Fabrication of porous metal by selective laser melting as catalyst support for hydrogen production microreactor

To improve the hydrogen production performance of microreactors, the selective laser melting method was proposed to fabricate the porous metals as catalyst supports with different pore structures, porosities, and materials. The influence of the porous structures on the molecule distribution after passing through the porous metals was analyzed by molecular dynamics simulation. The developed porous metals were then used as catalyst supports in a methanol steam reforming microreactor for hydrogen production. Our results show that the porosity of the porous metal had significantly influence on the catalyst infiltration and the reaction process of hydrogen production. A lower degree of catalyst infiltration of the porous metal was obtained with lower porosity. A copper layer-coated stainless-steel porous metal with a staggered structure and gradient porosity of 80%–60% exhibited much larger methanol conversion and H₂ flow rate due to its better heat and mass transfer characteristic. Methanol conversion and H₂ flow rates could reach 97% and 0.62 mol/h, respectively. Finally, it was found that the experimental results were in good agreement with the simulation results.     

Release of hydrogen during transformation from porous silicon to silicon oxide at normal temperature

The use of porous silicon as an energy carrier is investigated. NaOH and solid Mg alloy are used to introduce OH⁻ in water to react with the porous silicon and the porous silicon treated with Mg alloy in water is converted to transparent silicon oxide hydride. The amount and release rate of hydrogen from the reaction between porous silicon and water are determined and the efficiency is also studied. The total amount of released hydrogen does not vary much with the pH value but the release rate is sensitive to the pH value. The average amount of hydrogen produced form porous silicon can reach 63.2 mmol per gram of porous silicon. A moderate rate of about 1.77 mol of H₂ per mol of porous silicon can be obtained per day with the aid of the Mg alloy. This technique is potential useful in supplying hydrogen to fuel cells at normal temperature.     

A simplified numerical approach to hydrogen and hydrocarbon combustion in single and double-layer porous burners

Motivated by the fuel hydrogen applications in porous combustors, as well as hydrogen production in syngas porous devices, this work shows a simplified one-dimensional, steady state heat and mass transfer model for stabilized premixed flames in porous inert media. Single-layer and double-layer porous burner are studied. The model has three conservation equations, describing the heat transfer in the solid and fluid phases and the mass transfer in the reacting flow. The model considers a plug flow and is solved numerically by using the finite volume method. The results are compared with benchmark data, depicting the superadiabatic flames and the heat recirculation process. A parametric analysis of the model reveals the effects of the porous media properties and the Lewis and Peclet numbers on the heat and mass transfer processes. Furthermore, the effects of the flame stand-off parameter in double layer porous burner are also analyzed. The results have considered the values of the dimensionless parameters based on reference data for hydrogen/air and methane/air combustion in porous burners built with SiC and Al₂O₃.     

The two dimension carbon quantum dots modified porous g-C3N4/TiO2 nano-heterojunctions for visible light hydrogen production enhancement

The dual function carbon quantum dots (C QDs) modified porous g-C₃N₄/TiO₂ two dimension (2D) nano-heterojunctions are prepared by a simple route, through which the porous g-C₃N₄ nanosheets are prepared by thermal polycondensation, the TiO₂ nanoparticles are introduced by hydrothermal method and the C QDs are introduced on the surface of the porous g-C₃N₄ and TiO₂ by coupling successively. The results indicate that TiO₂ and C QDs are well combined with the porous g-C₃N₄. The hydrogen production properties of those 2D nano-heterojunctions are investigated, which exhibit an obvious hydrogen production enhancement (nearly two orders of magnitude) compared with those of the unmodified samples. Through analysis, this enhancement of the photocatalystic hydrogen production is attributed to the dual function C QDs with high catalytic activity of H₂O₂ decomposition and unique up-conversion photoluminescence.     

Different effects of temperature on supramolecular protein and non-protein materials in hydrogen storage

The storage of large quantities of hydrogen at ambient temperature is a key factor in establishing a hydrogen-based economy. One strategy for hydrogen storage is to exploit the interaction between H₂ and a solid material by physisorption of hydrogen on porous materials. However, physisorption materials containing MOF, porous carbons, zeolites, clathrates, and synthesized organic polymers physisorb only about 1 wt% of H₂ at ambient temperature. One approach to solving this problem is to prepare new classes of physisorption materials which exhibits a mechanism different from the reported materials in hydrogen storage. Here we report the synthesis of apo cross-linked ferritin supramolecules by disulfide bonds, and their holo form. Unlike non-protein adsorbents, the hydrogen storage capacity of these protein materials increases as a function of temperature over the range of 20–40 °C. The holo supramolecules enable the adsorption of hydrogen up to 3.51 wt% at 40 °C and 40 bar H₂. In contrast, non-protein physisorption materials such as activated carbon and nano Fe₂O₃ marginally adsorb hydrogen, and, as reported, their ability to adsorb hydrogen decreases with increasing temperature under the same experimental condition. These results demonstrate that protein materials have a unique hydrogen storage mechanism which offers new opportunities in exploration of physisorption materials at ambient temperature.     

Application of immobilized Rhodobacter sphaeroides bacteria in hydrogen generation process under semi-continuous conditions

The non-modified and modified (AEAPTMS) VitraPOR^®Filter porous glasses with thickness of 6.8 mm and diameter of 100 mm were applied as carriers for immobilization of Rhodobacter sphaeroides O.U. 001 bacteria. Two different glasses with pores of 40–100 and 100–160 μm were applied. The Van Niel's medium was applied for bacteria growth, whereas hydrogen generation reaction was performed with modified Biebl and Pfennig medium. Our own construction of Flat Plate Photobioreactor (FPP) with capacity of 200 cm³ operating under semi-continuous conditions was applied in this study. The maximum hydrogen production rate obtained was 0.059 dm³ H₂/dm³/h, while the maximum hydrogen yield was 4.2 mol H₂/mol malic acid. System was relatively stable because each series lasted about 3 months. Then the hydrogen production decreased. In order to introduce amine groups on the surface of porous glass, modification with AEAPTMS (3-(2-aminoethyl)aminopropyl)trimetoxysilane was performed. Obtained results proved that both modified and non-modified porous glasses are appropriate materials for stable immobilization of microbiological culture. The best activity and stability was achieved with porous glass matrix representing larger pores, whereas modification of the surface of these matrices with amine improved the amount of immobilized cells but did not improve the hydrogen yield.     

Enhanced photoelectrocatalytic hydrogen production performance of porous MoS2/PPy/ZnO film under visible light irradiation

Photoelectrochemical (PEC) water splitting provides a “green” approach for hydrogen production. However, the design and fabrication of high-efficient catalysts are the bottleneck for PEC water splitting owing to the involved thermodynamic and kinetic challenges. Herein, we report a new strategy for constructing a porous MoS₂/PPy/ZnO thin film photocatalyst with large specific surface area and excellent conductivity to achieve photoelectrochemical water splitting under visible light irradiation. Porous PPy/ZnO was synthesized via template-assisted electrodeposition, and MoS₂ was further electrodeposited to construct porous MoS₂/PPy/ZnO thin film photocatalyst. The hydrogen evolution rate of MoS₂/PPy/ZnO exhibits about 3.5-fold increase to 40.22 μmol cm⁻² h⁻¹ under visible light irradiation. The enhancement for photoelectrochemical hydrogen production is not only ascribed to enlarged specific surface area of the porous structure, but also attributed to the synergistic effects of MoS₂ and porous PPy/ZnO, which could dramatically improve its visible light absorption capacity and enhance the separation and transfer of photogenerated charges. Thus, more abundant photogenerated electrons and holes participate in photoelectrochemical process, which significantly enhances its photoelectrochemical hydrogen production performance.     

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.     

Thermal decomposition synthesis,characterization and electrochemical hydrogen storage characteristics of Co3O4–CeO2 porous nanocomposite

Particle-like Co₃O₄–CeO₂ nanocomposite was synthesized via a facile thermal decomposition process in the presence of fructose as a green capping agent and ammonium cerium(IV) nitrate as Ce source. The effect of various parameters such as different cobalt sources, calcination temperature and time were investigated on the size and morphology of products. The transmission electron microscopy observations indicated that the synthesized products have a particle-like shape with an average diameter of 18–35 nm. For the first time, the electrochemical hydrogen storage performance of Co₃O₄–CeO₂ porous nanocomposite was investigated via chronopotentiometry method in aqueous KOH solution in this paper. The electrochemical measurements showed that this product has a good hydrogen storage capacity at room temperature. Its maximum discharge capacity was 5200 mAh/g after 20 cycles. Therefore, Co₃O₄–CeO₂ porous nanocomposite showed that it is a good candidate for electrochemical hydrogen storage.     

Coating the porous Al2O3 substrate with a natural mineral of Nontronite-15A for fabrication of hydrogen-permeable palladium membranes

Substrate surface modification is a key pretreatment during fabrication of composite palladium membranes for hydrogen purification in hydrogen energy applications. The suspension of a natural porous material, Nontronite-15A mineral, without any organic additives was employed in dip-coating of the porous Al₂O₃ substrate. The Nontronite-15A mineral was characterized by SEM, XRD, TG−DSC and granulometry analysis. The surface and cross-section of the coated porous Al₂O₃ tubes were observed by SEM, and their pore size distribution and nitrogen flux were also measured. Palladium membranes were fabricated over the coated Al₂O₃ tubes by a suction-assisted electroless plating. The optimal loading amount of the Nontronite-15A mineral is just to fill in and level up the surface cavities of the Al₂O₃ substrate rather than to form an extra continuous layer. A thin and selective palladium membrane was successfully obtained, and its permeation performances were tested. The kinetic analyses on the hydrogen flux indicate that the hydrogen permeation behavior exhibits typical characteristics for most of the palladium membranes. During the stability test at 450 °C for 192 h, no membrane damage was detected, and the hydrogen flux increased slightly.     

Spillover enhanced hydrogen uptake of Pt/Pd doped corncob-derived activated carbon with ultra-high surface area at high pressure

Corncob-derived activated carbon (CAC) was prepared by potassium hydroxide activation. The Pt/Pd-doped CAC samples were prepared by two-step reduction method (ethylene glycol reduction plus hydrogen reduction). The as-obtained samples were characterized by N₂-sorption, TEM and XRD. The results show the texture of CAC is varied after doping Pt/Pd. The Pd particles are easier to grow up than Pt particles on the surface of activated carbon. For containing Pt samples, the pore size distributions are different from original sample and Pd loaded sample. The hydrogen uptake results show excess hydrogen uptake capacity on the Pt/Pd-doped CAC samples are higher than pure CAC at 298 K, which should be attributed to hydrogen spillover effects. The 2.5%Pt and 2.5%Pd hybrid doped CAC sample shows the highest hydrogen uptake capacity (1.65 wt%) at 298 K and 180 bar, The particle size and distribution of Pt/Pd catalysts could play a crucial role on hydrogen uptake by spillover. The total hydrogen storage capacity analysis show that total H₂ storage capacities for all samples are similar, and spillover enhanced H₂ uptakes of metal-doped samples could not well support total H₂ storage capacity. The total pore volume of porous materials also is a key factor to affect total hydrogen storage capacity.     

Preparation and electrochemical hydrogen storage properties of Ti49Zr26Ni25 alloy covered with porous polyaniline

A facile saturated solution synthesis method is used to obtain the porous polyaniline (P-PANI). The materials exhibit unique sea urchin-like morphology and special porous structure. Ti₄₉Zr₂₆Ni₂₅ quasicrystal is fabricated via mechanical alloying followed by annealing treatment. Different amounts of P-PANI are coated on the surface of hydrogen storage alloy by ball milling. For comparison, Ti₄₉Zr₂₆Ni₂₅ alloy doped with conventional PANI (C-PANI) is also prepared. The electrochemical characterizations of the composites are conducted in the standard tri-electrode system. Ultimately, the P-PANI coated Ti₄₉Zr₂₆Ni₂₅ electrode shows preferable performance compared with the C-PANI modified alloy (230.6 mAh/g) and original alloy (209.3 mAh/g). As the additive content of P-PANI is 6 wt%, a maximum discharge capacity of 258.7 mAh/g is obtained. Furthermore, the cycle stability and high-rate dischargeability of the electrodes are also enhanced. The P-PANI materials with distinctive morphology and unique porous structure can not only improve the electrocatalytic activity of polyaniline but also increase the specific surface area of Ti₄₉Zr₂₆Ni₂₅ alloy. The P-PANI can further facilitate the hydrogen diffusion, expedite the charge transfer in/on the alloy and improve the corrosion resistance, thus enhancing the electrochemical performance and reaction kinetics of the hydrogen storage alloys.     

Impedance of a tubular electrochemical cell with BZCY electrolyte and Ni-BZCY cermet electrodes for proton ceramic membrane reactors

In this work, impedance spectroscopy has been employed to explore the electrochemical behaviour of a 15 cm² complete tubular cell with BaZr_0.8Ce_0.1Y_0.1O_3-δ (BZCY) electrolyte and two asymmetric Ni-BCZY cermet electrodes for hydrogen separation. Analyses of impedance spectra at different temperatures and gas compositions reveal that the thick inner electrode contributes most to the total polarisation resistance (R_p). For R_p there are four contributions with well-separated time constants of which gas phase hydrogen diffusion within the porous Ni-BZCY anode is predominant. The other three can be ascribed to proton migration through the space charge layer of the BZCY electrolyte adjacent to the Ni electrode, hydrogen redox charge transfer reactions, and hydrogen diffusion within Ni bulk. The present study guides the way to parameterise and, on this basis, optimise electrodes for scalable proton ceramic electrochemical cells.     

Modelling and experimental results of heat transfer in a metal hydride store during hydrogen charge and discharge

A numerical model for the transient hydrogen charge/discharge rates and thermal behaviour of metal hydride stores was developed and verified against experiments using a cylindrical reactor filled with AB₅-type metal hydride. The model assumes local thermal equilibrium between the gas and solid phases, and incorporates the pressure and temperature-dependent hydrogen reaction rates, as well as heat transfer in the porous metal hydride bed. The model was verified through experimental data. The experiments were performed using a unit with hydrogen storage capacity of 130 Nl H₂; the store was submerged in an isothermal water bath. Experiments at different water bath temperatures and charge/discharge hydrogen pressures indicated a relation between charge/discharge time and these parameters. The reactor's ability to deliver a constant hydrogen flow at different water bath temperatures was experimentally investigated. During simulations it was found that the model applied is sensitive to perturbations of some of its parameters; activation energy of absorption, effective conductivity and heat of reaction were found to be the most important ones. The charge and discharge performances of the store are controlled by the reaction rate in the first half-part of the H absorption/desorption experiments and by a heat transfer in the second half-part of charge/discharge.     

Fabrication of porous titanium dioxide fibers and their photocatalytic activity for hydrogen evolution

TiO₂ semiconductor is one of the important photocatalysts for solar light conversion. The challenge is how to improve their efficiency. Creation of porous structures on/in the fibers could favor them a higher surface area as compared to the conventional solid counterparts, which thus could make the achievement for the desired high efficiency. In present work, we report the fabrication of porous TiO₂ fibers with high purity via electrospinning of butyl titanate (TBOT) and polyvinylpyrrolidone (PVP) combined with the subsequent calcination in air. It is found that the TBOT content in the spinning solution plays a profound effect on the growth of the fibers, enabling the synthesis of porous TiO₂ fibers with tunable structures and high purity. The photocatalytic activity for hydrogen evolution of the as-fabricated TiO₂ nanostrcutres has been investigated, suggesting that porous TiO₂ nanomaterials with a high purity and well-defined one-dimensional fiber shape could be an excellent candidate to be utilized as the photocatalyst for hydrogen evolution.     

Co-application of liquid phase plasma process for hydrogen production and degradation of acetaldehyde over NiTiO2 supported on porous materials

Photocatalytic decomposition of acetaldehyde-contained wastewater was assessed for the degradation of pollutants and the production of hydrogen. Liquid phase plasma was applied in the photoreaction as a light source. The evolution of hydrogen and acetaldehyde degradation were characterized by the photocatalytic decomposition system. Ni-loaded TiO₂ photocatalysts and various porous materials were introduced to the photocatalytic reaction. The photochemical decomposition by irradiation of the liquid phase plasma without photocatalysts produced some hydrogen evolution with the degradation of acetaldehyde, which was attributed to the decomposition of the reactant by active species generated by the irradiation of liquid phase plasma. The Ni loading on TiO₂ brought out an enhancement of acetaldehyde degradation and hydrogen evolution. In the photocatalysis of acetaldehyde-contained wastewater using the liquid phase plasma, hydrogen evolution was accelerated due to the additional hydrogen production by the photocatalytic decomposition of acetaldehyde. The porous materials could be used as an effective photocatalytic support. MCM-41 mesoporous material has acted as a highly efficient photocatalytic support to the TiO₂ photocatalyst.     

Hydrogen-rich gas production from biomass steam gasification in an updraft fixed-bed gasifier combined with a porous ceramic reformer

This paper investigates the hydrogen-rich gas produced from biomass employing an updraft gasifier with a continuous biomass feeder. A porous ceramic reformer was combined with the gasifier for producer gas reforming. The effects of gasifier temperature, equivalence ratio (ER), steam to biomass ratio (S/B), and porous ceramic reforming on the gas characteristic parameters (composition, density, yield, low heating value, and residence time, etc.) were investigated. The results show that hydrogen-rich syngas with a high calorific value was produced, in the range of 8.10–13.40 MJ/Nm³, and the hydrogen yield was in the range of 45.05–135.40 g H₂/kg biomass. A higher temperature favors the hydrogen production. With the increasing gasifier temperature varying from 800 to 950 °C, the hydrogen yield increased from 74.84 to 135.4 g H₂/kg biomass. The low heating values first increased and then decreased with the increased ER from 0 to 0.3. A steam/biomass ratio of 2.05 was found as the optimum in the all steam gasification runs. The effect of porous ceramic reforming showed the water-soluble tar produced in the porous ceramic reforming, the conversion ratio of total organic carbon (TOC) contents is between 22.61% and 50.23%, and the hydrogen concentration obviously higher than that without porous ceramic reforming.     

Biomass-derived hierarchical porous CdS/M/TiO2 (M = Au,Ag, pt,pd) ternary heterojunctions for photocatalytic hydrogen evolution

We demonstrate a general method for the synthesis of biomass-derived hierarchical porous CdS/M/TiO₂ (M = Au, Ag, Pt, Pd) ternary heterojunctions for efficient photocatalytic hydrogen evolution. A typical biomass—wood are used as the raw sources while five species of wood (Fir, Ash, White Pine, Lauan and Shiraki) are chosen as templates for the synthesis of hierarchical porous TiO₂. The as-obtained products inherited the hierarchical porous features with pores ranging from micrometers to nanometers, with improved photocatalytic hydrogen evolution activity than non-templated counterparts. Noble metals M (M = Pt, Au, Ag, Pd) and CdS are loaded via a two-step photodeposition method to form core (metal)/shell (CdS) structures. The photocatalytic modules—CdS(shell)/metal (core)/TiO₂ heterostructures, have demonstrated to increase visible light harvesting significantly and to increase the photocatalytic hydrogen evolution activity. The H₂ evolution rates of CdS/Pd/TiO₂ ternary heterostructures are about 6.7 times of CdS/TiO₂ binary heterojunctions and 4 times higher than Pd/CdS/TiO₂ due to the vertical electron transfer process. The design of such system is beneficial for enhanced activity from morphology control and composition adjustment, which would provide some new pathways for the design of promising photocatalytic systems for enhanced performance.     

Synthesis of NaAlH4/Al composites and their applications in hydrogen storage

In solid-state hydrogen storage in light metal hydrides, nanoconfinement and the use of catalysts represent promising solutions to overcoming limitations such as poor reversibility and slow kinetics. In this work, the morphology and hydrogen desorption kinetics of NaAlH₄ melt-infiltrated into a previously developed Ti-based doped porous Al scaffold is analysed. Small-angle X-ray scattering and scanning electron microscopy analysis of low NaAlH₄ loading in the porous Al scaffold has revealed that mesopores and small macropores are filled first, leaving the larger macropores/voids empty. Temperature-programmed desorption experiments have shown that NaAlH₄-infiltrated porous Al scaffolds show a higher relative H₂ release, with respect to NaAlH₄ + TiCl₃, in the temperature range 148–220 °C, with the temperature of H₂ desorption trending to bulk NaAlH₄ with increasing scaffold loading. The Ti-based catalytic effect is reproduced when the dopant is present in the scaffold. Further work is required to increase the mesoporous volume in order to enhance the nanoconfinement effect.     

Water consumption during solid state sodium borohydride hydrolysis

In this paper nickel acetate catalyzed sodium borohydride cartridges have been prepared and hydrolyzed with water for hydrogen production. Two technological solutions have been tested to increase the overall hydrogen yield, namely a porous water diffuser and a hydrophobic membrane. The first was used to improve water diffusion inside the hydride while the second to confine water inside the cartridge. The generated hydrogen flow showed a very reproducible behavior. Hydrogen promptly evolved just after water was pumped into the cartridge. After some initial peaks, a constant hydrogen flow has been recorded for the whole reaction time. The constant flow was related to the presence of the porous diffuser. The use of a hydrophobic membrane to confine the water inside the cartridge allowed to increase the overall hydrogen yield: about 6 water molecules per mol of hydride were required to complete the reaction. The reaction product was identified by XRD as Na₂B₂O₄*8H₂O. The cartridge hydrogen gravimetric content, based on water and sodium borohydride weight, was as high as 4.64%.