Catalytic effect of Gd2O3 and Nd2O3 on hydrogen desorption behavior of NaAlH4

This study investigated the effect of Nd₂O₃ and Gd₂O₃ as catalyst on hydrogen desorption behavior of NaAlH₄. Pressure-content-temperature (PCT) equipment measurement proved that both two oxides enhanced the dehydrogenation kinetics distinctly and increasing Nd₂O₃ and Gd₂O₃ from 0.5 mol% to 5 mol% caused a similar effect trend that the dehydrogenation amount and average dehydrogenation rate increased firstly and then decreased under the same conditions. 1 mol% Gd₂O₃–NaAlH₄ presented the largest hydrogen desorption amount of 5.94 wt% while 1 mol% Nd₂O₃–NaAlH₄ exerted the fastest dehydrogenation rate. Scanning Electron microscopy (SEM) analysis revealed that Gd₂O₃–NaAlH₄ samples displayed uniform surface morphology that was bulky, uneven and flocculent. The difference of Nd₂O₃–NaAlH₄ was that with the increasing of Nd₂O₃ content, the particles turned more and more big. Compared to dehydrogenation behavior, this phenomenon demonstrated that small particles structure were beneficial to hydrogen desorption. Besides, the further study found that different catalysts and addition amounts had different effects on the microstructure of NaAlH_4.     

Study of sensitivity and response kinetics changes for SnO2 thin-film hydrogen sensors

We present results of investigations devoted to searching of ways for sol–gel derived SnO₂ thin-film hydrogen sensors performance improvement. To that end we studied the as-prepared sensors parameters changes in real time during short- and long-term operation in gas–air mixture and known operating temperature conditions. It was established that in comparison with as-prepared sensor parameters such initial operation mode leads to the rise of the sensors sensitivity on more than two orders of magnitude, improvement of the sensor parameters stability in time. Obtained experimental data are in a good accordance with known theoretical results.     

SnO2 functionalized AlGaN/GaN high electron mobility transistor for hydrogen sensing applications

In this study, we report on a demonstration of hydrogen sensing at low temperature using SnO₂ functionalized AlGaN/GaN high electron mobility transistors (HEMT). The SnO₂ dispersion was synthesized via a hydrothermal method and selectively deposited on the gate region of a HEMT device through a photolithography process. The high electron sheet carrier concentration of nitride HEMTs provides an increased sensitivity relative to simple Schottky diodes fabricated on GaN layers. The morphology and crystalline properties of the SnO₂-gate, together with the texture of the multilayer films on the device were investigated by SEM, HRTEM, EDS and XRD. The effects of annealing treatment on the crystalline properties of the SnO₂-gate, and gas sensing properties of SnO₂-gated HEMT sensors were studied. The SnO₂-gated HEMT sensor showed fast and reversible hydrogen gas sensing response at low temperature.     

Influence of the method of synthesis on hydrogen adsorption properties of mesoporous binary B2O3/Al2O3 gel systems

Three series of binary oxide systems B₂O₃/Al₂O₃ were prepared and the effect of alumina on dispersion of boron (B₂O₃) component was investigated. The aim of the study was to achieve a maximum dispersion of B₂O₃ in the Al₂O₃ a gel matrix that would lead to increased sorption capacity on boron oxide. Many attempts were made to establish the preparation conditions that would lead to a maximum dispersion of B₂O₃ in the Al₂O₃ gel matrix needed to increase the hydrogen sorption capacity on boron oxide. The systems were characterized by X-ray diffraction, SEM, TEM and low temperature nitrogen adsorption. Hydrogen adsorption was tested in the volumetric system.Results of the study showed that the amount of hydrogen adsorbed on B₂O₃ depended not only on the surface area of the system but also on the separation of B₂O₃ domains in Al₂O₃ gel network. Irrespective of the method of synthesis of the binary oxide system, the dispersion of B₂O₃ phase reflected in the amount of hydrogen adsorbed was the highest for the systems of the lowest B/Al molar ratios studied, i.e. for B/Al = 0.25.     

Characterization of new heterosystem CuFeO2/SnO2 application to visible-light induced hydrogen evolution

Photo-assisted H₂ evolution has been realized over the new heterosystem CuFeO₂/SnO₂ without any noble metal and was studied in connection with some physical parameters. The delafossite CuFeO₂ has been prepared by thermal decomposition from various salts. The polarity of generated voltage is positive indicating that the materials exhibit p-type conductivity whereas the electroneutrality is achieved by oxygen insertion. The plot of the logarithm (conductivity) vs. T⁻¹ gives average activation energy of 0.12 eV. CuFeO₂ is a narrow band gap semiconductor with an optical gap of 1.32 eV. The oxide was characterized photoelectrochemically; its conduction band (−1.09 V_RHE) is located below that of SnO₂ (−0.86 V_RHE) at pH ∼13.5 itself more negative than the H₂O/H₂ level leading to a thermodynamically favorable H₂ evolution under visible irradiation. The sensitizer CuFeO₂, working as an electron pump, is stable towards photocorrosion by hole consumption reactions involving the reducing agents X²⁻ (=S₂O₃²⁻ and SO₃²⁻). The photoactivity was dependent on the precursor and the best performance (0.026 ml h⁻¹ mg⁻¹) was obtained in S₂O₃²⁻ (pH ∼13.5) over CuFeO₂ synthesized from nitrate with a mass ratio (CuFeO₂/SnO₂) equal to unity. A quantum yield of 0.5% was obtained under polychromatic light. H₂ liberation occurs concomitantly with the oxidation of S₂O₃²⁻ to dithionate and sulfate. The tendency towards saturation, in a closed system, is mainly ascribed to the competitive reduction of the end product S₂O₆²⁻.     

Reforming of bioethanol over Ni/Al2O3 and Ni/CeZrO2/Al2O3 catalysts in supercritical water for hydrogen production

Bioethanol was reformed in supercritical water (SCW) at 500 °C and 25 MPa on Ni/Al₂O₃ and Ni/CeZrO₂/Al₂O₃ catalysts to produce high-pressure hydrogen. The results were compared with non-catalytic reactions. Under supercritical water and in a non-catalytic environment, ethanol was reformed to H₂, CO₂ and CH₄ with small amounts of CO and C2 gas and liquid products. The presence of either Ni/Al₂O₃ or Ni/CeZrO₂/Al₂O₃ promoted reactions of ethanol reforming, dehydrogenation and decomposition. Acetaldehyde produced from the decomposition of ethanol was completely decomposed into CH₄ and CO, which underwent a further water-gas shift reaction in SCW. This led to great increases in ethanol conversion and H₂ yield on the catalysts of more than 3-4 times than that of the non-catalytic condition. For the catalytic operation, adding small amounts of oxygen at oxygen to ethanol molar ratio of 0.06 into the feed improved ethanol conversion, at the expense of some H₂ oxidized to water, resulting in a slightly lower H₂ yield. The ceria-zirconia promoted catalyst was more active than the unpromoted catalyst. On the promoted catalyst, complete ethanol conversion was achieved and no coke formation was found. The ceria-zirconia promoter has important roles in improving the decomposition of acetaldehyde, the enhancement of the water-gas shift as well as the methanation reactions to give an extremely low CO yield and a tremendously high H₂/CO ratio. The SCW environment for ethanol reforming caused the transformation of gamma-alumina towards the corundum phase of the alumina support in the Ni/Al₂O₃ catalyst, but this transformation was slowed down by the presence of the ceria-zirconia promoter.     

Evaluation of Ni/Y2O3/Al2O3 catalysts for hydrogen production by autothermal reforming of methane

Ni/xY₂O₃–Al₂O₃ (x = 5, 10, 15, 20 wt%) catalysts were prepared by sequential impregnation synthesis. The catalytic performance for the autothermal reforming of methane was evaluated and compared with Ni/γ-Al₂O₃ catalyst. The physicochemical properties of catalysts were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-Ray Photoelectron Spectrometer (XPS), Thermo Gravimetric Analyzer (TGA) and H₂-temperature programmed reduction techniques (TPR). The decrease of nickel particle size and the change of reducibility were found with Y modification. The CH₄ conversion increased with elevating levels of Y₂O₃ from 5% to 10%, then decreased with Y content from 10% to 20%. Ni/xY₂O₃–Al₂O₃ catalysts maintained high activity after 24 h on stream, while Ni/Al₂O₃ had a significant deactivation. The characterization of spent catalysts indicated that the addition of Y retarded Ni sintering and decreased the amount of coke.     

Photo-catalytic hydrogen production over Fe2O3 based catalysts

The hydrogen photo-evolution was successfully achieved in aqueous (Fe_1−xCr_x)₂O₃ suspensions (0 ≤ x ≤ 1). The solid solution has been prepared by incipient wetness impregnation and characterized by X-ray diffraction, BET, transport properties and photo-electrochemistry. The oxides crystallize in the corundum structure, they exhibit n-type conductivity with activation energy of ∼0.1 eV and the conduction occurs via adiabatic polaron hops. The characterization of the band edges has been studied by the Mott Schottky plots. The onset potential of the photo-current is ∼0.2 V cathodic with respect to the flat band potential, implying a small existence of surface states within the gap region. The absorption of visible light promotes electrons into (Fe_1−xCr_x)₂O₃-CB with a potential (∼−0.5 V_SCE) sufficient to reduce water into hydrogen. As expected, the quantum yield increases with decreasing the electro affinity through the substitution of iron by the more electropositive chromium which increases the band bending at the interface and favours the charge separation. The generated photo-voltage was sufficient to promote simultaneously H₂O reduction and SO₃²⁻ oxidation in the energetically downhill reaction (H₂O + SO₃²⁻ → H₂ + SO₄²⁻, ΔG = −17.68 kJ mol⁻¹). The best activity occurs over Fe_1.2Cr_0.8O₃ in SO₃²⁻ (0.1 M) solution with H₂ liberation rate of 21.7 μmol g⁻¹ min⁻¹ and a quantum yield 0.06% under polychromatic light. Over time, a pronounced deceleration occurs, due to the competitive reduction of the end product S₂O₆²⁻.     

La0.75Sr0.25Cr0.5Mn0.5O3 as hydrogen electrode for solid oxide electrolysis cells

La_0.75Sr_0.25Cr_0.5Mn_0.5O₃ (LSCM) has been applied as hydrogen electrode (cathode) material in solid oxide electrolysis cells operating with different steam concentrations (20, 40, 60 and 80 vol.% absolute humidity (AH)) using 40 sccm H₂ carrier gas at 800, 850 and 900 °C, respectively. Impedance spectra and voltage-current curves were measured as a function of cell electrolysis current density and steam concentration to characterize the cell performance. The cell resistance decreased with the increase in electrolysis current density while increased with the increase in steam concentration under the same electrolysis current density. At 1.6 V applied electrolysis voltage, the maximum consumed current density increased from 431 mA cm⁻² for 20 vol.% AH to 593 mA cm⁻² for 80 vol.% AH at 850 °C. Polarization and impedance spectra experiments revealed that LSCM-YSZ hydrogen electrode played a major role in the electrolysis reaction.     

Stability of Y2O3 hydrogen isotope permeation barriers in hydrogen at high temperatures

Hydrogen isotope permeation barriers (HIPB) have great potential applications in the fields of hydrogen energy and thermonuclear fusion energy. Here, we report the stability of Y₂O₃ HIPB in gaseous hydrogen at high temperatures including the structures, mechanical properties and electrical properties. With increasing hydrogen treatment time at 700 °C, the high-index diffractions of Y₂O₃ became weak gradually whereas the (400) diffraction was strengthened. The color of the Y₂O₃ HIPB changed from brown to gray. The bonding strength decreased by 61% with increasing hydrogen treatment time, and finally remained unchanged. Meanwhile, the electrical resistivity of the Y₂O₃ HIPB decreased from 8.2 × 10⁹ Ω cm by over two orders of magnitude and then tended to be constant. The oxygen loss as well as hydrogen incorporation was proposed to be responsible for these modifications and indications of the present work for preparation of HIPB with high reliability were discussed.     

Hydrogen permeation on Al2O3-based nickel/cobalt composite membranes

Al₂O₃ was synthesized using the sol-gel process with aluminum isopropoxide as the precursor and primary distilled water as the solvent. Nickel and cobalt metal powders were used to increase the strength of the membranes. The Al₂O₃-based membranes were prepared using HPS following a mechanical alloying process. The phase transformation, thermal evolution, surface and cross-section morphology of Al₂O₃ and Al₂O₃-based membranes were characterized by XRD, TG-DTA and FE-SEM. The hydrogen permeation of Al₂O₃-based membranes was examined at 300–473 K under increasing pressure. Hydrogen permeation flux through an Al₂O₃-20wt%Co membrane was obtained to 2.36 mol m⁻² s⁻¹. Reaction enthalpy was calculated to 4.5 kJ/mol using a Van’t Hoff’s plot.     

Electrospun TiO2/SnO2 nanofibers with innovative structure and chemical properties for highly efficient photocatalytic H2 generation

Innovative TiO₂/SnO₂ nanofibers were fabricated via electrospinning an innovated precursor solution and used for photocatalytic H₂ generation. The nanofibers exhibited greatly enhanced H₂ evolution rate compared to bare TiO₂ nanofiber and P25. The enhanced efficiency of the TiO₂/SnO₂ nanofibers was attributed to its excellent synergistic properties: (1) its good mesoporosity; (2) the red-shift of absorbance spectra to enhance light absorbance capability; (3) its long nanofibrous structure and (4) anatase TiO₂ – rutile TiO₂ – rutile SnO₂ ternary junctions favorable for the separation of electrons and holes. Based on our experimental results, the optimum ratio of TiO₂/SnO₂ nanofibers with 3% Sn demonstrated the highest efficiency in H₂ generation.     

Al2O3-coated nanoporous TiO2 electrode for solid-state dye-sensitized solar cell

This paper reports the preparation of a core-shell nanoporous electrode consisting of an inner TiO₂ porous matrix and a thin overlayer of Al₂O₃, and its application for solid-state dye-sensitized solar cell using p-CuI as hole conductor. Al₂O₃ overlayer was coated onto TiO₂ porous film by the surface sol–gel process. The role of Al₂O₃ layer thickness on the cell performance was investigated. The solar cells fabricated from Al₂O₃-coated electrodes showed superior performance to the bare TiO₂ electrode. Under illumination of AM 1.5 simulated sunlight (89 mW/cm²), a ca. 0.19 nm Al₂O₃ overlayer increased the photo-to-electric conversion efficiency from 1.94% to 2.59%.     

Co-effects of Tm2O3 and porous silica on reversible hydrogen storage in NaAlH4

The co-effects of lanthanide oxide Tm₂O₃ and porous silica on the hydrogen storage properties of sodium alanate are investigated. NaAlH₄-Tm₂O₃ (10 wt%) and NaAlH₄-Tm₂O₃ (10 wt%)-porous SiO₂ (10 wt%) are prepared by the ball milling method, and their hydrogen desorption/re-absorption capacities are compared. Dehydrogenation process was performed at 150 °C under vacuum and rehydrogenation was performed at 150 °C for 4 h under ∼9 MPa in highly pure hydrogen. The results show that Tm₂O₃ has a catalytic effect on the hydrogen desorption and re-absorption of NaAlH₄. The hydrogen desorption capacity of Tm₂O₃ single-doped NaAlH₄ is 4.6 wt%, higher than that of undoped NaAlH₄ (4.3 wt%). During the dehydrogenation process, NaAlH₄ is completely decomposed and no intermediate product Na₃AlH₆ is detected. The addition of porous silica improves the dehydrogenation performance of NaAlH₄. Tm₂O₃ and porous silica co-doped NaAlH₄ could release a maximum hydrogen amount of 4.7 wt%, higher than that of undoped NaAlH₄ and Tm₂O₃ single-doped NaAlH₄. Moreover, porous silica improves the reversibility of hydrogen storage in NaAlH₄.     

Visible-light sensitive hydrogen evolution photocatalyst ZnRh2O4

We investigated the ability of the oxide ZnRh₂O₄ to serve as a solar H₂-evolution photocatalyst due to the predicted potential of its conduction band bottom, which may allow thermodynamically favorable H₂ evolution in spite of its small band-gap of 1.2 eV. ZnRh₂O₄ produced H₂ in the presence of HCHO, but only scarcely in the presence of CH₃OH, indicating that the potential of the valence band top of ZnRh₂O₄ lies at ∼0.1 V (vs. SHE). Thus, the conduction band bottom potential (∼−1.1 V) lies much more negative than the potential of H⁺/H₂, allowing thermodynamically favorable H₂ evolution. In addition, the irradiated-light-wavelength dependence of the quantum efficiency (QE) for H₂ evolution was consistent with the solar spectrum, and the QE was quite high (∼27%), even at a wavelength of 770 ± 25 nm. Taken together, our findings indicate that ZnRh₂O₄ can utilize solar light effectively, not only the entire range of UV and visible light, but is also sensitive to infrared light.     

Highly selective hydrogen sensing of Pt-loaded WO3 synthesized by hydrothermal/impregnation methods

Unloaded and 0.25–1.0 wt% Pt-loaded WO₃ nanoparticles were synthesized by hydrothermal method using sodium tungstate dihydrate and sodium chloride as precursors in an acidic condition and impregnated using platinum acetylacetonate. Pt-loaded WO₃ films on an Al₂O₃ substrate with interdigitated Au electrodes were prepared by spin-coating technique. The response of WO₃ sensors with different Pt-loading concentrations was tested towards 0.01–1.0 vol% of H₂ in air as a function of operating temperature (200–350 °C). The 1.0 wt% Pt-loaded WO₃ sensing film showed the highest response of ∼2.16 × 10⁴ to 1.0 vol% H₂ at 250 °C. Therefore, an operating temperature of 250 °C was optimal for H₂ detection. The responses of 1.0 wt% Pt-loaded WO₃ sensing film to other flammable gases, including C₂H₅OH, C₂H₄ and CO, were considerably less, demonstrating Pt-loaded WO₃ sensing film to be highly selective to H₂.     

Flowerlike microspheres catalyst NiO/La2O3 for ethanol-H2 production

Catalysts of nano-sized nickel oxide particles based on flowerlike lanthanum oxide microspheres with high disperse were prepared to achieve simultaneous dehydrogenation of ethanol and water molecules on multi-active sites. XRD, SEM, 77K N₂ adsorption were used to analyze and observe the catalysts’ structure, morphology and porosity. Catalytic parameters with respect to yield of H₂, activity, selectivity towards gaseous products and stability with time-on-stream and time-on-off-stream were all determined. This special morphology NiO/La₂O₃ catalyst represented more than 1000 h time-on-stream stability test and 500 h time-on-off-stream stability test for hydrogen fuel production from ethanol steam reforming at 300 °C without any deactivation. During the 1000 h time-on-stream stability test, ethanol–water mixtures could be converted into H₂, CO, and CH₄ with average selectivity values of 57.0, 20.1, 19.6 and little CO₂ of 3.2 mol%, respectively, and average ethanol conversion values of 96.7 mol%, with H₂ yield of 1.61 mol H₂/mol C₂H₅OH. During the 500 h time-on-off-stream stability test, ethanol–water mixtures could be converted into H₂, CO, CH₄ and CO₂ with average selectivity values of 65.1, 17.3, 15.1 and 2.5 mol%, respectively, and average ethanol conversion values of 80.0 mol%. For the ethanol-H₂ and petrolic hybrid vehicle (EH–HV), the combustion value is the most important factor. So, it was very suitable for the EH–HV application that the low temperature ethanol steam reforming products’ distribution was with high H₂, CO, CH₄ and very low CO₂ selectivity over the special NiO/La₂O₃ flowerlike microspheres.     

Visible light induced hydrogen evolution on new hetero-system ZnFe2O4/SrTiO3

The physical properties and photoelectrochemical characterization of the spinel ZnFe₂O₄, elaborated by chemical route, have been investigated for the hydrogen production under visible light. The forbidden band is found to be 1.92 eV and the transition is indirectly allowed. The electrical conduction occurs by small polaron hopping with activation energy of 0.20 eV. p-type conductivity is evidenced from positive thermopower and cathodic photocurrent. The flat band potential (0.18 V_SCE) determined from the capacitance measurements is suitably positioned with respect to H₂O/H₂ level (−0.85 V_SCE). Hence, ZnFe₂O₄ is found to be an efficient photocatalyst for hydrogen generation under visible light. The photoactivity increases significantly when the spinel is combined with a wide band gap semiconductor. The best performance with a hydrogen rate evolution of 9.2 cm³ h⁻¹ (mg catalyst)⁻¹ occurs over the new hetero-system ZnFe₂O₄/SrTiO₃ in Na₂S₂O₃ (0.025 M) solution.     

Novel Al2O3-based compressive seals for IT-SOFC applications

Novel compressive Al₂O₃-based seals were developed and characterized under simulated intermediate temperature solid oxide fuel cell (IT-SOFC) environment. The seals were prepared by tape casting, mainly composed of fine Al₂O₃ powder with various contents of fine Al powder addition. The leakage rates were determined at 800 °C under 0.14–0.69 MPa compressive stresses, and the stabilities were evaluated at 750 °C under constant 0.35 MPa compressive stress. The leakage rates at 800 °C were in range of 0.2–0.01 sccm cm⁻¹, decreasing with increasing the compressive stress and Al content; Al addition significantly improved the stability, the leakage rate with 20 wt% Al addition was as low as 0.025 sccm cm⁻¹ at 800 °C under 0.35 MPa compressive stress with a gauge pressure of 6.9 kPa, and exhibited good stability at 750 °C. Single cell test also confirmed the effectiveness of the tape cast Al₂O₃-based seal for planar IT-SOFC applications.     

Facile fabrication of Bi2O3/TiO2-xNx nanocomposites for excellent visible light driven photocatalytic hydrogen evolution

Mesoporous Bi₂O₃/TiO_2−xN_x nanocomposites (BiNT) were synthesized by soft chemical template free homogeneous co-precipitation technique. XRD, XPS, TEM, UV-Vis DRS and photoluminescence studies were adapted to determine the structural, electronic and optical properties. The photocatalytic activities of the catalysts were evaluated for water splitting to generate clean hydrogen fuel under visible light irradiation (λ ≥ 400 nm). BiNT-400 catalyst showed highest results towards hydrogen production (198.4 μmol/h) with an apparent quantum efficiency of 4.3%. The pronounced activity of BiNT-400 sample towards hydrogen production was well consistent with high crystallinity, large surface area, proper excitation by N doping and Bi₂O₃ sensitization.