Alkaline water electrolysis(AWE)represents a promising approach for green hydrogen production,yet the development of high-performance separators with gas impermeability,high ion conductivity,and stability under alkali...Alkaline water electrolysis(AWE)represents a promising approach for green hydrogen production,yet the development of high-performance separators with gas impermeability,high ion conductivity,and stability under alkaline operating conditions has proven challenging.To address this challenge,we develop a pre-concentration regulated phase separation strategy for scalable fabrication of asymmetric hierarchical porous membranes(AHPMs)for AWE.The resulting AHPMs demonstrate a hierarchical structure composed of an ultrathin dense skin layer and highly interconnected porous support.Benefitting from the structural advantages,the AHPMs exhibit outstanding characteristics,including a high bubble point pressure up to 12.4 bar,extremely low area resistance of 0.03Ωcm^(2) in 30 wt%KOH at 80℃,and excellent hydrophilicity and long-term alkaline stability.When applied in AWE with commercial catalysts,the AHPMs achieved an impressive current density of 1.9 A cm^(-2) at 2.0 V in 30 wt%KOH and the anodic hydrogen contents(AHCs)below 0.5 vol.%at a low current density of 0.1 A cm^(-2),differential pressure of 2 bar,and temperature of 80℃.Moreover,AHPMs demonstrate exceptional stability over 2,400 h of continuous operation and maintain superior performance in a 1 Nm^(3) h^(-1) industrialscale electrolyzer stack.This work advances the development of efficient separators for highperformance AWE systems,contributing to the advancement of hydrogen technologies in sustainable energy applications.展开更多
With the in-depth implementation of sustainable development strategies,hydrogen energy as a clean energy source is receiving increasing attention[1,2].Among the various methods of hydrogen production,the electrocataly...With the in-depth implementation of sustainable development strategies,hydrogen energy as a clean energy source is receiving increasing attention[1,2].Among the various methods of hydrogen production,the electrocatalytic decomposition of abundant seawater into hydrogen utilizing renewable energy has emerged as a green and promising approach.However,natural seawater contains complex components,such as halide ions,which lead to the corrosion of catalysts or the occurrence of competitive side reactions during the electrolysis process[3].展开更多
The global energy crisis and the growing demand for sustainable energy sources have driven considerable interest in green hydrogen production via water electrolysis.Among non-noble metal catalysts,nickel-based materia...The global energy crisis and the growing demand for sustainable energy sources have driven considerable interest in green hydrogen production via water electrolysis.Among non-noble metal catalysts,nickel-based materials have emerged as promising candidates for the hydrogen evolution reaction(HER) in alkaline media,owing to their natural abundance and intrinsic catalytic activity.However,their practical application remains hindered by poor stability under high current densities,challenges in regulating active site distribution,and obstacles to large-scale implementation.This review systematically explores the fundamental principles of alkaline water electrolysis(AWE) and alkaline anion exchange membrane water electrolysis(AEMWE),critically assesses the key barriers to commercialization of nickel-based catalysts,and discusses targeted modification strategies for high-current operation.Emphasis is placed on approaches such as electronic structure modulation,stabilization of active sites,optimization of mass transport,and mitigation of catalyst degradation.Finally,future perspectives are proposed to guide the rational design of durable nickel-based electrocatalysts and promote their integration into industrial-scale alkaline electrolyzers.展开更多
Large-scale green hydrogen production technology,based on the electrolysis of water powered by renewable energy,relies heavily on non-precious metal oxygen evolution reactions(OER)electrocatalysts with high activity a...Large-scale green hydrogen production technology,based on the electrolysis of water powered by renewable energy,relies heavily on non-precious metal oxygen evolution reactions(OER)electrocatalysts with high activity and stability under industrial conditions(6 M KOH,60℃-80℃)at large current density.Here,we construct Fe and Co co-incorporated nickel(oxy)hydroxide(Fe_(2.5)Co_(2.5)Ni_(10)O_(y)H_(z)@NFF)via a multi-metal electrodeposition,which exhibits outstanding OER performance(overpotential:185 mV@10 mA cm^(-2)).Importantly,an overwhelming stability for more than 1100 h at 500 mA cm^(-2)under industrial conditions is achieved.Our combined experimental and computational investigation reveals the surface-reconstructedγ-NiOOH with a high valence state is the active layer,where the optimal(Fe,Co)co-incorporation tunes its electronic structure,changes the potential determining step,and reduces the energy barrier,leading to ultrahigh activity and stability.Our findings demonstrate a facile way to achieve an electrocatalyst with high performance for the industrial production of green hydrogen.展开更多
Seawater electrolysis for hydrogen production faces inherent challenges, including side reactions, corrosion, and scaling, stemming from the intricate composition of seawater. In response, researchers have turned to c...Seawater electrolysis for hydrogen production faces inherent challenges, including side reactions, corrosion, and scaling, stemming from the intricate composition of seawater. In response, researchers have turned to continuous water splitting using forward osmosis(FO)-driven seawater desalination. However, the necessity of a neutral electrolyte hampers this strategy due to the limited current density and scarcity of precious metals. Herein, this study applies alkali-durable FO membranes to enable self-sustaining seawater splitting, which can selectively withdraw water molecules, from seawater, via concentration gradient. The membranes demonstrates outstanding perm-selectivity of water/ions(~5830 mol mol^(-1)) during month-long alkaline resistance tests, preventing electrolyte leaching(>97% OHàretention) while maintaining ~95%water balance(V_(FO)= V_(electrolysis)) via preserved concentration gradient for consistent forward-osmosis influx of water molecules. With the consistent electrolyte environment protected by the polyamide FO membranes, the Ni Fe-Ar-P catalyst exhibits promising performance: a sustain current density of 360 m A cmà2maintained at the cell voltage of 2.10 V and 2.15 V for 360 h in the offshore seawater, preventing Cl/Br corrosion(98% rejection) and Mg/Ca passivation(99.6% rejection). This research marks a significant advancement towards efficient and durable seawater-based hydrogen production.展开更多
NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsi...NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.展开更多
Since the beginning of the 20th century,alkaline electrolysis has been used as a proven method for producing hydrogen on a megawatt scale.The existence of parasitic shunt currents in alkaline water electrolysis,which ...Since the beginning of the 20th century,alkaline electrolysis has been used as a proven method for producing hydrogen on a megawatt scale.The existence of parasitic shunt currents in alkaline water electrolysis,which is utilized to produce clean hydrogen,is investigated in this work.Analysis has been done on a 20-cell stack.Steel end plates,bipolar plates,and an electrolyte concentration of 6 M potassium hydroxide are all included in the model.The Butler-Volmer kinetics equations are used to simulate the electrode surfaces.Ohmic losses are taken into consideration in both the electrode and electrolyte phases,although mass transport constraints in the gas phase are not.Using an auxiliary sweep to solve equations,the model maintains an isothermal condition at 85℃ while adjusting the average cell voltage between 1.3 and 1.8 V.The results show that lower shunt currents in the outlet channels as opposed to the intake channels are the result of the electrolyte’s lower effective conductivity in the upper channels,which is brought on by a lower volume fraction of the electrolyte.Additionally,it has been seen that the shunt currents intensify as the stack gets closer to the conclusion.Efficiency is calculated by dividing the maximum energy output(per unit of time)that a fuel cell operating under comparable conditions might produce by the electrical energy needed to generate that output inside the stack.At first,energy efficiency increases due to the rise in coulombic efficiency,peaking around 1400 mA.The subsequent decline after reaching 1400 mA is linked to an increase in stack voltage at elevated current levels.展开更多
Optimizing the energy barrier of 2H-to-1T phase transformation plays a crucial role in modulating the intrinsic electronic structure of MoS_(2)to achieve satisfactory water-splitting performance,but remains a signific...Optimizing the energy barrier of 2H-to-1T phase transformation plays a crucial role in modulating the intrinsic electronic structure of MoS_(2)to achieve satisfactory water-splitting performance,but remains a significant challenge.Herein,we report a vacancy occupation-triggered phase transition strategy to fabricate a core-shell 1T phase nanorod structure,which is composed of S-vacancies decorated MoS_(2)as the core,and N,P co-doped carbons as the shell(1T-MoS_(2)@NPC).The co-insertion of N and P dopants into MoS_(2)can occupy partial S-vacancies,triggering a phase transformation from the semiconducting 2H phase to the conducting 1T phase with a reduced energy barrier.Profiting from the strong coupling effect between N,P dopants and S-vacancies,the as-made 1T-MoS_(2)@NPC exhibits excellent electrocatalytic activity for both HER(η_(10)=148 m V)and OER(η_(10)=232 mV)in alkaline solution.Meanwhile,a low cell voltage of 1.62 V is needed to drive a current density of 10mA cm^(-2)in 1.0 M KOH electrolyte.The theoretical calculation results reveal that the S-vacancies decorated C atoms in the meta-position relative to N,P atoms represent the most active HER and OER sites,which synergistically upshift the d band center and balance the rate-determining step,thus ensuring the simultaneous optimization of adsorption free energy and electronic structure.This vacancy-occupation-derived phase transformation strategy caused by non-metallic doping may provide valuable guidance for enhancing the performance of alkaline water electrolysis.展开更多
In alkaline water electrolysis(AWE),the development of high-performance membranes with excellent ionic conductivity,robust mechanical stability,and superior gas barrier properties is crucial for efficient hydrogen ene...In alkaline water electrolysis(AWE),the development of high-performance membranes with excellent ionic conductivity,robust mechanical stability,and superior gas barrier properties is crucial for efficient hydrogen energy conversion.This study proposes a superhydrophilic composite membrane based on a synergistic hydrogen bonding and coordination strategy for structural regulation and performance enhancement in AWE.During the non-solvent-induced phase separation(NIPS)process,polyvinylpyrrolidone(PVP)and tannic acid(TA)form a stable hydrogen-bonded network in the water coagulation bath,effectively inducing the construction of a hierarchical porous structure with coexisting finger-like and sponge-like pores.This design enables efficient OH^(-)transport while significantly improving gas barrier properties.On this basis,coordination between TA and ZrO_(2) particles further establishes an organicinorganic micro-interlocking structure,enhancing structural stability and interfacial continuity of the membrane.The optimized PTP3 composite membrane exhibits outstanding comprehensive properties,including high tensile strength(38.77 MPa),elevated bubble point pressure(4.27 bar),and low area resistance(0.12Ωcm^(2)),achieving a current density of 779 mA cm^(-2)at 2 V.In addition,the membrane maintains excellent structural integrity and performance stability after continuous operation for 300 h in a high-temperature,strongly alkaline environment,with negligible degradation.This study offers a novel interfacial hydrogen bonding-coordination design strategy for the development of high-performance,energy-efficient AWE membranes,providing a solid foundation for improving hydrogen production efficiency and enabling large-scale alkaline electrolysis applications.展开更多
The high chloride(Cl)concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation,highlighting the need for cataly...The high chloride(Cl)concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation,highlighting the need for catalyst innovation.Herein,in situ boron-doped Co_(2)P/CoP(B-Co_(x)P)ultrathin nanosheet arrays are prepared as high-performance bifunctional electrocatalysts for seawater decomposition.Density functional theory(DFT)simulations,comprehensive characterizations,and in-situ analyses reveal that boron doping enhances electron density around Co centers,induces lattice distortions,and significantly elevates catalytic activity and durability.Moreover,boron doping reduces*Cl retention time at active sites—defined as the DFT-derived residence time of adsorbed Cl intermediates based on their adsorption energies—effectively mitigating Cl-induced poisoning.In a three-electrode system,B-Co_(x)P achieves exceptional bifunctional performance with overpotentials of 11 mV for hydrogen evolution reaction and 196 mV for oxygen evolution reaction to deliver 10 and 50 mA·cm^(-2),respectively—a result that showcases its superior bifunctional properties surpassing noble metal-based counterparts.In an alkaline electrolyzer,it delivers 1.56 A·cm^(-2)at 2.87 V for seawater electrolysis with outstanding stability over 500 h,preserving active site integrity via boron's robust protective role.This study defines a paradigm for designing advanced seawater electrolysis catalysts through a strategic in-situ doping approach.展开更多
Ion-solvaing membranes(ISMs)have received extensive attention in recent years as a key component in electrochemical energy conversion and storage devices.This article provides an overview of structural composition,per...Ion-solvaing membranes(ISMs)have received extensive attention in recent years as a key component in electrochemical energy conversion and storage devices.This article provides an overview of structural composition,performance advan-tages,research progress,ion conduction mechanism and existing issues of ISMs,primarily classifying them according to the matrix structure.A detailed analysis of performance enhancement methods,key performance indicators of ISMs and performance influencing factors is also presented.The article contributes to further optimizing the design and application of ion-solvation membranes,providing theoretical support for the development of fields such as hydrogen production through electrolysis of water and electrochemical energy in the future.展开更多
Seawater electrolysis has attracted considerable attention in hydrogen production.However,the chloride ions(Cl^(-))in seawater can corrode metal sites and decrease the lifespans of the oxygen evolution reaction(OER).H...Seawater electrolysis has attracted considerable attention in hydrogen production.However,the chloride ions(Cl^(-))in seawater can corrode metal sites and decrease the lifespans of the oxygen evolution reaction(OER).Herein,we report a reversed-active sites strategy,converting Cl^(-)-affinitive metal sites to Cl^(-)-repellent oxygen sites,for OER in alkaline seawater electrolysis.First,ex/in situ experiments confirm the effectiveness of such a strategy using typical perovskites following the adsorbate evolution mechanism(AEM)or lattice oxygen-mediated mechanism(LOM).Furthermore,the origins of the superior activity and durability of as-prepared La_(0.3)SrCo_(0.5)Fe_(0.5)Ox(La_(0.3))can be ascribed to higher participation of lattice oxygen in OER,rapid bulk oxygen diffusion,and excellent OH-adsorption kinetics.Hence,an alkaline seawater electrolytic cell with La_(0.3)as the anode produces 10 mA cm^(-2)at just 1.57 V and maintains near-constant activity over 150 hours.This work introduces novel concepts for the production of superactive and steady electrocatalysts for the electrolysis of seawater.展开更多
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...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.展开更多
The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conduci...The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conducive to the enhancement of electrocatalytic activity.Herein,theoretical simulations first disclose the charge transfer trend and reinforced inherent electron conduction around the epitaxial heterointerface between Ru clusters and Ni_(3)N substrate(cRu-Ni_(3)N),thus leading to the optimized adsorption behaviors and reduced activation energy barriers.Subsequently,the defectrich nanosheets with the epitaxially grown cRu-Ni_(3)N heterointerface are successfully constructed.Impressively,by virtue of the superiority of intrinsic activity and reaction kinetics,such unique epitaxial heterostructure exhibits remarkable bifunctional catalytic activity toward electrocatalytic OER(226 mV@20 mA cm^(−2))and HER(32 mV@10 mA cm^(−2))in alkaline media.Furthermore,it also shows great application prospect in alkaline freshwater and seawater splitting,as well as solar-to-hydrogen integrated system.This work could provide beneficial enlightenment for the establishment of advanced electrocatalysts with epitaxial heterointerfaces.展开更多
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(...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.展开更多
An advantageous porous architecture of electrodes is pivotal in significantly enhancing alkaline water electrolysis(AWE)efficiency by optimizing the mass transport mechanisms.This effect becomes even more pronounced w...An advantageous porous architecture of electrodes is pivotal in significantly enhancing alkaline water electrolysis(AWE)efficiency by optimizing the mass transport mechanisms.This effect becomes even more pronounced when aiming to achieve elevated current densities.Herein,we employed a rapid and scalable laser texturing process to craft novel multi-channel porous electrodes.Particularly,the obtained electrodes exhibit the lowest Tafel slope of 79 mV dec^(-1)(HER)and 49 mV dec^(-1)(OER).As anticipated,the alkaline electrolyzer(AEL)cell incorporating multi-channel porous electrodes(NP-LT30)exhibited a remarkable improvement in cell efficiency,with voltage drops(from 2.28 to 1.97 V)exceeding 300 mV under 1 A cm^(-1),compared to conventional perforated Ni plate electrodes.This enhancement mainly stemmed from the employed multi-channel porous structure,facilitating mass transport and bubble dynamics through an innovative convection mode,surpassing the traditional convection mode.Furthermore,the NP-LT30-based AEL cell demonstrated exceptional durability for 300 h under 1.0 A cm^(-2).This study underscores the capability of the novel multi-channel porous electrodes to expedite mass transport in practical AWE applications.展开更多
Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to thei...Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.展开更多
Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically slug...Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.展开更多
The hydrogen evolution reaction(HER)in alkaline water electrolysis faces significant kinetic and thermodynamic challenges that hinder its efficiency and scalability for sustainable hydrogen production.Herein,we employ...The hydrogen evolution reaction(HER)in alkaline water electrolysis faces significant kinetic and thermodynamic challenges that hinder its efficiency and scalability for sustainable hydrogen production.Herein,we employed an in-situ synthesis strategy to incorporate H atoms into the PdRu alloy lattice to form H_(Inc)-PdRu electrocatalyst,thereby modulating its electronic structure and enhancing its alkaline HER performance.We demonstrate that the incorporation of H atoms significantly improves electrocatalytic activity,achieving a remarkably low overpotential of 25 mV at 10 mA cm^(-2)compared with the Pd,Ru and PdRu catalysts while maintaining robust catalyst stability.Operando spectroscopic analysis indicates that H insertion into the H_(Inc)-PdRu electrocatalyst enhances the availability of H_(2)O^(*)at the surface,promoting water dissociation at the active sites.Theoretical calculations proposed that the co-incorporating H and Ru atoms induces s-d orbital coupling within the Pd lattices,effectively weakening hydrogen adsorption strength and optimizing the alkaline HER energetics.This work presents a facile approach for the rational design of bimetallic electrocatalysts for efficient and stable alkaline water electrolysis for renewable hydrogen production.展开更多
Ensuring high electrocatalytic performance simultaneously with low or even no precious-metal usage is still a big challenge for the development of electrocatalysts toward oxygen evolution reaction(OER)in anion exchang...Ensuring high electrocatalytic performance simultaneously with low or even no precious-metal usage is still a big challenge for the development of electrocatalysts toward oxygen evolution reaction(OER)in anion exchange membrane water electrolysis.Here,homogeneous high entropy oxide(HEO)film is in-situ fabricated on nickel foam(NF)substrate via magnetron sputtering technology without annealing process in air,which is composed of many spinel-structured(FeCoNiCrMo)_(3)O_(4) grains with an average particle size of 2.5 nm.The resulting HEO film(abbreviated as(FeCoNiCr-Mo)_(3)O_(4))exhibits a superior OER performance with a low OER overpotential of 216 mV at 10 mA cm^(–2) and steadily operates at 100 mA cm^(–2) for 200 h with a decay of only 272μV h^(–1),which is far better than that of commercial IrO_(2) catalyst(290 mV,1090μV h^(–1)).Tetramethylammonium cation(TMA^(+))probe experiment,activation energy analysis and theoretical calculations unveil that the OER on(FeCoNiCrMo)_(3)O_(4) follows an adsorbate evolution mechanism pathway,where the energy barrier of rate-determining step for OER on(FeCoNiCrMo)_(3)O_(4) is substantially lowered.Also,methanol molecular probe experiment suggests that a weakened ^(*)OH bonding on the(FeCoNiCrMo)_(3)O_(4) surface and a rapid deprotonation of ^(*)OH,further enhancing its OER performance.This work provides a feasible solution for designing efficient high entropy oxides electrocatalysts for OER,accelerating the practical process of water electrolysis for H2 production.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52273059 and 52473219)the Natural Science Foundation of Tianjin(Grant Nos.22JCYBJC01030 and 23JCYBJC00650)provided by Yantai Tayho Advanced Materials Group Co.,Ltd.
文摘Alkaline water electrolysis(AWE)represents a promising approach for green hydrogen production,yet the development of high-performance separators with gas impermeability,high ion conductivity,and stability under alkaline operating conditions has proven challenging.To address this challenge,we develop a pre-concentration regulated phase separation strategy for scalable fabrication of asymmetric hierarchical porous membranes(AHPMs)for AWE.The resulting AHPMs demonstrate a hierarchical structure composed of an ultrathin dense skin layer and highly interconnected porous support.Benefitting from the structural advantages,the AHPMs exhibit outstanding characteristics,including a high bubble point pressure up to 12.4 bar,extremely low area resistance of 0.03Ωcm^(2) in 30 wt%KOH at 80℃,and excellent hydrophilicity and long-term alkaline stability.When applied in AWE with commercial catalysts,the AHPMs achieved an impressive current density of 1.9 A cm^(-2) at 2.0 V in 30 wt%KOH and the anodic hydrogen contents(AHCs)below 0.5 vol.%at a low current density of 0.1 A cm^(-2),differential pressure of 2 bar,and temperature of 80℃.Moreover,AHPMs demonstrate exceptional stability over 2,400 h of continuous operation and maintain superior performance in a 1 Nm^(3) h^(-1) industrialscale electrolyzer stack.This work advances the development of efficient separators for highperformance AWE systems,contributing to the advancement of hydrogen technologies in sustainable energy applications.
基金financially supported by the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications(No.NY223016)Qinglan Project of Jiangsu Province of China2024 Nanjing Science and Technology Innovation Program(No.NJKCZYZZ2024-06)。
文摘With the in-depth implementation of sustainable development strategies,hydrogen energy as a clean energy source is receiving increasing attention[1,2].Among the various methods of hydrogen production,the electrocatalytic decomposition of abundant seawater into hydrogen utilizing renewable energy has emerged as a green and promising approach.However,natural seawater contains complex components,such as halide ions,which lead to the corrosion of catalysts or the occurrence of competitive side reactions during the electrolysis process[3].
基金financially supported by the Fundamental Research Funds for the Central Universities(No.2232025A-05)the National Natural Science Foundation of China(No.42442040)+2 种基金the National Key Research and Development Program of China(No.2022YFB3803502)the International Cooperation Fund of the Science and Technology Commission of Shanghai Municipality(No.24520713300)Shanghai Rising-Star Program(No.24QA2700100)
文摘The global energy crisis and the growing demand for sustainable energy sources have driven considerable interest in green hydrogen production via water electrolysis.Among non-noble metal catalysts,nickel-based materials have emerged as promising candidates for the hydrogen evolution reaction(HER) in alkaline media,owing to their natural abundance and intrinsic catalytic activity.However,their practical application remains hindered by poor stability under high current densities,challenges in regulating active site distribution,and obstacles to large-scale implementation.This review systematically explores the fundamental principles of alkaline water electrolysis(AWE) and alkaline anion exchange membrane water electrolysis(AEMWE),critically assesses the key barriers to commercialization of nickel-based catalysts,and discusses targeted modification strategies for high-current operation.Emphasis is placed on approaches such as electronic structure modulation,stabilization of active sites,optimization of mass transport,and mitigation of catalyst degradation.Finally,future perspectives are proposed to guide the rational design of durable nickel-based electrocatalysts and promote their integration into industrial-scale alkaline electrolyzers.
基金supported by the Science and Technology Development Fund(FDCT)from Macao SAR(0050/2023/RIB2,0023/2023/AFJ,006/2022/ALC,0111/2022/A2,0105/2023/RIA2)Multi-Year Research Grants(MYRG-GRG2023-00010-IAPME,and MYRG2022-00026-IAPME)from Research&Development Office at University of MacaoShenzhen-Hong Kong-Macao Science and Technology Research Programme(Type C)(SGDX20210823103803017)from Shenzhen.
文摘Large-scale green hydrogen production technology,based on the electrolysis of water powered by renewable energy,relies heavily on non-precious metal oxygen evolution reactions(OER)electrocatalysts with high activity and stability under industrial conditions(6 M KOH,60℃-80℃)at large current density.Here,we construct Fe and Co co-incorporated nickel(oxy)hydroxide(Fe_(2.5)Co_(2.5)Ni_(10)O_(y)H_(z)@NFF)via a multi-metal electrodeposition,which exhibits outstanding OER performance(overpotential:185 mV@10 mA cm^(-2)).Importantly,an overwhelming stability for more than 1100 h at 500 mA cm^(-2)under industrial conditions is achieved.Our combined experimental and computational investigation reveals the surface-reconstructedγ-NiOOH with a high valence state is the active layer,where the optimal(Fe,Co)co-incorporation tunes its electronic structure,changes the potential determining step,and reduces the energy barrier,leading to ultrahigh activity and stability.Our findings demonstrate a facile way to achieve an electrocatalyst with high performance for the industrial production of green hydrogen.
基金funding provided by the National Key R&D Program of China (Grant No. 2021YFB3801301)National Natural Science Foundation of China (Grant Nos. 22075076, 22208097 and 22378119)Shanghai Pilot Program for Basic Research (22TQ1400100-4)。
文摘Seawater electrolysis for hydrogen production faces inherent challenges, including side reactions, corrosion, and scaling, stemming from the intricate composition of seawater. In response, researchers have turned to continuous water splitting using forward osmosis(FO)-driven seawater desalination. However, the necessity of a neutral electrolyte hampers this strategy due to the limited current density and scarcity of precious metals. Herein, this study applies alkali-durable FO membranes to enable self-sustaining seawater splitting, which can selectively withdraw water molecules, from seawater, via concentration gradient. The membranes demonstrates outstanding perm-selectivity of water/ions(~5830 mol mol^(-1)) during month-long alkaline resistance tests, preventing electrolyte leaching(>97% OHàretention) while maintaining ~95%water balance(V_(FO)= V_(electrolysis)) via preserved concentration gradient for consistent forward-osmosis influx of water molecules. With the consistent electrolyte environment protected by the polyamide FO membranes, the Ni Fe-Ar-P catalyst exhibits promising performance: a sustain current density of 360 m A cmà2maintained at the cell voltage of 2.10 V and 2.15 V for 360 h in the offshore seawater, preventing Cl/Br corrosion(98% rejection) and Mg/Ca passivation(99.6% rejection). This research marks a significant advancement towards efficient and durable seawater-based hydrogen production.
基金supported by the Natural Science Foundation of China Grant No.52272289 and 5240223,and JSPS(Japan Society for the Promotion of Science)of Grant No.22K19088,23H00313,24H02202,and 24H02205。
文摘NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.
文摘Since the beginning of the 20th century,alkaline electrolysis has been used as a proven method for producing hydrogen on a megawatt scale.The existence of parasitic shunt currents in alkaline water electrolysis,which is utilized to produce clean hydrogen,is investigated in this work.Analysis has been done on a 20-cell stack.Steel end plates,bipolar plates,and an electrolyte concentration of 6 M potassium hydroxide are all included in the model.The Butler-Volmer kinetics equations are used to simulate the electrode surfaces.Ohmic losses are taken into consideration in both the electrode and electrolyte phases,although mass transport constraints in the gas phase are not.Using an auxiliary sweep to solve equations,the model maintains an isothermal condition at 85℃ while adjusting the average cell voltage between 1.3 and 1.8 V.The results show that lower shunt currents in the outlet channels as opposed to the intake channels are the result of the electrolyte’s lower effective conductivity in the upper channels,which is brought on by a lower volume fraction of the electrolyte.Additionally,it has been seen that the shunt currents intensify as the stack gets closer to the conclusion.Efficiency is calculated by dividing the maximum energy output(per unit of time)that a fuel cell operating under comparable conditions might produce by the electrical energy needed to generate that output inside the stack.At first,energy efficiency increases due to the rise in coulombic efficiency,peaking around 1400 mA.The subsequent decline after reaching 1400 mA is linked to an increase in stack voltage at elevated current levels.
基金supported by the National Natural Science Foundation of China(Grant No.22275210)the Natural Science Foundation of Shandong Province(Grant No.ZR2024QB025,ZR2023ME155)the Taishan Scholar Project of Shandong Province(tsqn202306226)。
文摘Optimizing the energy barrier of 2H-to-1T phase transformation plays a crucial role in modulating the intrinsic electronic structure of MoS_(2)to achieve satisfactory water-splitting performance,but remains a significant challenge.Herein,we report a vacancy occupation-triggered phase transition strategy to fabricate a core-shell 1T phase nanorod structure,which is composed of S-vacancies decorated MoS_(2)as the core,and N,P co-doped carbons as the shell(1T-MoS_(2)@NPC).The co-insertion of N and P dopants into MoS_(2)can occupy partial S-vacancies,triggering a phase transformation from the semiconducting 2H phase to the conducting 1T phase with a reduced energy barrier.Profiting from the strong coupling effect between N,P dopants and S-vacancies,the as-made 1T-MoS_(2)@NPC exhibits excellent electrocatalytic activity for both HER(η_(10)=148 m V)and OER(η_(10)=232 mV)in alkaline solution.Meanwhile,a low cell voltage of 1.62 V is needed to drive a current density of 10mA cm^(-2)in 1.0 M KOH electrolyte.The theoretical calculation results reveal that the S-vacancies decorated C atoms in the meta-position relative to N,P atoms represent the most active HER and OER sites,which synergistically upshift the d band center and balance the rate-determining step,thus ensuring the simultaneous optimization of adsorption free energy and electronic structure.This vacancy-occupation-derived phase transformation strategy caused by non-metallic doping may provide valuable guidance for enhancing the performance of alkaline water electrolysis.
基金the Natural Science Foundation of Tianjin(No.22JCZDJC00100)the Sinopec Technology Development Project(No.224211)the National Natural Science Foundation of China(No.21878231)。
文摘In alkaline water electrolysis(AWE),the development of high-performance membranes with excellent ionic conductivity,robust mechanical stability,and superior gas barrier properties is crucial for efficient hydrogen energy conversion.This study proposes a superhydrophilic composite membrane based on a synergistic hydrogen bonding and coordination strategy for structural regulation and performance enhancement in AWE.During the non-solvent-induced phase separation(NIPS)process,polyvinylpyrrolidone(PVP)and tannic acid(TA)form a stable hydrogen-bonded network in the water coagulation bath,effectively inducing the construction of a hierarchical porous structure with coexisting finger-like and sponge-like pores.This design enables efficient OH^(-)transport while significantly improving gas barrier properties.On this basis,coordination between TA and ZrO_(2) particles further establishes an organicinorganic micro-interlocking structure,enhancing structural stability and interfacial continuity of the membrane.The optimized PTP3 composite membrane exhibits outstanding comprehensive properties,including high tensile strength(38.77 MPa),elevated bubble point pressure(4.27 bar),and low area resistance(0.12Ωcm^(2)),achieving a current density of 779 mA cm^(-2)at 2 V.In addition,the membrane maintains excellent structural integrity and performance stability after continuous operation for 300 h in a high-temperature,strongly alkaline environment,with negligible degradation.This study offers a novel interfacial hydrogen bonding-coordination design strategy for the development of high-performance,energy-efficient AWE membranes,providing a solid foundation for improving hydrogen production efficiency and enabling large-scale alkaline electrolysis applications.
基金supported by the National Natural Science Foundation of China(No.U24A20550,52273264)Youth Science Foundation Project ofChina(No.22409056)+1 种基金the Key Project of the Heilongjiang Provincial Natural Science Foundation(No.ZD2024B001)the Excellent Youth Project ofHeilongjiang Provincial Natural Science Foundation of China(No.LH2019B020).
文摘The high chloride(Cl)concentration in seawater presents a critical challenge for hydrogen production via seawater electrolysis by deactivating catalysts through active site passivation,highlighting the need for catalyst innovation.Herein,in situ boron-doped Co_(2)P/CoP(B-Co_(x)P)ultrathin nanosheet arrays are prepared as high-performance bifunctional electrocatalysts for seawater decomposition.Density functional theory(DFT)simulations,comprehensive characterizations,and in-situ analyses reveal that boron doping enhances electron density around Co centers,induces lattice distortions,and significantly elevates catalytic activity and durability.Moreover,boron doping reduces*Cl retention time at active sites—defined as the DFT-derived residence time of adsorbed Cl intermediates based on their adsorption energies—effectively mitigating Cl-induced poisoning.In a three-electrode system,B-Co_(x)P achieves exceptional bifunctional performance with overpotentials of 11 mV for hydrogen evolution reaction and 196 mV for oxygen evolution reaction to deliver 10 and 50 mA·cm^(-2),respectively—a result that showcases its superior bifunctional properties surpassing noble metal-based counterparts.In an alkaline electrolyzer,it delivers 1.56 A·cm^(-2)at 2.87 V for seawater electrolysis with outstanding stability over 500 h,preserving active site integrity via boron's robust protective role.This study defines a paradigm for designing advanced seawater electrolysis catalysts through a strategic in-situ doping approach.
基金supported by the National Key Research and Development Program of China (2022YFE0138900)the “Scientific and Technical Innovation Action Plan” Basic Research Field of Shanghai Science and Technology Committee (19JC1410500)。
文摘Ion-solvaing membranes(ISMs)have received extensive attention in recent years as a key component in electrochemical energy conversion and storage devices.This article provides an overview of structural composition,performance advan-tages,research progress,ion conduction mechanism and existing issues of ISMs,primarily classifying them according to the matrix structure.A detailed analysis of performance enhancement methods,key performance indicators of ISMs and performance influencing factors is also presented.The article contributes to further optimizing the design and application of ion-solvation membranes,providing theoretical support for the development of fields such as hydrogen production through electrolysis of water and electrochemical energy in the future.
基金supported by the National Natural Science Foundation of China(No.22278203).
文摘Seawater electrolysis has attracted considerable attention in hydrogen production.However,the chloride ions(Cl^(-))in seawater can corrode metal sites and decrease the lifespans of the oxygen evolution reaction(OER).Herein,we report a reversed-active sites strategy,converting Cl^(-)-affinitive metal sites to Cl^(-)-repellent oxygen sites,for OER in alkaline seawater electrolysis.First,ex/in situ experiments confirm the effectiveness of such a strategy using typical perovskites following the adsorbate evolution mechanism(AEM)or lattice oxygen-mediated mechanism(LOM).Furthermore,the origins of the superior activity and durability of as-prepared La_(0.3)SrCo_(0.5)Fe_(0.5)Ox(La_(0.3))can be ascribed to higher participation of lattice oxygen in OER,rapid bulk oxygen diffusion,and excellent OH-adsorption kinetics.Hence,an alkaline seawater electrolytic cell with La_(0.3)as the anode produces 10 mA cm^(-2)at just 1.57 V and maintains near-constant activity over 150 hours.This work introduces novel concepts for the production of superactive and steady electrocatalysts for the electrolysis of seawater.
基金supported by the National Key Research and Development Program(No.2022YFB4202200)the Fundamental Research Funds for the Central Universities.
文摘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.
基金financially sponsored by the National Natural Science Foundation of China(Grant No.22075223,22179104)the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology)(2021-ZD-4)the Fundamental Research Funds for the Central Universities(No.2020-YB-012)。
文摘The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conducive to the enhancement of electrocatalytic activity.Herein,theoretical simulations first disclose the charge transfer trend and reinforced inherent electron conduction around the epitaxial heterointerface between Ru clusters and Ni_(3)N substrate(cRu-Ni_(3)N),thus leading to the optimized adsorption behaviors and reduced activation energy barriers.Subsequently,the defectrich nanosheets with the epitaxially grown cRu-Ni_(3)N heterointerface are successfully constructed.Impressively,by virtue of the superiority of intrinsic activity and reaction kinetics,such unique epitaxial heterostructure exhibits remarkable bifunctional catalytic activity toward electrocatalytic OER(226 mV@20 mA cm^(−2))and HER(32 mV@10 mA cm^(−2))in alkaline media.Furthermore,it also shows great application prospect in alkaline freshwater and seawater splitting,as well as solar-to-hydrogen integrated system.This work could provide beneficial enlightenment for the establishment of advanced electrocatalysts with epitaxial heterointerfaces.
基金supported by the Fundamental Research Program of the Korean Institute of Materials Science(PNK7550)the National Research Council of Science&Technology(NST)grant by the MSIT(CAP21000-000)the New&Renewable Energy Core Technology Program of the KETEP(20213030040520)in the Republic of Korea。
文摘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.
基金financial support from the National Key R&D Program(2023YFE0108000)the Academy of Sciences Project of Guangdong Province(2019GDASYL-0102007,2021GDASYL-20210103063)+1 种基金GDAS’Project of Science and Technology Development(2022GDASZH-2022010203-003)financial support from the China Scholarship Council(202108210128)。
文摘An advantageous porous architecture of electrodes is pivotal in significantly enhancing alkaline water electrolysis(AWE)efficiency by optimizing the mass transport mechanisms.This effect becomes even more pronounced when aiming to achieve elevated current densities.Herein,we employed a rapid and scalable laser texturing process to craft novel multi-channel porous electrodes.Particularly,the obtained electrodes exhibit the lowest Tafel slope of 79 mV dec^(-1)(HER)and 49 mV dec^(-1)(OER).As anticipated,the alkaline electrolyzer(AEL)cell incorporating multi-channel porous electrodes(NP-LT30)exhibited a remarkable improvement in cell efficiency,with voltage drops(from 2.28 to 1.97 V)exceeding 300 mV under 1 A cm^(-1),compared to conventional perforated Ni plate electrodes.This enhancement mainly stemmed from the employed multi-channel porous structure,facilitating mass transport and bubble dynamics through an innovative convection mode,surpassing the traditional convection mode.Furthermore,the NP-LT30-based AEL cell demonstrated exceptional durability for 300 h under 1.0 A cm^(-2).This study underscores the capability of the novel multi-channel porous electrodes to expedite mass transport in practical AWE applications.
基金financial support by the National Natural Science Foundation of China(No.52102241)Doctor of Suzhou University Scientific Research Foundation(Nos.2022BSK019,2020BS015)+2 种基金the Primary Research and Development Program of Anhui Province(No.201904a05020087)the Natural Science Research Project in Universities of Anhui Province in China(Nos.2022AH051386,KJ2021A1114)the Foundation(No.GZKF202211)of State Key Laboratory of Biobased Material and Green Papermaking Qilu University of Technology。
文摘Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.
基金financially supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(No.2024GXNSFFA010008)the Natural Science Foundation of Jilin Province of China(No.20240101098JC)the National Natural Science Foundation of China(No.22469002)。
文摘Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development.Compared with the kinetically sluggish oxygen evolution reaction(OER),the thermodynamically advantageous sulfion oxidation reaction(SOR)enables the S^(2-)pollutants recovery while reducing the energy input of water electrolysis.Here,a nanoporous NiMo alloy ligament(np-NiMo)with AlNi_(3)/Al_(5)Mo heterostructure was prepared for hydrogen evolution reaction(HER,-0.134V versus reversible hydrogen electrode(vs.RHE)at 50mA/cm^(2)),which needs an Al_(89)Ni_(10)Mo_(1)as a precursor and dealloying operation.Further,the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS_(2)(np-NiMo-S)for OER(1.544V vs.RHE at 50mA/cm^(2))and SOR(0.364 V vs.RHE at 50mA/cm^(2)),while still maintaining the nanostructuring advantages.Moreover,for a two-electrode electrolyzer system with np-NiMo cathode(1M KOH+seawater)coupling np-NiMo-S anode(1mol/L KOH+seawater+1 mol/L Na_(2)S),a remarkably ultra-low cell potential of 0.532 V is acquired at 50mA/cm^(2),which is about 1.015 V below that of normal alkaline seawater splitting.The theory calculations confirmed that the AlNi_(3)/Al_(5)Mo heterostructure within np-NiMo promotes H_(2)O dissociation for excellent HER,while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from^(*)S_(4)to^(*)S_(8).This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.
文摘The hydrogen evolution reaction(HER)in alkaline water electrolysis faces significant kinetic and thermodynamic challenges that hinder its efficiency and scalability for sustainable hydrogen production.Herein,we employed an in-situ synthesis strategy to incorporate H atoms into the PdRu alloy lattice to form H_(Inc)-PdRu electrocatalyst,thereby modulating its electronic structure and enhancing its alkaline HER performance.We demonstrate that the incorporation of H atoms significantly improves electrocatalytic activity,achieving a remarkably low overpotential of 25 mV at 10 mA cm^(-2)compared with the Pd,Ru and PdRu catalysts while maintaining robust catalyst stability.Operando spectroscopic analysis indicates that H insertion into the H_(Inc)-PdRu electrocatalyst enhances the availability of H_(2)O^(*)at the surface,promoting water dissociation at the active sites.Theoretical calculations proposed that the co-incorporating H and Ru atoms induces s-d orbital coupling within the Pd lattices,effectively weakening hydrogen adsorption strength and optimizing the alkaline HER energetics.This work presents a facile approach for the rational design of bimetallic electrocatalysts for efficient and stable alkaline water electrolysis for renewable hydrogen production.
文摘Ensuring high electrocatalytic performance simultaneously with low or even no precious-metal usage is still a big challenge for the development of electrocatalysts toward oxygen evolution reaction(OER)in anion exchange membrane water electrolysis.Here,homogeneous high entropy oxide(HEO)film is in-situ fabricated on nickel foam(NF)substrate via magnetron sputtering technology without annealing process in air,which is composed of many spinel-structured(FeCoNiCrMo)_(3)O_(4) grains with an average particle size of 2.5 nm.The resulting HEO film(abbreviated as(FeCoNiCr-Mo)_(3)O_(4))exhibits a superior OER performance with a low OER overpotential of 216 mV at 10 mA cm^(–2) and steadily operates at 100 mA cm^(–2) for 200 h with a decay of only 272μV h^(–1),which is far better than that of commercial IrO_(2) catalyst(290 mV,1090μV h^(–1)).Tetramethylammonium cation(TMA^(+))probe experiment,activation energy analysis and theoretical calculations unveil that the OER on(FeCoNiCrMo)_(3)O_(4) follows an adsorbate evolution mechanism pathway,where the energy barrier of rate-determining step for OER on(FeCoNiCrMo)_(3)O_(4) is substantially lowered.Also,methanol molecular probe experiment suggests that a weakened ^(*)OH bonding on the(FeCoNiCrMo)_(3)O_(4) surface and a rapid deprotonation of ^(*)OH,further enhancing its OER performance.This work provides a feasible solution for designing efficient high entropy oxides electrocatalysts for OER,accelerating the practical process of water electrolysis for H2 production.
