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1.
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   

2.
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   

3.
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   

4.
Carbonaceous materials containing non-precious metal atoms and doped with nitrogen have enthralled stunning attention in the field of electrochemical energy conversion systems. Herein, we demonstrated a facile method to fabricate iron and nitrogen doped carbon nanofiber (FeN-CNFs) catalyst material from ferric chloride and interfacial synthesized polyaniline (PANI) nanofibers, by carbonization process in an inert atmosphere at 800 °C. Further, synthesized material was characterized by elemental analysis and X-ray photoelectron spectroscopy (XPS) that confirms the presence of FeN bonds. The structural and morphological features are studied using various microscopy and spectroscopy techniques. The oxygen reduction reaction (ORR) activity of synthesized catalyst materials was examined by rotating disk electrode experiments in 0.1 M KOH. Among all these synthesized materials FeN-CNFs material showed enhanced ORR activity regarding current density and onset potential. Also, FeN-CNFs catalyst exhibited tolerance to methanol and durability in comparison to commercial Pt/C catalyst. The superior performance of FeN-CNFs may be attributed due to the introduction of Fe and formation of FeN bond in catalyst material.  相似文献   

5.
A one-pot synthesis method is utilized for the fabrication of ultrasmall platinum-silver nanoparticles decorated on graphene (PtAg/G) catalyst. This method has several advantages such as inexpensiveness, simplicity, low temperature, surfactant free, reductant free, being environmentally friendly and greenness. In this work, graphene and silver formate were dispersed in ultrapure water in an ultrasonic bath at 25 °C followed by through a galvanic displacement reaction; to prepare PtAg/G, PtCl2 was added to the suspension under mild stirring condition. The morphology, crystal structure and chemical compositions of the as-fabricated PtAg/G and Pt/C catalysts were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Energy dispersive X-ray spectroscopy (EDS) techniques. Electrochemical techniques, including cyclic voltammetry (CV) and chronoamperometry (CA) measurements were used to analyze the electrochemical activity of the PtAg/G and Pt/C catalysts. The TEM images illustrate the uniform distribution of ultrasmall PtAg nanoparticles with the average size of 2–3 nm on the graphene nanosheets. The PtAg/G promoted the current density 2.46 times as much as Pt/C with a negative shift in onset oxidation potential and peak potential for oxidation reaction of methanol. Besides, the novel PtAg/G catalyst shows large electrochemically active surface area, lower apparent activation energy, and higher levels of durability in comparison to the Pt/C catalyst for the oxidation of methanol. The PtAg/G catalyst depicts extraordinary catalytic performance and stability to those of the Pt/C catalyst toward methanol oxidation in alkaline media.  相似文献   

6.
A compact and adherent CoCu spinel coating on ferritic stainless steel was developed by electroplating a CoCu alloy layer followed by oxidation. The CoCu alloy was oxidized into a three-layer structure consisted of a thinner CuO outer layer, a middle thicker Cu0.92Co2.08O4 layer and an inner Co3O4 layer after an oxidation treatment of 2 h at 800 °C in air. The three-layer oxide structure was transformed into a double-layer scale with a (Co,Cr,Cu,Mn,Fe)3O4 spinel outer layer and an inner Cr-rich oxide layer after an oxidation of 500 h at 800 °C in air. The CuCo coating enhanced the oxidation resistance of the alloy and served as a diffusion barrier against the outward migration of Cr elements. Meanwhile, the area specific resistance (ASR) of the scale for the CuCo coated alloy was significantly lower than that for the bare sample.  相似文献   

7.
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   

8.
Hydrogen is envisaged to become an alternative clean energy source to fossil fuels that eventually lead to gradually increasing demand to design an efficient adsorbent for high storage capacity. Being inspired from the metal-doped adsorbents, mesoporous KIT-6 was functionalized with different metals namely Ce, Co, Cr, Cu, Ni, Pd, Pt, Sn and Ti with constant loading by wet impregnation method. Hydrogen adsorption performance showed that the metal doping improves the hydrogen storage capacity of KIT-6 except for KCu. Adsorbents KPd and KPt showed small hysteresis during adsorption/desorption analysis. Among all the metals, Pd-doped KIT-6 (KPd) showed the maximum uptake capacity (0.31 wt%) at atmospheric conditions. However, Sn-doped KIT-6 (KSn) showed the maximum uptake of 4.74 wt% at 77 K and 40 bar. This study provides a thorough insight in to the hydrogen adsorption/desorption behavior of the various metal–doped KIT-6 studied, which could be important first-hand information before designing the hydrogen storage material for the practical application.  相似文献   

9.
A supercapacitor electrode comprising conducting polypyrrole (PPy) coated on manganese oxide-carbon fiber (CNFMnO2) was successfully synthesized using electrospinning, followed by carbonization and in-situ polymerization. A non-uniform distribution of PPy on the surface of CNFMnO2 was observed via FESEM analysis. The chemical bonding of CNFMnO2/PPy and the valence state of manganese were revealed via FTIR, Raman spectroscopy, XRD and XPS measurements. CNFMnO2/PPy composite possessed high specific capacitance and specific energy of 315.80 Fg?1 and 13.68 Wh/kg, respectively. In addition, good electrochemical reversibility was proven upon CNFMnO2/PPy even at higher sweep rate (5–200 mV/s). Moreover, this one-dimensional electrode achieved an excellent long-term cycling stability (82.46%) over 2000 CV cycles with low charge transfer resistance (4.61 Ω). The modification of CNFMnO2/PPy contributes to good synergistic effects among the material which improve the electrochemical behavior of manganese oxide-based fiber composite for future supercapacitor.  相似文献   

10.
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   

11.
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   

12.
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   

13.
Cobalt nanoparticles encapsulated in nitrogen-doped carbon nanotubes (Co@NC) are obtained by a simple pyrolysis of Co-MOF (ZIF-67) for the bifunctional water recovery and hydrogen production. The results showed that calcination temperature of ZIF-67 significantly affected the morphology and catalytic performance. Wastewater are effectively recovered in the presence of the Co@NC and oxidant, which is promoted by anodic oxidation reactions. Co@NC as the cathode catalyst exhibited excellent hydrogen evolution reaction catalytic activity with a low onset potential of ?51 mV (vs. RHE, current density of 0.5 mA/cm2), Tafel slope of 96.73 mV/dec and extraordinary long-term durability. Finally, as a proof of concept, a home-made two-electrode device employed Co@NC as both anode and cathode catalyst for continuous water recovery and simultaneous hydrogen production, which possesses the possibly applications in solving the environmental pollution and energy crisis.  相似文献   

14.
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   

15.
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   

16.
This work first reports AuCu alloys deposited on the surface of TiO2 nanosheets (TiNs) to form heterojunction. A simple deposition-precipitation method was used to construct a new type of AuCu/TiNs heterostructures through gradually depositing Au and Cu nanoparticles on TiNs. Such structures served the dual advantage of constructing a heterostructure which can improve visible light absorption, and the formation of a Schottky barrier between AuCu alloys (lower Fermi level) and TiNs (higher Fermi level) which can suppress the recombination of photo-generated charge carriers to improve the overall photocatalytic activity. The mass ratio of Au and Cu in the AuCu/TiNs heterostructures and the sequence and method of their deposition are found to be the important factors which affect the photocatalytic performance. When the mass ratio of Au to Cu was determined to be 1: 1, the AuCu/TiNs heterostructure exhibited the best photocatalytic performance for hydrogen production from water splitting (over 9 times than TiNs, 1.47 times than Au/TiNs, and 1.75 times than Cu/TiNs).  相似文献   

17.
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   

18.
Through electrodeposition, controlling hydrogen evolution reaction and selective electrochemical dealloying of copper from NiCu porous foam, highly nanoporous nickel and nickel oxide is fabricated on the copper surface. Electrochemically reduced graphene oxide (ERGO) is loaded on the NiNiO foam as high-performance electrodes for supercapacitors through pulsed galvanostatic reduction of drop casted graphene oxide nanosheets at different duty cycles and frequencies. Surface morphology and composition of fabricated ERGO/NiNiO foam composite electrodes are characterized using scanning electron microscopy (SEM), powder X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Raman Spectroscopy. Electrochemical impedance spectroscopy (EIS) measurements, galvanostatic charge/discharge (GCD) and cyclic voltammetry (CV) are carried out to study the electrochemical behavior of ERGO/NiNiO foam electrodes. From structural and electrochemical characterizations, optimized parameters for pulse duty cycle and frequency were found to be 10% and 1000 Hz, respectively. As a result, the ERGO/NiNiO foam film (ic = ?10 mA/cm2, f = 1000 Hz and DC = 10%) provides a specific capacitance of 2298 F/g in 1 M KOH at a current density of 1 A/g. Stability study of fabricated film represents a long cycling life up to 4000 cycles with 0.7% decay in specific capacitance at the high current density of 20 A/g in the potential range of 0–0.6 V vs. saturated calomel electrode (SCE).  相似文献   

19.
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   

20.
Zeolitic Imidazolate Frameworks (ZIF) is one of the potential candidates as highly conducting networks with large surface area with a possibility to be used as catalyst support for low temperature fuel cells. In the present study, highly active state-of-the-art PtCo@NCNTs (Nitrogen Doped Carbon Nanotube) catalyst was synthesized by pyrolyzing ZIF-67 along with Pt precursor under flowing ArH2 atmosphere. The multi-walled NCNTs were densely grown on the surface of ZIF particles after pyrolysis. The high resolution TEM examination was employed to examine the nature of the PtCo particles as well as multi-walled NCNTs. Rotating disk electrode study was used for measuring oxygen reduction reaction performance for PtCo@NCNTs in 0.1 M HClO4 and compared with commercial Pt/C catalyst. Fuel cell performance with PtCo@NCNT and commercial Pt/C catalysts was evaluated at 70 °C using Nafion-212 electrolyte using H2 and O2 gases (100% RH) and the observed peak power density of 630 and 560 mW cm?2, respectively.  相似文献   

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