Hydrogen gettering of titaniumpalladium/palladium nanocomposite films synthesized by cosputtering and vacuum-annealing

Nano-engineered composite film, prepared by the combination of titanium (Ti) nanoparticles with surrounding layers of palladium (Pd), has been suggested as a high performance hydrogen (H₂) getter. Uniform TiPd film covered by a 35-nm-thick Pd layer was deposited on a silicon wafer via cosputtering and post-vacuum-annealing. As the annealing temperature increased from 200 to 400 °C, amorphous alloy and nano-aggregates were observed, and efficient structural modulation occurred at 400 °C, where dewetting of Pd cover layer from the getter surface was observed. This led to the enhancement of the chemisorption capacity of the 400^oC-annealed sample, two-times higher than that of the 300^oC-annealed sample. Abrupt change in residual gases, which typically come from a bonding process, can be mitigated by minimizing the gas transfer distance through the dewetting of the cover layer; since Ti nanoparticles surrounded by Pd exist independently of each other in the gettering layer, external H₂ gas molecules can be continuously adsorbed onto still-unreacted Ti particles by passing through the dewetted channels in the Pd cover layer. This concept demonstrates a pathway towards a useful synthetic approach for high-performance thin-film getters with high adsorption capacity, fast gettering rate and good device compatibility.     

Tuning concave PtSn nanocubes for efficient ethylene glycol and glycerol electrocatalysis

Shape-controlled synthesis of well-defined nanostructures offers a great opportunity to promote electrocatalytic performances while reducing the mass loading of noble metals. Herein, we show how morphology can effectively affect the electrocatalytic properties of nanocrystals for alcohol electrooxidation reaction, a key barrier to the application of fuel cells. We report the synthesis of a new generation of alloyed PtSn concave nanocubes (CNCs) through a facile one-pot wet-chemical method. Owing to strong synergistic effect between Pt and Sn, modified electronic structure, as well as high surface areas, the as-obtained alloyed PtSn CNCs can display outstanding electrocatalytic performances for liquid fuel electrooxidation. Impressively, the optimized Pt₄Sn₁ concave nanocubes (CNCs) can achieve a factor of 5.1 enhancements in mass activity and a factor of 5.9 enhancements in specific activity towards ethylene glycol oxidation (EGOR) in comparison with commercial Pt/C catalysts. Moreover, 4.6 and 5.3-fold enhancements in mass and specific activity were also acquired for glycerol oxidation reaction (GOR) compared to those of the commercial Pt/C, holding great promise for future application in fuel cells.     

Hydrogen storage properties of nanocrystalline Mg2Ni prepared from compressed 2MgH2Ni powder

In the present work, nanocrystalline Mg₂Ni with an average size of 20–50 nm was prepared via ball milling of a 2MgH₂Ni powder followed by compression under a pressure of 280 MPa. The phase component, microstructure, and hydrogen sorption properties were characterized by using X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), pressure-composition-temperature (PCT) and synchronous thermal analyses (DSC/TG). Compared to the non-compressed 2MgH₂Ni powder, the compressed 2MgH₂Ni pellet shows lower dehydrogenation temperature (290 °C) and a single-phase Mg₂Ni is obtained after hydrogen desorption. PCT measurements show that the nanocrystalline Mg₂Ni obtained from dehydrogenated 2MgH₂Ni pellet has a single step hydrogen absorption and desorption with fairly low absorption (?57.47 kJ/mol H₂) and desorption (61.26 kJ/mol H₂) enthalpies. It has very fast hydrogen absorption kinetics at 375 °C with about 3.44 wt% hydrogen absorbed in less than 5 min. The results gathered in this study show that ball milling followed by compression is an efficient method to produce Mg-based ternary hydrides.     

A sea cucumber-like nanoporous TiO2 modified by bimetal PtAu through the dealloying for water splitting

Bimetal PtAu modifying nanoporous TiO₂ composites are prepared by dealloying. X-ray diffraction is used to determine the phase constitution. The specific surface area and mesoporous pores are measured by Brunauer-Emmett-Teller. X-ray photoelectron spectroscopy, photoluminescence spectroscopy, UV–Vis diffuse reflectance spectroscopy and Raman spectroscopy are employed to analyse the mutual synergy between Pt and Au. The hydrogen generation rate is measured to determine the photocatalytic performance. The results reveal that TiO₂ is the anatase structure and possess a sea cucumber-like morphology with a large specific surface area. The hydrogen generation rate is 1.745 mmol h^?1 g^?1 for the dealloyed Al₉₂Ti_7.86Pt_0.04Au_0.1 ribbons under the full spectrum irradiation. This value is 29.6 times, 4.4 times and 1.8 times those of the dealloyed Al₉₂Ti₈, Al₉₂Ti_7.9Au_0.1, and Al₉₂Ti_7.96Pt_0.04 ribbons, respectively. The above results indicate that the addition of a small amount of Au and Pt significantly enhances the photocatalytic activity for H₂ production. The Au promotes the absorption of visible light, and Pt serve as an electron sink for effective electron-hole pairs separation during the photocatalytic process. It is a feasible and an effective strategy to take full advantages of respective virtues of noble metals and their strong interactions to enhance photocatalytic activity.     

Synthesis of nanocrystalline mesoporous Ni/Al2O3SiO2 catalysts for CO2 methanation reaction

A series of nanocrystalline mesoporous Ni/Al₂O₃SiO₂ catalysts with various SiO₂/Al₂O₃ molar ratios were prepared by the sol-gel method for the carbon dioxide methanation reaction. The synthesized catalysts were evaluated in terms of catalytic performance and stability. The catalysts were studied using XRD, BET, TPR and SEM. The BET results indicated that the specific surface area of the samples with composite oxide support changed from 254 to 163.3 m²/g, and an increase in the nickel crystallite size from 3.53 to 5.14 nm with an increment of Si/Al molar ratio was visible. The TPR results showed a shift towards lower temperatures, indicating a better reducibility and easier reduction of the nickel oxide phase into the nickel metallic phase. Furthermore, the catalyst with SiO₂/Al₂O₃ molar ratio of 0.5 was selected as the optimal catalyst, which showed 82.38% CO₂ conversion and 98.19% CH₄ selectivity at 350 °C, high stability, and resistivity toward sintering. Eventually, the optimal operation conditions were specified by investigating the effect of H₂/CO₂ molar ratio and gas hourly space velocity (GHSV) on the catalytic behavior of the denoted catalyst.     

Numerical analysis of H2 formation during partial oxidation of H2SH2O upon activation of oxidizer by an electric discharge

The numerical analysis of H₂ production during partial oxidation of H₂SH₂O in a plug-flow reactor at atmospheric pressure and a rather low temperature (T₀ = 500 K) was conducted, when the oxidizer (oxygen or air) was preliminarily activated by an electrical discharge with different values of reduced electric field and input energy. It was shown that a significant hydrogen yield in flow reactor can be obtained only after ignition of the mixture. The ignition delay length depends on the reduced electric field E/N and input energy E_s in the discharge and is minimal at E/N～8–10 Td for the discharge in oxygen and at E/N～4–10 and 120–150 Td in air discharge, when O₂(a¹Δ_g) mole fraction in the discharge products is maximal. If the H₂SH₂OO₂(air) mixture ignites inside the flow reactor, the mole fraction of hydrogen and its relative yield do not depend on E/N. The relative hydrogen yield increases monotonically with an addition of water to H₂S. It was found, that the approach based on the partial oxidation of the H₂SH₂O mixture upon activation of oxygen by an electric discharge can ensure very low energy cost for H₂ production. The minimum specific energy requirement, obtained for the H₂SO₂ mixture, was found to be 0.83 eV/(molecule H₂) and 0.18 eV/(molecule H₂S) at atmospheric pressure and can be further decreased if the energy released during partial oxidation of H₂S is spent on heating the reagents. The use of air as an oxidizer requires higher energy costs and seems to be less promising.     

Study on steam reforming of coal tar over NiCo/ceramic foam catalyst for hydrogen production: Effect of Ni/Co ratio

The effect of Ni/Co ratio on the catalytic performance of NiCo/ceramic foam catalyst for hydrogen production by steam reforming of real coal tar was studied. The NiCo/ceramic foam catalyst was synthesized by deposition-precipitation (DP) method and characterized with different methods. The experiments were conducted in a two-stage fixed-bed reactor. The results showed that the reducibility of the metallic oxides in bimetallic NiCo/ceramic foam catalysts was influenced obviously by the Ni/Co ratio.Both gas and hydrogen yield increased first and then decreased with the decline of Ni/Co ratio, and the highest hydrogen yield of 31.46 mmol g^?1 was obtained when the Ni/Co ratio was 5/5. The lowest coke deposition of 0.34 wt% was generated at the same Ni/Co ratio. The lifetime test showed the catalyst maintained catalytic activity after 14 cycles (28 h), indicating the coal tar steam reforming on NiCo/ceramic foam catalyst is a promising method for hydrogen production.     

Nanostructured CeCu mixed oxide synthesized by solid state reaction for medium temperature shift reaction: Optimization using response surface method

Solid state reaction was applied as a simple and cheap process for synthesizing Ce_0.9Cu_0.1O_1.9 mixed oxide by milling of CuO and CeO₂. Response surface methodology (RSM) technique was used to design a three-levels-two-factors (milling times of 20, 95 and 170 min and milling speeds of 100, 150 and 200 rpm) to investigate and optimize CO conversion in medium temperature shift (MTS) reaction (300–390 °C). According to contour plots, the interaction between parameters (time and speed of) is so important. Determined optimal values of milling time and speed which lead to conversions of 34.9, 47.2, 61.4 and 71.7% at 300, 330, 360 and 390 °C, are 120 min and 162 rpm, respectively. X-ray diffraction (XRD) analysis showed that the trend of crystalline size versus milling speed is different for each milling time: constant for low times, with a maximum for medium times and incremental for high times. Increasing milling time and speed leads to BET surface area decrease and CuCe spices formation which causes better reducibility (TPR) and larger particles (SEM). It was determined that mild values of time and speed (95 min and 150 rpm) lead to the best catalytic performance with good catalytic stability.     

Mechanism of Ni-catalyzed selective CO cleavage of lignin model compound benzyl phenyl ether under mild conditions

Selective cleavage of CO bonds in benzyl phenyl ether (BPE) as a typical lignin α-O-4 ether to produce aromatics is a challenging and attractive topic. Herein, the earth-abundant first-row transition metals, such as Co, Ni and Cu were supported on activated carbon (Co/AC, Ni/AC and Cu/AC) to identify their ability for cleaving CO bond of BPE. Among these catalysts, Ni/AC exhibit highest activity for cleavage of CO bond. The reaction with BPE was carried out at pretty mild condition of 140 °C and 2 MPa H₂, which is highly selective afforded toluene and phenol as the major products with the optimum yields of 88.5 and 86.5%, respectively. Based on the test, the reaction pathways were proposed. A abundant of dissociated H· atoms on Ni(0) sites forms surface active NiH species; Ni(0) activates and facilitates cleavage of the CO bond in BPE to form benzyl (C₆H₅C·) and phenoxy radicals (C₆H₅O·); H· atoms spill from active species NiH recombined together with C₆H₅C· and C₆H₅O· forming the products of toluene and phenol, respectively.     

Preferential CO oxidation over CuOCeO2 catalyst synthesized from MOF with nitrogen-containing ligand as precursor

A set of highly dispersed copper ceria catalysts were synthesized by using the CeMOF precursor featured rich nitrogen-containing ligand. Owing to the existence of coordination interactions between metal ions and nitrogen atoms, the copper ions could be adsorbed into the pore of Ce-MOF and stabilized by the ordered nitrogen atom on the pore wall. After calcinations, the generated CuO/CeO₂ catalyst featured more well-dispersed active sites, which was evidenced by varieties of characterizations such as FT-IR, UV-vis spectroscopy, PXRD, TEM, H₂-TPR, Raman spectroscopy and XPS. The as-synthesized CuO/CeO₂ catalysts displayed outstanding catalytic activities and stabilities for preferential carbon monoxide oxidation in H₂-rich stream.     

Extraordinary room-temperature hydrogen sensing capabilities with high humidity tolerance of PtSnO2 composite nanoceramics prepared using SnO2 agglomerate powder

Two kinds of PtSnO₂ composite nanoceramics have been prepared using SnO₂ nanoparticles and SnO₂ agglomerate powder separately. One is of a relatively uniform and porous microstructure with a specific surface area of 8.1 m²/g, and the other is of a rather non-uniform microstructure with large SnO₂ agglomerates and crack-like pores and a specific surface area of 6.4 m²/g. While the samples of uniform microstructure typically show a sensitivity of 150 to 1% H₂ – 20% O₂ – N₂ in air of 50% relative humidity (RH) at room temperature, those of non-uniform microstructure surprisingly show much higher sensitivities of 850 and 450 in air of 50% and 70% RH, respectively, to the same concentration of hydrogen. The influence of humidity on the samples has been further studied and a much higher humidity tolerance has been revealed for those samples of non-uniform microstructure. All these results demonstrate a clear and unexpected advantage of a non-uniform microstructure over a uniform one in humidity tolerance for room-temperature hydrogen-sensitive PtSnO₂ composite nanoceramics.     

Energy and exergy analyses of hybrid photocatalytic hydrogen production reactor for CuCl cycle

The present paper concerns electrochemical, energy, exergy and exergoeconomic analyses of a hybrid photocatalytic-based hydrogen production reactor which is capable of replacing the electrolysis sub-system of the CuCl thermochemical cycle. Several operating parameters, such as current density, reactor temperature, ambient temperature and electrode distance, are varied to study their effects on the hydrogen production rate, the cost of hydrogen production and energy and exergy efficiencies. The present results show that the voltage drops across the anolyte solution (sol 1), catholyte solution (sol 2), an anode, cathode, and cation exchange membrane vary from 0.005 to 0.016 V, 0.004–0.013 V, 1.67–2.168 V, 0.18–0.22 V and 0.06–0.19 V, respectively with an increase in current density from 0.5 to 1.5 A/cm². The energy and exergy efficiencies of the hybrid photocatalytic hydrogen production reactor decrease from 5.74 to 4.54% and 5.11 to 4.04%, respectively with an increase in current density.     

Development of hydrogen production by liquid phase plasma process of water with NiTiO2/carbon nanotube photocatalysts

Hydrogen evolution by water photocatalysis using liquid phase plasma system was disserted over metal-loaded TiO₂ photocatalysts. Carbon nanotube was applied as a support for the metal-loaded TiO₂ nanocrystallites. Photocatalytic activities of the photocatalysts were estimated for hydrogen production from water. Hydrogen was produced from the photodecomposition of water by liquid phase plasma irradiation. The rate of hydrogen evolution was improved by the metal loading on the TiO₂ surface. TiO₂ nanocrystallites were incorporated above 40 wt% onto the carbon nanotube support. The carbon nanotubes could be applied as a useful photocatalytic support for the fixation of TiO₂. Hydrogen evolution was enhanced by the Ni loading on the TiO₂ nanocrystallites supported on the carbon nanotube. Hydrogen evolution was increased apparently with addition of the alcohols which contributes as a kind of sacrificial reagent promoting the photocatalysis.     

Mesocrystalline Ta2O5 nanosheets supported PdPt nanoparticles for efficient photocatalytic hydrogen production

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.     

Hydrogen permeation properties of CrxCy@Cr2O3/Al2O3 composite coating derived from selective oxidation of a CrC alloy and atomic layer deposition

Metal oxides and carbides are promising tritium permeation barrier coatings for fusion reactors. However, the thermomechanical mismatch between the coating and substrate poses a threat to their interface's integrity during fabrication and operation. To address this issue, a metallic interlayer coating was introduced followed by selective oxidation in which a compact and uniform CrC amorphous alloy coating was successfully deposited on the stainless steel substrate by pulsed electrochemical deposition. A new composite coating of Cr_xC_y@Cr₂O₃/Al₂O₃ was formed by subsequent controlled oxidation conversion and atomic layer deposition. The phase, morphology, chemical state and defects of the films were analyzed and compared both before and after hydrogen exposure at 300 °C. The results show that this new kind of composite coating, based on the principles of grain boundary pinning of chromic oxide with carbide and defect healing of alumina, can remarkably improve the hydrogen permeation barrier performance of these materials.     

Temperature-hydrogen pressure phase boundaries and corresponding thermodynamics for ZrCoH system

The thermodynamically and kinetically stable regions of the temperature–H₂ pressure phase boundaries for the ZrCoH system were established using the Temperature-Concentration-Isobar (TCI) method. Based on this, the enthalpy change and entropy change values of dehydrogenation and disproportionation reactions were successfully obtained. The average enthalpy change (ΔH) and entropy change (ΔS) estimated from the phase boundaries for dehydrogenation of ZrCoH₃ to ZrCo are respectively 103.07 kJ mol^?1H₂ and 148.85 J mol^?1 H₂ K^?1, which are well agreement with the data reported in literature. The average ΔH and ΔS were estimated to be ?120.91 kJ mol^?1H₂ and -149.32 J mol^?1 H₂ K^?1 for the disproportionation of ZrCoH₃, whereas the ΔH and ΔS were calculated to be ?84.6 kJ mol^?1H₂ and -92.29 J mol^?1 H₂ K^?1 for disproportionation of ZrCo. In addition, it was found from the established phase boundaries that the anti-disproportionation property of ZrCo alloy can be enhanced if the phase boundaries of hydrogenation/dehydrogenation are far away from the phase boundaries of disproportionation by adjusting the thermodynamics. Meanwhile, it is possible to keep ZrCo away from disproportionation even at high temperature of 650 °C under hydrogen atmosphere, if the temperature-H₂ pressure trajectory is carefully controlled without crossing the phase boundaries of disproportionation. Therefore, the established phase boundaries can be used as a guide to the eye avoiding disproportionation and improving the anti-disproportionation property of ZrCo alloy.     

Fabrication of CdS/NiFe LDH heterostructure for improved photocatalytic hydrogen evolution from aqueous methanol solution

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.     

The catalytic effect of an inert additive (SrTiO3) on the hydrogen storage properties of 4MgH2Na3AlH6

Investigations on the catalytic effects of a non-reactive and stable additive, SrTiO₃, on the hydrogen storage properties of the 4MgH₂Na₃AlH₆ destabilized system were carried out for the first time. The Na₃AlH₆ compound and the destabilized systems used in the investigations are prepared using ball milling method. The doped system, 4MgH₂Na₃AlH₆SrTiO₃, had an initial dehydrogenation temperature of 145 °C, which 25 °C lower as compared to the un-doped system. The isothermal absorption and desorption capacity at 320 °C has increased by 1.2 wt% and 1.6 wt% with the addition of SrTiO₃ as compared to the 4MgH₂Na₃AlH₆ destabilized system. The decomposition activation energy of the doped system is estimated to be 117.1 kJ/mol. As for the XRD analyses at different decomposition stages, SrTiO₃ is found to be stable and inert. In addition to SrTiO₃, similar phases are found in the doped and the un-doped system during the decomposition and dehydrogenation processes. Therefore, the catalytic effect of the SrTiO₃ is speculated owing to its ability to modify the physical structure of the 4MgH₂Na₃AlH₆ particles through pulverization effect.