Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.

Design Principles and Mechanistic Understandings of Non-Noble-Metal Bifunctional Electrocatalysts for Zinc-Air Batteries

Zinc-air batteries(ZABs)are promising energy storage systems because of high theoretical energy density,safety,low cost,and abundance of zinc.However,the slow multi-step reaction of oxygen and heavy reliance on noble-metal catalysts hinder the practical applications of ZABs.Therefore,feasible and advanced non-noble-metal elec-trocatalysts for air cathodes need to be identified to promote the oxygen catalytic reaction.In this review,we initially introduced the advancement of ZABs in the past two decades and provided an overview of key developments in this field.Then,we discussed the work-ing mechanism and the design of bifunctional electrocatalysts from the perspective of morphology design,crystal structure tuning,interface strategy,and atomic engineering.We also included theoretical studies,machine learning,and advanced characterization technologies to provide a comprehensive understanding of the structure-performance relationship of electrocatalysts and the reaction pathways of the oxygen redox reactions.Finally,we discussed the challenges and prospects related to designing advanced non-noble-metal bifunctional electrocatalysts for ZABs.

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.

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.

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..

Defects and morphology engineering for constructing V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S nanotube heterojunction arrays toward efficient bifunctional electrocatalyst for overall water splitting

The development of highly active,stable and inexpensive electrocatalysts for hydrogen production by defects and morphology engineering remains a great challenge.Herein,S vacancies-rich Ni_(3)S_(2)@Cu_(2)S nan-otube heterojunction arrays were in-situ grown on copper foam(V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF)for efficient electrocatalytic overall water splitting.With the merits of nanotube arrays and efficient electronic mod-ulation drived by the OD vacancy defect and 2D heterojunction defect,the resultant V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF electrocatalyst exhibits excellent electrocatalytic activity with a low overpotential of 47 mV for the hydrogen evolution reaction(HER)at 10 mA cm^(-2) current density,and 263 mV for the oxygen evolution reaction(OER)at 50 mA cm^(-2) current density,as well as a cell voltage of 1.48 V at 10 mA cm^(-2).Moreover,the nanotube heterojunction arrays endows V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF with outstanding stability in long-term catalytic processes,as confirmed by the continuous chronopotentiom-etry tests at current densities of 10 mA cm^(-2) for 100 h.

Recent progress in two-dimensional metallenes and their potential application as electrocatalyst

In this article,we looked at metallenes,a novel class of two-dimensional(2D)metals that are attracting interest in the energy and catalysis sectors.Catalysis is one area where their exceptional physicochemical and electrical characteristics might be useful.Metallenes are unique because they include several metal atoms that are not in a coordinated bond.This makes them more active and improves their atomic uti-lization,which in turn increases their catalytic potential.This article delves into the potential of two-dimensional metals as electrocatalysts for carbon dioxide reduction,fuel oxidation,oxygen evolution,and oxygen reduction reactions in the context of sustainable energy conversion.Owing to the exception-ally high surface-to-volume ratio,large surface area as well as their optimized atomic use efficiency,2D materials defined by atomic layers are crucial for surface-related sustainable energy applications.Due to its exceptional properties,such as high conductivity and the ability to enhance the exposure of active metal sites,2D metallenes have recently attracted a lot of interest for use in catalysis,electronics,and energy-related applications.With their highly mobility,adjustable surface states,and electrical struc-tures that can be fine-tuned,2D metallenes are promising nanostructure materials for use in energy con-version with the sustainable applications.

Fullerenes and derivatives as electrocatalysts: Promises and challenges

Carbon-based metal-free nanomaterials are promising alternatives to precious metals as electrocatalysts of key energy storage and conversion technologies.Of paramount significance are the establishment of design principles by understanding the catalytic mechanisms and identifying the active sites.Distinct from sp2-conjugated graphene and carbon nanotube,fullerene possesses unique characteristics that are growingly being discovered and exploited by the electrocatalysis community.For instance,the well-defined atomic and molecular structures,the good electron affinity to tune the electronic structures of other substances,the intermolecular self-assembly into superlattices,and the on-demand chemical modification have endowed fullerene with incomparable advantages as electrocatalysts that are otherwise not applicable to other carbon ma-terials.As increasing studies are being reported on this intriguing topic,it is necessary to provide a state-of-the-art overview of the recent progress.This review takes such an initiative by summarizing the promises and challenges in the electrocatalytic applications of fullerene and its derivatives.The content is structured according to the composition and structure of fullerene,including intact fullerene(e.g.,fullerene composite and superlattices)and fullerene derivatives(e.g.,doped,endohedral,and disintegrated fullerene).The synthesis,characterization,catalytic mechanisms,and deficiencies of these fullerene-based materials are explicitly elaborated.We conclude it by sharing our perspectives on the key aspects that future efforts shall consider.

Ribosome-inspired electrocatalysts inducing preferential nucleation and growth of three-dimensional lithium sulfide for high-performance lithium-sulfur batteries

Nucleation of lithium sulfide(Li_(2)S)induced by electrocatalysts plays a crucial role in mitigating the shut-tle effect.However,short-chain polysulfides on electrocatalysts surfaces tend to re-dissolve into elec-trolytes,delaying Li_(2)S supersaturation and its nucleation.In this study,we draw inspiration from the ribosome-driven protein synthesis process in cells to prepare ultrasmall nitrogen-doped MoS_(2) nanocrys-tals anchored on porous nitrogen-doped carbon networks(N-MoS_(2)-NC)electrocatalysts.Excitedly,the ex-situ SEM demonstrates that ribosome-inspired N-MoS_(2)-NC electrocatalysts induce early nucleation and rapid growth of three-dimensional Li_(2)s during discharge.Theoretical calculations reveal that the Li-s bond length in N-MoS_(2)-Li_(2)S(100)is shorter,and the corresponding interfacial formation energy is lower than in MoS_(2)-Li_(2)S(100).This accelerated conversion of lithium polysulfides to Li_(2)S can enhance the utilization of active substances and inhibit the shuttle effect.This study highlights the potential of ribosome-inspired N-MoS_(2)-NC in improving the electrochemical stability of Li-S batteries,providing valuable insights for future electrocatalyst design.

Trifunctional robust electrocatalysts based on 3D Fe/N-doped carbon nanocubes encapsulating Co4N nanoparticles for efficient battery-powered water electrolyzers

Herein,we have designed a highly active and robust trifunctional electrocatalyst derived from Prussian blue analogs,where Co_(4)N nanoparticles are encapsulated by Fe embedded in N-doped carbon nanocubes to synthesize hierarchically structured Co_(4)N@Fe/N-C for rechargeable zinc-air batteries and overall water-splitting electrolyzers.As confirmed by theoretical and experimental results,the high intrinsic oxygen reduction reaction,oxygen evolution reaction,and hydrogen evolution reaction activities of Co_(4)N@Fe/N-C were attributed to the formation of the heterointerface and the modulated local electronic structure.Moreover,Co_(4)N@Fe/N-C induced improvement in these trifunctional electrocatalytic activities owing to the hierarchical hollow nanocube structure,uniform distribution of Co_(4)N,and conductive encapsulation by Fe/N-C.Thus,the rechargeable zinc-air battery with Co_(4)N@Fe/N-C delivers a high specific capacity of 789.9 mAh g^(-1) and stable voltage profiles over 500 cycles.Furthermore,the overall water electrolyzer with Co_(4)N@Fe/N-C achieved better durability and rate performance than that with the Pt/C and IrO2 catalysts,delivering a high Faradaic efficiency of 96.4%.Along with the great potential of the integrated water electrolyzer powered by a zinc-air battery for practical applications,therefore,the mechanistic understanding and active site identification provide valuable insights into the rational design of advanced multifunctional electrocatalysts for energy storage and conversion.

Electrocatalysts with atomic-level site for nitrate reduction to ammonia

Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.

Boosting overall saline water splitting by constructing a strain-engineered high-entropy electrocatalyst

High-entropy materials(HEMs),which are newly manufactured compounds that contain five or more metal cations,can be a platform with desired properties,including improved electrocatalytic performance owing to the inherent complexity.Here,a strain engineering methodology is proposed to design transition-metal-based HEM by Li manipulation(LiTM)with tunable lattice strain,thus tailoring the electronic structure and boosting electrocatalytic performance.As confirmed by the experiments and calculation results,tensile strain in the LiTM after Li manipulation can optimize the d-band center and increase the electrical conductivity.Accordingly,the asprepared LiTM-25 demonstrates optimized oxygen evolution reaction and hydrogen evolution reaction activity in alkaline saline water,requiring ultralow overpotentials of 265 and 42 mV at 10 mA cm−2,respectively.More strikingly,LiTM-25 retains 94.6%activity after 80 h of a durability test when assembled as an anion-exchange membrane water electrolyzer.Finally,in order to show the general efficacy of strain engineering,we incorporate Li into electrocatalysts with higher entropies as well.

Striking Stabilization Effect of Spinel Cobalt Oxide Oxygen Evolution Electrocatalysts in Neutral pH by Dual-Sites Iron Incorporation

Developing stable and efficient nonprecious-metal-based oxygen evolution catalysts in the neutral electrolyte is a challenging but essential goal for various electrochemical systems.Particularly,cobalt-based spinels have drawn a considerable amount of attention but most of them operate in alkali solutions.However,the frequently studied Co-Fe spinel system never exhibits appreciable stability in nonbasic conditions,not to mention attract further investigation on its key structural motif and transition states for activity loss.Herein,we report exceptional stable Co-Fe spinel oxygen evolution catalysts(~30%Fe is optimal)in a neutral electrolyte,owing to its unique metal ion arrangements in the crystal lattice.The introduced iron content enters both the octahedral and tetrahedral sites of the spinel as Fe^(2+)and Fe^(3+)(with Co ions having mixed distribution as well).Combining density functional theory calculations,we find that the introduction of Fe to Co_(3)O_(4)lowers the covalency of metal-oxygen bonds and can help suppress the oxidation of Co^(2+/3+)and 0^(2-).It implies that the Co-Fe spinel will have minor surface reconstruction and less lattice oxygen loss during the oxygen evolution reaction process in comparison with Co_(3)O_(4)and hence show much better stability.These findings suggest that there is still much chance for the spinel structures,especially using reasonable sublattices engineering via multimetal doping to develop advanced oxygen evolution catalysts.

Durable hierarchical phosphorus‐doped biphase MoS_(2)electrocatalysts with enhanced H^(*)adsorption

Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)nanoflakes for hydrogen evolution reaction(HER).The doping of MoS_(2)with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics,which significantly enhances its electrical conductivity and structural stability,which are verified by various characterization tools,including X‐ray photoelectron spectroscopy,high‐resolution transmission electron microscopy,X‐ray absorption near‐edge spectroscopy,and extended X‐ray absorption fine structure.Moreover,the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites,which remarkably enhance its HER activity.The optimized P‐BMS electrocatalysts exhibit low overpotentials(60 and 72 mV at 10 mA cm^(−2))in H_(2)SO_(4)(0.5 M)and KOH(1.0 M),respectively.The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques.This study has shown that phase engineering is a promising strategy for enhancing the H*adsorption of metal sulfides.

Recent Advances on Ruthenium-based Electrocatalysts for Lithium-oxygen Batteries

Rechargeable lithium-oxygen(Li-O_(2))batteries have attracted wide attention due to their high energy density.However,the sluggish cathode kinetics results in high overvoltage and poor cycling performance.Ruthenium(Ru)-based electrocatalysts have been demonstrated to be promising cathode catalysts to promote oxygen evolution reaction(OER).It facilitates decomposition of lithium peroxide(Li_(2)O_(2))by adjusting Li_(2)O_(2) morphologies,which is due to the strong interaction between Ru-based catalyst and superoxide anion(O_(2))intermediate.In this review,the design strategies of Ru-based electrocatalysts are introduced to enhance their OER catalytic kinetics in Li-O_(2) batteries.Different configurations of Ru-based catalysts,including metal particles(Ru metal and alloys),single-atom catalysts,and Ru-loaded compounds with various substrates(carbon materials,metal oxides/sulfides),have been summarized to regulate the electronic structure and the matrix architecture of the Ru-based electrocatalysts.The structure-property relationship of Ru-based catalysts is discussed for a better understanding of the Li_(2)O_(2) decomposition mechanism at the cathode interface.Finally,the challenges of Ru-based electrocatalysts are proposed for the future development of Li-O_(2) batteries.

Co_(3)S_(4)-pyrolysis lotus fiber flexible textile as a hybrid electrocatalyst for overall water splitting

Electrocatalytic overall water splitting(OWS),a pivotal approach in addressing the global energy crisis,aims to produce hydrogen and oxygen.However,most of the catalysts in powder form are adhesively bounding to the electrodes,resulting in catalyst detachment by bubble generation and other uncertain interference,and eventually reducing the OWS performance.To surmount this challenge,we synthesized a hybrid material of Co_(3)S_(4)-pyrolysis lotus fiber(labeled as Co_(3)S_(4)-p LF)textile by hydrothermal and hightemperature pyrolysis processes for electrocatalytic OWS.Owing to the natural LF textile exposing the uniformly distributed functional groups(AOH,ANH_(2),etc.)to anchor Co_(3)S_(4)nanoparticles with hierarchical porous structure and outstanding hydrophily,the hybrid Co_(3)S_(4)-p LF catalyst shows low overpotentials at 10 m A cm^(-2)(η_(10,HER)=100 m Vη_(10,OER)=240 mV)alongside prolonged operational stability during electrocatalytic reactions.Theoretical calculations reveal that the electron transfer from p LF to Co_(3)S_(4)in the hybrid Co_(3)S_(4)-p LF is beneficial to the electrocatalytic process.This work will shed light on the development of nature-inspired carbon-based materials in hybrid electrocatalysts for OWS.

Data-Driven Design of Single-Atom Electrocatalysts with Intrinsic Descriptors for Carbon Dioxide Reduction Reaction

The strategic manipulation of the interaction between a central metal atom and its coordinating environment in single-atom catalysts(SACs)is crucial for catalyzing the CO_(2)reduction reaction(CO_(2)RR).However,it remains a major challenge.While density-functional theory calculations serve as a powerful tool for catalyst screening,their time-consuming nature poses limitations.This paper presents a machine learning(ML)model based on easily accessible intrinsic descriptors to enable rapid,cost-effective,and high-throughput screening of efficient SACs in complex systems.Our ML model comprehensively captures the influences of interactions between 3 and 5d metal centers and 8 C,N-based coordination environments on CO_(2)RR activity and selectivity.We reveal the electronic origin of the different activity trends observed in early and late transition metals during coordination with N atoms.The extreme gradient boosting regression model shows optimal performance in predicting binding energy and limiting potential for both HCOOH and CO production.We confirm that the product of the electronegativity and the valence electron number of metals,the radius of metals,and the average electronegativity of neighboring coordination atoms are the critical intrinsic factors determining CO_(2)RR activity.Our developed ML models successfully predict several high-performance SACs beyond the existing database,demonstrating their potential applicability to other systems.This work provides insights into the low-cost and rational design of high-performance SACs.

Progress in metal oxide-based electrocatalysts for sustainable water splitting

Metal oxide-based electrocatalysts are promising alternatives to platinum group metals for water splitting due to their low cost,abundant raw materials,and impressive stability.This review covers recent progress in various metal oxides tailored for hydrogen and oxygen evolution reactions,discussing their crystal structure,composition,and surface modification influence on performance.Strategies like surface engineering,doping,and nanostructuring are evaluated for enhancing catalytic activity and stability.The key considerations for commercialization are highlighted,emphasizing ongoing research,innovation,and future scope to drive widespread adoption of water-splitting technology for a cleaner and sustainable future.

Li intercalation in an MoSe_(2) electrocatalyst:In situ observation and modulation of its precisely controllable phase engineering for a high-performance flexible Li-S battery

Sophisticated efficient electrocatalysts are essential to rectifying the shuttle effect and realizing the high performance of flexible lithium-sulfur batteries(LSBs).Phase transformation of MoSe_(2) from the 2H phase to the 1T phase has been proven to be a significant method to improve the catalytic activity.However,precisely controllable phase engineering of MoSe_(2) has rarely been reported.Herein,by in situ Li ions intercalation in MoSe_(2),a precisely controllable phase evolution from 2H-MoSe_(2) to 1T-MoSe_(2) was realized.More importantly,the definite functional relationship between cut-off voltage and phase structure was first identified for phase engineering through in situ observation and modulation methods.The sulfur host(CNFs/1T-MoSe_(2))presents high charge density,strong polysulfides adsorption,and catalytic kinetics.Moreover,Li-S cells based on it display capacity retention of 875.3mAh g^(-1) after 500 cycles at 1 C and an areal capacity of 8.71mAh cm^(-2) even at a high sulfur loading of 8.47mg cm^(-2).Furthermore,the flexible pouch cell exhibiting decent performance will endow a promising potential in the wearable energy storage field.This study proposes an effective strategy to precisely control the phase structure of MoSe_(2),which may provide the reference to fabricate the highly efficient electrocatalysts for LSBs and other energy systems.

A high‐performance transition‐metal phosphide electrocatalyst for converting solar energy into hydrogen at 19.6% STH efficiency

The construction of high-efficiency and low-cost non-noble metal bifunctional electrocatalysts for water electrolysis is crucial for commercial large-scale application of hydrogen energy.Here,we report a novel strategy with erbiumdoped NiCoP nanowire arrays in situ grown on conductive nickel foam(Er-NiCoP/NF).Significantly,the developed electrode shows exceptional bifunctional catalytic activity,which only requires overpotentials of 46 and 225 mV to afford a current density of 10 mAcm^(−2) for the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER),respectively.Density functional theory calculations reveal that the appropriate Er incorporation into the NiCoP lattice can significantly modulate the electronic structure with the d-band centers of Ni and Co atoms by shifting to lower energies with respect to the Fermi level,and optimize the Gibbs free energies of HER/OER intermediates,thereby accelerating water-splitting kinetics.When assembled as a solar-driven overall water-splitting electrolyzer,the as-prepared electrode shows a high and stable solar-to-hydrogen efficiency of 19.6%,indicating its potential for practical storage of intermittent energy.