Hydrogen generation from NaBH_(4) for portable proton exchange membrane fuel cell

Sodium borohydride(NaBH_(4)) is considered as the most potential hydrogen storage material for portable proton exchange membrane fuel cells(PEMFC)because of its high theoretical hydrogen capacity.However,the slow and poor kinetic stability of hydrogen generation from NaBH_(4) hydrolysis limits its application.There are two main factors influencing the kinetics stability of hydrogen generation from NaBH_(4).One factor is that the alkaline byproducts(NaBO_(2)) of the hydrolysis reaction can increase the pH of the solution,thus inhibiting the reaction process.It mainly happens in the NaBH_(4) solution hydrolysis system.Another factor is that the monotonous increase in reaction temperature leads to uncontrollable and unpredictable hydrolysis rates in the solid NaBH_(4) hydrolysis system.This is due to the excess heat generated from this exothermic reaction in the initial reaction of NaBH_(4) hydrolysis.In this perspective,we summarize the latest research progress in hydrogen generation from NaBH_(4) and emphasize the design principles of catalysts for hydrogen generation from NaBH_(4) solution and solid state NaBH_(4).The importance of carbon as catalyst support material for NaBH_(4) hydrolysis is also highlighted.

Defect engineering of ternary Cu-In-Se quantum dots for boosting photoelectrochemical hydrogen generation

Heavy-metal-free ternary Cu–In–Se quantum dots(CISe QDs)are promising for solar fuel production because of their low toxicity,tunable band gap,and high light absorption coefficient.Although defects significantly affect the photophysical properties of QDs,the influence on photoelectrochemical hydrogen production is not well understood.Herein,we present the defect engineering of CISe QDs for efficient solar-energy conversion.Lewis acid–base reactions between metal halide–oleylamine complexes and oleylammonium selenocarbamate are modulated to achieve CISe QDs with the controlled amount of Cu vacancies without changing their morphology.Among them,CISe QDs with In/Cu=1.55 show the most outstanding photoelectrochemical hydrogen generation with excellent photocurrent density of up to 10.7 mA cm-2(at 0.6 VRHE),attributed to the suitable electronic band structures and enhanced carrier concentrations/lifetimes of the QDs.The proposed method,which can effectively control the defects in heavy-metal-free ternary QDs,offers a deeper understanding of the effects of the defects and provides a practical approach to enhance photoelectrochemical hydrogen generation.

Polar O-Co-P Surface for Bimolecular Activation in Catalytic Hydrogen Generation

Boron hydrides release an abundant amount of hydrogen in the presence of a suitable catalyst.Accelerating bimolecular activation kinetics is the key to designing cost-effective catalysts for borohydride hydrolysis.In this study,the bimolecular activation of a polar O-Co-P site demonstrated superior hydrogen-generation kinetics(turnover frequency,TOF=37 min−1,298 K)and low activation energy(41.0 kJ mol^(−1))close to that of noble-metal-based catalysts.Through a combination of experiments and theoretical calculations,it was revealed that the activated dangling oxygen atom in the Co–O precursor effectively replaced via surface-phosphorization because of strong electronic interactions between the dangling oxygen and P atoms.This substitution modulated the local coordination environment and electronegativity around the surface Co sites and formed a new polar O-Co-P active site for optimizing the activation kinetics of ammonia borane and water.This strategy based on bimolecular activation may create new avenues in the field of catalysis.

Hydrogen generation from polyvinyl alcohol-contaminated wastewater by a process of supercritical water gasification

Gasification of polyvinyl alcohol （PVA）-contaminated wastewater in supercritical water （SCW） was investigated in a continuous flow reactor at 723-873 K, 20-36 MPa and residence time of 20-450 s. The gas and liquid products were analyzed by GC/TCD, and TOC analyzer. The main gas products were H2, CH4, CO and CO2. Pressure change had no significant influence on gasification efficiency. Higher temperature and longer residence time enhanced gasification efficiency, and lower temperature favored the production of H2. The effects of KOH catalyst on gas product composition were studied, and gasification efficiency were analyzed. The TOC removal efficiency （RTOC）, carbon gasification ratio （RCG） and hydrogen gasification ratio （RHG） were up to 96.00%, 95.92% and 126.40% at 873 K and 60 s, respectively, which suggests PVA can be completely gasified in SCW. The results indicate supercritical water gasification for hydrogen generation is a promising process for the treatment ofPVA wastewater.

Polyoxometalates-engineered hydrogen generation rate and durability of Pt/CNT catalysts from ammonia borane

Heterogeneously catalyzed hydrolytic dehydrogenation of ammonia borane is a remarkable structure sensitive reaction. In this work, a strategy by using polyoxometalates(POMs) as the ligands is proposed to engineer the surface and electronic properties of Pt/CNT catalysts toward the enhanced hydrogen generation rate and durability. Three kinds of POMs, i.e., silicotungstic acid(STA), phosphotungstic acid(PTA)and molybdophosphoric acid(PMA), are comparatively studied, among which the STA shows positive effects on the catalytic activity and durability. A catalyst structure-performance relationship is established by a combination of kinetic and isotopic analyses with multiple characterization techniques, such as HAADF-STEM, EDS, Raman spectroscopy and XPS. It is shown that the STA compared to the other two POMs can increase the Pt binding energy and thus promote the reaction. The insights demonstrated here could open a new avenue for boosting the reaction by employing the POMs as the ligands to engineer the catalyst electronic properties.

Hydrogen generation from methanolysis of sodium borohydride over Co/Al_2O_3 catalyst

Co/Al2O3 catalyst is prepared with an impregnation-chemical reduction method and used to catalyze the methanolysis of sodium borohydride （NaBH 4） for hydrogen generation.At solution temperature of 0 C,the methanolysis reaction can be effectively accelerated using Co/Al2O3 catalyst and provide a desirable hydrogen generation rate,which makes it suitable for applications under the circumstance of low environmental temperature.The byproduct of methanolysis reaction is analyzed by X-ray diffraction （XRD） and Fourier transform infrared spectroscopy （FTIR）.The characterization results indicate that methanol can be easily recovered after methanolysis reaction by hydrolysis of the methanolysis byproduct,NaB（OCH 3） 4.The catalytic activity of Co/Al2O3 towards NaBH 4 methanolysis can be further improved by appropriate calcination treatment.The catalytic methanolysis kinetics and catalyst reusability are also studied over the Co/Al2O3 catalyst calcined at the optimized temperature.

An Improved Method for Evaluating Hydrocarbon Generation of Shale:A Case Study of the Lower Cretaceous Qingshankou Formation Shale in the Songliao Basin

Because of the influence of hydrocarbons,especially adsorbed hydrocarbons,on the detection of cracked hydrocarbon(S2)and total organic carbon(TOC),the hydrogen index(HI)-based hydrocarbon generation model deviates from actual practice.In this study,the shale in the first member of the Qingshankou Formation in the central depression of the Songliao Basin,where in northeastern China,was taken as the research object and a correction method for S2 and TOC was established.By correcting the experimental results of different maturity samples,the actual hydrocarbon generation model has been revealed,the differences before and after correction compared,and the evolutionary characteristics of the adsorbed hydrocarbon content were clarified.The results show that the organic matter enters the hydrocarbon generation threshold at R_(o)-0.5% and reaches the hydrocarbon generation peak at R_(o)-1.0% and that the hydrocarbon generation process ends at R_(o)-1.3%.The hydrocarbon generation model established based on the measured values has a‘lag effect’compared to actual values,and this extends the hydrocarbon generation window of organic matter and delays the hydrocarbon generation peak.With the increase of maturity,adsorbed hydrocarbon content shows the characteristics of‘first increasing,then stabilizing,and then decreasing’,and reache s the most abundant stage at Roof 0.9%-1.3%.

Co-CoO_x supported onto TiO_(2) coated with carbon as a catalyst for efficient and stable hydrogen generation from ammonia borane

Ammonia borane(AB) can be catalytically hydrolyzed to provide hydrogen at room temperature due to its high potentaial for hydrogen storage. Non-precious metal heterogeneous catalysts have broad application in the field of energy catalysis. In this article, catalysts precursor is obtained from Co-Ti-resorcinol-formaldehyde resin by sol–gel method. Co/TiO_(2)@N-C(CTC) catalyst is prepared by calcining the precursor under high temperature conditions in nitrogen atmosphere. Co-CoO_x/TiO_(2)@N-C(COTC) is generated by the controllable oxidation reaction of CTC. The catalyst can effectively promote the release of hydrogen during the hydrolytic dehydrogenation of AB. High hydrogen generation at a specific rate of 5905 m L min^(-1) g_(Co)^(-1) is achieved at room temperature. The catalyst retains its 85% initial catalytic activity even for its fifth time use in AB hydrolysis. The synergistic effect among Co, Co_(3)O_(4) and TiO_(2) promotes the rate limiting step with dissociation and activation of water molecules by reducing its activation energy. The applied method in this study promotes the development of non-precious metals in catalysis for utilization in clean energy sources.

Oxalic Acid Promoted Hydrolysis of Sodium Borohydride for Transition Metal Free Hydrogen Generation

We reported an inexpensive and high-efficiency hydrogen generation method from NaBH4 hydrolysis promoted by oxalic acid.NaBH4 and H2C2O4 were premixed and hydrogen generation was initiated by adding water into the solid mixture.H2C2O4 was selected as the acid promotor due to its solid state and low mass per proton.The effect of reactant ratio on the hydrogen yield and hydrogen storage density was investigated.With optimized reactant ratio,high gravimetric hydrogen storage up to 4.4wt%based on all the reactants can be achieved with excellent hydrogen generation kinetics.

Boosting electrocatalytic hydrogen generation by a renewable porous wood membrane decorated with Fe-doped NiP alloys

Porous biomass electrodes have emerged as a critical material for electrocatalytic hydrogen evolution reaction(HER).However,most approaches for synthesizing porous electrodes from biomass require high energy consumption,which is resulted from the smash of biomass and the undergoing of serial assembly.Herein,a self-supported wood-derived"breathable"membrane is utilized directly as electrodes for highefficient HER via an assembly of Fe-doped NiP alloys.The well-designed hierarchical porous structures in natural wood membrane(NWM)are unusually beneficial for electrolytes accessibility and hydrogen gas removal.The obtained wood-derived membrane exhibits a high electrocatalytic activity and good cycling durability in acidic and alkaline electrolytes.Remarkably,the Fe_(0.074) NiP alloys/NWM electrode affords a large current density of 100 m A cm^(-2) at extremely low overpotentials of 168 mV in acidic electrolyte and174 m V in alkaline electrolyte.Density functional theory calculations unveil that the Fe atom doped in NiP alloys can create much more charge accumulation around Fe and Ni active sites,which helps decrease the △GH_(*)and △G_(H2O)and significantly promote the HER process.This new insight will promote further explorations of economic,high-efficient,and biodegradable wood-derived electrocatalysts for HER.

Effect of doped Ni-Bi-B alloy on hydrogen generation performance of Al-InCl3

In this work,Ni-Bi-B alloy has been synthesized via chemical synthesis method.A new kind of Al-InCl3-(Ni-Bi-B)composite has been prepared by high energy mechanical ball grinding A1 powder with additives.Results show that the doped Ni-Bi-B alloy can significantly improve the hydrogen generation performance of Al-InCl3 and the catalytic activity is enhanced with the increasing content of Bi in Ni-Bi-B alloy.Under optimal conditions,the hydrogen generation yield and conversion yield of Al-InCl3-(Ni-Bi-B)reached1196.8 mL g^-1 and 100.0%at room temperature,respectively.Mechanism study shows five kinds of active sites,such as the fresh surface/defect of Al particle,Al-AlCl3,Al-In,Al-Bi/B and Al-Ni/B produced during the ball milling process.Their synergistic effect enhances the hydrogen generation performance of AlInCl3-(Ni-Bi-B)remarkably.In general,the proposed Al-InCl3-(Ni-Bi-B)composite is possible to serve as hydrogen generation material for fuel cells.

Mesoporous cadmium bismuth niobate(CdBi2Nb2O9)nanospheres for hydrogen generation under visible light

Herein, we report visible light active mesoporous cadmium bismuth niobate（CBN） nanospheres as a photocatalyst for hydrogen（H） generation from copious hydrogen sulfide（HS）. CBN has been synthesized by solid state reaction（SSR） and also using combustion method（CM） at relatively lower temperatures.The as-synthesized materials were characterized using different techniques. X-ray diffraction analysis shows the formation of single phase orthorhombic CBN. Field emission scanning electron microscopy and high resolution-transmission electron microscopy showed the particle size in the range of.5–1 μm for CBN obtained by SSR and 50–70 nm size nanospheres using CM, respectively. Interestingly, nanospheres of size 50–70 nm self assembled with 5–7 nm nanoparticles were observed in case of CBN prepared by CM.The optical properties were studied using UV–visible diffuse reflectance spectroscopy and showed band gap around.0 eV for SSR and 3.1 eV for CM. The slight shift in band gap of CM is due to nanocrystalline nature of material. Considering the band gap in visible region, the photocatalytic activity of CBN for hydrogen production from HS has been performed under visible light. CBN prepared by CM has shown utmost hydrogen evolution i.e. 6912 μmol/h/0.5 g which is much higher than CBN prepared using SSR.The enhanced photocatalytic property can be attributed to the smaller particle size, crystalline nature,high surface area and mesoporous structure of CBN prepared by combustion method. The catalyst was found to be stable, active and can be utilized for water splitting.

Integrated Ni-P-S nanosheets array as superior electrocatalysts for hydrogen generation

Searching for efficient and robust non-noble electrocatalysts for hydrogen generation is extremely desirable for future green energy systems.Here, we present the synthesis of integrated Ni-P-S nanosheets array including Ni_2P and NiS on nickel foam by a simple simultaneous phosphorization and sulfurization strategy. The resultant sample with optimal composition exhibits superior electrocatalytic performance for hydrogen evolution reaction(HER) in a wide pH range. In alkaline media, it can generate current densities of 10, 20 and 100 mA cm^(-2) at low overpotentials of only-101.9,-142.0 and-207.8 mV with robust durability. It still exhibits high electrocatalytic activities even in acid or neutral media. Such superior electrocatalytic performances can be mainly attributed to the synergistic enhancement of the hybrid Ni-P-S nanosheets array with integration microstructure. The kind of catalyst gives a new insight on achieving efficient and robust hydrogen generation.

Low-order harmonic generation of hydrogen molecular ion in laser field studied by the two-state model

The low-order harmonic generation of hydrogen molecular ion interacting with a linearly polarized laser field has been investigated theoretically by using a simple two-state model. The validity of the two-state model is carefully examined by comparing the harmonic spectra of hydrogen molecular ion obtained from this model with those from the three-dimensional time-dependent Schr¨odinger equation. When combined with the Morlet transform of quantum time-frequency spectrum,the two-state model can be used to study the dynamical origin of the low-order harmonic generation of hydrogen molecular ion driven by low-frequency pulses. In addition, some interesting structures of the time profiles for low order harmonics are obtained.

Effects of Aluminum Particle Size, Galinstan Content and Reaction Temperature on Hydrogen Generation Rate Using Activated Aluminum and Water

Aluminum, in its normal passive oxidized state, does not react with water. In this work, aluminum activation is carried out using liquid metal eutectics Ga-In-Sn-Zn (60:25:10:5). Subsequently, the reaction with water of activated aluminum to produce hydrogen has been examined. The effects of aluminum particle size, liquid eutectics content, and reaction temperature on hydrogen production rates are investigated. The liquid eutectics interaction with aluminum is discussed and the mechanisms of liquid eutectics penetration within the Al particles have been investigated. The specific surface area of the Al particles, the mass ratio of Al to eutectics content and the reaction temperature were found to determine the hydrogen production rate and yield. It is observed that micro-aluminum particles of ~30 μm size display lower reaction rates and hydrogen yields than ~350 μm size particles.

MXenes and heterostructures-based electrocatalysts for hydrogen evolution reaction:Recent developments and future outlook

The increasing focus on electrocatalysis for sustainable hydrogen(H_(2))production has prompted significant interest in MXenes,a class of two-dimensional(2D)materials comprising metal carbides,carbonitrides,and nitrides.These materials exhibit intriguing chemical and physical properties,including excellent electrical conductivity and a large surface area,making them attractive candidates for the hydrogen evolution reaction(HER).This scientific review explores recent advancements in MXene-based electrocatalysts for HER kinetics.It discusses various compositions,functionalities,and explicit design principles while providing a comprehensive overview of synthesis methods,exceptional properties,and electro-catalytic approaches for H_(2) production via electrochemical reactions.Furthermore,challenges and future prospects in designing MXenes-based electrocatalysts with enhanced kinetics are highlighted,emphasizing the potential of incorporating different metals to expand the scope of electrochemical reactions.This review suggests possible efforts for developing advanced MXenes-based electrocatalysts,particularly for efficient H_(2) generation through electrochemical water-splitting reactions..

Integration of morphology and electronic structure modulation on cobalt phosphide nanosheets to boost photocatalytic hydrogen evolution from ammonia borane hydrolysis

The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.

Mitigating Carbon Emissions:A Comprehensive Analysis of Transitioning to Hydrogen-Powered Plants in Japan’s Energy Landscape Post-Fukushima

One of the impacts of the Fukushima disaster was the shutdown of all nuclear power plants in Japan,reaching zero production in 2015.In response,the country started importing more fossil energy including coal,oil,and natural gas to fill the energy gap.However,this led to a significant increase in carbon emissions,hindering the efforts to reduce its carbon footprint.In the current situation,Japan is actively working to balance its energy requirements with environmental considerations,including the utilization of hydrogen fuel.Therefore,this paper aims to explore the feasibility and implications of using hydrogen power plants as a means to reduce emissions,and this analysis will be conducted using the energy modeling of the MARKAL-TIMES Japan framework.The hydrogen scenario(HS)is assumed with the extensive integration of hydrogen into the power generation sector,supported by a hydrogen import scheme.Additionally,this scenario will be compared with the Business as Usual(BAU)scenario.The results showed that the generation capacities of the BAU and HS scenarios have significantly different primary energy supplies.The BAU scenario is highly dependent on fossil fuels,while the HS scenario integrates hydrogen contribution along with an increase in renewable energy,reaching a peak contribution of 2,160 PJ in 2050.In the HS scenario,the target of reducing CO2 emissions by 80%is achieved through significant hydrogen penetration.By 2050,the total CO2 emissions are estimated to be 939 million tons for the BAU scenario and 261 million tons for the Hydrogen scenario.In addition,the contribution of hydrogen to electricity generation is expected to be 153 TWh,smaller than PV and wind power.

Enhancement in solar hydrogen generation efficiency using InGaN photoelectrode after surface roughening treatment with nano-sized Ni mask

A significant enhancement in solar hydrogen generation efficiency has been achieved by inductive coupled etching （ICP） surface roughening treatment using nano-sized nickel mask. As much as 7 times improvement of photocurrent is demonstrated in comparison with a planar one fabricated from the same parent wafer. Under identical illumination conditions in HBr solution, the incident photon conversion efficiency （IPCE） shows an enhancement with a factor of 3, which even exceed 54% at 400 nm wavelength. We believe the enhancement is attributed to several facts including improvement in absorption, reacting area, carder localization and carrier lifetime.

Experimental Study of Plasma Under-liquid Electrolysis in Hydrogen Generation

The application and characteristics of relatively big volume plasma produced with cathodic glow discharges taking place across a gaseous envelope over the cathode which was dipped into electrolyte in hydrogen generation were studied. A critical investigation of the influence of methanol concentration and voltage across the circuit on the composition and power consumption per cubic meter of cathode liberating gas was carried out. The course of plasma under-liquid electrolysis has the typical characteristics of glow discharge electrolysis. The cathode liberating gas was in substantial excess of the Faraday law value. When the voltage across the circuit was equal to 550 V,the volume of cathodic gas with sodium carbonate solution was equal to 16.97 times the Faraday law value. The study showed that methanol molecules are more active than water molecules. The methanol molecules were decomposed at the plasma-catholyte interface by the radicals coming out the plasma mantle. Energy consumption per cubic meter of cathodic gases (WV) decreased while methanol concentration of the electrolytes increased. When methanol concentration equaled 5% (-),WV was 10.381×103 kJ/m3,less than the corresponding theoretic value of conventional water electrolysis method. The cathodic liberating gas was a mixture of hydrogen,carbon dioxide and carbon monoxide with over 95% hydrogen,if methanol concentration was more than 15% (-). The present research work revealed an innovative application of glow discharge and a new highly efficient hydrogen generation method,which depleted less resource and energy than normal electrolysis and is environmentally friendly.