    Prasad, Sheo S.; Lee, Timothy J.

    1994-01-01

    Possible existence and chemistry of ClO (center dot) O2 was originally proposed to explain the Norrish-Neville effect that O2 suppresses chlorine photosensitized loss of ozone. It was also thought that ClO (center dot) O2 might have some atmospheric chemistry significance. Recently, doubts have been cast on this proposal, because certain laboratory data seem to imply that the equilibrium constant of the title reaction is so small that ClO (center dot) O2 may be too unstable to matter. However, those data create only a superficial illusion to that effect, because on a closer analysis they do not disprove a moderately stable and chemically significant ClO (center dot) O2. Furthermore, our state-of-the-science accurate computational chemistry calculations also suggest that ClO (center dot) O2 may be a weakly bound ClOOO radical with a reactive (2)A ground electronic state. There is therefore a need to design and perform definitive experimental tests of the existence and chemistry of the ClO (center dot) O2 species, which we discuss and which have the potential to mediate the chlorine-catalyzed stratospheric ozone depletion.

  8. Diamagnetic susceptibility of an off-center hydrogenic donor in pyramid-like and cone-like quantum dots

    NASA Astrophysics Data System (ADS)

    Avazzadeh, Z.; Bahramiyan, H.; Khordad, R.; Mohammadi, S. A.

    2016-04-01

    In this study, the diamagnetic susceptibility of an off-center hydrogenic donor impurity confined by pyramid and cone-like quantum dots has been investigated. To this end, the finite-element method and the Arnoldi algorithm are used to find energy eigenvalues and eigenvectors of the systems. Then, the effect of impurity position and dot size has been investigated on the diamagnetic susceptibility. We have found that the diamagnetic susceptibility has a maximum around the impurity position 4nm for two quantum dots. The diamagnetic susceptibility in the cone-like quantum dot is smaller than that in the pyramid quantum dot. Numerical studies reveal that the diamagnetic susceptibility depends strongly on the geometry of the dot.

  9. Photocatalytic activity of quantum dots incorporated in molecular sieves for generation of hydrogen.

    PubMed

    Pourahmad, Afshin

    2012-08-01

    MCM-41 molecular sieve coupled with lead sulfide quantum dots (PbS-MCM-41) was prepared by ion-exchange method. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis spectroscopy, infrared spectroscopy (IR) and BET (Brunauer-Emmett-Teller) experiments. Exciton absorption peak at higher energy than the fundamental absorption edge of bulk lead sulfide indicates quantum confinement effects in quantum dots as a consequence of their small size. The hydrogen production rate from water photocatalytic decomposition under visible light irradiation (λ>400nm) over PbS nanoparticles formed in mesoporous material was much higher compared to the bulk PbS. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. Development of carbon dots modified fluorescent molecular imprinted Polymer@Ag/AgCl nanoparticle for hepatocellular carcinoma marker

    NASA Astrophysics Data System (ADS)

    Karfa, Paramita; Madhuri, Rashmi; Sharma, Prashant K.

    2017-05-01

    In this work, a sensitive and selective fluorescent molecularly imprinted polymer (MIP) was developed for detection of hepatocellular carcinoma (HCC) biomarker i.e. alpha feto protein (AFP) using Ag/AgCl as platform. Here, the carbon dots and Ag/AgCl nanoparticles were functionalized with vinyl groups and used as functional monomer for synthesis of AFP-imprinted polymer. The imprinted polymer shows a linear range of 3.96 ng mL-1 to 80.0 ng mL-1 with detection limit of 0.42 ng mL-1.The adsorption property of the MIP@Ag/AgCl was studied and shows the high affinity binding towards their target analyte without any cross-reactivity and false-positive or false-negative results.

  11. Linear and nonlinear optical properties of a hydrogenic donor in lens-shaped quantum dots

    NASA Astrophysics Data System (ADS)

    Vahdani, M. R. K.; Rezaei, G.

    2009-08-01

    Optical transitions in a Lens-Shaped Quantum Dot (LSD) are investigated in the presence of a hydrogenic impurity. The electronic wave functions are obtained analytically and the energy eigenvalues are calculated numerically. The density matrix formulation with the intersubband relaxation are used to evaluate the (linear and third order nonlinear) absorption coefficient (AC) and the change in the refractive indices (RI) analytically. The effect of the size of the LSD and optical intensity on the AC and RI are investigated. It is found that AC and RI are strongly affected by the optical intensity and the size of the LSD.

  12. CsPbxMn1-xCl3 Perovskite Quantum Dots with High Mn Substitution Ratio.

    PubMed

    Liu, Huiwen; Wu, Zhennan; Shao, Jieren; Yao, Dong; Gao, Hang; Liu, Yi; Yu, Weili; Zhang, Hao; Yang, Bai

    2017-02-28

    CsPbX3 (X = Cl, Br, I) perovskite quantum dots (QDs) are potential emitting materials for illumination and display applications, but toxic Pb is not environment- and user-friendly. In this work, we demonstrate the partial replacement of Pb with Mn through phosphine-free hot-injection preparation of CsPbxMn1-xCl3 QDs in colloidal solution. The Mn substitution ratio is up to 46%, and the as-prepared QDs maintain the tetragonal crystalline structure of the CsPbCl3 host. Meaningfully, Mn substitution greatly enhances the photoluminescence quantum yields of CsPbCl3 from 5 to 54%. The enhanced emission is attributed to the energy transfer of photoinduced excitons from the CsPbCl3 host to the doped Mn, which facilitates exciton recombination via a radiative pathway. The intensity and position of this Mn-related emission are also tunable by altering the experimental parameters, such as reaction temperature and the Pb-to-Mn feed ratio. A light-emitting diode (LED) prototype is further fabricated by employing the as-prepared CsPbxMn1-xCl3 QDs as color conversion materials on a commercially available 365 nm GaN LED chip.

  13. Application of non-extensive entropy to study of decoherence of RbCl quantum dot qubit: Tsallis entropy

    NASA Astrophysics Data System (ADS)

    Khordad, R.; Rastegar Sedehi, H. R.

    2017-01-01

    In this work, an electron which is strongly coupled to the LO-phonon in triangular quantum dots with Coulomb impurity is considered. The eigenenergies and eigenfunctions of the ground and the first-excited states of the electron are obtained using the Pekar variational method. We have studied decoherence of RbCl quantum dot qubit using the non-extensive entropy (Tsallis entropy) for different values of Coulomb impurity parameter, polaronic radius and electron-LO phonon coupling strength. Numerical analysis shows that the entropy has the oscillatory periodic evolution as function of the time due to the triangular form of the confinement. It is found that entropy oscillates under a standing wave envelope with increasing the Coulomb impurity parameter, electron-LO phonon coupling strength and polaronic radius. With reducing the non-extensive parameter q, the entropy increases and thereby we can miss information about the system.

  14. Formation of the bismuth-bilayer film at BiTeCl surface by atomic hydrogen deposition

    NASA Astrophysics Data System (ADS)

    Shvets, I. A.; Eremeev, S. V.; Chulkov, E. V.

    2017-07-01

    On the base of density functional theory calculations we investigate the atomic hydrogen adsorption on Cl- and Te-terminations of giant Rashba-split semiconductor BiTeCl and show that it leads to removal of the halogen and chalcogen top layer atoms by means of desorption of HCl and H2Te molecules. This mechanism accompanied by swapping of next Bi and deeper Te(Cl) layers with subsequent hydrogen-induced removal of Te(Cl) layer results in formation of Bi2 layer covering BiTeCl. The electronic structure of the formed Bi2@BiTeCl[Cl-term] and Bi2@BiTeCl[Te-term] interfaces shows a strong hybridization between Bi2-derived spin-split bands and BiTeCl interface states.

  15. Detecting hydrogen using graphene quantum dots/WO3 thin films

    NASA Astrophysics Data System (ADS)

    Fardindoost, Somayeh; Iraji zad, Azam; Sadat Hosseini, Zahra; Hatamie, Shadie

    2016-11-01

    In the present work we report an approach to resistive hydrogen sensing based on graphene quantum dots (GQDs)/WO3 thin films that work reproducibly at low temperatures. GQDs were chemically synthesized and evenly dispersed in WO3 solution with 1:1 molar ratio. The structural evaluation and crystallization of the prepared films was studied by x-ray diffraction, Raman and scanning electron microscopy (SEM) techniques. The SEM images showed uniform distribution of the GQDs in WO3 films with sizes around 50 nm. Raman experiment showed the GQDs are partially reduced with high edge defects as hydroxyl and carboxyl groups which involve both in bridging between WO3 grains via bindings as well as interacting with target gas molecules. GQDs can develop an electron conductive network and shorten the current transport paths inside the sensitive films. As a result, they improved the poor electrical properties and charge transfer of pure WO3. Resistive hydrogen sensing showed significant decrease in the working temperature for GQDs/WO3 films compared to pure WO3 films. The working temperature of about 150 °C with 15 and 40 s response and recovery times are significant characteristics of the introduced sensing structure. Then palladium (Pd) was added as a catalyst in GQDs/WO3 film to make the sensing materials selective to hydrogen. Pd doped film worked at temperature of 120 °C with high selectivity and improved response magnitude to hydrogen gas.

  16. The synthesis of rhodium/carbon dots nanoparticles and its hydrogenation application

    NASA Astrophysics Data System (ADS)

    Zhang, Jie; Chen, Yao; Tan, Jing; Sang, Haitao; Zhang, Liqun; Yue, Dongmei

    2017-02-01

    Rhodium (Rh) nanoparticles have been widely used as potent hydrogenation catalysts. Herein, a new convenient method has been developed to synthesize rhodium nanoparticles, in which carbon dots (CDs) were used both as stabilizing and reducing agents. The fluorescent CDs were prepared by microwave-assisted heating method using chitosan as raw material and the presences of hydroxyl and carbonyl on the surface of CDs were supported by FTIR spectra. Subsequently, CDs could directly reduce Rh3+ to Rh0 without additional reducing and stabilizing agents by heating Rh3+ with CDs for 1 h at 120 °C. The resulting Rh nanoparticles have an average size of about 2.8 nm and the Rh/CDs nanoparticles also retain the fluorescent property of CDs. The hydrogenation activities of Rh/CDs nanoparticles were investigated. The results demonstrated that the nanoparticles had highly catalytic activity in the hydrogenation reaction of hydroxyl-terminated polybutadiene (HTPB) and hydroxy-terminated butadiene-acrylonitrile (HTBN). Also, the presence of CDs could improve the fluorescent properties of rubbers after hydrogenation.

  17. Effects of Temperature and Magnetic Field on the Coherence Time of a RbCl Parabolic Quantum Dot Qubit

    NASA Astrophysics Data System (ADS)

    Sun, Yong; Ding, Zhao-Hua; Xiao, Jing-Lin

    2017-01-01

    Employing the Pekar variational method, quantum statistics theory and the Fermi golden rule, the temperature and magnetic field effects on the qubit in rubidium chloride (RbCl) parabolic quantum dots (PQDs) are investigated. We then obtain the eigenenergies and corresponding eigenfunctions of ground and first-excited states coupled strongly to an electron to bulk longitudinal optical phonons in a RbCl PQD with applied magnetic field. A two-level system of PQDs may be regarded as a single qubit. The spontaneous emission of phonons causes the qubit decoherence. The numerical results indicate that the coherence time decreases with elevating temperature. The coherence increases the effective confinement length, whereas there is a decrease of the magnetic field's cyclotron frequency.

  18. 35Cl NQR study of geometric isotope effect in hydrogen bonded chlorooctanes

    NASA Astrophysics Data System (ADS)

    Zdanowska-Fraçzek, M.

    1994-05-01

    35Cl NQR spectroscopy was applied to study the geometric isotope effect in a wide range of 2 : 1 salts of chloroacetic, trichloroacetic and difluorochloroacetic acids. The NQR results were correlated with IR spectroscopic studies, which provided information on the potential shape for proton motion. The NQR results were discussed on the basis of a variational correlated ground state wave function theory of a single hydrogen bond.

  19. Investigation of hydrogen plasma treatment for reducing defects in silicon quantum dot superlattice structure with amorphous silicon carbide matrix

    PubMed Central

    2014-01-01

    We investigate the effects of hydrogen plasma treatment (HPT) on the properties of silicon quantum dot superlattice films. Hydrogen introduced in the films efficiently passivates silicon and carbon dangling bonds at a treatment temperature of approximately 400°C. The total dangling bond density decreases from 1.1 × 1019 cm-3 to 3.7 × 1017 cm-3, which is comparable to the defect density of typical hydrogenated amorphous silicon carbide films. A damaged layer is found to form on the surface by HPT; this layer can be easily removed by reactive ion etching. PMID:24521208

  20. Enhanced photoelectric performance of PbS/CdS quantum dot co-sensitized solar cells via hydrogenated TiO2 nanorod arrays.

    PubMed

    Chen, Yanli; Tao, Qiang; Fu, Wuyou; Yang, Haibin; Zhou, Xiaoming; Su, Shi; Ding, Dong; Mu, Yannan; Li, Xue; Li, Minghui

    2014-08-28

    The enhanced photoelectric performance of quantum dot sensitized solar cells via hydrogenated TiO2 is proposed. The best energy conversion efficiency is 1.5 times higher than cells without hydrogen treatment. We demonstrated that introducing oxygen vacancies by hydrogenation is an effective and feasible method for enhanced photoelectric performance.

  1. Sulfur-Doped Graphene Oxide Quantum Dots as Photocatalysts for Hydrogen Generation in the Aqueous Phase.

    PubMed

    Gliniak, Jacek; Lin, Jia-Hoa; Chen, Yi-Ting; Li, Chuen-Ru; Jokar, Efat; Chang, Chin-Hao; Peng, Chun-Sheng; Lin, Jui-Nien; Lien, Wan-Hsiang; Tsai, Hui-Min; Wu, Tung-Kung

    2017-08-24

    Sulfur-doped graphene oxide quantum dots (S-GOQDs) were synthesized and investigated for efficient photocatalytic hydrogen generation application. The UV/Vis, FTIR, and photoluminescence spectra of the synthesized S-GOQDs exhibit three absorption bands at 333, 395, and 524 nm, characteristic of C=S and C-S stretching vibration signals at 1075 and 690 cm(-1) , and two excitation-wavelength-independent emission signals with maxima at 451 and 520 nm, respectively, confirming the successful doping of S atom into the GOQDs. Electronic structural analysis suggested that the S-GOQDs exhibit conduction band minimum (CBM) and valence band maximum (VBM) levels suitable for water splitting. Under direct sunlight irradiation, an initial rate of 18 166 μmol h(-1)  g(-1) in pure water and 30 519 μmol h(-1)  g(-1) in 80 % ethanol aqueous solution were obtained. Therefore, metal-free and inexpensive S-GOQDs hold great potential in the development of sustainable and environmentally friendly photocatalysts for efficient hydrogen generation from water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Organic Polymer Dots as Photocatalysts for Visible Light-Driven Hydrogen Generation.

    PubMed

    Wang, Lei; Fernández-Terán, Ricardo; Zhang, Lei; Fernandes, Daniel L A; Tian, Lei; Chen, Hong; Tian, Haining

    2016-09-26

    For the first time, organic semiconducting polymer dots (Pdots) based on poly[(9,9'-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1',3} thiadiazole)] (PFBT) and polystyrene grafting with carboxyl-group-functionalized ethylene oxide (PS-PEG-COOH) are introduced as a photocatalyst towards visible-light-driven hydrogen generation in a completely organic solvent-free system. With these organic Pdots as the photocatalyst, an impressive initial rate constant of 8.3 mmol h(-1)  g(-1) was obtained for visible-light-driven hydrogen production, which is 5-orders of magnitude higher than that of pristine PFBT polymer under the same catalytic conditions. Detailed kinetics studies suggest that the productive electron transfer quench of the excited state of Pdots by an electron donor is about 40 %. More importantly, we also found that the Pdots can tolerate oxygen during catalysis, which is crucial for further application of this material for light-driven water splitting.

  3. Charge Transfer Dynamics in Semiconductor Quantum Dots Relevant to Solar Hydrogen Production

    NASA Astrophysics Data System (ADS)

    Krauss, Todd

    Artificial conversion of sunlight to chemical fuels has attracted attention for several decades as a potential source of clean, renewable energy. For example, in light-driven proton reduction to molecular hydrogen, a light-absorbing molecule (the photosensitizer) rapidly transfers a photoexcited electron to a catalyst for reducing protons. We recently found that CdSe quantum dots (QDs) and simple aqueous Ni2+ salts in the presence of a sacrificial electron donor form a highly efficient, active, and robust system for photochemical reduction of protons to molecular hydrogen. To understand why this system has such extraordinary catalytic behavior, ultrafast transient absorption (TA) spectroscopy studies of electron transfer (ET) processes from the QDs to the Ni catalysts were performed. CdSe QDs transfer photoexcited electrons to a Ni-dihydrolipoic acid (Ni-DHLA) catalyst complex extremely fast and with high efficiency. Even under high fluence, the relative fraction of TA signal due to ET remains well over 80%, and depopulation from exciton-exciton annihilation is minimal (6%). We also found that increasing QD size and/or shelling the core CdSe QDs with a shell of CdS slowed the ET rate, in agreement with the relative efficiency of photochemical H2 generation. The extremely fast ET provides a fundamental explanation for the exceptional photocatalytic H2 activity of the CdSe QD/Ni-DHLA system and guides new directions for further improvements.

  4. Water electrolysis with a conducting carbon cloth: subthreshold hydrogen generation and superthreshold carbon quantum dot formation.

    PubMed

    Biswal, Mandakini; Deshpande, Aparna; Kelkar, Sarika; Ogale, Satishchandra

    2014-03-01

    A conducting carbon cloth, which has an interesting turbostratic microstructure and functional groups that are distinctly different from other ordered forms of carbon, such as graphite, graphene, and carbon nanotubes, was synthesized by a simple one-step pyrolysis of cellulose fabric. This turbostratic disorder and surface chemical functionalities had interesting consequences for water splitting and hydrogen generation when such a cloth was used as an electrode in the alkaline electrolysis process. Importantly, this work also gives a new twist to carbon-assisted electrolysis. During electrolysis, the active sites in the carbon cloth allow slow oxidation of its surface to transform the surface groups from COH to COOH and so forth at a voltage as low as 0.2 V in a two-electrode system, along with platinum as the cathode, instead of 1.23 V (plus overpotential), which is required for platinum, steel, or even graphite anodes. The quantity of subthreshold hydrogen evolved was 24 mL cm(-2)  h(-1) at 1 V. Interestingly, at a superthreshold potential (>1.23 V+overpotential), another remarkable phenomenon was found. At such voltages, along with the high rate and quantity of hydrogen evolution, rapid exfoliation of the tiny nanoscale (5-7 nm) units of carbon quantum dots (CQDs) are found in copious amounts due to an enhanced oxidation rate. These CQDs show bright-blue fluorescence under UV light. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Hydrolysis of CuCl{sub 2} in the Cu-Cl thermochemical cycle for hydrogen production : experimental studies using a spray reactor with an ultrasonic atomizer.

    SciTech Connect

    Ferrandon, M. S.; Lewis, M. A.; Alvarez, F.; Shafirovich, E.; Chemical Sciences and Engineering Division; Univ. of Texas at El Paso

    2010-03-01

    The Cu-Cl thermochemical cycle is being developed as a hydrogen production method. Prior proof-of-concept experimental work has shown that the chemistry is viable while preliminary modeling has shown that the efficiency and cost of hydrogen production have the potential to meet DOE's targets. However, the mechanisms of CuCl{sub 2} hydrolysis, an important step in the Cu-Cl cycle, are not fully understood. Although the stoichiometry of the hydrolysis reaction, 2CuCl{sub 2} + H{sub 2}O {leftrightarrow} Cu{sub 2}OCl{sub 2} + 2HCl, indicates a necessary steam-to-CuCl{sub 2} molar ratio of 0.5, a ratio as high as 23 has been typically required to obtain near 100% conversion of the CuCl{sub 2} to the desired products at atmospheric pressure. It is highly desirable to conduct this reaction with less excess steam to improve the process efficiency. Per Le Chatelier's Principle and according to the available equilibrium-based model, the needed amount of steam can be decreased by conducting the hydrolysis reaction at a reduced pressure. In the present work, the experimental setup was modified to allow CuCl{sub 2} hydrolysis in the pressure range of 0.4-1 atm. Chemical and XRD analyses of the product compositions revealed the optimal steam-to-CuCl{sub 2} molar ratio to be 20-23 at 1 atm pressure. The experiments at 0.4 atm and 0.7 atm showed that it is possible to lower the steam-to-CuCl{sub 2} molar ratio to 15, while still obtaining good yields of the desired products. An important effect of running the reaction at reduced pressure is the significant decrease of CuCl concentration in the solid products, which was not predicted by prior modeling. Possible explanations based on kinetics and residence times are suggested.

  6. Anomalous effect in a hydrogenic impurity in a spherical quantum dot under the influence of parallel electric and magnetic fields

    NASA Astrophysics Data System (ADS)

    Ho, Y. K.; Lin, Y. C.; Sahoo, S.

    2004-03-01

    We will present calculations for the energy levels and the resonance widths of the quasi-bound states of a confined hydrogenic impurity in an isolate quantum dot subjected to external electric and magnetic fields in parallel directions. A method of complex absorbing potential [1] is used in our present investigation. Resonance positions and widths are reported for a wide range of dot sizes to demonstrate that Stark resonances in a confined hydrogen atom leads to a new phenomenon as a consequence of the quantum confinement of the atom, contrary to the Stark effect on a free atom. * This work was supported by the National Science Council of ROC. [1] S. Sahoo and Y. K. Ho, Chin. J. Phys. 38, 127 (2000); J. Phys. B 33, 2195 (2000); J. Phys. B 33, 5151 (2000); Phys. Rev. A 65, 015403 (2001);

  7. Reduction of hazards from copper(I) chloride in a Cu-Cl thermochemical hydrogen production plant.

    PubMed

    Ghandehariun, Samane; Wang, Zhaolin; Rosen, Marc A; Naterer, Greg F

    2012-08-30

    The copper-chlorine cycle of thermochemical water splitting, using various heat sources, is a promising technology for hydrogen production. The chemical hazards accompanying the new technology affect significantly the industrialization of the cycle, but have scarcely been examined. This paper addresses this need by examining the copper(I) chloride (CuCl) hazards that may be generated in the cycle. Regardless of the variations of Cu-Cl cycle, copper(I) chloride is always present, serving as an intermediate compound that may cause health concerns. In this paper, the CuCl hazards are quantified for each process from the generation source of the hazards along with the paths where the CuCl may be present. The processes of greatest relevance include oxygen production, heat recovery, solidification, and dissolution. The options for reducing the CuCl hazards in a Cu-Cl thermochemical hydrogen production plant are evaluated from the perspectives of variations of the Cu-Cl cycle, process integration, heat recovery, and equipment design. It is concluded that using the intake reactant Cu(2)OCl(2) for the oxygen production step to absorb CuCl vapor is the most preferable option compared with other alternatives such as absorbing CuCl vapor with water or CuCl(2), building additional structures inside the oxygen production reactor, and cooling the exiting gas at the outlet of the oxygen reactor. Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.

  8. Interaction of a conjugated polyaromatic molecule with a single dangling bond quantum dot on a hydrogenated semiconductor.

    PubMed

    Godlewski, Szymon; Kolmer, Marek; Engelund, Mads; Kawai, Hiroyo; Zuzak, Rafal; Garcia-Lekue, Aran; Saeys, Mark; Echavarren, Antonio M; Joachim, Christian; Sanchez-Portal, Daniel; Szymonski, Marek

    2016-02-07

    Controlling the strength of the coupling between organic molecules and single atoms provides a powerful tool for tuning electronic properties of single-molecule devices. Here, using scanning tunneling microscopy and spectroscopy (STM/STS) supported by theoretical modeling, we study the interaction of a planar organic molecule (trinaphthylene) with a hydrogen-passivated Ge(001):H substrate and a single dangling bond quantum dot on that surface. The electronic structure of the molecule adsorbed on the hydrogen-passivated surface is similar to the gas phase structure and the measurements show that HOMO and LUMO states contribute to the STM filled and empty state images, respectively. Furthermore, we show that the electronic properties are not significantly affected when the molecule is attached to the single dangling bond, which is in contrast with the strong interaction of the molecule with a dangling bond dimer. Our results show that the dangling bond quantum dots could stabilize organic molecules on a hydrogenated semiconductor without affecting their originally designed gas phase electronic properties. Together with the ability to laterally manipulate the molecules on the surface, this will be advantageous in the construction of single-molecule devices, where the coupling and positioning of the molecules on the substrate could be tuned by a proper design of the surface quantum dot arrays, comprising both single and dimerized dangling bonds.

  9. Dehydrogenation properties and mechanisms of MgH2-NiCl2 and MgH2-NiCl2-graphene hydrogen storage composites

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Qu, H.; Yan, S.; Yin, L. R.; Zhou, D. W.

    2017-07-01

    The four hydrogen storage systems including pure MgH2, MgH2-5 wt%NiCl2, MgH2-10 wt%NiCl2 and MgH2-10 wt%NiCl2-10 wt%graphene were prepared by ball-milling in this work. Using experimental X-ray diffraction, scanning electron microscopy and differential scanning calorimetry testing methods in combination with first-principle calculations, the dehydrogenation properties and mechanisms of NiCl2 single-doped and NiCl2-graphene co-doped MgH2 composites were systematically investigated. Experimental results show that the NiCl2 single-doping is conductive to decreasing the size of MgH2 grains and particles. The co-doping of NiCl2 and graphene not only reduces the size of MgH2 grains and particles, but also contributes to the uniformity of MgH2 particles. As compared with milled pure MgH2, the dehydrogenation peak temperatures are decreased by 24 °C and 47 °C for the 10 wt%NiCl2 single-doped and 10 wt%NiCl2-10 wt%graphene co-doped MgH2 systems, respectively. It is demonstrated that the co-doping of NiCl2 and graphene exhibits the synergistic effects of confinement and catalysis on improving the dehydrogenation properties of MgH2. The first-principle calculations indicate that the co-doping of NiCl2 and graphene leads to the distortion of MgH2 atomic-configuration and results in the charge transfer between the dopants and MgH2, which induce the weakened structural stability and decreased dehydrogenation enthalpy of MgH2.

  10. Hydrogen Generation from Al-NiCl2/NaBH4 Mixture Affected by Lanthanum Metal

    PubMed Central

    Qiang Sun, Wen; Fan, Mei-Qiang; Fei, Yong; Pan, Hua; Wang, Liang Liang; Yao, Jun

    2012-01-01

    The effect of La on Al/NaBH4 hydrolysis was elaborated in the present paper. Hydrogen generation amount increases but hydrogen generation rate decreases with La content increasing. There is an optimized composition that Al-15 wt% La-5 wt% NiCl2/NaBH4 mixture (Al-15 wt% La-5 wt% NiCl2/NaBH4 weight ratio, 1 : 3) has 126 mL g−1 min−1 maximum hydrogen generation rate and 1764 mL g−1 hydrogen generation amount within 60 min. The efficiency is 88%. Combined with NiCl2, La has great effect on NaBH4 hydrolysis but has little effect on Al hydrolysis. Increasing La content is helpful to decrease the particle size of Al-La-NiCl2 in the milling process, which induces that the hydrolysis byproduct Ni2B is highly distributed into Al(OH)3 and the catalytic reactivity of Ni2B/Al(OH)3 is increased therefore. But hydrolysis byproduct La(OH)3 deposits on Al surface and leads to some side effect. The Al-La-NiCl2/NaBH4 mixture has good stability in low temperature and its hydrolytic performance can be improved with increasing global temperature. Therefore, the mixture has good safety and can be applied as on board hydrogen generation material. PMID:22619596

  11. Characterisation of potential barriers in a donor quantum dot defined by hydrogen resist lithography

    NASA Astrophysics Data System (ADS)

    Fuhrer, Andreas; Pascher, Nikola

    We use a four terminal donor quantum dot (QD) to characterize potential barriers between degenerately doped nanoscale contacts. The QD is fabricated by hydrogen resist lithography on Si(001) in combination with n-type doping from the gas-phase. The four contacts have different separations (d = 9, 12, 16 and 29 nm) to a central 6 nm x 6 nm island, leading to different tunnel- and capacitive coupling. We use cryogenic transport measurements in the Coulomb blockade regime to simultaneously probe current flow in the four terminals for various voltage configurations. The magnitude of the measured tunnelling currents as a function of applied bias and contact separation sets a limit of about 15 nm for tunnelling contacts and shows a strong increase of the barrier transmission with applied bias. Using a constant interaction picture we extract the mutual capacitances between the QD and the four contacts which are found to be in excellent agreement with numerically calculated values. Our results contribute to a better understanding of tunnelling barriers and gate electrodes in planar dopant devices and pave the way towards reliable quantum device fabrication at the atomic scale. Support from EU grants PAMS, SiSpin, SiAM and from Swiss NCCR QSIT is gratefully acknowledged.

  12. Nanoparticles based on quantum dots and a luminol derivative: implications for in vivo imaging of hydrogen peroxide by chemiluminescence resonance energy transfer.

    PubMed

    Lee, Eun Sook; Deepagan, V G; You, Dong Gil; Jeon, Jueun; Yi, Gi-Ra; Lee, Jung Young; Lee, Doo Sung; Suh, Yung Doug; Park, Jae Hyung

    2016-03-18

    Overproduction of hydrogen peroxide is involved in the pathogenesis of inflammatory diseases such as cancer and arthritis. To image hydrogen peroxide via chemiluminescence resonance energy transfer in the near-infrared wavelength range, we prepared quantum dots functionalized with a luminol derivative.

  13. Brightly Luminescent and Color-Tunable Colloidal CH3NH3PbX3 (X = Br, I, Cl) Quantum Dots: Potential Alternatives for Display Technology.

    PubMed

    Zhang, Feng; Zhong, Haizheng; Chen, Cheng; Wu, Xian-gang; Hu, Xiangmin; Huang, Hailong; Han, Junbo; Zou, Bingsuo; Dong, Yuping

    2015-04-28

    Organometal halide perovskites are inexpensive materials with desirable characteristics of color-tunable and narrow-band emissions for lighting and display technology, but they suffer from low photoluminescence quantum yields at low excitation fluencies. Here we developed a ligand-assisted reprecipitation strategy to fabricate brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies. To illustrate the photoluminescence enhancements in these quantum dots, we conducted comprehensive composition and surface characterizations and determined the time- and temperature-dependent photoluminescence spectra. Comparisons between small-sized CH3NH3PbBr3 quantum dots (average diameter 3.3 nm) and corresponding micrometer-sized bulk particles (2-8 μm) suggest that the intense increased photoluminescence quantum yield originates from the increase of exciton binding energy due to size reduction as well as proper chemical passivations of the Br-rich surface. We further demonstrated wide-color gamut white-light-emitting diodes using green emissive CH3NH3PbBr3 quantum dots and red emissive K2SiF6:Mn(4+) as color converters, providing enhanced color quality for display technology. Moreover, colloidal CH3NH3PbX3 quantum dots are expected to exhibit interesting nanoscale excitonic properties and also have other potential applications in lasers, electroluminescence devices, and optical sensors.

  14. New amide-chloride phases in the Li-Al-N-H-Cl system: formation and hydrogen storage behaviour.

    PubMed

    Fernández Albanesi, L; Garroni, S; Enzo, S; Gennari, F C

    2016-04-07

    New amide-chloride phases were successfully synthesized by mechanical milling of the LiNH2-AlCl3 mixture at a molar ratio of 1 : 0.11 and further heating at 150 °C under argon (0.1 MPa) or under hydrogen pressure (0.7 MPa). Powder X-ray diffraction measurements as a function of milling time increase revealed that the milling of the LiNH2-0.11AlCl3 mixture results in the formation of a FCC solid solution with an excess of LiNH2. Subsequent heating of the LiNH2-0.11AlCl3 sample ball milled for 5 hours at 150 °C under argon or under hydrogen induces the appearance of an amide-chloride phase isostructural with cubic Li4(NH2)3Cl. This Li-Al-N-H-Cl phase transforms progressively into the trigonal phase after prolonged heating at 300 °C under hydrogen pressure. The thermal behaviour of the amide-chloride without and with LiH addition displays dissimilar decomposition pathways. The decomposition of amide-chloride alone involves the formation of ammonia and hydrogen from 120 to 300 °C. Conversely, the amide-chloride material in the presence of LiH only releases hydrogen avoiding the emission of ammonia. The resultant material is able to be rehydrogenated under moderate conditions (300 °C, 0.7 MPa H2), providing a new reversible hydrogen storage system.

  15. Diamagnetic susceptibility of a hydrogenic donor in a group IV-VI quantum dot-quantum well heterostructure

    SciTech Connect

    Saravanamoorthy, S. N.; Peter, A. John

    2016-05-23

    Electronic properties of a hydrogenic donor impurity in a CdSe/Pb{sub 0.8}Cd{sub 0.2}Se/CdSe quantum dot quantum well system are investigated for various radii of core with shell materials. Confined energies are obtained taking into account the geometrical size of the system and thereby the donor binding energies are found. The diamagnetic susceptibility is estimated for a confined shallow donor in the well system. The results show that the diamagnetic susceptibility strongly depends on core and shell radii and it is more sensitive to variations of the geometrical size of the well material.

  16. Effect of Rasbha spin-orbit interaction on the ground state energy of a hydrogenic D{sup 0} complex in a Gaussian quantum dot

    SciTech Connect

    Boda, Aalu Kumar, D. Sanjeev; Chatterjee, Ashok; Mukhopadhyay, Soma

    2015-06-24

    The ground state energy of a hydrogenic D{sup 0} complex trapped in a three-dimensional GaAs quantum dot with Gaussian confinement is calculated variationally incorporating the effect of Rashba spin-orbit interaction. The results are obtained as a function of the quantum dot size and the Rashba spin-orbit interaction. The results show that the Rashba interaction reduces the ground state energy of the system.

  17. Si quantum dots embedded in an amorphous SiC matrix: nanophase control by non-equilibrium plasma hydrogenation.

    PubMed

    Cheng, Qijin; Tam, Eugene; Xu, Shuyan; Ostrikov, Kostya Ken

    2010-04-01

    Nanophase nc-Si/a-SiC films that contain Si quantum dots (QDs) embedded in an amorphous SiC matrix were deposited on single-crystal silicon substrates using inductively coupled plasma-assisted chemical vapor deposition from the reactive silane and methane precursor gases diluted with hydrogen at a substrate temperature of 200 degrees C. The effect of the hydrogen dilution ratio X (X is defined as the flow rate ratio of hydrogen-to-silane plus methane gases), ranging from 0 to 10.0, on the morphological, structural, and compositional properties of the deposited films, is extensively and systematically studied by scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy, Fourier-transform infrared absorption spectroscopy, and X-ray photoelectron spectroscopy. Effective nanophase segregation at a low hydrogen dilution ratio of 4.0 leads to the formation of highly uniform Si QDs embedded in the amorphous SiC matrix. It is also shown that with the increase of X, the crystallinity degree and the crystallite size increase while the carbon content and the growth rate decrease. The obtained experimental results are explained in terms of the effect of hydrogen dilution on the nucleation and growth processes of the Si QDs in the high-density plasmas. These results are highly relevant to the development of next-generation photovoltaic solar cells, light-emitting diodes, thin-film transistors, and other applications.

  18. Towards Visible Light Hydrogen Generation: Quantum Dot-Sensitization via Efficient Light Harvesting of Hybrid-TiO2

    PubMed Central

    Kim, Kwanghyun; Kim, Myeong-Jong; Kim, Sun-I; Jang, Ji-Hyun

    2013-01-01

    We report pronounced enhancement of photoelectrochemical hydrogen generation of a quantum dot-sensitized hybrid-TiO2 (QD/H-TiO2) electrode that is composed of a mesoporous TiO2 layer sandwiched by a double sided energy harvesting layer consisting of a surface-textured TiO2 inverse opals layer on the bottom and a patterned mesoporous TiO2 layer on the top. CdSe/H-TiO2 exhibits a maximum photocurrent density of ~16.2 mA/cm2, which is 35% higher than that of the optimized control sample (CdSe/P25), achieved by matching of the bandgap of quantum dot-sensitization with the wavelength where light harvesting of H-TiO2 is observed. Furthermore, CdSe/H-TiO2 under filtered exposure conditions recorded current density of ~14.2 mA/cm2, the greatest value in the visible range. The excellent performance of the quantum dot-sensitized H-TiO2 suggests that alteration of the photoelectrodes to suitable nanostructures with excellent light absorption may offer optimal strategies for attaining maximum efficiency in a variety of photoconversion systems. PMID:24270426

  19. Towards Visible Light Hydrogen Generation: Quantum Dot-Sensitization via Efficient Light Harvesting of Hybrid-TiO2

    NASA Astrophysics Data System (ADS)

    Kim, Kwanghyun; Kim, Myeong-Jong; Kim, Sun-I.; Jang, Ji-Hyun

    2013-11-01

    We report pronounced enhancement of photoelectrochemical hydrogen generation of a quantum dot-sensitized hybrid-TiO2 (QD/H-TiO2) electrode that is composed of a mesoporous TiO2 layer sandwiched by a double sided energy harvesting layer consisting of a surface-textured TiO2 inverse opals layer on the bottom and a patterned mesoporous TiO2 layer on the top. CdSe/H-TiO2 exhibits a maximum photocurrent density of ~16.2 mA/cm2, which is 35% higher than that of the optimized control sample (CdSe/P25), achieved by matching of the bandgap of quantum dot-sensitization with the wavelength where light harvesting of H-TiO2 is observed. Furthermore, CdSe/H-TiO2 under filtered exposure conditions recorded current density of ~14.2 mA/cm2, the greatest value in the visible range. The excellent performance of the quantum dot-sensitized H-TiO2 suggests that alteration of the photoelectrodes to suitable nanostructures with excellent light absorption may offer optimal strategies for attaining maximum efficiency in a variety of photoconversion systems.

  20. ZnO-dotted porous ZnS cluster microspheres for high efficient, Pt-free photocatalytic hydrogen evolution

    PubMed Central

    Wu, Aiping; Jing, Liqiang; Wang, Jianqiang; Qu, Yang; Xie, Ying; Jiang, Baojiang; Tian, Chungui; Fu, Honggang

    2015-01-01

    The Pt-free photocatalytic hydrogen evolution (PHE) has been the focus in the photocatalysis field. Here, the ZnO-dotted porous ZnS cluster microsphere (PCMS) is designed for high efficient, Pt-free PHE. The PCMS is designed through an easy “controlling competitive reaction” strategy by selecting the thiourea as S2− source and Zn(Ac)2·2H2O as Zn source in ethylene glycol medium. Under suitable conditions, one of the PCMS, named PCMS-1, with high SBET specific area of 194 m2g−1, microsphere size of 100 nm and grain size of 3 nm can be obtained. The formation of PCMS is verified by TEM, XAES, XPS, Raman and IR methods. Importantly, a series of the experiments and theoretical calculation demonstrate that the dotting of ZnO not only makes the photo-generated electrons/hole separate efficiently, but also results in the formation of the active catalytic sites for PHE. As a result, the PCMS-1 shows the promising activity up to 367 μmol h−1 under Pt-free condition. The PHE activity has no obvious change after addition 1 wt.% Pt, implying the presence of active catalytic sites for hydrogen evolution in the PCMS-1. The easy synthesis process, low preparation cost of the PCMS makes their large potential for Pt-free PHE. PMID:25748688

  1. Nano-design of quantum dot-based photocatalysts for hydrogen generation using advanced surface molecular chemistry.

    PubMed

    Yu, Weili; Noureldine, Dalal; Isimjan, Tayirjan; Lin, Bin; Del Gobbo, Silvano; Abulikemu, Mutalifu; Hedhili, Mohamed Nejib; Anjum, Dalaver H; Takanabe, Kazuhiro

    2015-01-14

    Efficient photocatalytic hydrogen generation in a suspension system requires a sophisticated nano-device that combines a photon absorber with effective redox catalysts. This study demonstrates an innovative molecular linking strategy for fabricating photocatalytic materials that allow effective charge separation of excited carriers, followed by efficient hydrogen evolution. The method for the sequential replacement of ligands with appropriate molecules developed in this study tethers both quantum dots (QDs), as photosensitizers, and metal nanoparticles, as hydrogen evolution catalysts, to TiO2 surfaces in a controlled manner at the nano-level. Combining hydrophobic and hydrophilic interactions on the surface, CdSe-ZnS core-shell QDs and an Au-Pt alloy were attached to TiO2 without overlapping during the synthesis. The resultant nano-photocatalysts achieved substantially high-performance visible-light-driven photocatalysis for hydrogen evolution. All syntheses were conducted at room temperature and in ambient air, providing a promising route for fabricating visible-light-responsive photocatalysts.

  2. Dependence of (35)Cl NQR on hydrogen bonding and temperature in dichlorophenol-aniline charge transfer complexes.

    PubMed

    Ramananda, D; Ramesh, K P; Uchil, J

    2007-10-01

    The hydrogen-bonded charge transfer complexes of aniline with pi-acceptors (or proton donors) such as 2,5-, 2,6-, 3,4- and 3,5-dichlorophenol were prepared. The (35)Cl nuclear quadrupole resonance (NQR) frequencies of these charge transfer complexes in the temperature range 77-300 K were measured to ascertain the existence or otherwise of a phase transition upon complex formation. Further, the NQR frequency and asymmetry parameter of the electric field gradient at the site of quadrupole nucleus were used to estimate the chemical bond parameters, namely ionic bond, double bond character of the carbon-chlorine(C--Cl) bond and the percentage charge transfer between the donor-acceptor components in charge transfer complexes. The effect of hydrogen bonding and temperature on the charge transfer process is analysed. (c) 2007 John Wiley & Sons, Ltd.

  3. Selective conversion of polyenes to monoenes by RuCl(3) -catalyzed transfer hydrogenation: the case of cashew nutshell liquid.

    PubMed

    Perdriau, Sébastien; Harder, Sjoerd; Heeres, Hero J; de Vries, Johannes G

    2012-12-01

    Cardanol, a constituent of cashew nutshell liquid (CNSL), was subjected to transfer hydrogenation catalyzed by RuCl(3) using isopropanol as a reductant. The side chain of cardanol, which is a mixture of a triene, a diene, and a monoene, was selectively reduced to the monoene. Surprisingly, it is the C8-C9 double bond that is retained with high selectivity. A similar transfer hydrogenation of linoleic acid derivatives succeeded only if the substrate contained an aromatic ring, such as a benzyl ester. TEM and a negative mercury test showed that the catalyst was homogeneous. By using ESI-MS, ruthenium complexes were identified that contained one, two, or even three molecules of substrate, most likely as allyl complexes. The interaction between ruthenium and the aromatic ring determines selectivity in the hydrogenation reaction.

  4. Effects of the large distribution of CdS quantum dot sizes on the charge transfer interactions into TiO2 nanotubes for photocatalytic hydrogen generation

    NASA Astrophysics Data System (ADS)

    González-Moya, Johan R.; Garcia-Basabe, Yunier; Rocco, Maria Luiza M.; Pereira, Marcelo B.; Princival, Jefferson L.; Almeida, Luciano C.; Araújo, Carlos M.; David, Denis G. F.; Ferreira da Silva, Antonio; Machado, Giovanna

    2016-07-01

    Hydrogen fuels generated by water splitting using a photocatalyst and solar irradiation are currently gaining the strength to diversify the world energy matrix in a green way. CdS quantum dots have revealed a hydrogen generation improvement when added to TiO2 materials under visible-light irradiation. In the present paper, we investigated the performance of TiO2 nanotubes coupled with CdS quantum dots, by a molecular bifunctional linker, on photocatalytic hydrogen generation. TiO2 nanotubes were obtained by anodization of Ti foil, followed by annealing to crystallize the nanotubes into the anatase phase. Afterwards, the samples were sensitized with CdS quantum dots via an in situ hydrothermal route using 3-mercaptopropionic acid as the capping agent. This sensitization technique permits high loading and uniform distribution of CdS quantum dots onto TiO2 nanotubes. The XPS depth profile showed that CdS concentration remains almost unchanged (homogeneous), while the concentration relative to the sulfate anion decreases by more than 80% with respect to the initial value after ˜100 nm in depth. The presence of sulfate anions is due to the oxidation of sulfide and occurs in greater proportion in the material surface. This protection for air oxidation inside the nanotubular matrix seemingly protected the CdS for photocorrosion in sacrificial solution leading to good stability properties proved by long duration, stable photocurrent measurements. The effect of the size and the distribution of sizes of CdS quantum dots attached to TiO2 nanotubes on the photocatalytic hydrogen generation were investigated. The experimental results showed three different behaviors when the reaction time of CdS synthesis was increased in the sensitized samples, i.e. similar, deactivation and activation effects on the hydrogen production with regard to TiO2 nanotubes. The deactivation effect was related to two populations of sizes of CdS, where the population with a shorter band gap acts as a

  5. Effects of the large distribution of CdS quantum dot sizes on the charge transfer interactions into TiO2 nanotubes for photocatalytic hydrogen generation.

    PubMed

    González-Moya, Johan R; Garcia-Basabe, Yunier; Rocco, Maria Luiza M; Pereira, Marcelo B; Princival, Jefferson L; Almeida, Luciano C; Araújo, Carlos M; David, Denis G F; da Silva, Antonio Ferreira; Machado, Giovanna

    2016-07-15

    Hydrogen fuels generated by water splitting using a photocatalyst and solar irradiation are currently gaining the strength to diversify the world energy matrix in a green way. CdS quantum dots have revealed a hydrogen generation improvement when added to TiO2 materials under visible-light irradiation. In the present paper, we investigated the performance of TiO2 nanotubes coupled with CdS quantum dots, by a molecular bifunctional linker, on photocatalytic hydrogen generation. TiO2 nanotubes were obtained by anodization of Ti foil, followed by annealing to crystallize the nanotubes into the anatase phase. Afterwards, the samples were sensitized with CdS quantum dots via an in situ hydrothermal route using 3-mercaptopropionic acid as the capping agent. This sensitization technique permits high loading and uniform distribution of CdS quantum dots onto TiO2 nanotubes. The XPS depth profile showed that CdS concentration remains almost unchanged (homogeneous), while the concentration relative to the sulfate anion decreases by more than 80% with respect to the initial value after ∼100 nm in depth. The presence of sulfate anions is due to the oxidation of sulfide and occurs in greater proportion in the material surface. This protection for air oxidation inside the nanotubular matrix seemingly protected the CdS for photocorrosion in sacrificial solution leading to good stability properties proved by long duration, stable photocurrent measurements. The effect of the size and the distribution of sizes of CdS quantum dots attached to TiO2 nanotubes on the photocatalytic hydrogen generation were investigated. The experimental results showed three different behaviors when the reaction time of CdS synthesis was increased in the sensitized samples, i.e. similar, deactivation and activation effects on the hydrogen production with regard to TiO2 nanotubes. The deactivation effect was related to two populations of sizes of CdS, where the population with a shorter band gap acts as a

  6. The chemistry of boron and titanium diboride formation: Decomposition of TiCl{sub 4} and BCl{sub 3} in hydrogen and helium

    SciTech Connect

    Osterheld, T.H.; Allendorf, M.D.

    1995-12-01

    Measurements of the decomposition of mixtures of boron trichloride (BCl{sub 3}), titanium tetrachloride (TiCl{sub 4}), and hydrogen at elevated temperatures are presented. The decomposition of BCl{sub 3} with hydrogen appears to drive the chemistry in this system. The species depositing boron on the surface contains at least 2 chlorine atoms. Once deposited, the surface chlorine is removed by reaction with hydrogen to form HCl and, presumably, surface B-H bonds.

  7. Dichloroacetonitrile hydrogenation by osmium cluster: Crystal structure of (μ-Cl)Os3(CO)10(μ-N=CHCHCl2)

    NASA Astrophysics Data System (ADS)

    Savkov, Boris Yu.; Virovets, Alexander V.; Maksakov, Vladimir A.

    2017-08-01

    Dichloroacetonitrile undergoes hydrogenation by triosmium dihydride cluster under mild conditions. The reaction of cluster complex (μ-H)2Os3(CO)10 (1) with CHCl2CN in the presence of morpholine as a base results in two novel compounds (μ-Cl)Os3(CO)10(μ-N=CHCHCl2) (2) and (μ-H)Os3(CO)10(μ,η2-HN=CHCHCl2) (3). Both compounds were characterized using FTIR, 13C, 1H NMR spectra, and CHN analysis, molecular structure of 2 was determined by X-Ray diffraction study.

  8. Plasmonic effect in Au(core)-CdS(shell) quantum dot-sensitized photoelectrochemical cell for hydrogen generation from water

    NASA Astrophysics Data System (ADS)

    Ikeda, Takuya; Akashi, Ryo; Fujishima, Musashi; Tada, Hiroaki

    2017-09-01

    UV-light irradiation of Au nanoparticle (NP)-loaded mesoporous TiO2 nanocrystalline films in an ethanol solution of Cd(NO3)2 and S8 at 298 K gives rise to selective CdS deposition on Au NPs to yield Au(core)-CdS(shell) hybrid quantum dots (Au@CdS/mp-TiO2). Two-electrode quantum dot-sensitized photoelectrochemical cells with the structure of photoanode|0.25 M Na2S, 0.35 M Na2SO3 (solvent = water)|cathode were fabricated. The Au@CdS/mp-TiO2 photoanode cell yields hydrogen (H2) with a rate of 0.18 ml h-1 [solar-to-current efficiency (STCE) = 0.028%] without external bias far surpassing the rate of 0.028 ml h-1 (solar-to-current efficiency = 0.006%) for the CdS/mp-TiO2 photoanode cell under illumination of simulated sunlight (λ > 430 nm, AM 1.5, one sun). The 3D finite-difference time-domain calculations for a model Au@CdS/TiO2 system indicate that an intense local electric field with an enhancement factor of ˜103 is generated at the Au-CdS-TiO2 three-phase interface. The striking effect of the Au core stems from the enhancement of the excitation of the CdS shell and subsequent charge separation by the intense local electric field.

  9. Photocatalytic hydrogen evolution from glycerol and water over nickel-hybrid cadmium sulfide quantum dots under visible-light irradiation.

    PubMed

    Wang, Jiu-Ju; Li, Zhi-Jun; Li, Xu-Bing; Fan, Xiang-Bing; Meng, Qing-Yuan; Yu, Shan; Li, Cheng-Bo; Li, Jia-Xin; Tung, Chen-Ho; Wu, Li-Zhu

    2014-05-01

    Natural photosynthesis offers the concept of storing sunlight in chemical form as hydrogen (H2), using biomass and water. Herein we describe a robust artificial photocatalyst, nickel-hybrid CdS quantum dots (Nih-CdS QDs) made in situ from nickel salts and CdS QDs stabilized by 3-mercaptopropionic acid, for visible-light-driven H2 evolution from glycerol and water. With visible light irradiation for 20 h, 403.2 μmol of H2 was obtained with a high H2 evolution rate of approximately 74.6 μmol h(-1)  mg(-1) and a high turnover number of 38 405 compared to MPA-CdS QDs (mercaptopropionic-acid-stabilized CdS quantum dots). Compared to CdTe QDs and CdSe QDs, the modified CdS QDs show the greatest affinity toward Ni(2+) ions and the highest activity for H2 evolution. X-ray photoelectron spectroscopy (XPS), inductively-coupled plasma atomic emission spectrometry (ICP-AES), and photophysical studies reveal the chemical nature of the Nih-CdS QDs. Electron paramagnetic resonance (EPR) and terephthalate fluorescence measurements clearly demonstrate water splitting to generate ⋅OH radicals. The detection of DMPO-H and DMPO-C radicals adduct in EPR also indicate that ⋅H radicals and ⋅C radicals are the active species in the catalytic cycle. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Green synthesis of fluorescent carbon dots for sensitive detection of Fe2+ and hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Shi, Jing; Ni, Gang; Tu, Jinchun; Jin, Xiaoyong; Peng, Juan

    2017-06-01

    In this paper, the green synthesis of fluorescent carbon dots (CDs) via one-step hydrothermal treatment of cornstalk was investigated. This approach is facile, economical, and effective. The obtained CDs with an average diameter of 5.2 nm possess many excellent properties such as emitting blue fluorescence under UV light (365 nm), high monodispersity, good stability, excellent water dispersibility, and absolute quantum yield of 7.6%. Then, these CDs were used as sensing probes for the detection of Fe2+ and H2O2 with detection limits as low as 0.18 and 0.21 μM, respectively. This sensing platform shows advantages such as high selectivity, good precision, rapid operation, and avoiding the precipitation of iron oxyhydroxides.

  11. A highly efficient noble metal free photocatalytic hydrogen evolution system containing MoP and CdS quantum dots

    NASA Astrophysics Data System (ADS)

    Yin, Shengming; Han, Jianyu; Zou, Yinjun; Zhou, Tianhua; Xu, Rong

    2016-07-01

    We report the construction of a highly efficient noble metal free photocatalytic hydrogen (H2) evolution system using CdS quantum dots as the light absorber and metallic MoP as the cocatalyst. MoP can be prepared by a facile temperature programmed reduction method and small clusters of MoP nanoparticles sized 10-30 nm were obtained by probe ultrasonication. The effect of synthesis conditions on the electrocatalytic and photocatalytic H2 evolution activity of MoP was investigated. The highest H2 evolution rate of 1100 μmol h-1 can be achieved by the optimized system under visible light (λ >= 420 nm), which is comparable to that when Pt was used as the cocatalyst. A high quantum efficiency of 45% is obtained at 460 nm irradiation.We report the construction of a highly efficient noble metal free photocatalytic hydrogen (H2) evolution system using CdS quantum dots as the light absorber and metallic MoP as the cocatalyst. MoP can be prepared by a facile temperature programmed reduction method and small clusters of MoP nanoparticles sized 10-30 nm were obtained by probe ultrasonication. The effect of synthesis conditions on the electrocatalytic and photocatalytic H2 evolution activity of MoP was investigated. The highest H2 evolution rate of 1100 μmol h-1 can be achieved by the optimized system under visible light (λ >= 420 nm), which is comparable to that when Pt was used as the cocatalyst. A high quantum efficiency of 45% is obtained at 460 nm irradiation. Electronic supplementary information (ESI) available: SEM image with EDS, XPS survey spectrum, XRD and TEM images of MoP samples prepared under different conditions; XRD, TEM, UV-vis and photoluminescence spectra of CdS QDs; H2 evolution activity comparison for different MoP/CdS samples; the effect of pH value on H2 evolution activity of a MoP/CdS system; the XPS spectrum of MoP/CdS after photoreaction; table of literature studies on H2 evolution activity by different noble metal free photocatalytic systems

  12. Integration of epitaxially-grown InGaAs/GaAs quantum dot lasers with hydrogenated amorphous silicon waveguides on silicon.

    PubMed

    Yang, Jun; Bhattacharya, Pallab

    2008-03-31

    The monolithic integration of epitaxially-grown InGaAs/GaAs self-organized quantum dot lasers with hydrogenated amorphous silicon (a:Si-H) waveguides on silicon substrates is demonstrated. Hydrogenated amorphous silicon waveguides, formed by plasma-enhanced-chemical-vapor deposition (PECVD), exhibit a propagation loss of approximately 10 dB/cm at a wavelength of 1.05 microm. The laser-waveguide coupling, with coupling coefficient of 22%, is achieved through a 3.2 microm-width groove etched by focused-ion-beam (FIB) milling which creates high-quality etched GaAs facets.

  13. Hydrogen Sulfide Inhibits the Development of Atherosclerosis with Suppressing CX3CR1 and CX3CL1 Expression

    PubMed Central

    Wu, Duojiao; Zhang, Alian; Gu, Ting; Wang, Liansheng; Wang, Changqian

    2012-01-01

    Hydrogen sulfide, as a novel gaseous mediator, has been suggested to play a key role in atherogenesis. However, the precise mechanisms by which H2S affects atherosclerosis remain unclear. Therefore, the present study aimed to investigate the potential role of H2S in atherosclerosis and the underlying mechanism with respect to chemokines (CCL2, CCL5 and CX3CL1) and chemokine receptors (CCR2, CCR5, and CX3CR1) in macrophages. Mouse macrophage cell line RAW 264.7 or mouse peritoneal macrophages were pre-incubated with saline or NaHS (50 µM, 100 µM, 200 µM), an H2S donor, and then stimulated with interferon-γ (IFN-γ) or lipopolysaccharide (LPS). It was found that NaHS dose-dependently inhibited IFN-γ or LPS-induced CX3CR1 and CX3CL1 expression, as well as CX3CR1-mediated chemotaxis in macrophages. Overexpression of cystathionine γ-lyase (CSE), an enzyme that catalyzes H2S biosynthesis resulted in a significant reduction in CX3CR1 and CX3CL1 expression as well as CX3CR1-mediated chemotaxis in stimulated macrophages. The inhibitory effect of H2S on CX3CR1 and CX3CL1 expression was mediated by modulation of proliferators-activated receptor-γ (PPAR-γ) and NF-κB pathway. Furthermore, male apoE−/− mice were fed a high-fat diet and then randomly given NaHS (1 mg/kg, i.p., daily) or DL-propargylglycine (PAG, 10 mg/kg, i.p., daily). NaHS significantly inhibited aortic CX3CR1 and CX3CL1 expression and impeded aortic plaque development. NaHS had a better anti-atherogenic benefit when it was applied at the early stage of atherosclerosis. However, inhibition of H2S formation by PAG increased aortic CX3CR1 and CX3CL1 expression and exacerbated the extent of atherosclerosis. In addition, H2S had minimal effect on the expression of CCL2, CCL5, CCR2 and CCR5 in vitro and in vivo. In conclusion, these data indicate that H2S hampers the progression of atherosclerosis in fat-fed apoE−/− mice and downregulates CX3CR1 and CX3CL1 expression on macrophages and in lesion

  14. Hydrogen sulfide inhibits the development of atherosclerosis with suppressing CX3CR1 and CX3CL1 expression.

    PubMed

    Zhang, Huili; Guo, Changfa; Wu, Duojiao; Zhang, Alian; Gu, Ting; Wang, Liansheng; Wang, Changqian

    2012-01-01

    Hydrogen sulfide, as a novel gaseous mediator, has been suggested to play a key role in atherogenesis. However, the precise mechanisms by which H(2)S affects atherosclerosis remain unclear. Therefore, the present study aimed to investigate the potential role of H(2)S in atherosclerosis and the underlying mechanism with respect to chemokines (CCL2, CCL5 and CX3CL1) and chemokine receptors (CCR2, CCR5, and CX3CR1) in macrophages. Mouse macrophage cell line RAW 264.7 or mouse peritoneal macrophages were pre-incubated with saline or NaHS (50 µM, 100 µM, 200 µM), an H(2)S donor, and then stimulated with interferon-γ (IFN-γ) or lipopolysaccharide (LPS). It was found that NaHS dose-dependently inhibited IFN-γ or LPS-induced CX3CR1 and CX3CL1 expression, as well as CX3CR1-mediated chemotaxis in macrophages. Overexpression of cystathionine γ-lyase (CSE), an enzyme that catalyzes H(2)S biosynthesis resulted in a significant reduction in CX3CR1 and CX3CL1 expression as well as CX3CR1-mediated chemotaxis in stimulated macrophages. The inhibitory effect of H(2)S on CX3CR1 and CX3CL1 expression was mediated by modulation of proliferators-activated receptor-γ (PPAR-γ) and NF-κB pathway. Furthermore, male apoE(-/-) mice were fed a high-fat diet and then randomly given NaHS (1 mg/kg, i.p., daily) or DL-propargylglycine (PAG, 10 mg/kg, i.p., daily). NaHS significantly inhibited aortic CX3CR1 and CX3CL1 expression and impeded aortic plaque development. NaHS had a better anti-atherogenic benefit when it was applied at the early stage of atherosclerosis. However, inhibition of H(2)S formation by PAG increased aortic CX3CR1 and CX3CL1 expression and exacerbated the extent of atherosclerosis. In addition, H(2)S had minimal effect on the expression of CCL2, CCL5, CCR2 and CCR5 in vitro and in vivo. In conclusion, these data indicate that H(2)S hampers the progression of atherosclerosis in fat-fed apoE(-/-) mice and downregulates CX3CR1 and CX3CL1 expression on macrophages and in

  15. Functionalization of TiO2 with graphene quantum dots for efficient photocatalytic hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Hao, Xuqiang; Jin, Zhiliang; Xu, Jing; Min, Shixiong; Lu, Gongxuan

    2016-06-01

    Graphene quantum dots (GQDs) serve as a novel solid-state electron transfer reagent anchored on TiO2 by in situ photo-assisted strategy and greatly enhanced photocatalytic H2 evolution activity in methanol aqueous solution without the noble mental cocatalyst. The excellent photocatalytic activities were ascribed to the GQDs which act as an excellent electron transporters and acceptors, as well as photosensitizer. GQDs not only acted as efficient electron reservoirs and a solid-state electron transfer reagent from the conduction band of TiO2 to GQDs, but also acted as an excellent photosensitizer to sensitize TiO2, in which the photoinduced electrons transfer from excited GQDs to TiO2 to produce H2. In addition, GQDs is nanoscale fragments of graphene which can provide a larger active surface and greatly increase the contact area with the TiO2, which is conducive to rapidly transfer photo-generated electrons due to the large specific area and high carrier mobility of GQDs. Thus, GQDs improved the photocatalytic activity for H2 evolution.

  16. Synthesis of Cobalt Phosphide Nanoparticles Supported on Pristine Graphene by Dynamically Self-Assembled Graphene Quantum Dots for Hydrogen Evolution.

    PubMed

    Wang, Xiaoyan; Yuan, Weiyong; Yu, Yanan; Li, Chang Ming

    2017-03-09

    A highly active, durable, and low-cost hydrogen evolution reaction (HER) catalyst is desirable for energy storage through water splitting but its fabrication presents great challenges. Herein, mediated by dynamically self-assembled graphene quantum dots (GQDs), small, uniform, high-density, and well-dispersed CoP nanoparticles were grown in situ on pristine graphene for the first time. This hybrid nanostructure was then employed as HER electrocatalyst, showing an onset potential of 7 mV, an overpotential of 91.3 mV to achieve 10 mA cm(-2) , a Tafel slope of 42.6 mV dec(-1) , and an exchange current density of 0.1225 mA cm(-2) , all of which compare favorably to those of most reported non-noble-metal catalysts. The developed catalyst also exhibits excellent durability with negligible current loss after 2000 cyclic voltammetry cycles (+0.01 to -0.17 V vs. RHE) or 34 h of chronoamperometric measurement at an overpotential of 91.3 mV. This work not only develops a new strategy for the fabrication of high-performance and inexpensive electrocatalysts for HER but also provides scientific insight into the mechanism of the dynamically self-assembled GQDsmediated synthesis process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Temperature-Dependent Exciton and Trap-Related Photoluminescence of CdTe Quantum Dots Embedded in a NaCl Matrix: Implication in Thermometry.

    PubMed

    Kalytchuk, Sergii; Zhovtiuk, Olga; Kershaw, Stephen V; Zbořil, Radek; Rogach, Andrey L

    2016-01-27

    Temperature-dependent optical studies of semiconductor quantum dots (QDs) are fundamentally important for a variety of sensing and imaging applications. The steady-state and time-resolved photoluminescence properties of CdTe QDs in the size range from 2.3 to 3.1 nm embedded into a protective matrix of NaCl are studied as a function of temperature from 80 to 360 K. The temperature coefficient is found to be strongly dependent on QD size, with the highest sensitivity obtained for the smallest size of QDs. The emission from solid-state CdTe QD-based powders is maintained with high color purity over a wide range of temperatures. Photoluminescence lifetime data suggest that temperature dependence of the intrinsic radiative lifetime in CdTe QDs is rather weak, and it is mostly the temperature-dependent nonradiative decay of CdTe QDs which is responsible for the thermal quenching of photoluminescence intensity. By virtue of the temperature-dependent photoluminescence behavior, high color purity, photostability, and high photoluminescence quantum yield (26%-37% in the solid state), CdTe QDs embedded in NaCl matrices are useful solid-state probes for thermal imaging and sensing over a wide range of temperatures within a number of detection schemes and outstanding sensitivity, such as luminescence thermochromic imaging, ratiometric luminescence, and luminescence lifetime thermal sensing. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Hydrogen and oxygen isotope fractionation between brucite and aqueous NaCl solutions from 250 to 450°C

    USGS Publications Warehouse

    Saccocia, Peter J.; Seewald, Jeffrey S.; Shanks, Wayne C.

    1998-01-01

    Hydrogen and oxygen isotope fractionation factors between brucite and aqueous NaCl solutions (1000lnαbr-sw) have been calibrated by experiment from 250 to 450°C at 0.5 Kb. For D/H fractionation, 1000lnα br-sw values are as follows: −32 ± 6‰ (250°C, 3.2 wt% NaCl), −21 ± 2‰ (350°C, 10.0 wt% NaCl), and −22 ± 2‰ (450°C, 3.2 wt% NaCl), indicating that brucite is depleted in D relative to coexisting aqueous NaCl solutions. These results are in good agreement with previous D/H fractionation factors determined in the brucite-water system, indicating that any effects of dissolved salt on D/H fractionation are relatively small, particularly in solutions with near seawater salinity. The maximum salt effect (+4‰) was observed in 10.0 wt% NaCl solutions at 350°C, suggesting that the addition of dissolved NaCl increases the amount of deuterium fractionated into mineral structures. For 18O/16O fractionation, 1000lnαbr-sw values in 3.0 wt% NaCl solutions are −6.0 ± 1.3‰, −5.6 ± 0.7‰ and −4.1 ± 0.2‰, at 250, 350, and 450°C, respectively, and −5.8 ± 0.6‰ in 10.0 wt % NaCl at 350°C. These data indicate that brucite is depleted in 18O relative to coexisting aqueous NaCl solutions and that the degree of depletion decreases slightly with increasing temperature and is not strongly dependent on salinity. We calculated 18O/16O brucite-water fractionation factors from available calibrations of the salt-effect on 18O/16O fractionation between coexisting phases. The resulting values were fit to the following equation that is valid from 250 to 450°C 1000ln αbr-w = 9.54 × 106T−2 − 3.53 × 104T−1 + 26.58 where T is temperature in Kelvins. These new data have been used to improve the prediction of 18O/16O fractionation factors in the talc-water and serpentine-water systems by modifying existing empirical bond-water models. The results of this analysis indicate that the δ18O composition of talc-brucite and serpentine

  19. Quantum confinement controlled solar hydrogen production from hydrogen sulfide using a highly stable CdS(0.5)Se(0.5)/CdSe quantum dot-glass nanosystem.

    PubMed

    Apte, Sanjay K; Garaje, Sunil N; Naik, Sonali D; Waichal, Rupali P; Baeg, Jin-Ook; Kale, Bharat B

    2014-01-21

    We have demonstrated unique CdS0.5Se0.5 and CdSe quantum dot-glass nanosystems with quantum confinement effect. The stable, monodispersed CdS0.5Se0.5 and CdSe quantum dots (QDs) of size 2 to 12 nm have been grown in a germanate glass matrix by a simple melt quench technique at moderate temperature. XRD and Raman studies show formation of hexagonal CdS0.5Se0.5 and CdSe in the glass matrix. The quantum confinement of CdS0.5Se0.5 and CdSe was studied using TEM and UV-Vis spectroscopy. The band gap of the glass nanosystem was tuned from 3.6 to 1.8 eV by controlling the CdS0.5Se0.5 quantum dot size in the glass matrix. It can be further tuned to 1.68 eV using growth of CdSe quantum dots in the glass matrix. Considering the tuneable band gap of the CdS0.5Se0.5 and CdSe quantum dot-glass nanosystem for the visible light absorption, a study of size tuneable photocatalytic activity for hydrogen generation from hydrogen sulfide splitting was performed under visible light irradiation for the first time. The utmost hydrogen evolution, i.e. 8164.53 and 7257.36 μmol h(-1) g(-1) was obtained for the CdS0.5Se0.5 and CdSe quantum dot-glass nanosystems, respectively. The apparent quantum yield (AQY) was observed to be 26% and 21% for the CdS0.5Se0.5 and CdSe quantum dot-glass nanosystems, respectively. It is noteworthy that the present glass nanosystem as a photocatalyst was found to be very stable as compared to naked powder photocatalysts.

  20. Stable hydrogen generation from vermiculite sensitized by CdS quantum dot photocatalytic splitting of water under visible-light irradiation.

    PubMed

    Zhang, Jian; Zhu, Wenfeng; Liu, Xiaoheng

    2014-06-28

    CdS quantum dot/vermiculite (CdS/VMT) nanocomposites have been synthesized via a facile one-step method and characterized by X-ray diffraction, UV-vis diffuse reflection spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. The photocatalytic hydrogen generation activities of these samples were evaluated using Na2S and Na2SO3 as sacrificial reagents in water under visible-light illumination (λ ≥ 420 nm). The most important aspect of this work is the use of natural products (VMT) as host photocatalysts. The effect of CdS content on the rate of visible light photocatalytic hydrogen generation was investigated for different CdS loadings. The synergistic effect of VMT and CdS quantum dots (QDs) leads to efficient separation of the photogenerated charge carriers and, consequently, enhances the visible light photocatalytic hydrogen production activity of the photocatalyst. The CdS/VMT composite with an optimal ratio of 5% exhibits the highest hydrogen evolution rate of 92 μmol h(-1) under visible light irradiation and the highest apparent quantum efficiency of 17.7% at 420 nm. A possible photocatalytic mechanism of the CdS/VMT nanocomposite is proposed and corroborated by photoelectrochemical curves.

  1. C-HCl(-) hydrogen bonds in solution and in the solid-state: HgCl2 complexes with cyclen-based cryptands.

    PubMed

    Ikeda, Mari; Sah, Ajay Kumar; Iwase, Miki; Murashige, Rina; Ishi-I, Jun-Ichi; Hasegawa, Masatoshi; Kachi-Terajima, Chihiro; Park, Ki-Min; Kuwahara, Shunsuke; Habata, Yoichi

    2017-03-21

    Structural evidence is reported for C-HCl(-) hydrogen bonds in solution and in the solid state of HgCl2 complexes with cyclen-based cryptands. These cyclen-based cryptands (1) and (2) are bridged by di- and triethylene glycol units, respectively, between two aromatic rings. The X-ray structure indicates that the 2/HgCl2 complex contains an acetonitrile molecule in the cavity.

  2. Loading Cd0.5Zn0.5S Quantum Dots onto Onion-Like Carbon Nanoparticles to Boost Photocatalytic Hydrogen Generation.

    PubMed

    Zhou, Xiaolong; Wang, Xina; Feng, Xi; Zhang, Kun; Peng, Xiaoniu; Wang, Hanbin; Liu, Chunlei; Han, Yibo; Wang, Hao; Li, Quan

    2017-07-12

    Carbon dots (C dots, size < 10 nm) have been conventionally decorated onto semiconductor matrixes for photocatalytic H2 evolution, but the efficiency is largely limited by the low loading ratio of the C dots on the photocatalyst. Here, we propose an inverse structure of Cd0.5Zn0.5S quantum dots (QDs) loaded onto the onionlike carbon (OLC) matrix for noble metal-free photocatalytic H2 evolution. Cd0.5Zn0.5S QDs (6.9 nm) were uniformly distributed on an OLC (30 nm) matrix with both upconverted and downconverted photoluminescence property. Such an inverse structure allows the full optimization of the QD/OLC interfaces for effective energy transfer and charge separation, both of which contribute to efficient H2 generation. An optimized H2 generation rate of 2018 μmol/h/g (under the irradiation of visible light) and 58.6 μmol/h/g (under the irradiation of 550-900 nm light) was achieved in the Cd0.5Zn0.5S/OLC composite samples. The present work shows that using the OLC matrix in such a reverse construction is a promising strategy for noble metal-free solar hydrogen production.

  3. Hydrogen bonding in cubic (H{sub 2}O){sub 8} and OH{center_dot}(H{sub 2}O){sub 7} clusters

    SciTech Connect

    Belair, Stephen D.; Francisco, Joseph S.; Singer, Sherwin J.

    2005-01-01

    A systematic study is presented for OH{center_dot}(H{sub 2}O){sub 7} clusters derived from the cubic (H{sub 2}O){sub 8} octamer by replacing one water with a hydroxyl radical. The system is a prototype for atmospheric water clusters containing the environmentally important OH species, and for OH adsorbed at the surface of ice. The full set of 39 symmetry-distinct cubic OH{center_dot}(H{sub 2}O){sub 7} clusters is enumerated, and the structures are determined using ab initio quantum chemical methods. Graph invariants are employed to obtain a unified analysis of the stability and structure of cubic (H{sub 2}O){sub 8} and OH{center_dot}(H{sub 2}O){sub 7}, relating these physical properties to the various hydrogen-bond topologies present in these clusters. To accomplish this the graph invariant formalism is extended to treat a hydrogen bonding impurity within a pure water network.

  4. Hydrogenic impurity, external electric and magnetic fields effects on the nonlinear optical properties of a multi-layer spherical quantum dot

    NASA Astrophysics Data System (ADS)

    Tanhaei, M. H.; Rezaei, G.

    2016-10-01

    In this work, effects of an on-center hydrogenic impurity, external electric and magnetic fields on the optical rectification coefficient (ORC), second and third harmonic generations (SHG and THG) of a multi-layer spherical quantum dot (MLSQD) are studied. Energy eigenvalues and eigenvectors are calculated using the direct matrix diagonalization method and optical properties are obtained using the compact density matrix approach. Our results reveal that the hydrogenic impurity and external fields have a great influence on these optical quantities. Hydrogenic impurity reduces the magnitude of the resonant peaks and shifts them to the higher energies. An increase in the magnetic (electric) field, leads to increase (decrease) the interval energies and the dipole moment matrix elements. Therefore, resonant peaks of these optical quantities find an obvious blue (red) shift and their magnitudes enhance (diminish) with increasing the external magnetic (electric) field.

  5. Diphosphine- and CO-Induced Fragmentation of Chloride-bridged Dinuclear Complex and Cp*Ir(mu-Cl)(3)Re(CO)(3) and Attempted Synthesis of Cp*Ir(mu-Cl)(3)Mn(CO)(3): Spectroscopic Data and X-ray Diffraction Structures of the Pentamethylcyclopentadienyl Compounds [Cp*IrCl{(Z)-Ph2PCH = CHPPh2}][Cl]center dot 2CHCl(3) and Cp*Ir(CO)Cl-2

    SciTech Connect

    Hammons, Casey; Wang, Xiaoping; Nesterov, Vladimir; Richmond, Michael G.

    2010-01-01

    The confacial bioctahedral compound Cp*Ir(mu-Cl)(3)Re(CO)(3) (1) undergoes rapid fragmentation in the presence of the unsaturated diphosphine ligand (Z)-Ph2PCH = CHPPh2 to give the mononuclear compounds [Cp*IrCl {(Z)-Ph2PCH = CHPPh2}][Cl] (2) and fac-ClRe(CO)(3)[(Z)-Ph2PCH = CHPPh2] (3). 2 has been characterized by H-1 and P-31 NMR spectroscopy and X-ray diffraction analysis. 2 center dot 2CHCl(3) crystallizes in the monoclinic space group C2/c, a = 35.023 (8) angstrom, b = 10.189 (2) angstrom, c = 24.003 (6) angstrom, b = 103.340 (3), V = 8,335 (3) angstrom 3, Z = 8, and d(calc) = 1.647 Mg/m(3); R = 0.0383, R-w = 0.1135 for 8,178 reflections with I> 2 sigma(I). The Ir(III) center in 2 exhibits a six-coordinate geometry and displays a chelating diphosphine group. Compound 1 reacts with added CO with fragmentation to yield the known compounds Cp*Ir(CO)Cl-2 (4) and ClRe(CO)(5) (5) in near quantitative yield by IR spectroscopy. Using the protocol established by our groups for the synthesis of 1, we have explored the reaction of [Cp*IrCl2](2) with ClMn(CO)(5) as a potential route to Cp*Ir(mu-Cl)(3)Mn(CO)(3); unfortunately, 4 was the only product isolated from this reaction. The solid-state structure of 4 was determined by X-ray diffraction analysis. 4 crystallizes in the triclinic space group P-1, a = 7.4059 (4) angstrom, b = 7.8940 (4) angstrom, c = 11.8488 (7) angstrom, alpha = 80.020 (1), beta = 79.758 (1), gamma = 68.631 (1), V = 630.34 (6) angstrom(3), Z = 2, and d(calc) = 2.246 Mg/m(3); R = 0.0126, R-w = 0.0329 for 2,754 reflections with I> 2 sigma(I). The expected three-legged piano-stool geometry in 4 has been crystallographically confirmed.

  6. The effects of temperature, hydrostatic pressure and size on optical gain for GaAs spherical quantum dot laser with hydrogen impurity

    NASA Astrophysics Data System (ADS)

    Owji, Erfan; Keshavarz, Alireza; Mokhtari, Hosein

    2016-10-01

    In this paper, the effects of temperature, hydrostatic pressure and size on optical gain for GaAs spherical quantum dot laser with hydrogen impurity are investigated. For this purpose, the effects of temperature, pressure and quantum dot size on the band gap energy, effective mass, and dielectric constant are studied. The eigenenergies and eigenstates for valence and conduction band are calculated by using Runge-Kutta numerical method. Results show that changes in the temperature, pressure and size lead to the alteration of the band gap energy and effective mass. Also, increasing the temperature redshifts the optical gain peak and at special temperature ranges lead to increasing or decreasing of it. Further, by reducing the size, temperature-dependent of optical gain is decreased. Additionally, enhancing of the hydrostatic pressure blueshifts the peak of optical gain, and its behavior as a function of pressure which depends on the size. Finally, increasing the radius rises the redshifts of the peak of optical gain.

  7. Enhancement of periodate-hydrogen peroxide chemiluminescence by nitrogen doped carbon dots and its application for the determination of pyrogallol and gallic acid.

    PubMed

    Shah, Syed Niaz Ali; Li, Haifang; Lin, Jin-Ming

    2016-06-01

    A new sensitized chemiluminescence (CL) was developed to broaden the analytical application of KIO4-H2O2 system. The nitrogen doped carbon dots (N-CDs) dramatically boosted the CL intensity of KIO4-H2O2 system which was further enriched by basic medium. In light of EPR analysis, free radical scavenging studies and CL spectra the detail mechanism for the enhancement was conferred in the presence of N-CDs and NaOH. The results suggested that CL of KIO4-H2O2 system in the presence and absence of N-CDs and NaOH proceeds via radical pathway. The enhanced CL was used for the determination of pyrogallol and gallic acid in range of 1.0×10(-4)-1.0×10(-7)M with 4.6×10(-8) and 6.1×10(-8)M limit of detection respectively. The relative standard deviation (RSD) at a concentration of 10(-5) for gallic acid and pyrogallol was 1.4% and 2.3% respectively (n=11). The attained results unveil that the present method is sensitive, faster, simpler and less costly compared to other methods and could be applied to determine polyphenols in real samples.

  8. Critical slowing of quantum atomic deuterium/hydrogen with features of multiferroicity in the geometrically frustrated system C o2(OD) 3Cl /C o2(OH) 3Cl

    NASA Astrophysics Data System (ADS)

    Xu, Xing-Liang; Meng, Dong-Dong; Zheng, Xu-Guang; Yamauchi, Ichihiro; Watanabe, Isao; Guo, Qi-Xin

    2017-01-01

    An extensive study of hydroxyl salts C o2(OD) 3Cl /C o2(OH) 3Cl utilizing muon-spin-relaxation (μSR), nuclear magnetic resonance (NMR), and Raman spectroscopy, supplemented by dielectric constant and magnetic susceptibility measurements, has revealed a unique multiferroic system with deuterium-order-type ferroelectricity and geometrically frustrated magnetism. Through the temperature-dependent dynamics of the nuclear fields probed by μSR, the deuterium atoms in C o2(OD) 3Cl were found to be rapidly fluctuating in the paraelectric phase. Upon cooling, they showed a critical slowing down toward the ferroelectric transition at Tc=Tɛ= 230 K , below which eight new Raman-active phonon bands appeared as a result of symmetry breaking due to deuterium ordering. Meanwhile, the hydrogen atoms in C o2(OH) 3Cl became quasistatic at a reduced temperature near 210 K, wherein only one new Raman band appeared with a broad dielectric anomaly, suggesting incomplete ordering. Furthermore, the μSR, NMR, Raman spectroscopy, and the magnetic susceptibility all suggested an increase in magnetic couplings below ˜250 K in both C o2(OD) 3Cl and C o2(OH) 3Cl , demonstrating a multiferroic feature for C o2(OD) 3Cl . This work presents a new and unique multiferroic system with an exceptional high Tc. It also demonstrates that conventional μSR can be an effective tool for studying ferroelectrics.

  9. Stereo-specificity for pro-(R) hydrogen of NAD(P)H during enzyme-catalyzed hydride transfer to CL-20

    SciTech Connect

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal . E-mail: jalal.hawari@nrc.ca

    2005-12-02

    A dehydrogenase from Clostridium sp. EDB2 and a diaphorase from Clostridium kluyveri were reacted with CL-20 to gain insights into the enzyme-catalyzed hydride transfer to CL-20, and the enzyme's stereo-specificity for either pro-R or pro-S hydrogens of NAD(P)H. Both enzymes biotransformed CL-20 at rates of 18.5 and 24 nmol/h/mg protein, using NADH and NADPH as hydride-source, respectively, to produce a N-denitrohydrogenated product with a molecular weight of 393 Da. In enzyme kinetics studies using reduced deuterated pyridine nucleotides, we found a kinetic deuterium isotopic effect of 2-fold on CL-20 biotransformation rate using dehydrogenase enzyme against (R)NADD as a hydride-source compared to either (S)NADD or NADH. Whereas, in case of diaphorase, the kinetic deuterium isotopic effect of about 1.5-fold was observed on CL-20 biotransformation rate using (R)NADPD as hydride-source. In a comparative study with LC-MS, using deuterated and non-deuterated NAD(P)H, we found a positive mass-shift of 1 Da in the N-denitrohydrogenated product suggesting the involvement of a deuteride (D{sup -}) transfer from NAD(P)D. The present study thus revealed that both dehydrogenase and diaphorase enzymes from the two Clostridium species catalyzed a hydride transfer to CL-20 and showed stereo-specificity for pro-R hydrogen of NAD(P)H.

  10. Multiple additions of Vaska-type iridium complexes to C{sub 60}. Preferential crystallization of the {open_quotes}para{close_quotes} double addition products C{sub 60}(Ir(CO)Cl(PMe{sub 3}){sub 2}){sub 2}{center_dot}2C{sub 6}H{sub 6} and C{sub 60}(Ir(CO)Cl(Pet{sub 3}){sub 2}){sub 2}{center_dot}C{sub 6}H{sub 6}

    SciTech Connect

    Balch, A.L.; Lee, Joong, W.; Noll, B.C.

    1994-11-09

    The authors investigated addition of Vaska-type iridium complexes to C{sub 60} fullerene. Two products were observed and characterized: C{sub 60}(Ir(CO)Cl(PMe{sub 3}){sub 2}){sub 2}{center_dot}2C{sub 6}H{sub 6} and C{sub 60}(Ir(CO)Cl(PEt{sub 3}){sub 2}){sub 2}{center_dot}C{sub 6}H{sub 6}. These compounds were structurally characterized by X-ray crystallography and NMR spectroscopy. It is suggested that many isomers of the adducts are present in the reaction liquor, but low solubility of the observed products drives the observed distribution of solid products.

  11. Coral-Shaped MoS2 Decorated with Graphene Quantum Dots Performing as a Highly Active Electrocatalyst for Hydrogen Evolution Reaction.

    PubMed

    Guo, Bangjun; Yu, Ke; Li, Honglin; Qi, Ruijuan; Zhang, Yuanyuan; Song, Haili; Tang, Zheng; Zhu, Ziqiang; Chen, Mingwei

    2017-02-01

    We report a new CVD method to prepare coral-shaped monolayer MoS2 with a large amount of exposed edge sites for catalyzing hydrogen evolution reaction. The electrocatalytic activities of the coral-shaped MoS2 can be further enhanced by electronic band engineering via decorated with graphene quantum dot (GQD) decoration. Generally, GQDs improve the electrical conductivity of the MoS2 electrocatalyst. First-principles calculations suggest that the coral MoS2@GQD is a zero-gap material. The high electric conductivity and pronounced catalytically active sites give the hybrid catalyst outstanding electrocatalytic performance with a small onset overpotential of 95 mV and a low Tafel slope of 40 mV/dec as well as excellent long-term electrocatalytic stability. The present work provides a potential way to design two-dimensional hydrogen evolution reaction (HER) electrocatalysts through controlling the shape and modulating the electric conductivity.

  12. Photoluminescence properties and crystallization of silicon quantum dots in hydrogenated amorphous Si-rich silicon carbide films

    SciTech Connect

    Wen, Guozhi; Zeng, Xiangbin Wen, Xixin; Liao, Wugang

    2014-04-28

    Silicon quantum dots (QDs) embedded in hydrogenated amorphous Si-rich silicon carbide (α-SiC:H) thin films were realized by plasma-enhanced chemical vapor deposition process and post-annealing. Fluorescence spectroscopy was used to characterize the room-temperature photoluminescence properties. X-ray photoelectron spectroscopy was used to analyze the element compositions and bonding configurations. Ultraviolet visible spectroscopy, Raman scattering, and high-resolution transmission electron microscopy were used to display the microstructural properties. Photoluminescence measurements reveal that there are six emission sub-bands, which behave in different ways. The peak wavelengths of sub-bands P1, P2, P3, and P6 are pinned at about 425.0, 437.3, 465.0, and 591.0 nm, respectively. Other two sub-bands, P4 is red-shifted from 494.6 to 512.4 nm and P5 from 570.2 to 587.8 nm with temperature increasing from 600 to 900 °C. But then are both blue-shifted, P4 to 500.2 nm and P5 to 573.8 nm from 900 to 1200 °C. The X-ray photoelectron spectroscopy analysis shows that the samples are in Si-rich nature, Si-O and Si-N bonds consumed some silicon atoms. The structure characterization displays that a separation between silicon phase and SiC phase happened; amorphous and crystalline silicon QDs synthesized with increasing the annealing temperature. P1, P2, P3, and P6 sub-bands are explained in terms of defect-related emission, while P4 and P5 sub-bands are explained in terms of quantum confinement effect. A correlation between the peak wavelength shift, as well as the integral intensity of the spectrum and crystallization of silicon QDs is supposed. These results help clarify the probable luminescence mechanisms and provide the possibility to optimize the optical properties of silicon QDs in Si-rich α-SiC: H materials.

  13. Synthesis, structure, and physical properties for a series of trigonal bipyramidal M(II)-Cl complexes with intramolecular hydrogen bonds.

    PubMed

    Sickerman, Nathaniel S; Park, Young Jun; Ng, Gary K-Y; Bates, Jefferson E; Hilkert, Mark; Ziller, Joseph W; Furche, Filipp; Borovik, A S

    2012-04-21

    A series of transition metal chloro complexes with the tetradentate tripodal tris(2-amino-oxazoline)amine ligand (TAO) have been synthesized and characterized. X-Ray structural analyses of these compounds demonstrate the formation of the mononuclear complexes [M(II)(TAO)(Cl)](+), where M(II) = Cr, Mn, Fe, Co, Ni, Cu and Zn. These complexes exhibit distorted trigonal-bipyramidal geometry, coordinating the metal through an apical tertiary amine, three equatorial imino nitrogen atoms, and an axial chloride anion. All the complexes possess an intramolecular hydrogen-bonding (H-bonding) network within the cavity occupied by the metal-bound chloride ion. The metal-chloride bond distances are atypically long, which is attributed to the effects of the H-bonding network. Nuclear magnetic resonance (NMR) spectroscopy of the Zn complex suggests that the solid-state structures are representative of that observed in solution, and that the H-bonding interactions persist as well. Additionally, density functional theory (DFT) calculations were carried out to probe the electronic structures of the complexes.

  14. Vectorial electron transfer for improved hydrogen evolution by mercaptopropionic-acid-regulated CdSe quantum-dots-TiO2 -Ni(OH)2 assembly.

    PubMed

    Yu, Shan; Li, Zhi-Jun; Fan, Xiang-Bing; Li, Jia-Xin; Zhan, Fei; Li, Xu-Bing; Tao, Ye; Tung, Chen-Ho; Wu, Li-Zhu

    2015-02-01

    A visible-light-induced hydrogen evolution system based on a CdSe quantum dots (QDs)-TiO2 -Ni(OH)2 ternary assembly has been constructed under an ambient environment, and a bifunctional molecular linker, mercaptopropionic acid, is used to facilitate the interaction between CdSe QDs and TiO2 . This hydrogen evolution system works effectively in a basic aqueous solution (pH 11.0) to achieve a hydrogen evolution rate of 10.1 mmol g(-1)  h(-1) for the assembly and a turnover frequency of 5140 h(-1) with respect to CdSe QDs (10 h); the latter is comparable with the highest value reported for QD systems in an acidic environment. X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and control experiments demonstrate that Ni(OH)2 is an efficient hydrogen evolution catalyst. In addition, inductively coupled plasma optical emission spectroscopy and the emission decay of the assembly combined with the hydrogen evolution experiments show that TiO2 functions mainly as the electron mediator; the vectorial electron transfer from CdSe QDs to TiO2 and then from TiO2 to Ni(OH)2 enhances the efficiency for hydrogen evolution. The assembly comprises light antenna CdSe QDs, electron mediator TiO2 , and catalytic Ni(OH)2 , which mimics the strategy of photosynthesis exploited in nature and takes us a step further towards artificial photosynthesis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Chloride-hydrogen antiporters ClC-3 and ClC-5 drive osteoblast mineralization and regulate fine-structure bone patterning in vitro.

    PubMed

    Larrouture, Quitterie C; Nelson, Deborah J; Robinson, Lisa J; Liu, Li; Tourkova, Irina; Schlesinger, Paul H; Blair, Harry C

    2015-11-01

    Osteoblasts form an epithelium-like layer with tight junctions separating bone matrix from extracellular fluid. During mineral deposition, calcium and phosphate precipitation in hydroxyapatite liberates 0.8 mole of H(+) per mole Ca(+2). Thus, acid export is needed for mineral formation. We examined ion transport supporting osteoblast vectorial mineral deposition. Previously we established that Na/H exchangers 1 and 6 are highly expressed at secretory osteoblast basolateral surfaces and neutralize massive acid loads. The Na/H exchanger regulatory factor-1 (NHERF1), a pdz-organizing protein, occurs at mineralizing osteoblast basolateral surfaces. We hypothesized that high-capacity proton transport from matrix into osteoblast cytosol must exist to support acid transcytosis for mineral deposition. Gene screening in mineralizing osteoblasts showed dramatic expression of chloride-proton antiporters ClC-3 and ClC-5. Antibody localization showed that ClC-3 and ClC-5 occur at the apical secretory surface facing the bone matrix and in membranes of buried osteocytes. Surprisingly, the Clcn3(-/-) mouse has only mildly disordered mineralization. However, Clcn3(-/-) osteoblasts have large compensatory increases in ClC-5 expression. Clcn3(-/-) osteoblasts mineralize in vitro in a striking and novel trabecular pattern; wild-type osteoblasts form bone nodules. In mesenchymal stem cells from Clcn3(-/-) mice, lentiviral ClC-5 shRNA created Clcn3(-/-), ClC-5 knockdown cells, validated by western blot and PCR. Osteoblasts from these cells produced no mineral under conditions where wild-type or Clcn3(-/-) cells mineralize well. We conclude that regulated acid export, mediated by chloride-proton exchange, is essential to drive normal bone mineralization, and that CLC transporters also regulate fine patterning of bone.

  16. Comparison of phosgene, chlorine, and hydrogen chloride as reagents for converting molten CaO. CaCl/sub 2/ to CaCl/sub 2/

    SciTech Connect

    Fife, K.W.; Bowersox, D.F.; McCormick, E.D.

    1985-09-01

    One method used at Los Alamos for preparing impure plutonium metal from the impure oxide is batch reduction with calcium metal at 850/sup 0/C in a CaCl/sub 2/ solvent. The solvent salt from this reduction is currently discarded as low-level radioactive waste only because it is saturated with the CaO by-product. We have demonstrated a pyrochemical technique for converting the CaO to CaCl/sub 2/, thereby incorporating solvent recycle into the batch reduction process. We discuss the effectiveness of HCl, Cl/sub 2/, and COCl/sub 2/ as chlorinating agents and present initial data on regenerating and recycling actual, spent-solvent salts. 6 refs., 8 figs., 1 tab.

  17. Comparison of phosgene, chlorine, and hydrogen chloride as reagents for converting molten CaO. CaCl/sub 2/ to CaCl/sub 2/

    SciTech Connect

    Fife, K.W.

    1985-01-01

    One method at Los Alamos for preparing impure plutonium metal from the impure oxide is by batch reduction with calcium metal at 850/sup 0/C in a CaCl/sub 2/ solvent. The solvent salt from this reduction is currently discarded as low-level radioactivity waste only because it is saturated with the CaO byproduct. We have demonstrated a pyrochemical technique for converting the CaO to CaCl/sub 2/ thereby incorporating solvent recycling into the batch reduction process. We will discuss the effectiveness of HCl, Cl/sub 2/, and COCl/sub 2/ as chlorinating agents and recycling actual spent process solvent salts. 6 refs., 8 figs.

  18. {gamma}-Radiolysis of NaCl Brine in the Presence of UO{sub 2}(s): Effects of Hydrogen and Bromide

    SciTech Connect

    Metz, Volker; Bohnert, Elke; Kelm, Manfred; Schild, Dieter; Kienzler, Bernhard

    2007-07-01

    A concentrated NaCl solution was {gamma}-irradiated in autoclaves under a pressure of 25 MPa. A set of experiments were conducted in 6 mol (kg H{sub 2}O){sup -1} NaCl solution in the presence of UO{sub 2}(s) pellets; in a second set of experiments, {gamma}-radiolysis of the NaCl brine was studied without UO{sub 2}(s). Hydrogen, oxygen and chlorate were formed as long-lived radiolysis products. Due to the high external pressure, all radiolysis products remained dissolved. H{sub 2} and O{sub 2} reached steady state concentrations in the range of 5.10{sup -3} to 6.10{sup -2} mol (kg H{sub 2}O){sup -1} corresponding to a partial gas pressure of {approx}2 to {approx}20 MPa. Radiolytic formation of hydrogen and oxygen increased with the concentration of bromide added to solution. Both, in the presence of bromide, resulting in a relatively high radiolytic yield, and in the absence of bromide surfaces of the UO{sub 2}(s) samples were oxidized, and concentration of dissolved uranium reached the solubility limit of the schoepite / NaUO{sub 2}O(OH)(cr) transition. At the end of the experiments, the pellets were covered by a surface layer of a secondary solid phase having a composition close to Na{sub 2}U{sub 2}O{sub 7}. The experimental results demonstrate that bromide counteracts an H{sub 2} inhibition effect on radiolysis gas production, even at a concentration ratio of [H{sub 2}] / [Br{sup -}] > 100. The present observations are related to the competitive reactions of OH radicals with H{sub 2}, Br{sup -} and Cl{sup -}. A similar competition of hydrogen and bromide, controlling the yield of {gamma}-radiolysis products, is expected for solutions of lower Cl{sup -} concentration. (authors)

  19. Trans/cis isomerization of [RuCl2(diphosphine)(diamine)] complexes: Synthesis, X-ray structure and catalytic activity in hydrogenation

    NASA Astrophysics Data System (ADS)

    Warad, Ismail; AlHussen, Hanan; Alanazi, Hamdah; Mahfouz, Refaat; Hammouti, Belkheir; Al-Dosari, Mohammad A.; Al-Far, Rawhi; Ben Hadda, Taibi

    2013-03-01

    The diamine (Nsbnd N) co-ligand 2,2-dimethyl-1,3-propanediamine and 2,3-diaminophathalene react individually with [RuCl2(dppb)2(μ-dppb)] to afford complexes with kinetically stable trans-[Cl2Ru(dppb)(Nsbnd N)] as the favoured isomer. The thermodynamically stable cis-[Cl2Ru(dppb)(Nsbnd N)] isomer of complex 1 was formed from the trans-1 isomer. The trans to cis isomerization reaction was conducted in CHCl3 at RT and monitored by 31P{1H} NMR. The structures of the desired complexes were characterized via elemental analyses, IR and, UV-visible spectroscopy, FAB-MS and NMR. The structure of the cis-1 isomer was determined by single crystal X-ray measurements. Both the trans-1 and cis-1 isomers were shown to have a significant catalytic role in selective hydrogenation reactions under mild conditions using cinnamic aldehyde as typical model reaction.

  20. Density functional study of hydrogen bond formation between methanol and organic molecules containing Cl, F, NH2, OH, and COOH functional groups.

    PubMed

    Kolev, Stefan K; St Petkov, Petko; Rangelov, Miroslav A; Vayssilov, Georgi N

    2011-12-08

    Various hydrogen-bonded complexes of methanol with different proton accepting and proton donating molecules containing Cl, F, NH(2), OH, OR, and COOH functional groups have been modeled using DFT with hybrid B3LYP and M05-2X functionals. The latter functional was found to provide more accurate estimates of the structural and thermodynamic parameters of the complexes of halides, amines, and alcohols. The characteristics of these complexes are influenced not only by the principle hydrogen bond of the methanol OH with the proton acceptor heteroatom, but also by additional hydrogen bonds of a C-H moiety with methanol oxygen as a proton acceptor. The contribution of the former hydrogen bond in the total binding enthalpy increases in the order chlorides < fluorides < alcohols < amines, while the contribution of the second type of hydrogen bond increases in the reverse order. A general correlation was found between the binding enthalpy of the complex and the electrostatic potential at the hydrogen center participating in the formation of the hydrogen bond. The calculated binding enthalpies of different complexes were used to clarify which functional groups can potentially form a hydrogen bond to the 2'-OH hydroxyl group in ribose, which is strong enough to block it from participation in the intramolecular catalytic activation of the peptide bond synthesis. Such blocking could result in inhibition of the protein biosynthesis in the living cell if the corresponding group is delivered as a part of a drug molecule in the vicinity of the active site in the ribosome. According to our results, such activity can be accomplished by secondary or tertiary amines, alkoxy groups, deprotonated carboxyl groups, and aliphatic fluorides, but not by the other modeled functional groups.

  1. Confinement effect of monolayer MoS2 quantum dots on conjugated polyimide and promotion of solar-driven photocatalytic hydrogen generation.

    PubMed

    Ma, Chenghai; Zhu, Haoyue; Zhou, Jun; Cui, Zhiwei; Liu, Teng; Wang, Yicong; Wang, Ying; Zou, Zhigang

    2017-03-21

    A monolayer MoS2 quantum dot confined polyimide (MQDs/PI) photocatalyst was synthesized by using a facile immersion-hydrothermal method. The investigations on the optical and electronic properties of MQDs/PI composites reveal that the strong quantum confinement effect of MQDs results in a blue-shift of the absorption band edge of PI, and the interfacial electronic interaction between MQDs and PI improves the charge transfer rate of MQDs/PI. The ultra-small size of 3.0 nm and perfect crystals of MQDs endow MQDs/PI composites with plenty of active sites and fast charge transfer, thus resulting in a 360% enhancement in photocatalytic hydrogen production compared with that of Pt/PI at the same loading amount of Pt. This discovery provides a new clue for the development of an efficient and sustainable non-noble metal photocatalyst.

  2. Proline and glycinebetaine ameliorated NaCl stress via scavenging of hydrogen peroxide and methylglyoxal but not superoxide or nitric oxide in tobacco cultured cells.

    PubMed

    Banu, Mst Nasrin Akhter; Hoque, Md Anamul; Watanabe-Sugimoto, Megumi; Islam, Mohammad Muzahidul; Uraji, Misugi; Matsuoka, Ken; Nakamura, Yoshimasa; Murata, Yoshiyuki

    2010-01-01

    Efficient detoxification of the reactive oxygen species, nitric oxide (NO) and methylglyoxal (MG), provides protection against NaCl-induced damage in plants. To elucidate the protective mechanisms of proline and glycinebetaine (betaine) against NaCl stress, intracellular levels of hydrogen peroxide (H(2)O(2)), superoxide (O(2)(-)), NO, and MG were investigated in tobacco Bright Yellow-2 cells. The Levels of H(2)O(2), O(2)(-), NO and MG were higher in the short-term and long-term NaCl-stressed cells than in the non-stressed cells, whereas the O(2)(-) level was higher in the long-term stressed cells. Exogenous proline and betaine decreased the H(2)O(2) level in both the short-term and the long-term NaCl-stressed cells and the MG level in the long-term NaCl-stressed cells, but did not change the O(2)(-) or NO levels. Under salt stress, both proline and betaine increased the transcription levels of glutathione peroxidase, which can contribute to the reduction of H(2)O(2). In conclusion, proline and betaine mitigated salt stress via reduction of H(2)O(2) accumulation during short-term incubation and via reduction of the accumulation of H(2)O(2) and MG during long-term incubation.

  3. Temperature dependence of the rate constant for hydrogen atom reaction with Cl2-• in water by pulse radiolysis of aqueous HCl solution

    NASA Astrophysics Data System (ADS)

    Kazmierczak, L.; Szala-Bilnik, J.; Wolszczak, M.; Swiatla-Wojcik, D.

    2015-12-01

    The temperature dependence of the rate constant for the reaction of dichloride anion radical (Cl2- •) with atomic hydrogen (H•) in water up to 75 °C has been determined by pulse radiolysis of deaerated 0.1 M HCl solution. The room temperature value is (6.1±0.6)×109 M-1 s-1. The activation energy of (13.2±0.6) kJ mol-1 is less than 16.7 kJ mol-1, expected for the diffusion-controlled reaction. Based on the temperature dependence of the rate constant for the reactions H•+Cl2- • and H•+Cl2, derived in this work, and on that reported earlier (Szala-Bilnik et al., 2014) for Cl2- • + Cl2- • , we show that a value of (10±2) M-1 s-1 determined by Hartig and Getoff (1982) for k (H•+H2O) in water at 25 °C is overestimated by at least two orders of magnitude.

  4. Action mechanism of hydrogen gas on deposition of HfC coating using HfCl4-CH4-H2-Ar system

    NASA Astrophysics Data System (ADS)

    Wang, Yalei; Li, Zehao; Xiong, Xiang; Li, Xiaobin; Chen, Zhaoke; Sun, Wei

    2016-12-01

    Hafnium carbide coatings were deposited on carbon/carbon composites by low pressure chemical vapor deposition using HfCl4-CH4-H2-Ar system. The microstructure, mechanical and ablation resistance performance of HfC coatings deposited with various H2 concentrations were investigated. The effect of hydrogen gas on the deposition of HfC coating was also discussed. Results show that all of the deposited coatings are composed of single cubic HfC phase, the hydrogen gas acted as a crucial role in determining the preferred orientation, microstructure and growth behavior of HfC coatings. During the deposition process, the gas phase supersaturation of the reaction species can be controlled by adjusting the hydrogen gas concentration. When deposited with low hydrogen gas concentration, the coating growth was dominated by the nucleation of HfC, which results in the particle-stacked structure of HfC coating. Otherwise, the coating growth was dominated by the crystal growth at high hydrogen gas concentration, which leads to the column-arranged structure of HfC coating. Under the ablation environment, the coating C2 exhibits better configurational stability and ablation resistance. The coating structure has a significant influence on the mechanical and ablation resistance properties of HfC coating.

  5. 40 CFR 266.107 - Standards to control hydrogen chloride (HCl) and chlorine gas (Cl2) emissions.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... other thermal treatment unit subject to controls on HCl or Cl2 emissions under a RCRA operating permit... assuming all hazardous waste is fed into the device with the worst-case stack based on dispersion... testing to determine the emission rate for HCl and Cl2, air dispersion modeling to predict the maximum...

  6. 40 CFR 266.107 - Standards to control hydrogen chloride (HCl) and chlorine gas (Cl2) emissions.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... other thermal treatment unit subject to controls on HCl or Cl2 emissions under a RCRA operating permit... assuming all hazardous waste is fed into the device with the worst-case stack based on dispersion... testing to determine the emission rate for HCl and Cl2, air dispersion modeling to predict the maximum...

  7. 40 CFR 266.107 - Standards to control hydrogen chloride (HCl) and chlorine gas (Cl2) emissions.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... other thermal treatment unit subject to controls on HCl or Cl2 emissions under a RCRA operating permit... assuming all hazardous waste is fed into the device with the worst-case stack based on dispersion... testing to determine the emission rate for HCl and Cl2, air dispersion modeling to predict the maximum...

  8. 40 CFR 266.107 - Standards to control hydrogen chloride (HCl) and chlorine gas (Cl2) emissions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... other thermal treatment unit subject to controls on HCl or Cl2 emissions under a RCRA operating permit... assuming all hazardous waste is fed into the device with the worst-case stack based on dispersion... testing to determine the emission rate for HCl and Cl2, air dispersion modeling to predict the maximum...

  9. 40 CFR 266.107 - Standards to control hydrogen chloride (HCl) and chlorine gas (Cl2) emissions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... other thermal treatment unit subject to controls on HCl or Cl2 emissions under a RCRA operating permit... assuming all hazardous waste is fed into the device with the worst-case stack based on dispersion... testing to determine the emission rate for HCl and Cl2, air dispersion modeling to predict the maximum...

  10. Genotoxic and oxidative responses in coelomocytes of Eisenia fetida and Hediste diversicolor exposed to lipid-coated CdSe/ZnS quantum dots and CdCl2.

    PubMed

    Saez, Gladys; Aye, Mélanie; De Meo, Michel; Aimé, Ahissan; Bestel, Isabelle; Barthélémy, Philippe; Di Giorgio, Carole

    2015-07-08

    The emerging of Quantum Dots utilization in industrial or medicinal fields involved a potentially increase of these nanoparticles in environment. In this work, the genotoxic (comet assay) and oxidative effects (SOD activity, TBARS) of functionalized-QDs and cadmium chloride were investigated on Hediste diversicolor and Eisenia fetida coelomocytes. Results demonstrated that functionalized-QDs (QDNs) and cadmium chloride induced DNA damages through different mechanisms that depended on the nano- or ionic nature of Cd. The minimal genotoxic concentrations for H. diversicolor (<0.001ng/g for QDNs and CdCl2 ) were lower than for E. fetida (between 0.01 and 0.1 ng/g for QDNs, and between 0.001 and 0.01 ng/g for CdCl2 ). These results showed that H. diversicolor was more sensitive than E. fetida. The two contaminants had a low impact on the oxidative stress markers.

  11. Electric field induced optical gain of a hydrogenic impurity in a Cd{sub 0.8}Zn{sub 0.2}Se/ZnSe parabolic quantum dot

    SciTech Connect

    Jasmine, P. Christina Lily; Peter, A. John

    2015-06-24

    The dependence of electric field on the electronic and optical properties is investigated in a Cd{sub 0.8}Zn{sub 0.2}Se/ZnSe quantum dot. The hydrogenic binding energy, in the presence of electric field, is calculated with the spatial confinement effect. The electric field dependent optical gain with the photon energy is found using compact density matrix method. The results show that the electric field has a great influence on the optical properties of II-VI semiconductor quantum dot.

  12. Algal toxicity of the alternative disinfectants performic acid (PFA), peracetic acid (PAA), chlorine dioxide (ClO2) and their by-products hydrogen peroxide (H2O2) and chlorite (ClO2(-)).

    PubMed

    Chhetri, Ravi Kumar; Baun, Anders; Andersen, Henrik Rasmus

    2016-12-01

    Environmental effect evaluation of disinfection of combined sewer overflow events with alternative chemical disinfectants requires that the environmental toxicity of the disinfectants and the main by-products of their use are known. Many disinfectants degrade quickly in water which should be included in the evaluation of both their toxicity as determined in standardized tests and their possible negative effect in the water environment. Here we evaluated according to the standardized ISO 8692 test the toxicity towards the green microalgae, Pseudokirchneriella subcapitata, of three disinfectants: performic acid (PFA), peracetic acid (PAA) and chlorine dioxide (ClO2) as well as two by-products of their use: hydrogen peroxide (H2O2) and chlorite. All of the five chemicals investigated showed clear toxicity to the algae with well-defined dose response curves. The EC50 values ranged from 0.16 to 2.9mg/L based on nominal concentrations leading to the labeling of the chemicals as either toxic or very toxic. The five investigated chemicals decreased in toxicity in the order chlorine dioxide, performic acid, peracetic acid, chlorite and hydrogen peroxide. The stability of the chemicals increased in the same order as the toxicity decrease. This indicates that even though ClO2 has the highest environmental hazard potential, it may still be suitable as an alternative disinfectant due to its rapid degradation in water.

  13. The Synthesis and Structural Properties of Crystalline Silicon Quantum Dots upon Thermal Annealing of Hydrogenated Amorphous Si-Rich Silicon Carbide Films

    NASA Astrophysics Data System (ADS)

    Wen, Guozhi; Zeng, Xiangbin; Li, Xianghu

    2016-08-01

    Silicon quantum dots (QDs) embedded in non-stoichiometric hydrogenated silicon carbide (SiC:H) thin films have been successfully synthesized by plasma-enhanced chemical vapor deposition and post-annealing. The chemical composition analyses have been carried out by x-ray photoelectron spectroscopy (XPS). The bonding configurations have been deduced from Fourier transform infrared absorption measurements (FTIR). The evolution of microstructure with temperature has been characterized by glancing incident x-ray diffraction (XRD) and Raman diffraction spectroscopy. XPS and FTIR show that it is in Si-rich feature and there are a few hydrogenated silicon clusters in the as-grown sample. XRD and Raman diffraction spectroscopy show that it is in amorphous for the as-grown sample, while crystalline silicon QDs have been synthesized in the 900°C annealed sample. Silicon atoms precipitation from the SiC matrix or silicon phase transition from amorphous SiC is enhanced with annealing temperature increase. The average sizes of silicon QDs are about 5.1 nm and 5.6 nm, the number densities are as high as 1.7 × 1012 cm-2 and 3.2 × 1012 cm-2, and the crystalline volume fractions are about 58.3% and 61.3% for the 900°C and 1050°C annealed samples, respectively. These structural properties analyses provide an understanding about the synthesis of silicon QDs upon thermal annealing for applications in next generation optoelectronic and photovoltaic devices.

  14. Plasmonic silver quantum dots coupled with hierarchical TiO2 nanotube arrays photoelectrodes for efficient visible-light photoelectrocatalytic hydrogen evolution.

    PubMed

    Lian, Zichao; Wang, Wenchao; Xiao, Shuning; Li, Xin; Cui, Yingying; Zhang, Dieqing; Li, Guisheng; Li, Hexing

    2015-06-12

    A plasmonic Ag/TiO2 photocatalytic composite was designed by selecting Ag quantum dots (Ag QDs) to act as a surface plasmon resonance (SPR) photosensitizer for driving the visible-light driven photoelectrocatalytic hydrogen evolution. Vertically oriented hierarchical TiO2 nanotube arrays (H-TiO2-NTAs) with macroporous structure were prepared through a two-step method based on electrochemical anodization. Subsequently, Ag QDs, with tunable size (1.3-21.0 nm), could be uniformly deposited on the H-TiO2 NTAs by current pulsing approach. The unique structure of the as-obtained photoelectrodes greatly improved the photoelectric conversion efficiency. The as-obtained Ag/H-TiO2-NTAs exhibited strong visible-light absorption capability, high photocurrent density, and enhanced photoelectrocatalytic (PEC) activity toward photoelectrocatalytic hydrogen evolution under visible-light irradiation (λ>420 nm). The enhancement in the photoelectric conversion efficiency and activity was ascribed to the synergistic effects of silver and the unique hierarchical structures of TiO2 nanotube arrays, strong SPR effect, and anti-shielding effect of ultrafine Ag QDs.

  15. Infrared absorption of 1-chloro-2-methyl-2-propyl [(⋅)C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [(⋅)CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i-C4H8) in solid para-hydrogen.

    PubMed

    Chou, Ching-Yin; Lee, Yuan-Pern

    2016-10-07

    The addition reactions of chlorine atom with isobutene (i-C4H8) in solid para-hydrogen (p-H2) were investigated with infrared (IR) absorption spectra. When a p-H2 matrix containing Cl2 and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm(-1), and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, (⋅)C(CH3)2CH2Cl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm(-1) due to the 2-chloro-2-methylpropyl radical, (⋅)CH2C(CH3)2Cl, appeared; the ratio of (⋅)C(CH3)2CH2Cl to (⋅)CH2C(CH3)2Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H2 in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H2 matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-C4H8⋅Cl2 and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CH2ClCCl(CH3)2, are also characterized.

  16. Synthesis, spectral, thermal, X-ray single crystal of new RuCl2(dppb)diamine complexes and their application in hydrogenation of Cinnamic aldehyde

    NASA Astrophysics Data System (ADS)

    Warad, Ismail; Al-Hussain, Hanan; Al-Far, Rawhi; Mahfouz, Refaat; Hammouti, Belkheir; Hadda, Taibi Ben

    The preparation of new three trans-[RuCl2(dppb)(N-N)] with mixed diamine (N-N) and 1,4-bis-(diphenylphosphino)butane (dppb) ligands, starting from RuCl2(PPh3)3 as precursor is presented. The complexes are characterized on the basis of elemental analysis, IR, 1H, 13C and 31P{1H}NMR, FAB-MS, TG/DTA and single crystal X-ray diffraction studies. Complex (2L1) crystallizes in the monoclinic unit cells with the space group P21. The catalysts are evaluated for their Cinnamic aldehyde hydrogenation. The catalysts show excellent activity and selectivity for the unsaturated carbonyl compound under mild conditions.

  17. ZnCl2 -promoted asymmetric hydrogenation of β-secondary-amino ketones catalyzed by a P-chiral Rh-bisphosphine complex.

    PubMed

    Hu, Qiupeng; Zhang, Zhenfeng; Liu, Yangang; Imamoto, Tsuneo; Zhang, Wanbin

    2015-02-09

    A new catalytic system has been developed for the asymmetric hydrogenation of β-secondary-amino ketones using a highly efficient P-chiral bisphosphine-rhodium complex in combination with ZnCl2 as the activator of the catalyst. The chiral γ-secondary-amino alcohols were obtained in 90-94 % yields, 90-99 % enantioselectivities, and with high turnover numbers (up to 2000 S/C; S/C=substrate/catalyst ratio). A mechanism for the promoting effect of ZnCl2 on the catalytic system has been proposed on the basis of NMR spectroscopy and HRMS studies. This method was successfully applied to the asymmetric syntheses of three important drugs, (S)-duloxetine, (R)-fluoxetine, and (R)-atomoxetine, in high yields and with excellent enantioselectivities.

  18. Effects of surface residual species in SBA-16 on encapsulated chiral (1S,2S)-DPEN-RuCl2(TPP)2 in asymmetric hydrogenation of acetophenone

    NASA Astrophysics Data System (ADS)

    Shi, Xiufeng; Xing, Bin; Fan, Binbin; Xue, Zhaoteng; Li, Ruifeng

    2016-03-01

    The SBA-16 obtained by different routes of elimination of organic templates were used as the hosts for encapsulation of chiral Ru complex (1S,2S)-DPEN-RuCl2(TPP)2 ( 1) (DPEN = 1,2-diphenylethylene-diamine, TPP = triphenyl phosphine). The methods for removing templates had distinct effects on the amount of residual template in SBA-16, which made the SBA-16 with different surface and structure properties. 1 encapsulated in SBA-16 extracted with the mixture of pyridine and ethanol showed higher activity and enantioselectivity for acetophenone asymmetric hydrogenation.

  19. CB-TE2A(+)·Cl(-)·3H2O: a short intermolecular hydrogen bond between zwitterionic bicyclo[6.6.2]tetraamine macrocycles.

    PubMed

    Jurek, Paul; Reibenspies, Joseph H; Kiefer, Garry E

    2016-02-01

    1,4,8,11-Tetraazabicyclo[6.6.2]hexadecane-4,11-diacetic acid (CB-TE2A) is of much interest in nuclear medicine for its ability to form copper complexes that are kinetically inert, which is beneficial in vivo to minimize the loss of radioactive copper. The structural chemistry of the hydrated HCl salt of CB-TE2A, namely 11-carboxymethyl-1,8-tetraaza-4,11-diazoniabicyclo[6.6.2]hexadecane-4-acetate chloride trihydrate, C16H31N4O4(+)·Cl(-)·3H2O, is described. The compound crystallized as a positively charged zwitterion with a chloride counter-ion. Two of the amine groups in the macrocyclic ring are protonated. Formally, a single negative charge is shared between two of the carboxylic acid groups, while one chloride ion balances the charge. Two intramolecular hydrogen bonds are observed between adjacent pairs of N atoms of the macrocycle. Two intramolecular hydrogen bonds are also observed between the protonated amine groups and the pendant carboxylate groups. A short intermolecular hydrogen bond is observed between two partially negatively charged O atoms on adjacent macrocycles. The result is a one-dimensional polymeric zigzag chain that propagates parallel to the crystallographic a direction. A second intermolecular interaction is a hydrogen-bonding network in the crystallographic b direction. The carbonyl group of one macrocycle is connected through the three water molecules of hydration to the carbonyl group of another macrocycle.

  20. Binding energy of the ground and first few excited states of hydrogenic donor impurity in a rectangular GaAs quantum dot in the presence of electric field

    NASA Astrophysics Data System (ADS)

    Wang, Sheng; Kang, Yun; Li, Xian-Li

    2014-12-01

    Within the quasi-one-dimensional effective potential model and effective mass approximation, we calculate the ground and the first 9 excited-state binding energies of a hydrogenic donor impurity in a rectangular quantum dot (RQD) in the presence of electric field. The analytical form of the quasi-one-dimensional effective potential replacing the three-dimensional Coulomb potential in our model is derived by Fourier transforms. We discuss detailedly dependence of the binding energies on the impurity positions and electric fields. For the ground-state binding energy, our results qualitatively agree with that of Mendoza et al. (2005) in which they only calculated the ground-state binding energies in cubic quantum dots by variational method. However, for first 9 excited-state binding energies, such dependence has complex manner since there are two or three peaks in the electronic probability density distribution curves. The strengths and positions of these peaks in RQD affect the interaction potential between electron and impurity, which appears to be the critical control on the binding energies of impurity. The applied electric field pushes the positions of these peaks downwards, and the strengths of peaks located at the upper half of RQD increase while the strengths of lower peaks firstly decrease, then increase with increasing electric field. The high peak strength can lead to increase of the binding energy while the large distance between the position of peak and impurity center results in reduce of the energy, which is an interesting competition. This competition is more obvious for excited-state binding energies of off-central impurity.

  1. Modification of g-C3N4 nanosheets by carbon quantum dots for highly efficient photocatalytic generation of hydrogen

    NASA Astrophysics Data System (ADS)

    Li, Kui; Su, Feng-Yun; Zhang, Wei-De

    2016-07-01

    Carbon quantum dots (CQDs) were deposited onto graphite-like carbon nitride nanosheets (CNNS) to form CNNS/CQDs composites. The prepared CNNS/CQDs composites exhibit much higher photocatalytic activity under visible light irradiation than pure CNNS do. The CNNS/CQDs-7 sample displays the highest photocatalytic performance, with H2 production rate of 116.1 μmol h-1, which is three times of that over pure CNNS (37.8 μmol h-1). Photoluminescence spectroscopy and photoelectrochemical (PEC) analysis reveal that the CQDs are favorable for trapping electrons and promoting the separation of photogenerated electron-hole pairs in CNNS. A possible photocatalytic mechanism of the enhanced photocatalytic performance for H2 generation over CNNS/CQDs will be proposed in this paper.

  2. Graphdiyne: A Metal-Free Material as Hole Transfer Layer To Fabricate Quantum Dot-Sensitized Photocathodes for Hydrogen Production.

    PubMed

    Li, Jian; Gao, Xin; Liu, Bin; Feng, Qingliang; Li, Xu-Bing; Huang, Mao-Yong; Liu, Zhongfan; Zhang, Jin; Tung, Chen-Ho; Wu, Li-Zhu

    2016-03-30

    Graphdiyne (GDY), a novel large π-conjugated carbon material, for the first time, is introduced as the hole transfer layer into a photoelectrochemical water splitting cell (PEC). Raman and ultraviolet photoelectron spectroscopic studies indicate the existence of relatively strong π-π interactions between GDY and 4-mercaptopyridine surface-functionalized CdSe quantum dots, beneficial to the hole transportation and enhancement of the photocurrent performance. Upon exposure to a Xe lamp, the integrated photocathode produces a current density of nearly -70 μA cm(-2) at a potential of 0 V vs NHE in neutral aqueous solution. Simultaneously, the photocathode evolves H2 with 90 ± 5% faradic efficiency over three times and exhibits good stability within 12 h. All of the results indicate that GDY is a promising hole transfer material to fabricate a PEC device for water splitting by solar energy.

  3. Mediating relaxation and polarization of hydrogen-bonds in water by NaCl salting and heating.

    PubMed

    Zhang, Xi; Yan, Tingting; Huang, Yongli; Ma, Zengsheng; Liu, Xinjuan; Zou, Bo; Sun, Chang Q

    2014-12-07

    Infrared spectroscopy and contact-angle measurements revealed that NaCl salting has the same effect as heating on O:H phonon softening and H-O phonon stiffening, but has the opposite effect on skin polarization of liquid water. The mechanics of thermal modulation of O-O Coulomb repulsion [Sun, et al., J. Phys. Chem. Lett., 2013, 4, 3238] may suggest a possible mechanism for this NaCl involved Hofmeister effect, aqueous solution modulated surface tension and its abilities in protein dissolution, from the perspective of Coulomb mediation of interaction within the O:H-O bond.

  4. Possibility of direct exchange diffusion of hydrogen on the Cl/Si(100)-2×1 surface

    NASA Astrophysics Data System (ADS)

    Hsieh, Ming-Feng; Lin, Deng-Sung; Tsay, Shiow-Fon

    2009-07-01

    The diffusion behavior of hydrogen substitutional sites on the chlorine-terminated Si(100) surface was investigated at elevated temperatures using time-lapse scanning tunneling microscopy (STM). STM movies show that each hydrogen atom undergoes Brownian motion within a monochloride dimer row. The position of a hydrogen substitutional site is exchanged directly with that of an immediate neighboring chlorine atom in either the same dimer (intradimer diffusion) or in one of the two adjacent dimers in the same row (intrarow diffusion). Accordingly, conceptual direct exchange diffusion (DED) in a two-dimensional lattice was experimentally observed. Analysis of STM movies at various temperatures yielded rather low attempt frequencies and energy barriers, leading to the suggestion that the diffusion mechanism involves an intermediate low-energy molecular state. Density-functional theory (DFT) calculations were also performed and provided partial support for the proposed diffusion mechanism.

  5. Atmospheric chemistry of the reaction ClO + O{sub 2} {leftrightarrow} ClO {center_dot} O{sub 2}: Where it stands, what needs to be done, and why?

    SciTech Connect

    Prasad, S.S.; Lee, T.J.

    1994-04-20

    Possible existence and chemistry of ClO x O{sub 2} was originally proposed to explain the Norrish-Neville effect that O{sub 2} suppresses chlorine photosensitized loss of ozone. It was also thought that ClO x O{sub 2} might have some atmospheric chemistry significance. Recently, doubts have been cast on this proposal, because certain laboratory data seem to imply that the equilibrium constant of the title reaction is so small that ClO x O{sub 2} may be too unstable to matter. However, those data create only a superficial illusion to that effect, because on a closer analysis they do not disprove a moderately stable and chemically significant ClO x O{sub 2}. Furthermore, our state-of-the-science accurate computational chemistry calculations also suggest that ClO x O{sub 2} may be a weakly bound ClOOO radical with a reactive {sup 2}A ground electronic state. There is therefore a need to design and perform definitive experimental tests of the existence and chemistry of the ClO x O{sub 2} species, which we discuss and which have the potential to mediate the chlorine-catalyzed stratospheric ozone depletion.

  6. The system NaCl-CaCl[sub 2]-H[sub 2]O; 2: Densities for ionic strengths of 0. 1--19. 2 mol[center dot]kg[sup [minus]1] at 298. 15 and 308. 15 K and at 0. 1 MPa

    SciTech Connect

    Oakes, C.S.; Bodnar, R.J. . Dept. of Geological Sciences); Simonson, J.M. . Chemistry Division)

    1990-01-01

    Data on the physical properties of the ternary system NaCl-CaCl[sub 2]-H[sub 2]O are of particular importance in the processing and disposal of brines produced from industrial processes, chemical manufacture, and petroleum and geothermal reservoirs. Densities for ternary solutions in the system NaCl-CaCl[sub 2]-H[sub 2]O were measured with a vibrating-tube densimeter at 298.15 [+-] 0.09 and 308.15 [+-] 0.03 K and 0.1 MPa and over a range of ionic strengths from 0.1 to 19.2 mol[center dot]kg[sup [minus]1]. The present results are in excellent agreement with previously published data for the NaCl-H[sub 2]O binary and are in very good agreement with the more precise of the available data for the CaCl[sub 2]-H[sub 2]O binary at 298.15 K. Very large discrepancies between the results of the three most recent reports of densities for the CaCl[sub 2]-H[sub 2]O system at 308.15 K are resolved here, improving both the accuracy and precision for this system. Most significantly, the results reported here substantially expand the volumetric data base for ternary solutions. On the basis of the results of this study, most of the previously reported 308.15 K density data in the ternary system appear to contain large errors. The authors have evaluated the data within the framework of the Pitzer formalism and obtain new values for the ion interaction and mixing parameters for this ternary system. In addition to the parameters determined from the binary end-member solutions, it was found that only [theta][sub NaCa][sup v] was needed to represent the ternary results.

  7. Hydrogen Isotope Fractionation during the Biodegradation of 1,2-Dichloroethane: Potential for Pathway Identification Using a Multi-element (C, Cl, and H) Isotope Approach.

    PubMed

    Palau, Jordi; Shouakar-Stash, Orfan; Hatijah Mortan, Siti; Yu, Rong; Rosell, Monica; Marco-Urrea, Ernest; Freedman, David L; Aravena, Ramon; Soler, Albert; Hunkeler, Daniel

    2017-09-19

    Even though multi-element isotope fractionation patterns provide crucial information with which to identify contaminant degradation pathways in the field, those involving hydrogen are still lacking for many halogenated groundwater contaminants and degradation pathways. This study investigates for the first time hydrogen isotope fractionation during both aerobic and anaerobic biodegradation of 1,2-dichloroethane (1,2-DCA) using five microbial cultures. Transformation-associated isotope fractionation values (εbulk(H)) were -115 ± 18‰ (aerobic C-H bond oxidation), -34 ± 4‰ and -38 ± 4‰ (aerobic C-Cl bond cleavage via hydrolytic dehalogenation), and -57 ± 3‰ and -77 ± 9‰ (anaerobic C-Cl bond cleavage via reductive dihaloelimination). The dual-element C-H isotope approach (ΛC-H = Δδ(2)H/Δδ(13)C ≈ εbulk(H)/εbulk(C), where Δδ(2)H and Δδ(13)C are changes in isotope ratios during degradation) resulted in clearly different ΛC-H values: 28 ± 4 (oxidation), 0.7 ± 0.1 and 0.9 ± 0.1 (hydrolytic dehalogenation), and 1.76 ± 0.05 and 3.5 ± 0.1 (dihaloelimination). This result highlights the potential of this approach to identify 1,2-DCA degradation pathways in the field. In addition, distinct trends were also observed in a multi- (i.e., Δδ(2)H versus Δδ(37)Cl versus Δδ(13)C) isotope plot, which opens further possibilities for pathway identification in future field studies. This is crucial information to understand the mechanisms controlling natural attenuation of 1,2-DCA and to design appropriate strategies to enhance biodegradation.

  8. Replacing C6F5 groups with Cl and H atoms in frustrated Lewis pairs: H2 additions and catalytic hydrogenations.

    PubMed

    Chernichenko, K; Kótai, B; Nieger, M; Heikkinen, S; Pápai, I; Repo, T

    2017-02-14

    2-(Dialkylamino)phenylboranes containing the BXZ group, where X, Z = C6F5, Cl, and H, were prepared in a few synthetic steps and demonstrated the cleavage of H2 under mild conditions. Depending on the nature of the dialkylamino group, X, and Z, the stability of the produced zwitterionic H2 adducts varies from isolated solids indefinitely stable in an inert atmosphere to those quickly equilibrating with the initial aminoborane and H2. Using a combined experimental/computational approach on a series of isostructural aminoboranes (dialkylamino = 2,2,6,6-tetramethylpiperid-1-yl), it was demonstrated that the electronegativity and the steric effect of the substituents generally follow the trend C6F5 ∼ Cl ≫ H. This observation is useful for designing new FLPs for practical applications. As an example, we demonstrated the hydrogenation of alkynes to cis-alkenes under mild conditions that was catalyzed by a chloro-analogue of the C6F5-substituted aminoborane developed previously. The presence of a BHCl group in the aminochloroboranes or in their H2 adducts features facile redistribution of the H and Cl atoms and the formation of polychloro and polyhydrido species.

  9. Hydrogen

    PubMed Central

    Bockris, John O’M.

    2011-01-01

    The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan). Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs) by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech. PMID:28824125

  10. Image Charge and Electric Field Effects on Hydrogen-like Impurity-bound Polaron Energies and Oscillator Strengths in a Quantum Dot

    NASA Astrophysics Data System (ADS)

    Vardanyan, L. A.; Vartanian, A. L.; Asatryan, A. L.; Kirakosyan, A. A.

    2016-11-01

    By using Landau-Pekar variational method, the ground and the first excited state energies and the transition frequencies between the ground and the first excited states of a hydrogen-like impurity-bound polaron in a spherical quantum dot (QD) have been studied by taking into account the image charge effect (ICE). We employ the dielectric continuum model to describe the phonon confinement effects. The oscillator strengths (OSs) of transitions from the 1 s-like state to excited states of 2 s, 2 p x , and 2 p z symmetries are calculated as functions of the applied electric field and strength of the confinement potential. We have shown that with and without image charge effect, the increase of the strength of the parabolic confinement potential leads to the increase of the oscillator strengths of 1 s - 2 p x and 1 s - 2 p z transitions. This indicates that the energy differences between 1 s- and 2 p x - as well as 1 s- and 2 p z -like states have a dominant role determining the oscillator strength. Although there is almost no difference in the oscillator strengths for transitions 1 s - 2 p x and 1 s -2 p z when the image charge effect is not taken into account, it becomes significant with the image charge effect.

  11. Estimating the hydrogen ion concentration in concentrated NaCl and Na{sub 2}SO{sub 4} electrolytes

    SciTech Connect

    Rai, D.; Felmy, A.R.; Juracich, S.P.; Rao, F.

    1995-06-01

    Combination glass electrodes were tested for determining H{sup +} concentrations in concentrated pure and mixed NaCl and Na{sub 2}SO{sub 4} solutions, as well as natural brine systems. NaCl, Na{sub 2}SO{sub 4}, and mixtures of NaCl and Na{sub 2}SO{sub 4} solutions were analyzed. Correction factors for estimating pC{sub H}{sup +} (negative logarithm of H{sup +} concentration) were determined from measured/observed pH values. Required Gran-type titrations were done with HCl and/or NaOH. The titration method is described and a step-by-step procedure provided; it has been used previously for determining pC{sub H}{sup +} values of synthetic chloride-dominated brines. Precautions are required to determine correction factors for electrolytes that react with H{sup +} or OH{sup {minus}} [sulfate brines for titration with acid; magnesium brines for titration with base because of precipitation of Mg(OH)2]. Correction factors A (pC{sub H}{sup +} = pH{sub ob} + A) from HCl titrations were similar to those from NaOH titrations where the concentration of free H{sup +} was calculated using a thermodynamic model. These values should be applicable to solns with a very large range in measured pH values (2 to 12). Because a large number of solns were titrated with HCl and the A values are similar for HCl and NaOH titrations, the A values for NaCl and Na2SO4 solns were fit as a function of molality to allow extrapolation. For NaCl solns 0 to 6.0 M, A can be obtained by multiplying the molality by 0.159. For Na2SO4 solns 0 to 2.0 M, the values of A can be obtained from (0.221 {minus} 0.549X + 0.201X{sup 2}), where X is the molality of Na{sub 2}SO{sub 4}. Orion-Ross electrode evaluations indicated that the A values did not differ significantly for different electrodes. Results suggest that the data in this report can be used to estimate A values for different NaCl and Na{sub 2}SO{sub 4} solns even for noncalibrated electrodes.

  12. Chiral and nonchiral [OsX2(diphosphane)(diamine)] (X: Cl, OCH2CF3) complexes for fast hydrogenation of carbonyl compounds.

    PubMed

    Baratta, Walter; Barbato, Cinzia; Magnolia, Santo; Siega, Katia; Rigo, Pierluigi

    2010-03-08

    The osmium complexes trans-[OsCl(2)(dppf)(diamine)] (dppf: 1,1'-bis(diphenylphosphino)ferrocene; diamine: ethylenediamine in 3, propylenediamine in 4) were prepared by the reaction of [OsCl(2)(PPh(3))(3)] (1) with the ferrocenyl diphosphane, dppf and the corresponding diamine in dichloromethane. The reaction of derivative 3 with NaOCH(2)CF(3) in toluene afforded the alkoxide cis-[Os(OCH(2)CF(3))(2)(dppf)(ethylenediamine)] (5). The novel precursor [Os(2)Cl(4)(P(m-tolyl)(3))(5)] (2) allows the synthesis of the chiral complexes trans-[OsCl(2)(diphosphane)(1,2-diamine)] (6-9; diphosphane: (R)-[6,6'-dimethoxy(1,1'-biphenyl)-2,2'-diyl]bis[1,1-bis(3,5-dimethylphenyl)phosphane] (xylMeObiphep) or (R)-(1,1'-binaphthalene)-2,2'-diylbis[1,1-bis(3,5-dimethylphenyl)phosphane] (xylbinap); diamine=(R,R)-1,2-diphenylethylenediamine (dpen) or (R,R)-1,2-diaminocyclohexane (dach)), obtained by the treatment of 2 with the diphosphane and the 1,2-diamine in toluene at reflux temperature. Compounds 3-5 in ethanol and in the presence of NaOEt catalyze the reduction of methyl aryl, dialkyl, and diaryl ketones and aldehydes with H(2) at low pressure (5 atm), with substrate/catalyst (S/C) ratios of 10,000-200,000 and achieving turnover frequencies (TOFs) of up to 3.0 x 10(5) h(-1) at 70 degrees C. By employment of the chiral compounds 6-9, different ketones, including alkyl aryl, bulky tert-butyl, and cyclic ketones, have successfully been hydrogenated with enantioselectivities up to 99% and with S/C ratios of 5000-100,000 and TOFs of up to 4.1 x 10(4) h(-1) at 60 degrees C.

  13. Hydrogen abstraction reactions of OH radicals with CH₃CH₂CH₂Cl and CH₃CHClCH₃: a mechanistic and kinetic study.

    PubMed

    Wang, Li; Li, Yanjie; He, Hongqing; Zhang, Jinglai

    2012-01-05

    The hydrogen abstraction reactions of OH radicals with CH₃CH₂CH₂Cl and CH₃CHClCH₃ (R2) have been investigated theoretically by a dual-level direct dynamics method. The optimized geometries and frequencies of the stationary points are calculated at the B3LYP/6-311G(d,p) level. To improve the reaction enthalpy and potential barrier of each reaction channel, the single point energy calculation is performed by the BMC-CCSD method. Using canonical variational transition-state theory (CVT) with the small-curvature tunneling correction, the rate constants are evaluated over a wide temperature range of 200-2000 K at the BMC-CCSD//B3LYP/6-311G(d,p) level. For the reaction channels with the negative barrier heights, the rate constants are calculated by using the CVT. The calculated total rate constants are consistent with available experimental data. The results show that at lower temperatures, the tunneling correction has an important contribution in the calculation of rate constants for all the reaction channels with the positive barrier heights, while the variational effect is found negligible for some reaction channels. For reactions OH radicals with CH₃CH₂CH₂Cl (R1) and CH₃CHClCH₃ (R2), the channels of H-abstraction from -CH₂ - and -CHCl groups are the major reaction channels, respectively, at lower temperatures. With temperature increasing, contributions from other channels should be taken into account. Finally, the total rate constants are fitted by two models, i.e., three-parameter and four-parameter expressions. The enthalpies of formation of the species CH₃CHClCH₂, CH₃CHCH₂Cl, and CH₃CH₂CH₂Cl are evaluated by isodesmic reactions.

  14. Growth, structural, spectral, mechanical and dielectric characterization of RbCl-doped L-alanine hydrogen chloride monohydrate single crystals

    NASA Astrophysics Data System (ADS)

    Lucia Rose, A. S. J.; Selvarajan, P.; Perumal, S.

    2011-02-01

    Pure (undoped) and RbCl-doped LAHC single crystals were grown successfully by the solution method with the slow evaporation technique at room temperature. The grown crystals were colourless and transparent. The solubility of the grown samples were found out at various temperatures. The lattice parameters of the grown crystals were determined by the single crystal X-ray diffraction technique and the diffracting planes were indentified by recording the powder X-ray diffraction pattern. UV-visible transmittance studies were carried out for the grown samples. Chemical analysis and atomic absorption studies indicate the presence of rubidium in the doped LAHC crystals. Nonlinear optical studies reveal that the SHG efficiency increases when the LAHC crystal is doped with rubidium chloride (RbCl). From microhardness studies, it is observed that the RbCl-doped LAHC crystal is harder than the pure sample. It is observed that the dielectric properties of the LAHC crystal are altered when it is doped with rubidium chloride.

  15. Absolute rate of the reaction of Cl(p-2) with molecular hydrogen from 200 - 500 K

    NASA Technical Reports Server (NTRS)

    Whytock, D. A.; Lee, J. H.; Michael, J. V.; Payne, W. A.; Stief, L. J.

    1976-01-01

    Rate constants for the reaction of atomic chlorine with hydrogen are measured from 200 - 500 K using the flash photolysis-resonance fluorescence technique. The results are compared with previous work and are discussed with particular reference to the equilibrium constant for the reaction and to relative rate data for chlorine atom reactions. Theoretical calculations, using the BEBO method with tunneling, give excellent agreement with experiment.

  16. Cadmium sulfide quantum dots supported on gallium and indium oxide for visible-light-driven hydrogen evolution from water.

    PubMed

    Pan, Yun-xiang; Zhuang, Huaqiang; Hong, Jindui; Fang, Zheng; Liu, Hai; Liu, Bin; Huang, Yizhong; Xu, Rong

    2014-09-01

    In this work, CdS quantum dots (QDs) supported on Ga2O3 and In2O3 are applied for visible-light-driven H2 evolution from aqueous solutions that contain lactic acid. With Pt as the cocatalyst, the H2 evolution rates on CdS/Pt/Ga2O3 and CdS/Pt/In2O3 are as high as 995.8 and 1032.2 μmol h(-1), respectively, under visible light (λ>420 nm) with apparent quantum efficiencies of 43.6 and 45.3% obtained at 460 nm, respectively. These are much higher than those on Pt/CdS (108.09 μmol h(-1)), Pt/Ga2O3 (0.12 μmol h(-1)), and Pt/In2O3 (0.05 μmol h(-1)). The photocatalysts have been characterized thoroughly and their band structures and photocurrent responses have been measured. The band alignment between the CdS QDs and In2O3 can lead to interfacial charge separation, which cannot occur between the CdS QDs and Ga2O3. Among the various possible factors that contribute to the high H2 evolution rates on CdS/Pt/oxide, the surface properties of the metal oxides play important roles, which include (i) the anchoring of CdS QDs and Pt nanoparticles for favorable interactions and (ii) the efficient trapping of photogenerated electrons from the CdS QDs because of surface defects (such as oxygen defects) based on photoluminescence and photocurrent studies.

  17. Cesium lead halide (CsPbX3, X=Cl, Br, I) perovskite quantum dots-synthesis, properties, and applications: a review of their present status

    NASA Astrophysics Data System (ADS)

    Ananthakumar, Soosaimanickam; Kumar, Jeyagopal Ram; Babu, Sridharan Moorthy

    2016-10-01

    Metal halide-based perovskite quantum dots (QDs) have emerged as promising materials for optoelectronics and future energy applications. Among them, cesium lead halide-based perovskite quantum dots (Cs-LHQDs) have been found to be potential luminescent candidates and alternatives for the II-VI and I-III-VI2 groups semiconductor nanoparticles. These perovskites provide an excellent quantum yield (90%) larger than any other semiconductor QDs. At present, synthesis of Cs-LHQDs has been successfully achieved through a traditional colloidal-based hot-injection method and a room temperature precipitation method. Some of the interesting results in their structural, optical, and morphological properties are being analyzed to understand their energy-transfer mechanism in the colloidal state. Morphology of nanoplates, nanowires, nanocube, and nanosheets in these materials confirms their physical parameters-dependent self-assembly nature in a colloidal medium. Their potential use for light emitting diodes, photodetectors, and lasers is also highly motivated. This review provides a collective view of recent developments made in the synthesis of Cs-LHQDs and their properties.

  18. Temperature-controlled syntheses of substituted 1,2,4-triazolelead(II) complexes: active lone pair and N-H...X (X = Cl, Br, I) hydrogen bonds.

    PubMed

    Cheng, Jian-Kai; Zhang, Jian; Yin, Pei-Xiu; Lin, Qi-Pu; Li, Zhao-Ji; Yao, Yuan-Gen

    2009-11-02

    Three isomorphous lead(II) complexes with a new {N(3)SX}-coordinated (X = Cl, Br, I) mode have been synthesized and characterized by X-ray diffraction. The structural analyses reveal that the coordination environment around the center metal is distinctly influenced by the stereochemical 6s(2) lone pair and N-H...X hydrogen bonds. Additionally, doubly deprotonated trzS(2-) (HtrzSH = 1,2,4-triazole-3-thiol) generated in situ via deamination and dehydrazination of ahtrzS(-) (ahtrzSH = 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole) was first observed in a semiconducting three-dimensional coordination network at higher reaction temperature.

  19. On the Versatility of BH2 X (X=F, Cl, Br, and I) Compounds as Halogen-, Hydrogen-, and Triel-Bond Donors: An Ab Initio Study.

    PubMed

    Bauzá, Antonio; Frontera, Antonio

    2016-10-18

    In this manuscript, the ability of BH2 X compounds (X=F, Cl, Br, and I) to establish halogen-, hydrogen-, and triel-bonding interactions was studied at the RI-MP2/aug-cc-pVQZ level of theory. Several homodimers were taken into account, highlighting the versatility of these compounds to act as both electron donors and electron acceptors. Natural bond orbital analysis showed that orbital effects were important contributors to the global stabilization of the σ- and π-hole bonded complexes studied. Finally, some X-ray solid-state structures retrieved from the Cambridge structural database were described to demonstrate the importance of these interactions involving boron derivatives in the solid state.

  20. Solubility of hydrogen sulfide in pure water and in NaCl solutions, from 20 to 320°C and at saturation pressures

    NASA Astrophysics Data System (ADS)

    Suleimenov, O. M.; Krupp, R. E.

    1994-06-01

    The solubility of hydrogen sulfide in pure water and in NaCl solutions has been studied experimentally from 20 to 320°C and at saturation pressures. Hydrogen sulfide solutions in equilibrium with their vapor phase were contained in a pressurized titanium bellows of known total volume. The bellows transmitted inside-vapor pressures via a thermally stable oil (pressure medium) to a high-precision pressure sensor. Temperatures were measured by a sheathed thermocouple immersed into the oil surrounding the bellows. Values for the Henry constants were derived from measurements of equilibrium vapor pressure, volume, temperature, and bulk composition. The Henry constants agree well with previously published data up to about 200°C, but then deviate towards lower values (higher solubilities) at higher temperatures. Henry constants from 20 to 320°C and at saturation pressures may be obtained from the correlation log kH( T, Psat,1 ) = +0.6342702616 e + 3 + 0.2709284796 e + 0 · T - 0.1 113202904 e - 3 · T2 - 0.1671907660 e + 5/ T -0.2619219571 e + 3 · logT, where khis in units of bar/molality and T in Kelvin. The experimental Henry constants have been fitted to a scaled particle theory model and have been tested by a recently proposed linearization procedure. The salting-out effect of NaCl on H 2S solubility is nearly independent of temperature up to about 250°C, but then increases sharply as temperatures approach the critical point of water. Skeleton tables to 365°C and for ionic strengths μ = 0, 1, 2, 3 have been prepared.

  1. Exogenous hydrogen peroxide, nitric oxide and calcium mediate root ion fluxes in two non-secretor mangrove species subjected to NaCl stress.

    PubMed

    Lu, Yanjun; Li, Niya; Sun, Jian; Hou, Peichen; Jing, Xiaoshu; Zhu, Huipeng; Deng, Shurong; Han, Yansha; Huang, Xuxin; Ma, Xujun; Zhao, Nan; Zhang, Yuhong; Shen, Xin; Chen, Shaoliang

    2013-01-01

    Using 3-month-old seedlings of Bruguiera gymnorrhiza (L.) Savigny and Kandelia candel (L.) Druce, we compared species differences in ionic homeostasis control between the two non-secretor mangrove species. A high salinity (400 mM NaCl, 4 weeks) resulted in a decline of the K(+)/Na(+) ratio in root and leaf tissues, and the reduction was more pronounced in K. candel (41-66%) as compared with B. gymnorrhiza (5-36%). Salt-altered flux profiles of Na(+), K(+), H(+) and Ca(2+) in roots and effects of exogenous hydrogen peroxide (H(2)O(2)), nitric oxide (NO) and Ca(2+) on root ion fluxes were examined in seedlings that were hydroponically treated short term with 100 mM NaCl (ST, 24 h) and long term with 200 mM NaCl (LT, 7 days). Short term and LT salinity resulted in Na(+) efflux and a correspondingly increased H(+) influx in roots of both species, although a more pronounced effect was observed in B. gymnorrhiza. The salt-enhanced exchange of Na(+) with H(+) was obviously inhibited by amiloride (a Na(+)/H(+) antiporter inhibitor) or sodium orthovanadate (a plasma membrane H(+)-ATPase inhibitor), indicating that the Na(+) efflux resulted from active Na(+) exclusion across the plasma membrane. Short term and LT salinity accelerated K(+) efflux in the two species, but K. candel exhibited a higher flux rate. The salt-induced K(+) efflux was markedly restricted by the K(+) channel blocker, tetraethylammonium chloride, indicating that the K(+) efflux is mediated by depolarization-activated channels, e.g., KORCs (outward rectifying K(+) channels) and NSCCs (non-selective cation channels). Exogenous H(2)O(2) application (10 mM) markedly increased the apparent Na(+) efflux and limited K(+) efflux in ST-treated roots, although H(2)O(2) caused a higher Na(+) efflux in B. gymnorrhiza roots. CaCl(2) (10 mM) reduced the efflux of K(+) in salinized roots of the two mangroves, but its enhancement of Na(+) efflux was found only in B. gymnorrhiza. Under ST treatment, sodium nitroprusside

  2. The vibration characterization of synthetic crystalline lead hydrogen arsenite chloride precipitates Pb2(HAsO3)Cl2-implications of solidification of As (III) and Pb (II)

    NASA Astrophysics Data System (ADS)

    Liu, Juan; Jia, Ru; Liu, Jing

    2014-01-01

    The lead hydrogen arsenite chloride precipitates (Pb2(HAsO3)Cl2) are synthesized hydrothermally due to its structure trap for lead and arsenic. The synthetic precipitates have well-developed crystalline. The crystals of lead hydrogen arsenite chloride have a series of obvious IR bands at 790, 721, 645, 589 and 554 cm-1. These bands are assigned to the Ag mode of As-O stretching vibration (790), the antisymmetric stretch of As-OH (721), Ag modes (554 and 589) and E1g (645) of the symmetric deformation (ν1 and ν3) of AsO3 unit. The Raman bands at 782, 723, 586, 559 cm-1 are attributed to As-O stretching vibration (ν1) and the symmetric deformation (ν1 and ν3), of which the positions and assignments display in accordance with IR result. The most intense Raman band is found in 814 cm-1 and is attributed to the Ag mode of ν1 symmetric stretching vibration of AsO3 unit, which is not active in IR. The SEM image shows that the precipitates have needle morphology.

  3. The vibration characterization of synthetic crystalline lead hydrogen arsenite chloride precipitates Pb2(HAsO3)Cl2-implications of solidification of As (III) and Pb (II).

    PubMed

    Liu, Juan; Jia, Ru; Liu, Jing

    2014-01-03

    The lead hydrogen arsenite chloride precipitates (Pb2(HAsO3)Cl2) are synthesized hydrothermally due to its structure trap for lead and arsenic. The synthetic precipitates have well-developed crystalline. The crystals of lead hydrogen arsenite chloride have a series of obvious IR bands at 790, 721, 645, 589 and 554 cm(-1). These bands are assigned to the Ag mode of As-O stretching vibration (790), the antisymmetric stretch of As-OH (721), Ag modes (554 and 589) and E1g (645) of the symmetric deformation (ν1 and ν3) of AsO3 unit. The Raman bands at 782, 723, 586, 559 cm(-1) are attributed to As-O stretching vibration (ν1) and the symmetric deformation (ν1 and ν3), of which the positions and assignments display in accordance with IR result. The most intense Raman band is found in 814 cm(-1) and is attributed to the Ag mode of ν1 symmetric stretching vibration of AsO3 unit, which is not active in IR. The SEM image shows that the precipitates have needle morphology.

  4. GuHCl and NaCl-dependent hydrogen exchange in MerP reveals a well-defined core with an unusual exchange pattern.

    PubMed

    Brorsson, Ann-Christin; Lundqvist, Martin; Sethson, Ingmar; Jonsson, Bengt-Harald

    2006-04-14

    We have analysed hydrogen exchange at amide groups to characterise the energy landscape of the 72 amino acid residue protein MerP. From the guanidine hydrochloride (GuHCl) dependence of exchange in the pre-transitional region we have determined free energy values of exchange (DeltaG(HX)) and corresponding m-values for individual amide protons. Detailed analysis of the exchange patterns indicates that for one set of amide protons there is a weak dependence on denaturant, indicating that the exchange is dominated by local fluctuations. For another set of amide protons a linear, but much stronger, denaturant dependence is observed. Notably, the plots of free energy of exchange versus [GuHCl] for 16 amide protons show pronounced upward curvature, and a close inspection of the structure shows that these residues form a well-defined core in the protein. The hydrogen exchange that was measured at various concentrations of NaCl shows an apparent selective stabilisation of this core. Detailed analysis of this exchange pattern indicates that it may originate from selective destabilisation of the unfolded state by guanidinium ions and/or selective stabilisation of the core in the native state by chloride ions.

  5. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; Sparks, Dennis E.; Shafer, Wilson D.; Khalid, Syed; Xiao, Qunfeng; Hu, Yongfeng; Davis, Burtron H.

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts is explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.

  6. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    DOE PAGES

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; ...

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts ismore » explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.« less

  7. Fischer-Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co

    SciTech Connect

    Pendyala, Venkat Ramana Rao; Jacobs, Gary; Ma, Wenping; Sparks, Dennis E.; Shafer, Wilson D.; Khalid, Syed; Xiao, Qunfeng; Hu, Yongfeng; Davis, Burtron H.

    2016-07-23

    The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer-Tropsch (FT) catalysts was investigated in our earlier studies [ACS Catal. 5 (2015) 3124-3136 and DOE final report 2011; Catal. Lett. 144 (2014) 1127-1133]. For an iron catalyst, lower HCl concentrations (< 2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts is explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate HCl poisoning mechanism on the iron and cobalt catalysts. Cl K-edge normalized XANES results indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g.,cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.

  8. Properties of {sup 20}Na, {sup 24}Al, {sup 28}P, {sup 32}Cl, and {sup 36}K for studies of explosive hydrogen burning

    SciTech Connect

    Wrede, C.; Clark, J. A.; Deibel, C. M.; Faestermann, T.; Parikh, A.; Bishop, S.; Eppinger, K.; Kruecken, R.; Lepyoshkina, O.; Rugel, G.; Hertenberger, R.; Wirth, H.-F.; Chen, A. A.; Freeman, B. M.; Setoodehnia, K.

    2010-09-15

    The radiative proton-capture reactions {sup 19}Ne(p,{gamma}){sup 20}Na, {sup 23}Mg(p,{gamma}){sup 24}Al, {sup 27}Si(p,{gamma}){sup 28}P, {sup 31}S(p,{gamma}){sup 32}Cl, and {sup 35}Ar(p,{gamma}){sup 36}K potentially influence energy generation and/or nucleosynthesis during explosive hydrogen burning in classical novae and/or type I x-ray bursts. The thermonuclear rates of these reactions are dependent on resonance energies E{sub r}=E{sub x}-Q and strengths {omega}{gamma}. The {sup 20}Ne({sup 3}He,t){sup 20}Na, {sup 24}Mg({sup 3}He,t){sup 24}Al, {sup 28}Si({sup 3}He,t){sup 28}P, {sup 32}S({sup 3}He,t){sup 32}Cl, and {sup 36}Ar({sup 3}He,t){sup 36}K reactions have been measured using a 32-MeV, {sup 3}He{sup 2+} beam; ion-implanted carbon-foil targets developed at the University of Washington; and the Munich Q3D magnetic spectrograph. This experiment has already yielded precision mass measurements of {sup 20}Na, {sup 24}Al, {sup 28}P, and {sup 32}Cl [C. Wrede et al., Phys. Rev. C 81, 055503 (2010)], which are used presently to constrain the corresponding (p,{gamma}) reaction Q values. The new {sup 24}Al and {sup 28}P masses resolve a discrepancy in the energy of the lowest-energy resonance in the {sup 23}Mg(p,{gamma}){sup 24}Al reaction and better constrain a direct measurement of its strength. Excitation energies in {sup 32}Cl and {sup 36}K have also been measured. An important new proton-unbound level has been found at E{sub x}=2196.9(7) keV in {sup 36}K and the uncertainties in {sup 36}K excitation energies have been reduced by over an order of magnitude. Using the new data on {sup 36}K, the A=36, T=1 triplets have been reassigned. The thermonuclear {sup 35}Ar(p,{gamma}){sup 36}K reaction rate is found to be much higher than a commonly adopted rate and this could affect energy generation in type I x-ray bursts.

  9. The Role of Vibrational Excitation on the Dynamics of the F(^2P) + HCl → FH + Cl(2P) Hydrogen-Transfer Reaction

    NASA Astrophysics Data System (ADS)

    Ray, Sara E.; Vissers, G. W. M.; McCoy, Anne B.

    2010-06-01

    Recently, open-shell systems have gained interest in experimental and theoretical science. What proves interesting about these open-shell systems is that the potential energy surfaces often contain a van der Waals well in the reactant or product channel that allows researchers to probe the pre-reactive species. Here we present the results of time-dependent quantum wave packet calculations on the asymmetric hydrogen-transfer reaction of F(^SUP>2P) + HCl. In these calculations, the reaction is initiated by vibrationally exciting the HCl stretching motion of the pre-reactive F\\cdotsHCl complex in the van der Waals well. The wave packet is propagated on a three-dimensional, fully coupled potential energy surface that has been constructed based on electronic energies calculated at the multi-reference configuration interation+Davidson correction (MRCI+Q) level of theory with an aug-cc-pVnZ (n=2,3,4) basis. Product state distributions were calculated for reactions initiated in the first three vibrationally excited states of HCl, v=1, 2, and 3. Specifically, we analyzed the final electronic, vibrational, and rotational distributions. Previous studies on the hydrogen-transfer reaction of the Cl(^2P) + HCl system focused on whether vibrational excitation of the HCl stretch would promote the reaction and if so, how the reaction dynamics reflect the coupling among the diabatic potential surfaces that describe this system. We also compare our F(^2P) + HCl results to those of this related system. M. P. Deskevich, M. Y. Hayes, K. Takahashi, R. T. Skodje, and D. J. Nesbitt J. Chem. Phys., 124(22) 224303 (2006) G. W. M. Vissers and A. B. McCoy J. Phys Chem. A, 110 5978 (2006)

  10. Quantum Dots

    NASA Astrophysics Data System (ADS)

    Tartakovskii, Alexander

    2012-07-01

    Part I. Nanostructure Design and Structural Properties of Epitaxially Grown Quantum Dots and Nanowires: 1. Growth of III/V semiconductor quantum dots C. Schneider, S. Hofling and A. Forchel; 2. Single semiconductor quantum dots in nanowires: growth, optics, and devices M. E. Reimer, N. Akopian, M. Barkelid, G. Bulgarini, R. Heeres, M. Hocevar, B. J. Witek, E. Bakkers and V. Zwiller; 3. Atomic scale analysis of self-assembled quantum dots by cross-sectional scanning tunneling microscopy and atom probe tomography J. G. Keizer and P. M. Koenraad; Part II. Manipulation of Individual Quantum States in Quantum Dots Using Optical Techniques: 4. Studies of the hole spin in self-assembled quantum dots using optical techniques B. D. Gerardot and R. J. Warburton; 5. Resonance fluorescence from a single quantum dot A. N. Vamivakas, C. Matthiesen, Y. Zhao, C.-Y. Lu and M. Atature; 6. Coherent control of quantum dot excitons using ultra-fast optical techniques A. J. Ramsay and A. M. Fox; 7. Optical probing of holes in quantum dot molecules: structure, symmetry, and spin M. F. Doty and J. I. Climente; Part III. Optical Properties of Quantum Dots in Photonic Cavities and Plasmon-Coupled Dots: 8. Deterministic light-matter coupling using single quantum dots P. Senellart; 9. Quantum dots in photonic crystal cavities A. Faraon, D. Englund, I. Fushman, A. Majumdar and J. Vukovic; 10. Photon statistics in quantum dot micropillar emission M. Asmann and M. Bayer; 11. Nanoplasmonics with colloidal quantum dots V. Temnov and U. Woggon; Part IV. Quantum Dot Nano-Laboratory: Magnetic Ions and Nuclear Spins in a Dot: 12. Dynamics and optical control of an individual Mn spin in a quantum dot L. Besombes, C. Le Gall, H. Boukari and H. Mariette; 13. Optical spectroscopy of InAs/GaAs quantum dots doped with a single Mn atom O. Krebs and A. Lemaitre; 14. Nuclear spin effects in quantum dot optics B. Urbaszek, B. Eble, T. Amand and X. Marie; Part V. Electron Transport in Quantum Dots Fabricated by

  11. Reactions between atomic chlorine and pyridine in solid para-hydrogen: Infrared spectrum of the 1-chloropyridinyl (C{sub 5}H{sub 5}N-Cl) radical

    SciTech Connect

    Das, Prasanta; Bahou, Mohammed; Lee, Yuan-Pern

    2013-02-07

    With infrared absorption spectra we investigated the reaction between Cl atom and pyridine (C{sub 5}H{sub 5}N) in a para-hydrogen (p-H{sub 2}) matrix. Pyridine and Cl{sub 2} were co-deposited with p-H{sub 2} at 3.2 K; a planar C{sub 5}H{sub 5}N-Cl{sub 2} complex was identified from the observed infrared spectrum of the Cl{sub 2}/C{sub 5}H{sub 5}N/p-H{sub 2} matrix. Upon irradiation at 365 nm to generate Cl atom in situ and annealing at 5.1 K for 3 min to induce secondary reaction, the 1-chloropyridinyl radical (C{sub 5}H{sub 5}N-Cl) was identified as the major product of the reaction Cl + C{sub 5}H{sub 5}N in solid p-H{sub 2}; absorption lines at 3075.9, 1449.7, 1200.6, 1148.8, 1069.3, 1017.4, 742.9, and 688.7 cm{sup -1} were observed. The assignments are based on comparison of observed vibrational wavenumbers and relative IR intensities with those predicted using the B3PW91/6-311++G(2d, 2p) method. The observation of the preferential addition of Cl to the N-site of pyridine to form C{sub 5}H{sub 5}N-Cl radical but not 2-, 3-, or 4-chloropyridine (ClC{sub 5}H{sub 5}N) radicals is consistent with the reported theoretical prediction that formation of the former proceeds via a barrierless path.

  12. Anticooperativity of FHF hydrogen bonds in clusters of the type F- × (HF)n, RF × (HF)n and XF × (HF)n, R = alkyl and X = H, Br, Cl, F

    NASA Astrophysics Data System (ADS)

    Kucherov, S. Yu.; Bureiko, S. F.; Denisov, G. S.

    2016-02-01

    Properties of twenty five hydrogen-bonded complexes, namely, F- × (HF)n (n = 1-6), RF × (HF)n (R = t-Bu, i-Pr, Et, Me; n = 1-3), XF × (HF)n (X = H, Br, Cl; n = 1-2), and FF…HF with the hydrogen bond energy varying in a wide range have been calculated using ab initio methods at the MP2/6-31++G** level. For the first time, the energies, geometrical parameters and vibrational frequencies are obtained for the series of clusters, where the bonding character changes from covalent to van der Waals on the variation of proton-acceptor ability of the base, and the energies are in the range of 45-1 kcal/mol. The mutual influence of multiple hydrogen bonds of F…HF type in clusters, in which a fluorine anion or an atom participates in hydrogen bond formation as the acceptor, is systematically investigated. The relative changes in the values of the considered parameters on the sequential addition of an HF molecule (anticooperativity) were determined. It was shown that non-additivity of the interaction is most strongly pronounced in the energy and vibrational frequency values, geometrical parameters of hydrogen bonds are less sensitive to the mutual influence. The anticooperative effect is more pronounced on the hydrogen bridge length R(F...F) than on the geometry of proton donor r(HF). The hydrogen bond formation and the increase of the number n of ligands lead to successive lengthening of the r(XF) bond adjacent to the hydrogen bridge. The length of an XF bond changes stronger on formation of each hydrogen bond than the HF bond length.

  13. Kinetics of NiO and NiCl2 Hydrogen Reduction as Precursors and Properties of Produced Ni/Al2O3 and Ni-Pd/Al2O3 Catalysts

    PubMed Central

    Sokić, Miroslav; Kamberović, Željko; Nikolić, Vesna; Marković, Branislav; Korać, Marija; Anđić, Zoran; Gavrilovski, Milorad

    2015-01-01

    The objects of this investigation were the comparative kinetic analysis of the NiO and NiCl2 reduction by hydrogen during an induction period and elimination of the calcination during the synthesis of Ni/Al2O3 catalysts. The effect of temperature and time on NiO and NiCl2 reduction degrees was studied. Avrami I equation was selected as the most favorable kinetic model and used to determine activation energy of the NiO and NiCl2 reduction for the investigated temperature range (623–923 K) and time intervals (1–5 minutes). The investigation enabled reaching conclusions about the reaction ability and rate of the reduction processes. Afterward, Ni/Al2O3 catalysts were obtained by using oxide and chloride precursor for Ni. The catalysts were supported on alumina-based foam and prepared via aerosol route. Properties of the samples before and after low-temperature hydrogen reduction (633 K) were compared. Obtained results indicated that the synthesis of Ni/Al2O3 catalysts can be more efficient if chloride precursor for Ni is directly reduced by hydrogen during the synthesis process, without the calcination step. In addition, Ni-Pd/Al2O3 catalysts with different metal content were prepared by using chloride precursors. Lower reduction temperature was utilized and the chlorides were almost completely reduced at 533 K. PMID:25789335

  14. Impact of deformation energy on the hydrogen bonding interactions in gas phase 3-X catechol ⋯ H2O complexes (X = H, F, Cl, Br): The effect of approach of a water molecule

    NASA Astrophysics Data System (ADS)

    Deb, Debojit Kumar; Sarkar, Biplab

    2016-06-01

    The conformations and nature of hydrogen bonding interactions for 3-X catechol ⋯ H2O (X = H, F, Cl, Br) has been investigated by ab initio MP2, CCSD(T), and density functional B3LYP, wB97XD and M06-2X methods. The changes in interaction energies due to deformation of the structures has been studied in detail. The intra- and intermolecular hydrogen bonding interactions due to the different direction of approach of water molecule have been discussed. A detailed natural bond orbital (NBO) analysis and the symmetry-adapted perturbation theory (SAPT) based energy decomposition analysis has been carried out to elucidate interaction strength and properties in these hydrogen bonded systems. The charge transfer percentage (CTP) has been derived which will be universally useful for correlating binding energy, deformation energy and the geometrical parameters such as angles, bond lengths, etc. for other systems as well.

  15. Observation of a Moderate Strength Interaction of Hydrogen with a Coinage Metal Halide: the Rotational Spectrum and Structure of the {p}{-H}_2{-CuCl} and {o}{-H}_2{-CuCl} Complexes

    NASA Astrophysics Data System (ADS)

    Pickett, Herbert M.; Obenchain, Daniel A.; Grubbs, G. S. Grubbs, Ii; Novick, Stewart E.

    2013-06-01

    Rotational transitions of the p-H_2-CuCl and o-H_2-CuCl have been observed on a laser ablation equipped FTMW cavity instrument. Computational studies preformed using the APFD density functional and MP2 level of theory were used to predict the structure of the p-H_2-CuCl. Measurements from the J=1-0 to the J=3-2 transitions were used to determine the rotational constants, centrifugal distortion constants, and quadrupole coupling constants for multiple isotopologues of the p-H_2-CuCl species. Similar constants, including spin-spin coupling constants, have also been determined for the o-H_2-CuCl species for the J=2-1 and the J=3-2 transitions. The eQq of the copper in p-H_2-^{63}Cu^{35}Cl was found to be 52.058(2) MHz, a change from the monomer ^{63}Cu^{35}Cl value of 16.1712(24) MHz. A. Austin, G. A. Petersson, M. J. Frisch, F. J. Dobek, G. Scalmani, and K. J. Throssell. Chem. Theor. Comp. 8 (2012) 4989. K. D. Hensel, C. Styger, W. Jager, A. J. Merer, and M. C. L. Gerry, J. Chem. Phys. 99(1993) 3320.

  16. Hydrogen-bond-directed assemblies of [La(18-crown-6)(H2O)4](BiCl6)·3H2O and [Nd(18-crown-6)(H2O)4](BiCl6)·3.5H2O regulated by different symmetries

    NASA Astrophysics Data System (ADS)

    Zhang, Shi-Yong; Li, Jian; Zeng, Ying; Wen, He-Rui; Du, Zi-Yi

    2016-12-01

    The reactions of La2O3 or Nd2O3 with BiCl3 and 18-crown-6 in the presence of excessive hydrochloric acid afforded two ion-pair compounds, namely [La(18-crown-6)(H2O)4](BiCl6)·3H2O (1) and [Nd(18-crown-6)(H2O)4](BiCl6)·3.5H2O (2). Although these two compounds contain similar building blocks, they exhibit two distinct hydrogen-bonded networks, which are mainly induced by the slightly different geometries of their large-sized cationic [Ln(18-crown-6)(H2O)4]3+ components.

  17. Selective recognition of dysprosium(III) ions by enhanced chemiluminescence CdSe quantum dots.

    PubMed

    Hosseini, Morteza; Ganjali, Mohammad R; Vaezi, Zahra; Faridbod, Farnoush; Arabsorkhi, Batool; Sheikhha, Mohammad H

    2014-01-01

    The intensity of emitted light from CdSe quantum dots (QDs)-H2O2 is described as a novel chemiluminescence (CL) reaction for determination of dysprosium. This reaction is based on the catalytic effect of Dy(3+) ions, causing a significant increase in the light emission, as a result of the reaction of quantum dots (QDs) with hydrogen peroxide. In the optimum conditions, this method was satisfactorily described by linear calibration curve in the range of 8.3×10(-7)-5.0×10(-6)M, the detection limit of 6.0×10(-8)M, and the relative standard deviation for five determinations of 2.5×10(-6)M Dy(3+) 3.2%. The main experimental advantage of the proposed method is its selective to Dy(3+) ions compared with common coexisting cations, therefore, it was successfully applied for the determination of dysprosium ions in water samples.

  18. Bridging the gap between homogeneous and heterogeneous catalysis: ortho/para H(2) conversion, hydrogen isotope scrambling, and hydrogenation of olefins by Ir(CO)Cl(PPh(3))(2).

    PubMed

    Matthes, Jochen; Pery, Tal; Gründemann, Stephan; Buntkowsky, Gerd; Sabo-Etienne, Sylviane; Chaudret, Bruno; Limbach, Hans-Heinrich

    2004-07-14

    Some transition metal complexes are known to catalyze ortho/para hydrogen conversion, hydrogen isotope scrambling, and hydrogenation reactions in liquid solution. Using the example of Vaska's complex, we present here evidence by NMR that the solvent is not necessary for these reactions to occur. Thus, solid frozen solutions or polycrystalline powdered samples of homogeneous catalysts may become heterogeneous catalysts. Comparative liquid- and solid-state studies provide novel insight into the reaction mechanisms.

  19. Low-Cost Solar Array Project. Task I. Silicon material: investigation of the hydrogenation of SiCl/sub 4/. Fourth quarterly report

    SciTech Connect

    Mui, J.Y.P.; Seyferth, D.

    1980-04-15

    Reaction kinetic measurements on the hydrochlorination of SiCl/sub 4/ and m.g. silicon metal were last reported as a function of reaction temperature, reactor pressure and H/sub 2//SiCl/sub 4/ feed ratio. 3 SiCl/sub 4/ + S H/sub 2/ + Si reversible 4 SiHCl/sub 3/. The same reaction has been studied in the presence of a copper catalyst. The presence of copper approximately doubles the reaction rates. A cement-type copper supplied by Union Carbide was evaluated at 5 wt % loading. After an induction period of about 22 hours, it began to show significant catalytic activity. Reaction kinetic measurements were then made as a function of reaction temperature (450/sup 0/, 500/sup 0/C), reactor pressure (300, 500 psig) and H/sub 2//SiCl/sub 4/ feed ratio (1.0 and 2.8). Another copper compound (CuCl) also was evaluated as a catalyst at 5 wt %. With CuCl, there was no induction period and full catalytic activity was observed soon after the reactor was brought to reaction conditions. Both cement copper and CuCl show about the same catalytic activity by doubling the reaction rate. Results of the copper studies provide some experimental evidence on the mechanism of the hydrochlorination reaction and on the nature of the copper catalyst.

  20. Rate constants for aqueous-phase reactions of hydroxyl radical ({center_dot}OH) with aldehydes and ketones

    SciTech Connect

    Allen, J.M.; Allen, S.K.

    1995-12-31

    A wide variety of aldehydes and ketones are formed in the troposphere by the gas-phase oxidation of hydrocarbons. These compounds are expected to readily partition into cloud, fog, and aquated aerosol drops where they can participate in a variety of aqueous-phase reactions. It has been previously demonstrated by other researchers that aqueous-phase photochemical reactions involving aromatic aldehydes and ketones may lead to the formation of hydrogen peroxide. Hydrogen peroxide is an important oxidant for S(IV) and is also an {center_dot}OH precursor. Aldehydes and ketones may also participate in other aqueous-phase reactions within atmospheric water drops including reactions with {center_dot}OH. Rate constants for reactions involving {center_dot}OH in aqueous solutions have been reported for only a limited number of tropospheric aldehydes and ketones. The authors have measured the rate constants for aqueous-phase reactions of {center_dot}OH with several tropospheric aldehydes and ketones by the technique of competition kinetics. Hydroxyl radicals were generated by continuous illumination at 313 nm of an aqueous acidified solution containing Fe(ClO{sub 4}){sub 3}, an {center_dot}OH scavenger, the aldehyde or ketone whose rate constant was to be measured, and a standard for which the rate constant for reaction with {center_dot}OH is well known. Nitrobenzene was used as the standard in all experiments. Loss of the aldehyde or ketone and the standard were monitored by HPLC. Losses attributable to direct photolysis and dark reactions were minimal.

  1. Hydrogen peroxide- and nitric oxide-induced systemic antioxidant prime-like activity under NaCl-stress and stress-free conditions in citrus plants.

    PubMed

    Tanou, Georgia; Molassiotis, Athanassios; Diamantidis, Grigorios

    2009-11-15

    We tested whether pre-treatments of roots with H(2)O(2) (10mM for 8h) or sodium nitroprusside (SNP; 100microM for 48h), a donor of ()NO, could induce prime antioxidant defense responses in the leaves of citrus plants grown in the absence or presence of 150mM NaCl for 16d. Both root pre-treatments increased leaf superoxide dismutase (SOD), catalase (CAT), ascorbate peroxidase (APX) and glutathione reductase (GR) activities, and induced related-isoform(s) expression under non-NaCl-stress conditions. When followed by salinity, certain enzymatic activities also exhibited an up-regulation in response to H(2)O(2) or SNP pre-exposure. An NaCl-stress-provoked decrease in the ascorbate redox state was partially prevented by both pre-treatments, whereas the glutathione redox state under normal and NaCl-stress conditions was increased by SNP. Real-time imaging of ()NO production was found in vascular tissues and epidermal cells. Furthermore, NaCl-induced inhibition in ()OH scavenging activity and promotion of ()OH-mediated DNA strand cleavage was partially prevented by SNP. Moreover, NaCl-dependent protein oxidation (carbonylation) was totally reversed by both pre-treatments as revealed by quantitative assay and protein blotting analysis. These results provide strong evidence that H(2)O(2) and ()NO elicit long-lasting systemic primer-like antioxidant activity in citrus plants under physiological and NaCl-stress conditions.

  2. CONDENSED MATTER: ELECTRONIC STRUCTURE, ELECTRICAL, MAGNETIC, AND OPTICAL PROPERTIES: Spectrum and Binding Energy of an Off-Center Hydrogenic Donor in a Spherical Quantum Dot

    NASA Astrophysics Data System (ADS)

    Yuan, Jian-Hui; Huang, Jin-Sheng; Yin, Miao; Zeng, Qi-Jun; Zhang, Jun-Pei

    2010-08-01

    Off-center impurity effects in a spherical quantum dot are theoretically studied by degenerate perturbation method in strong confinement. The energy levels and binding energies are computed for the typical GaAs material as function of the donor position. The numerical results show the quantum size effect. We note that the energy levels and binding energies are not only related to the position of donor and the strength of confinement, but also related to the fold of degenerate states. We can see obviously that gaps will appear among the degenerate states and the splitting of energy levels and binding energies will appear as the position of the impurity is shifted away off the center.

  3. Immobilization of quantum dots via conjugated self-assembled monolayers and their application as a light-controlled sensor for the detection of hydrogen peroxide.

    PubMed

    Khalid, Waqas; El Helou, Mira; Murböck, Tobias; Yue, Zhao; Montenegro, Jose-Maria; Schubert, Kirsten; Göbel, Gero; Lisdat, Fred; Witte, Gregor; Parak, Wolfgang J

    2011-12-27

    A light-addressable gold electrode modified with CdS and FePt or with CdS@FePt nanoparticles via an interfacial dithiol linker layer is presented. XPS measurements reveal that trans-stilbenedithiol provides high-quality self-assembled monolayers compared to benzenedithiol and biphenyldithiol, in case they are formed at elevated temperatures. The CdS nanoparticles in good electrical contact with the electrode allow for current generation under illumination and appropriate polarization. FePt nanoparticles serve as catalytic sites for the reduction of hydrogen peroxide to water. Advantageously, both properties can be combined by the use of hybrid nanoparticles fixed on the electrode by means of the optimized stilbenedithiol layer. This allows a light-controlled analysis of different hydrogen peroxide concentrations.

  4. Electrical anharmonicity in hydrogen bonded systems: complete interpretation of the IR spectra of the Cl-H[combining right harpoon above] stretching band in the gaseous (CH3)2OHCl complex.

    PubMed

    Rekik, Najeh; Suleiman, Jamal; Blaise, Paul; Wojcik, Marek J; Flakus, Henryk T; Nakajima, Takahito

    2017-02-22

    Following the previous developments to simulate the fully infrared spectra of weak hydrogen bond systems within the linear response theory, an extension of the adiabatic model is presented here. A general formulation including the electrical anharmonicities in the calculation of the damped autocorrelation function of weak H-bonds is adopted to facilitate the support of the additional properties, and thus the IR spectra of the Cl-H[combining right harpoon above] stretching band in the gaseous (CH3)2OHCl complex. We have explored the origins of the broadening of the Cl-H[combining right harpoon above] stretching band. We found that the main features of the lineshape are attributed to electrical anharmonicity as a consequence of the large mixed second derivatives of the dipole moment with respect to the Cl-H[combining right harpoon above] bond and of the intermonomer elongations . In addition to providing more accurate theoretical band shapes, inclusion of the electrical anharmonicity in the present model paves the way for a more complete interpretation by generating three new Franck-Condon superposed distributions.

  5. Improved activity and thermo-stability of the horse radish peroxidase with graphene quantum dots and its application in fluorometric detection of hydrogen peroxide

    NASA Astrophysics Data System (ADS)

    Xiaoyan, Zhou; Yuanyuan, Jiang; Zaijun, Li; Zhiguo, Gu; Guangli, Wang

    2016-08-01

    Graphene quantum dots (GQDs) have received extensive concern in many fields such as optical probe, bioimaging and biosensor. However, few reports refer on the influence of GQDs on enzyme performance. The paper reports two kinds of graphene quantum dots (termed as GO-GQDs and N,S-GQDs) that were prepared by cutting of graphene oxide and pyrolysis of citric acid and L-cysteine, and their use for the horse radish peroxidase (HRP) modification. The study reveals that GO-GQDs and N,S-GQDs exhibit an opposite effect on the HRP performance. Only HRP modified with GO-GQDs offers an enhanced activity (more than 1.9 times of pristine enzyme) and thermo-stability. This is because GO-GQDs offer a larger conjugate rigid plane and fewer hydrophilic groups compared to N,S-GQDs. The characteristics can make GO-GQDs induce a proper conformational change in the HRP for the catalytic performance, improving the enzyme activity and thermo-stability. The HRP modified with green luminescent GO-GQDs was also employed as a biocatalyst for sensing of H2O2 by a fluorometric sensor. The colorless tetramethylbenzidine (TMB) is oxidized into blue oxidized TMB in the presence of H2O2 by the assistance of HRP/GO-GQDs, leading to an obvious fluorescence quenching. The fluorescence intensity linearly decreases with the increase of H2O2 concentration in the range from 2 × 10 - 9 to 2 × 10 - 4 M with the detection limit of 6.8 × 10 - 10 M. The analytical method provides the advantage of sensitivity, stability and accuracy compared with present H2O2 sensors based on the pristine HRP. It has been successfully applied in the determination of H2O2 in real water samples. The study also opens a new avenue for modification of enzyme activity and stability that offers great promise in applications such as biological catalysis, biosensing and enzyme engineering.

  6. Improved activity and thermo-stability of the horse radish peroxidase with graphene quantum dots and its application in fluorometric detection of hydrogen peroxide.

    PubMed

    Xiaoyan, Zhou; Yuanyuan, Jiang; Zaijun, Li; Zhiguo, Gu; Guangli, Wang

    2016-08-05

    Graphene quantum dots (GQDs) have received extensive concern in many fields such as optical probe, bioimaging and biosensor. However, few reports refer on the influence of GQDs on enzyme performance. The paper reports two kinds of graphene quantum dots (termed as GO-GQDs and N,S-GQDs) that were prepared by cutting of graphene oxide and pyrolysis of citric acid and l-cysteine, and their use for the horse radish peroxidase (HRP) modification. The study reveals that GO-GQDs and N,S-GQDs exhibit an opposite effect on the HRP performance. Only HRP modified with GO-GQDs offers an enhanced activity (more than 1.9 times of pristine enzyme) and thermo-stability. This is because GO-GQDs offer a larger conjugate rigid plane and fewer hydrophilic groups compared to N,S-GQDs. The characteristics can make GO-GQDs induce a proper conformational change in the HRP for the catalytic performance, improving the enzyme activity and thermo-stability. The HRP modified with green luminescent GO-GQDs was also employed as a biocatalyst for sensing of H2O2 by a fluorometric sensor. The colorless tetramethylbenzidine (TMB) is oxidized into blue oxidized TMB in the presence of H2O2 by the assistance of HRP/GO-GQDs, leading to an obvious fluorescence quenching. The fluorescence intensity linearly decreases with the increase of H2O2 concentration in the range from 2×10-9 to 2×10-4M with the detection limit of 6.8×10-10M. The analytical method provides the advantage of sensitivity, stability and accuracy compared with present H2O2 sensors based on the pristine HRP. It has been successfully applied in the determination of H2O2 in real water samples. The study also opens a new avenue for modification of enzyme activity and stability that offers great promise in applications such as biological catalysis, biosensing and enzyme engineering.

  7. Synthesis of Cesium Lead Halide Perovskite Quantum Dots

    ERIC Educational Resources Information Center

    Shekhirev, Mikhail; Goza, John; Teeter, Jacob D.; Lipatov, Alexey; Sinitskii, Alexander

    Synthesis of quantum dots is a valuable experiment for demonstration and discussion of quantum phenomena in undergraduate chemistry curricula. Recently, a new class of all-inorganic perovskite quantum dots (QDs) with a formula of CsPbX[subscript 3] (X = Cl, Br, I) was presented and attracted tremendous attention. Here we adapt the synthesis of…

  8. Enhance photoelectrochemical hydrogen-generation activity and stability of TiO2 nanorod arrays sensitized by PbS and CdS quantum dots under UV-visible light.

    PubMed

    Li, Lei; Dai, Haitao; Feng, Liefeng; Luo, Dan; Wang, Shuguo; Sun, Xiaowei

    2015-12-01

    We develop a composite photoanode by sensitizing TiO2 nanorod arrays with PbS quantum dots (QDs) and CdS QDs. Benefitted from additional introduced PbS QDs and CdS QDs onto TiO2, the absorption of the composite photoanodes are broaden from UV to visible region. The experimental results showed that the PbS sandwiched between TiO2 and CdS cannot only broad the absorption properties but also improve the stability. The stability can be explained by the hole facile transmission from PbS to CdS because of the valence band offsets between PbS and CdS which cause a small energy barrier and reduce the hole accumulation. The photocurrent density reached 1.35 mA cm(-2) at 0.9716 V vs. RHE (0 V vs. Ag/AgCl, under 60 mW cm(-2) illumination) for TiO2/PbS/CdS. The highest photocurrent of TiO2/PbS/CdS can be explained by the smallest of total resistance (138 Ω cm(-2)) compared to TiO2/CdS and pristine TiO2.

  9. Enhance photoelectrochemical hydrogen-generation activity and stability of TiO2 nanorod arrays sensitized by PbS and CdS quantum dots under UV-visible light

    NASA Astrophysics Data System (ADS)

    Li, Lei; Dai, Haitao; Feng, Liefeng; Luo, Dan; Wang, Shuguo; Sun, Xiaowei

    2015-10-01

    We develop a composite photoanode by sensitizing TiO2 nanorod arrays with PbS quantum dots (QDs) and CdS QDs. Benefitted from additional introduced PbS QDs and CdS QDs onto TiO2, the absorption of the composite photoanodes are broaden from UV to visible region. The experimental results showed that the PbS sandwiched between TiO2 and CdS cannot only broad the absorption properties but also improve the stability. The stability can be explained by the hole facile transmission from PbS to CdS because of the valence band offsets between PbS and CdS which cause a small energy barrier and reduce the hole accumulation. The photocurrent density reached 1.35 mA cm-2 at 0.9716 V vs. RHE (0 V vs. Ag/AgCl, under 60 mW cm-2 illumination) for TiO2/PbS/CdS. The highest photocurrent of TiO2/PbS/CdS can be explained by the smallest of total resistance (138 Ω cm-2) compared to TiO2/CdS and pristine TiO2.

  10. Facile one-step hydrothermal synthesis toward strongly coupled TiO2/graphene quantum dots photocatalysts for efficient hydrogen evolution

    NASA Astrophysics Data System (ADS)

    Min, Shixiong; Hou, Jianhua; Lei, Yonggang; Ma, Xiaohua; Lu, Gongxuan

    2017-02-01

    The coupling of semiconductor photocatalysts with graphene quantum dots (GQDs) has been proven to be an effective strategy to enhance the photocatalytic and photoelectrical conversion performances of the resulted composites; however, the preparation of semiconductor/GQDs composites usually involves several time-inefficient and tedious post-treatment steps. Herein, we present a facile one-step hydrothermal route for the preparation of GQDs coupled TiO2 (TiO2/GQDs) photocatalysts using 1,3,6-trinitropyrene (TNP) as the sole precursor of GQDs. During the hydrothermal process, TNP molecules undergo an intramolecular fusion to form GQDs, which simultaneously decorate on the surface of TiO2 nanoparticles, leading to a strong surface interaction between the two components. The effective coupling of GQDs on TiO2 can effectively extend the light absorption of the TiO2 to visible region and enhance the charge separation efficiency of TiO2/GQDs composites as a result of GQDs acting as a photosensitizer and an excellent electron acceptor. These key advances make the TiO2/GQDs photocatalyst highly active towards the H2 evolution reaction, resulting in 7 and 3 times higher H2 evolution rate and photocurrent response at optimal GQDs content than TiO2 alone, respectively. This study provides a new methodology for the development of high-performance GQDs modified semiconductor photocatalysts for energy conversion applications.

  11. A theoretical study of X ligand effect on catalytic activity of complexes RuHX(diamine)(PPh(3))(2) (X = NCMe, CO, Cl, OMe, OPh, CCMe and H) in H(2)-hydrogenation of ketones.

    PubMed

    Chen, Zhuo; Chen, Yue; Tang, Yanhui; Lei, Ming

    2010-02-28

    In this paper, the catalytic activities of RuHX(diamine)(PPh(3))(2) complexes with different X ligands (X = NCMe, CO, Cl, OMe, OPh, CCMe and H, corresponding catalytic processes are abbreviated in A, B, C, D, E, F and G systems, respectively) in the H(2)-hydrogenation of ketones were investigated using density functional theory (DFT) method. Calculated results indicate that the rate-determining step in the whole catalytic cycle is hydrogen transfer (HT) for A-E but dihydrogen activation (DA) for F and G. The free energy barriers of the HT step for A-G are 36.1, 32.3, 21.2, 14.9, 21.9, 9.4 and 6.9 kcal mol(-1), respectively. The DA step consists of hydrogen coordination (HC) and hydrogen splitting (HS) steps if dihydrogen coordinates with the Ru center. The transition states (TSs) of H(2) coordinating with the Ru atom for A-G except B are located. The free energy barriers of DA for A-G are 17.8 (17.8, 2.6), 21.5, 12.8 (12.8, 3.8), 12.2 (11.2, 6.2), 13.6 (13.6, 4.1), 17.1 (9.7, 7.5) and 22.0 (10.4, 11.0) kcal mol(-1), respectively (the data in parentheses correspond to the barriers of HC and HS). HT barriers correlate well with the charges of hydride (H) in complex . HC barriers are closely related to the Ru[double bond, length as m-dash]N(1) double bond in , and HS are in line with the proton-moved-distances (PMDs) from to . This study demonstrates that catalysts D, F and G show better catalytic activities than the others, which is in good agreement with experimental results.

  12. 1D and 2D assembly structures by imidazole···chloride hydrogen bonds of iron(II) complexes [Fe(II)(HL(n-Pr))3]Cl·Y (HL(n-Pr) = 2-methylimidazol-4-yl-methylideneamino-n-propyl; Y = AsF6, BF4) and their spin states.

    PubMed

    Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Iijima, Seiichiro; Halcrow, Malcolm A; Sunatsuki, Yukinari; Kojima, Masaaki

    2011-12-07

    Two Fe(II) complexes fac-[Fe(II)(HL(n-Pr))(3)]Cl·Y (Y = AsF(6) (1) and BF(4) (2)) were synthesized, where HL(n-Pr) is 2-methylimidazole-4-yl-methylideneamino-n-propyl. Each complex-cation has the same octahedral N(6) geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[Fe(II)(HL(n-Pr))(3)](2+) with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) are hydrogen-bonded to three Cl(-) ions or, from the viewpoint of the Cl(-) ion, one Cl(-) ion is hydrogen-bonded to three neighbouring fac-[Fe(II)(HL(n-Pr))(3)](2+) cations. The 3 : 3 NH···Cl(-) hydrogen bonds between Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) and Cl(-) generate two kinds of assembly structures. The directions of the 3 : 3 NH···Cl(-) hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) enantiomorphs are bridged by two NH···Cl(-) hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[Fe(II)(HL(n-Pr))(3)](2+)···Cl(-)}(3) giving a smaller cavity, in which Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) species with the same chirality are linked by NH···Cl(-) hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and Mössbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T(c↓) = 125.5 K and T(c↑) = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.

  13. Tolerance of Intrinsic Defects in PbS Quantum Dots.

    PubMed

    Zherebetskyy, Danylo; Zhang, Yingjie; Salmeron, Miquel; Wang, Lin-Wang

    2015-12-03

    Colloidal quantum dots exhibit various defects and deviations from ideal structures due to kinetic processes, although their band gap frequently remains open and clean. In this Letter, we computationally investigate intrinsic defects in a real-size PbS quantum dot passivated with realistic Cl-ligands. We show that the colloidal intrinsic defects are ionic in nature. Unlike previous computational results, we find that even nonideal, atomically nonstoichiometric quantum dots have a clean band gap without in-gap-states provided that quantum dots satisfy electronic stoichiometry.

  14. Metal composition of layered double hydroxides (LDHs) regulating ClO(-)4 adsorption to calcined LDHs via the memory effect and hydrogen bonding.

    PubMed

    Lin, Yajie; Fang, Qile; Chen, Baoliang

    2014-03-01

    A series of calcined carbonate layered double hydroxides (CLDHs) with various metal compositions and different M(2+)/M(3+) ratios were prepared as adsorbents for perchlorate. Adsorption isotherms fit Langmuir model well, and the adsorption amount followed the order of MgAl-CLDHs ≥ MgFe-CLDHs > ZnAl-CLDHs. The isotherms of MgAl-CLDHs and MgFe-CLDHs displayed a two-step shape at low and high concentration ranges and increased with an increase in the M(2+)/M(3+) ratio from 2 to 4. The two-step isotherm was not observed for ZnAl-CLDHs, and the adsorption was minimally affected by the M(2+)/M(3+) ratio. The LDHs, CLDHs and the reconstructed samples were characterized by X-ray diffraction, SEM, FT-IR and Raman spectra to delineate the analysis of perchlorate adsorption mechanisms. The perchlorate adsorption of MgAl-CLDHs and MgFe-CLDHs was dominated by the structural memory effect and the hydrogen bonds between the free hydroxyl groups on the reconstructed-LDHs and the oxygen atoms of the perchlorates. For ZnAl-CLDHs, the perchlorate adsorption was controlled by the structural memory effect only, as the hydroxyl groups on the hydroxide layers preferred to form strong hydrogen bonds with carbonate over perchlorate, which locked the intercalated perchlorate into a more confined nano-interlayer. Several distinct binding mechanisms of perchlorate by CLDHs with unique M(2+) ions were proposed.

  15. Theoretical Studies of the Role of Vibrational Excitation on the Dynamics of the Hydrogen-Transfer Reaction of F(^2P) + HCl → FH + Cl({^2}P)

    NASA Astrophysics Data System (ADS)

    Ray, Sara E.; Vissers, Gé W. M.; McCoy, Anne B.

    2009-06-01

    Hydrogen-transfer reactions are probed through vibrational excitation of the HCl bond in the pre-reactive F\\cdotsHCl complex. Such open-shell species provide a challenge for quantum dynamical calculations due to the need to take into account multiple potential energy surfaces to accurately describe the system.A three-dimensional, fully-coupled potential energy surface has been constructed based on electronic energies calculated at the multireference configuration interaction+Davidson correction (MRCI+Q) level of theory with an aug-cc-pVnZ (n=2,3,4) basis. Spin orbit calculations have also been included. Here we present the results of time-dependent quantum wave packet calculations on the asymmetric hydrogen-transfer reaction of F(^2P) + HCl. In these calculations, the reaction is initiated by vibrationally exciting the HCl stretching motion in the pre-reactive F\\cdotsHCl complex. The wave packet is propagated on the coupled potential energy surfaces. Product state distributions were calculated for reactions initiated in the first three vibrationally excited states of HCl, v=1-3. M. P. Deskevich, M. Y. Hayes, K. Takahashi, R. T. Skodje, and D. J. Nesbitt J. Chem. Phys. 124 (22) 224303 (2006) M. P. Deskevich and D. J. Nesbitt private communication(2007)

  16. Free radical hydrogen atom abstraction from saturated hydrocarbons: A crossed-molecular-beams study of the reaction Cl + C{sub 3}H{sub 8} {yields} HCl + C{sub 3}H{sub 7}

    SciTech Connect

    Blank, D.A.; Hemmi, N.; Suits, A.G.; Lee, Y.T.

    1997-04-01

    The abstraction of hydrogen atoms from saturated hydrocarbons are reactions of fundamental importance in combustion as well as often being the rate limiting step in free radical substitution reactions. The authors have begun studying these reactions under single collision conditions using the crossed molecular beam technique on beamline 9.0.2.1, utilizing VUV undulator radiation to selectively ionize the scattered hydrocarbon free radical products (C{sub x}H{sub 2x+1}). The crossed molecular beam technique involves two reactant molecular beams fixed at 90{degrees}. The molecular beam sources are rotatable in the plane defined by the two beams. The scattered neutral products travel 12.0 cm where they are photoionized using the VUV undulator radiation, mass selected, and counted as a function of time. In the authors initial investigations they are using halogen atoms as protypical free radicals to abstract hydrogen atoms from small alkanes. Their first study has been looking at the reaction of Cl + propane {r_arrow} HCl + propyl radical. In their preliminary efforts the authors have measured the laboratory scattering angular distribution and time of flight spectra for the propyl radical products at collision energies of 9.6 kcal/mol and 14.9 kcal/mol.

  17. Ionic hydrogen bond and ion solvation. 6. Interaction energies of the acetate ion with organic molecules. Comparison of CH/sub 3/COO/sup -/ with Cl/sup -/, CN/sup -/, and SH/sup -/

    SciTech Connect

    Meot-Ner Mautner, M.

    1988-06-08

    The interaction energies of CH/sub 3/COO/sup -/ with protic and aprotic molecules were measured by pulsed high-pressure mass spectrometry. The attachment energies of the first three water molecules are 15.8, 12.8, and 11.8 kcal/mol. The rapid approach to ..delta..H/sub condsn/(H/sub 2/O) shows that ionic interactions are accounted for mostly by the first two solvent molecules. CH/sub 3/COO/sup -/ hydrogen bonds strongly to NH acids such as pyrrole, amides, and aniline, with ..delta..H/sup 0//sub D/ = 25-31 kcal/mol. With the carbon acids CH/sub 3/CHO, CH/sub 3/COCH/sub 3/, and CH/sub 3/CN as ligands, the attachment energies are 14-16 kcal/mol and the interactions may involve multiple O/sup -/..HC bonds. Despite the fact that the ions CH/sub 3/COO/sup -/, Cl/sup -/, CN/sup -/, and SH/sup -/ differ in size, structure, electronegativity, isotropy, and available bonding sites, they bond with similar strengths to most OH, NH, and CH hydrogen donors, from H/sub 2/O to large organic molecules such as the dipeptide analogue CH/sub 3/CO-Ala-OCH/sub 3/. Also, the four ions show similar clustering energies with n H/sub 2/O and HCN molecules (n = 1-4).

  18. Ternary Isothermal Diffusion Coefficients of NaCl-MgCl2-H2O at 25 C. 7. Seawater Composition

    SciTech Connect

    Miller, D G; Lee, C M; Rard, J A

    2007-02-12

    The four diffusion coefficients D{sub ij} of the ternary system NaCl-MgCl{sub 2}-H{sub 2}O at the simplified seawater composition 0.48877 mol {center_dot} dm{sup -3} NaCl and 0.05110 mol {center_dot} dm{sup -3} MgCl{sub 2} have been remeasured at 25 C. The diffusion coefficients were obtained using both Gouy and Rayleigh interferometry with the highly precise Gosting diffusiometer. The results, which should be identical in principle, are essentially the same within or very close to their combined 'realistic' errors. This system has a cross-term D{sub 12} that is larger than the D{sub 22} main-term, where subscript 1 denotes NaCl and 2 denotes MgCl{sub 2}. The results are compared with earlier, less-precise measurements. Recommended values for this system are (D{sub 11}){sub V} = 1.432 x 10{sup -9} m{sup 2} {center_dot} sec{sup -1}, (D{sub 12}){sub V} = 0.750 x 10{sup -9} m{sup 2} {center_dot} sec{sup -1}, (D{sub 21}){sub V} = 0.0185 x 10{sup -9} m{sup 2} {center_dot} sec{sup -1}, and (D{sub 22}){sub V} = 0.728 x 10{sup -9} m{sup 2} {center_dot} sec{sup -1}.

  19. Solvation Thermodynamic Properties of Hydrogen Sulfide in [C4mim][PF6], [C4mim][BF4], and [C4mim][Cl] Ionic Liquids, Determined by Molecular Simulations.

    PubMed

    Sánchez-Badillo, Joel; Gallo, Marco; Alvarado, Sandra; Glossman-Mitnik, Daniel

    2015-08-20

    Removal of hydrogen sulfide (H2S) and acid gases from natural gas is accomplished by absorption processes using a solvent. The gas solubility in a liquid can be used to measure the degree of removal of the gas and is quantified by the Henry's constant, the free energy of solvation at infinite dilution, or the excess chemical potential. In this work, Henry's constants and thermodynamic properties of solvation of H2S were calculated in three ionic liquids: [C4mim][PF6], [C4mim][BF4], and [C4mim][Cl] ([C4mim], 1-butyl-3-methyl imidazolium). The first step in this work was the evaluation of the force fields for the gas and condensed phases in order to obtain accurate values for the excess chemical potential for H2S on each ionic liquid using free energy perturbation techniques. In the H2S-[C4mim][PF6] and H2S-[C4mim][BF4] systems, the results obtained by molecular simulation agree with the experimental values reported in the literature. However, the solvation free energy calculated for the H2S-[C4mim][Cl] system can be considered predictive because of the lack of experimental data at the simulated conditions. Based on these results, the best solvent for removing H2S is [C4mim][Cl] because it has the highest affinity for this species (lowest value of the Henry's constant). Also, solvation thermodynamic properties such as enthalpy and entropy were calculated in order to evaluate their contribution to the free energy of solvation.

  20. Studies of site selective hydrogen atom abstractions by Cl atoms from isobutane and propane by laser flash photolysis/IR diode laser spectroscopy.

    PubMed

    Choi, N; Pilling, M J; Seakins, P W; Wang, L

    2006-05-14

    The kinetics of chlorine atom abstractions from normal and selectively deuterated propane and isobutane have been measured at room temperature and 195 K using a laser flash photolysis system, and following the course of the reaction via IR diode laser absorption measurements of HCl product. In conjunction with the kinetic measurements, a comparison of the HCl signal heights from pairs of measurements on normal and selectively deuterated systems has allowed the determination of the branching fractions of the reactions at the primary, secondary (propane) and tertiary (isobutane) positions. The kinetic data (all in units of cm(3) molecule(-1) s(-1)) for the reaction of Cl atoms with propane ((1.22 +/- 0.02) x10(-10), 195 K; (1.22 +/- 0.03) x10(-10) 298 K) and isobutane ((1.52 +/- 0.02) x10(-10), 195 K; (1.25 +/- 0.04) x10(-10), 298 K) are generally in good agreement with literature data. No data are available for comparison with our measurements for the reactions of Cl atoms with CH(3)CD(2)CH(3) ((1.02 +/- 0.03) x10(-10), 195 K; (1.09 +/- 0.02) x10(-10), 298 K) or (CH(3))(3)CD ((1.32 +/- 0.03) x10(-10), 195 K; (1.12 +/- 0.04) x10(-10), 298 K). Rate coefficients at 195 K for the reactions of Cl atoms with ethane ((5.04 +/- 0.08) x10(-11) and n-butane ((2.19 +/- 0.03) x10(-10)) were also measured. The branching fractions for abstraction at the primary position increased with temperature for both propane ((40 +/- 3)% at 195 K to (48 +/- 3)% at 298 K) and isobutane ((49 +/- 4)% at 195 K to (62 +/- 5)% at 298 K). The direct measurements from this study are in good agreement with most calculations based on structure activity relationships.

  1. Is It Homogeneous or Heterogeneous Catalysis Derived from [RhCp*Cl2]2? In Operando-XAFS, Kinetic and Crucial Kinetic Poisoning Evidence for Subnanometer Rh4 Cluster-Based Benzene Hydrogenation Catalysis

    SciTech Connect

    Bayram, Ercan; Linehan, John C.; Fulton, John L.; Roberts, John A.; Szymczak, Nathaniel; Smurthwaite, Tricia D.; Ozkar, Saim; Balasubramanian, Mahalingam; Finke, Richard G.

    2011-11-23

    Determining the true, kinetically dominant catalytically active species, in the classic benzene hydrogenation system pioneered by Maitlis and co-workers 34 years ago starting with [RhCp*Cl2]2 (Cp* = [{eta}5-C5(CH3)5]), has proven to be one of the most challenging case studies in the quest to distinguish single-metal-based 'homogeneous' from polymetallic, 'heterogeneous' catalysis. The reason, this study will show, is the previous failure to use the proper combination of (i) operando spectroscopy to determine the dominant form(s) of the precatalyst's mass under catalysis (i.e., operating) conditions, plus then and crucially also (ii) the previous lack of the necessary kinetic studies, catalysis being a 'wholly kinetic phenomenon' as J. Halpern long ago noted. An important contribution from this study will be to reveal the power of quantitiative kinetic poisoning experiments for distinguishing single-metal, or in this case subnanometer Rh4 cluster-based catalysis from larger, polymetallic Rh(0)n nanoparticle catalysis, at least under favorable conditions. The combined operando-XAFS (X-ray absorption fine structure) spectroscopy and kinetic evidences provide a compelling case for Rh4-based, with average stoichiometry 'Rh4Cp*2.4Cl4Hc', benzene hydrogenation catalysis in 2-propanol with added Et3N and at 100 C and 50 atm initial H2 pressure. The results also reveal, however, that if even ca. 1.4% of the total soluble Rh(0)n had formed nanoparticles, then those Rh(0)n nanoparticles would have been able to account for all the observed benzene hydrogenation catalytic rate (using commercial, ca. 2 nm, polyethyleneglycol-dodecylether hydrosol stabilized Rh(0)n nanoparticles as a model system). The results 'especially the poisoning methodology developed and employed' are of significant, broader interest since determining the nature of the true catalyst continues to be a central, often vexing issue in any and all catalytic reactions. The results are also of fundamental

  2. Is it homogeneous or heterogeneous catalysis derived from [RhCp*Cl2]2? In operando XAFS, kinetic, and crucial kinetic poisoning evidence for subnanometer Rh4 cluster-based benzene hydrogenation catalysis.

    PubMed

    Bayram, Ercan; Linehan, John C; Fulton, John L; Roberts, John A S; Szymczak, Nathaniel K; Smurthwaite, Tricia D; Özkar, Saim; Balasubramanian, Mahalingam; Finke, Richard G

    2011-11-23

    Determining the true, kinetically dominant catalytically active species, in the classic benzene hydrogenation system pioneered by Maitlis and co-workers 34 years ago starting with [RhCp*Cl(2)](2) (Cp* = [η(5)-C(5)(CH(3))(5)]), has proven to be one of the most challenging case studies in the quest to distinguish single-metal-based "homogeneous" from polymetallic, "heterogeneous" catalysis. The reason, this study will show, is the previous failure to use the proper combination of: (i) in operando spectroscopy to determine the dominant form(s) of the precatalyst's mass under catalysis (i.e., operating) conditions, and then crucially also (ii) the previous lack of the necessary kinetic studies, catalysis being a "wholly kinetic phenomenon" as J. Halpern long ago noted. An important contribution from this study will be to reveal the power of quantitiative kinetic poisoning experiments for distinguishing single-metal, or in the present case subnanometer Rh(4) cluster-based catalysis, from larger, polymetallic Rh(0)(n) nanoparticle catalysis, at least under favorable conditions. The combined in operando X-ray absorption fine structure (XAFS) spectroscopy and kinetic evidence provide a compelling case for Rh(4)-based, with average stoichiometry "Rh(4)Cp*(2.4)Cl(4)H(c)", benzene hydrogenation catalysis in 2-propanol with added Et(3)N and at 100 °C and 50 atm initial H(2) pressure. The results also reveal, however, that if even ca. 1.4% of the total soluble Rh(0)(n) had formed nanoparticles, then those Rh(0)(n) nanoparticles would have been able to account for all the observed benzene hydrogenation catalytic rate (using commercial, ca. 2 nm, polyethyleneglycol-dodecylether hydrosol stabilized Rh(0)(n) nanoparticles as a model system). The results--especially the poisoning methodology developed and employed--are of significant, broader interest since determining the nature of the true catalyst continues to be a central, often vexing issue in any and all catalytic reactions

  3. Direct ab initio dynamics studies on the hydrogen-abstraction reactions of OH radicals with HOX (X = F, Cl, and Br).

    PubMed

    Wang, Li; Liu, Jing-Yao; Li, Ze-Sheng; Sun, Chia-Chung

    2004-03-01

    The hydrogen abstract reactions of OH radicals with HOF (R1), HOCl (R2), and HOBr (R3) have been studied systematically by a dual-level direct-dynamics method. The geometries and frequencies of all the stationary points are optimized at the MP2/6-311+G(2d, 2p) level of theory. A hydrogen-bonded complex is located at the product channel for the OH + HOBr reaction. To improve the energetics information along the minimum energy path (MEP), single-point energy calculations are carried out at the CCSD(T)/6-311++G(3df, 3pd) level of theory. Interpolated single-point energy (ISPE) method is employed to correct the energy profiles for the three reactions. It is found that neither the barrier heights (DeltaE) nor the H-O bond dissociation energies [D(H-O)] exhibit any clear-cut linear correlations with the halogen electronegative. The decrease of DeltaE and D(H-O) for the three reactions are in order of HOF > HOBr > HOCl. Rate constants for each reaction are calculated by canonical variational transition-state theory (CVT) with a small-curvature tunneling correction (SCT) within 200-2000 K. The agreement of the rate constants with available experimental values for reactions R2 and R3 at 298 K is good. Our results show that the variational effect is small while the tunneling correction has an important contribution in the calculation of rate constants in the low-temperature range. Due to the lack of the kinetic data of these reactions, the present theoretical results are expected to be useful and reasonable to estimate the dynamical properties of these reactions over a wide temperature range where no experimental value is available.

  4. Direct chemiluminescence of carbon dots induced by potassium ferricyanide and its analytical application

    NASA Astrophysics Data System (ADS)

    Amjadi, Mohammad; Manzoori, Jamshid L.; Hallaj, Tooba; Sorouraddin, Mohammad H.

    2014-03-01

    The chemiluminescence (CL) of water-soluble fluorescent carbon dots (C-dots) induced by direct chemical oxidation was investigated. C-dots were prepared by solvothermal method and characterized by fluorescence spectra and transmission electron microscopy. It was found that K3Fe(CN)6 could directly oxidize C-dots to produce a relatively intense CL emission. The mechanism of CL generation was investigated based on the fluorescence and CL emission spectra and the effect of radical scavengers on the CL intensity. The inhibitive effect of some metal ions and biologically important molecules on the CL intensity of the system was examined and the potential of the system for the determination of these species at trace levels was studied. In order to evaluate the capability of method to real sample analysis, it was applied to the determination of Cr(VI) and adrenaline in water and injection samples, respectively.

  5. Chlorine-functionalized carbon dots for highly efficient photodegradation of pollutants under visible-light irradiation

    NASA Astrophysics Data System (ADS)

    Hu, Shengliang; Ding, Yanli; Chang, Qing; Yang, Jinlong; Lin, Kui

    2015-11-01

    Chlorine-functionalized carbon dots (Cl-CDs) were prepared by the substitution reaction between Cl radicals into thionyl chloride molecules and carbon dots with containing OH/COOH groups at their surface (O-CDs). The obtained Cl-CDs with a size of 2-5 nm contain 2-3% Cl atoms and emit blue light. Compared with amine-functionalzed carbon dots (N-CDs) and O-CDs, Cl-CDs exhibit much higher photocatalytic activity under visible-light irradiation. The thermally and chemically stable phthalocyanine can be even degraded quickly through Cl-CDs. This work suggests that surface engineering of carbon dots with heteroatoms can be used to enhance their photochemical properties.

  6. Chemiluminescence of nitrogen-rich quantum dots in diperiodatoargentate(III) solution and its application in ferulic acid analysis.

    PubMed

    Fu, Zhaofu; Li, Gongke; Hu, Yufei

    2016-12-01

    A novel chemiluminescence (CL) system based on the reaction of fluorescent water-soluble nitrogen-rich quantum dots (N-dots) and diperiodatoargentate(III) (DPA) was developed. The prepared N-dots have a small size (≤10 nm) and high percentage of nitrogen (39.9 %), which exceeds the content of carbon in the same N-dots. The N-dots exhibit characteristic blue fluorescence under UV light and up-conversion luminescence. The relatively intense CL emission is based on the direct oxidation of N-dots by DPA. The CL emission may be attributed to the high nitrogen content and the special structure of the N-dots. The CL mechanism of N-dots and DPA was investigated by using CL, UV-Vis absorption, IR, fluorescence, and radical scavenging experiments. This investigation provides a way to study the optical properties of N-dots. The analytical applicability of the N-dots and DPA CL system in the determination of ferulic acid (FA) was explored. The CL intensity was linearly proportional to the concentration of ferulic acid from 3.0 × 10(-7) to 1.0 × 10(-5) g mL(-1) with a detection limit of 8.0 × 10(-8) g mL(-1) (3σ); the relative standard deviation was 2.4 % for 4.0 × 10(-7) g mL(-1) FA (n = 9). The proposed method was successfully applied to the determination of ferulic acid in Angelica sinensis. The study provides valuable insight into the role of nitrogen-rich quantum dots in CL.

  7. Synthesis, structure, and catalytic properties of the layered oxide SbOReO[sub 4][center dot]2H[sub 2]O: Location of hydrogen-atom positions by powder neutron diffraction

    SciTech Connect

    Harrison, W.T.A. ); McManus, A.V.P. ); Kaminsky, M.P. ); Cheetham, A.K. )

    1993-11-01

    A new hydrated antimony rhenium oxide, SbOReO[sub 4][center dot]2H[sub 2]O, has been prepared by hydrothermal methods and fully characterized by powder neutron diffraction. The structure consists of double layers built up from infinite, interconnected arrays of [SbO[sup +

  8. Random-Dot Stereogram

    NASA Astrophysics Data System (ADS)

    Kuwayama, Tetsuro

    The technology and history of random-dot stereogram are described. The paper on two-picture type random-dot stereogram is delivered in 1960, and this technology came to be known widely in 1960s. On the other hand, the principle of the single image random-dot stereogram (Autostereogram) was invented in 1979, but came to be known since the announcement of SPIE conference in 1990. Wallpaper stereogram is also described.

  9. A computational mechanistic investigation of hydrogen production in water using the [Rh(III)(dmbpy)2Cl2](+)/[Ru(II)(bpy)3](2+)/ascorbic acid photocatalytic system.

    PubMed

    Kayanuma, Megumi; Stoll, Thibaut; Daniel, Chantal; Odobel, Fabrice; Fortage, Jérôme; Deronzier, Alain; Collomb, Marie-Noëlle

    2015-04-28

    We recently reported an efficient molecular homogeneous photocatalytic system for hydrogen (H2) production in water combining [Rh(III)(dmbpy)2Cl2](+) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine) as a H2 evolving catalyst, [Ru(II)(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and ascorbic acid as a sacrificial electron donor (Chem. - Eur. J., 2013, 19, 781). Herein, the possible rhodium intermediates and mechanistic pathways for H2 production with this system were investigated at DFT/B3LYP level of theory and the most probable reaction pathways were proposed. The calculations confirmed that the initial step of the mechanism is a reductive quenching of the excited state of the Ru photosensitizer by ascorbate, affording the reduced [Ru(II)(bpy)2(bpy˙(-))](+) form, which is capable, in turn, of reducing the Rh(III) catalyst to the distorted square planar [Rh(I)(dmbpy)2](+) species. This two-electron reduction by [Ru(II)(bpy)2(bpy˙(-))](+) is sequential and occurs according to an ECEC mechanism which involves the release of one chloride after each one-electron reduction step of the Rh catalyst. The mechanism of disproportionation of the intermediate Rh(II) species, much less thermodynamically favoured, cannot be barely ruled out since it could also be favoured from a kinetic point of view. The Rh(I) catalyst reacts with H3O(+) to generate the hexa-coordinated hydride [Rh(III)(H)(dmbpy)2(X)](n+) (X = Cl(-) or H2O), as the key intermediate for H2 release. The DFT study also revealed that the real source of protons for the hydride formation as well as the subsequent step of H2 evolution is H3O(+) rather than ascorbic acid, even if the latter does govern the pH of the aqueous solution. Besides, the calculations have shown that H2 is preferentially released through an heterolytic mechanism by reaction of the Rh(III)(H) hydride and H3O(+); the homolytic pathway, involving the reaction of two Rh(III)(H) hydrides, being clearly less favoured. In parallel to this

  10. Simultaneous quantification of 5-hydroxyindoleacetic acid and 5-hydroxytryptamine by capillary electrophoresis with quantum dot and horseradish peroxidase enhanced chemiluminescence detection.

    PubMed

    Zhang, Liangliang; Zhao, Yunsha; Huang, Junming; Zhao, Shulin

    2014-09-15

    A capillary electrophoresis (CE) with chemiluminescence (CL) detection method was developed for the simultaneous quantification of 5-hydroxyindoleacetic acid (5-HIAA) and 5-hydroxytryptamine (5-HT). In this method, CdTe quantum dot (QD) and horseradish peroxidase (HRP) were used as enhancing reagents to co-catalyze the post-column CL reaction between luminol and hydrogen peroxide, achieving highly efficient CL emission. 5-HIAA and 5-HT inhibit the CL emission resulting to the formation of negative peaks in electropherogram. The degree of CL suppression is proportional to the concentration of 5-HT and 5-HIAA. The linear ranges for the determination of 5-HIAA and 5-HT were 2.5×10(-8)-2.5×10(-6) M and 2.5×10(-8)-5.0×10(-6) M with detection limits (signal/noise=3) of 7.0×10(-9) M and 6.0×10(-9) M, respectively. Intraday precision do not exceed 5.0%. The accuracy was confirmed by the recoveries ranged from 98% to 104%. The present method was successfully applied for the quantification of 5-HIAA and 5-HT in human urine. The concentrations of 5-HT and 5-HIAA in human urine were found to be in the range of 0.78-1.2 μM and 3.2-5.1 μM, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Quantum Dots: Theory

    SciTech Connect

    Vukmirovic, Nenad; Wang, Lin-Wang

    2009-11-10

    This review covers the description of the methodologies typically used for the calculation of the electronic structure of self-assembled and colloidal quantum dots. These are illustrated by the results of their application to a selected set of physical effects in quantum dots.

  12. Quantum Dot Solar Cells

    NASA Technical Reports Server (NTRS)

    Raffaelle, Ryne P.; Castro, Stephanie L.; Hepp, Aloysius; Bailey, Sheila G.

    2002-01-01

    We have been investigating the synthesis of quantum dots of CdSe, CuInS2, and CuInSe2 for use in an intermediate bandgap solar cell. We have prepared a variety of quantum dots using the typical organometallic synthesis routes pioneered by Bawendi, et. al., in the early 1990's. However, unlike previous work in this area we have also utilized single-source precursor molecules in the synthesis process. We will present XRD, TEM, SEM and EDS characterization of our initial attempts at fabricating these quantum dots. Investigation of the size distributions of these nanoparticles via laser light scattering and scanning electron microscopy will be presented. Theoretical estimates on appropriate quantum dot composition, size, and inter-dot spacing along with potential scenarios for solar cell fabrication will be discussed.

  13. Quantum Dot Solar Cells

    NASA Technical Reports Server (NTRS)

    Raffaelle, Ryne P.; Castro, Stephanie L.; Hepp, Aloysius; Bailey, Sheila G.

    2002-01-01

    We have been investigating the synthesis of quantum dots of CdSe, CuInS2, and CuInSe2 for use in an intermediate bandgap solar cell. We have prepared a variety of quantum dots using the typical organometallic synthesis routes pioneered by Bawendi, et. al., in the early 1990's. However, unlike previous work in this area we have also utilized single-source precursor molecules in the synthesis process. We will present XRD, TEM, SEM and EDS characterization of our initial attempts at fabricating these quantum dots. Investigation of the size distributions of these nanoparticles via laser light scattering and scanning electron microscopy will be presented. Theoretical estimates on appropriate quantum dot composition, size, and inter-dot spacing along with potential scenarios for solar cell fabrication will be discussed.

  14. Highly sensitive humidity sensing properties of carbon quantum dots films

    SciTech Connect

    Zhang, Xing; Ming, Hai; Liu, Ruihua; Han, Xiao; Kang, Zhenhui; Liu, Yang; Zhang, Yonglai

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► A humidity sensing device was fabricated based on carbon quantum dots (CQDs) films. ► The conductivity of the CQDs films shows a linear and rapid response to atmosphere humidity. ► The humidity sensing property was due to the hydrogen bonds between the functional groups on CQDs. -- Abstract: We reported the fabrication of a humidity sensing device based on carbon quantum dots (CQDs) film. The conductivity of the CQDs film has a linear and rapid response to relative humidity, providing the opportunity for the fabrication of humidity sensing devices. The mechanism of our humidity sensor was proposed to be the formation of hydrogen bonds between carbon quantum dots and water molecules in the humidity environment, which significantly promote the electrons migration. In a control experiment, this hypothesis was confirmed by comparing the humidity sensitivity of candle soot (i.e. carbon nanoparticles) with and without oxygen containing groups on the surfaces.

  15. Hydrogen production

    NASA Technical Reports Server (NTRS)

    England, C.; Chirivella, J. E.; Fujita, T.; Jeffe, R. E.; Lawson, D.; Manvi, R.

    1975-01-01

    The state of hydrogen production technology is evaluated. Specific areas discussed include: hydrogen production fossil fuels; coal gasification processes; electrolysis of water; thermochemical production of hydrogen; production of hydrogen by solar energy; and biological production of hydrogen. Supply options are considered along with costs of hydrogen production.

  16. Hydrogen production

    NASA Technical Reports Server (NTRS)

    England, C.; Chirivella, J. E.; Fujita, T.; Jeffe, R. E.; Lawson, D.; Manvi, R.

    1975-01-01

    The state of hydrogen production technology is evaluated. Specific areas discussed include: hydrogen production fossil fuels; coal gasification processes; electrolysis of water; thermochemical production of hydrogen; production of hydrogen by solar energy; and biological production of hydrogen. Supply options are considered along with costs of hydrogen production.

  17. Hydrogen systems

    SciTech Connect

    Veziroglu, T.N.; Zhu, Y.; Bao, D.

    1985-01-01

    This book presents the papers given at a symposium on hydrogen fuels. Topics considered at the symposium included hydrogen from fossil fuels, electrolysis, photolytic hydrogen generation, thermochemical and photochemical methods of hydrogen production, catalysts, hydrogen biosynthesis, novel and hybrid methods of hydrogen production, storage and handling, metal hydrides and their characteristics, utilization, hydrogen fueled internal combustion engines, hydrogen gas turbines, hydrogen flow and heat transfer, fuel cells, synthetic hydrocarbon fuels, thermal energy transfer, hydrogen purification, research programs, economics, primary energy sources, environmental impacts, and safety.

  18. Density functional calculation of the structural and electronic properties of germanium quantum dots

    NASA Astrophysics Data System (ADS)

    Anas, M. M.; Gopir, G.

    2015-04-01

    We apply first principles density functional computational methods to study the structures, densities of states (DOS), and higher occupied molecular orbital (HOMO) - lowest unoccupied molecular orbital (LUMO) gaps of selected free-standing Ge semiconductor quantum dots up to 1.8nm. Our calculations are performed using numerical atomic orbital approach where linear combination of atomic orbital was applied. The surfaces of the quantum dots was passivized by hydrogen atoms. We find that surface passivation does affect the electronic properties associated with the changes of surface state, electron localization, and the energy gaps of germanium nanocrystals as well as the confinement of electrons inside the quantum dots (QDs). Our study shows that the energy gaps of germanium quantum dots decreases with the increasing dot diameter. The size-dependent variations of the computed HOMO-LUMO gaps in our quantum dots model were found to be consistent with the effects of quantum confinement reported in others theoretical and experimental calculation.

  19. Density functional calculation of the structural and electronic properties of germanium quantum dots

    SciTech Connect

    Anas, M. M.; Gopir, G.

    2015-04-24

    We apply first principles density functional computational methods to study the structures, densities of states (DOS), and higher occupied molecular orbital (HOMO) – lowest unoccupied molecular orbital (LUMO) gaps of selected free-standing Ge semiconductor quantum dots up to 1.8nm. Our calculations are performed using numerical atomic orbital approach where linear combination of atomic orbital was applied. The surfaces of the quantum dots was passivized by hydrogen atoms. We find that surface passivation does affect the electronic properties associated with the changes of surface state, electron localization, and the energy gaps of germanium nanocrystals as well as the confinement of electrons inside the quantum dots (QDs). Our study shows that the energy gaps of germanium quantum dots decreases with the increasing dot diameter. The size-dependent variations of the computed HOMO-LUMO gaps in our quantum dots model were found to be consistent with the effects of quantum confinement reported in others theoretical and experimental calculation.

  20. Structure and effects of annealing in colloidal matrix-free Ge quantum dots.

    PubMed

    Zhang, Yuanpeng; Karatutlu, Ali; Ersoy, Osman; Little, William; Cibin, Giannantonio; Dent, Andy; Sapelkin, Andrei

    2015-01-01

    The structure of small (2-5 nm) Ge quantum dots prepared by the colloidal synthesis route is examined. Samples were synthesized using either GeO2 or GeCl4 as precursor. As-prepared samples were further annealed under Ar or H2/Ar atmosphere at different temperatures in order to understand the effect of annealing on their structure. It was found that as-prepared samples possess distinctly different structures depending on their synthesis route as indicated by their long-range ordering. An appreciable amount of oxygen was found to be bound to Ge in samples prepared with GeO2 as a precursor; however, not for GeCl4. Based on combined transmission electron microscope, Raman, X-ray diffraction and X-ray absorption measurements, it is suggested that as-prepared samples are best described by the core-shell model with a small nano-crystalline core and an amorphous outer layer terminated either with oxygen or hydrogen depending on the synthesis route. Annealing in an H2Ar atmosphere leads to sample crystallization and further nanoparticle growth, while at the same time reducing the Ge-O bonding. X-ray diffraction measurements for as-prepared and annealed samples indicate that diamond-type and metastable phases are present.

  1. A theoretical study of hydrogen complexes of the XH-pi type between propyne and HF, HCL or HCN.

    PubMed

    Tavares, Alessandra M; da Silva, Washington L V; Lopes, Kelson C; Ventura, Elizete; Araújo, Regiane C M U; do Monte, Silmar A; da Silva, João Bosco P; Ramos, Mozart N

    2006-05-15

    The present manuscript reports a systematic investigation of the basis set dependence of some properties of hydrogen-bonded (pi type) complexes formed by propyne and a HX molecule, where X=F, Cl and CN. The calculations have been performed at Hartree-Fock, MP2 and B3LYP levels. Geometries, H-bond energies and vibrational have been considered. The more pronounced effects on the structural parameters of the isolated molecules, as a result of complexation, are verified on RCtriple bondC and HX bond lengths. As compared to double-zeta (6-31G**), triple-zeta (6-311G**) basis set leads to an increase of RCtriple bondC bond distance, at all three computational levels. In the case where diffuse functions are added to both hydrogen and 'heavy' atoms, the effect is more pronounced. The propyne-HX structural parameters are quite similar to the corresponding parameters of acetylene-HX complexes, at all levels. The largest difference is obtained for hydrogen bond distance, RH, with a smaller value for propyne-HX complex, indicating a stronger bond. Concerning the electronic properties, the results yield the following ordering for H-bond energies, DeltaE: propynecdots, three dots, centeredHF>propynecdots, three dots, centeredHCl>propynecdots, three dots, centeredHCN. It is also important to point out that the inclusion of BSSE and zero-point energies (ZPE) corrections cause significant changes on DeltaE. The smaller effect of ZPE is obtained for propynecdots, three dots, centeredHCN at HF/6-311++G** level, while the greatest difference is obtained at MP2/6-31G** level for propynecdots, three dots, centeredHF system. Concerning the IR vibrational it was obtained that larger shift can be associated with stronger hydrogen bonds. The more pronounced effect on the normal modes of the isolated molecule after the complexation is obtained for HX stretching frequency, which is shifted downward.

  2. Quantum dots for biophotonics.

    PubMed

    Yong, Ken-Tye

    2012-01-01

    This theme issue provides an excellent collection of reviews and original research articles on the study of various bioconjugated quantum dot formulations for diagnostics and therapy applications using biophotonic imaging and sensing approaches.

  3. Dots for Dummies

    NASA Astrophysics Data System (ADS)

    Shankar, R.

    2006-12-01

    Quantum dots pose an interesting problem in which three complications- disorder, interaction and finite size- come together. I describe progress that can be made by combining Random Matrix Theory (RMT) and the Renormalization Group (RG) to attack the problem.

  4. Ultraviolet optical properties of silica controlled by hydrogen trapping at Ge-related defects

    SciTech Connect

    Cannas, M.; Origlio, G.

    2007-06-15

    We studied the effects induced by the ultraviolet-laser and -lamp exposure sequences on the twofold coordinated germanium (=Ge{sup {center_dot}}{sup {center_dot}}) and the H(II) center (=Ge{sup {center_dot}}-H) in silica. The H(II) centers, generated after the first laser irradiation stage by the trapping of atomic hydrogen H{sup 0} at the (=Ge{sup {center_dot}}{sup {center_dot}}), are destroyed by the subsequent lamp exposure with efficiency depending on photon energy. The H(II) photodestruction is activated from {approx}4 eV, and its cross section is here quantitatively measured, so giving the absorption profile of this center. Consistent with the observed correlated recovering of (=Ge{sup {center_dot}}{sup {center_dot}}), the photodestruction is mainly due to the photolysis of the Ge-H bond leading to hydrogen detrapping.

  5. A quantum dot-lucigenin probe for Cl-.

    PubMed

    Ruedas-Rama, Maria Jose; Hall, Elizabeth A H

    2008-11-01

    In this work, the first chloride ion sensor based on QD-lucigenin nanoparticles is reported. The mechanism uses the ability of semiconductor QDs to engage in short range exchange processes, leading to fluorescence changes. An acridinium dication (lucigenin) which is an electron acceptor, was self-assembled on the surface of negative charged QDs (capped with mercaptopropionic acid). Mutual quenching of the lucigenin and QD were observed. From a sphere of action, Perrin-type model, exchange was estimated to occur over a range of the order of 2 nm. The possibility of spin-orbit coupling (SOC) or electron transfer between the QD and the lucigenin dication (Luc(2+)) is discussed. The radical cation Luc(+*) was not identified, but electron transfer from the QD conduction band to the Luc(2+), then electron transfer back, from the Luc(+*) to the QD valence band, could lead to mutual quenching, without build up of Luc(+*) . SOC between the QD and lucigenin, with or without charge transfer being involved, can also account for the results obtained. Lucigenin is also a chloride-sensitive indicator dye, with a sensing mechanism based on SOC. In the QD-MPA-lucigenin conjugate luminescence is restored by adding chloride ion. Thus, the presence of chloride is transduced into an enhancement of the luminescence of QDs. Using this operating principle, a chloride ion sensor based on CdSe-ZnS core-shell QD nanoparticles, showed a very good linearity in the range 1-250 mM, with a detection limit 0.29 mM and a RSD of 2.5% (n = 10). In a study of interferences, the chloride sensitive QDs showed good selectivity to most of the other anions tested. The versatility of the system was also demonstrated in terms of fluorescent emission wavelength, which could be selected across a wide range through choice of QDs. Examples are shown for lambda(max) = 500, 540 and 620 nm. The results from samples mimicking physiological conditions suggested very good applicability in the determination of chloride ion in physiological samples.

  6. Photoelectrochemical Water Splitting of Nitrogen and Hydrogen Treated P25 TiO2 Films

    NASA Astrophysics Data System (ADS)

    Zavodivker, Liat S.

    Photoelectrochemical data is reported for P25 TiO2 films deposited as a pristine film on FTO. The pristine P25 films show a photocurrent of 0.06 mA/cm2 and an onset potential of -0.5 V vs. Ag/AgCl. After TiCl4 Treatment to form a compact TiO 2 layer on the bottom and the surface layer, the TiCl4 sandwich films have a photocurrent of 0.19 mA/cm2 and an onset potential of -0.8 V. We have also investigated the effects of hydrogen treatment, ammonia treatment, and the combination of hydrogen treatment followed by ammonia treatment (co-treatment) on the photocurrent, the incident photon-to-current efficiency (IPCE), and the electron donor density of the P25 TiCl4 sandwich films. Treating the P25 films had almost no effect on the size and d-spacing of the particles, but EPR evidence, as well as color change, indicated the formation of N 2p nitrogen sites and oxygen vacancies (VO) for each film treatment. I-V data for the treated TiCl4 sandwich films show an increase in photocurrent from 0.19 mA/cm2 for the pristine P25 TiO2 film to 0.4 mA/cm 2 for the co-treated TiO2 film compared to 0.23 mA/cm 2 for hydrogen treatment and 0.25 mA/cm2 for ammonia treatment. For the P25 treated films, there is negligible increase of UV absorption in the visible for the singly treated films as well as the co-treated films. However, the improved photocurrent for the ammonia treated, hydrogen treated, and co-treated films may be explained by increased donor density. Mott-Schottky plots are used to characterize donor density, showing that the co-treated P25 TiCl4 sandwich films have an increased donor density over the nitrogen-treated P25 TiO2 and pristine P25 TiO2 films. The improved donor density of the treated P25 films over the untreated films may prove to be useful when completing future dye or semiconducting quantum dot sensitization experiments.

  7. Vacancy clusters in graphane as quantum dots.

    PubMed

    Singh, Abhishek K; Penev, Evgeni S; Yakobson, Boris I

    2010-06-22

    Complementary electronic properties and a tendency to form sharp graphene-graphane interfaces open tantalizing possibilities for two-dimensional nanoelectronics. First-principles density functional and tight-binding calculations show that graphane can serve as natural host for graphene quantum dots, clusters of vacancies in the hydrogen sublattice. Their size n, shape, and stability are governed by the aromaticity and interfaces, resulting in formation energies approximately 1/ radicaln eV/atom and preference to hexagonal clusters congruent with lattice hexagons (i.e., with armchair edge). Clusters exhibit large gaps approximately 15/ radicaln eV with size dependence typical for confined Dirac fermions.

  8. Magnetism in quantum dots on graphene-graphane nanoribbons

    NASA Astrophysics Data System (ADS)

    Chernozatonskii, L. A.; Demin, V. A.; Gusyatnikova, P. P.

    2013-07-01

    The magnetic properties of quantum dots on a graphene nanoribbon are investigated in the context of the method of the generalized gradient approximation of spin-polarized density functional theory. It is shown that the antiferromagnetic ordering of magnetic moments is most stable for ribbons with periodic alternation of graphene-graphane nanosegments. When the graphene nanoribbon is separated by the rows of C atoms with hydrogen atoms adsorbed on them in the form of a two-periodic superlattice, the ferrimagnetic ordering in the coupled unequal quantum dots turns out to be most favorable.

  9. Reactions of hydrogen halides with clusters of ammonia molecules

    SciTech Connect

    Breen, J.J.; Kilgore, K.; Wei, S.; Tzeng, W.B.; Keesee, R.G.; Castleman, A.W. Jr. )

    1989-11-02

    Reactions between an ammonia cluster beam and an effusive source of hydrogen halide molecules are shown to form mixed clusters containing as many as four hydrogen halide molecules. Multiphoton ionization of the product clusters using the third harmonic of a Q-switched Nd:YAG laser leads mainly to species of the comparison H{sup +}(NH{sub 3}){sub n}(NH){sub m}, where X = Cl or I and n is greater than m. In addition, for the case where X = I the species NH{sub 3}{center dot}HX{sup +} and H{sup +}(NH{sub 4})(HX) are positively observed. Evidently they arise due to the fragmentation of clusters containing more than one HI molecule; H{sup +}(NH{sub 3}){sub 2}HI is the smallest mixed cluster observed to be formed under single collision conditions. These results, along with information contained in the mixed cluster distributions, suggest a replacement reaction mechanism for the formation of the mixed clusters. Evidence is obtained which suggests that a solvated ion pair arises in HI-ammonia clusters containing about 10 NH{sub 3} molecules.

  10. Hydrogen sensor

    DOEpatents

    Duan, Yixiang; Jia, Quanxi; Cao, Wenqing

    2010-11-23

    A hydrogen sensor for detecting/quantitating hydrogen and hydrogen isotopes includes a sampling line and a microplasma generator that excites hydrogen from a gas sample and produces light emission from excited hydrogen. A power supply provides power to the microplasma generator, and a spectrometer generates an emission spectrum from the light emission. A programmable computer is adapted for determining whether or not the gas sample includes hydrogen, and for quantitating the amount of hydrogen and/or hydrogen isotopes are present in the gas sample.

  11. Trans/cis isomerization of [RuCl2{H2Cdbnd C(CH2PPh2)2)}(diamine)] complexes: Synthesis, spectral, crystal structure and DFT calculations and catalytic activity in the hydrogenation of α,β-unsaturated ketones

    NASA Astrophysics Data System (ADS)

    Warad, Ismail; Al-Noaimi, Mousa; Abdel-Rahman, Obadah S.; Awwadi, Firas F.; Hammouti, Belkheir; Hadda, Taibi B.

    2014-01-01

    Three complexes of the general formula trans/cis-[Ru(II)(dppme)(Nsbnd N)Cl2] {dppme is H2Cdbnd C(CH2PPh2)2 and Nsbnd N is 1,2-diaminocyclohexane (trans/cis-(1)) and 1-methyl-1,2-diaminopropane (trans-(2)} were obtained by reacting trans-[RuCl2(dppme)2] with an excess amount of corresponding diamine in CH2Cl2 as a solvent. The complexes were characterized by an elemental analysis, IR, 1H, 13C and 31P{1H} NMR, FAB-MS and UV-visible. The trans-(1) (kinetic product) readily isomerizes to the cis-(1) (thermodynamic product) and this process was followed by using 31P{1H} NMR, cyclic voltammetry and UV-vis spectroscopy. The electrochemical studies on complex (1) reveal that the Ru(III)/Ru(II) couples are sensitive to the isomer (trans/cis) formed. The cis-(1) was confirmed by X-ray structure and 31P{1H} NMR. Transfer-hydrogenation reactions for reduction of trans-4-phenyl-3-butene-2-one were conducted using complexes trans/cis-(1) and trans-(2). The electronic spectra of cis/trans-(1) in dichloromethane were calculated with the use of time-dependent DFT methods.

  12. Hydrogenation apparatus

    DOEpatents

    Friedman, Joseph [Encino, CA; Oberg, Carl L [Canoga Park, CA; Russell, Larry H [Agoura, CA

    1981-01-01

    Hydrogenation reaction apparatus comprising a housing having walls which define a reaction zone and conduits for introducing streams of hydrogen and oxygen into the reaction zone, the oxygen being introduced into a central portion of the hydrogen stream to maintain a boundary layer of hydrogen along the walls of the reaction zone. A portion of the hydrogen and all of the oxygen react to produce a heated gas stream having a temperature within the range of from 1100.degree. to 1900.degree. C., while the boundary layer of hydrogen maintains the wall temperature at a substantially lower temperature. The heated gas stream is introduced into a hydrogenation reaction zone and provides the source of heat and hydrogen for a hydrogenation reaction. There also is provided means for quenching the products of the hydrogenation reaction. The present invention is particularly suitable for the hydrogenation of low-value solid carbonaceous materials to provide high yields of more valuable liquid and gaseous products.

  13. Controlled hydrogenation of P(VDF-co-CTFE) to prepare P(VDF-co-TrFE-co-CTFE) in the presence of CuX (X = Cl, Br) complexes.

    PubMed

    Tan, Shaobo; Liu, Erqiang; Zhang, Qiuping; Zhang, Zhicheng

    2011-04-21

    An environmentally friendly and controllable P(VDF-co-CTFE) hydrogenation route involving the transition-metal complex mediated radical chain transfer reaction is successfully developed to synthesize P(VDF-co-CTFE-co-TrFE). The typical transition metal catalysts of ATRP reaction could be applied in this process.

  14. Quantum dot resonant tunneling spectroscopy

    NASA Astrophysics Data System (ADS)

    Reed, Mark A.; Randall, John N.; Luscombe, James H.; Frensley, William R.; Aggarwal, Raj J.; Matyi, Richard J.; Moore, Tom M.; Wetsel, Anna E.

    The electronic transport through 3-dimensionally confined semiconductor quantum wells (quantum dots) is investigated and analyzed. The spectra corresponds to resonant tunneling from laterally-confined emitter contact subbands through the discrete 3-dimensionally confined quantum dot states. Momentum nonconservation is observed in these structures. Results on coupled quantum dot states (molccules) will be presented.

  15. Plasmonic fluorescent quantum dots.

    PubMed

    Jin, Yongdong; Gao, Xiaohu

    2009-09-01

    Combining multiple discrete components into a single multifunctional nanoparticle could be useful in a variety of applications. Retaining the unique optical and electrical properties of each component after nanoscale integration is, however, a long-standing problem. It is particularly difficult when trying to combine fluorophores such as semiconductor quantum dots with plasmonic materials such as gold, because gold and other metals can quench the fluorescence. So far, the combination of quantum dot fluorescence with plasmonically active gold has only been demonstrated on flat surfaces. Here, we combine fluorescent and plasmonic activities in a single nanoparticle by controlling the spacing between a quantum dot core and an ultrathin gold shell with nanometre precision through layer-by-layer assembly. Our wet-chemistry approach provides a general route for the deposition of ultrathin gold layers onto virtually any discrete nanostructure or continuous surface, and should prove useful for multimodal bioimaging, interfacing with biological systems, reducing nanotoxicity, modulating electromagnetic fields and contacting nanostructures.

  16. Dot junction solar cells

    NASA Technical Reports Server (NTRS)

    Daud, T.; Crotty, G. T.

    1986-01-01

    A design of solar cells with reduced junction area on the cell surface is investigated for reduction of saturation current and increase in open-circuit voltage. Equidiameter dot junctions distributed across the surface of the cell offer an efficient alternative, with variations in dot diameter and in the spacing between dots giving the required variations in the ratio of junction area to total surface area. A simplified analysis for short-circuit current and other cell parameters, which enables cell design optimization, is presented. Experimental solar-cell performance results, as functions of different area ratios, are presented and compared with the model. It is shown that saturation current reduction is possible for achieving efficiencies as high as 18 percent in flat-plate terrestrial applications.

  17. Nanoscale and Single-Dot Patterning of Colloidal Quantum Dots.

    PubMed

    Xie, Weiqiang; Gomes, Raquel; Aubert, Tangi; Bisschop, Suzanne; Zhu, Yunpeng; Hens, Zeger; Brainis, Edouard; Van Thourhout, Dries

    2015-11-11

    Using an optimized lift-off process we develop a technique for both nanoscale and single-dot patterning of colloidal quantum dot films, demonstrating feature sizes down to ~30 nm for uniform films and a yield of 40% for single-dot positioning, which is in good agreement with a newly developed theoretical model. While first of all presenting a unique tool for studying physics of single quantum dots, the process also provides a pathway toward practical quantum dot-based optoelectronic devices.

  18. DOT Transmit Module

    NASA Technical Reports Server (NTRS)

    Quirk, Kevin J.; Gin, Jonathan W.; Sahasrabudhe, Adit; Patawaran, Ferze D.; Nguyen, Danh H.; Nguyen, Huy

    2013-01-01

    The Deep Space Optical Terminal (DOT) transmit module demonstrates the DOT downlink signaling in a flight electronics assembly that can be qualified for deep space. The assembly has the capability to generate an electronic pulse-position modulation (PPM) waveform suitable for driving a laser assembly to produce the optical downlink signal. The downlink data enters the assembly through a serializer/ deserializer (SERDES) interface, and is encoded using a serially concatenated PPM (SCPPM) forward error correction code. The encoded data is modulated using PPM with an inter-symbol guard time to aid in receiver synchronization. Monitor and control of the assembly is via a low-voltage differential signal (LVDS) interface

  19. Lifetime extension of XeCl and KrCl lasers with additives

    NASA Astrophysics Data System (ADS)

    McKee, T. J.; James, D. J.; Nip, W. S.; Weeks, R. W.; Willis, C.

    1980-06-01

    The stabilization and extension of operation of XeCl (308 nm) and KrCl (222 nm) excimer lasers by the addition of very low concentrations of hydrogen gas is described. Lifetime extension of a sealed-off XeCl laser operating at 8 W and 150 Hz is reported, with more than three million shots to half power. Spectroscopic analysis of the laser gas indicates a large reduction in a discharge-induced absorption feature below 230 nm; no absorption is observed at 308 nm.

  20. Synthesis of highly fluorescent nitrogen and phosphorus doped carbon dots for the detection of Fe(3+) ions in cancer cells.

    PubMed

    Chandra, Soumen; Laha, Dipranjan; Pramanik, Arindam; Ray Chowdhuri, Angshuman; Karmakar, Parimal; Sahu, Sumanta Kumar

    2016-02-01

    Highly fluorescent nitrogen and phosphorus-doped carbon dots with a quantum yield 59% have been successfully synthesized from citric acid and di-ammonium hydrogen phosphate by single step hydrothermal method. The synthesized carbon dots have high solubility as well as stability in aqueous medium. The as-obtained carbon dots are well monodispersed with particle sizes 1.5-4 nm. Owing to a good tunable fluorescence property and biocompatibility, the carbon dots were applied for intercellular sensing of Fe(3+) ions as well as cancer cell imaging. Copyright © 2015 John Wiley & Sons, Ltd.

  1. Nanostructure, hydrogen bonding and rheology in choline chloride deep eutectic solvents as a function of the hydrogen bond donor.

    PubMed

    Stefanovic, Ryan; Ludwig, Michael; Webber, Grant B; Atkin, Rob; Page, Alister J

    2017-01-25

    Deep eutectic solvents (DESs) are a mixture of a salt and a molecular hydrogen bond donor, which form a eutectic liquid with a depressed melting point. Quantum mechanical molecular dynamics (QM/MD) simulations have been used to probe the 1 : 2 choline chloride-urea (ChCl : U), choline chloride-ethylene glycol (ChCl : EG) and choline chloride-glycerol (ChCl : Gly) DESs. DES nanostructure and interactions between the ions is used to rationalise differences in DES eutectic point temperatures and viscosity. Simulations show that the structure of the bulk hydrogen bond donor is largely preserved for hydroxyl based hydrogen bond donors (ChCl:Gly and ChCl:EG), resulting in a smaller melting point depression. By contrast, ChCl:U exhibits a well-established hydrogen bond network between the salt and hydrogen bond donor, leading to a larger melting point depression. This extensive hydrogen bond network in ChCl:U also leads to substantially higher viscosity, compared to ChCl:EG and ChCl:Gly. Of the two hydroxyl based DESs, ChCl:Gly also exhibits a higher viscosity than ChCl:EG. This is attributed to the over-saturation of hydrogen bond donor groups in the ChCl:Gly bulk, which leads to more extensive hydrogen bond donor self-interaction and hence higher cohesive forces within the bulk liquid.

  2. Highly Efficient Perovskite-Quantum-Dot Light-Emitting Diodes by Surface Engineering.

    PubMed

    Pan, Jun; Quan, Li Na; Zhao, Yongbiao; Peng, Wei; Murali, Banavoth; Sarmah, Smritakshi P; Yuan, Mingjian; Sinatra, Lutfan; Alyami, Noktan M; Liu, Jiakai; Yassitepe, Emre; Yang, Zhenyu; Voznyy, Oleksandr; Comin, Riccardo; Hedhili, Mohamed N; Mohammed, Omar F; Lu, Zheng Hong; Kim, Dong Ha; Sargent, Edward H; Bakr, Osman M

    2016-10-01

    A two-step ligand-exchange strategy is developed, in which the long-carbon- chain ligands on all-inorganic perovskite (CsPbX3 , X = Br, Cl) quantum dots (QDs) are replaced with halide-ion-pair ligands. Green and blue light-emitting diodes made from the halide-ion-pair-capped quantum dots exhibit high external quantum efficiencies compared with the untreated QDs.

  3. Multinuclear magnetic resonance studies of the 2Feter dot 2S sup * ferredoxin from Anabaena species strain PCC 7120. 1. Sequence-specific hydrogen-1 resonance assignments and secondary structure in solution of the oxidized form

    SciTech Connect

    Oh, Byung-Ha; Markley, J.L. )

    1990-04-24

    Complete sequence-specific assignments were determined for the diamagnetic {sup 1}H resonances from Anabaena 7120 ferredoxin. A novel assignment procedure was followed whose first step was the identification of the {sup 13}C spin systems of the amino acids by a {sup 13}C({sup 13}C) double quantum correlation experiment. Then, the {sup 1}H spin systems of the amino acids were identified from the {sup 13}C spin systems by means of direct and relayed {sup 1}H({sup 13}C) single-bond correlations. The sequential resonance assignments were based mainly on conventional interresidue {sup 1}H{sup {alpha}}{sub i}-{sup 1}H{sup N}{sub i+1} NOE connectivities. Resonances from 18 residues were not resolved in two-dimensional {sup 1}H NMR spectra. When these residues were mapped onto the X-ray crystal structure of the homologous ferredoxin from Spirulina platensis, it was found that they correspond to amino acids close to the paramagnetic 2Fe{center dot}2S cluster. Cross peaks in two-dimensional homonuclear {sup 1}H NMR spectra were not observed for any protons closer than about 7.8 {angstrom} to both iron atoms. Secondary structural features identified in solution include two antiparallel {beta}-sheets, one parallel {beta}-sheet, and one {alpha}-helix.

  4. A Theoretical Model of Pyramidal InAs/inP Quantum Dots

    NASA Astrophysics Data System (ADS)

    Alford, Brian

    2002-03-01

    A quantum dot is an atomic-like system consisting of a semiconductor nanoparticle surrounded by an insulator. When an electron in the valence band of the semiconductor becomes excited, the electron-hole pair that is created (called an exiton) acts much like a hydrogen atom. Investigations have demonstrated the potential application of quantum dots for optical switching and optical memory. A model of a truncated pyramidal InAs quantum dot in an InP matrix will be presented and described. The model uses a single band envelope theory that accurately describes the truncated pyramidal shape of the dot. The matrix representation of the Hamiltonian is calculated in a basis consisting of kinetic energy eigenfunctions that vanish on the surface of a cube containing the dot. The eigenvalues of this matrix are the energy levels. These results will then be compared with photoluminescence measurements of energy levels conducted at the Microelectronics-Photonics Center at the University of Arkansas - Fayetteville

  5. The interactions of glutathione-capped CdTe quantum dots with trypsin.

    PubMed

    Yang, Bingjun; Liu, Rutao; Hao, Xiaopeng; Wu, Yongzhong; Du, Jie

    2012-06-01

    Due to their unique fluorescent properties, quantum dots present a great potential for biolabelling applications; however, the toxic interactions of quantum dots with biopolymers are little known. The toxic interactions of glutathione-capped CdTe quantum dots with trypsin were studied in this paper using synchronous fluorescence spectroscopy, fluorescence emission spectra, and UV-vis absorption spectra. The interaction between CdTe quantum dots and trypsin resulted in structure changes of trypsin and inhibited trypsin's activity. Fluorescence emission spectra revealed that the quenching mechanism of trypsin by CdTe quantum dots was a static quenching process. The binding constant and the number of binding sites at 288 and 298 K were calculated to be 1.98 × 10(6) L mol(-1) and 1.37, and 6.43 × 10(4) L mol(-1) and 1.09, respectively. Hydrogen bonds and van der Waals' forces played major roles in this process.

  6. Nitrite sensing based on the carbon dots-enhanced chemiluminescence from peroxynitrous acid and carbonate.

    PubMed

    Lin, Zhen; Dou, Xiangnan; Li, Haifang; Ma, Yuan; Lin, Jin-Ming

    2015-01-01

    In this work, chemiluminescence (CL) from peroxynitrous acid (ONOOH)-carbonate system greatly amplified by carbon dots was observed. The CL mechanism of the ONOOH-carbonate-carbon dots system has been investigated and the results reveal that the carbon dots could serve as the energy acceptor, which gives us new insight into the optical properties of the new emerging carbon nanomaterial. There is a good linear relationship between the CL signal and the concentration of the nitrite using for ONOOH formation, which provides us a nitrite sensing method with sensitivity as high as 5.0×10(-9) M (S/N=3). The method has been successfully applied to the determination of nitrite in tap water with the recovery of 98%. The standard deviations are within 2.5%. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. PREFACE: Quantum Dot 2010

    NASA Astrophysics Data System (ADS)

    Taylor, Robert A.

    2010-09-01

    These conference proceedings contain the written papers of the contributions presented at Quantum Dot 2010 (QD2010). The conference was held in Nottingham, UK, on 26-30 April 2010. The conference addressed topics in research on: 1. Epitaxial quantum dots (including self-assembled and interface structures, dots defined by electrostatic gates etc): optical properties and electron transport quantum coherence effects spin phenomena optics of dots in cavities interaction with surface plasmons in metal/semiconductor structures opto-electronics applications 2. Novel QD structures: fabrication and physics of graphene dots, dots in nano-wires etc 3. Colloidal quantum dots: growth (shape control and hybrid nanocrystals such as metal/semiconductor, magnetic/semiconductor) assembly and surface functionalisation optical properties and spin dynamics electrical and magnetic properties applications (light emitting devices and solar cells, biological and medical applications, data storage, assemblers) The Editors Acknowledgements Conference Organising Committee: Maurice Skolnick (Chair) Alexander Tartakovskii (Programme Chair) Pavlos Lagoudakis (Programme Chair) Max Migliorato (Conference Secretary) Paola Borri (Publicity) Robert Taylor (Proceedings) Manus Hayne (Treasurer) Ray Murray (Sponsorship) Mohamed Henini (Local Organiser) International Advisory Committee: Yasuhiko Arakawa (Tokyo University, Japan) Manfred Bayer (Dortmund University, Germany) Sergey Gaponenko (Stepanov Institute of Physics, Minsk, Belarus) Pawel Hawrylak (NRC, Ottawa, Canada) Fritz Henneberger (Institute for Physics, Berlin, Germany) Atac Imamoglu (ETH, Zurich, Switzerland) Paul Koenraad (TU Eindhoven, Nethehrlands) Guglielmo Lanzani (Politecnico di Milano, Italy) Jungil Lee (Korea Institute of Science and Technology, Korea) Henri Mariette (CNRS-CEA, Grenoble, France) Lu Jeu Sham (San Diego, USA) Andrew Shields (Toshiba Research Europe, Cambridge, UK) Yoshihisa Yamamoto (Stanford University, USA) Artur

  8. Colloidal Double Quantum Dots

    PubMed Central

    2016-01-01

    Conspectus Pairs of coupled quantum dots with controlled coupling between the two potential wells serve as an extremely rich system, exhibiting a plethora of optical phenomena that do not exist in each of the isolated constituent dots. Over the past decade, coupled quantum systems have been under extensive study in the context of epitaxially grown quantum dots (QDs), but only a handful of examples have been reported with colloidal QDs. This is mostly due to the difficulties in controllably growing nanoparticles that encapsulate within them two dots separated by an energetic barrier via colloidal synthesis methods. Recent advances in colloidal synthesis methods have enabled the first clear demonstrations of colloidal double quantum dots and allowed for the first exploratory studies into their optical properties. Nevertheless, colloidal double QDs can offer an extended level of structural manipulation that allows not only for a broader range of materials to be used as compared with epitaxially grown counterparts but also for more complex control over the coupling mechanisms and coupling strength between two spatially separated quantum dots. The photophysics of these nanostructures is governed by the balance between two coupling mechanisms. The first is via dipole–dipole interactions between the two constituent components, leading to energy transfer between them. The second is associated with overlap of excited carrier wave functions, leading to charge transfer and multicarrier interactions between the two components. The magnitude of the coupling between the two subcomponents is determined by the detailed potential landscape within the nanocrystals (NCs). One of the hallmarks of double QDs is the observation of dual-color emission from a single nanoparticle, which allows for detailed spectroscopy of their properties down to the single particle level. Furthermore, rational design of the two coupled subsystems enables one to tune the emission statistics from single

  9. Colloidal Double Quantum Dots.

    PubMed

    Teitelboim, Ayelet; Meir, Noga; Kazes, Miri; Oron, Dan

    2016-05-17

    Pairs of coupled quantum dots with controlled coupling between the two potential wells serve as an extremely rich system, exhibiting a plethora of optical phenomena that do not exist in each of the isolated constituent dots. Over the past decade, coupled quantum systems have been under extensive study in the context of epitaxially grown quantum dots (QDs), but only a handful of examples have been reported with colloidal QDs. This is mostly due to the difficulties in controllably growing nanoparticles that encapsulate within them two dots separated by an energetic barrier via colloidal synthesis methods. Recent advances in colloidal synthesis methods have enabled the first clear demonstrations of colloidal double quantum dots and allowed for the first exploratory studies into their optical properties. Nevertheless, colloidal double QDs can offer an extended level of structural manipulation that allows not only for a broader range of materials to be used as compared with epitaxially grown counterparts but also for more complex control over the coupling mechanisms and coupling strength between two spatially separated quantum dots. The photophysics of these nanostructures is governed by the balance between two coupling mechanisms. The first is via dipole-dipole interactions between the two constituent components, leading to energy transfer between them. The second is associated with overlap of excited carrier wave functions, leading to charge transfer and multicarrier interactions between the two components. The magnitude of the coupling between the two subcomponents is determined by the detailed potential landscape within the nanocrystals (NCs). One of the hallmarks of double QDs is the observation of dual-color emission from a single nanoparticle, which allows for detailed spectroscopy of their properties down to the single particle level. Furthermore, rational design of the two coupled subsystems enables one to tune the emission statistics from single photon

  10. The development of a fullerene based hydrogen storage system

    SciTech Connect

    Brosha, E.L.; Davey, J.R.; Garzon, F.H.; Gottesfeld, S.

    1998-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The project objective was to evaluate hydrogen uptake by fullerene substrates and to probe the potential of the hydrogen/fullerene system for hydrogen fuel storage. As part of this project, the authors have completed and tested a fully automated, computer controlled system for measuring hydrogen uptake that is capable of handling both a vacuum of 1 x 10{sup -6} torr and pressures greater than 200 bars. The authors have first established conditions for significant uptake of hydrogen by fullerenes. Subsequently, hydrogenation and dehydrogenation of pure and catalyst-doped C60 was further studied to probe suitability for hydrogen storage applications. C60 {center_dot} H18.7 was prepared at 100 bar H2 and 400 C, corresponding to hydrogen uptake of 2.6 wt%. Dehydrogenation of C60 {center_dot} H18.7 was studied using thermogravimetric and powder x-ray diffraction analysis. The C60 {center_dot} H18.7 molecule was found to be stable up to 430 C in Ar, at which point the release of hydrogen took place simultaneously with the collapse of the fullerene structure. X-ray diffraction analysis performed on C60 {center_dot} H18.7 samples dehydrogenated at 454 C, 475 C, and 600 C showed an increasing volume fraction of amorphous material due to randomly oriented, single-layer graphine sheets. Evolved gas analysis using gas chromatography and mass spectroscopy confirmed the presence of both H{sub 2} and methane upon dehydrogenation, indicating decomposition of the fullerene. The remaining carbon could not be re-hydrogenated. These results provide the first complete evidence for the irreversible nature of fullerene hydrogenation and for limitations imposed on the hydrogenation/dehydrogenation cycle by the limited thermal stability of the molecular crystal of fullerene.

  11. GaN quantum dots as optical transducers for chemical sensors

    SciTech Connect

    Weidemann, O.; Jegert, G.; Stutzmann, M.; Kandaswamy, P. K.; Monroy, E.

    2009-03-16

    GaN/AlN quantum dots were investigated as optical transducers for field effect chemical sensors. The structures were synthesized by molecular-beam epitaxy and covered by a semitransparent catalytic Pt top contact. Due to the thin (3 nm) AlN barriers, the variation of the quantum dot photoluminescence with an external electric field along the [0001] axis is dominated by the tunneling current rather than by the quantum confined Stark effect. An increasing field results in a blueshift of the luminescence and a decreasing intensity. This effect is used to measure the optical response of quantum dot superlattices upon exposure to molecular hydrogen.

  12. Exciton binding energy in GaAsBiN spherical quantum dot heterostructures

    NASA Astrophysics Data System (ADS)

    Das, Subhasis; Dhar, S.

    2017-03-01

    The ground state exciton binding energies (EBE) of heavy hole excitons in GaAs1-x-yBixNy - GaAs spherical quantum dots (QD) are calculated using a variational approach under 1s hydrogenic wavefunctions within the framework of effective mass approximation. Both the nitrogen and the bismuth content in the material are found to affect the binding energy, in particular for larger nitrogen content and lower dot radii. Calculations also show that the ground state exciton binding energies of heavy holes increase more at smaller dot sizes as compared to that for the light hole excitons.

  13. Fast characterisation of InAs quantum dot structures using AFM

    NASA Astrophysics Data System (ADS)

    Basnar, B.; Hirner, H.; Gornik, E.; Strasser, G.

    2004-03-01

    We present a fast and straightforward method for the cross-sectional analysis of self-assembled InAs quantum dots using atomic force microscopy. The new approach needs a minimum amount of time and sample preparation (cleaving and, if necessary, etching with a solution of hydroxylamine/hydrogen-peroxide) to obtain the cross-sectional dot density and information on the degree of stacking, which are important parameters in the production of self-assembled quantum dot devices, and provides the means for fast cross-sectional wafer mapping.

  14. Pressure-Induced Phase Transition in Guanidinium Perchlorate: A Supramolecular Structure Directed by Hydrogen Bonding and Electrostatic Interactions

    SciTech Connect

    Li, Shourui; Li, Qian; Wang, Kai; Tan, Xiao; Zhou, Mi; Li, Bing; Liu, Bingbing; Zou, Guangtian; Zou, Bo

    2012-01-20

    In situ Raman spectroscopy and synchrotron X-ray diffraction (XRD) experiments have been performed to investigate the response of guanidinium perchlorate (C(NH{sub 2}){sub 3}{sup +} {center_dot} ClO{sub 4}{sup -}, GP) to high pressures of {approx}11 GPa. GP exhibits a typical supramolecular structure of two-dimensional (2D) hydrogen-bonded ionic networks at ambient conditions. A subtle phase transition, accompanied by the symmetry transformation from R3m to C2, has been confirmed by obvious changes in both Raman and XRD patterns at 4.5 GPa. The phase transition is attributed to the competition between hydrogen bonds and close packing of the supramolecular structure at high pressure. Hydrogen bonds have been demonstrated to evolve into a distorted state through the phase transition, accompanied by the reduction in separation of oppositely charged ions in adjacent sheet motifs. A detailed mechanism of the phase transition, as well as the cooperativity between hydrogen bonding and electrostatic interactions, is discussed by virtue of the local nature of the structure.

  15. Calculation of exchange interaction for modified Gaussian coupled quantum dots

    NASA Astrophysics Data System (ADS)

    Khordad, R.

    2017-08-01

    A system of two laterally coupled quantum dots with modified Gaussian potential has been considered. Each quantum dot has an electron under electric and magnetic field. The quantum dots have been considered as hydrogen-like atoms. The physical picture has translated into the Heisenberg spin Hamiltonian. The Schrödinger equation using finite element method has been numerically solved. The exchange energy factor has been calculated as a functions of electric field, magnetic field, and the separation distance between the centers of the dots ( d). According to the results, it is found that there is the transition from anti-ferromagnetic to ferromagnetic for constant electric field. Also, the transition occurs from ferromagnetic to anti-ferromagnetic for constant magnetic field (B>1 T). With decreasing the distance between the centers of the dots and increasing magnetic field, the transition occurs from anti-ferromagnetic to ferromagnetic. It is found that a switching of exchange energy factor is presented without canceling the interactions of the electric and magnetic fields on the system.

  16. Calculation of exchange interaction for modified Gaussian coupled quantum dots

    NASA Astrophysics Data System (ADS)

    Khordad, R.

    2017-03-01

    A system of two laterally coupled quantum dots with modified Gaussian potential has been considered. Each quantum dot has an electron under electric and magnetic field. The quantum dots have been considered as hydrogen-like atoms. The physical picture has translated into the Heisenberg spin Hamiltonian. The Schrödinger equation using finite element method has been numerically solved. The exchange energy factor has been calculated as a functions of electric field, magnetic field, and the separation distance between the centers of the dots (d). According to the results, it is found that there is the transition from anti-ferromagnetic to ferromagnetic for constant electric field. Also, the transition occurs from ferromagnetic to anti-ferromagnetic for constant magnetic field (B>1 T). With decreasing the distance between the centers of the dots and increasing magnetic field, the transition occurs from anti-ferromagnetic to ferromagnetic. It is found that a switching of exchange energy factor is presented without canceling the interactions of the electric and magnetic fields on the system.

  17. Anchored [RuCl2(p-cymene)]2 in hybrid zirconium phosphate-phosphonate coated and pillared with double-stranded hydrophobic linear polystyrene as heterogeneous catalyst suitable for aqueous asymmetric transfer hydrogenation.

    PubMed

    Wang, Rui; Wan, Jingwei; Ma, Xuebing; Xu, Xiao; Liu, Liu

    2013-05-14

    A novel type of phosphonate-containing polystyrene copolymers 1a-e bearing an N'-alkylated TsDPEN chiral ligand and double-stranded polystyrene chains were prepared for the first time using simple radical copolymerization of 1-phosphonate styrene with (R,R)-N'-4'-vinylbenzyl-N-4-vinylbenzenesulfonyl-1,2-diphenylethylene-1,2-diamine. Through the coprecipitation of their supported Ru polystyrene copolymers 2a-e and NaH2PO4 with ZrOCl2, pillared hybrid zirconium phosphate-phosphonate-anchored Ru catalysts 3a-e and 4d1-d5 were obtained as heterogeneous catalysts suitable for aqueous asymmetric transfer hydrogenation. In the aqueous asymmetric transfer hydrogenation of aromatic ketones, the anchored Ru catalysts showed good catalytic activities, chemoselectivities (~100%), and enantioselectivities (73.6% ee to 95.6% ee). The Ru catalysts retained their catalytic properties even at the fifth recycle time (92.2% conv., 92.1% ee). However, corresponding supported Ru catalyst 3d' resulted in disappointing reusability because of the loss of ruthenium in every recycle process. The conversions of aromatic ketones were closely related to the o-, m- or p-positions of the substituents on the aromatic ring caused by shape-selective matching.

  18. Hydrogen generator

    SciTech Connect

    Adlhart, O. J.

    1985-04-23

    This disclosure relates to a replaceable cartridge hydrogen generator of the type which relies at least partially on the process of anodic corrosion to produce hydrogen. A drum contains a plurality of the cartridges.

  19. Lighting Up Enzymes for Solar Hydrogen Production (Fact Sheet)

    SciTech Connect

    Not Available

    2011-02-01

    Scientists at the National Renewable Energy Laboratory (NREL) have combined quantum dots, which are spherical nanoparticles that possess unique size-tunable photophysical properties, with the high substrate selectivity and fast turnover of hydrogenase enzymes to achieve light-driven hydrogen (H2) production. They found that quantum dots of cadmium telluride coated in carboxylic acids easily formed highly stable complexes with the hydrogenase and that these hybrid assemblies functioned to catalyze H2 production using the energy of sunlight.

  20. Hydrogen Generator

    NASA Technical Reports Server (NTRS)

    1983-01-01

    A unit for producing hydrogen on site is used by a New Jersey Electric Company. The hydrogen is used as a coolant for the station's large generator; on-site production eliminates the need for weekly hydrogen deliveries. High purity hydrogen is generated by water electrolysis. The electrolyte is solid plastic and the control system is electronic. The technology was originally developed for the Gemini spacecraft.

  1. Hydrogen Production

    SciTech Connect

    2014-09-01

    This 2-page fact sheet provides a brief introduction to hydrogen production technologies. Intended for a non-technical audience, it explains how different resources and processes can be used to produce hydrogen. It includes an overview of research goals as well as “quick facts” about hydrogen energy resources and production technologies.

  2. Hydrogen Storage

    SciTech Connect

    2008-11-01

    This 2-page fact sheet provides a brief introduction to hydrogen storage technologies. Intended for a non-technical audience, it explains the different ways in which hydrogen can be stored, as well as the technical challenges and research goals for storing hydrogen on board a vehicle.

  3. Quantum dynamics of the Walden inversion reaction Cl - +CH3Cl --> ClCH3+Cl -

    NASA Astrophysics Data System (ADS)

    Clary, David C.; Palma, Juliana

    1997-01-01

    Quantum scattering calculations on the SN2 reaction Cl-+CH3Cl→ClCH3+Cl- are reported. The rotating bond approximation (RBA) has been adapted so that three degrees of freedom including the C-Cl stretching vibration and the CH3 umbrella mode are treated explicitly. The calculations have been done with minor modifications of a potential due to Vande Linde and Hase. It is found that initial excitation of the C-Cl vibration has a large effect on the reaction probabilities, while excitation of the CH3 umbrella vibration is less significant. The reaction is dominated by scattering resonances with lifetimes ranging from 0.1 to 10 ps. It is found that the length of the C-Cl bond at the transition state of the reaction has a particularly pronounced effect on the reaction probabilities. The magnitude of the quantum reaction probabilities compares quite well with those calculated using the quasiclassical trajectory method.

  4. Quantum Dot Sensitized Photoelectrodes

    PubMed Central

    Macdonald, Thomas J.; Nann, Thomas

    2011-01-01

    Quantum Dots (QDs) are promising alternatives to organic dyes as sensitisers for photocatalytic electrodes. This review article provides an overview of the current state of the art in this area. More specifically, different types of QDs with a special focus on heavy-metal free QDs and the methods for preparation and adsorption onto metal oxide electrodes (especially titania and zinc oxide) are discussed. Eventually, the key areas of necessary improvements are identified and assessed.

  5. Quantum DOT IR Photodetectors

    DTIC Science & Technology

    2012-07-01

    4.1.3  ROIC Control and Readout Electronics ................................................................ 16  4.2  Device measurements...the voltage of the detector modifies its spectral response. In this effort a DWELL Quantum Dot device was fabricated and tested. The results...agility. Because of delays in the fabrication of the ROIC device by MOSIS, those results will not available for the final report until approximately

  6. Plasmonic fluorescent quantum dots

    PubMed Central

    Jin, Yongdong

    2009-01-01

    Combining multiple discrete components into a single multifunctional nanoparticle could be useful in a variety of applications. Retaining the unique optical and electrical properties of each component after nanoscale integration is, however, a long-standing problem1,2. It is particularly difficult when trying to combine fluorophores such as semiconductor quantum dots with plasmonic materials such as gold, because gold and other metals can quench the fluorescence3,4. So far, the combination of quantum dot fluorescence with plasmonically active gold has only been demonstrated on flat surfaces5. Here, we combine fluorescent and plasmonic activities in a single nanoparticle by controlling the spacing between a quantum dot core and an ultrathin gold shell with nanometre precision through layer-by-layer assembly. Our wet-chemistry approach provides a general route for the deposition of ultrathin gold layers onto virtually any discrete nanostructure or continuous surface, and should prove useful for multimodal bioimaging6, interfacing with biological systems7, reducing nanotoxicity8, modulating electromagnetic fields5 and contacting nanostructures9,10. PMID:19734929

  7. One-dimensional spin-crossover Iron(II) complexes bridged by intermolecular imidazole-pyridine NH...N hydrogen bonds, [Fe(HL(Me))(3)]X(2) (HL(Me) = (2-methylimidazol-4-yl-methylideneamino-2-ethylpyridine; X = PF(6), ClO(4), BF(4)).

    PubMed

    Nishi, Koshiro; Arata, Shinobu; Matsumoto, Naohide; Iijima, Seiichiro; Sunatsuki, Yukinari; Ishida, Hiroyuki; Kojima, Masaaki

    2010-02-15

    2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine (abbreviated as HL(Me)) is the 1:1 condensation product of 2-methyl-4-formylimidazole and 2-aminoethylpyridine and functions as a bidentate ligand to the iron(II) ion to produce the 3:1 complexes together with anions, [Fe(HL(Me))(3)]X(2) (X = PF(6) (1), ClO(4) (2), BF(4) (3)). The magnetic susceptibilities, differential scanning calorimetric measurements, and Mossbauer spectral measurements demonstrated that complexes 1, 2, and 3 showed a steep one-step spin crossover (SCO) between the high-spin (HS, S = 2) and low-spin (LS, S = 0) states with small thermal hysteresis. Three complexes have an isomorphous structure and are crystallized in the same monoclinic space group, C2/c, both in the HS and LS states. The iron(II) ion has the octahedral coordination geometry of a facial isomer with N(6) donor atoms of three bidentate ligands, in which an imidazole and an imine nitrogen atom per ligand participate in the formation of the coordination bond, but the pyridine nitrogen is free from coordination. The complex cation fac-[Fe(HL(Me))(3)](2+) is a chiral species with a Delta or Lambda isomer, and the adjacent Delta and Lambda isomers are linked alternately by an intermolecular imidazole-pyridine NH...N hydrogen bond to produce an achiral 1D chain. The two remaining imidazole moieties per complex are hydrogen-bonded to the anions that occupy the space among the chains. The SCO profile becomes steeper with the decrease of the anion size (73.0 A(3) for PF(6)(-), 54.4 A(3) for ClO(4)(-), and 53.4 A(3) for BF(4)(-)). The SCO transition temperature T(1/2) of the PF(6) (1), ClO(4) (2), and BF(4) (3) salts estimated from the magnetic susceptibility measurements are (T( downward arrow) = 151.8 K, T( upward arrow) = 155.3 K), (T( downward arrow) = 184.5 K, T( upward arrow) = 186.0 K), and (T( downward arrow) = 146.4 K, T( upward arrow) = 148.2 K), respectively, indicating that the T(1/2) value is not in accord with the anion

  8. Extracting inter-dot tunnel couplings between few donor quantum dots in silicon

    NASA Astrophysics Data System (ADS)

    Gorman, S. K.; Broome, M. A.; Keizer, J. G.; Watson, T. F.; Hile, S. J.; Baker, W. J.; Simmons, M. Y.

    2016-05-01

    The long term scaling prospects for solid-state quantum computing architectures relies heavily on the ability to simply and reliably measure and control the coherent electron interaction strength, known as the tunnel coupling, t c. Here, we describe a method to extract the t c between two quantum dots (QDs) utilising their different tunnel rates to a reservoir. We demonstrate the technique on a few donor triple QD tunnel coupled to a nearby single-electron transistor (SET) in silicon. The device was patterned using scanning tunneling microscopy-hydrogen lithography allowing for a direct measurement of the tunnel coupling for a given inter-dot distance. We extract {t}{{c}}=5.5+/- 1.8 {{GHz}} and {t}{{c}}=2.2+/- 1.3 {{GHz}} between each of the nearest-neighbour QDs which are separated by 14.5 nm and 14.0 nm, respectively. The technique allows for an accurate measurement of t c for nanoscale devices even when it is smaller than the electron temperature and is an ideal characterisation tool for multi-dot systems with a charge sensor.

  9. Direct Conversion of Hydride- to Siloxane-Terminated Silicon Quantum Dots

    SciTech Connect

    Anderson, Ryan T.; Zang, Xiaoning; Fernando, Roshan; Dzara, Michael J.; Ngo, Chilan; Sharps, Meredith; Pinals, Rebecca; Pylypenko, Svitlana; Lusk, Mark T.; Sellinger, Alan

    2016-11-17

    Peripheral surface functionalization of hydride-terminated silicon quantum dots (SiQD) is necessary in order to minimize their oxidation/aggregation and allow for solution processability. Historically thermal hydrosilylation addition of alkenes and alkynes across the Si-H surface to form Si-C bonds has been the primary method to achieve this. Here we demonstrate a mild alternative approach to functionalize hydride-terminated SiQDs using bulky silanols in the presence of free-radical initiators to form stable siloxane (~Si-O-SiR3) surfaces with hydrogen gas as a byproduct. This offers an alternative to existing methods of forming siloxane surfaces that require corrosive Si-Cl based chemistry with HCl byproducts. A 52 nm blue shift in the photoluminescent spectra of siloxane versus alkyl-functionalized SiQDs is observed that we explain using computational theory. Model compound synthesis of silane and silsesquioxane analogues is used to optimize surface chemistry and elucidate reaction mechanisms. Thorough characterization on the extent of siloxane surface coverage is provided using FTIR and XPS. TEM is used to demonstrate SiQD size and integrity after surface chemistry and product isolation.

  10. Direct conversion of hydride- to siloxane-terminated silicon quantum dots

    DOE PAGES

    Anderson, Ryan T.; Zang, Xiaoning; Fernando, Roshan; ...

    2016-10-20

    Here, peripheral surface functionalization of hydride-terminated silicon quantum dots (SiQD) is necessary in order to minimize their oxidation/aggregation and allow for solution processability. Historically thermal hydrosilylation addition of alkenes and alkynes across the Si-H surface to form Si-C bonds has been the primary method to achieve this. Here we demonstrate a mild alternative approach to functionalize hydride-terminated SiQDs using bulky silanols in the presence of free-radical initiators to form stable siloxane (~Si-O-SiR3) surfaces with hydrogen gas as a byproduct. This offers an alternative to existing methods of forming siloxane surfaces that require corrosive Si-Cl based chemistry with HCl byproducts. Amore » 52 nm blue shift in the photoluminescent spectra of siloxane versus alkyl-functionalized SiQDs is observed that we explain using computational theory. Model compound synthesis of silane and silsesquioxane analogues is used to optimize surface chemistry and elucidate reaction mechanisms. Thorough characterization on the extent of siloxane surface coverage is provided using FTIR and XPS. As a result, TEM is used to demonstrate SiQD size and integrity after surface chemistry and product isolation.« less

  11. Hydrogenation apparatus

    DOEpatents

    Friedman, J.; Oberg, C. L.; Russell, L. H.

    1981-06-23

    Hydrogenation reaction apparatus is described comprising a housing having walls which define a reaction zone and conduits for introducing streams of hydrogen and oxygen into the reaction zone, the oxygen being introduced into a central portion of the hydrogen stream to maintain a boundary layer of hydrogen along the walls of the reaction zone. A portion of the hydrogen and all of the oxygen react to produce a heated gas stream having a temperature within the range of from 1,100 to 1,900 C, while the boundary layer of hydrogen maintains the wall temperature at a substantially lower temperature. The heated gas stream is introduced into a hydrogenation reaction zone and provides the source of heat and hydrogen for a hydrogenation reaction. There also is provided means for quenching the products of the hydrogenation reaction. The present invention is particularly suitable for the hydrogenation of low-value solid carbonaceous materials to provide high yields of more valuable liquid and gaseous products. 2 figs.

  12. Surfactant-induced hydrogen production in cyanobacteria

    SciTech Connect

    Famiglietti, M.; Luisi, P.L. ); Hochkoeppler, A. . Dept. di Biologia)

    1993-10-01

    Addition of Tween 85 to aqueous suspensions of Anabaena variabilis induced photosynthetic evolution of hydrogen over a time span of several weeks: as much as 148 nmol H[sub 2]/h [center dot] mg dry weight was produced in the first week by a suspension containing 4.2 mg dry weight of cells and 77 mM Tween 85. The chemical structure of Tween 85 was a necessary prerequisite for inducing hydrogen production, as compounds such as Tween 20, 60, and 80 had a quite different effect. There was a coupling between photosynthetic oxygen evolution and hydrogen evolution: Hydrogen evolution started to be effective only when oxygen evolution subdued. The presence of heterocysts in A. variabilis was also required for the Tween-induced hydrogen production. Based on these observations, possible mechanisms for the photosynthetic effect of Tween 85 are advanced and discussed.

  13. Effects of Solution Chemistry on Quantum Dot Transport and Retention in Porous Media

    NASA Astrophysics Data System (ADS)

    Englehart, J.; Wang, Y.; Zhu, H.; Colvin, V. L.; Pennell, K. D.

    2010-12-01

    Engineered nanomaterials with tunable surface chemistries, such as quantum dots, are becoming increasingly prevalent in commercial and medical applications. This increase in usage corresponds to an elevated risk of environmental exposures, and limited data are available on the fate and transport of quantum dots in the environment. The objective of this study was to quantify quantum dot transport and retention behavior under a variety of solution chemistries and in the presence of a non-aqueous phase liquid (NAPL) phase. The quantum dots were prepared with a CdSe/CdZnS core/shell that was coated with an amphiphilic copolymer. The primary quantum dot coating used in this study was octylamine modified polyacrylic acid, which yields a negative surface charge (zeta potential) ranging from -30 to -40 mV in water. The mean diameter of the quantum dots in deionized water ranged from 20-30 nm based on dynamic light scattering (DLS) analysis. Higher salt concentrations, ranging from 3 to 1000 mM NaCl, resulted in increased diameters of the quantum dots (28 to 190 nm, respectively). Transport and retention behavior of the quantum dots was evaluated using borosilicate glass columns (2.5 cm i.d. x 10 cm length) packed with 40-50 mesh (d50 = 355 µm) Ottawa sand that had been completely saturated with water. A pulse (ca. 60mL) of quantum dot suspension was introduced to the column at a flow rate of 1mL/min (pore-water velocity of 8m/d), followed by three pore volumes of particle-free solution. To evaluate effects of the presence of a NAPL phase, a uniform distribution of residual NAPL (Soltrol 220) was established prior to the quantum dot pulse injection. Concentrations of quantum dots in the column effluent and extracted from solid samples, quantified using an Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES), were used to construct an effluent breakthrough curve and retention profile for each experiment. The presence of a residual NAPL phase had negligible

  14. ADVANCED HYDROGEN TRANSPORT MEMBRANES FOR VISION 21 FOSSIL FUEL PLANTS

    SciTech Connect

    Carl R. Evenson; Anthony F. Sammells; Richard Mackay; Richard Treglio; Sara L. Rolfe; Richard Blair; U. Balachandran; Richard N. Kleiner; James E. Stephan; Frank E. Anderson; Chandra Ratnasamy; Jon P. Wagner; Clive Brereton; Warren Wolfs

    2004-07-26

    During this quarter, work was focused on testing layered composite membranes under varying feed stream flow rates at high pressure. By optimizing conditions, H{sub 2} permeation rates as high as 423 mL {center_dot} min{sup -1} {center_dot} cm{sup -2} at 440 C were measured. Membrane stability was investigated by comparison to composite alloy membranes. Permeation of alloyed membranes showed a strong dependence on the alloying element. Impedance analysis was used to investigate bulk and grain boundary conductivity in cermets. Thin film cermet deposition procedures were developed, hydrogen dissociation catalysts were evaluated, and hydrogen separation unit scale-up issues were addressed.

  15. Hydrogen Embrittlement

    NASA Technical Reports Server (NTRS)

    Woods, Stephen; Lee, Jonathan A.

    2016-01-01

    Hydrogen embrittlement (HE) is a process resulting in a decrease in the fracture toughness or ductility of a metal due to the presence of atomic hydrogen. In addition to pure hydrogen gas as a direct source for the absorption of atomic hydrogen, the damaging effect can manifest itself from other hydrogen-containing gas species such as hydrogen sulfide (H2S), hydrogen chloride (HCl), and hydrogen bromide (HBr) environments. It has been known that H2S environment may result in a much more severe condition of embrittlement than pure hydrogen gas (H2) for certain types of alloys at similar conditions of stress and gas pressure. The reduction of fracture loads can occur at levels well below the yield strength of the material. Hydrogen embrittlement is usually manifest in terms of singular sharp cracks, in contrast to the extensive branching observed for stress corrosion cracking. The initial crack openings and the local deformation associated with crack propagation may be so small that they are difficult to detect except in special nondestructive examinations. Cracks due to HE can grow rapidly with little macroscopic evidence of mechanical deformation in materials that are normally quite ductile. This Technical Memorandum presents a comprehensive review of experimental data for the effects of gaseous Hydrogen Environment Embrittlement (HEE) for several types of metallic materials. Common material screening methods are used to rate the hydrogen degradation of mechanical properties that occur while the material is under an applied stress and exposed to gaseous hydrogen as compared to air or helium, under slow strain rates (SSR) testing. Due to the simplicity and accelerated nature of these tests, the results expressed in terms of HEE index are not intended to necessarily represent true hydrogen service environment for long-term exposure, but rather to provide a practical approach for material screening, which is a useful concept to qualitatively evaluate the severity of

  16. Hydrogen Generator

    NASA Technical Reports Server (NTRS)

    1978-01-01

    Another spinoff from spacecraft fuel cell technology is the portable hydrogen generator shown. Developed by General Electric Company, it is an aid to safer operation of systems that use hydrogen-for example, gas chromatographs, used in laboratory analysis of gases. or flame ionization detectors used as $ollution monitors. The generator eliminates the need for high-pressure hydrogen storage bottles, which can be a safety hazard, in laboratories, hospitals and industrial plants. The unit supplies high-purity hydrogen by means of an electrochemical process which separates the hydrogen and oxygen in distilled water. The oxygen is vented away and the hydrogen gas is stored within the unit for use as needed. GE's Aircraft Equipment Division is producing about 1,000 of the generators annually.

  17. Scanning Quantum Dot Microscopy

    NASA Astrophysics Data System (ADS)

    Wagner, Christian; Green, Matthew F. B.; Leinen, Philipp; Deilmann, Thorsten; Krüger, Peter; Rohlfing, Michael; Temirov, Ruslan; Tautz, F. Stefan

    2015-07-01

    We introduce a scanning probe technique that enables three-dimensional imaging of local electrostatic potential fields with subnanometer resolution. Registering single electron charging events of a molecular quantum dot attached to the tip of an atomic force microscope operated at 5 K, equipped with a qPlus tuning fork, we image the quadrupole field of a single molecule. To demonstrate quantitative measurements, we investigate the dipole field of a single metal adatom adsorbed on a metal surface. We show that because of its high sensitivity the technique can probe electrostatic potentials at large distances from their sources, which should allow for the imaging of samples with increased surface roughness.

  18. Hydrogen energy progress 5678

    SciTech Connect

    Veziroglu, T.N. )

    1990-01-01

    This book covers the proceedings of the 8th World Hydrogen Energy Conference, and includes: international hydrogen energy programs; hydrogen production; storage of hydrogen; hydrogen transmission and distribution; combustion systems/hydrogen engines; fuel cells; and synfuel production.

  19. Isopiestic Determination of the Osmotic and Activity Coefficients of NaCl + SrCl2 + H2O at 298.15 K, and Representation with an Extended Ion-Interaction Model

    SciTech Connect

    Clegg, S L; Rard, J A; Miller, D G

    2004-11-09

    Isopiestic vapor-pressure measurements were made at 298.15 K for aqueous NaCl + SrCl{sub 2} solutions, using NaCl(aq) as the reference standard. The measurements for these ternary solutions were made at NaCl ionic strength fractions of y{sub 1} = 0.17066, 0.47366, and 0.82682 for the water activity range 0.9835 {ge} a{sub w} {ge} 0.8710. Our results, and those from two previous isopiestic studies, were combined and used with previously determined parameters for NaCl(aq) and those for SrCl{sub 2}(aq) determined here to evaluate the mixing parameters{sup S}{Theta}{sub Na,Sr} = (0.0562 {+-} 0.0007) kg {center_dot} mol{sup -1} and {Psi}{sub Na,Sr,Cl} = -(0.00705 {+-} 0.00017) kg{sup 2} {center_dot} mol{sup -2} for an extended form of Pitzer's ion-interaction model. These model parameters are valid for ionic strengths of I {le} 7.0 mol {center_dot} kg{sup -1}, where higher-order electrostatic effects have been included in the mixture model. If the fitting range is extended to the saturated solution molalities, then {sup S}{Theta}{sub Na,Sr} = (0.07885 {+-} 0.00195) kg {center_dot} mol{sup -1} and {Psi}{sub Na,Sr,Cl} = -(0.01230 {+-} 0.00033) kg{sup 2} {center_dot} mol{sup -2}. The extended ion-interaction model parameters obtained from available isopiestic data for SrCl{sub 2}(aq) at 298.15 K yield recommended values of the water activities and osmotic and activity coefficients.

  20. Hydrogen generator

    SciTech Connect

    Hansen, J.R.

    1984-06-19

    A hydrogen generator decomposes water into hydrogen and oxygen, and includes an induction coil which is electrically heated to a temperature sufficient to decompose water passing therethrough. A generator coil is connected in communicating relation to the induction coil, and is positioned in a fire resistant crucible containing ferrous oxide pellets. Oxygen and hydrogen produced by decomposition of water pass through the ferrous oxide pellets where the oxygen reacts with the ferrous oxide and the hydrogen is burned to produce heat for heating a building, such as a conventional home.

  1. Association quotients of aluminum sulphate complexes in NaCl media from 50 to 125 C: Results of a potentiometric and solubility study

    SciTech Connect

    Ridley, M.K.; Kettler, R.M.; Wesolowski, D.J.; Palmer, D.A.

    1999-02-01

    The speciation and molal formation quotients for the complexation of aluminum with sulphate were measured based on potentiometric and solubility experiments. Potentiometric titrations, utilizing a hydrogen-electrode concentration cell, were performed from 50 to 125 C at ionic strengths of 0.1, 0.3 and 1.0 molal in aqueous NaCl media. Two aluminum-sulphate species, AlSO{sub 4}{sup +} and Al(SO{sub 4}){sub 2}{sup {minus}}, were identified from the titration data and the formation quotients for these species were modeled by empirical equations to describe their temperature and ionic strength dependencies. Thermodynamic parameters for the complexation reactions were obtained by differentiating the empirical equations with respect to temperature. The thermodynamic quantities obtained for the formation of AlSO{sub 4}{sup +} at 50 C and infinite dilution are: logK{sub 1} = 3.7 {+-} 0.4, {Delta}H{sub 1}{degree} = {minus}10 {+-} 30 kJ/mol, {Delta}S{sub 1}{degree} = 40 {+-} 100 J/K{center_dot}mol and {Delta}C{sub p 1}{degree} = 1900 {+-} 800 J/K{center_dot}mol; whereas the values for Al(SO{sub 4}){sub 2}{sup {minus}} are: logK{sub 2} = 5.6 {+-} 0.7, {Delta}H{sub 2}{degree} = 10 {+-} 50 kJ/mol, {Delta}S{sub 2}{degree} = 100 {+-} 100 J/K{center_dot}mol and {Delta}C{sub p 2}{degree} = 2800 {+-} 800 J/K{center_dot}mol. A solubility study, which was undertaken to verify the 50 C potentiometric data, was performed by reacting powdered gibbsite (Al(OH){sub 3}) with sulphate solutions at 10{sup {minus}3.5} and 10{sup {minus}4} molal H{sup +}, total sulphate concentrations from 0.005 to 0.080 molal, and 0.1 and 1.0 molal ionic strength in aqueous NaCl media. The results of the solubility study are in good agreement with the potentiometric data and establish that Al-sulphate complexation substantially enhances the equilibrium solubility of gibbsite.

  2. Structures and stabilities of group 13 adducts [(NHC)(EX3)] and [(NHC)2(E2X(n))] (E=B to In; X=H, Cl; n=4, 2, 0; NHC=N-heterocyclic carbene) and the search for hydrogen storage systems: a theoretical study.

    PubMed

    Holzmann, Nicole; Stasch, Andreas; Jones, Cameron; Frenking, Gernot

    2011-11-25

    Quantum chemical calculations using density functional theory at the BP86/TZVPP level and ab initio calculations at the SCS-MP2/TZVPP level have been carried out for the group 13 complexes [(NHC)(EX(3))] and [(NHC)(2)(E(2)X(n))] (E=B to In; X=H, Cl; n=4, 2, 0; NHC=N-heterocyclic carbene). The monodentate Lewis acids EX(3) and the bidentate Lewis acids E(2) X(n) bind N-heterocyclic carbenes rather strongly in donor-acceptor complexes [(NHC)(EX(3))] and [(NHC)(2)(E(2)X(n))]. The equilibrium structures of the bidentate complexes depend on the electronic reference state of E(2)X(n), which may vary for different atoms E and X. All complexes [(NHC)(2)(E(2)X(4))] possess C(s) symmetry in which the NHC ligands bind in a trans conformation to the group 13 atoms E. The complexes [(NHC)(2)(E(2)H(2))] with E=B, Al, Ga have also C(s) symmetry with a trans arrangement of the NHC ligands and a planar CE(H)E(H)C moiety that has a E=E π bond. In contrast, the indium complex [(NHC)(2)(In(2) H(2))] has C(i) symmetry with pyramidal-coordinated In atoms in which the hydrogen atoms are twisted above and below the CInInC plane. The latter C(i) form is calculated for all chloride systems [(NHC)(2)(E(2)Cl(2))], but the boron complex [(NHC)(2)(B(2)Cl(2))] deviates only slightly from C(s) symmetry. The B(2) fragment in the linear coordinated complex [(NHC)(2)(B(2))] has a highly excited (3)(1)Σ(g)(-) reference state, which gives an effective B≡B triple bond with a very short interatomic distance. The heavier homologues [(NHC)(2)(E(2))] (E=Al to In) exhibit a anti-periplanar arrangement of the NHC ligands in which the E(2) fragments have a (1)(1) Δ(g) reference state and an E=E double bond. The calculated energies suggest that the dihydrogen release from the complexes [(NHC)(EH(3))] and [(NHC)(2)(E(2)H(n))] becomes energetically more favourable when atom E becomes heavier. The indium complexes should therefore be the best candidates of the investigated series for hydrogen-storage systems

  3. The Coherent Nonlinear Optical Response and Control of Single Quantum Dots

    DTIC Science & Technology

    2005-07-20

    2002). Quantum Dots, in Proceedings of the 5. J.R. Guest, T.H. Stievater, Xiaoqin Li, International School of Physics " Enrico D.G. Steel, D. Gammon, D...S. Katzer Fermi ", Course CL, edited by B. and D. Park, C. Ell, A. Thranhardt, G. Deveaud, A. Quattropani, and P. Khitrova, H. Gibbs, "Direct

  4. Efficient quantum dot-quantum dot and quantum dot-dye energy transfer in biotemplated assemblies.

    PubMed

    Achermann, Marc; Jeong, Sohee; Balet, Laurent; Montano, Gabriel A; Hollingsworth, Jennifer A

    2011-03-22

    CdSe semiconductor nanocrystal quantum dots are assembled into nanowire-like arrays employing microtubule fibers as nanoscale molecular "scaffolds." Spectrally and time-resolved energy-transfer analysis is used to assess the assembly of the nanoparticles into the hybrid inorganic biomolecular structure. Specifically, we demonstrate that a comprehensive study of energy transfer between quantum dot pairs on the biotemplate and, alternatively, between quantum dots and molecular dyes embedded in the microtubule scaffold comprises a powerful spectroscopic tool for evaluating the assembly process. In addition to revealing the extent to which assembly has occurred, the approach allows determination of particle-to-particle (and particle-to-dye) distances within the biomediated array. Significantly, the characterization is realized in situ, without need for further sample workup or risk of disturbing the solution-phase constructs. Furthermore, we find that the assemblies prepared in this way exhibit efficient quantum dot-quantum dot and quantum dot-dye energy transfer that affords faster energy-transfer rates compared to densely packed quantum dot arrays on planar substrates and to small-molecule-mediated quantum dot-dye couples, respectively.

  5. Quantum Dot Light-Emitting Diodes Based on Inorganic Perovskite Cesium Lead Halides (CsPbX3 ).

    PubMed

    Song, Jizhong; Li, Jianhai; Li, Xiaoming; Xu, Leimeng; Dong, Yuhui; Zeng, Haibo

    2015-11-25

    Novel quantum-dot light-emitting diodes based on all-inorganic perovskite CsPbX3 (X = Cl, Br, I) nanocrystals are reported. The well-dispersed, single-crystal quantum dots (QDs) exhibit high quantum yields, and tunable light emission wavelength. The demonstration of these novel perovskite QDs opens a new avenue toward designing optoelectronic devices, such as displays, photodetectors, solar cells, and lasers.

  6. High efficiency stationary hydrogen storage

    SciTech Connect

    Hynek, S.; Fuller, W.; Truslow, S.

    1995-09-01

    Stationary storage of hydrogen permits one to make hydrogen now and use it later. With stationary hydrogen storage, one can use excess electrical generation capacity to power an electrolyzer, and store the resultant hydrogen for later use or transshipment. One can also use stationary hydrogen as a buffer at fueling stations to accommodate non-steady fueling demand, thus permitting the hydrogen supply system (e.g., methane reformer or electrolyzer) to be sized to meet the average, rather than the peak, demand. We at ADL designed, built, and tested a stationary hydrogen storage device that thermally couples a high-temperature metal hydride to a phase change material (PCM). The PCM captures and stores the heat of the hydriding reaction as its own heat of fusion (that is, it melts), and subsequently returns that heat of fusion (by freezing) to facilitate the dehydriding reaction. A key component of this stationary hydrogen storage device is the metal hydride itself. We used nickel-coated magnesium powder (NCMP) - magnesium particles coated with a thin layer of nickel by means of chemical vapor deposition (CVD). Magnesium hydride can store a higher weight fraction of hydrogen than any other practical metal hydride, and it is less expensive than any other metal hydride. We designed and constructed an experimental NCM/PCM reactor out of 310 stainless steel in the form of a shell-and-tube heat exchanger, with the tube side packed with NCMP and the shell side filled with a eutectic mixture of NaCL, KCl, and MgCl{sub 2}. Our experimental results indicate that with proper attention to limiting thermal losses, our overall efficiency will exceed 90% (DOE goal: >75%) and our overall system cost will be only 33% (DOE goal: <50%) of the value of the delivered hydrogen. It appears that NCMP can be used to purify hydrogen streams and store hydrogen at the same time. These prospects make the NCMP/PCM reactor an attractive component in a reformer-based hydrogen fueling station.

  7. Quantum dot cascade laser

    PubMed Central

    2014-01-01

    We demonstrated an unambiguous quantum dot cascade laser based on InGaAs/GaAs/InAs/InAlAs heterostructure by making use of self-assembled quantum dots in the Stranski-Krastanow growth mode and two-step strain compensation active region design. The prototype generates stimulated emission at λ ~ 6.15 μm and a broad electroluminescence band with full width at half maximum over 3 μm. The characteristic temperature for the threshold current density within the temperature range of 82 to 162 K is up to 400 K. Moreover, our materials show the strong perpendicular mid-infrared response at about 1,900 cm-1. These results are very promising for extending the present laser concept to terahertz quantum cascade laser, which would lead to room temperature operation. PACS 42.55.Px; 78.55.Cr; 78.67.Hc PMID:24666965

  8. New quantum dot sensors

    NASA Astrophysics Data System (ADS)

    Gun'ko, Y. K.; Moloney, M. M.; Gallagher, S.; Govan, J.; Hanley, C.

    2010-04-01

    Quantum dots (QDs) are fluorescent semiconductor (e.g. II-VI) nanocrystals, which have a strong characteristic spectral emission. This emission is tunable to a desired energy by selecting variable particle size, size distribution and composition of the nanocrystals. QDs have recently attracted enormous interest due to their unique photophysical properties and range of potential applications in photonics and biochemistry. The main aim of our work is develop new chiral quantum dots (QDs) and establish fundamental principles influencing their structure, properties and biosensing behaviour. Here we present the synthesis and characterisation of chiral CdSe semiconductor nanoparticles and their utilisation as new chiral biosensors. Penicillamine stabilised CdSe nanoparticles have shown both very strong and very broad luminescence spectra. Circular dichroism (CD) spectroscopy studies have revealed that the D- and Lpenicillamine stabilised CdSe QDs demonstrate circular dichroism and possess almost identical mirror images of CD signals. Studies of photoluminescence and CD spectra have shown that there is a clear relationship between defect emission and CD activity. We have also demonstrated that these new QDs can serve as fluorescent nanosensors for various chiral biomolecules including nucleic acids. These novel nanosensors can be potentially utilized for detection of various chiral biological and chemical species with the broad range of potential applications.

  9. Alkyl Chlorides as Hydrogen Bond Acceptors

    SciTech Connect

    Nadas, Janos I; Vukovic, Sinisa; Hay, Benjamin

    2012-01-01

    To gain an understanding of the role of an alkyl chloride as a hydrogen bond acceptor, geometries and interaction energies were calculated at the MP2/aug-cc-pVDZ level of theory for complexes between ethyl chloride and representative hydrogen donor groups. The results establish that these donors, which include hydrogen cyanide, methanol, nitrobenzene, pyrrole, acetamide, and N-methylurea, form X-H {hor_ellipsis} Cl hydrogen bonds (X = C, N, O) of weak to moderate strength, with {Delta}E values ranging from -2.8 to -5.3 kcal/mol.

  10. Freezing Hydrogen

    NASA Image and Video Library

    2009-11-17

    An engineer loads hydrogen gas into the Wide-Field Infrared Survey Explorer in a clean room at the Vandenberg Air Force Base, Calif. The hydrogen is cooled and frozen inside a Thermos-like bottle, called the cryostat, which keeps the science instrument

  11. Hydrogen Bibliography

    SciTech Connect

    Not Available

    1991-12-01

    The Hydrogen Bibliography is a compilation of research reports that are the result of research funded over the last fifteen years. In addition, other documents have been added. All cited reports are contained in the National Renewable Energy Laboratory (NREL) Hydrogen Program Library.

  12. Hydrogen carriers

    NASA Astrophysics Data System (ADS)

    He, Teng; Pachfule, Pradip; Wu, Hui; Xu, Qiang; Chen, Ping

    2016-12-01

    Hydrogen has the potential to be a major energy vector in a renewable and sustainable future energy mix. The efficient production, storage and delivery of hydrogen are key technical issues that require improvement before its potential can be realized. In this Review, we focus on recent advances in materials development for on-board hydrogen storage. We highlight the strategic design and optimization of hydrides of light-weight elements (for example, boron, nitrogen and carbon) and physisorbents (for example, metal-organic and covalent organic frameworks). Furthermore, hydrogen carriers (for example, NH3, CH3OH-H2O and cycloalkanes) for large-scale distribution and for on-site hydrogen generation are discussed with an emphasis on dehydrogenation catalysts.

  13. Experimental investigation of a hydrogen plasma railgun

    SciTech Connect

    Harden, B.; Howell, J.R. . Center for Energy Studies)

    1991-10-01

    This paper reports that the plasma velocity and temperature and composition distributions in a hydrogen plasma railgun were measured. Typical velocities near the muzzle were {approximately}95 km/s at an initial capacitor bank stored energy of 4.1 kJ. Temperatures ranged from a peak of {approximately}24000 K in the current-carrying plasma, to {approximately}85000 K in the tail. The current-carrying plasma was composed of roughly equal parts of hydrogen and copper. Also, computer modeling of armature B-dot probe signals has yielded a simple interpretation of the signal.

  14. Illusory movement of dotted lines

    PubMed Central

    Ito, Hiroyuki; Anstis, Stuart; Cavanagh, Patrick

    2013-01-01

    When oblique rows of black and white dots drifted horizontally across a mid-grey surround, the perceived direction of motion was shifted to be almost parallel to the dotted lines and was often nearly orthogonal to the real motion. The reason is that the black/white contrast signals between adjacent dots along the length of the line are stronger than black/grey or white/grey contrast signals across the line, and the motion is computed as a vector sum of local contrast-weighted motion signals. PMID:19911636

  15. Low Threshold Quantum Dot Lasers.

    PubMed

    Iyer, Veena Hariharan; Mahadevu, Rekha; Pandey, Anshu

    2016-04-07

    Semiconductor quantum dots have replaced conventional inorganic phosphors in numerous applications. Despite their overall successes as emitters, their impact as laser materials has been severely limited. Eliciting stimulated emission from quantum dots requires excitation by intense short pulses of light typically generated using other lasers. In this Letter, we develop a new class of quantum dots that exhibit gain under conditions of extremely low levels of continuous wave illumination. We observe thresholds as low as 74 mW/cm(2) in lasers made from these materials. Due to their strong optical absorption as well as low lasing threshold, these materials could possibly convert light from diffuse, polychromatic sources into a laser beam.

  16. DOT`s perspective on in-line inspection

    SciTech Connect

    Ulrich, L.W.

    1996-12-01

    The US Department of Transportation (DOT) and its Office of Pipeline Safety (OPS) have been involved with in-line inspection (ILI) pigs since the construction of the Alaska crude oil pipeline. Congressionally mandated reports concerning ILI pigs, and a regulation requiring new and replaced pipe and components be designed and constructed to accommodate ILI pigs, were issued by DOT. DOT also may mandate ILI pigs to be run on some pipelines. There is no current federal requirement to run ILI pigs. They are required by OPS in selected compliance cases. DOT supports future ILI pig research. The use of ILI pig surveys, incorporated in pipeline operators` future risk management plans developed as safety alternatives to the established pipeline safety regulations, will be supported.

  17. Local Effects in the X-ray Absorption Spectrum of CaCl2, MgCl2, and NaCl Solutions

    SciTech Connect

    Kulik, H J; Correa Tedesco, A A; Schwegler, E; Prendergast, D; Galli, G

    2010-04-12

    Both first principles molecular dynamics and theoretical X-ray absorption spectroscopy have been used to investigate the aqueous solvation of cations in 0.5 M MgCl{sub 2}, CaCl{sub 2}, and NaCl solutions. We focus here on the species-specific effects that Mg{sup 2+}, Ca{sup 2+}, and Na{sup +}, have on the X-ray absorption spectrum of the respective solutions. For the divalent cations, we find that the hydrogen bonding characteristics of the more rigid magnesium first shell water molecules differ from those in the more flexible solvation shell surrounding calcium. In particular, the first solvation shell water molecules of calcium are accessible to forming acceptor hydrogen bonds, and this results in an enhancement of a post-edge peak near 540 eV. The absence of acceptor hydrogen bonds for magnesium first shell water molecules provides an explanation for the experimental and theoretical observation of a lack of enhancement at the post-main-edge peak. For the sodium monovalent cation we find that the broad tilt angle distribution results in a broadening of post-edge features, despite populations in donor-and-acceptor configurations consistent with calcium. We also present the re-averaged spectra of the MgCl{sub 2}, CaCl{sub 2}, and NaCl solutions and show that trends apparent with increasing concentration (0.5 M, 2.0 M, 4.0 M) are consistent with experiment. Finally, we examine more closely both the effect that cation coordination number has on the hydrogen bonding network and the relative perturbation strength of the cations on lone pair oxygen orbitals.

  18. Effective photoreduction of a Pt(IV) complex with quantum dots: a feasible new light-induced method of releasing anticancer Pt(II) drugs.

    PubMed

    Blanco, Nina Gomez; Maldonado, Carmen R; Mareque-Rivas, Juan C

    2009-09-21

    Irradiation of CdSe-ZnS quantum dots (QDs) with visible light in the presence of [PtCl(4)(bpy)] (1) (bpy = 2,2'-bipyridine) produced with high efficiency [PtCl(2)(bpy)] (2) by photoinduced electron transfer; a reaction and strategy which opens up new opportunities for cancer therapy.

  19. Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    Silvera, Isaac F.; Dias, Ranga; Noked, Ori; Salamat, Ashkan; Zaghoo, Mohamed

    2017-04-01

    One of the great challenges in condensed matter physics has been to produce metallic hydrogen (MH) in the laboratory. There are two approaches: solid molecular hydrogen can be compressed to high density at extreme pressures of order 5-6 megabars. The transition to MH should take place at low temperatures and is expected to occur as a structural first-order phase transition with dissociation of molecules into atoms, rather than the closing of a gap. A second approach is to produce dense molecular hydrogen at pressures of order 1-2 megabars and heat the sample. With increasing temperature, it was predicted that molecular hydrogen first melts and then dissociates to atomic metallic liquid hydrogen as a first-order phase transition. We have observed this liquid-liquid phase transition to metallic hydrogen, also called the plasma phase transition. In low-temperature studies, we have pressurized HD to over 3 megabars and observed two new phases. Molecular hydrogen has been pressurized to 4.2 megabars. A new phase transition has been observed at 3.55 megabars, but it is not yet metallic.

  20. Cl(-) channels in apoptosis.

    PubMed

    Wanitchakool, Podchanart; Ousingsawat, Jiraporn; Sirianant, Lalida; MacAulay, Nanna; Schreiber, Rainer; Kunzelmann, Karl

    2016-10-01

    A remarkable feature of apoptosis is the initial massive cell shrinkage, which requires opening of ion channels to allow release of K(+), Cl(-), and organic osmolytes to drive osmotic water movement and cell shrinkage. This article focuses on the role of the Cl(-) channels LRRC8, TMEM16/anoctamin, and cystic fibrosis transmembrane conductance regulator (CFTR) in cellular apoptosis. LRRC8A-E has been identified as a volume-regulated anion channel expressed in many cell types. It was shown to be required for regulatory and apoptotic volume decrease (RVD, AVD) in cultured cell lines. Its presence also determines sensitivity towards cytostatic drugs such as cisplatin. Recent data point to a molecular and functional relationship of LRRC8A and anoctamins (ANOs). ANO6, 9, and 10 (TMEM16F, J, and K) augment apoptotic Cl(-) currents and AVD, but it remains unclear whether these anoctamins operate as Cl(-) channels or as regulators of other apoptotic Cl(-) channels, such as LRRC8. CFTR has been known for its proapoptotic effects for some time, and this effect may be based on glutathione release from the cell and increase in cytosolic reactive oxygen species (ROS). Although we find that CFTR is activated by cell swelling, it is possible that CFTR serves RVD/AVD through accumulation of ROS and activation of independent membrane channels such as ANO6. Thus activation of ANO6 will support cell shrinkage and induce additional apoptotic events, such as membrane phospholipid scrambling.

  1. Quantum dots: Rethinking the electronics

    SciTech Connect

    Bishnoi, Dimple

    2016-05-06

    In this paper, we demonstrate theoretically that the Quantum dots are quite interesting for the electronics industry. Semiconductor quantum dots (QDs) are nanometer-scale crystals, which have unique photo physical, quantum electrical properties, size-dependent optical properties, There small size means that electrons do not have to travel as far as with larger particles, thus electronic devices can operate faster. Cheaper than modern commercial solar cells while making use of a wider variety of photon energies, including “waste heat” from the sun’s energy. Quantum dots can be used in tandem cells, which are multi junction photovoltaic cells or in the intermediate band setup. PbSe (lead selenide) is commonly used in quantum dot solar cells.

  2. Quantum Dot Spins and Photons

    NASA Astrophysics Data System (ADS)

    Atature, Mete

    2012-02-01

    Self-assembled semiconductor quantum dots are interesting and rich physical systems. Their inherently mesoscopic nature leads to a multitude of interesting interaction mechanisms of confined spins with the solid state environment of spins, charges and phonons. In parallel, the relatively clean spin-dependent optical transitions make quantum dots strong candidates for stationary and flying qubits within the context of spin-based quantum information science. The recently observed quantum dot resonance fluorescence has become a key enabler for further progress in this context. I will first discuss the real-time optical detection (or single-shot readout) of quantum dot spins, and then I will discuss how resonance fluorescence allows coherent generation of single photons suitable (and tailored) for linear-optics quantum computation and for establishing a high-efficiency spin-photon quantum interface within a distributed quantum network.

  3. Quantum dots: Rethinking the electronics

    NASA Astrophysics Data System (ADS)

    Bishnoi, Dimple

    2016-05-01

    In this paper, we demonstrate theoretically that the Quantum dots are quite interesting for the electronics industry. Semiconductor quantum dots (QDs) are nanometer-scale crystals, which have unique photo physical, quantum electrical properties, size-dependent optical properties, There small size means that electrons do not have to travel as far as with larger particles, thus electronic devices can operate faster. Cheaper than modern commercial solar cells while making use of a wider variety of photon energies, including "waste heat" from the sun's energy. Quantum dots can be used in tandem cells, which are multi junction photovoltaic cells or in the intermediate band setup. PbSe (lead selenide) is commonly used in quantum dot solar cells.

  4. Quantum-Dot Cellular Automata

    NASA Astrophysics Data System (ADS)

    Snider, Gregory

    2000-03-01

    Quantum-dot Cellular Automata (QCA) [1] is a promising architecture which employs quantum dots for digital computation. It is a revolutionary approach that holds the promise of high device density and low power dissipation. A basic QCA cell consists of four quantum dots coupled capacitively and by tunnel barriers. The cell is biased to contain two excess electrons within the four dots, which are forced to opposite "corners" of the four-dot cell by mutual Coulomb repulsion. These two possible polarization states of the cell will represent logic "0" and "1". Properly arranged, arrays of these basic cells can implement Boolean logic functions. Experimental results from functional QCA devices built of nanoscale metal dots defined by tunnel barriers will be presented. The experimental devices to be presented consist of Al islands, which we will call quantum dots, interconnected by tunnel junctions and lithographically defined capacitors. Aluminum/ aluminum-oxide/aluminum tunnel junctions were fabricated using a standard e-beam lithography and shadow evaporation technique. The experiments were performed in a dilution refrigerator at a temperature of 70 mK. The operation of a cell is evaluated by direct measurements of the charge state of dots within a cell as the input voltage is changed. The experimental demonstration of a functioning cell will be presented. A line of three cells demonstrates that there are no metastable switching states in a line of cells. A QCA majority gate will also be presented, which is a programmable AND/OR gate and represents the basic building block of QCA systems. The results of recent experiments will be presented. 1. C.S. Lent, P.D. Tougaw, W. Porod, and G.H. Bernstein, Nanotechnology, 4, 49 (1993).

  5. Hydrophobin-Encapsulated Quantum Dots.

    PubMed

    Taniguchi, Shohei; Sandiford, Lydia; Cooper, Maggie; Rosca, Elena V; Ahmad Khanbeigi, Raha; Fairclough, Simon M; Thanou, Maya; Dailey, Lea Ann; Wohlleben, Wendel; von Vacano, Bernhard; de Rosales, Rafael T M; Dobson, Peter J; Owen, Dylan M; Green, Mark

    2016-02-01

    The phase transfer of quantum dots to water is an important aspect of preparing nanomaterials that are suitable for biological applications, and although numerous reports describe ligand exchange, very few describe efficient ligand encapsulation techniques. In this report, we not only report a new method of phase transferring quantum dots (QDs) using an amphiphilic protein (hydrophobin) but also describe the advantages of using a biological molecule with available functional groups and their use in imaging cancer cells in vivo and other imaging applications.

  6. Impurity-modulated Aharonov-Bohm oscillations and intraband optical absorption in quantum dot-ring nanostructures

    NASA Astrophysics Data System (ADS)

    Barseghyan, M. G.; Manaselyan, A. Kh.; Laroze, D.; Kirakosyan, A. A.

    2016-07-01

    In this work we study the electronic states in quantum dot-ring complex nanostructures with an on-center hydrogenic impurity. The influence of the impurity on Aharonov-Bohm energy spectra oscillations and intraband optical absorption is investigated. It is shown that in the presence of a hydrogenic donor impurity the Aharonov-Bohm oscillations in quantum dot-ring structures become highly tunable. Furthermore, the presence of the impurity drastically changes the intraband absorption spectra due to the strong controllability of the electron localization type.

  7. Effect of chloride ions on adsorption and permeation of hydrogen in iron

    SciTech Connect

    Allam, A.M.; Pickering, H.W.; Ateya, B.G.

    1997-04-01

    Effects of chloride ions on hydrogen absorption into iron and on the hydrogen evolution reaction (HER) on an iron surface were studied in acid and alkaline solutions at 23 C using the permeation method of Devanathan and Stachurski. Cl{sup {minus}} ions reduced the overpotential ({eta}) for HER and, in turn, reduced hydrogen coverage and permeation.Effects on hydrogen permeation were more pronounced in alkaline than in acid solutions. Permeation transients at constant electrode potential of he charging surface and subsequent surface analyses of the uppermost atom layers of the hydrogen-charged iron surface indicated a reversible or low coverage with Cl{sup {minus}} ions, a low hydrogen coverage that was not influenced significantly by Cl{sup {minus}} ion concentration at low {eta}, and a marked effect of Cl{sup {minus}} ions in reducing hydrogen coverage of the surface and permeability in alkaline solutions at high cathodic polarizations.

  8. Single to quadruple quantum dots with tunable tunnel couplings

    SciTech Connect

    Takakura, T.; Noiri, A.; Obata, T.; Yoneda, J.; Yoshida, K.; Otsuka, T.; Tarucha, S.

    2014-03-17

    We prepare a gate-defined quadruple quantum dot to study the gate-tunability of single to quadruple quantum dots with finite inter-dot tunnel couplings. The measured charging energies of various double dots suggest that the dot size is governed by the gate geometry. For the triple and quadruple dots, we study the gate-tunable inter-dot tunnel couplings. For the triple dot, we find that the effective tunnel coupling between side dots significantly depends on the alignment of the center dot potential. These results imply that the present quadruple dot has a gate performance relevant for implementing spin-based four-qubits with controllable exchange couplings.

  9. Imaging and Manipulating Energy Transfer Among Quantum Dots at Individual Dot Resolution.

    PubMed

    Nguyen, Duc; Nguyen, Huy A; Lyding, Joseph W; Gruebele, Martin

    2017-06-27

    Many processes of interest in quantum dots involve charge or energy transfer from one dot to another. Energy transfer in films of quantum dots as well as between linked quantum dots has been demonstrated by luminescence shift, and the ultrafast time-dependence of energy transfer processes has been resolved. Bandgap variation among dots (energy disorder) and dot separation are known to play an important role in how energy diffuses. Thus, it would be very useful if energy transfer could be visualized directly on a dot-by-dot basis among small clusters or within films of quantum dots. To that effect, we report single molecule optical absorption detected by scanning tunneling microscopy (SMA-STM) to image energy pooling from donor into acceptor dots on a dot-by-dot basis. We show that we can manipulate groups of quantum dots by pruning away the dominant acceptor dot, and switching the energy transfer path to a different acceptor dot. Our experimental data agrees well with a simple Monte Carlo lattice model of energy transfer, similar to models in the literature, in which excitation energy is transferred preferentially from dots with a larger bandgap to dots with a smaller bandgap.

  10. NMR structural studies of intramolecular (Y+) sub n ter dot (R+) sub n (Y minus ) sub n DNA triplexes in solution: Imino and amino proton and nitrogen markers of Gter dot TA base triple formation

    SciTech Connect

    Radhakrishnan, I.; de los Santos, C.; Patel, D.J. ); Gao, Xiaolian ); Live, D. )

    1991-09-17

    The authors reported previously on NMR studies of (Y+){sub n}{center dot}(R+){sub n}(Y{minus}){sub n}DNA triple helices containing one oligopurine strand (R){sub n} and two oligopyrimidine strands (Y){sub n} stabilized by T{center dot}AT and C{sup +}{center dot}GC base triples. Recently, it has been established that guanosine can recognize a thymidine{center dot}adenosine base pair to form a G{center dot}TA triple in an otherwise (Y+){sub n}{center dot}(R+){sub n}(Y{minus}){sub n} triple-helix motif. The present study extends the NMR research to the characterization of structural features of a 31-mer deoxyoligonucleotide that folds intramolecularly into a 7-mer (Y+){sub n}{center dot}(R+){sub n}(Y{minus}){sub n} triplex with the strands linked through two T{sub 5} loops and that contains a central G{center dot}TA triple flanked by T{center dot}AT triples. The NMR data are consistent with the proposed pairing alignment for the G{center dot}TA triple where the guanosine in an anti orientation pairs through a single hydrogen bond from one of its 2-amino protons to the 4-carbonyl group of thymidine in the Watson-Crick TA pair. They detect a set of NOEs between adjacent triples that establishes that the G{center dot}TA triple stacks between flanking T{center dot}AT triples in the G{center dot}TA triplex. These results demonstrate the capabilities of the NMR approach in monitoring individual base triples and their pairing alignments, as well as establishing that the G{center dot}TA triple can be readily accommodated in an otherwise intramolecular (Y+){sub n}{center dot}(R+){sub n}(Y{minus}){sub n} triple helix in solution.

  11. Optically active quantum dots

    NASA Astrophysics Data System (ADS)

    Gerard, Valerie; Govan, Joseph; Loudon, Alexander; Baranov, Alexander V.; Fedorov, Anatoly V.; Gun'ko, Yurii K.

    2015-10-01

    The main goal of our research is to develop new types of technologically important optically active quantum dot (QD) based materials, study their properties and explore their biological applications. For the first time chiral II-VI QDs have been prepared by us using microwave induced heating with the racemic (Rac), D- and L-enantiomeric forms of penicillamine as stabilisers. Circular dichroism (CD) studies of these QDs have shown that D- and L-penicillamine stabilised particles produced mirror image CD spectra, while the particles prepared with a Rac mixture showed only a weak signal. It was also demonstrated that these QDs show very broad emission bands between 400 and 700 nm due to defects or trap states on the surfaces of the nanocrystals. These QDs have demonstrated highly specific chiral recognition of various biological species including aminoacids. The utilisation of chiral stabilisers also allowed the preparation of new water soluble white emitting CdS nano-tetrapods, which demonstrated circular dichroism in the band-edge region of the spectrum. Biological testing of chiral CdS nanotetrapods displayed a chiral bias for an uptake of the D- penicillamine stabilised nano-tetrapods by cancer cells. It is expected that this research will open new horizons in the chemistry of chiral nanomaterials and their application in nanobiotechnology, medicine and optical chemo- and bio-sensing.

  12. Fluctuating defect density probed with noise spectroscopy in hydrogenated amorphous silicon

    SciTech Connect

    Verleg, P.A.W.E.; Uca, O.; Dijkhuis, J.I.

    1997-07-01

    Resistance fluctuations have been studied in hydrogenated amorphous silicon in the temperature range between 300 K and 450 K. The primary noise source has a power spectrum of approximately 1/f and is ascribed to hydrogen motion. Hopping of weakly bound hydrogen is thermally activated at such low temperatures with an average activation energy of 0.85 eV. The attempt rate amounts to 7 {center_dot} 10{sup 12} s{sup {minus}1}.

  13. Storing Hydrogen

    SciTech Connect

    Kim, Hyun Jeong; Karkamkar, Abhijeet J.; Autrey, Thomas; Chupas, Peter; Proffen, Thomas E.

    2010-05-31

    Researchers have been studying mesoporous materials for almost two decades with a view to using them as hosts for small molecules and scaffolds for molding organic compounds into new hybrid materials and nanoparticles. Their use as potential storage systems for large quantities of hydrogen has also been mooted. Such systems that might hold large quantities of hydrogen safely and in a very compact volume would have enormous potential for powering fuel cell vehicles, for instance. A sponge-like form of silicon dioxide, the stuff of sand particles and computer chips, can soak up and store other compounds including hydrogen. Studies carried out at the XOR/BESSRC 11-ID-B beamline at the APS have revealed that the nanoscopic properties of the hydrogenrich compound ammonia borane help it store hydrogen more efficiently than usual. The material may have potential for addressing the storage issues associated with a future hydrogen economy. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  14. Hydrogen program overview

    SciTech Connect

    Gronich, S.

    1997-12-31

    This paper consists of viewgraphs which summarize the following: Hydrogen program structure; Goals for hydrogen production research; Goals for hydrogen storage and utilization research; Technology validation; DOE technology validation activities supporting hydrogen pathways; Near-term opportunities for hydrogen; Market for hydrogen; and List of solicitation awards. It is concluded that a full transition toward a hydrogen economy can begin in the next decade.

  15. Heterogeneous Reaction of ClONO2(g) + NaCl(s) to Cl2(g) + NaNO3(s)

    NASA Technical Reports Server (NTRS)

    Timonen, Raimo S.; Chu, Liang T.; Leu, Ming-Taun; Keyser, Leon F.

    1994-01-01

    The heterogeneous reaction of ClON02 + NaCl yields Cl2 + NaNO3 (eq 1) was investigated over a temperature range 220-300 K in a flow-tube reactor interfaced with a differentially pumped quadrupole mass spectrometer. Partial pressures of ClON02 in the range 10(exp -8) - 10(exp -5) Torr were used. Granule sizes and surface roughness of the NaCl substrates were determined by using a scanning electron microscope, and in separate experiments, surface areas of the substrates were measured by using BET analysis of gas-adsorption isotherms. For dry NaCl substrates, both the decay rates of ClON02 and the growth rates Of C12 were used to obtain reaction probabilities, gamma(sub l) = (4.6 +/- 3.0) x 10(exp -3) at 296 K and (6.7 +/- 3.2) x 10(exp -1) at 225 K, after considering the internal surface area, The error bars represent 1 standard deviation. The Cl2 yield based on the ClONO2 reacted was measured to be 1.0 +/- 0.2. In order to mimic the conditions encountered in the lower stratosphere, the effect of water vapor pressures between 5 x 10(exp -5) and 3 x 10(exp -4) Torr on reaction 1 was also studied. With added H20, reaction probabilities, gamma = (4.1 +/- 2.1) x 10(exp -3) at 296 K and (4.7 +/- 2.9) x 10(exp -3) at 225 K, were obtained. A trace of HOCl, the reaction product from the ClON02 + H20 yield HOCl + HN03 reaction, was observed in addition to the C12 product from reaction 1. The implications of this result for the enhancement of hydrogen chloride in the stratosphere after the El Chichon volcanic eruption and for the marine troposphere are discussed.

  16. Capillary electrophoretic system incorporating an UV/CL dual detector.

    PubMed

    Tsukagoshi, Kazuhiko; Sawanoi, Kaori; Nakajima, Riichiro

    2006-02-15

    We developed a capillary electrophoretic system incorporating an ultra-violet absorption (UV)/chemiluminescence (CL) dual detector, taking advantage of the CL reaction of luminol-hydrogen peroxide and the batch-type CL detection cell. UV detection was carried out using the on-capillary method while CL detection was performed using the end-capillary method. Examination of isoluminol isothiocyanate (ILITC) as a model sample revealed two main peaks with UV detection and one main peak with CL detection. The first peak in the UV detection data corresponded to the main peak in the CL detection data. We then determined that the ILITC sample included natural ILITC as well as an impurity that had absorption behavior but did not have CL properties and labeling ability. Furthermore, the components of a mixture containing glycine, glycylglycine and glycylglycylglycine, all labeled with ILITC, were well separated and detected using the present system. The present system easily, rapidly, and simultaneously produces useful information due to the presence of both UV and CL detectors.

  17. The histone methyltransferase Dot1/DOT1L as a critical regulator of the cell cycle

    PubMed Central

    Kim, Wootae; Choi, Minji; Kim, Ja-Eun

    2014-01-01

    Dot1/DOT1L catalyzes the methylation of histone H3 lysine 79 (H3K79), which regulates diverse cellular processes, such as development, reprogramming, differentiation, and proliferation. In regards to these processes, studies of Dot1/DOT1L-dependent H3K79 methylation have mainly focused on the transcriptional regulation of specific genes. Although the gene transcription mediated by Dot1/DOT1L during the cell cycle is not fully understood, H3K79 methylation plays a critical role in the progression of G1 phase, S phase, mitosis, and meiosis. This modification may contribute to the chromatin structure that controls gene expression, replication initiation, DNA damage response, microtubule reorganization, chromosome segregation, and heterochromatin formation. Overall, Dot1/DOT1L is required to maintain genomic and chromosomal stability. This review summarizes the several functions of Dot1/DOT1L and highlights its role in cell cycle regulation. PMID:24526115

  18. Hydrogen gas purification apparatus

    SciTech Connect

    Yanagihara, N.; Gamo, T.; Iwaki, T.; Moriwaki, Y.

    1984-04-24

    A hydrogen gas purification apparatus which includes at least one set of two hydrogen purification containers coupled to each other for heat exchanging therebetween, each of the hydrogen purification containers containing a hydrogen absorbing alloy. The hydrogen gas purification apparatus is so arranged as to cause hydrogen gas to be selectively desorbed from and absorbed into the hydrogen absorbing alloy by the amount of heat produced when the hydrogen gas is selectively absorbed into and desorbed from the hydrogen absorbing alloy.

  19. Optical Fiber Sensing Using Quantum Dots

    PubMed Central

    Jorge, Pedro; Martins, Manuel António; Trindade, Tito; Santos, José Luís; Farahi, Faramarz

    2007-01-01

    Recent advances in the application of semiconductor nanocrystals, or quantum dots, as biochemical sensors are reviewed. Quantum dots have unique optical properties that make them promising alternatives to traditional dyes in many luminescence based bioanalytical techniques. An overview of the more relevant progresses in the application of quantum dots as biochemical probes is addressed. Special focus will be given to configurations where the sensing dots are incorporated in solid membranes and immobilized in optical fibers or planar waveguide platforms.

  20. Quantum dot behavior in graphene nanoconstrictions.

    PubMed

    Todd, Kathryn; Chou, Hung-Tao; Amasha, Sami; Goldhaber-Gordon, David

    2009-01-01

    Graphene nanoribbons display an imperfectly understood transport gap. We measure transport through nanoribbon devices of several lengths. In long (>/=250 nm) nanoribbons we observe transport through multiple quantum dots in series, while shorter (dots. New measurements indicate that dot size may scale with constriction width. We propose a model where transport occurs through quantum dots that are nucleated by background disorder potential in the presence of a confinement gap.

  1. Biosynthesis of luminescent quantum dots in an earthworm.

    PubMed

    Stürzenbaum, S R; Höckner, M; Panneerselvam, A; Levitt, J; Bouillard, J-S; Taniguchi, S; Dailey, L-A; Ahmad Khanbeigi, R; Rosca, E V; Thanou, M; Suhling, K; Zayats, A V; Green, M

    2013-01-01

    The synthesis of designer solid-state materials by living organisms is an emerging field in bio-nanotechnology. Key examples include the use of engineered viruses as templates for cobalt oxide (Co(3)O(4)) particles, superparamagnetic cobalt-platinum alloy nanowires and gold-cobalt oxide nanowires for photovoltaic and battery-related applications. Here, we show that the earthworm's metal detoxification pathway can be exploited to produce luminescent, water-soluble semiconductor cadmium telluride (CdTe) quantum dots that emit in the green region of the visible spectrum when excited in the ultraviolet region. Standard wild-type Lumbricus rubellus earthworms were exposed to soil spiked with CdCl(2) and Na(2)TeO(3) salts for 11 days. Luminescent quantum dots were isolated from chloragogenous tissues surrounding the gut of the worm, and were successfully used in live-cell imaging. The addition of polyethylene glycol on the surface of the quantum dots allowed for non-targeted, fluid-phase uptake by macrophage cells.

  2. Hydrogen from renewable resources monthly progress report

    SciTech Connect

    Rocheleau, R.E.

    1995-02-01

    During February, we achieved two significant results in our hydrogen storage activates. Reversible hydrogen uptake and release was measured at room temperature, near ambient pressure on the (IrClH{sub 2}(H{sub 2})Pr{sup i}{sub 3}) complex. Dr. Jensen also observed that certain polyhydzide complexes catalyze the low temperature, reversible dehydrogenation of cycloalkanes to aromatic hydrocarbons at temperatures as low as 130{degrees}C. This discovery may represent a breakthrough in chemical storage of hydrogen as all other cycloalkane dehydrogenation systems require temperatures in excess of 300{degrees}C.

  3. Chiral Graphene Quantum Dots.

    PubMed

    Suzuki, Nozomu; Wang, Yichun; Elvati, Paolo; Qu, Zhi-Bei; Kim, Kyoungwon; Jiang, Shuang; Baumeister, Elizabeth; Lee, Jaewook; Yeom, Bongjun; Bahng, Joong Hwan; Lee, Jaebeom; Violi, Angela; Kotov, Nicholas A

    2016-02-23

    Chiral nanostructures from metals and semiconductors attract wide interest as components for polarization-enabled optoelectronic devices. Similarly to other fields of nanotechnology, graphene-based materials can greatly enrich physical and chemical phenomena associated with optical and electronic properties of chiral nanostructures and facilitate their applications in biology as well as other areas. Here, we report that covalent attachment of l/d-cysteine moieties to the edges of graphene quantum dots (GQDs) leads to their helical buckling due to chiral interactions at the "crowded" edges. Circular dichroism (CD) spectra of the GQDs revealed bands at ca. 210-220 and 250-265 nm that changed their signs for different chirality of the cysteine edge ligands. The high-energy chiroptical peaks at 210-220 nm correspond to the hybridized molecular orbitals involving the chiral center of amino acids and atoms of graphene edges. Diverse experimental and modeling data, including density functional theory calculations of CD spectra with probabilistic distribution of GQD isomers, indicate that the band at 250-265 nm originates from the three-dimensional twisting of the graphene sheet and can be attributed to the chiral excitonic transitions. The positive and negative low-energy CD bands correspond to the left and right helicity of GQDs, respectively. Exposure of liver HepG2 cells to L/D-GQDs reveals their general biocompatibility and a noticeable difference in the toxicity of the stereoisomers. Molecular dynamics simulations demonstrated that d-GQDs have a stronger tendency to accumulate within the cellular membrane than L-GQDs. Emergence of nanoscale chirality in GQDs decorated with biomolecules is expected to be a general stereochemical phenomenon for flexible sheets of nanomaterials.

  4. Dynamic observing tonometry (DOT)

    NASA Astrophysics Data System (ADS)

    Kanngiesser, Hartmut E.; Robert, Yves C.

    1999-06-01

    To help improve early detection of vascular eye diseases, a method, named Dynamic Observing Tonometry (DOT), for measuring the intra-ocular pressure (IOP) has been developed, which allows for simultaneous ophthalmoscopy and dynamic tonometry of the human eye. Material and Method. A system for the application of this method is presented, consisting of a transducer to be placed on the corneal surface and of a stand-alone base unit. The latter can be connected to a personal computer for further data processing and storage. The transducer consists of a Goldmann-type contact lens modified by implementing means for transparent pressure-measurement of IOP. A small flat membrane in the center of the lens applanates the cornea. A liquid transmits the applanation pressure from the opposite side of this membrane to a pressure sensor located outside the optical pathway. Time-dependent IOP's are transmitted telemetrically to the base unit for processing. Results. Current initial tests provide evidence for the viability of the concept and have demonstrated the performance of the system. Typical time dependent IOP measurements obtained with an experimental device are presented. Clinical trials with two prototypes are underway. Conclusion: The proposed device allows the ophthalmology to perform the ordinary slit-lamp fundus examinations combined with simultaneous dynamic tonometry. It offers for the first time easy and precise analysis of cardiac and respiratory- modulated intra-ocular pressure while directly observing the choroid and the papilla, as well as the analysis of heart rate variability and inspection of the iridocorneal angle at varying applied pressure. Moreover, dynamic observing tonometry gives easy access to examination procedures such as tonography and ophthalmodynamometry, which have been rarely performed despite their potential diagnostic value due to the complexity of experimental protocols hitherto used.

  5. Energetics of the O-H bond and of intramolecular hydrogen bonding in HOC6H4C(O)Y (Y = H, CH3, CH2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds.

    PubMed

    Bernardes, Carlos E S; Minas da Piedade, Manuel E

    2008-10-09

    The energetics of the phenolic O-H bond in a series of 2- and 4-HOC 6H 4C(O)Y (Y = H, CH3, CH 2CH=CH2, C[triple bond]CH, CH2F, NH2, NHCH 3, NO2, OH, OCH3, OCN, CN, F, Cl, SH, and SCH3) compounds and of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y, was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-hydroxybenzaldehyde (2HBA), 4-hydroxybenzaldehyde (4HBA), 2'-hydroxyacetophenone (2HAP), 2-hydroxybenzamide (2HBM), and 4-hydroxybenzamide (4HBM), at 298.15 K, were determined by micro- or macrocombustion calorimetry. The corresponding enthalpies of vaporization or sublimation were also measured by Calvet drop-calorimetry and Knudsen effusion measurements. The combination of the obtained experimental data led to Delta f H m (o)(2HBA, g) = -238.3 +/- 2.5 kJ.mol (-1), DeltafHm(o)(4HBA, g) = -220.3 +/- 2.0 kJ.mol(-1), Delta f H m (o)(2HAP, g) = -291.8 +/- 2.1 kJ.mol(-1), DeltafHm(o)(2HBM, g) = -304.8 +/- 1.5 kJ.mol (-1), and DeltafHm(o) (4HBM, g) = -278.4 +/- 2.4 kJ.mol (-1). These values, were used to assess the predictions of the B3LYP/6-31G(d,p), B3LYP/6-311+G(d,p), B3LYP/aug-cc-pVDZ, B3P86/6-31G(d,p), B3P86/6-311+G(d,p), B3P86/aug-cc-pVDZ, and CBS-QB3 methods, for the enthalpies of a series of isodesmic gas phase reactions. In general, the CBS-QB3 method was able to reproduce the experimental enthalpies of reaction within their uncertainties. The B3LYP/6-311+G(d,p) method, with a slightly poorer accuracy than the CBS-QB3 approach, achieved the best performance of the tested DFT models. It was further used to analyze the trends of the intramolecular O...H hydrogen bond in 2-HOC 6H 4C(O)Y evaluated by the ortho-para method and to compare the energetics of the phenolic O-H bond in 2- and 4-HOC 6H 4C(O)Y compounds. It was concluded that the O-H bond "strength" is systematically larger for 2-hydroxybenzoyl than for the corresponding 4-hydroxybenzoyl isomers mainly due to the presence of

  6. Morphological and luminescent characteristics of GaN dots deposited on AlN by alternate supply of TMG and NH 3

    NASA Astrophysics Data System (ADS)

    Tsai, Yu-Li; Gong, Jyh-Rong; Lin, Tai-Yuan; Lin, Hsia-Yu; Chen, Yang-Fang; Lin, Kun-Ming

    2006-03-01

    GaN dots were deposited on AlN underlayers by alternate supply of trimethylgallium (TMG) and ammonia (NH 3) in an inductively heated quartz reactor operated at atmospheric pressure. Various growth parameters including deposition temperature, TMG admittance and pulse time between TMG and NH 3 exposures were proposed to investigate the influence of growth parameters on the size distribution of GaN dots. It appears that GaN dots with uniform size distribution can be achieved under certain growth conditions. Based on the study of atomic force microscopy (AFM), high deposition temperature was found to be in favor of forming large GaN dots with small dot density. Decrement of TMG flow rate or reduction in the number of growth cycle tends to enable the formation of GaN dots with small dot sizes. The results of room temperature (RT) cathodoluminescence (CL) measurements of the GaN dots exhibit an emission peak at 3.735 eV. A remarkable blue shift of GaN dot emission was observed by reduced temperature photoluminescence (PL) measurements.

  7. A colloidal quantum dot spectrometer

    NASA Astrophysics Data System (ADS)

    Bao, Jie; Bawendi, Moungi G.

    2015-07-01

    Spectroscopy is carried out in almost every field of science, whenever light interacts with matter. Although sophisticated instruments with impressive performance characteristics are available, much effort continues to be invested in the development of miniaturized, cheap and easy-to-use systems. Current microspectrometer designs mostly use interference filters and interferometric optics that limit their photon efficiency, resolution and spectral range. Here we show that many of these limitations can be overcome by replacing interferometric optics with a two-dimensional absorptive filter array composed of colloidal quantum dots. Instead of measuring different bands of a spectrum individually after introducing temporal or spatial separations with gratings or interference-based narrowband filters, a colloidal quantum dot spectrometer measures a light spectrum based on the wavelength multiplexing principle: multiple spectral bands are encoded and detected simultaneously with one filter and one detector, respectively, with the array format allowing the process to be efficiently repeated many times using different filters with different encoding so that sufficient information is obtained to enable computational reconstruction of the target spectrum. We illustrate the performance of such a quantum dot microspectrometer, made from 195 different types of quantum dots with absorption features that cover a spectral range of 300 nanometres, by measuring shifts in spectral peak positions as small as one nanometre. Given this performance, demonstrable avenues for further improvement, the ease with which quantum dots can be processed and integrated, and their numerous finely tuneable bandgaps that cover a broad spectral range, we expect that quantum dot microspectrometers will be useful in applications where minimizing size, weight, cost and complexity of the spectrometer are critical.

  8. Biocompatible ZnS:Mn quantum dots for reactive oxygen generation and detection in aqueous media

    NASA Astrophysics Data System (ADS)

    Diaz-Diestra, Daysi; Beltran-Huarac, Juan; Bracho-Rincon, Dina P.; González-Feliciano, José A.; González, Carlos I.; Weiner, Brad R.; Morell, Gerardo

    2015-12-01

    We report here the versatility of Mn-doped ZnS quantum dots (ZnS:Mn QDs) synthesized in aqueous medium for generating reactive oxygen species and for detecting cells. Our experiments provide evidence leading to the elimination of Cd-based cores in CdSe/ZnS systems by substitution of Mn-doped ZnS. Advanced electron microscopy, X-ray diffraction, and optical spectroscopy were applied to elucidate the formation, morphology, and dispersion of the products. We study for the first time the ability of ZnS:Mn QDs to act as immobilizing agents for Tyrosinase (Tyr) enzyme. It was found that ZnS:Mn QDs show no deactivation of Tyr enzyme, which efficiently catalyzed the hydrogen peroxide (H2O2) oxidation and its eventual reduction (-0.063 V vs. Ag/AgCl) on the biosensor surface. The biosensor showed a linear response in the range of 12 μmol/L-0.1 mmol/L at low operation potential. Our observations are explained in terms of a catalase-cycled kinetic mechanism based on the binding of H2O2 to the axial position of one of the active copper sites of the oxy-Tyr during the catalase cycle to produce deoxy-Tyr. A singlet oxygen quantum yield of 0.62 in buffer and 0.54 in water was found when ZnS:Mn QDs were employed as a photosensitizer in the presence of a chemical scavenger and a standard dye. These results are consistent with a chemical trapping energy transfer mechanism. Our results also indicate that ZnS:Mn QDs are well tolerated by HeLa Cells reaching cell viabilities as high as 88 % at 300 µg/mL of QDs for 24 h of incubation. The ability of ZnS:Mn QDs as luminescent nanoprobes for bioimaging is also discussed.

  9. Cl- sensitive biosensor used electrolyte-solution-gate diamond FETs.

    PubMed

    Song, Kwang-Soup; Sakai, Toshikatsu; Kanazawa, Hirofumi; Araki, Yuta; Umezawa, Hitoshi; Tachiki, Minoru; Kawarada, Hiroshi

    2003-11-15

    We have investigated the electrolyte-solution-gate field effect transisitors (SGFETs) used hydrogen terminated (H-terminated) or partially oxygen terminated (O-terminated) polycrystalline diamond surface in the Cl- and Br- ionic solutions. The H-terminated channel SGFETs are insensitive to pH values in electrolyte solutions. The threshold voltages of the diamond SGFETs shift according to the density of Cl- and Br- ions about 30 mV/decade. One of the attractive biomedical applications for the Cl- sensitive SGFETs is the detection of chloride density in blood or in sweat especially in the case of cystic fibrosis. The sensitivities of Cl- and Br- ions have been lost on the partially O-terminated diamond surface. These phenomena can be explained by the polarity of surface change on the H-terminated and the O-terminated surface.

  10. Hydrogen chloride

    Integrated Risk Information System (IRIS)

    Hydrogen chloride ; CASRN 7647 - 01 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogeni

  11. Hydrogen technologies

    SciTech Connect

    Not Available

    1992-05-01

    To the non-nonsense engineer, any talk of a hydrogen economy may seem like so much hot air. This paper reports that as legislative, safety and environmental issues continue to tighten, they're promoting hydrogen's chances as an energy source and, more immediately, its prospects as a chemical feedstock. Paradoxically, the environmental demands that are stimulating hydrogen demand are also inhibiting the gas's production. Previously, gasoline was made with benzene, which means that H{sub 2} was rejected. But now that the laws mandate lower aromatic and higher oxygenate levels in gasolines, there's less H{sub 2} available as byproduct. At the same time, H{sub 2} demand is rising in hydrodesulfurization units, since the same laws require refiners to cut sulfur levels in fuels. Supplementary sources for the gas are also shrinking. In the chlor-alkali industry, H{sub 2} output is dropping, as demand for its coproduct chlorine weakens. At the same time, H{sub 2} demand for the making of hydrogen peroxide is growing, as that environmentally safer bleach gains chlorine's market share.

  12. Hydrogen sulfide

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 03 / 005 www.epa.gov / iris TOXICOLOGICAL REVIEW OF HYDROGEN SULFIDE ( CAS No . 7783 - 06 - 4 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) June 2003 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been

  13. Nanoscale quantum-dot supercrystals

    NASA Astrophysics Data System (ADS)

    Baimuratov, Anvar S.; Turkov, Vadim K.; Rukhlenko, Ivan D.; Baranov, Alexander V.; Fedorov, Anatoly V.

    2013-09-01

    We develop a theory allowing one to calculate the energy spectra and wave functions of collective excitations in twoand three-dimensional quantum-dot supercrystals. We derive analytical expressions for the energy spectra of twodimensional supercrystals with different Bravias lattices, and use them to analyze the possibility of engineering the supercrystals' band structure. We demonstrate that the variation of the supercrystal's parameters (such as the symmetry of the periodic lattice and the properties of the quantum dots or their environment) enables an unprecedented control over its optical properties, thus paving a way towards the development of new nanophotonics materials.

  14. Reversible Photoswitching of Carbon Dots

    PubMed Central

    Khan, Syamantak; Verma, Navneet Chandra; Gupta, Abhishek; Nandi, Chayan Kanti

    2015-01-01

    We present a method of reversible photoswitching in carbon nanodots with red emission. A mechanism of electron transfer is proposed. The cationic dark state, formed by the exposure of red light, is revived back to the bright state with the very short exposure of blue light. Additionally, the natural on-off state of carbon dot fluorescence was tuned using an electron acceptor molecule. Our observation can make the carbon dots as an excellent candidate for the super-resolution imaging of nanoscale biomolecules within the cell. PMID:26078266

  15. Metallic Hydrogen

    NASA Astrophysics Data System (ADS)

    Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

    2015-03-01

    Hydrogen is the simplest and most abundant element in the Universe. At high pressure it is predicted to transform to a metal with remarkable properties: room temperature superconductivity, a metastable metal at ambient conditions, and a revolutionary rocket propellant. Both theory and experiment have been challenged for almost 80 years to determine its condensed matter phase diagram, in particular the insulator-metal transition. Hydrogen is predicted to dissociate to a liquid atomic metal at multi-megabar pressures and T =0 K, or at megabar pressures and very high temperatures. Thus, its predicted phase diagram has a broad field of liquid metallic hydrogen at high pressure, with temperatures ranging from thousands of degrees to zero Kelvin. In a bench top experiment using static compression in a diamond anvil cell and pulsed laser heating, we have conducted measurements on dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K. We observe a first-order phase transition in the liquid phase, as well as sharp changes in optical transmission and reflectivity when this phase is entered. The optical signature is that of a metal. The mapping of the phase line of this transition is in excellent agreement with recent theoretical predictions for the long-sought plasma phase transition to metallic hydrogen. Research supported by the NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H.

  16. Highly Efficient Photoelectrochemical Hydrogen Generation Using Zn(x)Bi2S(3+x) Sensitized Platelike WO₃ Photoelectrodes.

    PubMed

    Liu, Canjun; Yang, Yahui; Li, Wenzhang; Li, Jie; Li, Yaomin; Shi, Qilin; Chen, Qiyuan

    2015-05-27

    Zn(x)Bi2S(3+x) sensitized platelike WO3 photoelectrodes on FTO substrates were for the first time prepared via a sequential ionic layer adsorption reaction (SILAR) process. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet visible spectrometry (UV-vis), and Raman spectra. The results show that the ZnxBi2S3+x quantum dots (QDs) are uniformly coated on the entire surface of WO3 plates, forming a WO3/Zn(x)Bi2S(3+x) core/shell structure. The Zn(x)Bi2S(3+x)/WO3 films show a superior ability to capture visible light. High-efficiency photoelectrochemical (PEC) hydrogen generation is demonstrated using the prepared electrodes as photoanodes in a typical three-electrode electrochemical cell. Compared to the Bi2S3/WO3 photoelectrodes, the Zn(x)Bi2S(3+x)/WO3 photoelectrodes exhibit good photostability and excellent PEC activity, and the photocurrent density is up to 7.0 mA cm(-2) at -0.1 V versus Ag/AgCl under visible light illumination. Investigation of the electron transport properties of the photoelectrodes shows that the introduction of ZnS enhances the photoelectrons' transport rate in the photoelectrode. The high PEC activity demonstrates the potential of the Zn(x)Bi2S(3+x)/WO3 film as an efficient photoelectrode for hydrogen generation.

  17. Hydrogen peroxide poisoning

    MedlinePlus

    Hydrogen peroxide is used in these products: Hydrogen peroxide Hair bleach Some contact lens cleaners Note: Household hydrogen peroxide has a 3% concentration. That means it contains 97% water and 3% hydrogen peroxide. Hair ...

  18. Energy spectrum of D{sup 0} centre in a spherical Gaussian quantum dot

    SciTech Connect

    Boda, Aalu Chatterjee, Ashok

    2015-05-15

    The properties of a neutral hydrogenic donor (D{sup 0}) centres have been studied for a GaAs semiconductor quantum dot with the Gaussian confinement potential. The energy levels of the ground state (n = 1) and the excited states of both the first excited (n = 2) and second excited (n = 3) configurations have been calculated by variational method. It has been shown that the excited states of the (D{sup 0}) centre in quantum dot are bound for sufficiently strong confinement potential. The conditions of binding for the ground state as well as excited states have been determined as functions of the potential strength and quantum dot radius. The ground state electron energy is compared with those available in the literature.

  19. Hydrogen forming reaction process

    SciTech Connect

    Marianowski, L.G.; Fleming, D.K.

    1989-03-07

    A hydrogen forming process is described, comprising: conducting in a hydrogen production zone a chemical reaction forming mixed gases comprising molecular hydrogen; contacting one side of a hydrogen ion porous and molecular gas nonporous metallic foil with the mixed gases in the hydrogen production zone; dissociating the molecular hydrogen to ionic hydrogen on the one side of the metallic foil; passing the ionic hydrogen through the metallic foil to its other side; and withdrawing hydrogen from the other side of the metallic foil, thereby removing hydrogen from the hydrogen production zone.

  20. Low temperature synthesis of silicon quantum dots with plasma chemistry control in dual frequency non-thermal plasmas.

    PubMed

    Sahu, Bibhuti Bhusan; Yin, Yongyi; Han, Jeon Geon; Shiratani, Masaharu

    2016-06-21

    The advanced materials process by non-thermal plasmas with a high plasma density allows the synthesis of small-to-big sized Si quantum dots by combining low-temperature deposition with superior crystalline quality in the background of an amorphous hydrogenated silicon nitride matrix. Here, we make quantum dot thin films in a reactive mixture of ammonia/silane/hydrogen utilizing dual-frequency capacitively coupled plasmas with high atomic hydrogen and nitrogen radical densities. Systematic data analysis using different film and plasma characterization tools reveals that the quantum dots with different sizes exhibit size dependent film properties, which are sensitively dependent on plasma characteristics. These films exhibit intense photoluminescence in the visible range with violet to orange colors and with narrow to broad widths (∼0.3-0.9 eV). The observed luminescence behavior can come from the quantum confinement effect, quasi-direct band-to-band recombination, and variation of atomic hydrogen and nitrogen radicals in the film growth network. The high luminescence yields in the visible range of the spectrum and size-tunable low-temperature synthesis with plasma and radical control make these quantum dot films good candidates for light emitting applications.

  1. Chlorine doped graphene quantum dots: Preparation, properties, and photovoltaic detectors

    SciTech Connect

    Zhao, Jianhong; Xiang, Jinzhong; Tang, Libin Ji, Rongbin Yuan, Jun; Zhao, Jun; Yu, Ruiyun; Tai, Yunjian; Song, Liyuan

    2014-09-15

    Graphene quantum dots (GQDs) are becoming one of the hottest advanced functional materials because of the opening of the bandgap due to quantum confinement effect, which shows unique optical and electrical properties. The chlorine doped GQDs (Cl-GQDs) have been fabricated by chemical exfoliation of HCl treated carbon fibers (CFs), which were prepared from degreasing cotton through an annealing process at 1000 °C for 30 min. Raman study shows that both G and 2D peaks of GQDs may be redshifted (softened) by chlorine doping, leading to an n-type doping. The first vertical (Cl)-GQDs based photovoltaic detectors have been demonstrated, both the light absorbing and electron-accepting roles for (Cl)-GQDs in photodetection have been found, resulting in an exceptionally big ratio of photocurrent to dark current as high as ∼10{sup 5} at room temperature using a 405 nm laser irradiation under the reverse bias voltage. The study expands the application of (Cl)-GQDs to the important optoelectronic detection devices.

  2. Hydrogen environment embrittlement.

    NASA Technical Reports Server (NTRS)

    Gray, H. R.

    1972-01-01

    Hydrogen embrittlement is classified into three types: internal reversible hydrogen embrittlement, hydrogen reaction embrittlement, and hydrogen environment embrittlement. Characteristics of and materials embrittled by these types of hydrogen embrittlement are discussed. Hydrogen environment embrittlement is reviewed in detail. Factors involved in standardizing test methods for detecting the occurrence of and evaluating the severity of hydrogen environment embrittlement are considered. The effects of test technique, hydrogen pressure, purity, strain rate, stress concentration factor, and test temperature are discussed.

  3. The statistical theory of quantum dots

    NASA Astrophysics Data System (ADS)

    Alhassid, Y.

    2000-10-01

    A quantum dot is a sub-micron-scale conducting device containing up to several thousand electrons. Transport through a quantum dot at low temperatures is a quantum-coherent process. This review focuses on dots in which the electron's dynamics are chaotic or diffusive, giving rise to statistical properties that reflect the interplay between one-body chaos, quantum interference, and electron-electron interactions. The conductance through such dots displays mesoscopic fluctuations as a function of gate voltage, magnetic field, and shape deformation. The techniques used to describe these fluctuations include semiclassical methods, random-matrix theory, and the supersymmetric nonlinear σ model. In open dots, the approximation of noninteracting quasiparticles is justified, and electron-electron interactions contribute indirectly through their effect on the dephasing time at finite temperature. In almost-closed dots, where conductance occurs by tunneling, the charge on the dot is quantized, and electron-electron interactions play an important role. Transport is dominated by Coulomb blockade, leading to peaks in the conductance that at low temperatures provide information on the dot's ground-state properties. Several statistical signatures of electron-electron interactions have been identified, most notably in the dot's addition spectrum. The dot's spin, determined partly by exchange interactions, can also influence the fluctuation properties of the conductance. Other mesoscopic phenomena in quantum dots that are affected by the charging energy include the fluctuations of the cotunneling conductance and mesoscopic Coulomb blockade.

  4. A ketone/alcohol polymer for cycle of electrolytic hydrogen-fixing with water and releasing under mild conditions

    NASA Astrophysics Data System (ADS)

    Kato, Ryo; Yoshimasa, Keisuke; Egashira, Tatsuya; Oya, Takahiro; Oyaizu, Kenichi; Nishide, Hiroyuki

    2016-09-01

    Finding a safe and efficient carrier of hydrogen is a major challenge. Recently, hydrogenated organic compounds have been studied as hydrogen storage materials because of their ability to stably and reversibly store hydrogen by forming chemical bonds; however, these compounds often suffer from safety issues and are usually hydrogenated with hydrogen at high pressure and/or temperature. Here we present a ketone (fluorenone) polymer that can be moulded as a plastic sheet and fixes hydrogen via a simple electrolytic hydrogenation at -1.5 V (versus Ag/AgCl) in water at room temperature. The hydrogenated alcohol derivative (the fluorenol polymer) reversibly releases hydrogen by heating (80 °C) in the presence of an aqueous iridium catalyst. Both the use of a ketone polymer and the efficient hydrogen fixing with water as a proton source are completely different from other (de)hydrogenated compounds and hydrogenation processes. The easy handling and mouldable polymers could suggest a pocketable hydrogen carrier.

  5. An electrochemical hydrogen meter for measuring hydrogen in sodium using a ternary electrolyte mixture

    NASA Astrophysics Data System (ADS)

    Sridharan, R.; Mahendran, K. H.; Nagaraj, S.; Gnanasekaran, T.; Periaswami, G.

    2003-01-01

    An electrochemical sensor for measuring hydrogen concentration in liquid sodium that is based on a ternary mixture of LiCl, CaCl 2 and CaHCl as the electrolyte has been developed. DSC experiments showed the eutectic temperature of this ternary system to be ˜725 K. Impedance spectroscopic analysis of the electrolyte indicated ionic conduction through a molten phase at ˜725 K. Two electrochemical hydrogen sensors were constructed using the ternary electrolyte of composition 70 mol% LiCl:16 mol% CaHCl:14 mol% CaCl 2 and tested at 723 K in a mini sodium loop and at hydrogen levels of 60-250 ppb in sodium. The sensors show linear response in this concentration range and are capable of detecting a change of 10 ppb hydrogen in sodium over a background level of 60 ppb. Identification of this electrolyte system and its use in a sensor for measuring hydrogen in sodium are described in this paper.

  6. Systematic safety evaluation on photoluminescent carbon dots

    NASA Astrophysics Data System (ADS)

    Wang, Kan; Gao, Zhongcai; Gao, Guo; Wo, Yan; Wang, Yuxia; Shen, Guangxia; Cui, Daxiang

    2013-03-01

    Photoluminescent carbon dots (C-dots) were prepared using the improved nitric acid oxidation method. The C-dots were characterized by tapping-mode atomic force microscopy, and UV-vis absorption spectroscopy. The C-dots were subjected to systematic safety evaluation via acute toxicity, subacute toxicity, and genotoxicity experiments (including mouse bone marrow micronuclear test and Salmonella typhimurium mutagenicity test). The results showed that the C-dots were successfully prepared with good stability, high dispersibility, and water solubility. At all studied C-dot dosages, no significant toxic effect, i.e., no abnormality or lesion, was observed in the organs of the animals. Therefore, the C-dots are non-toxic to mice under any dose and have potential use in fluorescence imaging in vivo, tumor cell tracking, and others.

  7. Modeling of the quantum dot filling and the dark current of quantum dot infrared photodetectors

    SciTech Connect

    Ameen, Tarek A.; El-Batawy, Yasser M.; Abouelsaood, A. A.

    2014-02-14

    A generalized drift-diffusion model for the calculation of both the quantum dot filling profile and the dark current of quantum dot infrared photodetectors is proposed. The confined electrons inside the quantum dots produce a space-charge potential barrier between the two contacts, which controls the quantum dot filling and limits the dark current in the device. The results of the model reasonably agree with a published experimental work. It is found that increasing either the doping level or the temperature results in an exponential increase of the dark current. The quantum dot filling turns out to be nonuniform, with a dot near the contacts containing more electrons than one in the middle of the device where the dot occupation approximately equals the number of doping atoms per dot, which means that quantum dots away from contacts will be nearly unoccupied if the active region is undoped.

  8. Photoluminescence, chemiluminescence and anodic electrochemiluminescence of hydrazide-modified graphene quantum dots

    NASA Astrophysics Data System (ADS)

    Dong, Yongqiang; Dai, Ruiping; Dong, Tongqing; Chi, Yuwu; Chen, Guonan

    2014-09-01

    Single-layer graphene quantum dots (SGQDs) were refluxed with hydrazine (N2H4) to prepare hydrazide-modified SGQDs (HM-SGQDs). Compared with SGQDs, partial oxygen-containing groups have been removed from HM-SGQDs. At the same time, a lot of hydrazide groups have been introduced into HM-SGQDs. The introduced hydrazide groups provide HM-SGQDs with a new kind of surface state, and give HM-SGQDs unique photoluminescence (PL) properties such as blue-shifted PL emission and a relatively high PL quantum yield. More importantly, the hydrazide-modification made HM-SGQDs have abundant luminol-like units. Accordingly, HM-SGQDs exhibit unique and excellent chemiluminescence (CL) and anodic electrochemiluminescence (ECL). The hydrazide groups of HM-SGQDs can be chemically oxidized by the dissolved oxygen (O2) in alkaline solutions, producing a strong CL signal. The CL intensity is mainly dependent on the pH value and the concentration of O2, implying the potential applications of HM-SGQDs in pH and O2 sensors. The hydrazide groups of HM-SGQDs can also be electrochemically oxidized in alkaline solutions, producing a strong anodic ECL signal. The ECL intensity can be enhanced sensitively by hydrogen peroxide (H2O2). The enhanced ECL intensity is proportional to the concentration of H2O2 in a wide range of 3 μM to 500 μM. The detection limit of H2O2 was calculated to be about 0.7 μM. The results suggest the great potential applications of HM-SGQDs in the sensors of H2O2 and bio-molecules that are able to produce H2O2 in the presence of enzymes.Single-layer graphene quantum dots (SGQDs) were refluxed with hydrazine (N2H4) to prepare hydrazide-modified SGQDs (HM-SGQDs). Compared with SGQDs, partial oxygen-containing groups have been removed from HM-SGQDs. At the same time, a lot of hydrazide groups have been introduced into HM-SGQDs. The introduced hydrazide groups provide HM-SGQDs with a new kind of surface state, and give HM-SGQDs unique photoluminescence (PL) properties such

  9. Colloidal quantum dot solar cells

    NASA Astrophysics Data System (ADS)

    Sargent, Edward H.

    2012-03-01

    Solar cells based on solution-processed semiconductor nanoparticles -- colloidal quantum dots -- have seen rapid advances in recent years. By offering full-spectrum solar harvesting, these cells are poised to address the urgent need for low-cost, high-efficiency photovoltaics.

  10. Reading Comprehension Strategy: Rainbow Dots

    ERIC Educational Resources Information Center

    Moore, Claire; Lo, Lusa

    2008-01-01

    An action research study was conducted using the Rainbow Dots strategy to evaluate its effectiveness on reading comprehension skills in a third-grade class with students both with and without a specific learning disability. Results of the study indicated that students' overall performances in reading comprehension have increased. Students also…

  11. Inhibition in Dot Comparison Tasks

    ERIC Educational Resources Information Center

    Clayton, Sarah; Gilmore, Camilla

    2015-01-01

    Dot comparison tasks are commonly used to index an individual's Approximate Number System (ANS) acuity, but the cognitive processes involved in completing these tasks are poorly understood. Here, we investigated how factors including numerosity ratio, set size and visual cues influence task performance. Forty-four children aged 7-9 years completed…

  12. Inhibition in Dot Comparison Tasks

    ERIC Educational Resources Information Center

    Clayton, Sarah; Gilmore, Camilla

    2015-01-01

    Dot comparison tasks are commonly used to index an individual's Approximate Number System (ANS) acuity, but the cognitive processes involved in completing these tasks are poorly understood. Here, we investigated how factors including numerosity ratio, set size and visual cues influence task performance. Forty-four children aged 7-9 years completed…

  13. Reading Comprehension Strategy: Rainbow Dots

    ERIC Educational Resources Information Center

    Moore, Claire; Lo, Lusa

    2008-01-01

    An action research study was conducted using the Rainbow Dots strategy to evaluate its effectiveness on reading comprehension skills in a third-grade class with students both with and without a specific learning disability. Results of the study indicated that students' overall performances in reading comprehension have increased. Students also…

  14. Designing quantum dots for solotronics

    PubMed Central

    Kobak, J.; Smoleński, T.; Goryca, M.; Papaj, M.; Gietka, K.; Bogucki, A.; Koperski, M.; Rousset, J.-G.; Suffczyński, J.; Janik, E.; Nawrocki, M.; Golnik, A.; Kossacki, P.; Pacuski, W.

    2014-01-01

    Solotronics, optoelectronics based on solitary dopants, is an emerging field of research and technology reaching the ultimate limit of miniaturization. It aims at exploiting quantum properties of individual ions or defects embedded in a semiconductor matrix. It has already been shown that optical control of a magnetic ion spin is feasible using the carriers confined in a quantum dot. However, a serious obstacle was the quenching of the exciton luminescence by magnetic impurities. Here we show, by photoluminescence studies on thus-far-unexplored individual CdTe dots with a single cobalt ion and CdSe dots with a single manganese ion, that even if energetically allowed, nonradiative exciton recombination through single-magnetic-ion intra-ionic transitions is negligible in such zero-dimensional structures. This opens solotronics for a wide range of as yet unconsidered systems. On the basis of results of our single-spin relaxation experiments and on the material trends, we identify optimal magnetic-ion quantum dot systems for implementation of a single-ion-based spin memory. PMID:24463946

  15. 76 FR 4264 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2C10 (Regional Jet Series 700, 701, & 702...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-01-25

    ...), and CL-600-2D24 (Regional Jet Series 900) Airplanes AGENCY: Federal Aviation Administration (FAA), DOT... Part 39 Air transportation, Aircraft, Aviation safety, Incorporation by reference, Safety. The Proposed... TRANSPORTATION Federal Aviation Administration 14 CFR Part 39 RIN 2120-AA64 Airworthiness Directives; Bombardier...

  16. 76 FR 61633 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2C10 (Regional Jet Series 700, 701, & 702...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-05

    ...), and CL-600-2D24 (Regional Jet Series 900) Airplanes AGENCY: Federal Aviation Administration (FAA), DOT... Regional Jet Aircraft Maintenance Manual. We ] added Note 2 to this NPRM to refer to these tasks cards as... and 32-12-01-400-801-A01 of the Bombardier CRJ 700/900 Series Regional Jet Aircraft Maintenance Manual...

  17. 75 FR 69609 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2B19 (Regional Jet Series 100 & 440...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-11-15

    ...-69611] [FR Doc No: 2010-28604] DEPARTMENT OF TRANSPORTATION Federal Aviation Administration 14 CFR Part... Directives; Bombardier, Inc. Model CL-600-2B19 (Regional Jet Series 100 & 440) Airplanes AGENCY: Federal Aviation Administration (FAA), DOT. ACTION: Notice of proposed rulemaking (NPRM). SUMMARY: We propose...

  18. Physical and optical dot gain: characterization and relation to dot shape and paper properties

    NASA Astrophysics Data System (ADS)

    Namedanian, Mahziar; Nyström, Daniel; Zitinski Elias, Paula; Gooran, Sasan

    2014-01-01

    The tone value increase in halftone printing commonly referred to as dot gain actually encompasses two fundamentally different phenomena. Physical dot gain refers to the fact that the size of the printed halftone dots differs from their nominal size, and is related to the printing process. Optical dot gain originates from light scattering inside the substrate, causing light exchanges between different chromatic areas. Due to their different intrinsic nature, physical and optical dot gains need to be treated separately. In this study, we characterize and compare the dot gain properties for offset prints on coated and uncoated paper, using AM and first and second generation FM halftoning. Spectral measurements are used to compute the total dot gain. Microscopic images are used to separate the physical and optical dot gain, to study ink spreading and ink penetration, and to compute the Modulation Transfer Function (MTF) for the different substrates. The experimental results show that the physical dot gain depends on ink penetration and ink spreading properties. Microscopic images of the prints reveal that the ink penetrates into the pores and cavities of the uncoated paper, resulting in inhomogeneous dot shapes. For the coated paper, the ink spread on top of the surface, giving a more homogenous dot shape, but also covering a larger area, and hence larger physical dot gain. The experimental results further show that the total dot gain is larger for the uncoated paper, because of larger optical dot gain. The effect of optical dot gain depends on the lateral light scattering within the substrate, the size of the halftone dots, and on the halftone dot shape, especially the dot perimeter.

  19. Short term inhalation toxicity of a liquid aerosol of glutaraldehyde-coated CdS/Cd(OH)2 core shell quantum dots in rats.

    PubMed

    Ma-Hock, L; Farias, P M A; Hofmann, T; Andrade, A C D S; Silva, J N; Arnaud, T M S; Wohlleben, W; Strauss, V; Treumann, S; Chaves, C R; Gröters, S; Landsiedel, R; van Ravenzwaay, B

    2014-02-10

    Quantum dots exhibit extraordinary optical and mechanical properties, and the number of their applications is increasing. In order to investigate a possible effect of coating on the inhalation toxicity of previously tested non-coated CdS/Cd(OH)2 quantum dots and translocation of these very small particles from the lungs, rats were exposed to coated quantum dots or CdCl2 aerosol (since Cd(2+) was present as impurity), 6h/d for 5 consecutive days. Cd content was determined in organs and excreta after the end of exposure and three weeks thereafter. Toxicity was determined by examination of broncho-alveolar lavage fluid and microscopic evaluation of the entire respiratory tract. There was no evidence for translocation of particles from the respiratory tract. Evidence of a minimal inflammatory process was observed by examination of broncho-alveolar lavage fluid. Microscopically, minimal to mild epithelial alteration was seen in the larynx. The effects observed with coated quantum dots, non-coated quantum dots and CdCl2 were comparable, indicating that quantum dots elicited no significant effects beyond the toxicity of the Cd(2+) ion itself. Compared to other compounds with larger particle size tested at similarly low concentrations, quantum dots caused much less pronounced toxicological effects. Therefore, the present data show that small particle sizes with corresponding high surfaces are not the only factor triggering the toxic response or translocation. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

  20. Hydrogen scavengers

    SciTech Connect

    Carroll, David W.; Salazar, Kenneth V.; Trkula, Mitchell; Sandoval, Cynthia W.

    2002-01-01

    There has been invented a codeposition process for fabricating hydrogen scavengers. First, a .pi.-bonded allylic organometallic complex is prepared by reacting an allylic transition metal halide with an organic ligand complexed with an alkali metal; and then, in a second step, a vapor of the .pi.-bonded allylic organometallic complex is combined with the vapor of an acetylenic compound, irradiated with UV light, and codeposited on a substrate.

  1. Effect of electric and magnetic fields on impurity binding energy in zinc-blend symmetric InGaN/GaN multiple quantum dots.

    PubMed

    Sadeghi, Ebrahim; Naghdi, Elham

    2014-01-01

    The binding energy of ground state for hydrogenic impurity in multiple quantum dots is calculated in the framework of effective-mass approximation and using a variational method. It is shown that the binding energy is a function of the size of dots, impurity position and external fields strength. The binding energy has a maximum value when the impurity is located on the center of dots and decreases for other impurity positions. The external electric and magnetic fields change the magnitude and the position of peaks. PACS Codes 73.20.D; 71.21.La; 71.55.Eq.

  2. The stability of sodalite in the system NaAlSiO sub 4 -NaCl

    SciTech Connect

    Sharp, Z.D. ); Helffrich, G.R. ); Bohlen, S.R. ); Essene, E.J. )

    1989-08-01

    The reaction sodalite = {beta}-nepheline + NaCl (s) was reversed in solid-medium apparatus and the reaction sodalite = carnegieite + NaCl (l) was reversed at 1 bar (1,649-1,652 K). The experimental reversals between 923 K and 973 K can be fit with a dP/dT of {minus}11 bar/K, suggesting that the excess entropy for sodalite is present only above 923 K. A phase diagram for the NaAlSiO{sub 4}-NaCl system that is consistent with the measured thermochemical data and the experiments between 973 and 1,650 K can be generated if the 61.7 J/mol{center dot}K entropy contribution is included in the S{sup 0}{sub 298} of sodalite. This entropy contribution must be removed below 973 K for the experiments to fit with calculations. Previously unreported thermodynamic data estimated in this study are {Delta}G{sup 0}{sub 298} for sodalite ({minus}12,697 kJ/mol) and carnegieite (NaAlSiO{sub 4}) ({minus}1,958 kJ/mol), S{sup 0}{sub 298} of carnegieite (129.6 J/mol{center dot}K) and compressibility of NaCl{sub liquid} (V{sup P}{sub 298} (cm{sup 3}) = 31.6{center dot}(1 - 24.7{center dot}10{sup {minus}3}{center dot}P + 800{center dot}10{sup {minus}6}{center dot}P{sup 2}))(T in K; P in kbar). Sodalite is a high-temperature, low-pressure phase, stable well above the solidus in sodic silica-undersaturated magmas enriched in NaCl, and its presence constrains NaCl activities in magmas. Estimates of minimum NaCl (l) activities in the Mont St-Hilaire sodalite syenites are 0.05 at 1,073 K and 0.13 at 1,273 K. Density calculations are consistent with the field observations that sodalite phenocrysts will float in a nepheline syenite liquid. This explains the enrichment of sodalite in the upper levels of the sodalite syenites at Mont St.Hilaire and elsewhere.

  3. Synthesis of palm-based polyurethane-LiClO4 via prepolymerization

    NASA Astrophysics Data System (ADS)

    Sien, Jason Wong Chee; Badri, Khairiah Haji; Su'ait, Mohd. Sukor; Hassan, Nurul Izzati

    2015-09-01

    Palm-based polyurethane (pPU) with varying lithium salt (LiClO4) content was synthesized. Higher loading percentage of LiClO4 in the pPU led to the inhibition of prepolymerization process from taking place. Hydrogen bonded C=O was detected in the FTIR spectrum indicating the hydrogen bonding between the urethane bonds. Ordered complexed C=O was observed in the FTIR spectrum confirming the complex formation between urethane bond and Li+ ion. DSC thermogram showed the increase in the LiClO4 content could increase the glass transition temperature. SEM micrographs exhibited that more bubbles were formed when the LiClO4 increased from 10 to 30wt% indicating the reaction between free isocyanate groups with moisture presence in the salt due to the hygroscopic properties of LiClO4.

  4. Synthesis of palm-based polyurethane-LiClO{sub 4} via prepolymerization

    SciTech Connect

    Sien, Jason Wong Chee; Badri, Khairiah Haji; Su’ait, Mohd Sukor; Hassan, Nurul Izzati

    2015-09-25

    Palm-based polyurethane (pPU) with varying lithium salt (LiClO{sub 4}) content was synthesized. Higher loading percentage of LiClO{sub 4} in the pPU led to the inhibition of prepolymerization process from taking place. Hydrogen bonded C=O was detected in the FTIR spectrum indicating the hydrogen bonding between the urethane bonds. Ordered complexed C=O was observed in the FTIR spectrum confirming the complex formation between urethane bond and Li{sup +} ion. DSC thermogram showed the increase in the LiClO{sub 4} content could increase the glass transition temperature. SEM micrographs exhibited that more bubbles were formed when the LiClO{sub 4} increased from 10 to 30wt% indicating the reaction between free isocyanate groups with moisture presence in the salt due to the hygroscopic properties of LiClO{sub 4}.

  5. InAs/GaAs quantum dot solar cell with an AlAs cap layer

    NASA Astrophysics Data System (ADS)

    Tutu, F. K.; Lam, P.; Wu, J.; Miyashita, N.; Okada, Y.; Lee, K.-H.; Ekins-Daukes, N. J.; Wilson, J.; Liu, H.

    2013-04-01

    We report the effects of the deposition of an AlAs cap layer (CL) over InAs quantum dots (QDs) on the performance of QD solar cells (QDSCs). The growth of AlAs CL over InAs QDs led to the elimination of the wetting layer absorption and hence the enhancement of the open-current voltage, Voc, of a 20-layer InAs/GaAs QDSC from 0.69 V to 0.79 V. Despite a slight reduction in short-circuit current, Jsc, for the QDSC with AlAs CL, the enhancement of the Voc is enough to ensure that its efficiency is higher than the QDSC without AlAs CL.

  6. Hydrogen environment embrittlement

    NASA Technical Reports Server (NTRS)

    Gray, H. R.

    1972-01-01

    Hydrogen embrittlement is classified into three types: internal reversible hydrogen embrittlement, hydrogen reaction embrittlement, and hydrogen environment embrittlement. Characteristics of and materials embrittled by these types of hydrogen embrittlement are discussed. Hydrogen environment embrittlement is reviewed in detail. Factors involved in standardizing test methods for detecting the occurrence of and evaluating the severity of hydrogen environment embrittlement are considered. The effect of test technique, hydrogen pressure, purity, strain rate, stress concentration factor, and test temperature are discussed. Additional research is required to determine whether hydrogen environment embrittlement and internal reversible hydrogen embrittlement are similar or distinct types of embrittlement.

  7. Clean air program. Use of hydrogen to power the advanced technology transit bus (ATTB): An assessment. Final report, July 1996-June 1997

    SciTech Connect

    Raj, P.K.

    1997-11-01

    The Advanced Technology Transit Bus (ATTB), developed under primary funding from the U.S. DOT/Federal Transit Administration (FTA), currently uses a power plant based on a natural gas burning IC engine-generator set. FTA is interested in demonstrating the use of a hydrogen fuel cell-based power plant on the ATTB. This report analyzes several issues related to the proposed demonstration project including hydrogen safety, hydrogen storage options, and total hydrogen requirements.

  8. Recognition-Mediated Assembly of Quantum Dot Polymer Conjugates with Controlled Morphology

    PubMed Central

    Nandwana, Vikas; Subramani, Chandramouleeswaran; Eymur, Serkan; Yeh, Yi-Cheun; Tonga, Gulen Yesilbag; Tonga, Murat; Jeong, Youngdo; Yang, Boqian; Barnes, Michael D.; Cooke, Graeme; Rotello, Vincent M.

    2011-01-01

    We have demonstrated a polymer mediated “bricks and mortar” method for the self-assembly of quantum dots (QDs). This strategy allows QDs to self-assemble into structured aggregates using complementary three-point hydrogen bonding. The resulting nanocomposites have distinct morphologies and inter-particle distances based on the ratio between QDs and polymer. Time resolved photoluminescence measurements showed that the optical properties of the QDs were retained after self-assembly. PMID:22016664

  9. Probing silicon quantum dots by single-dot techniques

    NASA Astrophysics Data System (ADS)

    Sychugov, Ilya; Valenta, Jan; Linnros, Jan

    2017-02-01

    Silicon nanocrystals represent an important class of non-toxic, heavy-metal free quantum dots, where the high natural abundance of silicon is an additional advantage. Successful development in mass-fabrication, starting from porous silicon to recent advances in chemical and plasma synthesis, opens up new possibilities for applications in optoelectronics, bio-imaging, photovoltaics, and sensitizing areas. In this review basic physical properties of silicon nanocrystals revealed by photoluminescence spectroscopy, lifetime, intensity trace and electrical measurements on individual nanoparticles are summarized. The fabrication methods developed for accessing single Si nanocrystals are also reviewed. It is concluded that silicon nanocrystals share many of the properties of direct bandgap nanocrystals exhibiting sharp emission lines at low temperatures, on/off blinking, spectral diffusion etc. An analysis of reported results is provided in comparison with theory and with direct bandgap material quantum dots. In addition, the role of passivation and inherent interface/matrix defects is discussed.

  10. Effects of Lewis acid catalysts on the hydrogenation and cracking of two-ring aromatic and hydroaromatic structures related to coal

    SciTech Connect

    Salim, Sadie S.; Bell, Alexis T.

    1982-08-01

    Little is known about the hydrogenation of fused aromatic nuclei during the liquefaction of coal under the influence of Lewis acid catalysts. For this paper, this study was conducted to establish the effects of catalyst acidity on the activity and selectivity of Lewis acid catalysts, the sources of hydrogen involved in hydrogenation and cracking, and the relations between reactant structure and reactivity. Two-ring aromatic and hydroaromatic compounds were used to simulate some of the structural units present in coal. The catalysts examined were ZnCl2 and AlCl3. ZnCl2 is less active than AlCl3 for both hydrogenation and cracking but it does not promote the formation of tars via Scholl condensation: Methyl or hydroxyl substitution of the reactants greatly enhances their reactivity towards hydrogenation and cracking. The source of hydrogen consumed during hydrogenation depends on the choice of catalyst. In the presence of AlCl3, Scholl condensation of aromatic nuclei serves as the principal source of hydrogen. Molecular hydrogen is used exclusively, though, when hydrogenation is catalysed by ZnCl2. The formation of reaction products and the trends in reactant reactivity can be interpreted on the basis of carbonium ion mechanisms. Finally, the results of this study provide a basis for assessing the extent of hydrogenation occurring during the liquefaction of coal using ZnCl2 or AlCl3.

  11. High (36)Cl/Cl ratios in Chernobyl groundwater.

    PubMed

    Roux, Céline; Le Gal La Salle, Corinne; Simonucci, Caroline; Van Meir, Nathalie; Fifield, L Keith; Diez, Olivier; Bassot, Sylvain; Simler, Roland; Bugai, Dmitri; Kashparov, Valery; Lancelot, Joël

    2014-12-01

    After the explosion of the Chernobyl Nuclear Power Plant in April 1986, contaminated material was buried in shallow trenches within the exclusion zone. A (90)Sr plume was evidenced downgradient of one of these trenches, trench T22. Due to its conservative properties, (36)Cl is investigated here as a potential tracer to determine the maximal extent of the contamination plume from the trench in groundwater. (36)Cl/Cl ratios measured in groundwater, trench soil water and leaf leachates are 1-5 orders of magnitude higher than the theoretical natural (36)Cl/Cl ratio. This contamination occurred after the Chernobyl explosion and currently persists. Trench T22 acts as an obvious modern point source of (36)Cl, however other sources have to be involved to explain such contamination. (36)Cl contamination of groundwater can be explained by dilution of trench soil water by uncontaminated water (rainwater or deep groundwater). With a plume extending further than that of (90)Sr, radionuclide which is impacted by retention and decay processes, (36)Cl can be considered as a suitable tracer of contamination from the trench in groundwater provided that modern release processes of (36)Cl from trench soil are better characterized.

  12. Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction

    NASA Astrophysics Data System (ADS)

    Moradi, Christopher P.; Xie, Changjian; Kaufmann, Matin; Guo, Hua; Douberly, Gary E.

    2016-04-01

    Pyrolytic dissociation of Cl2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH3 → ClNH2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C3v symmetric top. Frequency shifts from NH3 and dipole moment measurements are consistent with a ClNH3 complex containing a relatively strong two-center three-electron (2c-3e) bond. The nature of the 2c-3e bonding in ClNH3 is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH3Cl and Cl-HNH2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH3 → HCl + NH2.

  13. Two-Center Three-Electron Bonding in ClNH3 Revealed via Helium Droplet Infrared Spectroscopy: Entrance Channel Complex Along the cl + NH3 → ClNH2 + H Reaction

    NASA Astrophysics Data System (ADS)

    Franke, Peter R.; Moradi, Christopher P.; Kaufmann, Matin; Xie, Changjian; Guo, Hua; Douberly, Gary E.

    2016-06-01

    Pyrolytic dissociation of Cl2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction, Cl + NH3 → ClNH2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C3v symmetric top. Frequency shifts from NH3 and dipole moment measurements are consistent with a ClNH3 complex containing a relatively strong two-center three-electron (2c-3e) bond. The nature of the 2c-3e bonding in ClNH3 is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence of two other complexes, NH3Cl and Cl-HNH2, which are predicted in the entry valley to the hydrogen abstraction reaction, Cl + NH3 → HCl + NH2

  14. Hydrogen detector

    DOEpatents

    Kanegae, Naomichi; Ikemoto, Ichiro

    1980-01-01

    A hydrogen detector of the type in which the interior of the detector is partitioned by a metal membrane into a fluid section and a vacuum section. Two units of the metal membrane are provided and vacuum pipes are provided independently in connection to the respective units of the metal membrane. One of the vacuum pipes is connected to a vacuum gauge for static equilibrium operation while the other vacuum pipe is connected to an ion pump or a set of an ion pump and a vacuum gauge both designed for dynamic equilibrium operation.

  15. Congruency effects in dot comparison tasks: convex hull is more important than dot area.

    PubMed

    Gilmore, Camilla; Cragg, Lucy; Hogan, Grace; Inglis, Matthew

    2016-11-16

    The dot comparison task, in which participants select the more numerous of two dot arrays, has become the predominant method of assessing Approximate Number System (ANS) acuity. Creation of the dot arrays requires the manipulation of visual characteristics, such as dot size and convex hull. For the task to provide a valid measure of ANS acuity, participants must ignore these characteristics and respond on the basis of number. Here, we report two experiments that explore the influence of dot area and convex hull on participants' accuracy on dot comparison tasks. We found that individuals' ability to ignore dot area information increases with age and display time. However, the influence of convex hull information remains stable across development and with additional time. This suggests that convex hull information is more difficult to inhibit when making judgements about numerosity and therefore it is crucial to control this when creating dot comparison tasks.

  16. Congruency effects in dot comparison tasks: convex hull is more important than dot area

    PubMed Central

    Gilmore, Camilla; Cragg, Lucy; Hogan, Grace; Inglis, Matthew

    2016-01-01

    ABSTRACT The dot comparison task, in which participants select the more numerous of two dot arrays, has become the predominant method of assessing Approximate Number System (ANS) acuity. Creation of the dot arrays requires the manipulation of visual characteristics, such as dot size and convex hull. For the task to provide a valid measure of ANS acuity, participants must ignore these characteristics and respond on the basis of number. Here, we report two experiments that explore the influence of dot area and convex hull on participants’ accuracy on dot comparison tasks. We found that individuals’ ability to ignore dot area information increases with age and display time. However, the influence of convex hull information remains stable across development and with additional time. This suggests that convex hull information is more difficult to inhibit when making judgements about numerosity and therefore it is crucial to control this when creating dot comparison tasks. PMID:28163886

  17. Charge induced enhancement of adsorption for hydrogen storage materials

    NASA Astrophysics Data System (ADS)

    Sun, Xiang

    2009-12-01

    The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl2 and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage

  18. A quantum dot in topological insulator nanofilm.

    PubMed

    Herath, Thakshila M; Hewageegana, Prabath; Apalkov, Vadym

    2014-03-19

    We introduce a quantum dot in topological insulator nanofilm as a bump at the surface of the nanofilm. Such a quantum dot can localize an electron if the size of the dot is large enough, ≳5 nm. The quantum dot in topological insulator nanofilm has states of two types, which belong to two ('conduction' and 'valence') bands of the topological insulator nanofilm. We study the energy spectra of such defined quantum dots. We also consider intraband and interband optical transitions within the dot. The optical transitions of the two types have the same selection rules. While the interband absorption spectra have multi-peak structure, each of the intraband spectra has one strong peak and a few weak high frequency satellites.

  19. Quantum transport in ballistic quantum dots

    NASA Astrophysics Data System (ADS)

    Ferry, D. K.; Akis, R. A.; Pivin, D. P., Jr.; Bird, J. P.; Holmberg, N.; Badrieh, F.; Vasileska, D.

    1998-10-01

    Carriers in small 3D quantum boxes take us from unintentional qquantum dots in MOSFETs (arising from the doping fluctuations) tto single-electron quantum dots in semiconductor hheterostructures. In between these two extremes are the realm of oopen, ballistic quantum dots, in which the transport can be quite regular. Several issues must be considered in treating the transport in these dots, among which are: (1) phase coherence within the dot; (2) the transition between semi-classical and fully quantum transport, (3) the role of the contacts, vis-à-vis the fabricated boundaries, and (4) the actual versus internal boundaries. In this paper, we discuss these issues, including the primary observables in experiment, the intrinsic nature of oscillatory behavior in magnetic field and dot size, and the connection to semi-classical transport emphasizing the importance of the filtering by the input (and output) quantum point contacts.

  20. Chemiluminescence behavior of CdTe-hydrogen peroxide enhanced by sodium hypochlorite and sensitized sensing of estrogens

    NASA Astrophysics Data System (ADS)

    Ling, Bo; Bi, Jianhong; Pi, Zongxin; Dong, Huaze; Dong, Ling

    2014-05-01

    It has been found that sodium hypochlorite enhanced the chemiluminescence (CL) of the CdTe nanocrystal (NC)-hydrogen peroxide system and that estrogens inhibited these CL signals in alkaline solution. CL spectra were used to investigate the mechanism of the CL enhancement. On the basis of the inhibition, a flow-injection CL method has been established for determination of three natural estrogens.

  1. Dot-in-Well Quantum-Dot Infrared Photodetectors

    NASA Technical Reports Server (NTRS)

    Gunapala, Sarath; Bandara, Sumith; Ting, David; Hill, cory; Liu, John; Mumolo, Jason; Chang, Yia Chung

    2008-01-01

    Dot-in-well (DWELL) quantum-dot infrared photodetectors (QDIPs) [DWELL-QDIPs] are subjects of research as potentially superior alternatives to prior QDIPs. Heretofore, there has not existed a reliable method for fabricating quantum dots (QDs) having precise, repeatable dimensions. This lack has constituted an obstacle to the development of uniform, high-performance, wavelength-tailorable QDIPs and of focal-plane arrays (FPAs) of such QDIPs. However, techniques for fabricating quantum-well infrared photodetectors (QWIPs) having multiple-quantum- well (MQW) structures are now well established. In the present research on DWELL-QDIPs, the arts of fabrication of QDs and QWIPs are combined with a view toward overcoming the deficiencies of prior QDIPs. The longer-term goal is to develop focal-plane arrays of radiationhard, highly uniform arrays of QDIPs that would exhibit high performance at wavelengths from 8 to 15 m when operated at temperatures between 150 and 200 K. Increasing quantum efficiency is the key to the development of competitive QDIP-based FPAs. Quantum efficiency can be increased by increasing the density of QDs and by enhancing infrared absorption in QD-containing material. QDIPs demonstrated thus far have consisted, variously, of InAs islands on GaAs or InAs islands in InGaAs/GaAs wells. These QDIPs have exhibited low quantum efficiencies because the numbers of QD layers (and, hence, the areal densities of QDs) have been small typically five layers in each QDIP. The number of QD layers in such a device must be thus limited to prevent the aggregation of strain in the InAs/InGaAs/GaAs non-lattice- matched material system. The approach being followed in the DWELL-QDIP research is to embed In- GaAs QDs in GaAs/AlGaAs multi-quantum- well (MQW) structures (see figure). This material system can accommodate a large number of QD layers without excessive lattice-mismatch strain and the associated degradation of photodetection properties. Hence, this material

  2. Plasmonic quantum dot solar concentrator

    NASA Astrophysics Data System (ADS)

    Chandra, S.; Ahmed, H.; Doran, J.; McCormack, S. J.

    2017-02-01

    The quantum dot solar concentrator optical efficiency is undermined by the parameters of re-absorption, scattering, and escape cone losses. These losses can be address through enhancing quantum dot (QDs) absorption and emission. This have been achieved through plasmonic coupling between QDs and gold nanoparticles (Au NPs). The plasmonic composite of various concertation of QDs and Au NPs were studied. The spacing between QDs and Au NPs is controlled through concentration distribution of both QD and Au NPs in the plasmonic composite, and it showed a significant increase in absorption and which is more pronounced for higher spectral overlap of QDs and surface plasmon resonance (SPR) frequency. The optimum plasmonic coupling showed a 17 % increase in the fluorescence emission for QDs in plasmonic composite. The results have shown significant enhancement in absorption, fluorescence emission for the p-QDSC.

  3. Quantitative multiplexed quantum dot immunohistochemistry

    SciTech Connect

    Sweeney, E.; Ward, T.H.; Gray, N.; Womack, C.; Jayson, G.; Hughes, A.; Dive, C.; Byers, R.

    2008-09-19

    Quantum dots are photostable fluorescent semiconductor nanocrystals possessing wide excitation and bright narrow, symmetrical, emission spectra. These characteristics have engendered considerable interest in their application in multiplex immunohistochemistry for biomarker quantification and co-localisation in clinical samples. Robust quantitation allows biomarker validation, and there is growing need for multiplex staining due to limited quantity of clinical samples. Most reported multiplexed quantum dot staining used sequential methods that are laborious and impractical in a high-throughput setting. Problems associated with sequential multiplex staining have been investigated and a method developed using QDs conjugated to biotinylated primary antibodies, enabling simultaneous multiplex staining with three antibodies. CD34, Cytokeratin 18 and cleaved Caspase 3 were triplexed in tonsillar tissue using an 8 h protocol, each localised to separate cellular compartments. This demonstrates utility of the method for biomarker measurement enabling rapid measurement of multiple co-localised biomarkers on single paraffin tissue sections, of importance for clinical trial studies.

  4. Brightness-equalized quantum dots

    PubMed Central

    Lim, Sung Jun; Zahid, Mohammad U.; Le, Phuong; Ma, Liang; Entenberg, David; Harney, Allison S.; Condeelis, John; Smith, Andrew M.

    2015-01-01

    As molecular labels for cells and tissues, fluorescent probes have shaped our understanding of biological structures and processes. However, their capacity for quantitative analysis is limited because photon emission rates from multicolour fluorophores are dissimilar, unstable and often unpredictable, which obscures correlations between measured fluorescence and molecular concentration. Here we introduce a new class of light-emitting quantum dots with tunable and equalized fluorescence brightness across a broad range of colours. The key feature is independent tunability of emission wavelength, extinction coefficient and quantum yield through distinct structural domains in the nanocrystal. Precise tuning eliminates a 100-fold red-to-green brightness mismatch of size-tuned quantum dots at the ensemble and single-particle levels, which substantially improves quantitative imaging accuracy in biological tissue. We anticipate that these materials engineering principles will vastly expand the optical engineering landscape of fluorescent probes, facilitate quantitative multicolour imaging in living tissue and improve colour tuning in light-emitting devices. PMID:26437175

  5. Brightness-equalized quantum dots.

    PubMed

    Lim, Sung Jun; Zahid, Mohammad U; Le, Phuong; Ma, Liang; Entenberg, David; Harney, Allison S; Condeelis, John; Smith, Andrew M

    2015-10-05

    As molecular labels for cells and tissues, fluorescent probes have shaped our understanding of biological structures and processes. However, their capacity for quantitative analysis is limited because photon emission rates from multicolour fluorophores are dissimilar, unstable and often unpredictable, which obscures correlations between measured fluorescence and molecular concentration. Here we introduce a new class of light-emitting quantum dots with tunable and equalized fluorescence brightness across a broad range of colours. The key feature is independent tunability of emission wavelength, extinction coefficient and quantum yield through distinct structural domains in the nanocrystal. Precise tuning eliminates a 100-fold red-to-green brightness mismatch of size-tuned quantum dots at the ensemble and single-particle levels, which substantially improves quantitative imaging accuracy in biological tissue. We anticipate that these materials engineering principles will vastly expand the optical engineering landscape of fluorescent probes, facilitate quantitative multicolour imaging in living tissue and improve colour tuning in light-emitting devices.

  6. Photovoltaic Current in Quantum Dots

    NASA Astrophysics Data System (ADS)

    Switkes, M.; Marcus, C. M.; Campman, K.; Gossard, A. C.

    1998-03-01

    We investigate the DC photovoltaic current, I_pv, due to coherent ``pumping'' in open ( g >= e^2/h ) quantum dots with radio-frequency modulation of the confining potential(B. Spivak, F. Zhou, and M. T. Beal Monod, Phys. Rev. B 51), p. 13226 (1995). I_pv is on the order of 20 pA≈ 10ef for a modulation frequency f = 15 MHz. The photovoltaic current exhibits mesoscopic fluctuations with magnetic field and with the static shape of the confining potential which do not appear to be correlated with fluctuations in the conductance of the dot. The photovoltaic current induced by pumping with two independent shape distortion gates depends on their relative phase; the relationship of this phase to time reversal symmetry is investigated with a view toward defining a generalized Landauer-Büttiker relation.

  7. Electron attachment to Cl 2

    NASA Astrophysics Data System (ADS)

    McCorkle, D. L.; Christodoulides, A. A.; Christophorou, L. G.

    1984-08-01

    The electron attachment rate constant for Cl 2 as a function of the mean electron energy (0.04-0.78 eV) and temperature (213-323 K) has been measured and is reported; it shows a maximum at near thermal energy and is attributed to dissociative electron attachment via the ground state 2Σ u+ of Cl 2- from the ground state 1Σ g+ of Cl 2.

  8. The NH3Cl+ Cation

    DTIC Science & Technology

    2007-11-02

    solutions of NH2Cl can conveniently be prepared by the chlorination of aqueous ammonia with hypochlorite.[13,14] However, the highest practical NH2Cl...at –40 °C, it decomposes continuously and often explosively, due to the formation of ammonium chloride and more highly chlorinated products, such as...existence of NH3Cl + is provided by its vibrational and NMR spectra and theoretical calculations. Experimental Section Caution! Chloramines are highly

  9. Ultralow Noise Monolithic Quantum Dot Photonic Oscillators

    DTIC Science & Technology

    2013-10-28

    laser, the dual-mode quantum dot laser, and the optically- injected quantum dot distributed feedback laser. The key milestones achieved were: 1.) the...distributed feedback device using optical injection to generate microwave, mm- wave and THz signals, and 5.) the generation of relaxation oscillations over...a continuous 5 octaves (below 1 GHz to 40 GHz) in an optically- injected quantum dot laser. UU N/A N/A N/A 100-200 words 15 Shannon Denetchiley (505

  10. Improved Dot Diffusion For Image Halftoning

    DTIC Science & Technology

    1999-01-01

    The dot diffusion method for digital halftoning has the advantage of parallelism unlike the error diffusion method. The method was recently improved...by optimization of the so-called class matrix so that the resulting halftones are comparable to the error diffused halftones . In this paper we will...first review the dot diffusion method. Previously, 82 class matrices were used for dot diffusion method. A problem with this size of class matrix is

  11. Graphane and hydrogenated graphene.

    PubMed

    Pumera, Martin; Wong, Colin Hong An

    2013-07-21

    Graphane, the fully hydrogenated analogue of graphene, and its partially hydrogenated counterparts are attracting increasing attention. We review here its structure and predicted material properties, as well as the current methods of preparation. Graphane and hydrogenated graphenes are far more complex materials than graphene, expected to have a tuneable band gap via the extent of hydrogenation, as well as exhibit ferromagnetism. The methods for hydrogenated graphene characterization are discussed. We show that hydrogenation methods based on low or high pressure gas hydrogenation lead to less hydrogen saturation than wet chemistry methods based on variations of Birch reduction. The special cases of patterning of hydrogenated graphene strips in a graphene lattice are discussed.

  12. Quantum dots in aperiodic order

    NASA Astrophysics Data System (ADS)

    Hörnquist, Michael; Ouchterlony, Thomas

    1998-12-01

    We study numerically with a Green-function technique one-dimensional arrays of quantum dots with two different models. The arrays are ordered according to the Fibonacci, the Thue-Morse, and the Rudin-Shapiro sequences. As a comparison, results from a periodically ordered chain and also from a random chain are included. The focus is on how the conductance (calculated within the Landauer-Büttiker formalism) depends on the Fermi level. In the first model, we find that in some cases rather small systems (≈60 dots) behave in the same manner as very large systems (>16,000 dots) and this makes it possible in these cases to interpret our results for the small systems in terms of the spectral properties of the infinite systems. In particular, we find that it is possible to see some consequences of the singular continuous spectra that some of the systems possess, at least for temperatures up to 100 mK. In the second model, we study the phenomenon ohmic addition, i.e. when the resistances of the constrictions add up to the total resistance. It results that of the systems studied, it is only the Rudin-Shapiro system that has this behaviour for large structures, while the resistances of the Fibonacci and the Thue-Morse systems might reach a limiting value (as a periodic system does).

  13. Few-electron quantum dots

    NASA Astrophysics Data System (ADS)

    Kouwenhoven, L. P.; Austing, D. G.; Tarucha, S.

    2001-06-01

    We review some electron transport experiments on few-electron, vertical quantum dot devices. The measurement of current versus source-drain voltage and gate voltage is used as a spectroscopic tool to investigate the energy characteristics of interacting electrons confined to a small region in a semiconducting material. Three energy scales are distinguished: the single-particle states, which are discrete due to the confinement involved; the direct Coulomb interaction between electron charges on the dot; and the exchange interaction between electrons with parallel spins. To disentangle these energies, a magnetic field is used to reorganize the occupation of electrons over the single-particle states and to induce changes in the spin states. We discuss the interactions between small numbers of electrons (between 1 and 20) using the simplest possible models. Nevertheless, these models consistently describe a large set of experiments. Some of the observations resemble similar phenomena in atomic physics, such as shell structure and periodic table characteristics, Hund's rule, and spin singlet and triplet states. The experimental control, however, is much larger than for atoms: with one device all the artificial elements can be studied by adding electrons to the quantum dot when changing the gate voltage.

  14. A 3-fold-symmetric ligand based on 2-hydroxypyridine: regulation of ligand binding by hydrogen bonding.

    PubMed

    Moore, Cameron M; Quist, David A; Kampf, Jeff W; Szymczak, Nathaniel K

    2014-04-07

    A tripodal ligand based on 2-hydroxypyridine is presented. Cu-Cl adducts of H3thpa with Cu(I) and Cu(II) provide complexes featuring highly directed, intramolecular hydrogen-bonding interactions. An upper limit for the hydrogen-bonding free energy to Cu(I)-Cl was estimated at ∼18 kcal/mol.

  15. Mechanochemical hydrogenation of coal

    DOEpatents

    Yang, Ralph T.; Smol, Robert; Farber, Gerald; Naphtali, Leonard M.

    1981-01-01

    Hydrogenation of coal is improved through the use of a mechanical force to reduce the size of the particulate coal simultaneously with the introduction of gaseous hydrogen, or other hydrogen donor composition. Such hydrogen in the presence of elemental tin during this one-step size reduction-hydrogenation further improves the yield of the liquid hydrocarbon product.

  16. The surface termination effect on the quantum confinement and electron affinities of 3C-SiC quantum dots: a first-principles study.

    PubMed

    Zhang, Zhenkui; Dai, Ying; Yu, Lin; Guo, Meng; Huang, Baibiao; Whangbo, Myung-Hwan

    2012-03-07

    In light of the established differences between the quantum confinement effect and the electron affinities between hydrogen-passivated C and Si quantum dots, we carried out theoretical investigations on SiC quantum dots, with surfaces uniformly terminated by C-H or Si-H bonds, to explore the role of surface terminations on these two aspects. Surprisingly, it was found that the quantum confinement effect is present (or absent) in the highest occupied (or lowest unoccupied) molecular orbital of the SiC quantum dots regardless of their surface terminations. Thus, the quantum confinement effect related to the energy gap observed experimentally (Phys. Rev. Lett., 2005, 94, 026102) is contributed to by the size-dependence of the highest occupied states; the absence of quantum confinement in the lowest unoccupied states is in contrary to the usual belief based on hydrogen-passivated C quantum dots. However, the cause of the absence of the quantum confinement in C nanodots is not transferable to SiC. We propose a model that provides a clear explanation for all findings on the basis of the nearest-neighbor and next-nearest-neighbor interactions between the valence atomic p-orbital in the frontier occupied/unoccupied states. We also found that the electron affinities of the SiC quantum dots, which closely depend on the surface environments, are negative for the C-H termination and positive for the Si-H termination. The prediction of negative electron affinities in SiC quantum dots by simple C-H termination indicates a promising application for these materials in electron-emitter devices. Our model predicts that GeC quantum dots with hydrogen passivation exhibit similar features to SiC quantum dots and our study confirms the crucial role that the surface environment plays in these nanoscale systems.

  17. Observations of Interstellar Hydrogen Fluoride and Hydrogen Chloride in the Galaxy

    NASA Astrophysics Data System (ADS)

    Monje, Raquel R.; Lis, Darek C.; Phillips, Thomas G.; Goldsmith, Paul F.; Emprechtinger, Martin; Neufeld, David A.

    2011-06-01

    We present Herschel/HIFI observations of interstellar hydrogen chloride (HCl) and hydrogen fluoride (HF) along the line-of-sight towards Galactic sources with strong submillimeter continuum emission from the PRISMAS and HEXOS GT KP. The halogen-containing molecules are of special interest because of their unique thermochemistry and their important role as tracers of the neutral ISM. The detection of foreground absorption by HF J = 1--0 transition line in each source probes the distribution of HF throughout the Milky Way, in diffuse clouds with varying values of the visual extinction, as a potential valuable surrogate for molecular hydrogen. For the optically thin absorption components we calculate the column densities of HF. We find that, in many of the background clouds, the abundances of HF with respect to H_2 is consistent with the theoretical prediction that HF is the main reservoir of gas-phase fluorine for these clouds. Observations of hydrogen chloride isotopologues, H35Cl and H37Cl J = 1--0 transition line at different galactocentric distances provide insights of how elemental abundances change with location in the Galaxy. We model the HCl observations with a non-LTE radiative transfer model to derive gas densities and HCl column densities for sources with HCl emission. Interstellar HCl abundances and isotopic ratios [Cl35/Cl37] are essential for improving our understanding of stellar nucleosynthesis and global chemical enrichment and evolution in the Galaxy.

  18. Chlorine isotope fractionation between chloride (Cl-) and dichlorine (Cl2)

    NASA Astrophysics Data System (ADS)

    Giunta, Thomas; Labidi, Jabrane; Eggenkamp, Hans G. M.

    2017-09-01

    The use of chlorine stable isotopes (35Cl and 37Cl) can help to constrain natural processes that involve chlorine species with different oxidation states. Theoretical studies based on thermodynamic and quantum mechanical approaches predict large isotope fractionation during redox reactions but to date, these reactions have not been studied experimentally.

  19. Charge state hysteresis in semiconductor quantum dots

    SciTech Connect

    Yang, C. H.; Rossi, A. Lai, N. S.; Leon, R.; Lim, W. H.; Dzurak, A. S.

    2014-11-03

    Semiconductor quantum dots provide a two-dimensional analogy for real atoms and show promise for the implementation of scalable quantum computers. Here, we investigate the charge configurations in a silicon metal-oxide-semiconductor double quantum dot tunnel coupled to a single reservoir of electrons. By operating the system in the few-electron regime, the stability diagram shows hysteretic tunnelling events that depend on the history of the dots charge occupancy. We present a model which accounts for the observed hysteretic behaviour by extending the established description for transport in double dots coupled to two reservoirs. We demonstrate that this type of device operates like a single-electron memory latch.

  20. Tuning the Emission Energy of Chemically Doped Graphene Quantum Dots

    PubMed Central

    Noor-Ul-Ain; Eriksson, Martin O.; Schmidt, Susann; Asghar, M.; Lin, Pin-Cheng; Holtz, Per Olof; Syväjärvi, Mikael; Yazdi, G. Reza

    2016-01-01

    Tuning the emission energy of graphene quantum dots (GQDs) and understanding the reason of tunability is essential for the GOD function in optoelectronic devices. Besides material-based challenges, the way to realize chemical doping and band gap tuning also pose a serious challenge. In this study, we tuned the emission energy of GQDs by substitutional doping using chlorine, nitrogen, boron, sodium, and potassium dopants in solution form. Photoluminescence data obtained from (Cl- and N-doped) GQDs and (B-, Na-, and K-doped) GQDs, respectively exhibited red- and blue-shift with respect to the photoluminescence of the undoped GQDs. X-ray photoemission spectroscopy (XPS) revealed that oxygen functional groups were attached to GQDs. We qualitatively correlate red-shift of the photoluminescence with the oxygen functional groups using literature references which demonstrates that more oxygen containing groups leads to the formation of more defect states and is the reason of observed red-shift of luminescence in GQDs. Further on, time resolved photoluminescence measurements of Cl- and N-GQDs demonstrated that Cl substitution in GQDs has effective role in radiative transition whereas in N-GQDs leads to photoluminescence (PL) quenching with non-radiative transition to ground state. Presumably oxidation or reduction processes cause a change of effective size and the bandgap. PMID:28335326

  1. Registration of 'Clara CL' Wheat

    USDA-ARS?s Scientific Manuscript database

    ‘Clara CL’ hard white winter wheat (Triticum aestivum L.) was developed at the Agricultural Research Center-Hays, Kansas State University and released by the Kansas Agricultural Experiment Station in 2011. Clara CL carries one Clearfield gene and has the tolerance to imazamox herbicide. Clara CL wa...

  2. NMR and molecular modeling evidence for a Gter dot A mismatch base pair in a purine-rich DNA duplex

    SciTech Connect

    Li, Ying; Wilson, W.D. ); Zon, G. )

    1991-01-01

    {sup 1}H NMR experiments indicate that the oligomer 5{prime}-d(ATGAGCGAATA) forms an unusual 10-base-pair duplex with 4 G{center dot}A base pairs and a 3{prime} unpaired adenosine. NMR results indicate that guanoxine imino protons of the F{center dot}A mismatches are not hydrogen bonded but are stacked in the helix. A G{r arrow} I substitution in either G{center dot}A base pair causes a dramatic decrtease in duplex stability and indicates that hydrogen bonding of the guanosine amino group is critical. Nuclear Overhauser effect spectroscopy (NOESY) and two-dimensional correlated spectroscopy (COSY) results indicate that the overall duplex conformation is in the B-family. Cross-strand NOEs in two-dimensional NOESY spectra between a mismatched AH2 and an AH1{prime} of the other mismatched base pair and between a mismatched GH8 and GNH1 of the other mismatch establish a purine-purine stacking pattern, adenosine over adenosine and guanosine over guanosine, which strongly stabilizes the duplex. A computer graphics molecular model of the ususual duplex was constructed with G{center dot}A base pairs containing A-NH{sub 2} to GN3 and G-NH{sub 2} to AN7 hydrogen bonds and B-form base pairs on both sides of the G{center dot}A pairs (5{prime}-d(ATGAGC)). The energy-minimized duplex satisfies all experimental constraints from NOESY and COSY results. A hydrogen bond from G-NH{sub 2} of the mismatch to a phosphate oxygen is predicted.

  3. Enhanced chemiluminescence of CdTe quantum dots-H2O2 by horseradish peroxidase-mimicking DNAzyme

    NASA Astrophysics Data System (ADS)

    Zhang, Junli; Li, Baoxin

    In this study, it was found that horseradish peroxidase (HRP)-mimicking DNAzyme could effectively enhance the CL emission of CdTe quantum dots (QDs)-H2O2 system, whereas HRP could not enhance the CL intensity. The CL enhancement mechanism was investigated, and the CL enhancement was supposed to originate from the catalysis of HRP-mimicking DNAzyme on the CL reaction between CdTe QDs and H2O2. Meantime, compared with CdTe QDs-H2O2 CL system, H2O2 concentration was markedly decreased in QDs-H2O2-HRP-mimicking DNAzyme CL system, improving the stability of QDs-H2O2 CL system. The QDs-based CL system was used to detect sensitively CdTe QDs and HRP-mimicking DNAzyme (as biologic labels). This work gives a path for enhancing CL efficiency of QDs system, and will be helpful to promote the step of QDs application in various fields such as bioassay and trace detection of analyte.

  4. Hydrogen heat treatment of hydrogen absorbing materials

    NASA Astrophysics Data System (ADS)

    Park, Choong-Nyeon

    2000-12-01

    This study introduces the hydrogen heat treatment of hydrogen absorbing materials and its applicability for practical use. This treatment is somewhat different from normal heat treatment because of the interaction between metal atoms and hydrogen. Since hydrogen can be removed very fast by pumping it out the hydrogen-induced new lattice phase which can not be obtained without hydrogen can be preserved in a meta-stable state. A thermodynamic interpretation of the hydrogen heat treatment established previously was reformulated for graphical and analytical methods and applied to Pd-Pt-H and Pd-Ag-H alloy systems and a fair correlation between the calculation and experimental results was shown. The feasibility of applying the thermodynamic interpretation to intermetallic compounds-hydrogen systems was also discussed.

  5. Hydrogenation of GaSb/GaAs quantum rings

    SciTech Connect

    Hodgson, P. D. Hayne, M.; Zhuang, Q. D.; Ahmad Kamarudin, M.; Birindelli, S.; Capizzi, M.

    2014-08-25

    We present the results of photoluminescence measurements on hydrogenated type-II GaSb/GaAs quantum dot/ring (QD/QR) samples at temperatures ranging from 4.2 K to 400 K. Hydrogenation is found to suppress optically induced charge depletion (associated with the presence of carbon acceptors in this system). A redshift of the QD\\QR emission energy of a few tens of meV is observed at temperatures ≥300 K, consistent with a reduction in average occupancy by ∼1 hole. These effects are accompanied by a reduction in PL intensity post-hydrogenation. We conclude that although hydrogenation may have neutralized the carbon acceptors, multiple hole occupancy of type-II GaSb/GaAs QD/QRs is very likely a precondition for intense emission, which would make extending the wavelength significantly beyond 1300 nm at room temperature difficult.

  6. Hydrogen Permeation Barrier Coatings

    SciTech Connect

    Henager, Charles H.

    2008-01-01

    Gaseous hydrogen, H2, has many physical properties that allow it to move rapidly into and through materials, which causes problems in keeping hydrogen from materials that are sensitive to hydrogen-induced degradation. Hydrogen molecules are the smallest diatomic molecules, with a molecular radius of about 37 x 10-12 m and the hydrogen atom is smaller still. Since it is small and light it is easily transported within materials by diffusion processes. The process of hydrogen entering and transporting through a materials is generally known as permeation and this section reviews the development of hydrogen permeation barriers and barrier coatings for the upcoming hydrogen economy.

  7. Diamond LED substrate and novel quantum dots.

    PubMed

    Sung, James C; Sung, Michael

    2009-02-01

    Nitride LED (e.g., GaN) has become the mainstream of blue light source. The blue light can be converted to white light by exciting a phosphor (e.g., Nichia's YAG or Osram's TAG) with the complementary yellow emission. However, GaN is typically deposited on sapphire (Al2O3) substrates formed by crystal pulling or hexagonal (e.g., 4 H or 6 H) SiC wafers condensed from SiC vapor. In either case, the nitride lattice is ridden (e.g., 10(9)/cm2) with dislocations. The high dislocation density with sapphire is due to the large (>13%) lattice mismatch; and with hexagonal SiC, because of intrinsic defects. Cubic (beta) SiC may be deposited epitaxially using a CVD reactor onto silicon wafer by diffusing the interface and by chemical gradation. A reactive echant (e.g., hydrogen or fluorine) can be introduced periodically to gasify mis-aligned atoms. In this case, large single crystal wafers would be available for the manufacture of high bright LED with superb electro-optical efficiency. The SiC wafer may be coated with diamond film that can eliminate heat in real time. As a result of lower temperature, the nitride LED can be brighter and it will last longer. The blue light of GaN LED formed on SiC on Diamond (SiCON) LED may also be scattered by using novel quantum dots (e.g., 33 atom pairs of CdSe) to form a broad yellow light that blend in with the original blue light to form sunlight-like white light. This would be the ideal source for general illumination (e.g., for indoor) or backlighting (e.g., for LCD).

  8. Single-dot optical emission from ultralow density well-isolated InP quantum dots

    SciTech Connect

    Ugur, A.; Hatami, F.; Masselink, W. T.; Vamivakas, A. N.; Lombez, L.; Atatuere, M.

    2008-10-06

    We demonstrate a straightforward way to obtain single well-isolated quantum dots emitting in the visible part of the spectrum and characterize the optical emission from single quantum dots using this method. Self-assembled InP quantum dots are grown using gas-source molecular-beam epitaxy over a wide range of InP deposition rates, using an ultralow growth rate of about 0.01 atomic monolayers/s, a quantum-dot density of 1 dot/{mu}m{sup 2} is realized. The resulting isolated InP quantum dots embedded in an InGaP matrix are individually characterized without the need for lithographical patterning and masks on the substrate. Such low-density quantum dots show excitonic emission at around 670 nm with a linewidth limited by instrument resolution. This system is applicable as a single-photon source for applications such as quantum cryptography.

  9. Hydrogen embrittlement in nickel-hydrogen cells

    NASA Technical Reports Server (NTRS)

    Gross, Sidney

    1989-01-01

    It was long known that many strong metals can become weakened and brittle as the result of the accumulation of hydrogen within the metal. When the metal is stretched, it does not show normal ductile properties, but fractures prematurely. This problem can occur as the result of a hydrogen evolution reaction such as corrosion or electroplating, or due to hydrogen in the environment at the metal surface. High strength alloys such as steels are especially susceptible to hydrogen embrittlement. Nickel-hydrogen cells commonly use Inconel 718 alloy for the pressure container, and this also is susceptible to hydrogen embrittlement. Metals differ in their susceptibility to embrittlement. Hydrogen embrittlement in nickel-hydrogen cells is analyzed and the reasons why it may or may not occur are discussed. Although Inconel 718 can display hydrogen embrittlement, experience has not identified any problem with nickel-hydrogen cells. No hydrogen embrittlement problem is expected with the 718 alloy pressure container used in nickel-hydrogen cells.

  10. Different intra- and inter­molecular hydrogen-bonding patterns in (3S,4aS,8aS)-2-[(2R,3S)-3-(2,5-X 2-benzamido)-2-(2,5-X 2-benzo­yloxy)-4-phenyl­butyl]-N-tert-butyldeca­hydro­iso­quinoline-3-carboxamides (X = H or Cl): compounds with moderate aspartyl protease inhibition activity

    PubMed Central

    Cunico, Wilson; Ferreira, Maria de Lourdes G.; Wardell, James L.; Harrison, William T. A.

    2017-01-01

    The crystal structures of (3S,4aS,8aS)-2-[(2R,3S)-3-benzamido-2-benzo­yloxy-4-phenyl­but­yl]-N-tert-butyldeca­hydro­iso­quinoline-3-carboxamide, C38H47N3O4, (I), and (3S,4aS,8aS)-2-[(2R,3S)-3-(2,5-di­chloro­benzamido)-2-(2,5-di­chloro­benzo­yloxy)-4-phenyl­but­yl]-N-tert-butyldeca­hydro­iso­quinoline-3-carboxamide, C38H43Cl4N3O4, (II), are described. Despite their chemical similarity, they adopt different conformations in the solid state: (I) features a bifurcated intra­molecular N—H⋯(N,O) hydrogen bond from the tert-butylamide NH group to the piperidine N atom and the benzoate O atom, whereas (II) has an intra­molecular N—H⋯O link from the benzamide NH group to the tert-butyl­amide O atom. In the crystal of (I), mol­ecules are linked by C(4) amide N—H⋯O hydrogen bonds into chains propagating in the [010] direction, with both donor and acceptor parts of the benzamide group. In the extended structure of (II), C(11) N—H⋯O chains propagating in the [010] direction arise, with the donor being the tert-butylamide NH group and the acceptor being the O atom of the benzamide group. PMID:28638658

  11. Synthesis and structure of and DFT-studies on 1,3,5-[P(O)( i-PrO) 2] 3C 6H 3 and its CHCl 3 adduct: analysis of the Cl 3C-H⋯OP hydrogen bond

    NASA Astrophysics Data System (ADS)

    Henn, Markus; Jurkschat, Klaus; Mansfeld, Dirk; Mehring, Michael; Schürmann, Markus

    2004-07-01

    The novel triphosphonic ester 1,3,5-[P(O)( i-PrO) 2] 3C 6H 3 ( 1) was synthesized and fully characterized including single crystal X-ray diffraction analysis. Crystallization in the presence of CHCl 3 gave the corresponding solvate, 1·CHCl 3, which shows moderate C-H⋯OP hydrogen bonding. The hydrogen bond strength in 1·CHCl 3 and the model compound [P(O)( i-PrO) 2]C 6H 5·CHCl 3 ( 2·CHCl 3) were analyzed using RHF, DFT and MP2 methods. The calculated C-H⋯OP hydrogen bond strength is in the range 5-6 kcal mol -1, which is comparable with hydrogen bond strength in the water dimer but higher than in comparable C-H⋯OC aggregates.

  12. Colloidal quantum dots as optoelectronic elements

    NASA Astrophysics Data System (ADS)

    Vasudev, Milana; Yamanaka, Takayuki; Sun, Ke; Li, Yang; Yang, Jianyong; Ramadurai, Dinakar; Stroscio, Michael A.; Dutta, Mitra

    2007-02-01

    Novel optoelectronic systems based on ensembles of semiconductor nanocrystals are addressed in this paper. Colloidal semiconductor quantum dots and related quantum-wire structures have been characterized optically; these optical measurements include those made on self-assembled monolayers of DNA molecules terminated on one end with a common substrate and on the other end with TiO II quantum dots. The electronic properties of these structures are modeled and compared with experiment. The characterization and application of ensembles of colloidal quantum dots with molecular interconnects are considered. The chemically-directed assembly of ensembles of colloidal quantum dots with biomolecular interconnects is demonstrated with quantum dot densities in excess of 10 +17 cm -3. A number of novel photodetectors have been designed based on the combined use of double-barrier quantum-well injectors, colloidal quantum dots, and conductive polymers. Optoelectronic devices including photodetectors and solar cells based on threedimensional ensembles of quantum dots are considered along with underlying phenomena such as miniband formation and the robustness of minibands to displacements of quantum dots in the ensemble.

  13. STED nanoscopy with fluorescent quantum dots

    NASA Astrophysics Data System (ADS)

    Hanne, Janina; Falk, Henning J.; Görlitz, Frederik; Hoyer, Patrick; Engelhardt, Johann; Sahl, Steffen J.; Hell, Stefan W.

    2015-05-01

    The widely popular class of quantum-dot molecular labels could so far not be utilized as standard fluorescent probes in STED (stimulated emission depletion) nanoscopy. This is because broad quantum-dot excitation spectra extend deeply into the spectral bands used for STED, thus compromising the transient fluorescence silencing required for attaining super-resolution. Here we report the discovery that STED nanoscopy of several red-emitting commercially available quantum dots is in fact successfully realized by the increasingly popular 775 nm STED laser light. A resolution of presently ~50 nm is demonstrated for single quantum dots, and sub-diffraction resolution is further shown for imaging of quantum-dot-labelled vimentin filaments in fibroblasts. The high quantum-dot photostability enables repeated STED recordings with >1,000 frames. In addition, we have evidence that the tendency of quantum-dot labels to blink is largely suppressed by combined action of excitation and STED beams. Quantum-dot STED significantly expands the realm of application of STED nanoscopy, and, given the high stability of these probes, holds promise for extended time-lapse imaging.

  14. Optically active quantum-dot molecules.

    PubMed

    Shlykov, Alexander I; Baimuratov, Anvar S; Baranov, Alexander V; Fedorov, Anatoly V; Rukhlenko, Ivan D

    2017-02-20

    Chiral molecules made of coupled achiral semiconductor nanocrystals, also known as quantum dots, show great promise for photonic applications owing to their prospective uses as configurable building blocks for optically active structures, materials, and devices. Here we present a simple model of optically active quantum-dot molecules, in which each of the quantum dots is assigned a dipole moment associated with the fundamental interband transition between the size-quantized states of its confined charge carriers. This model is used to analytically calculate the rotatory strengths of optical transitions occurring upon the excitation of chiral dimers, trimers, and tetramers of general configurations. The rotatory strengths of such quantum-dot molecules are found to exceed the typical rotatory strengths of chiral molecules by five to six orders of magnitude. We also study how the optical activity of quantum-dot molecules shows up in their circular dichroism spectra when the energy gap between the molecular states is much smaller than the states' lifetime, and maximize the strengths of the circular dichroism peaks by optimizing orientations of the quantum dots in the molecules. Our analytical results provide clear design guidelines for quantum-dot molecules and can prove useful in engineering optically active quantum-dot supercrystals and photonic devices.

  15. Thick-shell nanocrystal quantum dots

    SciTech Connect

    Hollingsworth, Jennifer A; Chen, Yongfen; Klimov, Victor I; Htoon, Han; Vela, Javier

    2011-05-03

    Colloidal nanocrystal quantum dots comprising an inner core having an average diameter of at least 1.5 nm and an outer shell, where said outer shell comprises multiple monolayers, wherein at least 30% of the quantum dots have an on-time fraction of 0.80 or greater under continuous excitation conditions for a period of time of at least 10 minutes.

  16. 14 CFR 302.18 - DOT decisionmaker.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 14 Aeronautics and Space 4 2014-01-01 2014-01-01 false DOT decisionmaker. 302.18 Section 302.18 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION PROCEEDINGS) PROCEDURAL... Proceedings § 302.18 DOT decisionmaker. (a) Assistant Secretary for Aviation and International Affairs....

  17. 14 CFR 302.18 - DOT decisionmaker.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false DOT decisionmaker. 302.18 Section 302.18 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION PROCEEDINGS) PROCEDURAL... Proceedings § 302.18 DOT decisionmaker. (a) Assistant Secretary for Aviation and International Affairs....

  18. 14 CFR 302.18 - DOT decisionmaker.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 4 2012-01-01 2012-01-01 false DOT decisionmaker. 302.18 Section 302.18 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION PROCEEDINGS) PROCEDURAL... Proceedings § 302.18 DOT decisionmaker. (a) Assistant Secretary for Aviation and International Affairs....

  19. 14 CFR 302.18 - DOT decisionmaker.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 14 Aeronautics and Space 4 2013-01-01 2013-01-01 false DOT decisionmaker. 302.18 Section 302.18 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION PROCEEDINGS) PROCEDURAL... Proceedings § 302.18 DOT decisionmaker. (a) Assistant Secretary for Aviation and International Affairs....

  20. Research on Self-Assembling Quantum Dots.

    DTIC Science & Technology

    1995-10-30

    0K. in a second phase of this contract we turned our efforts to the fabrication and studies of self assembled quantum dots . We first demonstrated a...method for producing InAs-GasAs self assembled quantum dots (SAD) using MBE. (AN)

  1. STED nanoscopy with fluorescent quantum dots.

    PubMed

    Hanne, Janina; Falk, Henning J; Görlitz, Frederik; Hoyer, Patrick; Engelhardt, Johann; Sahl, Steffen J; Hell, Stefan W

    2015-05-18

    The widely popular class of quantum-dot molecular labels could so far not be utilized as standard fluorescent probes in STED (stimulated emission depletion) nanoscopy. This is because broad quantum-dot excitation spectra extend deeply into the spectral bands used for STED, thus compromising the transient fluorescence silencing required for attaining super-resolution. Here we report the discovery that STED nanoscopy of several red-emitting commercially available quantum dots is in fact successfully realized by the increasingly popular 775 nm STED laser light. A resolution of presently ∼ 50 nm is demonstrated for single quantum dots, and sub-diffraction resolution is further shown for imaging of quantum-dot-labelled vimentin filaments in fibroblasts. The high quantum-dot photostability enables repeated STED recordings with >1,000 frames. In addition, we have evidence that the tendency of quantum-dot labels to blink is largely suppressed by combined action of excitation and STED beams. Quantum-dot STED significantly expands the realm of application of STED nanoscopy, and, given the high stability of these probes, holds promise for extended time-lapse imaging.

  2. Rapid DOTS expansion in India.

    PubMed Central

    Khatri, G. R.; Frieden, Thomas R.

    2002-01-01

    Since late 1998 the coverage of the DOTS strategy in India has been expanded rapidly. In both 2000 and 2001 the country probably accounted for more than half the global increase in the number of patients treated under DOTS and by early 2002 more than a million patients were being treated in this way in India. As a result, nearly 200 000 lives were saved. The lessons learnt relate to the importance of the following elements of the programme: (1) getting the science right and ensuring technical excellence; (2) building commitment and ensuring the provision of funds and flexibility in their utilization; (3) maintaining focus and priorities; (4) systematically appraising each area before starting service delivery; (5) ensuring an uninterrupted drug supply; (6) strengthening the established infrastructure and providing support for staff; (7) supporting the infrastructure required in urban areas; (8) ensuring full-time independent technical support and supervision, particularly during the initial phases of implementation; (9) monitoring intensively and giving timely feedback; and (10) continuous supervision. Tuberculosis (TB) control still faces major challenges in India. To reach its potential, the control programme needs to: continue to expand so as to cover the remaining half of the country, much of which has a weaker health infrastructure than the areas already covered; increase its reach in the areas already covered so that a greater proportion of patients is treated; ensure sustainability; improve the patient-friendliness of services; confront TB associated with human immunodeficiency virus (HIV) infection. It is expected that HIV will increase the number of TB cases by at least 10% and by a considerably higher percentage if HIV becomes much more widespread. India's experience shows that DOTS can achieve high case-detection and cure rates even with imperfect technology and often with an inadequate public health infrastructure. However, this can only happen if the

  3. Smart Utilization of Carbon Dots in Semiconductor Photocatalysis.

    PubMed

    Yu, Huijun; Shi, Run; Zhao, Yufei; Waterhouse, Geoffrey I N; Wu, Li-Zhu; Tung, Chen-Ho; Zhang, Tierui

    2016-11-01

    Efficient capture of solar energy will be critical to meeting the energy needs of the future. Semiconductor photocatalysis is expected to make an important contribution in this regard, delivering both energy carriers (especially H2 ) and valuable chemical feedstocks under direct sunlight. Over the past few years, carbon dots (CDs) have emerged as a promising new class of metal-free photocatalyst, displaying semiconductor-like photoelectric properties and showing excellent performance in a wide variety of photoelectrochemical and photocatalytic applications owing to their ease of synthesis, unique structure, adjustable composition, ease of surface functionalization, outstanding electron-transfer efficiency and tunable light-harvesting range (from deep UV to the near-infrared). Here, recent advances in the rational design of CDs-based photocatalysts are highlighted and their applications in photocatalytic environmental remediation, water splitting into hydrogen, CO2 reduction, and organic synthesis are discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Noble metal catalyzed hydrogen generation from formic acid in nitrite-containing simulated nuclear waste media

    SciTech Connect

    King, R.B.; Bhattacharyya, N.K.; Wiemers, K.D.

    1994-08-01

    Simulants for the Hanford Waste Vitrification Plant (HWVP) feed containing the major non-radioactive components Al, Cd, Fe, Mn, Nd, Ni, Si, Zr, Na, CO{sub 3}{sup 2{minus}}, NO{sub 3}-, and NO{sub 2}- were used as media to evaluate the stability of formic acid towards hydrogen evolution by the reaction HCO{sub 2}H {yields} H{sub 2} + CO{sub 2} catalyzed by the noble metals Ru, Rh, and/or Pd found in significant quantities in uranium fission products. Small scale experiments using 40-50 mL of feed simulant in closed glass reactors (250-550 mL total volume) at 80-100{degree}C were used to study the effect of nitrite and nitrate ion on the catalytic activities of the noble metals for formic acid decomposition. Reactions were monitored using gas chromatography to analyze the CO{sub 2}, H{sub 2}, NO, and N{sub 2}O in the gas phase as a function of time. Rhodium, which was introduced as soluble RhCl{sub 3}{center_dot}3H{sub 2}O, was found to be the most active catalyst for hydrogen generation from formic acid above {approx}80{degree}C in the presence of nitrite ion in accord with earlier observations. The inherent homogeneous nature of the nitrite-promoted Rh-catalyzed formic acid decomposition is suggested by the approximate pseudo first-order dependence of the hydrogen production rate on Rh concentration. Titration of the typical feed simulants containing carbonate and nitrite with formic acid in the presence of rhodium at the reaction temperature ({approx}90{degree}C) indicates that the nitrite-promoted Rh-catalyzed decomposition of formic acid occurs only after formic acid has reacted with all of the carbonate and nitrite present to form CO{sub 2} and NO/N{sub 2}O, respectively. The catalytic activities of Ru and Pd towards hydrogen generation from formic acid are quite different than those of Rh in that they are inhibited rather than promoted by the presence of nitrite ion.

  5. Analytical investigation of AlCl[3]/SO[2]Cl[2] catholyte materials for secondary fuze reserve batteries.

    SciTech Connect

    Butler, Paul Charles; Rodriguez, Mark Andrew; Segall, Judith M.; Malizia, Louis A., Jr.; Cherry, Brian Ray; Andrews, Nicholas L.; Clark, Nancy H.; Alam, Todd Michael; Ingersoll, David T.; Tallant, David Robert; Simpson, Regina Lynn; Boyle, Timothy J.; Garcia, Manuel Joseph

    2004-05-01

    Exploration of the fundamental chemical behavior of the AlCl{sub 3}/SO{sub 2}Cl{sub 2} catholyte system for the ARDEC Self-Destruct Fuze Reserve Battery Project under accelerated aging conditions was completed using a variety of analytical tools. Four different molecular species were identified in this solution, three of which are major. The relative concentrations of the molecular species formed were found to depend on aging time, initial concentrations, and storage temperature, with each variable affecting the kinetics and thermodynamics of this complex reaction system. We also evaluated the effect of water on the system, and determined that it does not play a role in dictating the observed molecular species present in solution. The first Al-containing species formed was identified as the dimer [Al({mu}-Cl)Cl{sub 2}]{sub 2}, and was found to be in equilibrium with the monomer, AlCl{sub 3}. The second species formed in the reaction scheme was identified by single crystal X-ray diffraction studies as [Cl{sub 2}Al({mu}-O{sub 2}SCl)]{sub 2} (I), a scrambled AlCl{sub 3}{center_dot}SO{sub 2} adduct. The SO{sub 2}(g) present, as well as CL{sub 2}(g), was formed through decomposition of SO{sub 2}CL{sub 2}. The SO{sub 2}(g) generated was readily consumed by AlCl{sub 3} to form the adduct 1 which was experimentally verified when 1 was also isolated from the reaction of SO{sub 2}(g) and AlCl {sub 3}. The third species found was tentatively identified as a compound having the general formula {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2}]{r_brace}{sub n}. This was based on {sup 27}Al NMR data that revealed a species with tetrahedrally coordinated Al metal centers with increased oxygen coordination and the fact that the precipitate, or gel, that forms over time was shown by Raman spectroscopic studies to possess a component that is consistent with SOCl{sub 2}. The precursor to the precipitate should have similar constituents, thus the assignment of {l_brace}[Al(O)Cl{sub 2}][OSCl{sub 2

  6. Quantum-dot supercrystals for future nanophotonics

    PubMed Central

    Baimuratov, Anvar S.; Rukhlenko, Ivan D.; Turkov, Vadim K.; Baranov, Alexander V.; Fedorov, Anatoly V.

    2013-01-01

    The study of supercrystals made of periodically arranged semiconductor quantum dots is essential for the advancement of emerging nanophotonics technologies. By combining the strong spatial confinement of elementary excitations inside quantum dots and exceptional design flexibility, quantum-dot supercrystals provide broad opportunities for engineering desired optical responses and developing superior light manipulation techniques on the nanoscale. Here we suggest tailoring the energy spectrum and wave functions of the supercrystals' collective excitations through the variation of different structural and material parameters. In particular, by calculating the excitonic spectra of quantum dots assembled in two-dimensional Bravais lattices we demonstrate a wide variety of spectrum transformation scenarios upon alterations in the quantum dot arrangement. This feature offers unprecedented control over the supercrystal's electromagnetic properties and enables the development of new nanophotonics materials and devices.

  7. Biocompatible Quantum Dots for Biological Applications

    PubMed Central

    Rosenthal, Sandra J.; Chang, Jerry C.; Kovtun, Oleg; McBride, James R.; Tomlinson, Ian D.

    2011-01-01

    Semiconductor quantum dots are quickly becoming a critical diagnostic tool for discerning cellular function at the molecular level. Their high brightness, long-lasting, sizetunable, and narrow luminescence set them apart from conventional fluorescence dyes. Quantum dots are being developed for a variety of biologically oriented applications, including fluorescent assays for drug discovery, disease detection, single protein tracking, and intracellular reporting. This review introduces the science behind quantum dots and describes how they are made biologically compatible. Several applications are also included, illustrating strategies toward target specificity, and are followed by a discussion on the limitations of quantum dot approaches. The article is concluded with a look at the future direction of quantum dots. PMID:21276935

  8. Biocompatible Quantum Dots for Biological Applications

    SciTech Connect

    Rosenthal, Sandra; Chang, Jerry; Kovtun, Oleg; McBride, James; Tomlinson, Ian

    2011-01-01

    Semiconductor quantum dots are quickly becoming a critical diagnostic tool for discerning cellular function at the molecular level. Their high brightness, long-lasting, size-tunable, and narrow luminescence set them apart from conventional fluorescence dyes. Quantum dots are being developed for a variety of biologically oriented applications, including fluorescent assays for drug discovery, disease detection, single protein tracking, and intracellular reporting. This review introduces the science behind quantum dots and describes how they are made biologically compatible. Several applications are also included, illustrating strategies toward target specificity, and are followed by a discussion on the limitations of quantum dot approaches. The article is concluded with a look at the future direction of quantum dots.

  9. Optophononics with Coupled Quantum Dots

    DTIC Science & Technology

    2014-02-18

    the molecular polaron can be used as an efficient and tunable coherent coupler for quantum states in spatially separated low-dimensional structures...cold finger of a closed cycle microscopy cryostat and kept at a temperature of 20K. A tunable diode laser with a tuning range from about 900 to 1,000...et al. Tunable exciton relaxation in vertically coupled semiconductor InAs quantum dots. Phys. Rev. B 84, 081404(R) (2011). 10 100 1,000 0 5 A m pl ifi

  10. Semiconductor double quantum dot micromaser.

    PubMed

    Liu, Y-Y; Stehlik, J; Eichler, C; Gullans, M J; Taylor, J M; Petta, J R

    2015-01-16

    The coherent generation of light, from masers to lasers, relies upon the specific structure of the individual emitters that lead to gain. Devices operating as lasers in the few-emitter limit provide opportunities for understanding quantum coherent phenomena, from terahertz sources to quantum communication. Here we demonstrate a maser that is driven by single-electron tunneling events. Semiconductor double quantum dots (DQDs) serve as a gain medium and are placed inside a high-quality factor microwave cavity. We verify maser action by comparing the statistics of the emitted microwave field above and below the maser threshold. Copyright © 2015, American Association for the Advancement of Science.

  11. Hydrogen supply system

    SciTech Connect

    Teitel, R.J.

    1981-11-24

    A system for supplying hydrogen to an apparatus which utilizes hydrogen contains a metal hydride hydrogen supply component and a microcavity hydrogen storage hydrogen supply component which in tandem supply hydrogen for the apparatus. The metal hydride hydrogen supply component includes a first storage tank filled with a composition which is capable of forming a metal hydride of such a nature that the hydride will release hydrogen when heated but will absorb hydrogen when cooled. This first storage tank is equipped with a heat exchanger for both adding heat to and extracting heat from the composition to regulate the absorption/deabsorption of hydrogen from the composition. The microcavity hydrogen storage hydrogen supply component includes a second tank containing the microcavity hydrogen supply. The microcavity hydrogen storage contains hydrogen held under high pressure within individual microcavities. The hydrogen is released from the microcavities by heating the cavities. This heating is accomplished by including within the tank for the microcavity hydrogen storage a heating element.

  12. Hydrogen sulphide.

    PubMed

    Guidotti, T L

    1996-10-01

    Hydrogen sulphide (H2S) is the primary chemical hazard in natural gas production in 'sour' gas fields. It is also a hazard in sewage treatment and manure-containment operations, construction in wetlands, pelt processing, certain types of pulp and paper production, and any situation in which organic material decays or inorganic sulphides exist under reducing conditions. H2S dissociates into free sulphide in the circulation. Sulphide binds to many macromolecules, among them cytochrome oxidase. Although this is undoubtedly an important mechanism of toxicity due to H2S, there may be others H2S provides little opportunity for escape at high concentrations because of the olfactory paralysis it causes, the steep exposure-response relationships, and the characteristically sudden loss of consciousness it can cause which is colloquially termed 'knockdown.' Other effects may include mucosal irritation, which is associated at lower concentrations with a keratoconjunctivitis called 'gas eye' and at higher concentrations with risk of pulmonary oedema. Chronic central nervous system sequelae may possibly follow repeated knockdowns: this is controversial and the primary effects of H2S may be confounded by anoxia or head trauma. Treatment is currently empirical, with a combination of nitrite and hyperbaric oxygen preferred. The treatment regimen is not ideal and carries some risk.

  13. Blood Compatibility Evaluations of Fluorescent Carbon Dots.

    PubMed

    Li, Sha; Guo, Zhong; Zhang, Yi; Xue, Wei; Liu, Zonghua

    2015-09-02

    Because of their unique advantages, fluorescent carbon dots are gaining popularity in various biomedical applications. For these applications, good biosafety is a prerequisite for their use in vivo. Studies have reported the preliminary biocompatibility evaluations of fluorescent carbon dots (mainly cytotoxicity); however, to date, little information is available about their hemocompatibility, which could impede their development from laboratory to bedside. In this work, we evaluated the hemocompatibility of fluorescent carbon dots, which we prepared by hydrothermal carbonization of α-cyclodextrin. The effects of the carbon dots on the structure and function of key blood components were investigated at cellular and molecular levels. In particular, we considered the morphology and lysis of human red blood cells, the structure and conformation of the plasma protein fibrinogen, the complement activation, platelet activation, and in vitro and in vivo blood coagulation. We found that the carbon dots have obvious concentration-dependent effects on the blood components. Overall, concentrations of the fluorescent carbon dots at ≤0.1 mg/mL had few adverse effects on the blood components, but at higher doses, the carbon dots impair the structure and function of the blood components, causing morphological disruptions and lysis of red blood cells, interference in the local microenvironments of fibrinogen, activation of the complement system, and disturbances in the plasma and whole blood coagulation function in vitro. However, the carbon dots tend to activate platelets only at low concentrations. Intravenous administration of the carbon dots at doses up to 50 mg/kg did not impair the blood coagulation function. These results provide valuable information for the clinical application of fluorescent carbon dots.

  14. Photophysical properties gallium octacarboxy phthalocyanines conjugated to CdSe@ZnS quantum dots.

    PubMed

    Tshangana, Charmaine; Nyokong, Tebello

    2015-01-01

    L-Glutathione (GSH) capped core CdSe (2.3 nm) and core shell CdSe@ZnS quantum dots (QDs) (3.0 nm and 3.5 nm) were coordinated to gallium octacarboxy phthalocyanine (ClGaPc(COOH)8) to form ClGaPc(COOH)8-QDs conjugates. An efficient transfer of energy from the QDs to the Pcs was demonstrated through Förster resonance energy transfer (FRET), the FRET efficiencies in all cases was above 50%. The photophysical parameters (triplet state and fluorescence quantum yields and lifetimes) were also determined for the conjugates. There was a decrease in the fluorescence lifetimes of ClGaPc(COOH)8 in the presence of all the QDs, due to the heavy atom effect. The triplet quantum yields increased in the conjugates. The lifetimes also became longer for the conjugates compared to Pc alone.

  15. Porous palladium coated conducting polymer nanoparticles for ultrasensitive hydrogen sensors.

    PubMed

    Lee, Jun Seop; Kim, Sung Gun; Cho, Sunghun; Jang, Jyongsik

    2015-12-28

    Hydrogen, a clean-burning fuel, is of key importance to various industrial applications, including fuel cells and in the aerospace and automotive industries. However, hydrogen gas is odorless, colorless, and highly flammable; thus appropriate safety protocol implementation and monitoring are essential. Highly sensitive hydrogen leak detection and surveillance sensor systems are needed; additionally, the ability to maintain uniformity through repetitive hydrogen sensing is becoming increasingly important. In this report, we detail the fabrication of porous palladium coated conducting polymer (3-carboxylate polypyrrole) nanoparticles (Pd@CPPys) to detect hydrogen gas. The Pd@CPPys are produced by means of facile alkyl functionalization and chemical reduction of a pristine 3-carboxylate polypyrrole nanoparticle-contained palladium precursor (PdCl(2)) solution. The resulting Pd@CPPy-based sensor electrode exhibits ultrahigh sensitivity (0.1 ppm) and stability toward hydrogen gas at room temperature due to the palladium sensing layer.

  16. Carbon-dot-decorated TiO2 nanotube arrays used for photo/voltage-induced organic pollutant degradation and the inactivation of bacteria

    NASA Astrophysics Data System (ADS)

    Feng, Lingyan; Sun, Hanjun; Ren, Jinsong; Qu, Xiaogang

    2016-03-01

    Photoluminescent carbon dots (c-dots) have recently attracted growing interest as a new member of the carbon-nanomaterial family. Here, we report for the first time that c-dot-decorated TiO2 nanotube arrays (c-dot/TiNTs) exhibit highly enhanced abilities regarding photo/voltage-induced organic pollutant degradation and bacterial inactivation. By applying UV irradiation (365 nm) or an electrochemical potential over 3 V (versus Ag/AgCl), an organic dye and a herbicide were efficiently degraded. Moreover, the inactivation of Gram-positive S. aureus and Gram-negative E. coli bacteria was realized on a c-dot/TiNT film. The c-dots were able to absorb light efficiently resulting in multiple exciton generation and also a reduction in the recombination of the e-/h+ pair produced in c-dot/TiNT film during photo/voltage-induced degradation. It was also possible to readily regenerate the surface using ultraviolet light irradiation, leaving the whole film structure undamaged and with high reproducibility and stability.

  17. Carbon-dot-decorated TiO₂ nanotube arrays used for photo/voltage-induced organic pollutant degradation and the inactivation of bacteria.

    PubMed

    Feng, Lingyan; Sun, Hanjun; Ren, Jinsong; Qu, Xiaogang

    2016-03-18

    Photoluminescent carbon dots (c-dots) have recently attracted growing interest as a new member of the carbon-nanomaterial family. Here, we report for the first time that c-dot-decorated TiO2 nanotube arrays (c-dot/TiNTs) exhibit highly enhanced abilities regarding photo/voltage-induced organic pollutant degradation and bacterial inactivation. By applying UV irradiation (365 nm) or an electrochemical potential over 3 V (versus Ag/AgCl), an organic dye and a herbicide were efficiently degraded. Moreover, the inactivation of Gram-positive S. aureus and Gram-negative E. coli bacteria was realized on a c-dot/TiNT film. The c-dots were able to absorb light efficiently resulting in multiple exciton generation and also a reduction in the recombination of the e(-)/h(+) pair produced in c-dot/TiNT film during photo/voltage-induced degradation. It was also possible to readily regenerate the surface using ultraviolet light irradiation, leaving the whole film structure undamaged and with high reproducibility and stability.

  18. Energies and wave functions of an off-centre donor in hemispherical quantum dot: Two-dimensional finite difference approach and ritz variational principle

    NASA Astrophysics Data System (ADS)

    Nakra Mohajer, Soukaina; El Harouny, El Hassan; Ibral, Asmaa; El Khamkhami, Jamal; Assaid, El Mahdi

    2016-09-01

    Eigenvalues equation solutions of a hydrogen-like donor impurity, confined in a hemispherical quantum dot deposited on a wetting layer and capped by an insulating matrix, are determined in the framework of the effective mass approximation. Conduction band alignments at interfaces between quantum dot and surrounding materials are described by infinite height barriers. Ground and excited states energies and wave functions are determined analytically and via one-dimensional finite difference approach in case of an on-center donor. Donor impurity is then moved from center to pole of hemispherical quantum dot and eigenvalues equation is solved via Ritz variational principle, using a trial wave function where Coulomb attraction between electron and ionized donor is taken into account, and by two-dimensional finite difference approach. Numerical codes developed enable access to variations of donor total energy, binding energy, Coulomb correlation parameter, spatial extension and radial probability density with respect to hemisphere radius and impurity position inside the quantum dot.

  19. Biodetection using fluorescent quantum dots

    NASA Astrophysics Data System (ADS)

    Speckman, Donna M.; Jennings, Travis L.; LaLumondiere, Steven D.; Klimcak, Charles M.; Moss, Steven C.; Loper, Gary L.; Beck, Steven M.

    2002-07-01

    Multi-pathogen biosensors that take advantage of sandwich immunoassay detection schemes and utilize conventional fluorescent dye reporter molecules are difficult to make into extremely compact and autonomous packages. The development of a multi-pathogen, immunoassay-based, fiber optic detector that utilizes varying sized fluorescent semiconductor quantum dots (QDs) as the reporter labels has the potential to overcome these problems. In order to develop such a quantum dot-based biosensor, it is essential to demonstrate that QDs can be attached to antibody proteins, such that the specificity of the antibody is maintained. We have been involved in efforts to develop a reproducible method for attaching QDs to antibodies for use in biodetection applications. We have synthesized CdSe/ZnS core-shell QDs of differing size, functionalized their surfaces with several types of organic groups for water solubility, and covalently attached these functionalized QDs to rabbit anti-ovalbumin antibody protein. We also demonstrated that these labeled antibodies exhibit selective binding to ovalbumin antigen. We characterized the QDs at each step in the overall synthesis by UV-VIS absorption spectroscopy and by picosecond (psec) transient photoluminescence (TPL) spectroscopy. TPL spectroscopy measurements indicate that QD lifetime depends on the size of the QD, the intensity of the optical excitation source, and whether or not they are functionalized and conjugated to antibodies. We describe details of these experiments and discuss the impact of our results on our biosensor development program.

  20. Chiral quantum dot based materials

    NASA Astrophysics Data System (ADS)

    Govan, Joseph; Loudon, Alexander; Baranov, Alexander V.; Fedorov, Anatoly V.; Gun'ko, Yurii

    2014-05-01

    Recently, the use of stereospecific chiral stabilising molecules has also opened another avenue of interest in the area of quantum dot (QD) research. The main goal of our research is to develop new types of technologically important quantum dot materials containing chiral defects, study their properties and explore their applications. The utilisation of chiral penicillamine stabilisers allowed the preparation of new water soluble white emitting CdS quantum nanostructures which demonstrated circular dichroism in the band-edge region of the spectrum. It was also demonstrated that all three types of QDs (D-, L-, and Rac penicillamine stabilised) show very broad emission bands between 400 and 700 nm due to defects or trap states on the surfaces of the nanocrystals. In this work the chiral CdS based quantum nanostructures have also been doped by copper metal ions and new chiral penicilamine stabilized CuS nanoparticles have been prepared and investigated. It was found that copper doping had a strong effect at low levels in the synthesis of chiral CdS nanostructures. We expect that this research will open new horizons in the chemistry of chiral nanomaterials and their application in biotechnology, sensing and asymmetric synthesis.

  1. Composition for absorbing hydrogen

    DOEpatents

    Heung, L.K.; Wicks, G.G.; Enz, G.L.

    1995-05-02

    A hydrogen absorbing composition is described. The composition comprises a porous glass matrix, made by a sol-gel process, having a hydrogen-absorbing material dispersed throughout the matrix. A sol, made from tetraethyl orthosilicate, is mixed with a hydrogen-absorbing material and solidified to form a porous glass matrix with the hydrogen-absorbing material dispersed uniformly throughout the matrix. The glass matrix has pores large enough to allow gases having hydrogen to pass through the matrix, yet small enough to hold the particles dispersed within the matrix so that the hydrogen-absorbing particles are not released during repeated hydrogen absorption/desorption cycles.

  2. Composition for absorbing hydrogen

    DOEpatents

    Heung, Leung K.; Wicks, George G.; Enz, Glenn L.

    1995-01-01

    A hydrogen absorbing composition. The composition comprises a porous glass matrix, made by a sol-gel process, having a hydrogen-absorbing material dispersed throughout the matrix. A sol, made from tetraethyl orthosilicate, is mixed with a hydrogen-absorbing material and solidified to form a porous glass matrix with the hydrogen-absorbing material dispersed uniformly throughout the matrix. The glass matrix has pores large enough to allow gases having hydrogen to pass through the matrix, yet small enough to hold the particles dispersed within the matrix so that the hydrogen-absorbing particles are not released during repeated hydrogen absorption/desorption cycles.

  3. Hydrogen production by Rhodopseudomonas palustris WP 3-5 in a serial photobioreactor fed with hydrogen fermentation effluent.

    PubMed

    Lee, Chi-Mei; Hung, Guo-Jan; Yang, Chu-Fang

    2011-09-01

    In this study, a lab-scale serial photobioreactor composed of three column reactors was constructed and continuously operated to investigate several parameters influencing photohydrogen production when using the synthetic wastewater and the anaerobic hydrogen fermentation effluents as the influents. The results indicated that better hydrogen production rate was obtained when the serial photobioreactor was operated under cellular recycling at a short HRT of 8h. The serial photobioreactor maintained high hydrogen content ca. 80% in the produced gas and 0.4× dilution ratio was the suitable ratio for hydrogen production. When the photobioreactor fed with the real wastewater (Effluent 1) containing 100 mg/L NH4Cl, Column 1 reactor successfully reduced ammonia concentration to about 60 mg/L for cell synthesis, resulting in a steady hydrogen production in the following two column reactors. The average hydrogen production rate was 205 mL-H2/L/d.

  4. NQR application to the study of hydrogen dynamics in hydrogen-bonded molecular dimers

    NASA Astrophysics Data System (ADS)

    Asaji, Tetsuo

    2016-12-01

    The temperature dependences of 1H NMR as well as 35Cl NQR spin-lattice relaxation times T 1 were investigated in order to study the hydrogen transfer dynamics in carboxylic acid dimers in 3,5-dichloro- and 2,6-dichlorobenzoic acids. The asymmetry energy A/ k B and the activation energy V/ k B for the hydrogen transfer were estimated to be 240 K and 900 K, and 840 K and 2500 K, respectively, for these compounds. In spite of a large asymmetric potential the quantum nature of hydrogen transfer is recognized in the slope of the temperature dependence of T 1 on the low-temperature side of the T 1 minimum. The NQR T 1 measurements was revealed to be a good probe for the hydrogen transfer dynamics.

  5. Thermochemical cycles for the production of hydrogen

    DOEpatents

    Steinberg, M.; Dang, V.D.

    Two-step processes for the preparation of hydrogen are described: CrCl/sub 3/(g) ..-->.. CrCl/sub 2/(g) + 1/2Cl/sub 2/(g) and CrCl/sub 2/(s) + HCl(g) reversible CrCl/sub 3/(s) + 1/2H/sub 2/(g); UCl/sub 4/(g) ..-->.. UCl/sub 3/(g) + 1/2Cl/sub 2/(g) and UCl/sub 3/(s) + HCl(g) ..-->.. UCl/sub 4/(s) + 1/2H/sub 2/(g); and CaSO/sub 4/(s) ..-->.. CaO(s) + SO/sub 2/(g) + 1/2O/sub 2/(g) and CaO(s) + SO/sub 2/(g) + H/sub 2/O(l) ..-->.. CaSO/sub 4/(s) + H/sub 2/(g). The high temperature available from solar collectors, high temperature gas reactors or fusion reactors is utilized in the first step in which the reaction is endothermic. The efficiency is at least 60% and with process heat recovery, the efficiency may be increased up to 74.4%. An apparatus fr carrying out the process in conjunction with a fusion reactor, is described.

  6. Hydrogen bonding in 1-butyl- and 1-ethyl-3-methylimidazolium chloride ionic liquids.

    PubMed

    Skarmoutsos, Ioannis; Dellis, Dimitris; Matthews, Richard P; Welton, Tom; Hunt, Patricia A

    2012-04-26

    A detailed investigation of hydrogen bonding in the pure ionic liquids [C4C1im]Cl and [C2C1im]Cl has been carried out using primarily molecular dynamics techniques. Analyses of the individual atom-atom pair radial distribution functions, and in particular those for C···Cl(-), have revealed that hydrogen bonding to the first methylene or methyl units of the substituent groups is important. Multiple geometric criteria for defining a hydrogen bond have been applied, and in particular the choice of the cutoff angle has been carefully examined. The interpretation of hydrogen bonding within these ionic liquids is highly angle dependent, and justification is provided for why it may be appropriate to employ a wider angle criteria than the 30° used for water or alcohol systems. The different types of hydrogen bond formed are characterized, and "top" conformations where the Cl anion resides above (or below) the imidazolium ring are investigated. The number of hydrogen bonds undertaken by each hydrogen atom (and the chloride anion) is quantified, and the propensity to form zero, one, or two hydrogen bonds is established. The effects of an increase in temperature on the static hydrogen bonding are also briefly examined.

  7. Quantum dots with single-atom precision.

    PubMed

    Fölsch, Stefan; Martínez-Blanco, Jesús; Yang, Jianshu; Kanisawa, Kiyoshi; Erwin, Steven C

    2014-07-01

    Quantum dots are often called artificial atoms because, like real atoms, they confine electrons to quantized states with discrete energies. However, although real atoms are identical, most quantum dots comprise hundreds or thousands of atoms, with inevitable variations in size and shape and, consequently, unavoidable variability in their wavefunctions and energies. Electrostatic gates can be used to mitigate these variations by adjusting the electron energy levels, but the more ambitious goal of creating quantum dots with intrinsically digital fidelity by eliminating statistical variations in their size, shape and arrangement remains elusive. We used a scanning tunnelling microscope to create quantum dots with identical, deterministic sizes. By using the lattice of a reconstructed semiconductor surface to fix the position of each atom, we controlled the shape and location of the dots with effectively zero error. This allowed us to construct quantum dot molecules whose coupling has no intrinsic variation but could nonetheless be tuned with arbitrary precision over a wide range. Digital fidelity opens the door to quantum dot architectures free of intrinsic broadening-an important goal for technologies from nanophotonics to quantum information processing as well as for fundamental studies of confined electrons.

  8. Metamorphic quantum dots: Quite different nanostructures

    SciTech Connect

    Seravalli, L.; Frigeri, P.; Nasi, L.; Trevisi, G.; Bocchi, C.

    2010-09-15

    In this work, we present a study of InAs quantum dots deposited on InGaAs metamorphic buffers by molecular beam epitaxy. By comparing morphological, structural, and optical properties of such nanostructures with those of InAs/GaAs quantum dot ones, we were able to evidence characteristics that are typical of metamorphic InAs/InGaAs structures. The more relevant are: the cross-hatched InGaAs surface overgrown by dots, the change in critical coverages for island nucleation and ripening, the nucleation of new defects in the capping layers, and the redshift in the emission energy. The discussion on experimental results allowed us to conclude that metamorphic InAs/InGaAs quantum dots are rather different nanostructures, where attention must be put to some issues not present in InAs/GaAs structures, namely, buffer-related defects, surface morphology, different dislocation mobility, and stacking fault energies. On the other hand, we show that metamorphic quantum dot nanostructures can provide new possibilities of tailoring various properties, such as dot positioning and emission energy, that could be very useful for innovative dot-based devices.

  9. Determination of hyperin in seed of Cuscuta chinensis Lam. by enhanced chemiluminescence of CdTe quantum dots on calcein/K3Fe(CN)6 system.

    PubMed

    Kang, Jing; Li, Xuwen; Geng, Jiayang; Han, Lu; Tang, Jieli; Jin, Yongri; Zhang, Yihua

    2012-10-15

    In this paper, 3-mercaptocarboxylic acid (MPA) modified CdTe quantum dots (QDs) were used as sensitizers, to enhance the chemiluminescence (CL) of the calcein/K(3)Fe(CN)(6) system. A new CL system of CdTe/calcein/K(3)Fe(CN)(6) was developed. The effects of reactant concentrations and the particle sizes of CdTe QDs on the CL emission were investigated in detail. The possible enhancement mechanism of the CL was also further investigated based on the photoluminescence (PL) and CL spectra. Polyphenols such as chlorogenic acid, quercetin, hyperin, catechin and kaempferol, were observed to inhibit the CL signal of the CdTe/calcein/K(3)Fe(CN)(6) system and determined by the proposed method. The proposed method was applied to the determination of hyperin in seed of Cuscuta chinensis Lam. and the results obtained were satisfactory. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Probing the conformation of a conserved glutamic acid within the Cl(-) pathway of a CLC H(+)/Cl(-) exchanger.

    PubMed

    Vien, Malvin; Basilio, Daniel; Leisle, Lilia; Accardi, Alessio

    2017-04-03

    The CLC proteins form a broad family of anion-selective transport proteins that includes both channels and exchangers. Despite extensive structural, functional, and computational studies, the transport mechanism of the CLC exchangers remains poorly understood. Several transport models have been proposed but have failed to capture all the key features of these transporters. Multiple CLC crystal structures have suggested that a conserved glutamic acid, Gluex, can adopt three conformations and that the interconversion of its side chain between these states underlies H(+)/Cl(-) exchange. One of these states, in which Gluex occupies the central binding site (Scen) while Cl(-) ions fill the internal and external sites (Sint and Sext), has only been observed in one homologue, the eukaryotic cmCLC. The existence of such a state in other CLCs has not been demonstrated. In this study, we find that during transport, the prototypical prokaryotic CLC exchanger, CLC-ec1, adopts a conformation with functional characteristics that match those predicted for a cmCLC-like state, with Gluex trapped in Scen between two Cl(-) ions. Transport by CLC-ec1 is reduced when [Cl(-)] is symmetrically increased on both sides of the membrane and mutations that disrupt the hydrogen bonds stabilizing Gluex in Scen destabilize this trapped state. Furthermore, inhibition of transport by high [Cl(-)] is abolished in the E148A mutant, in which the Gluex side chain is removed. Collectively, our results suggest that, during the CLC transport cycle, Gluex can occupy Scen as well as the Sext position in which it has been captured crystallographically and that hydrogen bonds with the side chains of residues that coordinate ion binding to Scen play a role in determining the equilibrium between these two conformations.

  11. SN2-like reaction in hydrogen-bonded complexes: a theoretical study.

    PubMed

    Wang, Weizhou; Zhang, Yu; Huang, Kaixun

    2005-10-20

    S(N)2-like reactions in hydrogen-bonded complexes have been investigated in this paper at a correlated MP2(full)/6-311++G(3df,3pd) level, employing FH...NH(3)...HF and ClH...NH(3)...HCl as model systems. The unconventional F(Cl)-H...N noncovalent bond and the conventional F(Cl)-H...N hydrogen bond can coexist in one complex which is taken as the reactant of the S(N)2-like reaction. The S(N)2-like reaction occurs along with the inversion of NH(3) and the interconversion of the unconventional F(Cl)-H...N noncovalent bond and the conventional F(Cl)-H...N hydrogen bond. In comparison with that of the isolated NH(3), the inversion barriers of the two complexes both are significantly reduced. The effect of carbon nanotube confinement on the inversion barrier is also discussed.

  12. Extracellular biosynthesis of CdTe quantum dots by the fungus Fusarium oxysporum and their anti-bacterial activity

    NASA Astrophysics Data System (ADS)

    Syed, Asad; Ahmad, Absar

    2013-04-01

    The growing demand for semiconductor [quantum dots (Q-dots)] nanoparticles has fuelled significant research in developing strategies for their synthesis and characterization. They are extensively investigated by the chemical route; on the other hand, use of microbial sources for biosynthesis witnessed the highly stable, water dispersible nanoparticles formation. Here we report, for the first time, an efficient fungal-mediated synthesis of highly fluorescent CdTe quantum dots at ambient conditions by the fungus Fusarium oxysporum when reacted with a mixture of CdCl2 and TeCl4. Characterization of these biosynthesized nanoparticles was carried out by different techniques such as Ultraviolet-visible (UV-Vis) spectroscopy, Photoluminescence (PL), X-ray Diffraction (XRD), X-ray Photoelectron spectroscopy (XPS), Transmission Electron Microscopy (TEM) and Fourier Transformed Infrared Spectroscopy (FTIR) analysis. CdTe nanoparticles shows antibacterial activity against Gram positive and Gram negative bacteria. The fungal based fabrication provides an economical, green chemistry approach for production of highly fluorescent CdTe quantum dots.

  13. A Few Facts about Hydrogen [and] Hydrogen Bibliography.

    ERIC Educational Resources Information Center

    Hinds, H. Roger

    Divided into two sections, this publication presents facts about and the characteristics of hydrogen and a bibliography on hydrogen. The first section lists nine facts on what hydrogen is, four on where hydrogen is found, nine on how hydrogen is used, nine on how hydrogen can be used, and 14 on how hydrogen is made. Also included are nine…

  14. Hydrogen-bond symmetry in difluoromaleate monoanion.

    PubMed

    Perrin, Charles L; Karri, Phaneendrasai; Moore, Curtis; Rheingold, Arnold L

    2012-05-09

    The symmetry of the hydrogen bond in hydrogen difluoromaleate monoanion is probed by X-ray crystallography and by the NMR method of isotopic perturbation in water, in two aprotic organic solvents, and in an isotropic liquid crystal. The X-ray crystal structure of potassium hydrogen difluoromaleate shows a remarkably short O-O distance of 2.41 Å and equal O-H distances of 1.206 Å, consistent with a strong and symmetric hydrogen bond. Incorporation of (18)O into one carboxyl group allows investigation of the symmetry of the H-bond in solution by the method of isotopic perturbation. The (19)F NMR spectra of the mono-(18)O-substituted monoanion in water, CD(2)Cl(2), and CD(3)CN show an AB spin system, corresponding to fluorines in different environments. The difference is attributed to the perturbation of the acidity of a carboxylic acid by (18)O, not to the mere presence of the (18)O, because the mono-(18)O dianion shows equivalent fluorines. Therefore, it is concluded that the monoanion exists as an equilibrating pair of interconverting tautomers and not as a single symmetric structure not only in water but also in organic solvents. However, in the isotropic liquid crystal phase of 4-cyanophenyl 4-heptylbenzoate, tetrabutylammonium hydrogen difluoromaleate-(18)O shows equivalent fluorines, consistent with a single symmetric structure. These results support earlier studies, which suggested that the symmetry of hydrogen bonds can be determined by the local environment.

  15. Determination of Hydrogen Bond Structure in Water versus Aprotic Environments To Test the Relationship Between Length and Stability

    SciTech Connect

    Sigala, Paul A.; Ruben, Eliza A.; Liu, Corey W.; Piccoli, Paula M. B.; Hohenstein, Edward G.; Martinez, Todd J.; Schultz, Arthur J.; Herschiag, Daniel

    2015-05-06

    Hydrogen bonds profoundly influence the architecture and activity of biological macromolecules. Deep appreciation of hydrogen bond contributions to biomolecular function thus requires a detailed understanding of hydrogen bond structure and energetics and the relationship between these properties. Hydrogen bond formation energies (Delta G(f)) are enormously more favorable in aprotic solvents than in water, and two classes of contributing factors have been proposed to explain this energetic difference, focusing respectively on the isolated and hydrogen-bonded species: (I) water stabilizes the dissociated donor and acceptor groups much better than aprotic solvents, thereby reducing the driving force for hydrogen bond formation; and (II) water lengthens hydrogen bonds compared to aprotic environments, thereby decreasing the potential energy within the hydrogen bond. Each model has been proposed to provide a dominant contribution to Delta G(f), but incisive tests that distinguish the importance of these contributions are lacking. Here we directly test the structural basis of model II. Neutron crystallography, NMR spectroscopy, and quantum mechanical calculations demonstrate that O-H center dot center dot center dot O hydrogen bonds in crystals, chloroform, acetone, and water have nearly identical lengths and very similar potential energy surfaces despite Delta G(f) differences >8 kcal/mol across these solvents. These results rule out a substantial contribution from solvent-dependent differences in hydrogen bond structure and potential energy after association (model II) and thus support the conclusion that differences in hydrogen bond Delta G(f) are predominantly determined by solvent interactions with the dissociated groups (model I). These findings advance our understanding of universal hydrogen-bonding interactions and have important implications for biology and engineering.

  16. Fluorescent Quantum Dots for Biological Labeling

    NASA Technical Reports Server (NTRS)

    McDonald, Gene; Nadeau, Jay; Nealson, Kenneth; Storrie-Lomardi, Michael; Bhartia, Rohit

    2003-01-01

    Fluorescent semiconductor quantum dots that can serve as "on/off" labels for bacteria and other living cells are undergoing development. The "on/off" characterization of these quantum dots refers to the fact that, when properly designed and manufactured, they do not fluoresce until and unless they come into contact with viable cells of biological species that one seeks to detect. In comparison with prior fluorescence-based means of detecting biological species, fluorescent quantum dots show promise for greater speed, less complexity, greater sensitivity, and greater selectivity for species of interest. There are numerous potential applications in medicine, environmental monitoring, and detection of bioterrorism.

  17. Quantum Dots Investigated for Solar Cells

    NASA Technical Reports Server (NTRS)

    Bailey, Sheila G.; Castro, Stephanie L.; Raffaelle, Ryne P.; Hepp, Aloysius F.

    2001-01-01

    The NASA Glenn Research Center has been investigating the synthesis of quantum dots of CdSe and CuInS2 for use in intermediate-bandgap solar cells. Using quantum dots in a solar cell to create an intermediate band will allow the harvesting of a much larger portion of the available solar spectrum. Theoretical studies predict a potential efficiency of 63.2 percent, which is approximately a factor of 2 better than any state-of-the-art devices available today. This technology is also applicable to thin-film devices--where it offers a potential four-fold increase in power-to-weight ratio over the state of the art. Intermediate-bandgap solar cells require that quantum dots be sandwiched in an intrinsic region between the photovoltaic solar cell's ordinary p- and n-type regions (see the preceding figure). The quantum dots form the intermediate band of discrete states that allow sub-bandgap energies to be absorbed. However, when the current is extracted, it is limited by the bandgap, not the individual photon energies. The energy states of the quantum dot can be controlled by controlling the size of the dot. Ironically, the ground-state energy levels are inversely proportional to the size of the quantum dots. We have prepared a variety of quantum dots using the typical organometallic synthesis routes pioneered by Ba Wendi et al., in the early 1990's. The most studied quantum dots prepared by this method have been of CdSe. To produce these dots, researchers inject a syringe of the desired organometallic precursors into heated triocytlphosphine oxide (TOPO) that has been vigorously stirred under an inert atmosphere (see the following figure). The solution immediately begins to change from colorless to yellow, then orange and red/brown, as the quantum dots increase in size. When the desired size is reached, the heat is removed from the flask. Quantum dots of different sizes can be identified by placing them under a "black light" and observing the various color differences in

  18. Zeeman transitions in spherical quantum dot

    NASA Astrophysics Data System (ADS)

    Yakar, Y.; ćakır, B.; Yılmazer, F.; Özmen, A.

    2017-02-01

    In this study, the effects of external magnetic field on the energy states of a spherical quantum dot with infinite potential barrier have been investigated by using Quantum Genetic Algorithm (QGA) and Hartree-Fock Roothaan (HFR) method. Linear Zeeman states and Zeeman transition energies are calculated as a function of dot radius and magnetic field strength. We also carry out the effect of external magnetic field on the ground state binding energy. The results show that the impurity energy states, binding energy and Zeeman transition energies are strongly affected by magnetic field strength and dot radius.

  19. Clocking an Array of Quantum Dots

    NASA Astrophysics Data System (ADS)

    Khatun, Mahfuza; Mandell, Eric

    2000-10-01

    Preferred Session: Condensed Matter Physics Clocking an Array of Quantum Dots* Eric Mandell and M. Khatun, Ball State University. We report a theoretical analysis of the time-dependent electric field due to a line of charged rods. The effects of both the real and image charge are taken into account. The rods are biased electrostatically to study the dynamical behavior of an array of quantum dots. The barrier heights between the quantum dots are controlled by the electric field. *Supported in part by the Indiana Academy of Science, Center for Energy Research/Education/Services(CERES) and the Office of Academic Research and Sponsored Programs, Ball State University.

  20. Coherent optoelectronics with single quantum dots

    NASA Astrophysics Data System (ADS)

    Zrenner, A.; Ester, P.; Michaelis de Vasconcellos, S.; Hübner, M. C.; Lackmann, L.; Stufler, S.; Bichler, M.

    2008-11-01

    The optical properties of semiconductor quantum dots are in many respects similar to those of atoms. Since quantum dots can be defined by state-of-the-art semiconductor technologies, they exhibit long-term stability and allow for well-controlled and efficient interactions with both optical and electrical fields. Resonant ps excitation of single quantum dot photodiodes leads to new classes of coherent optoelectronic functions and devices, which exhibit precise state preparation, phase-sensitive optical manipulations and the control of quantum states by electrical fields.

  1. Entangled exciton states in quantum dot molecules

    NASA Astrophysics Data System (ADS)

    Bayer, Manfred

    2002-03-01

    Currently there is strong interest in quantum information processing(See, for example, The Physics of Quantum Information, eds. D. Bouwmeester, A. Ekert and A. Zeilinger (Springer, Berlin, 2000).) in a solid state environment. Many approaches mimic atomic physics concepts in which semiconductor quantum dots are implemented as artificial atoms. An essential building block of a quantum processor is a gate which entangles the states of two quantum bits. Recently a pair of vertically aligned quantum dots has been suggested as optically driven quantum gate(P. Hawrylak, S. Fafard, and Z. R. Wasilewski, Cond. Matter News 7, 16 (1999).)(M. Bayer, P. Hawrylak, K. Hinzer, S. Fafard, M. Korkusinski, Z.R. Wasilewski, O. Stern, and A. Forchel, Science 291, 451 (2001).): The quantum bits are individual carriers either on dot zero or dot one. The different dot indices play the same role as a "spin", therefore we call them "isospin". Quantum mechanical tunneling between the dots rotates the isospin and leads to superposition of these states. The quantum gate is built when two different particles, an electron and a hole, are created optically. The two particles form entangled isospin states. Here we present spectrocsopic studies of single self-assembled InAs/GaAs quantum dot molecules that support the feasibility of this proposal. The evolution of the excitonic recombination spectrum with varying separation between the dots allows us to demonstrate coherent tunneling of carriers across the separating barrier and the formation of entangled exciton states: Due to the coupling between the dots the exciton states show a splitting that increases with decreasing barrier width. For barrier widths below 5 nm it exceeds the thermal energy at room temperature. For a given barrier width, we find only small variations of the tunneling induced splitting demonstrating a good homogeneity within a molecule ensemble. The entanglement may be controlled by application of electromagnetic field. For

  2. Electronic properties of aperiodic quantum dot chains

    NASA Astrophysics Data System (ADS)

    Korotaev, P. Yu.; Vekilov, Yu. Kh.; Kaputkina, N. E.

    2012-04-01

    The electronic spectral and transport properties of aperiodic quantum dot chains are investigated. The systems with singular continuous energy spectrum are considered: Thue-Morse chain, double-periodic chain, Rudin-Shapiro chain. The influence of electronic energy in quantum dot on the spectral properties, band structure, density of states and spectral resistivity, is discussed. Low resistivity regions correspond to delocalized states and these states could be current states. Also we discuss the magnetic field application as the way to tune electronic energy in quantum dot and to obtain metallic or insulating conducting states of the systems.

  3. High open circuit voltages of solar cells based on quantum dot and dye hybrid-sensitization

    SciTech Connect

    Zhao, Yujie; Zhao, Wanyu; Chen, Jingkuo; Li, Huayang; Fu, Wuyou E-mail: fuwy56@163.com; Sun, Guang; Cao, Jianliang; Zhang, Zhanying; Bala, Hari E-mail: fuwy56@163.com

    2014-01-06

    A type of solar cell based on quantum dot (QD) and dye hybrid-sensitized mesoporous TiO{sub 2} film electrode was designed and reported. The electrode was consisted of a TiO{sub 2} nanoparticle (NP) thin film layer sensitized with CdS quantum dot (QD) and an amorphous TiO{sub 2} coated TiO{sub 2} NP thin film layer that sensitized with C106 dye. The amorphous TiO{sub 2} layer was obtained by TiCl{sub 4} post-treatment to improve the properties of solar cells. Research showed that the solar cells fabricated with as-prepared hybrid-sensitized electrode exhibited excellent photovoltaic performances and a fairly high open circuit voltage of 796 mV was achieved.

  4. A structure of CdS/CuxS quantum dots sensitized solar cells.

    PubMed

    Shen, Ting; Bian, Lu; Li, Bo; Zheng, Kaibo; Pullerits, Tönu; Tian, Jianjun

    2016-05-23

    This work introduces a type of CdS/CuxS quantum dots (QDs) as sensitizers in quantum dot sensitized solar cells by in-situ cationic exchange reaction method where CdS photoanode is directly immersed in CuCl2 methanol solution to replace Cd(2+) by Cu(2+). The p-type CuxS layer on the surface of the CdS QDs can be considered as hole transport material, which not only enhances the light harvesting of photoanode but also boosts the charge separation after photo-excitation. Therefore, both the electron collection efficiency and power conversion efficiency of the solar cell are improved from 80% to 92% and from 1.21% to 2.78%, respectively.

  5. A structure of CdS/Cu{sub x}S quantum dots sensitized solar cells

    SciTech Connect

    Shen, Ting; Bian, Lu; Li, Bo; Tian, Jianjun; Zheng, Kaibo; Pullerits, Tönu

    2016-05-23

    This work introduces a type of CdS/Cu{sub x}S quantum dots (QDs) as sensitizers in quantum dot sensitized solar cells by in-situ cationic exchange reaction method where CdS photoanode is directly immersed in CuCl{sub 2} methanol solution to replace Cd{sup 2+} by Cu{sup 2+}. The p-type Cu{sub x}S layer on the surface of the CdS QDs can be considered as hole transport material, which not only enhances the light harvesting of photoanode but also boosts the charge separation after photo-excitation. Therefore, both the electron collection efficiency and power conversion efficiency of the solar cell are improved from 80% to 92% and from 1.21% to 2.78%, respectively.

  6. Geometry and Vibrational Spectra of the Alkaline Earth Dihalides. III. MgCl2, CaCl2, SrCl2 and BaCl2.

    DTIC Science & Technology

    The infrared spectra of MgCl2 , CaCl2, SrCl2 and BaCl2 trapped in solid krypton matrices at 20K are reported. From precise measurements of changes in...the vibrational modes on isotopic substitution, a linear configuration for MgCl2 and CaCl2 is confirmed and an apex angle of 120 degrees is...established for SrCl. For BaCl2 the bond angle has been estimated at 100 degrees. Using a valence force field a set of force constants has been obtained from

  7. Low severity coal conversion by ionic hydrogenation

    SciTech Connect

    Larsen, J.W.; Maioriello, J.; Cheng, J.C.

    1990-08-17

    The work accomplished in this project will be reported in two parts. Part one will focus on the development of catalytic ionic hydrogenation reactions utilizing a transition metal-H{sub 2} complex as the hydride donor and BF{sub 3}:H{sub 2}O as proton donor. This part reports the results of prelimiary work leading to the development of a new catalytic ionic hydrogenation system (MeCN){sub 2}PtCl{sub 2}/H{sub 2}/BF{sub 3}: H{sub 2}O. The results from some of this work have been published and the paper is included as the appendix. The second part focuses on the newly developed catalytic and other well characterized ionic hydrogenation reactions applied to lignites (Beulah-Zap), sub-bitumiuous (Wyodak), and bituminous coals (Pittsburgh {number sign}8). 19 refs., 10 tabs.

  8. Laser driven impurity states in two-dimensional quantum dots and quantum rings

    NASA Astrophysics Data System (ADS)

    Laroze, D.; Barseghyan, M.; Radu, A.; Kirakosyan, A. A.

    2016-11-01

    The hydrogenic donor impurity states in two-dimensional GaAs/Ga0.7Al0.3As quantum dot and quantum ring have been investigated under the action of intense laser field. A laser dressed effect on both electron confining and electron-impurity Coulomb interaction potentials has been considered. The single electron energy spectrum and wave functions have been found using the effective mass approximation and exact diagonalization technique. The accidental degeneracy of the impurity states have been observed for different positions of the impurity and versus values of the laser field parameter. The obtained theoretical results indicate a novel opportunity to tune the performance of quantum dots and quantum rings and to control their specific properties by means of laser field.

  9. A simple turn on fluorescent sensor for the selective detection of thiamine using coconut water derived luminescent carbon dots.

    PubMed

    Purbia, Rahul; Paria, Santanu

    2016-05-15

    In this study microwave-assisted hydrothermal method was used to prepare highly luminescent carbon dots (1-6 nm size) within a minute from tender coconut (Cocos nucifera) water. The synthesized carbon dots (C-dots) exhibit emission of blue and green lights while excited at 390 and 450 nm wavelengths, respectively. As an application, these C-dots were tested for a simple "turn on" fluorescent sensor for rapid detection of thiamine (vitamin B1). The detection of thiamine in human body is very important to prevent various diseases such as beriberi, neurological disorders, optic neuropathy, etc. The fluorescence emission intensity of C-dots quenches after addition of Cu(2+) ion and then again increases selectively (turn on) after the addition of thiamine. The fluorescence emission intensity enhancement of Cu(2+) ion modified C-dots in the presence of thiamine exhibits a linear relationship within the thiamine concentration range of 10-50 μM. The limit of detection was found to be 280 nM from this study. The selectivity of the detection was also tested in the presence of different organic molecules and inorganic ions (Ca(2+), Mg(2+), Na(+), K(+), Cl(-), SO4(2-), and NO3(-)) which are present in blood serum and urine and found to be almost no interference in the detection. Finally, to see the applicability in real samples a commercial vitamin capsule was tested and found less than 3% error in the detected concentration. The C-dots were also used for bioimaging of fungus and the results show they are also suitable for this application too.

  10. Size-dependent active effect of cadmium telluride quantum dots on luminol-potassium periodate chemiluminescence system for levodopa detection.

    PubMed

    Wang, Jianbo; Cui, Lijuan; Han, Suqin; Hao, Fang

    2015-06-01

    It was found that cadmium telluride (CdTe) quantum dots (QDs) with different sizes can have a great sensitizing effect on chemiluminescence (CL) emission from luminol-potassium periodate (KIO4) system. Levodopa, a widely prescribed drug in the treatment of Parkinson's disease, could inhibit luminol-KIO4-CdTe QDs CL reaction in alkaline solution. The inhibited CL intensity was proportional to the concentration of levodopa in the range from 8.0 nM to 10.0 μM. The detection limit was 3.8 nM. This method has been successfully applied to determine levodopa in pharmaceutical preparation and human urine and plasma samples with recoveries of 94.1-105.4%. This was the first work for inhibition effect determination of levodopa using a QD-based CL method.

  11. Optophononics with coupled quantum dots.

    PubMed

    Kerfoot, Mark L; Govorov, Alexander O; Czarnocki, Cyprian; Lu, Davis; Gad, Youstina N; Bracker, Allan S; Gammon, Daniel; Scheibner, Michael

    2014-01-01

    Modern technology is founded on the intimate understanding of how to utilize and control electrons. Next to electrons, nature uses phonons, quantized vibrations of an elastic structure, to carry energy, momentum and even information through solids. Phonons permeate the crystalline components of modern technology, yet in terms of technological utilization phonons are far from being on par with electrons. Here we demonstrate how phonons can be employed to render a single quantum dot pair optically transparent. This phonon-induced transparency is realized via the formation of a molecular polaron, the result of a Fano-type quantum interference, which proves that we have accomplished making typically incoherent and dissipative phonons behave in a coherent and non-dissipative manner. We find the transparency to be widely tunable by electronic and optical means. Thereby we show amplification of weakest coupling channels. We further outline the molecular polaron's potential as a control element in phononic circuitry architecture.

  12. Quantum dot-based theranostics

    NASA Astrophysics Data System (ADS)

    Ho, Yi-Ping; Leong, Kam W.

    2010-01-01

    Luminescent semiconductor nanocrystals, also known as quantum dots (QDs), have advanced the fields of molecular diagnostics and nanotherapeutics. Much of the initial progress for QDs in biology and medicine has focused on developing new biosensing formats to push the limit of detection sensitivity. Nevertheless, QDs can be more than passive bio-probes or labels for biological imaging and cellular studies. The high surface-to-volume ratio of QDs enables the construction of a ``smart'' multifunctional nanoplatform, where the QDs serve not only as an imaging agent but also a nanoscaffold catering for therapeutic and diagnostic (theranostic) modalities. This mini review highlights the emerging applications of functionalized QDs as fluorescence contrast agents for imaging or as nanoscale vehicles for delivery of therapeutics, with special attention paid to the promise and challenges towards QD-based theranostics.

  13. A Dot Does a Lot

    NASA Image and Video Library

    2014-07-14

    Seen by NASA Cassini spacecraft within the vast expanse of Saturn rings, Prometheus appears as little more than a dot. But that little moon still manages to shape the F ring, confining it to its narrow domain. Prometheus (53 miles, or 86 kilometers across) and its fellow moon Pandora (50 miles, or 81 kilometers across) orbit beside the F ring and keep the ring from spreading outward through a process dubbed "shepherding." This view looks toward the unilluminated side of the rings from about 45 degrees below the ringplane. The image was taken in green light with the Cassini spacecraft wide-angle camera on March 8, 2014. The view was obtained at a distance of approximately 533,000 miles (858,000 kilometers) from Prometheus and at a Sun-Prometheus-spacecraft, or phase, angle of 90 degrees. Image scale is 32 miles (51 kilometers) per pixel. http://photojournal.jpl.nasa.gov/catalog/PIA18272

  14. Tailoring Magnetism in Quantum Dots

    NASA Astrophysics Data System (ADS)

    Zutic, Igor; Abolfath, Ramin; Hawrylak, Pawel

    2007-03-01

    We study magnetism in magnetically doped quantum dots as a function of particle numbers, temperature, confining potential, and the strength of Coulomb interaction screening. We show that magnetism can be tailored by controlling the electron-electron Coulomb interaction, even without changing the number of particles. The interplay of strong Coulomb interactions and quantum confinement leads to enhanced inhomogeneous magnetization which persists at substantially higher temperatures than in the non-interacting case or in the bulk-like dilute magnetic semiconductors. We predict a series of electronic spin transitions which arise from the competition between the many-body gap and magnetic thermal fluctuations. Cond-mat/0612489. [1] R. Abolfath, P. Hawrylak, I. Zuti'c, preprint.

  15. Advanced Electrochemical Technologies for Hydrogen Production by Alternative Thermochemical Cycles

    SciTech Connect

    Lvov, Serguei; Chung, Mike; Fedkin, Mark; Lewis, Michele; Balashov, Victor; Chalkova, Elena; Akinfiev, Nikolay; Stork, Carol; Davis, Thomas; Gadala-Maria, Francis; Stanford, Thomas; Weidner, John; Law, Victor; Prindle, John

    2011-01-06

    Hydrogen fuel is a potentially major solution to the problem of climate change, as well as addressing urban air pollution issues. But a key future challenge for hydrogen as a clean energy carrier is a sustainable, low-cost method of producing it in large capacities. Most of the world's hydrogen is currently derived from fossil fuels through some type of reforming processes. Nuclear hydrogen production is an emerging and promising alternative to the reforming processes for carbon-free hydrogen production in the future. This report presents the main results of a research program carried out by a NERI Consortium, which consisted of Penn State University (PSU) (lead), University of South Carolina (USC), Tulane University (TU), and Argonne National Laboratory (ANL). Thermochemical water decomposition is an emerging technology for large-scale production of hydrogen. Typically using two or more intermediate compounds, a sequence of chemical and physical processes split water into hydrogen and oxygen, without releasing any pollutants externally to the atmosphere. These intermediate compounds are recycled internally within a closed loop. While previous studies have identified over 200 possible thermochemical cycles, only a few have progressed beyond theoretical calculations to working experimental demonstrations that establish scientific and practical feasibility of the thermochemical processes. The Cu-Cl cycle has a significant advantage over other cycles due to lower temperature requirements – around 530 °C and below. As a result, it can be eventually linked with the Generation IV thermal power stations. Advantages of the Cu-Cl cycle over others include lower operating temperatures, ability to utilize low-grade waste heat to improve energy efficiency, and potentially lower cost materials. Another significant advantage is a relatively low voltage required for the electrochemical step (thus low electricity input). Other advantages include common chemical agents and

  16. Hydrogen energy systems studies

    SciTech Connect

    Ogden, J.M.; Kreutz, T.G.; Steinbugler, M.

    1996-10-01

    In this report the authors describe results from technical and economic assessments carried out during the past year with support from the USDOE Hydrogen R&D Program. (1) Assessment of technologies for small scale production of hydrogen from natural gas. Because of the cost and logistics of transporting and storing hydrogen, it may be preferable to produce hydrogen at the point of use from more readily available energy carriers such as natural gas or electricity. In this task the authors assess near term technologies for producing hydrogen from natural gas at small scale including steam reforming, partial oxidation and autothermal reforming. (2) Case study of developing a hydrogen vehicle refueling infrastructure in Southern California. Many analysts suggest that the first widespread use of hydrogen energy is likely to be in zero emission vehicles in Southern California. Several hundred thousand zero emission automobiles are projected for the Los Angeles Basin alone by 2010, if mandated levels are implemented. Assuming that hydrogen vehicles capture a significant fraction of this market, a large demand for hydrogen fuel could evolve over the next few decades. Refueling a large number of hydrogen vehicles poses significant challenges. In this task the authors assess near term options for producing and delivering gaseous hydrogen transportation fuel to users in Southern California including: (1) hydrogen produced from natural gas in a large, centralized steam reforming plant, and delivered to refueling stations via liquid hydrogen truck or small scale hydrogen gas pipeline, (2) hydrogen produced at the refueling station via small scale steam reforming of natural gas, (3) hydrogen produced via small scale electrolysis at the refueling station, and (4) hydrogen from low cost chemical industry sources (e.g. excess capacity in refineries which have recently upgraded their hydrogen production capacity, etc.).

  17. Thermodynamic Assessment of EuCl3-MgCl2 and EuCl3-BaCl2 Systems

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Sun, Yimin

    2011-09-01

    Using the CALPHAD technique, an assessment of the binary EuCl3-MgCl2 and EuCl3-BaCl2 systems has been carried out in this study. The modified quasi-chemical model was defined to describe the Gibbs energies of the liquid phases, and the model parameters were optimized from the experimental phase diagram data. The phase diagrams and enthalpies of mixing of the EuCl3-MgCl2 and EuCl3-BaCl2 systems were calculated. The calculated results by the present method agree well with the experimental data. The Gibbs energies of formation of Mg3Eu2Cl12, Ba3Eu2Cl12, and Ba2Eu3Cl13 from the pure components were predicted.

  18. Charging energy spectrum of black phosphorus quantum dots

    NASA Astrophysics Data System (ADS)

    Lino, M. A.; de Sousa, J. S.; da Costa, D. R.; Chaves, A.; Pereira, J. M.; Farias, G. A.

    2017-08-01

    We present a theoretical study of the charging effects in single and double layer black phosphorus quantum dots (BPQDs) with lateral sizes of 2 nm and 3 nm. We demonstrate that the charging of BPQDs are able to store up to an N max electron (that depends on the lateral size and number of layers in the QD), after which structural instabilities arises. For example, 3 nm wide hydrogen-passivated single layer BPQDs can hold a maximum of 16 electrons, and an additional electron causes the expelling of hydrogen atoms from the QD borders. We also calculated the addition energy (E A ) spectrum. For single-layer QDs with 2 and 3 nm lateral sizes, the average E A is around 0.4 eV and 0.3 eV, respectively. For double layer QDs with the same sizes, the average E A is around 0.25 eV and 0.2 eV, respectively.

  19. Hydrogen bonding. Part 15. Infrared study of hydrogen bonding in betaine hydrate and betaine hydrofluoride

    NASA Astrophysics Data System (ADS)

    Harmon, Kenneth M.; Avci, Günsel F.

    1984-07-01

    Infrared spectroscopy at 300 and 10 K. deuterium labeling, internal coordinate analysis, and comparison with the spectra of compounds of known structure have been used to elucidate the nature of bound water in betaine hydrate. All evidence is consonant with a structure in which two carboxylate oxygens, one from each of two betaines, are mutually bridged by two water molecules to give a dimeric water—anion unit of D2h symmetry. The infrared spectrum of betaine hydrofluoride shows the presence of a very strong OHF hydrogen bond in this compound, in contrast to the normal OH⋯Cl hydrogen bond in betaine hydrochloride.

  20. Desmin detection by facile prepared carbon quantum dots for early screening of colorectal cancer.

    PubMed

    Li, Chang-Feng; Yan, Zhen-Kun; Chen, Li-Bo; Jin, Jing-Peng; Li, Dan-Dan

    2017-02-01

    Th aim of this study was to develop a new facile chemical method for early screening of colorectal cancer.The -C(O)OH groups modified Carbon Quantum Dots (CQDs) were prepared by an facile innovative route of acid attacking on carbon nanotubes (CNTs). The -C(O)OH groups were further transported into -C(O)Cl groups by SOCl2 treating. The obtained ClCQDs were conjugated onto the anti-Desmin, which were applied for testing the Desmin concentration in serum by using linearly fitted relationship with photoluminescence (PL) intensity.The obtained carbon quantum dots are quasispherical graphite nanocrystals with photoluminescence at about 455 nm. The Desmin with concentration of 1 ng/mL can lead to a decrease of PL intensity for anti-Desmin conjugated CQDs with good linearity. This assay had good specificity for Desmin with in interferential substances of immunoglobulin G (IgG), alpha fetoprotein (AFP), and carcinoembryoic antigen (CEA).A new facile acid attack method was developed to prepare ClCQDs, which could conjugate onto the anti-Desmin for detection of Desmin in serum with high sensitivity and specificity. As the detection limit is lower than 1 ng/ mL, this work provides a promising strategy for the evaluation of colorectal cancer risk with low cost and excellent sensing performance.

  1. Desmin detection by facile prepared carbon quantum dots for early screening of colorectal cancer

    PubMed Central

    Li, Chang-feng; Yan, Zhen-kun; Chen, Li-bo; Jin, Jing-peng; Li, Dan-dan

    2017-01-01

    Abstract Th aim of this study was to develop a new facile chemical method for early screening of colorectal cancer. The -C(O)OH groups modified Carbon Quantum Dots (CQDs) were prepared by an facile innovative route of acid attacking on carbon nanotubes (CNTs). The -C(O)OH groups were further transported into -C(O)Cl groups by SOCl2 treating. The obtained ClCQDs were conjugated onto the anti-Desmin, which were applied for testing the Desmin concentration in serum by using linearly fitted relationship with photoluminescence (PL) intensity. The obtained carbon quantum dots are quasispherical graphite nanocrystals with photoluminescence at about 455 nm. The Desmin with concentration of 1 ng/mL can lead to a decrease of PL intensity for anti-Desmin conjugated CQDs with good linearity. This assay had good specificity for Desmin with in interferential substances of immunoglobulin G (IgG), alpha fetoprotein (AFP), and carcinoembryoic antigen (CEA). A new facile acid attack method was developed to prepare ClCQDs, which could conjugate onto the anti-Desmin for detection of Desmin in serum with high sensitivity and specificity. As the detection limit is lower than 1 ng/ mL, this work provides a promising strategy for the evaluation of colorectal cancer risk with low cost and excellent sensing performance. PMID:28151847

  2. Concentration of Hydrogen Peroxide

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde F. (Inventor)

    2006-01-01

    Methods for concentrating hydrogen peroxide solutions have been described. The methods utilize a polymeric membrane separating a hydrogen peroxide solution from a sweep gas or permeate. The membrane is selective to the permeability of water over the permeability of hydrogen peroxide, thereby facilitating the concentration of the hydrogen peroxide solution through the transport of water through the membrane to the permeate. By utilizing methods in accordance with the invention, hydrogen peroxide solutions of up to 85% by volume or higher may be generated at a point of use without storing substantial quantities of the highly concentrated solutions and without requiring temperatures that would produce explosive mixtures of hydrogen peroxide vapors.

  3. Hydrogen conference: Workshop proceedings

    SciTech Connect

    Serfass, J.; Bugel, L. )

    1989-10-01

    This meeting was designed to encourage discussion of today's US industrial, utility, space and environmental interests in hydrogen and tommorrow's use of hydrogen as an energy system. The meeting began with a general session during which speakers gave presentations on a variety of hydrogen topics. Discussion following each presentation was lively. Some of the major points of discussion were: interpretation of global warming evidence; relevance of global warming to the interest in hydrogen; cost of hydrogen derived from fossil fuels vs. nuclear vs. solar; likely future importance of hydrogen -- major energy system vs. niche player. A number of interesting points were raised and data presented by speakers and participants. Highlights are presented.

  4. Quantum dot at a Luttinger liquid edge

    NASA Astrophysics Data System (ADS)

    Rylands, Colin; Andrei, Natan

    2017-09-01

    We study a system consisting of a Luttinger liquid coupled to a quantum dot on the boundary. The Luttinger liquid is expressed in terms of fermions interacting via density-density coupling, and the dot is modeled as an interacting resonant level onto which the bulk fermions can tunnel. We solve the Hamiltonian exactly and construct all eigenstates. We study both the zero- and finite-temperature properties of the system, in particular, we compute the exact dot occupation as a function of the dot energy in all parameter regimes. The system is seen to flow from weak to strong coupling for all values of the bulk interaction, with the flow characterized by a nonperturbative Kondo scale. We identify the critical exponents at the weak- and strong-coupling regimes.

  5. Double quantum dots defined in bilayer graphene

    NASA Astrophysics Data System (ADS)

    Żebrowski, D. P.; Peeters, F. M.; Szafran, B.

    2017-07-01

    Artificial molecular states of double quantum dots defined in bilayer graphene are studied with the atomistic tight-binding method and its low-energy continuum approximation. We indicate that the extended electron wave functions have opposite parities on sublattices of the layers and that the ground-state wave-function components change from bonding to antibonding with the interdot distance. In the weak-coupling limit, the one most relevant for quantum dots defined electrostatically, the signatures of the interdot coupling include, for the two-electron ground state, formation of states with symmetric or antisymmetric spatial wave functions split by the exchange energy. In the high-energy part of the spectrum the states with both electrons in the same dot are found with the splitting of energy levels corresponding to simultaneous tunneling of the electron pair from one dot to the other.

  6. Synthetic Developments of Nontoxic Quantum Dots.

    PubMed

    Das, Adita; Snee, Preston T

    2016-03-03

    Semiconductor nanocrystals, or quantum dots (QDs), are candidates for biological sensing, photovoltaics, and catalysis due to their unique photophysical properties. The most studied QDs are composed of heavy metals like cadmium and lead. However, this engenders concerns over heavy metal toxicity. To address this issue, numerous studies have explored the development of nontoxic (or more accurately less toxic) quantum dots. In this Review, we select three major classes of nontoxic quantum dots composed of carbon, silicon and Group I-III-VI elements and discuss the myriad of synthetic strategies and surface modification methods to synthesize quantum dots composed of these material systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Spin Dynamics of Charged Colloidal Quantum Dots

    NASA Astrophysics Data System (ADS)

    Stern, N. P.

    2005-03-01

    Colloidal semiconductor quantum dots are promising structures for controlling spin phenomena because of their highly size- tunable physical properties, ease of manufacture, and nanosecond-scale spin lifetimes at room temperature. Recent experiments have succeeded in controlling the charging of the lowest electronic state of colloidal quantum dots ootnotetextC. Wang, B. L. Wehrenberg, C. Y. Woo, and P. Guyot-Sionnest, J. Phys. Chem B 108, 9027 (2004).. Here we use time-resolved Faraday rotation measurements in the Voigt geometry to investigate the spin dynamics of colloidal CdSe quantum dot films in both a charged and uncharged state at room temperature. The charging of the film is controlled by applying a voltage in an electrochemical cell and is confirmed by absorbance measurements. Significant changes in the spin precession are observed upon charging, reflecting the voltage- controlled electron occupation of the quantum dot states and filling of surface states.

  8. Teleportation on a quantum dot array.

    PubMed

    de Pasquale, F; Giorgi, G; Paganelli, S

    2004-09-17

    We present a model of quantum teleportation protocol based on a double quantum dot array. The unknown qubit is encoded using a pair of quantum dots, with one excess electron, coupled by tunneling. It is shown how to create a maximally entangled state using an adiabatically increasing Coulomb repulsion between different dot pairs. This entangled state is exploited to perform teleportation again using an adiabatic coupling between itself and the incoming unknown state. Finally, a sudden separation of Bob's qubit allows a time evolution of Alice's, which amounts to a modified version of standard Bell measurement. A transmission over a long distance could be obtained by considering the entangled state of a chain of N coupled double quantum dots. The system is shown to be increasingly robust with N against decoherence due to phonons.

  9. EPA-DOT Memorandum of Understanding (MOU)

    EPA Pesticide Factsheets

    National Memorandum of Understanding Between the U.S. Department of Transportation and the U.S. Environmental Protection Agency (EPA Publication #EPA-420-F-00-020 and EPA-DOT Memorandum of Understanding (MOU) on Transportation Conformity.

  10. Nanomaterials: Earthworms lit with quantum dots

    NASA Astrophysics Data System (ADS)

    Tilley, Richard D.; Cheong, Soshan

    2013-01-01

    Yeast, bacteria and fungi have been used to synthesize a variety of nanocrystals. Now, the metal detoxification process in the gut of an earthworm is exploited to produce biocompatible cadmium telluride quantum dots.

  11. Novel cookie-with-chocolate carbon dots displaying extremely acidophilic high luminescence

    NASA Astrophysics Data System (ADS)

    Lu, Siyu; Zhao, Xiaohuan; Zhu, Shoujun; Song, Yubin; Yang, Bai

    2014-10-01

    A fluorescent carbon dot with a cookie-with-chocolate film structure (about 5 × 5 μm2) showed a high fluorescence quantum yield (61.12%) at low pH. It was hydrothermally synthesized from l-serine and l-tryptophan. The formation mechanism of the film with carbon dots (CDs) was investigated. The film structure was formed by hydrogen bonding and π-π stacking interactions between aromatic rings. The strong blue fluorescence of the CDs increased under strong acidic conditions owing to the changes in the N-groups. These cookie-like CDs are attractive for their potential use as effective fluorescent probes for the sensitive detection of aqueous H+ and Fe3+.A fluorescent carbon dot with a cookie-with-chocolate film structure (about 5 × 5 μm2) showed a high fluorescence quantum yield (61.12%) at low pH. It was hydrothermally synthesized from l-serine and l-tryptophan. The formation mechanism of the film with carbon dots (CDs) was investigated. The film structure was formed by hydrogen bonding and π-π stacking interactions between aromatic rings. The strong blue fluorescence of the CDs increased under strong acidic conditions owing to the changes in the N-groups. These cookie-like CDs are attractive for their potential use as effective fluorescent probes for the sensitive detection of aqueous H+ and Fe3+. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03965c

  12. First principle thousand atom quantum dot calculations

    SciTech Connect

    Wang, Lin-Wang; Li, Jingbo

    2004-03-30

    A charge patching method and an idealized surface passivation are used to calculate the single electronic states of IV-IV, III-V, II-VI semiconductor quantum dots up to a thousand atoms. This approach scales linearly and has a 1000 fold speed-up compared to direct first principle methods with a cost of eigen energy error of about 20 meV. The calculated quantum dot band gaps are parametrized for future references.

  13. Renormalization in Periodically Driven Quantum Dots.

    PubMed

    Eissing, A K; Meden, V; Kennes, D M

    2016-01-15

    We report on strong renormalization encountered in periodically driven interacting quantum dots in the nonadiabatic regime. Correlations between lead and dot electrons enhance or suppress the amplitude of driving depending on the sign of the interaction. Employing a newly developed flexible renormalization-group-based approach for periodic driving to an interacting resonant level we show analytically that the magnitude of this effect follows a power law. Our setup can act as a non-Markovian, single-parameter quantum pump.

  14. Exploring Extragalactic Emission: The Hα Dot Survey

    NASA Astrophysics Data System (ADS)

    Rampalli, Rayna; Salzer, John Joseph

    2016-01-01

    The Hα Dot Survey was established as a result of finding point sources of strong line emission in the data obtained for the ALFALFA Hα Survey (Van Sistine et al. 2015). In the latter survey, broad-band R and narrow-band Hα filters were used to examine target galaxies from the ALFALFA blind HI survey (Giovanelli et al. 2005, Haynes et al. 2011). In the process of reducing the ALFALFA Hα Survey data the "Hα Dots" were discovered (Kellar et al. 2008, 2012). Using specialized image analysis tools, a large population of dots has already been detected in the more than 1500 ALFALFA Hα narrow-band images taken with the 0.9m WIYN and 2.1m KPNO telescopes. Follow-up spectra of over 200 Hα Dots discovered from the 0.9m images reveal that these objects are a mix of nearby low-luminosity star-forming galaxies, compact starbursts and Seyfert 2 galaxies at intermediate redshifts, and high-redshift QSOs. Here we present the first list of Hα Dots detected using 2.1m telescope data. The 2.1m images yield a sample of Dots that average almost two magnitudes fainter than those detected with the 0.9m. The current REU project is designed to characterize the set of Hα Dots detected in the deeper 2.1m telescope images, while the broad goals of the Hα Dot Survey include the desire to understand better the chemical evolution of galaxies over cosmic time. This project was supported in part by the NSF REU grant 1358980, by the Maria Mitchell Association (Nantucket, MA), and by the Massachusetts Space Grant Consortium.

  15. 49 CFR 40.227 - May employers use the ATF for non-DOT tests, or non-DOT forms for DOT tests?

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 1 2010-10-01 2010-10-01 false May employers use the ATF for non-DOT tests, or..., Equipment and Supplies Used in Alcohol Testing § 40.227 May employers use the ATF for non-DOT tests, or non-DOT forms for DOT tests? (a) No, as an employer, BAT, or STT, you are prohibited from using the ATF...

  16. Chemical/hydrogen energy systems analysis

    NASA Astrophysics Data System (ADS)

    Beller, M.

    1982-12-01

    Four hydrogen energy technologies are addressed including: hydrogen recovery from hydrogen separation using hydride technology, photochemical hydrogen production, anode depolarization in electrolytic hydrogen production.

  17. DEVELOPMENT OF A CL-IMPREGNATED ACTIVATED CARBON FOR ENTRAINED-FLOW CAPTURE OF ELEMENTAL MERCURY

    EPA Science Inventory

    Efforts to discern the role of an activated carbon's surface functional groups on the adsorption of elemental mercury [Hg(0)] and mercuric chloride demonstrated that chlorine (Cl) impregnation of a virgin activated carbon using dilute solutions of hydrogen chloride leads to incre...

  18. DEVELOPMENT OF A CL-IMPREGNATED ACTIVATED CARBON FOR ENTRAINED-FLOW CAPTURE OF ELEMENTAL MERCURY

    EPA Science Inventory

    Efforts to discern the role of an activated carbon's surface functional groups on the adsorption of elemental mercury [Hg(0)] and mercuric chloride demonstrated that chlorine (Cl) impregnation of a virgin activated carbon using dilute solutions of hydrogen chloride leads to incre...

  19. Silicon quantum dots for optical applications

    NASA Astrophysics Data System (ADS)

    Wu, Jeslin J.

    Luminescent silicon quantum dots (SiQDs) are emerging as attractive materials for optoelectronic devices, third generation photovoltaics, and bioimaging. Their applicability in the real world is contingent on their optical properties and long-term environmental stability; and in biological applications, factors such as water solubility and toxicity must also be taken into consideration. The aforementioned properties are highly dependent on the QDs' surface chemistry. In this work, SiQDs were engineered for the respective applications using liquid-phase and gas-phase functionalization techniques. Preliminary work in luminescent downshifting for photovoltaic systems are also reported. Highly luminescent SiQDs were fabricated by grafting unsaturated hydrocarbons onto the surface of hydrogen-terminated SiQDs via thermal and photochemical hydrosilylation. An industrially attractive, all gas-phase, nonthermal plasma synthesis, passivation (aided by photochemical reactions), and deposition process was also developed to reduce solvent waste. With photoluminescence quantum yields (PLQYs) nearing 60 %, the alkyl-terminated QDs are attractive materials for optical applications. The functionalized SiQDs also exhibited enhanced thermal stability as compared to their unfunctionalized counterparts, and the photochemically-hydrosilylated QDs further displayed photostability under UV irradiation. These environmentally-stable SiQDs were used as luminescent downshifting layers in photovoltaic systems, which led to enhancements in the blue photoresponse of heterojunction solar cells. Furthermore, the QD films demonstrated antireflective properties, improving the coupling efficiency of sunlight into the cell. For biological applications, oxide, amine, or hydroxyl groups were grafted onto the surface to create water-soluble SiQDs. Luminescent, water-soluble SiQDs were produced in by microplasma treating the QDs in water. Stable QYs exceeding 50 % were obtained. Radical-based and

  20. Laser driven intraband optical transitions in two-dimensional quantum dots and quantum rings

    NASA Astrophysics Data System (ADS)

    Barseghyan, M. G.; Kirakosyan, A. A.; Laroze, D.

    2017-01-01

    The intraband optical absorption have been investigated in the presence of hydrogenic donor impurity in GaAs/GaAlAs quantum dot and quantum ring in the intense laser field. The single electron energy spectrum and wave functions have been found using the effective mass approximation and exact diagonalization technique. Different selection rules are obtained for intraband transitions depending on the direction of incident light polarization. Due to the accidental degeneracy of the laser dressed impurity states the crossings of the curves of the threshold energies and the dipole matrix elements on laser field parameter have been observed. The intraband absorption coefficient is calculated for different locations of hydrogenic donor impurity and different values of intense laser field parameter. The obtained results show that the absorption spectrum can exhibit either a blue- or redshift depending on the impurity location, values of the laser field parameter and direction of incident light polarization. The obtained theoretical results indicate a novel opportunity to tune the performance of new devices, based on the quantum dots and quantum rings and to control their specific properties by means of intense laser and hydrogenic donor impurity.

  1. Positioning of quantum dots on metallic nanostructures.

    PubMed

    Kramer, R K; Pholchai, N; Sorger, V J; Yim, T J; Oulton, R; Zhang, X

    2010-04-09

    The capability to position individual emitters, such as quantum dots, near metallic nanostructures is highly desirable for constructing active optical devices that can manipulate light at the single photon level. The emergence of the field of plasmonics as a means to confine light now introduces a need for high precision and reliability in positioning any source of emission, which has thus far been elusive. Placing an emission source within the influence of plasmonic structures now requires accuracy approaching molecular length scales. In this paper we report the ability to reliably position nanoscale functional objects, specifically quantum dots, with sub-100-nm accuracy, which is several times smaller than the diffraction limit of a quantum dot's emission light. Electron beam lithography-defined masks on metallic surfaces and a series of surface chemical functionalization processes allow the programmed assembly of DNA-linked colloidal quantum dots. The quantum dots are successfully functionalized to areas as small as (100 nm)(2) using the specific binding of thiolated DNA to Au/Ag, and exploiting the streptavidin-biotin interaction. An analysis of the reproducibility of the process for various pattern sizes shows that this technique is potentially scalable to the single quantum dot level with 50 nm accuracy accompanied by a moderate reduction in yield.

  2. Positioning of quantum dots on metallic nanostructures

    NASA Astrophysics Data System (ADS)

    Kramer, R. K.; Pholchai, N.; Sorger, V. J.; Yim, T. J.; Oulton, R.; Zhang, X.

    2010-04-01

    The capability to position individual emitters, such as quantum dots, near metallic nanostructures is highly desirable for constructing active optical devices that can manipulate light at the single photon level. The emergence of the field of plasmonics as a means to confine light now introduces a need for high precision and reliability in positioning any source of emission, which has thus far been elusive. Placing an emission source within the influence of plasmonic structures now requires accuracy approaching molecular length scales. In this paper we report the ability to reliably position nanoscale functional objects, specifically quantum dots, with sub-100-nm accuracy, which is several times smaller than the diffraction limit of a quantum dot's emission light. Electron beam lithography-defined masks on metallic surfaces and a series of surface chemical functionalization processes allow the programmed assembly of DNA-linked colloidal quantum dots. The quantum dots are successfully functionalized to areas as small as (100 nm)2 using the specific binding of thiolated DNA to Au/Ag, and exploiting the streptavidin-biotin interaction. An analysis of the reproducibility of the process for various pattern sizes shows that this technique is potentially scalable to the single quantum dot level with 50 nm accuracy accompanied by a moderate reduction in yield.

  3. Semiconductor Quantum Dots with Photoresponsive Ligands.

    PubMed

    Sansalone, Lorenzo; Tang, Sicheng; Zhang, Yang; Thapaliya, Ek Raj; Raymo, Françisco M; Garcia-Amorós, Jaume

    2016-10-01

    Photochromic or photocaged ligands can be anchored to the outer shell of semiconductor quantum dots in order to control the photophysical properties of these inorganic nanocrystals with optical stimulations. One of the two interconvertible states of the photoresponsive ligands can be designed to accept either an electron or energy from the excited quantum dots and quench their luminescence. Under these conditions, the reversible transformations of photochromic ligands or the irreversible cleavage of photocaged counterparts translates into the possibility to switch luminescence with external control. As an alternative to regulating the photophysics of a quantum dot via the photochemistry of its ligands, the photochemistry of the latter can be controlled by relying on the photophysics of the former. The transfer of excitation energy from a quantum dot to a photocaged ligand populates the excited state of the species adsorbed on the nanocrystal to induce a photochemical reaction. This mechanism, in conjunction with the large two-photon absorption cross section of quantum dots, can be exploited to release nitric oxide or to generate singlet oxygen under near-infrared irradiation. Thus, the combination of semiconductor quantum dots and photoresponsive ligands offers the opportunity to assemble nanostructured constructs with specific functions on the basis of electron or energy transfer processes. The photoswitchable luminescence and ability to photoinduce the release of reactive chemicals, associated with the resulting systems, can be particularly valuable in biomedical research and can, ultimately, lead to the realization of imaging probes for diagnostic applications as well as to therapeutic agents for the treatment of cancer.

  4. Luminescent Quantum Dots as Ultrasensitive Biological Labels

    NASA Astrophysics Data System (ADS)

    Nie, Shuming

    2000-03-01

    Highly luminescent semiconductor quantum dots have been covalently coupled to biological molecules for use in ultrasensitive biological detection. This new class of luminescent labels is considerably brighter and more resistant againt photobleaching in comparison with organic dyes. Quantum dots labeled with the protein transferrin undergo receptor-mediated endocytosis (RME) in cultured HeLa cells, and those dots that were conjugated to immunomolecules recognize specific antibodies or antigens. In addition, we show that DNA functionalized quantum dots can be used to target specific genes by hybridization. We expect that quantum dot bioconjugates will have a broad range of biological applications, such as ligand-receptor interactions, real-time monitoring of molecular trafficking inside living cells, multicolor fluorescence in-situ hybridization (FISH), high-sensitivity detection in miniaturized devices (e.g., DNA chips), and fluorescent tagging of combinatorial chemical libraries. A potential clinical application is the use of quantum dots for ultrasensitive viral RNA detection, in which as low as 100 copies of hepatitis C and HIV viruses per ml blood should be detected.

  5. Quantum-dot-in-perovskite solids.

    PubMed

    Ning, Zhijun; Gong, Xiwen; Comin, Riccardo; Walters, Grant; Fan, Fengjia; Voznyy, Oleksandr; Yassitepe, Emre; Buin, Andrei; Hoogland, Sjoerd; Sargent, Edward H

    2015-07-16

    Heteroepitaxy-atomically aligned growth of a crystalline film atop a different crystalline substrate-is the basis of electrically driven lasers, multijunction solar cells, and blue-light-emitting diodes. Crystalline coherence is preserved even when atomic identity is modulated, a fact that is the critical enabler of quantum wells, wires, and dots. The interfacial quality achieved as a result of heteroepitaxial growth allows new combinations of materials with complementary properties, which enables the design and realization of functionalities that are not available in the single-phase constituents. Here we show that organohalide perovskites and preformed colloidal quantum dots, combined in the solution phase, produce epitaxially aligned 'dots-in-a-matrix' crystals. Using transmission electron microscopy and electron diffraction, we reveal heterocrystals as large as about 60 nanometres and containing at least 20 mutually aligned dots that inherit the crystalline orientation of the perovskite matrix. The heterocrystals exhibit remarkable optoelectronic properties that are traceable to their atom-scale crystalline coherence: photoelectrons and holes generated in the larger-bandgap perovskites are transferred with 80% efficiency to become excitons in the quantum dot nanocrystals, which exploit the excellent photocarrier diffusion of perovskites to produce bright-light emission from infrared-bandgap quantum-tuned materials. By combining the electrical transport properties of the perovskite matrix with the high radiative efficiency of the quantum dots, we engineer a new platform to advance solution-processed infrared optoelectronics.

  6. Icm/Dot-Independent Entry of Legionella pneumophila into Amoeba and Macrophage Hosts

    PubMed Central

    Bandyopadhyay, Purnima; Xiao, Huifang; Coleman, Hope A.; Price-Whelan, Alexa; Steinman, Howard M.

    2004-01-01

    Legionella pneumophila, the causative agent of Legionnaires' disease, expresses a type IVB secretion apparatus that translocates bacterial proteins into amoeba and macrophage hosts. When stationary-phase cultures are used to infect hosts, the type IVB apparatus encoded by the icm/dot genes is required for entry, delay of phagosome-lysosome fusion, and intracellular multiplication within host cells. Null mutants with mutations in icm/dot genes are defective in these phenotypes. Here a new model is described in which hosts are infected with stationary-phase cultures that have been incubated overnight in pH 6.5 buffer. This model is called Ers treatment because it enhances the resistance to acid, hydrogen peroxide, and antibiotic stress beyond that of stationary-phase cultures. Following Ers treatment entry into amoeba and macrophage hosts does not require dotA, which is essential for Legionella virulence phenotypes when hosts are infected with stationary-phase cultures, dotB, icmF, icmV, or icmX. Defective host entry is also suppressed for null mutants with mutations in the KatA and KatB catalase-peroxidase enzymes, which are required for proper intracellular growth in amoeba and macrophage hosts. Ers treatment-induced suppression of defective entry is not associated with increased bacterial adhesion to host cells or with morphological changes in the bacterial envelope but is dependent on protein expression during Ers treatment. By using proteomic analysis, Ers treatment was shown to induce a protein predicted to contain eight tetratricopeptide repeats, a motif previously implicated in enhanced entry of L. pneumophila. Characterization of Ers treatment-dependent changes in expression is proposed as an avenue for identifying icm/dot-independent factors that function in the entry of Legionella into amoeba and macrophage hosts. PMID:15271914

  7. Variations in stratospheric HCl and ClO

    NASA Astrophysics Data System (ADS)

    Froidevaux, L.; Anderson, J.; Kinnison, D. E.; Fuller, R. A.; Santee, M. L.; Livesey, N. J.; Read, W.; Bernath, P. F.; Russell, J. M.

    2012-12-01

    We analyze temporal variations in stratospheric hydrogen chloride (HCl) and chlorine monoxide (ClO) measurements from satellites (for 1991-2011). The HCl dataset comes from a global long-term series of merged zonal averages using observations from the Halogen Occultation Experiment (HALOE) aboard the Upper Atmosphere Research Satellite (UARS), the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) aboard SCISAT-1, and the Microwave Limb Sounder (MLS) aboard Aura. This merged time series is a result of the NASA Making Earth System data records for Use in Research Environments (MEaSUREs) project entitled Global Ozone Chemistry And Related trace gas Data records for the Stratosphere (GOZCARDS). The ClO dataset includes MLS measurements from UARS and Aura. In relation to the observed variations in chlorine species, we investigate changes in model HCl and ClO abundances, based on simulations from the specified dynamics version of the Whole Atmosphere Community Climate Model (SD-WACCM). Meteorological fields used in this study are taken from the NASA Global Modeling and Assimilation Office (GMAO) Modern-Era Retrospective Analysis for Research and Applications (MERRA). Moreover, model fields are sampled following locations and local times corresponding to the MLS sampling. We present results of comparisons between these model and measured fields of HCl and ClO; this includes the underlying trends as well as the shorter-term (annual and interannual) changes.

  8. Investigation of the Hydrochlorination of SiCl4

    NASA Technical Reports Server (NTRS)

    Mui, J. Y. P.

    1983-01-01

    The hydrochlorination of silicon tetrachloride with hydrogen and metallurgical grade (m.g.) silicon metal, 3 SiCl4 + 2 H2 + Si yields 4 SiHCl3 was shown to be an efficient process to produce trichlorosilane. A research and development program was carried out to study the hydrochlorination reaction over a wide range of reaction conditions. Equilibrium constant and reaction kinetics measurements were made to provide the basis for a theoretical study on the hydrochlorination process. Thermodynamic properties of the hydrochlorination reaction were also measured. The effects of temperature, pressure, and concentration on the equilibrium constant, K sub p, were studied.

  9. Solubility of AgCl in molten NaCl-AlCl[sub 3] and KCl-AlCl[sub 3

    SciTech Connect

    Tumidajski, P.J. . Materials Lab.); Blander, M. ); Newman, D.S. . Dept. of Chemistry)

    1994-04-01

    Measurements of AgCl solubility (in mol fraction units) in molten NaCl-AlCl[sub 3] and KCl-AlCl[sub 3] were determined by an electromotive force technique. For the NaCl-AlCl[sub 3] experiments, the temperature was maintained at 448 K and the composition of the solvent varied from X = 0.500 to X = 0.530. There was a compositional dependence of the AgCl solubilities with a minimum near the equimolar solvent composition. The minimum solubility in mol fraction of AgCl was 5.75 [times] 10[sup [minus]3] at X = 0.505. The true solubility produce for AgCl at 448 K was calculated to be 7.35 [times] 10[sup [minus]9]. The magnitude of the solubility product is primarily related to the fact that the standard free energy of information of NaAlCl[sub 4] from NaCl and AlCl[sub 3] is about 67 kJ/mol more negative than the corresponding free energy for AgAlCl[sub 4] (i.e., AgAlCl[sub 4] is unstable). In basic and in somewhat acidic melts, the solubility is related to the formation of the associated ionic species such as AgCl, AgCl[sup [minus

  10. 49 CFR 40.227 - May employers use the ATF for non-DOT tests, or non-DOT forms for DOT tests?

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 1 2013-10-01 2013-10-01 false May employers use the ATF for non-DOT tests, or non-DOT forms for DOT tests? 40.227 Section 40.227 Transportation Office of the Secretary of Transportation PROCEDURES FOR TRANSPORTATION WORKPLACE DRUG AND ALCOHOL TESTING PROGRAMS Testing Sites, Forms, Equipment and Supplies Used in Alcohol Testing ...

  11. Hydrogenation of passivated aluminum with hydrogen fluid

    NASA Astrophysics Data System (ADS)

    Saitoh, H.; Machida, A.; Katayama, Y.; Aoki, K.

    2009-04-01

    Hydrogenation conditions of passivated aluminum were examined in a pressure and temperature range of 6-10 GPa and 300-800 °C, respectively. The relationship between the hydrogenation reaction yields and holding time was analyzed by Johnson-Mehl-Avrami equation. An Avrami exponent n of 0.3 indicated that the reaction decreased with time due to the low diffusivity of hydrogen in AlH3. The oxide layer on passivated aluminum seemed to be partly removed or modified by pressure-temperature treatment above 6 GPa and 600 °C in hydrogen fluid. The hydrogenation pressure of 9 GPa for the passivated aluminum was reduced to 6 GPa.

  12. Hydrogen Hotspots on Vesta

    NASA Image and Video Library

    2012-09-20

    This image shows that NASA Dawn mission detected abundances of hydrogen in a wide swath around the equator of the giant asteroid Vesta. The hydrogen probably exists in the form of hydroxyl or water bound to minerals in Vesta surface.

  13. Hydrogen production by Cyanobacteria.

    PubMed

    Dutta, Debajyoti; De, Debojyoti; Chaudhuri, Surabhi; Bhattacharya, Sanjoy K

    2005-12-21

    The limited fossil fuel prompts the prospecting of various unconventional energy sources to take over the traditional fossil fuel energy source. In this respect the use of hydrogen gas is an attractive alternate source. Attributed by its numerous advantages including those of environmentally clean, efficiency and renew ability, hydrogen gas is considered to be one of the most desired alternate. Cyanobacteria are highly promising microorganism for hydrogen production. In comparison to the traditional ways of hydrogen production (chemical, photoelectrical), Cyanobacterial hydrogen production is commercially viable. This review highlights the basic biology of cynobacterial hydrogen production, strains involved, large-scale hydrogen production and its future prospects. While integrating the existing knowledge and technology, much future improvement and progress is to be done before hydrogen is accepted as a commercial primary energy source.

  14. Hydrogen production by Cyanobacteria

    PubMed Central

    Dutta, Debajyoti; De, Debojyoti; Chaudhuri, Surabhi; Bhattacharya, Sanjoy K

    2005-01-01

    The limited fossil fuel prompts the prospecting of various unconventional energy sources to take over the traditional fossil fuel energy source. In this respect the use of hydrogen gas is an attractive alternate source. Attributed by its numerous advantages including those of environmentally clean, efficiency and renew ability, hydrogen gas is considered to be one of the most desired alternate. Cyanobacteria are highly promising microorganism for hydrogen production. In comparison to the traditional ways of hydrogen production (chemical, photoelectrical), Cyanobacterial hydrogen production is commercially viable. This review highlights the basic biology of cynobacterial hydrogen production, strains involved, large-scale hydrogen production and its future prospects. While integrating the existing knowledge and technology, much future improvement and progress is to be done before hydrogen is accepted as a commercial primary energy source. PMID:16371161

  15. Freezing WISE Hydrogen

    NASA Image and Video Library

    2009-11-12

    A scaffolding structure built around NASA Wide-field Infrared Survey Explorer allows engineers to freeze its hydrogen coolant. The WISE infrared instrument is kept extremely cold by a bottle-like tank filled with frozen hydrogen, called the cryostat.

  16. Hydrogen transport membranes

    DOEpatents

    Mundschau, Michael V.

    2005-05-31

    Composite hydrogen transport membranes, which are used for extraction of hydrogen from gas mixtures are provided. Methods are described for supporting metals and metal alloys which have high hydrogen permeability, but which are either too thin to be self supporting, too weak to resist differential pressures across the membrane, or which become embrittled by hydrogen. Support materials are chosen to be lattice matched to the metals and metal alloys. Preferred metals with high permeability for hydrogen include vanadium, niobium, tantalum, zirconium, palladium, and alloys thereof. Hydrogen-permeable membranes include those in which the pores of a porous support matrix are blocked by hydrogen-permeable metals and metal alloys, those in which the pores of a porous metal matrix are blocked with materials which make the membrane impervious to gases other than hydrogen, and cermets fabricated by sintering powders of metals with powders of lattice-matched ceramic.

  17. Etude structurale et vibrationnelle d’un nouveau composé complexe de cobalt: [Co(imidazole)4Cl]Cl

    PubMed Central

    Derbel, Amira; Mhiri, Tahar; Graia, Mohsen

    2015-01-01

    In the title complex, chlorido­tetra­kis­(1H-imidazole-κN 3)cobalt(II) chloride, [CoCl(C3H4N2)4]Cl, the CoII cation has a distorted square-pyramidal coordination environment. It is coordinated by four N atoms of four imidazole (Im) groups in the basal plane, and by a Cl atom in the apical position. It is isostructural with [Cu(Im)4Cl]Cl [Morzyk-Ociepa et al. (2012 ▸). J. Mol. Struct. 1028, 49–56] and [Cu(Im)4Br]Br [Hossaini Sadr et al. (2004 ▸). Acta Cryst. E60, m1324–m1326]. In the crystal, the [CoCl(C3H4N2)4]+ cations and Cl− anions are linked via N—H⋯Cl hydrogen bonds, forming layers parallel to (010). These layers are linked via C—H⋯Cl hydrogen bonds and C—H⋯π and π–π [inter-centroid distance = 3.794 (2) Å] inter­actions, forming a three-dimensional framework. The IR spectrum shows vibrational bands typical for imidazol groups. The monoclinic unit cell of the title compound emulates an ortho­rhom­bic cell as its β angle is close to 90°. The crystal is twinned, with the refined ratio of twin components being 0.569 (1):0.431 (1). PMID:26594402

  18. Chloride ion conduction without water coordination in the pore of ClC protein.

    PubMed

    Ko, Youn Jo; Jo, Won Ho

    2010-02-01

    In the present work, we have found by an atomistic molecular dynamics simulation that hydrogen atoms originating from the residues of a prokaryotic ClC protein (EcClC) stabilize the chloride ion without water molecules in the pore of ClC protein. When the chloride ion conduction is simulated by pulling a chloride ion along the pore axis, the free energy barrier for chloride ion conduction is calculated to be low (4 kcal/mol), although the chloride ion is stripped of its hydration shell as it passes through the dehydrated pore region. The calculation of the number of hydrogen atoms surrounding the chloride ion reveals that water molecules hydrating the chloride ion are replaced by polar and non-polar hydrogen atoms protruding from the protein residues. From the analysis of the pair interaction energy between the chloride ion and these hydrogen atoms, it is realized that the hydrogen atoms from the protein residues stabilize the chloride ion at the dehydrated region instead of water molecules, by which the energetic penalty for detaching water molecules from the permeating ion is compensated.

  19. Chlorine monoxide radical, ozone, and hydrogen peroxide - Stratospheric measurements by microwave limb sounding

    NASA Technical Reports Server (NTRS)

    Waters, J. W.; Hardy, J. C.; Jarnot, R. F.; Pickett, H. M.

    1981-01-01

    Profiles of stratospheric ozone and chlorine monoxide radical (ClO) have been obtained from balloon measurements of atmospheric limb thermal emission at millimeter wavelengths. The ClO measurements, important for assessing the predicted depletion of stratospheric ozone by chlorine from industrial sources, are in close agreement with present theory. The predicted decrease of ClO at sunset was measured. A tentative value for the stratospheric abundance of hydrogen peroxide was also determined.

  20. Hydrogen Technologies Safety Guide

    SciTech Connect

    Rivkin, C.; Burgess, R.; Buttner, W.

    2015-01-01

    The purpose of this guide is to provide basic background information on hydrogen technologies. It is intended to provide project developers, code officials, and other interested parties the background information to be able to put hydrogen safety in context. For example, code officials reviewing permit applications for hydrogen projects will get an understanding of the industrial history of hydrogen, basic safety concerns, and safety requirements.