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1.
The mechanism of tandem dimethylamine-borane (NHMe2BH3, DMAB) dehydrogenation and alkene hydrogenation catalyzed by [Pd(NHC)(PMe3)] are investigated by density functional theory (DFT) calculations [NHC = N,N′-bis(2,6-diisopropylphenyl) imidazole-2-ylidene]. Four possible DMAB dehydrogenation mechanisms have been carefully investigated involving concerted BH/NH activation, sequential BH/NH activation, sequential NH/BH activation, and proton transfer mechanism. DFT studies show that the NH proton transfers to ligated carbene carbon and sequential CH/BH activation is the most kinetically favorable pathway with the lowest activation barrier of 23.8 kcal/mol. For hydrogenation, it was found that a trans-dihydride Pd(II) complex, [Pd(H)2(NHC)(PMe3)], formed in the dehydrogenation process, serves as an effective catalyst for reduction of trans-stilbene.  相似文献   

2.
A highly active and stable catalyst for hydrogen-iodide decomposition reaction in sulfur-iodine (SI) cycle has been prepared in the form of PdCeO2 nanocatalyst by sol-gel method with different calcination temperatures (300 °C, 500 °C, and 700 °C). XRD and TEM confirmed a size around 6–8 nm for PdCeO2 particles calcined at 300 °C. Raman study revealed large number oxygen vacancies in PdCeO2-300 when compared to PdCeO2-500 and PdCeO2-700. With increase in calcination temperature, the average particle size increased whereas the specific surface area and number of oxygen vacancies decreased. Hydrogen-iodide catalytic-decomposition was carried out in the temperature range of 400°C–550 °C in a quartz-tube, vertical, fixed-bed reactor with 55 wt % aqueous hydrogen-iodide feed over PdCeO2 catalyst using nitrogen as a carrier gas. PdCeO2-300 showed hydrogen-iodide conversion of 23.3%, which is close to the theoretical equilibrium conversion of 24%, at 550 °C. It also showed a reasonable stability with a time-on-stream of 5 h.  相似文献   

3.
Efficient production of hydrogen through visible-light-driven water splitting mechanism using semiconductor-based composites has been identified as a promising strategy for converting light into clean H2 fuel. However, researchers are facing lots of challenges such as light absorption and electron-hole pair recombination and so on. Here, new sheet-shaped MoS2 and pyramid-shaped CdS in-situ co-grown on porous TiO2 photocatalysts (MoS2CdSTiO2) are successfully obtained via mild sulfuration of MoO3 and CdO coexisted inside porous TiO2 monolith by a hydrothermal route. The scanning electron microscopy and transmission electron microscopy results exhibit that the MoS2CdSTiO2 composites have average pore size about 500 nm. The 3%MoS210%CdSTiO2 demonstrated excellent photocatalytic activity and high stability for a hydrogen production with a high H2-generation rate of 4146 μmol h?1 g?1 under visible light irradiation even without noble-metal co-catalysts. The super photocatalytic performance of the visible-light-driven hydrogen evolution is predominantly attributed to the synergistic effect. The conduction band of MoS2 facilitates in transporting excited electrons from visible-light on CdS to the porous TiO2 for catalytic hydrogen production, and holes to MoS2 for inhibiting the photocorrosion of CdS, respectively, leading to enhancing the efficient separation of electrons and holes.  相似文献   

4.
By surface-decorating PtTiO2 hybrid catalyst with MoS2 nanosheets, we prepared a new MoS2/PtTiO2 ternary system as high-performance photocatalysts. The ternary MoS2/PtTiO2 outperforms both the binary MoS2TiO2 and PtTiO2 systems in photocatalytic hydrogen evolution with an AQY (apparent quantum yield) value of 12.54% at 420 nm, owing to the unique ternary design that creates more efficient electron transport path and electron-hole separation mechanism. Electrochemical characterization showed that the MoS2/PtTiO2 ternary electrode afford an efficient pathway of photo-excited electrons from TiO2 to surface-decorated Pt nanoparticles using MoS2 and internal Pt nanoparticles as bridges, thus significantly promoting electron transfer, reducing the system overpotential and leading to the activation of more reactive sites. This internal electron transfer pathway (TiO2 → Pt (internal) → MoS2 → Pt (surface)) eliminates the need of other metal cocatalysts because the Pt nanoparticles play two roles of storing the conduction band electrons of TiO2 and acting as co-catalyst for reduction of protons to hydrogen. This unique ternary metal-semiconductor heterojunction for efficient photocatalytic hydrogen evolution provides a meaningful reference for reasonable design of other hybrid photocatalysts.  相似文献   

5.
Vanadium trichloride (VCl3) is one of the best catalysts for the hydrogenation-dehydrogenation MgMgH2 system. X-ray photoelectron spectroscopy (XPS) has shown that VCl3 reduced to metallic vanadium during ball milling along with MgH2. The in-situ-formed metallic vanadium doped over the MgH2 surface which has shown an excellent catalytic effect on hydrogenation-dehydrogenation of the MgMgH2 system. The catalyzed surface reduced the activation energies of hydrogenation-dehydrogenation reactions and correspondingly on-set hydrogenation-dehydrogenation temperatures. The microstructural analysis has also shown an excellent grain refinement property of VCl3 which reduced the crystallite size of MgH2. The decreased crystallite size decreases the diffusion path length of hydrogen and increases the active surface area which eventually enhances the hydrogenation-dehydrogenation kinetics of MgMgH2.  相似文献   

6.
We successfully synthesized mesocrystalline Ta2O5 nanosheets supported bimetallic PdPt nanoparticles by the photo-reduction method. The as-prepared mesocrystalline Ta2O5 nanosheets in this work showed amazing visible-light absorption, mainly because of the formation of oxygen vacancy defects. And the as-prepared bimetallic PdPt/mesocrystalline Ta2O5 nanaosheets also showed highly enhanced UV–Vis light absorption and highly improved photocatalytic activity for hydrogen production in comparison to that of commercial Ta2O5, mesocrystalline Ta2O5 nanosheets, Pd/mesocrystalline Ta2O5 nanosheets and Pt/mesocrystalline Ta2O5 nanosheets. The highest photocatalytic hydrogen production rate of PdPt/mesocrystalline Ta2O5 nanaosheets was 21529.52 g?1 h?1, which was about 21.2 times of commercial Ta2O5, and the apparent quantum efficiency of PdPt/mesocrystalline Ta2O5 nanaosheets for hydrogen production was about 16.5% at 254 nm. The highly enhanced photocatalytic activity was mainly because of the significant roles of PdPt nanoparticles for accelerating the charge separation and transport upon illumination. The as-prepared PdPt/mesocrystalline Ta2O5 nanaosheets in this work could serve as an efficient photocatalyst for green energy production.  相似文献   

7.
Hydrogen embrittlement is a serious problem in the oil/gas industry. In this work, various iron sulfide (FeS) films, including iron monosulfide (FeS), pyrite (FeS2), and pyrrhotite (Fe7S8), were synthesized in X80 steel by chemical vapor deposition at 200 °C, 300 °C, 400 °C, and 500 °C. The corrosion resistance and hydrogen permeation properties of the FeS films were investigated through electrochemical methods. Results indicated that FeS films significantly improved the hydrogen barrier properties of the X80 steel, which was closely related to the crystal structure type and defects of FeS films. Defects like microcracks and pinholes during deposition can increase the porosity of the film, resulting in the film properties decreased. Moreover, FeS film (at 300 °C), which had the smallest apparent hydrogen diffusivity (D ? 2.64 × 10?7 cm2/s) and apparent subsurface concentration (Capp ? 1.12 μmol/cm3), had the best hydrogen barrier properties. The corrosion resistance of FeS film (300 °C) was excellent.  相似文献   

8.
In present work, we reported an novel oxide-salt Al2O3NaAlO2 composite, which was prepared by mixing Al2O3 and Na2CO3 two phase materials in different weight ratio, and then sintering at 1100 °C. The X-ray diffraction pattern, scanning-electron microscope and impedance spectra are applied to characterize the crystal structure, morphology and electrical properties of the Al2O3NaAlO2 composite. The Al2O3NaAlO2 composite as electrolyte membrane was sandwiched by two pieces of Ni0.8Co0.15Al0.05Li-oxide (NCAL) electrode layer to construct advanced fuel cell. Optimizing the weight ratio of Al2O3 and NaAlO2, such cell delivered an highest power density of 789 mW/cm2 and an open circuit voltage (Voc) of 1.13 V at 575 °C. The superior performance is mainly due to the excellent ion-conducting of Al2O3NaAlO2 composites and the outstanding catalysis activity of the NCAL eletrodes. The EIS results revealed that the Al2O3NaAlO2 composite possessed superior ionic conductivity of 0.121 S/cm at 575 °C. The interfacial effects between oxide-salt two phase including space-charge and structural misfit at the interface region dominated the ion transport for Al2O3NaAlO2 composite.  相似文献   

9.
To overcome the hydrogen-induced amorphization and phase disproportionation in the fast de-/hydrogenation of YFe2, the alloying of partial substituting Y with Zr was carried out to obtain Y1?xZrxFe2 (x = 0.1, 0.2, 0.3, 0.5) alloys. All YZrFe alloys remained single C15 Laves phase structure at states of as-annealed, hydrogenated and dehydrogenated. With the increasing of Zr content, the YZrFe alloys showed the decrease in the lattice constants and hydrogenation capacity, but the increase in the dehydrogenation capacity and dehydriding equilibrium pressure. The alloy Y0.9Zr0.1Fe2 showed maximum initial hydrogenation capacity of 1.87 wt% H, while the alloy Y0.5Zr0.5Fe2 showed highest desorption capacity of 1.26 wt% with obvious dehydriding plateau. Based on experiment analysis and first principle calculation of binding energy, the great improvement in the dehydriding thermodynamics for YZrFe alloys is attributed to the change in the unit cell volume, electron concentration and stability of hydrides due to the Zr substitution.  相似文献   

10.
Doping with the additives in metal-N–H system has been regarded as one of the most effective approaches to improve its hydrogen storage properties. Herein, we prepared super activated carbon (SuperC) through the activation of commercial activated carbon by KOH and evaluated its effect on dehydrogenation properties of 2LiNH2MgH2. Our studies show that doping with SuperC could effectively lower its dehydrogenation temperatures. For instance, 2LiNH2MgH2–10 wt% SuperC can release 4.86 wt% of hydrogen upon heating up to 300 °C with the onset and peak dehydrogenation temperatures of 71 °C and 168 °C, respectively. Moreover, the release of byproduct NH3 was successfully suppressed. Measurement of thermal diffusivity suggests that the enhanced dehydrogenation properties may be ascribed to the improved heat transfer for solid-solid reaction resulting from doping with SuperC.  相似文献   

11.
A hierarchically porous MoS2 on Ni3S2 nanorod array on Ni foam (MoS2/Ni3S2/NF) was firstly fabricated through a simple microwave-assisted hydrothermal method, and then followed by electrochemical deposition approach in which MoS2/Ni3S2/Ni foam is decorated with CoS (CoSMoS2/Ni3S2/NF). In contrast to conventional hydrothermal approach, microwave irradiation accelerates the synthesis of MoS2/Ni3S2/Ni foam from time of >20 h–2 h. The characterization of CoSMoS2/Ni3S2/NF by scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM) indicate that a whole scale of 1D the Ni3S2 nanorods were hierarchically integrated with MoS2 and CoS nanosheets. The as-synthesized CoSMoS2/Ni3S2/NF hybrid not only endows the ease transport of electrons along Ni3S2 nanorods to Ni foam, but also accommodates maximal exposure of active edge sites to the reactants through hierarchically porous CoS doped MoS2 nanosheets, accomplishing the promoted kinetics and activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). By electrochemical measurements such as linear sweep voltammetry (LSV) and electrochemical impedance spectroscope (EIS), we find that the CoSMoS2/Ni3S2/NF hybrid shows markedly enhanced electrochemical performance for both HER and OER. Specifically, the optimal CoSMoS2/Ni3S2/NF8C possesses the low overpotentials (η10) of 85 and 225 mV at current density (|j|) of 10 mA cm?2 in 1.0 M KOH and the small 62.3 and 46.1 mV dec?1 Tafel slope for HER and OER, respectively, outperforming those of most of the current noble metal-free electrocatalysts. These results highlight the fact that CoSMoS2/Ni3S2/NF is a high-performance, noble-metal-free electro-catalyst, and provide a potential avenue toward achieving an enhanced electrocatalytic activity towards both in HER and OER. Yet the duration of the as prepared catalyst in OER still need to be improved.  相似文献   

12.
Carbon deposition during carbon dioxide reforming reaction of C3H8 has been studied over alumina-supported bimetallic Mo/CoNi catalysts. To better understand the carbon-induced deactivation during the reforming reaction, changes in catalyst morphology and carbon deposition kinetics were examined. Different characterization techniques were used for both fresh and rejuvenated catalysts including liquid nitrogen adsorption/desorption, chemisorption via hydrogen, ammonia and CO2 desorption, and thermogravimetric measurement of the coked catalysts. The time dependant reaction rate profiles indicated that MoNi catalyst has higher syngas (H2/CO) formation rates with lower CO2 rate of consumption compared to CoNi catalyst. However, the H2:CO ratio values were almost the same for both catalysts suggesting similarity in the product formation pathway. Conversion-time analysis showed that MoNi catalyst was more stable and active during a 72-h run while CoNi suffered noticeable deactivation after 30 h on-stream. Reaction-deactivation models implicated a higher deactivation coefficient (kd) with activation energy of Ed = 78.1 kJ mol?1 for the cobalt-containing Ni catalyst, while the Ni catalyst with molybdenum had a lower deactivation coefficient with smaller activation energy of just under 70 kJ mol?1. Post-mortem analysis (TPR-TPO dual cycle and TOC) of spent catalysts confirmed that the surface of CoNi catalyst has more carbon residue than the MoNi sample which was consistent with the higher deactivation of CoNi.  相似文献   

13.
Multi-walled carbon nanotubes (MWCNTs) loaded with different wt % of tin oxide (MWCNT: SnO2) nanocomposites have been synthesized by impregnation method and their hydrogen uptake capacity is investigated. The hydrogen storage capacity of MWCNT: SnO2 (3 wt %), MWCNT: SnO2 (5 wt %), MWCNT: SnO2 (7 wt %) and MWCNT: SnO2 (9 wt %) composites is found to be 2.03, 1.95, 0.94 and 1.59 wt % respectively. The enhanced hydrogen storage capacity is due to SnOC bond formation and summative adsorption of hydrogen by MWCNT and SnO2 nanoparticles. Moreover, physical/chemical properties of composites are examined by Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction, thermogravimetric and Raman analyses. Hydrogen adsorption and desorption behavior of the composites are analyzed using Raman and thermogravimetric analyses. The stored hydrogen is desorbed in the temperature range of 183 ?C-536 °C.  相似文献   

14.
In this experimental studies, we report the synthesis of TiO2 co-doped by both cationic and anionic sites by simple sol-gel based method. All the prepared samples exhibit the anatase crystalline morphology however, showed lattice distortion caused by the displacement of Ti4+ sites by Gd3+. The improved visible absorption is witnessed by the Gd and N co-doping with an assured redshift in the absorption edge. The N and Gd displacement inside TiO2 lattice accompanied by the creation of OTiN and GdOTi bonds are characterized by the X-ray photoelectron spectra. The strong resonance signal by Gd4f electrons in the electron paramagnetic resonance spectroscopy further substantiate the displacement of lattice cites of TiO2 by Gd3+ ions. The longevity of the photo produced charges observed in fluorescence spectra of Gd and N co-doped TiO2 is because of the effective transfer of charges to the defect sites. The aforementioned catalysts are tested for their capacity for the H2 production from water splitting. The 2 wt% gadolinium and nitrogen co-doped TiO2 has shown 10764 μmol g?1 H2 production which is 26 times higher than the commercial Degussa P-25 catalyst. The enhanced activity for hydrogen production can be attributed to factors such as increased absorptivity under visible light and effective charge carrier separation.  相似文献   

15.
A novel photocatalyst comprises of ZrO2TiO2 immobilized on reduced graphene oxide (rGO) – a ternary heterojunction (ZrO2TiO2/rGO) was synthesized by using facile chemical method. The nanocomposite was prepared with a strategy to achieve better utilization of excitons for catalytic reactions by channelizing from metal oxide surfaces to rGO support. TEM and XRD analysis results revealed the heterojunction formed between ZrO2 and single crystalline anatase TiO2. The mesoporous structure of ZrO2TiO2 was confirmed using BET analysis. The red shift in absorption edge position of ZrO2TiO2/rGO photocatalyst was characterized by using diffuse reflectance UV–Visible spectra. ZrO2TiO2/rGO showed greater interfacial charge transfer efficiency than ZrO2TiO2, which was evidenced by well suppressed PL intensity and high photocurrent of ZrO2TiO2/rGO. The suitable band gap of 1.0 wt% ZrO2TiO2/rGO facilitated the utilization of solar light in a wide range by responding to the light of energy equal to as well as greater than 2.95 eV by the additional formation of excited high-energy electrons (HEEs). ZrO2TiO2/rGO showed the enhanced H2 production than TiO2/rGO, which revealed the role of ZrO2 for the effective charge separation at the heterojunction and the solar light response. The optimum loading of 1.0 wt% of ZrO2 and rGO on TiO2 showed the highest photocatalytic performance (7773 μmolh?1gcat?1) for hydrogen (H2) production under direct solar light irradiation.  相似文献   

16.
2D CdS/NiFe LDH (short for layered double hydroxide) heterostructures were designed and fabricated by following a facile in-situ growth method. The CdS nanoparticles are well dispersed on the surface of NiFe LDH to form nanoscale heterojunctions, as suggested from the TEM and elemental mapping images. The composites with optimum CdS amount (15 wt%) take on notably higher hydrogen evolution activity (469 μmol h?1 g?1) than the independent CdS and NiFe LDH from aqueous methanol solution under xenon lamp irradiation. The nano-heterojunction notably promotes the H2 evolution kinetics and greatly suppresses the recombination of photo-induced electrons and holes, which is responsible for the enhanced photocatalytic activity of the composites, as demonstrated by the reducing onset potential and increasing photocurrent of the composites in the photoelectrochemical experiments. The possible photocatalytic mechanism is proposed on the basis of the defined position of energy band edges.  相似文献   

17.
Mg-AB5 composites are promising systems for hydrogen storage applications, due to their possibility of hydrogen cycling at relatively low temperatures. Traditionally, these composites are mainly processed by high-energy ball milling (HEBM) techniques employing longer processing times. In this study, cold rolling was applied to prepare MgH2LaNi5 composites and the hydrogen storage properties were investigated. The materials were processed using a vertical rolling mill under argon atmosphere, leading to a good homogeneity and no contamination at shorter processing times. The mixture of MgH2-1.50 mol.% LaNi5 showed the best hydrogen storage properties at 200 °C and 100 °C and the lowest desorption temperature even when compared to cold rolled MgH2. The results indicate that the composite MgH2LaNi5 is transformed into a mixture of three phases MgH2, Mg2NiH4 and LaH3 upon hydrogen absorption/desorption cycles. The synergetic effect among these phases when in appropriate proportion in the sample seems to play a crucial role in the acceleration of hydrogen absorption/desorption kinetics at lower temperatures in comparison to MgH2.  相似文献   

18.
A series of PtRu and PtMo bimetallic catalysts were prepared via a chemical reduction method by bubbling CO to form carbonyl compounds as metal precursors. In both cases the PtRu and PtMo bimetallic electrocatalysts achieved the maximum activity when the amount of Ru and Mo in the material was 50%wt. The physicochemical characterization of the electrocatalytic materials through X-ray diffraction (XRD) and transmission electron microscopy (TEM) has determined the presence of bimetallic structures. The electrochemical characterization using cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and polarization curves in Proton Exchange Membrane Fuel Cells (PEMFC) and Direct Methanol Fuel Cell (DMFC) allowed to systematically investigate the electrocatalytic activity of the synthesized materials for the electrooxidation of hydrogen and methanol. The PtRu/SWCNT electrocatalysts showed a higher current density at least 7-fold and 3-fold compared with Pt/SWCNT and PtMo/SWCNT electrocatalysts, respectively. Besides, the Pt50%–Ru50%/SWCNT exhibited a shifting to negative values in the onset potential reaction for the electrooxidation of methanol of 200 mV in comparison with Pt100%/SWCNT and Pt50%–Mo50%/SWCNT electrocatalysts. The experimental and simulated polarization curves obtained from DMFC show that PtRu/SWCNT and PtMo/SWCNT electrocatalysts exhibited higher power and current densities values compared with the Pt/SWCNT electrocatalyst. The membrane-electrode assembly (MEA) with Nafion® and the PtRu/SWCNT electrocatalysts showed an open-circuit voltage value of 0.730 V, significantly higher than that the values for the MEAs with Pt/SWCNT (0.663 V) and PtMo/SWCNT (0.633 V), respectively.  相似文献   

19.
Development of photocatalysts with characters of low-cost, environment friendliness, visible light response and good performance is vital for the transformation of solar energy into hydrogen fuel. Here, we constructed CoPCdS nanorods hybrid composites via a novel two-step in-situ growth method for the first time. The obtained CoPCdS composites exhibited remarkably enhanced photocatalytic performance and excellent stability in comparison with bare CdS nanorods. Notably, the optimum H2 evolution rate of 1 wt%CoPCdS was 9.11 times higher than that of pristine CdS. The apparent quantum efficiency of the photocatalyst was calculated to be 11.6%. The superior activity of this material could be attributed to the role of well dispersed CoP nanoparticles and the intimate interface between CoP cocatalysts and CdS nanorods, which efficiently accelerated the separation and transfer of photogenerated electrons. This work provided a new in-situ growth method for the preparation of transition metal phosphides coated photocatalysts with boosted photocatalytic activity of hydrogen evolution.  相似文献   

20.
The present study aims at investigating, for the first time, a quinary mixture of light-metals borohydrides. The goal is to design combinations of borohydrides with multiple cations in equimolar ratio, following the concept of high entropy alloys. The equimolar composition of the LiBH4NaBH4KBH4Mg(BH4)2Ca(BH4)2 system was synthetized by ball milling. The obtained phases were analysed by X-ray diffraction and in-situ Synchrotron Radiation Powder X-ray Diffraction, in order to establish the amount of cations incorporated in the obtained crystalline phases and to study the thermal behaviour of the mixture. HP-DSC and DTA were also used to define the phase transformations and thermal decomposition reactions, leading to the release of hydrogen, that was detected by MS. The existence of a quinary liquid borohydride phase is reported for the first time. Effects of the presence of multi-cations compounds or a liquid phase on the hydrogen desorption reactions are described.  相似文献   

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