Hydrogenation reaction of metallic titanium prepared by molten salt electrolysis

The hydrogenation reaction of electrolyzed titanium, as the first step during hydrogenation-dehydrogenation for the preparation of titanium powder, was studied. The titanium hydride was prepared through the reaction between electrolyzed titanium and hydrogen at different hydrogenation temperatures and different time. The evolutions of hydrogen and oxygen contents, density, hardness and phase composition before and after hydrogenation were characterized under different hydrogenation conditions. The results show that the main phases of titanium hydride were TiHl.924, TiH1.971 and TiH2. Increasing the hydrogenation temperature could not enhance the hydrogen content but increase the oxygen content. The effect of the hydrogenation time on the hydrogen content was not obvious. The optimal parameters of the hydrogenation process were obtained： beating at 400℃ and holding for 2 h, by which the hydrogen content of 3.63% and oxygen content of 0.18% （mass fraction） can be obtained. In addition, the microstructure, orientations and tissues of electrolyzed titanium and titanium hydride were detected.

Low carbon alcohol fuel electrolysis of hydrogen generation catalyzed by a novel and effective Pt–CoTe/C bifunctional catalyst system

Low carbon alcohol fuels electrolysis under ambient conditions is promising for green hydrogen generation instead of the traditional alcohol fuels steam reforming technique,and highly efficient bifunctional catalysts for membrane electrode fabrication are required to drive the electrolysis reactions.Herein,the efficient catalytic promotion effect of a novel catalyst promoter,CoTe,on Pt is demonstrated for low carbon alcohol fuels of methanol and ethanol electrolysis for hydrogen generation.Experimental and density functional theory calculation results indicate that the optimized electronic structure of Pt–CoTe/C resulting from the synergetic effect between Pt and CoTe further regulates the adsorption energies of CO and H*that enhances the catalytic ability for methanol and ethanol electrolysis.Moreover,the good water activation ability of CoTe and the strong electronic effect of Pt and CoTe increased the tolerance ability to the poisoning species as demonstrated by the CO-stripping technique.The high catalytic kinetics and stability,as well as the promotion effect,were also carefully discussed.Specifically,71.9%and 75.5%of the initial peak current density was maintained after 1000 CV cycles in acid electrolyte for methanol and ethanol oxidation;and a low overpotential of 30 and 35 mV was required to drive the hydrogen evolution reaction in methanol and ethanol solution at the current density of 10 mA cm^(-2).In the two-electrode system for alcohol fuels electrolysis,using the optimal Pt–CoTe/C catalyst as bi-functional catalysts,the cell potential of 0.66 V(0.67 V)was required to achieve 10 mA cm^(-2) for methanol(ethanol)electrolysis,much smaller than that of water electrolysis(1.76 V).The current study offers a novel platform for hydrogen generation via low carbon alcohol fuel electrolysis,and the result is helpful to the catalysis mechanism understanding of Pt assisted by the novel promoter.

Development of advanced anion exchange membrane from the view of the performance of water electrolysis cell

Green hydrogen produced by water electrolysis combined with renewable energy is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.Among water electrolysis technologies,the anion exchange membrane(AEM) water electrolysis has gained intensive attention and is considered as the next-generation emerging technology due to its potential advantages,such as the use of low-cost non-noble metal catalysts,the relatively mature stack assembly process,etc.However,the AEM water electrolyzer is still in the early development stage of the kW-level stack,which is mainly attributed to severe performance decay caused by the core component,i.e.,AEM.Here,the review comprehensively presents the recent progress of advanced AEM from the view of the performance of water electrolysis cells.Herein,fundamental principles and critical components of AEM water electrolyzers are introduced,and work conditions of AEM water electrolyzers and AEM performance improvement strategies are discussed.The challenges and perspectives are also analyzed.

Classification and technical target of water electrolysis for hydrogen production

Continuous efforts are underway to reduce carbon emissions worldwide in response to global climate change.Water electrolysis technology,in conjunction with renewable energy,is considered the most feasible hydrogen production technology based on the viable possibility of large-scale hydrogen production and the zero-carbon-emission nature of the process.However,for hydrogen produced via water electrolysis systems to be utilized in various fields in practice,the unit cost of hydrogen production must be reduced to$1/kg H_(2).To achieve this unit cost,technical targets for water electrolysis have been suggested regarding components in the system.In this paper,the types of water electrolysis systems and the limitations of water electrolysis system components are explained.We suggest guideline with recent trend for achieving this technical target and insights for the potential utilization of water electrolysis technology.

Recent advances and future prospects on Ni_(3)S_(2)-Based electrocatalysts for efficient alkaline water electrolysis

Green hydrogen(H_(2))produced by renewable energy powered alkaline water electrolysis is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.However,efficient and economic H_(2) production by alkaline water electrolysis is hindered by the sluggish hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Therefore,it is imperative to design and fabricate high-active and low-cost non-precious metal catalysts to improve the HER and OER performance,which affects the energy efficiency of alkaline water electrolysis.Ni_(3)S_(2) with the heazlewoodite structure is a potential electrocatalyst with near-metal conductivity due to the Ni–Ni metal network.Here,the review comprehensively presents the recent progress of Ni_(3)S_(2)-based electrocatalysts for alkaline water electrocatalysis.Herein,the HER and OER mechanisms,performance evaluation criteria,preparation methods,and strategies for performance improvement of Ni_(3)S_(2)-based electrocatalysts are discussed.The challenges and perspectives are also analyzed.

A robust & weak-nucleophilicity electrocatalyst with an inert response for chlorine ion oxidation in large-current seawater electrolysis

Seawater splitting into hydrogen,a promising technology,is seriously limited by the durability and tolerance of electrocatalysts for chlorine ions in seawater at large current densities due to chloride oxidation and corrosion.Here,we present a robust and weak-nucleophilicity nickel-iron hydroxide electrocatalyst with excellent selectivity for oxygen evolution and an inert response for chlorine ion oxidation which are key and highly desired for efficient seawater electrolysis.Such a weak-nucleophilicity electrocatalyst can well match with strong-nucleophilicity OH-compared with the weak-nucleophilicity Cl^(-),resultantly,the oxidation of OH-in electrolyte can be more easily achieved relative to chlorine ion oxidation,confirmed by ethylenediaminetetraacetic acid disodium probing test.Further,no strongly corrosive hypochlorite is produced when the operating voltage reaches about 2.1 V vs.RHE,a potential that is far beyond the thermodynamic potential of chlorine ion oxidatio n.This concept and approach to reasonably designing weaknucleophilicity electrocatalysts that can greatly avoid chlorine ion oxidation under alkaline seawater environments can push forward the seawater electrolysis technology and also accelerate the development of green hydrogen technique.

Tandem hydroalkylation and deoxygenation of lignin-derived phenolics to synthesize high-density fuels

Lignin is the most abundant naturally phenolic biomass,and the synthesis of high-performance renewable fuel from lignin has attracted significant attention.We propose the efficient synthesis of high-density fuels using simulated lignin cracked oil in tandem with hydroalkylation and deoxygenation reactions.First,we investigated the reaction pathway for the hydroalkylation of phenol,which competes with the hydrodeoxygenation form cyclohexane.And then,we investigated the effects of metal catalyst types,the loading amount of metallic,acid dosage,and reactant ratio on the reaction results.The phenol hydroalkylation and hydrodeoxygenation were balanced when 180℃ and 5 MPa H_(2)with the alkanes yield of 95%.By extending the substrate to other lignin-derived phenolics and simulated lignin cracked oil,we obtained the polycyclic alkane fuel with high density of 0.918 g·ml^(-1)and calorific value of41.2 MJ·L^(-1).Besides,the fuel has good low-temperature properties(viscosity of 9.3 mm^(2)·s^(-1)at 20℃ and freezing point below-55℃),which is expected to be used as jet fuel.This work provides a promising way for the easy and green production of high-density fuel directly from real lignin oil.

Research on typical operating conditions of hydrogen production system with off-grid wind power considering the characteristics of proton exchange membrane electrolysis cell

Hydrogen energy,with its abundant reserves,green and low-carbon characteristic,high energy density,diverse sources,and wide applications,is gradually becoming an important carrier in the global energy transformation and development.In this paper,the off-grid wind power hydrogen production system is considered as the research object,and the operating characteristics of a proton exchange membrane(PEM)electrolysis cell,including underload,overload,variable load,and start-stop are analyzed.On this basis,the characteristic extraction of wind power output data after noise reduction is carried out,and then the self-organizing mapping neural network algorithm is used for clustering to extract typical wind power output scenarios and perform weight distribution based on the statistical probability.The trend and fluctuation components are superimposed to generate the typical operating conditions of an off-grid PEM electrolytic hydrogen production system.The historical output data of an actual wind farm are used for the case study,and the results confirm the feasibility of the method proposed in this study for obtaining the typical conditions of off-grid wind power hydrogen production.The results provide a basis for studying the dynamic operation characteristics of PEM electrolytic hydrogen production systems,and the performance degradation mechanism of PEM electrolysis cells under fluctuating inputs.

Generation of input spectrum for electrolysis stack degradation test applied to wind power PEM hydrogen production

Hydrogen production by proton exchange membrane electrolysis has good fluctuation adaptability,making it suitable for hydrogen production by electrolysis in fluctuating power sources such as wind power.However,current research on the durability of proton exchange membrane electrolyzers is insufficient.Studying the typical operating conditions of wind power electrolysis for hydrogen production can provide boundary conditions for performance and degradation tests of electrolysis stacks.In this study,the operating condition spectrum of an electrolysis stack degradation test cycle was proposed.Based on the rate of change of the wind farm output power and the time-averaged peak-valley difference,a fluctuation output power sample set was formed.The characteristic quantities that played an important role in the degradation of the electrolysis stack were selected.Dimensionality reduction of the operating data was performed using principal component analysis.Clustering analysis of the data segments was completed using an improved Gaussian mixture clustering algorithm.Taking the annual output power data of wind farms in Northwest China with a sampling rate of 1 min as an example,the cyclic operating condition spectrum of the proton-exchange membrane electrolysis stack degradation test was constructed.After preliminary simulation analysis,the typical operating condition proposed in this paper effectively reflects the impact of the original curve on the performance degradation of the electrolysis stack.This study provides a method for evaluating the degradation characteristics and system efficiency of an electrolysis stack due to fluctuations in renewable energy.

Towards high-performance and robust anion exchange membranes(AEMs)for water electrolysis:Super-acid-catalyzed synthesis of AEMs

The increasing demand for hydrogen energy to address environmental issues and achieve carbon neutrality has elevated interest in green hydrogen production,which does not rely on fossil fuels.Among various hydrogen production technologies,anion exchange membrane water electrolyzer(AEMWE)has emerged as a next-generation technology known for its high hydrogen production efficiency and its ability to use non-metal catalysts.However,this technology faces significant challenges,particularly in terms of the membrane durability and low ionic conductivity.To address these challenges,research efforts have focused on developing membranes with a new backbone structure and anion exchange groups to enhance durability and ionic conductivity.Notably,the super-acid-catalyzed condensation(SACC)synthesis method stands out due to its user convenience,the ability to create high molecular weight(MW)polymers,and the use of oxygen-tolerant organic catalysts.Although the synthesis of anion exchange membranes(AEMs)using the SACC method began in 2015,and despite growing interest in this synthesis approach,there remains a scarcity of review papers focusing on AEMs synthesized using the SACC method.The review covers the basics of SACC synthesis,presents various polymers synthesized using this method,and summarizes the development of these polymers,particularly their building blocks including aryl,ketone,and anion exchange groups.We systematically describe the effects of changes in the molecular structure of each polymer component,conducted by various research groups,on the mechanical properties,conductivity,and operational stability of the membrane.This review will provide insights into the development of AEMs with superior performance and operational stability suitable for water electrolysis applications.

A comprehensive review on catalysts for seawater electrolysis

Seawater electrolysis is a sustainable energy conversion technology that generates clean energy by splitting seawater into hydrogen and oxygen.However,the catalysts used in seawater electrolysis often face significant stability challenges because of the high concentration of salt ions and other impurities present in seawater.This review aims to discern the pivotal factors influencing catalyst stability in seawater electrolysis,elucidate the corrosion and electrochemical degradation mechanisms,and delve into the various strategies employed to enhance catalyst stability.These strategies encompass catalyst material selection,surface modification techniques,catalyst support materials,and catalyst design strategies.By gaining deeper insights into the obstacles and innovations concerning catalyst stability in seawater electrolysis,this review strives to expedite progress toward the commercialization and widespread adoption of this technology as a renewable and feasible approach for hydrogen production.Ultimately,the goal is to foster a cleaner and more sustainable future by enabling the efficient and enduring generation of hydrogen from seawater.

Decomposition of a β-O-4 lignin model compound over solid Cs-substituted polyoxometalates in anhydrous ethanol: acidity or redox property dependence?

Production o f aromatics from lignin has attracted much attention. Because of the coexistence of C-O and C-C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for developing a lignin catalytic decomposition process could be developed by exploring the transformation mechanisms of various model compounds. Herein, decomposition of a lignin model compound, 2-phenoxyacetophenone （2-PAP）, was investigated over several ce-sium-exchanged polyoxometalate （Cs-POM） catalysts. Decomposition of 2-PAP can follow two dif-ferent mechanisms： an active hydrogen transfer mechanism or an oxonium cation mechanism. The mechanism for most reactions depends on the competition between the acidity and redox proper-ties of the catalysts. The catalysts of POMs perform the following functions： promoting active hy-drogen liberated from ethanol and causing formation of and then temporarily stabilizing oxonium cations from 2-PAP. The use of Cs-PMo, which with strong redox ability, enhances hydrogen libera-tion and promotes liberated hydrogen transfer to the reaction intermediates. As a consequence, complete conversion of 2-PAP （〉99%） with excellent selectivities to the desired products （98.6% for phenol and 91.1% for acetophenone） can be achieved.

Hydrogen generation from ammonia electrolysis on bifunctional platinum nanocubes electrocatalysts

The ammonia electrolysis is a highly efficient and energy-saving method for ultra-pure hydrogen generation, which highly relies on electrocatalytic performance of electrocatalysts. In this work, high-quality platinum(Pt) nanocubes(Pt-NCs) with 4.5 nm size are achieved by facile hydrothermal synthesis. The physical morphology and structure of Pt-NCs are exhaustively characterized, revealing that Pt-NCs with special {100} facets have excellent uniformity, good dispersity and high crystallinity. Meanwhile, the electrocatalytic performance of Pt-NCs for ammonia electrolysis are carefully investigated in alkaline solutions, which display outstanding electroactivity and stability for both ammonia electrooxidation reaction(AEOR) and hydrogen evolution reaction(HER) in KOH solution. Furthermore, a symmetric Pt-NCs||Pt-NCs ammonia electrolyzer based on bifunctional Pt-NCs electrocatalyst is constructed, which only requires 0.68 V electrolysis voltage for hydrogen generation. Additionally, the symmetric Pt-NCs||Pt-NCs ammonia electrolyzer has excellent reversible switch capability for AEOR at anode and HER at cathode, showing outstanding alternating operation ability for ammonia electrolysis.

SnO_2-based gas(hydrogen) anodes for aluminum electrolysis

A novel SnO2-based gas anode was developed for aluminum electrolysis in molten cryolite at 850 ＆#176;C to reduce energy consumption and decrease CO2 emissions. Hydrogen was introduced into the anode, participating in the anode reaction. Carbon and aluminum were used as the cathode and reference electrodes, respectively. Cyclic voltammetry was applied in the cell to investigate the electrochemical behavior of oxygen ion on platinum and SnO2-based materials. The potential for oxygen evolution on these electrode materials was determined. Then, galvanostatic electrolysis was performed on the gas anode, showing a significant depolarization effect （a decrease of ~0.8 V of the anode potential） after the introduction of hydrogen, compared with no gas introduction or the introduction of argon. The results indicate the involvement of hydrogen in the anode reaction （three-phase-boundary reaction including gas, electrolyte and electrode） and give the possibility for the utilization of reducing gas anodes for aluminum electrolysis.

Ternary layered double hydroxide oxygen evolution reaction electrocatalyst for anion exchange membrane alkaline seawater electrolysis

Anion exchange membrane(AEM)water electrolyzers are promising energy devices for the production of clean hydrogen from seawater.However,the lack of active and robust electrocatalysts for the oxygen evolution reaction(OER)severely impedes the development of this technology.In this study,a ternary layered double hydroxide(LDH)OER electrocatalyst(NiFeCo-LDH)is developed for high-performance AEM alkaline seawater electrolyzers.The AEM alkaline seawater electrolyzer catalyzed by the NiFeCo LDH shows high seawater electrolysis performance(0.84 A/cm^(2)at 1.7 Vcell)and high hydrogen production efficiency(77.6%at 0.5 A/cm^(2)),thus outperforming an electrolyzer catalyzed by a benchmark IrO_(2)electrocatalyst.The NiFeCo-LDH electrocatalyst greatly improves the kinetics of the AEM alkaline seawater electrolyzer,consequently reducing its activation loss and leading to high performance.Based on the results,this NiFeCo-LDH-catalyzed AEM alkaline seawater electrolyzer can likely surpass the energy conversion targets of the US Department of Energy.

Copper foam-derived electrodes as efficient electrocatalysts for conventional and hybrid water electrolysis

Electrochemical water splitting has been demonstrated as a promising technology for the renewable generation of green hydrogen from water.Despite the extensive progress in materials science,one particular challenge for further development towards industrial application lies in the rational design and exploitation of efficient and cost-effective materials,especially oxygen evolution reaction(OER)electrocatalysts at the anode.In addition,attempts to replace the OER with other more oxidizable anode reactions are being evaluated as a groundbreaking strategy for generating hydrogen at lower potentials and reducing overall energy costs while producing valuable chemicals simultaneously.Compared with Fe/Co/Ni-based compounds,Cu-based materials have not received extensive research attention for electrode designs despite their high conductivity and abundant earth reserves.In this review,combining with the advantages of a three-dimensional network structure of metal foams,we summarize recent progress on Cu foam(CF)-derived materials as efficient electrocatalysts towards pure water electrolysis and hybrid water electrolysis.The advantages of CF and design strategies to enhance the electrocatalytic activity and operational durability are presented first.Catalyst design and fabrication strategies are then highlighted and the structure-activity relationship is also discussed.Finally,we propose challenges and perspectives on self-supported electrodes beyond CF-derived materials.

High yield production of 1,4-cyclohexanediol from lignin derived2,6-dimethoxybenzoquinone via Raney Ni Mn catalyst in hydrogen free conditions

Transformation of lignin to valuable chemicals via sustainable pathways is recognized as one of the most efficient ways to explore its value and replace the nonrenewable petroleum resource. In this work, an environmental-friendly transfer hydrogenation process has been developed to convert lignin derived2,6-dimethoxybenzoquinone to 1,4-cyclohexanediol. Compared with previous work under hydrogen pressure(30 bar), this process uses isopropanol as both solvent and hydrogen donor, which significantly simply the operation process. The core of this study is the design and preparation of Mn modified Raney Ni catalysts by ball milling process. A series of Raney Ni Mn catalysts with different ball milling time and Mn content were prepared and investigated. Characterizations by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscope(SEM) and transmission electron microscope(TEM) etc. showed that Ni Mn Al alloy was formed during the ball milling process and then transformed to Ni Mn alloy after treatment by aqueous Na OH. After optimization, a yield as high as 86.1% could be achieved for 1,4-cyclohexanediol at 200℃ in only 1 h.

Analytical Study, 1-D Optimization Modeling, and Testing of Electrode Supported Solid Oxide Electrolysis Cells

This paper presents a straightforward model studying the performance of a solid oxide electrolysis cell at less computational effort while is still comprehensive accounting for details of all physics involved. The model is one dimensional and can be used to optimize SOECs that have composite electrodes. It includes an average mass transfer analysis used to simulate concentration polarization, activation polarization, as well as ohmic loss. The electrochemical reaction that occurs within the electrode functional layers has been accounted for in the calculation of the concentration polarization. This is believed to give a more realistic view of the mass transfer that occurs in SOECs with composite electrodes via a simple and straightforward one dimensional model. Experimental work with SOECs also has been done and some results are reported. The simulation results are compared with experimental data and the agreement is satisfactory. The model can be conveniently used for optimization of the SOEC electrodes and operational conditions.

Water electrolysis based on renewable energy for hydrogen production

As an energy storage medium,hydrogen has drawn the attention of research institutions and industry over the past decade,motivated in part by developments in renewable energy,which have led to unused surplus wind and photovoltaic power.Hydrogen production from water electrolysis is a good option to make full use of the surplus renewable energy.Among various technologies for producing hydrogen,water electrolysis using electricity from renewable power sources shows greatpromise.To investigate the prospects of water electrolysis for hydrogen production,this review compares different water electrolysis processes,i.e.,alkaline water electrolysis,proton exchange membrane water electrolysis,solid oxide water electrolysis,and alkaline anion exchange membrane water electrolysis.The ion transfer mechanisms,operating characteristics,energy consumption,and industrial products of different water electrolysis apparatus are introduced in this review.Prospects for new water electrolysis technologies are discussed.

Catalytic transfer hydrogenolysis as an efficient route in cleavage of lignin and model compounds

Cleavage of aromatic ether bonds through hydrogenolysis is one of the most promising routes for depolymerisation and transformation of lignin into value-added chemicals. Instead of using pressurized hydrogen gas as hydrogen source, some reductive organic molecules, such as methanol, ethanol, isopropanol as well as formates and formic acid, can serve as hydrogen donor is the process called catalytic transfer hydrogenolysis. This is an emerging and promising research field but there are very few reports. In this paper, a comprehensive review of the works is presented on catalytic transfer hydrogenolysis of lignin and lignin model compounds aiming to breakdown the aromatic ethers including a-O-4, b-O-4 and 4-O-5 linkages, with focus on reaction mechanisms. The works are organised regarding to different hydrogen donors used, to gain an in-depth understanding of the special role of various hydrogen donors in this process. Perspectives on current challenges and opportunities of future research to develop catalytic transfer hydrogenolysis as a competitive and unique strategy for lignin valorisation are also provided.