This study presents a novel method to fabricate metal-decorated,sulfur-doped layered double hydroxides(M/SLDH)through spontaneous redox and sulfurization processes.The developed Ag/SLDH and Pt/SLDH catalysts with abun...This study presents a novel method to fabricate metal-decorated,sulfur-doped layered double hydroxides(M/SLDH)through spontaneous redox and sulfurization processes.The developed Ag/SLDH and Pt/SLDH catalysts with abundant heterogeneous interfaces and hierarchical nanostructures demonstrated outstanding oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performance,achieving low overpotentials of 212 and 35 mV at 10 mA cm^(-2)in 1 M KOH,respectively.As both anode and cathode in water splitting,they required only 1.47 V to reach 10 mA cm^(-2)and exhibited high structural robustness,maintaining stability at 1000 mA cm^(-2)for 300 h.In-situ Raman analysis revealed that the synergistic effects of metal nanoparticles and S doping significantly promote the transformation into the S-Co1-xFexOOH layer,which serves as the active phase for water oxidation.Additionally,ultraviolet photoelectron spectroscopy(UPS)and density functional theory(DFT)analyses indicated that incorporating metal nanoparticles and S doping increase electron density near the Fermi level and reduce reaction energy barriers,thus enhancing intrinsic OER and HER activities.This study provides a scalable strategy for synthesizing high-performance electrocatalysts for water splitting,with promising potential for broader applications.展开更多
The stability and electrocatalytic efficiency of transition metal oxides for water splitting is determined by geometric and electronic structure,especially under high current densities.Herein,a newly designed lamella-...The stability and electrocatalytic efficiency of transition metal oxides for water splitting is determined by geometric and electronic structure,especially under high current densities.Herein,a newly designed lamella-heterostructured nanoporous CoFe/CoFe_(2)O_(4) and CeO_(2−x),in situ grown on nickel foam(NF),holds great promise as a high-efficient bifunctional electrocatalyst(named R-CoFe/Ce/NF)for water splitting.Experimental characterization verifies surface reconstruction from CoFe alloy/oxide to highly active CoFeOOH during in situ electrochemical polarization.By virtues of three-dimensional nanoporous architecture and abundant electroactive CoFeOOH/CeO_(2−x) heterostructure interfaces,the R-CoFe/Ce/NF electrode achieves low overpotentials for oxygen evolution(η_(10)=227 mV;η_(500)=450 mV)and hydrogen evolution(η_(10)=35 mV;η_(408)=560 mV)reactions with high normalized electrochemical active surface areas,respectively.Additionally,the alkaline full water splitting electrolyzer of R-CoFe/Ce/NF||R-CoFe/Ce/NF achieves a current density of 50 mA·cm^(−2) only at 1.75 V;the decline of activity is satisfactory after 100-h durability test at 300 mA·cm^(−2).Density functional theory also demonstrates that the electron can transfer from CeO_(2−x) by virtue of O atom to CoFeOOH at CoFeOOH/CeO_(2−x) heterointerfaces and enhancing the adsorption of reactant,thus optimizing electronic structure and Gibbs free energies for the improvement of the activity for water splitting.展开更多
Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the ...Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the world’s shortage of fossil energy.However,efficient seawater splitting is hindered by slow kinetics caused by the ultra-low conductivity and the presence of bacteria,microorganisms,and stray ions in seawater.Additionally,producing hydrogen on an industrial scale is challenging due to the high production cost.The present review addresses these challenges from the catalyst point of view,namely,that designing catalysts with high catalytic activity and stability can directly affect the rate and effect of seawater splitting.From the ion transfer perspective,designing membranes can block harmful ions,improving the stability of seawater splitting.From the energy point of view,mixed seawater systems and self-powered systems also provide new and low-energy research systems for seawater splitting.Finally,ideas and directions for further research on direct seawater splitting in the future are pointed out,with the aim of achieving low-cost and high-efficiency hydrogen production.展开更多
The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplore...The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.展开更多
Altermagnets represent a newly discovered class of magnetically ordered materials.Among all the candidates,CrSb stands out due to its largest spin splitting energy and highest Néel temperature exceeding 700 K,mak...Altermagnets represent a newly discovered class of magnetically ordered materials.Among all the candidates,CrSb stands out due to its largest spin splitting energy and highest Néel temperature exceeding 700 K,making it promising for room-temperature spintronic applications.Here we have successfully grown high quality CrSb(100)thin film on GaAs(110)substrate by molecular beam epitaxy.Using angle-resolved photoemission spectroscopy,we successfully obtained the three-dimensional electronic structure of the thin film.Moreover,we observed the emergence of the altermagnetic splitting bands corresponding to the calculated results along the low symmetry pathsT-QandP-D.The bands near the Fermi level are only spin splitting bands along theP-Ddirection,with splitting energy reaching as high as 910 meV.This finding provides insights into the magnetic properties of CrSb thin films and paves the way for further studies on their electronic structure and potential applications in spintronics.展开更多
We report the observation of Zeeman splitting in multiple spectral lines emitted by a laser-produced,magnetized plasma(1–3×10^(18)cm^(-3),1–15 eV)in the context of a laboratory astrophysics experiment under a c...We report the observation of Zeeman splitting in multiple spectral lines emitted by a laser-produced,magnetized plasma(1–3×10^(18)cm^(-3),1–15 eV)in the context of a laboratory astrophysics experiment under a controlled magneticfield up to 20T.Nitrogen lines(NII)in the visible range were used to diagnose the magneticfield and plasma conditions.This was performed by coupling our data with(563–574 nm)the Stark–Zeeman line-shape code PPPB.The excellent agreement between experiment and simulations paves the way for a non-intrusive experimental platform to get time-resolved measurements of the local magneticfield in laboratory plasmas.展开更多
Water oxidation-a critical yet sluggish step in green hydrogen production-is a major bottleneck for electrolysis efficiency.Traditional catalysts often degrade quickly under the high current densities needed for indus...Water oxidation-a critical yet sluggish step in green hydrogen production-is a major bottleneck for electrolysis efficiency.Traditional catalysts often degrade quickly under the high current densities needed for industrial scale.展开更多
The development of stable and efficient non-noble metal cocatalysts has arisen as a promising yet challenging endeavor in the context of photocatalytic overall water splitting.In this study,NiCo alloy cocatalysts were...The development of stable and efficient non-noble metal cocatalysts has arisen as a promising yet challenging endeavor in the context of photocatalytic overall water splitting.In this study,NiCo alloy cocatalysts were synthesized with nickel/cobalt metal organic framework(NiCo-MOF)as source of nickel and cobalt.Systematic characterization results demonstrate the successful deposition of alloy cocatalysts onto the surface of SrTiO_(3).The prepared SrTiO_(3)loaded NiCo-alloy can generate hydrogen and oxygen in a stoichiometric ratio for photocatalytic overall water splitting,achieving an apparent quantum yield of 11.9%at 350±10 nm.Theoretical calculations indicate that the introduction of cobalt has a beneficial regulatory effect on the hydrogen evolution sites of Ni,reducing the free energy of H adsorption.The synergistic catalytic effect of bimetallic catalysts contributes to enhancing photocatalytic activity and stability.This study offers constructive insights for the development of high-efficiency and cost-effective cocatalyst systems.展开更多
Green hydrogen is crucial for advancing renewable energy technologies and protecting the environment.This study introduces a controllable method for bimetallic nickel-cobalt phosphide on reduced graphene oxide on nick...Green hydrogen is crucial for advancing renewable energy technologies and protecting the environment.This study introduces a controllable method for bimetallic nickel-cobalt phosphide on reduced graphene oxide on nickel foam(NiCo_(3)P.C/NF).The material demonstrated low overpotentials of 58 and 180 mV at10 mA cm^(-2)for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in 1.0 M KOH.It achieved excellent electrochemical water-splitting performance with operating voltages of 1.54 and 2.6 V at 10 and 500 mA cm^(-2),respectively.The overall water-splitting performance of NiCo_(3).C/NF was extremely stable after 75 h of operation at 53 mA cm^(-2),retaining 98%efficiency,better than the sample Pt-C+RuO_(2),and outperforming previous reports.Density functional theory(DFT)results revealed a synergistic NiCo_(3)P.C interaction that yields nearly zero Gibbs free energy change(-0.100 eV)and upshift d-band center,the real active site at the Ni in HER,and the lowest overpotentials 0.26 V at the P active sites for OER.Furthermore,electronic charge distribution shows the maximum charge distribution between the NiCo_(3)P phase and graphene sheet heterojunction,enhancing the electrocatalyst conductivity.This combined approach offers an innovative strategy to design sustainable electrocatalysts for water s plitting.展开更多
The reasonable design of material morphology and eco-friendly electrocatalysts are essential to highly efficient water splitting.It is proposed that a promising strategy effectively regulates the electronic structure ...The reasonable design of material morphology and eco-friendly electrocatalysts are essential to highly efficient water splitting.It is proposed that a promising strategy effectively regulates the electronic structure of the d-orbitals of CoP using cerium doping in this paper,thus significantly improving the intrinsic property and conductivity of CoP for water splitting.As a result,the as-synthesize porous Ce-doped CoP micro-polyhedron composite derived from Ce-ZIF-67 as bifunctional electrocatalytic materials exhibits excellent electrocatalytic performance in both the oxygen evolution reaction(OER)and the hydrogen evolution reaction(HER),overpotentials of about 152 mV for HER at 10 mA cm^(-2)and about 352 mV for OER at 50 mA cm^(-2),and especially it shows outstanding long-term stability.Besides,an alkaline electrolyzer,using Ce0.04Co0.96P electrocatalyst as both the anode and cathode,delivers a cell voltage value of1.55 V at the current density of 10 mA cm^(-2).The calculation results of the density functional theory(DFT)demonstrate that the introduction of an appropriate amount of Ce into CoP can enhance the conductivity,and can induce the electronic modulation to regulate the selective adsorption of reaction intermediates on catalytic surface and the formation of O*intermediates(CoOOH),which exhibits an excellent electrocatalytic performance.This study provides novel insights into the design of an extraordinary performance water-splitting of the multicomponent electrocatalysts.展开更多
The quest for sustainable energy solutions has intensified the need for efficient water electrolysis techniques,pivotal for hydrogen production.However,developing effective bifunctional electrocatalysts capable of dri...The quest for sustainable energy solutions has intensified the need for efficient water electrolysis techniques,pivotal for hydrogen production.However,developing effective bifunctional electrocatalysts capable of driving the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)remains a formidable challenge.Addressing this,we introduce a novel built-in electric field(BEF)strategy to synthesize NiCoP–Co nanoarrays directly on Ti_(3)C_(2)T_(x) MXene substrates(NiCoP–Co/MXene).This approach leverages a significant work function difference(ΔΦ),propelling these nanoarrays as adept bifunctional electrocatalysts for comprehensive water splitting.MXene,in this process,plays a dual role.It acts as a conductive support,enhancing the catalyst’s overall conductivity,and facilitates an effective charge transport pathway,ensuring efficient charge transfer.Our study reveals that the BEF induces an electric field at the interface,prompting charge transfer from Co to NiCoP.This transfer modulates asymmetric charge distributions,which intricately control intermediates’adsorption and desorption dynamics.Such regulation is crucial for enhancing the reaction kinetics of both HER and OER.Furthermore,under oxidative conditions,the NiCoP–Co/MXene catalyst undergoes a structural metamorphosis into Ni(Co)oxides/hydroxides/MXene,increasing OER performance.This research demonstrates the BEF’s role in fine-tuning interfacial charge redistribution and underscores its potential in crafting more sophisticated electrocatalytic designs.The insights gained here could pave the way for the next generation of electrocatalysis,with far-reaching implications for energy conversion and storage technologies.展开更多
Electrocatalytic water splitting(EWS)driven by renewable energy is vital for clean hydrogen(H2)production and reducing reliance on fossil fuels.While IrO_(2) and RuO_(2) are the leading electrocatalysts for the oxygen...Electrocatalytic water splitting(EWS)driven by renewable energy is vital for clean hydrogen(H2)production and reducing reliance on fossil fuels.While IrO_(2) and RuO_(2) are the leading electrocatalysts for the oxygen evolution reaction(OER)and Pt for the hydrogen evolution reaction(HER)in acidic environments,the need for efficient,stable,and affordable materials persists.Recently,transition-metal borides(TMBs),particularly metal diborides(MDbs),have gained attention due to their unique layered crystal structures with multicentered boron bonds,offering remarkable physicochemical properties.Their nearly 2D structures boost electrochemical performance by offering high conductivity and a large active surface area,making them well-suited for advanced energy storage and conversion technologies.This review provides a comprehensive overview of the critical factors for water splitting,the crystal and electronic structures of MDbs,and their synthetic strategies.Furthermore,it examines the relationship between catalytic performance and intermediate adsorption as elucidated by first-principle calculations.The review also highlights the latest experimental advancements in MDb-based electrocatalysts and addresses the current challenges and future directions for their development.展开更多
Harnessing solar energy for renewable fuel production through artificial photosynthesis offers an ideal solution to the current energy and environmental crises.Among various methods,photoelectrochemical(PEC)water spli...Harnessing solar energy for renewable fuel production through artificial photosynthesis offers an ideal solution to the current energy and environmental crises.Among various methods,photoelectrochemical(PEC)water splitting stands out as a promising approach for direct solar-driven hydrogen production.Enhancing the efficiency and stability of photoelectrodes is a key focus in PEC water-splitting research.Tantalum nitride(Ta_(3)N_(5)),with its suitable band gap and band-edge positions for PEC water splitting,has emerged as a highly promising photoanode material.This review begins by introducing the history and fundamental characteristics of Ta_(3)N_(5),emphasizing both its advantages and challenges.It then explores methods to improve light absorption efficiency,charge separation and transfer efficiency,surface reaction rate,and the stability of Ta_(3)N_(5) photoanodes.Additionally,the review discusses the progress of research on tandem PEC cells incorporating Ta_(3)N_(5) photoanodes.Finally,it looks ahead to future research directions for Ta_(3)N_(5) photoanodes.The strategic approach outlined in this review can also be applied to other photoelectrode materials,providing guidance for their development.展开更多
Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru...Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru/V-Co O/CP with doping strategy and heterostructure was synthesized for overall water splitting.The Ru/V-Co O exhibits excellent activity for HER and OER with low overpotentials of 49, 147 m V at a current density of 10 m A/cm^(2) in 1.0 mol/L KOH, respectively. The assembled electrolytic cell just needs voltages of 1.47 and 1.71 V to achieve 10 and 350 m A/cm^(2)current density under the same conditions and delivers an outstanding stability for over 100 h, which is far superior to the commercial Ru O_(2)||Pt/C cell. Experimental and theoretical results indicate that the doping of V species and the formation of heterostructures lead to charge redistribution. More importantly, the leaching of V species induces electron transfer form Co to O and then Ru through the Co-O-Ru electron bridge, optimizes the adsorption strength of the key intermediate, thereby reducing the free energy barrier of the rate-determining step and improving catalytic activity. This work proposes an effective strategy of using cation dissolution to induce electron transfer through the electron bridge and thus regulate the electronic structure of catalysts,providing new ideas for the design and development of efficient and stable electrocatalysts.展开更多
Recent advancements in electrocatalysis have highlighted the exceptional application value of amorphous electrocatalysts. Withtheir unique atomic configurations, these electrocatalysts exhibit superior catalytic perfo...Recent advancements in electrocatalysis have highlighted the exceptional application value of amorphous electrocatalysts. Withtheir unique atomic configurations, these electrocatalysts exhibit superior catalytic performance compared to that of their crystalline coun-terparts. Transition metal(TM) amorphous ribbon-shaped electrocatalysts have recently emerged as a new frontier in the catalysis field.Dealloying is widely considered a fascinating method for enhancing the electrocatalyst performance. In this review, we comprehensivelyexamine the principles of water electrolysis, discuss the prevalent methods for fabricating ribbon-configured electrocatalysts, and providean overview of amorphous alloys. Furthermore, we discuss binary, ternary, and high-entropy amorphous TM-based electrocatalysts,which satisfy the requirements necessary for effective water electrolysis. We also propose strategies to enhance the activity of amorphousTM-based ribbons, including morphology control, defect engineering, composition optimization, and heterostructure creation in differentelectrolytes. Our focus extends to the latest developments in the design of heterogeneous micro/nanostructures, management of prepara-tion techniques, and synthesis of different compositions. Finally, we address the ongoing challenges and provide a perspective on the fu-ture development of broadly applicable, self-supporting TM ribbon-shaped electrocatalysts.展开更多
Rational interface engineering via regulating the anchoring groups between molecular catalysts and light-absorbing semiconductors is essential and emergent to stabilize the semiconductor/molecular complex interaction ...Rational interface engineering via regulating the anchoring groups between molecular catalysts and light-absorbing semiconductors is essential and emergent to stabilize the semiconductor/molecular complex interaction and facilitate the photocarriers transport,thus realizing highly active and stable photoelectrochemical(PEC)water splitting.In this mini review,following a showcasing of the fundamental details of hybrid PEC systems containing semiconductor photoelectrodes and molecular catalysts for water splitting,the state-of-the-art progress of anchoring group regulation at semiconductor/molecular complex interface for efficient and stable PEC water splitting,as well as its effect on charge transfer kinetics,are comprehensively reviewed.Finally,potential research directions aimed at building high-efficiency hybrid PEC water splitting systems are summarized.展开更多
CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport e...CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport efficiency of photogenerated carriers.To address the above issues,a cost-effective ternary Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode was designed.Firstly,a thin Cu:NiO_(X)film was inserted between CuBi_(2)O_(4)and FTO conducting substrate as a hole-selective layer,which promotes the transmission of photogenerated holes to the FTO substrate effectively.Furthermore,the modification of CuO film on the CuBi_(2)O_(4)electrode not only increases the absorption of sunlight and generates more photogenerated carriers,but also constitutes a heterojunction with CuBi_(2)O_(4),creating a built-in electric field,which facilitates the separation of electrons and holes,and accelerates the electrons transfer to electrode–electrolyte interface.The fabricated Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode exhibits a surprisingly high photocurrent density of−1.51 mA·cm^(−2)at 0.4 V versus RHE,which is 2.6 times that of the pristine CuBi_(2)O_(4)photocathode.The improved PEC performance is attributed to the synergy effect of the Cu:NiO_(X)hole-selective layer and the CuBi_(2)O_(4)/CuO heterojunction.Moreover,the combination with the BiVO_(4)/CoS,an unbiased overall water splitting was achieved,which has a photocurrent of 0.193 mA·cm^(−2).展开更多
Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of C...Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.展开更多
Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and...Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and cost-effectiveness.Polymeric carbon nitride(PCN)represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability.Nevertheless,limited by rapid charge recombination and insufficient oxidative capability,little success has been achieved on pristine PCN photocatalyst in POWS.In this context,recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance.Based on the fundamental principles of photocatalysis,this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems.With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems,modification strategies including crystallinity engineering,supramolecular precursor design,cocatalyst modulation,and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years.Future perspectives for PCN-based photocatalysts are proposed,aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.展开更多
Transition metal selenides(TMSs)are effective pre-electrocatalysts and are commonly used in electrochemical processes.During the electrocatalytic oxygen evolution reaction(OER),metal cations in TMSs are in-situ recons...Transition metal selenides(TMSs)are effective pre-electrocatalysts and are commonly used in electrochemical processes.During the electrocatalytic oxygen evolution reaction(OER),metal cations in TMSs are in-situ reconstructed and converted into high-valence metal oxyhydroxides.However,a limited understanding of the effects of electro-oxidation and anion leaching has resulted in insufficient theoretical guidance for the rational design of efficient catalysts.Herein,FeSe@NiSe nanorods were fabricated for the OER using a facile hydrothermal selenization method supported on FeNi foam.In-situ Raman spectroscopy and multiple characterization techniques were employed to elucidate the mechanism of FeSe@NiSe surface evolution.Metal cations on the catalyst surface were reconstructed and converted into OER-active species Fe/NiOOH at low potential.As the applied potential increased,electro-oxidation and leaching of Se occurred,resulting in SeO_(4)^(2−)adsorption on the catalyst surface,which further enhanced catalytic activity.As a result,the reconstructed FeSe@NiSe/iron-nickel foam(INF)exhibited exceptional catalytic activity for OER,achieving an ultralow overpotential of 283 mV at a current density of 100 mA·cm^(−2).Notably,the bifunctional FeSe@NiSe/INF electrode facilitated overall water splitting,affording a current density of 10 mA·cm^(−2) only at 1.53 V,even superior to the noble RuO_(2)(+)||Pt/C(−).This work offers valuable insights into the surface evolution and electrocatalytic mechanisms of TMSs.展开更多
基金National Programs for NanoKey Project(2022YFA1504002)National Natural Science Foundation of China(22078233)。
文摘This study presents a novel method to fabricate metal-decorated,sulfur-doped layered double hydroxides(M/SLDH)through spontaneous redox and sulfurization processes.The developed Ag/SLDH and Pt/SLDH catalysts with abundant heterogeneous interfaces and hierarchical nanostructures demonstrated outstanding oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performance,achieving low overpotentials of 212 and 35 mV at 10 mA cm^(-2)in 1 M KOH,respectively.As both anode and cathode in water splitting,they required only 1.47 V to reach 10 mA cm^(-2)and exhibited high structural robustness,maintaining stability at 1000 mA cm^(-2)for 300 h.In-situ Raman analysis revealed that the synergistic effects of metal nanoparticles and S doping significantly promote the transformation into the S-Co1-xFexOOH layer,which serves as the active phase for water oxidation.Additionally,ultraviolet photoelectron spectroscopy(UPS)and density functional theory(DFT)analyses indicated that incorporating metal nanoparticles and S doping increase electron density near the Fermi level and reduce reaction energy barriers,thus enhancing intrinsic OER and HER activities.This study provides a scalable strategy for synthesizing high-performance electrocatalysts for water splitting,with promising potential for broader applications.
基金sponsored by the National Natural Science Foundation of China(Nos.5210125 and 52375422)the Science Research Project of Hebei Education Department(No.BJK2023058)the Natural Science Foundation of Hebei Province(Nos.E2020208069,B2020208083 and E202320801).
文摘The stability and electrocatalytic efficiency of transition metal oxides for water splitting is determined by geometric and electronic structure,especially under high current densities.Herein,a newly designed lamella-heterostructured nanoporous CoFe/CoFe_(2)O_(4) and CeO_(2−x),in situ grown on nickel foam(NF),holds great promise as a high-efficient bifunctional electrocatalyst(named R-CoFe/Ce/NF)for water splitting.Experimental characterization verifies surface reconstruction from CoFe alloy/oxide to highly active CoFeOOH during in situ electrochemical polarization.By virtues of three-dimensional nanoporous architecture and abundant electroactive CoFeOOH/CeO_(2−x) heterostructure interfaces,the R-CoFe/Ce/NF electrode achieves low overpotentials for oxygen evolution(η_(10)=227 mV;η_(500)=450 mV)and hydrogen evolution(η_(10)=35 mV;η_(408)=560 mV)reactions with high normalized electrochemical active surface areas,respectively.Additionally,the alkaline full water splitting electrolyzer of R-CoFe/Ce/NF||R-CoFe/Ce/NF achieves a current density of 50 mA·cm^(−2) only at 1.75 V;the decline of activity is satisfactory after 100-h durability test at 300 mA·cm^(−2).Density functional theory also demonstrates that the electron can transfer from CeO_(2−x) by virtue of O atom to CoFeOOH at CoFeOOH/CeO_(2−x) heterointerfaces and enhancing the adsorption of reactant,thus optimizing electronic structure and Gibbs free energies for the improvement of the activity for water splitting.
基金support by National Key Research and Development Program of China(2022YFB3803502)National Natural Science Foundation of China(52103076)+5 种基金Science and Technology Commission of Shanghai Municipality(23ZR1400300)special fund of Beijing Key Laboratory of Indoor Air Quality Evaluat ion and Control(NO.BZ0344KF21-02)State Key Laboratory of Electrical Insulation and Power Equipment(EIPE22203)JLF is a member of LSRE-LCM–Laboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials,supported by national funds through FCT/MCTES(PIDDAC):LSRE-LCM,UIDB/50020/2020(DOI:10.54499/UIDB/50020/2020)UIDP/50020/2020(DOI:10.54499/UIDP/50020/2020)ALiCE,LA/P/0045/2020(DOI:10.54499/LA/P/0045/2020).
文摘Direct seawater splitting has emerged as a popular and promising research direction for synthesising clean,green,non-polluting,and sustainable hydrogen energy without depending on high-purity water in the face of the world’s shortage of fossil energy.However,efficient seawater splitting is hindered by slow kinetics caused by the ultra-low conductivity and the presence of bacteria,microorganisms,and stray ions in seawater.Additionally,producing hydrogen on an industrial scale is challenging due to the high production cost.The present review addresses these challenges from the catalyst point of view,namely,that designing catalysts with high catalytic activity and stability can directly affect the rate and effect of seawater splitting.From the ion transfer perspective,designing membranes can block harmful ions,improving the stability of seawater splitting.From the energy point of view,mixed seawater systems and self-powered systems also provide new and low-energy research systems for seawater splitting.Finally,ideas and directions for further research on direct seawater splitting in the future are pointed out,with the aim of achieving low-cost and high-efficiency hydrogen production.
基金supported by the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2021L574)the Guizhou Provincial Science and Technology Foundation([2024]ZK General 425 and 438)+1 种基金the National Natural Science Foundation of China(22309033)the Academic Young Talent Foundation of Guizhou Normal University([2022]B05 and B06)。
文摘The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.
基金supported by the National Key R&D Program of China[Grant No.2023YFA1406304(J J)]the National Natural Science Foundation of China[Grant No.12174362(J J)]+2 种基金the Innovation Program for Quantum Science and Technology[Grant No.2021ZD0302803(D L F)]the New Cornerstone Science Foundation(D L F)Beamline 03U of the Shanghai Synchrotron Radiation Facility,which is supported by ME2 project under contract No.11227902 from the National Natural Science Foundation of China。
文摘Altermagnets represent a newly discovered class of magnetically ordered materials.Among all the candidates,CrSb stands out due to its largest spin splitting energy and highest Néel temperature exceeding 700 K,making it promising for room-temperature spintronic applications.Here we have successfully grown high quality CrSb(100)thin film on GaAs(110)substrate by molecular beam epitaxy.Using angle-resolved photoemission spectroscopy,we successfully obtained the three-dimensional electronic structure of the thin film.Moreover,we observed the emergence of the altermagnetic splitting bands corresponding to the calculated results along the low symmetry pathsT-QandP-D.The bands near the Fermi level are only spin splitting bands along theP-Ddirection,with splitting energy reaching as high as 910 meV.This finding provides insights into the magnetic properties of CrSb thin films and paves the way for further studies on their electronic structure and potential applications in spintronics.
基金supported by grants managed by l’Agence Nationale de la Recherche under the Investissements d’Avenir programs Grant Nos. ANR-18-EURE-0014, ANR-10-LABX-0039-PALM, and ANR-22-CE30-0044supported by grants from Japan Society for the Promotion of Science (JSPS) KAKENHI (Grant No. 23K20038)+2 种基金JSPS Core-to-Core program (Grant No. JPJSCCA20230003)carried out within the framework of the EUROfusion Consortium, funded by the European Union via the Euratom Research and Training Programme (Grant Agreement No. 101052200-EUROfusion)operated within the framework of the Enabling Research Project No. AWP24-ENR-IFE.02.CEA-01 “Magnetized ICF”
文摘We report the observation of Zeeman splitting in multiple spectral lines emitted by a laser-produced,magnetized plasma(1–3×10^(18)cm^(-3),1–15 eV)in the context of a laboratory astrophysics experiment under a controlled magneticfield up to 20T.Nitrogen lines(NII)in the visible range were used to diagnose the magneticfield and plasma conditions.This was performed by coupling our data with(563–574 nm)the Stark–Zeeman line-shape code PPPB.The excellent agreement between experiment and simulations paves the way for a non-intrusive experimental platform to get time-resolved measurements of the local magneticfield in laboratory plasmas.
文摘Water oxidation-a critical yet sluggish step in green hydrogen production-is a major bottleneck for electrolysis efficiency.Traditional catalysts often degrade quickly under the high current densities needed for industrial scale.
基金supported by the Basic Science Center Program for Ordered Energy Conversion of the National Natural Science Foundation of China(No.52488201)the National Natural Science Foundation of China(No.52376209)+1 种基金the China Postdoctoral Science Foundation(Nos.2020T130503 and 2020M673386)China Fundamental Research Funds for the Central Universities.
文摘The development of stable and efficient non-noble metal cocatalysts has arisen as a promising yet challenging endeavor in the context of photocatalytic overall water splitting.In this study,NiCo alloy cocatalysts were synthesized with nickel/cobalt metal organic framework(NiCo-MOF)as source of nickel and cobalt.Systematic characterization results demonstrate the successful deposition of alloy cocatalysts onto the surface of SrTiO_(3).The prepared SrTiO_(3)loaded NiCo-alloy can generate hydrogen and oxygen in a stoichiometric ratio for photocatalytic overall water splitting,achieving an apparent quantum yield of 11.9%at 350±10 nm.Theoretical calculations indicate that the introduction of cobalt has a beneficial regulatory effect on the hydrogen evolution sites of Ni,reducing the free energy of H adsorption.The synergistic catalytic effect of bimetallic catalysts contributes to enhancing photocatalytic activity and stability.This study offers constructive insights for the development of high-efficiency and cost-effective cocatalyst systems.
基金supported by the Regional Leading Research Center Program(2019R1A5A8080326)funding from the Basic Science Research Program(2021R1F1A1048758,2022R1I1A1A01053248)+1 种基金the Regional Innovation Strategy(RIS)(2023RIS-008)through the National Research Foundation of Korea(NRF),funded by the Ministry of Educationsupported by the National Supercomputing Center,which provided supercomputing resources and technical support(TS-2024-RE-0039)。
文摘Green hydrogen is crucial for advancing renewable energy technologies and protecting the environment.This study introduces a controllable method for bimetallic nickel-cobalt phosphide on reduced graphene oxide on nickel foam(NiCo_(3)P.C/NF).The material demonstrated low overpotentials of 58 and 180 mV at10 mA cm^(-2)for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in 1.0 M KOH.It achieved excellent electrochemical water-splitting performance with operating voltages of 1.54 and 2.6 V at 10 and 500 mA cm^(-2),respectively.The overall water-splitting performance of NiCo_(3).C/NF was extremely stable after 75 h of operation at 53 mA cm^(-2),retaining 98%efficiency,better than the sample Pt-C+RuO_(2),and outperforming previous reports.Density functional theory(DFT)results revealed a synergistic NiCo_(3)P.C interaction that yields nearly zero Gibbs free energy change(-0.100 eV)and upshift d-band center,the real active site at the Ni in HER,and the lowest overpotentials 0.26 V at the P active sites for OER.Furthermore,electronic charge distribution shows the maximum charge distribution between the NiCo_(3)P phase and graphene sheet heterojunction,enhancing the electrocatalyst conductivity.This combined approach offers an innovative strategy to design sustainable electrocatalysts for water s plitting.
基金supported by the National Natural Science Foundation of China(No.12162023&52268042)Key R&D Program of Gansu Province-International Cooperation Project(No.20YF8WA064)Natural Science Foundation of Gansu Province(No.22JR5RA253).
文摘The reasonable design of material morphology and eco-friendly electrocatalysts are essential to highly efficient water splitting.It is proposed that a promising strategy effectively regulates the electronic structure of the d-orbitals of CoP using cerium doping in this paper,thus significantly improving the intrinsic property and conductivity of CoP for water splitting.As a result,the as-synthesize porous Ce-doped CoP micro-polyhedron composite derived from Ce-ZIF-67 as bifunctional electrocatalytic materials exhibits excellent electrocatalytic performance in both the oxygen evolution reaction(OER)and the hydrogen evolution reaction(HER),overpotentials of about 152 mV for HER at 10 mA cm^(-2)and about 352 mV for OER at 50 mA cm^(-2),and especially it shows outstanding long-term stability.Besides,an alkaline electrolyzer,using Ce0.04Co0.96P electrocatalyst as both the anode and cathode,delivers a cell voltage value of1.55 V at the current density of 10 mA cm^(-2).The calculation results of the density functional theory(DFT)demonstrate that the introduction of an appropriate amount of Ce into CoP can enhance the conductivity,and can induce the electronic modulation to regulate the selective adsorption of reaction intermediates on catalytic surface and the formation of O*intermediates(CoOOH),which exhibits an excellent electrocatalytic performance.This study provides novel insights into the design of an extraordinary performance water-splitting of the multicomponent electrocatalysts.
基金supported by Guangdong Basic and Applied Basic Research Foundation(Nos.2021A1515010261 and 2023A1515140153)Guangdong Special Innovative Projects of General Universities(No.2022KTSCX136)+1 种基金the Major and Special Project in the Field of Intelligent Manufacturing of the Universities in Guangdong Province(No.2020ZDZX2067)the Innovative Team Project of the Universities in Guangdong Province(No.2023KCXTD035).
文摘The quest for sustainable energy solutions has intensified the need for efficient water electrolysis techniques,pivotal for hydrogen production.However,developing effective bifunctional electrocatalysts capable of driving the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)remains a formidable challenge.Addressing this,we introduce a novel built-in electric field(BEF)strategy to synthesize NiCoP–Co nanoarrays directly on Ti_(3)C_(2)T_(x) MXene substrates(NiCoP–Co/MXene).This approach leverages a significant work function difference(ΔΦ),propelling these nanoarrays as adept bifunctional electrocatalysts for comprehensive water splitting.MXene,in this process,plays a dual role.It acts as a conductive support,enhancing the catalyst’s overall conductivity,and facilitates an effective charge transport pathway,ensuring efficient charge transfer.Our study reveals that the BEF induces an electric field at the interface,prompting charge transfer from Co to NiCoP.This transfer modulates asymmetric charge distributions,which intricately control intermediates’adsorption and desorption dynamics.Such regulation is crucial for enhancing the reaction kinetics of both HER and OER.Furthermore,under oxidative conditions,the NiCoP–Co/MXene catalyst undergoes a structural metamorphosis into Ni(Co)oxides/hydroxides/MXene,increasing OER performance.This research demonstrates the BEF’s role in fine-tuning interfacial charge redistribution and underscores its potential in crafting more sophisticated electrocatalytic designs.The insights gained here could pave the way for the next generation of electrocatalysis,with far-reaching implications for energy conversion and storage technologies.
基金financial support from the Scientific and Technological Research Council of Türkiye(223M182).
文摘Electrocatalytic water splitting(EWS)driven by renewable energy is vital for clean hydrogen(H2)production and reducing reliance on fossil fuels.While IrO_(2) and RuO_(2) are the leading electrocatalysts for the oxygen evolution reaction(OER)and Pt for the hydrogen evolution reaction(HER)in acidic environments,the need for efficient,stable,and affordable materials persists.Recently,transition-metal borides(TMBs),particularly metal diborides(MDbs),have gained attention due to their unique layered crystal structures with multicentered boron bonds,offering remarkable physicochemical properties.Their nearly 2D structures boost electrochemical performance by offering high conductivity and a large active surface area,making them well-suited for advanced energy storage and conversion technologies.This review provides a comprehensive overview of the critical factors for water splitting,the crystal and electronic structures of MDbs,and their synthetic strategies.Furthermore,it examines the relationship between catalytic performance and intermediate adsorption as elucidated by first-principle calculations.The review also highlights the latest experimental advancements in MDb-based electrocatalysts and addresses the current challenges and future directions for their development.
文摘Harnessing solar energy for renewable fuel production through artificial photosynthesis offers an ideal solution to the current energy and environmental crises.Among various methods,photoelectrochemical(PEC)water splitting stands out as a promising approach for direct solar-driven hydrogen production.Enhancing the efficiency and stability of photoelectrodes is a key focus in PEC water-splitting research.Tantalum nitride(Ta_(3)N_(5)),with its suitable band gap and band-edge positions for PEC water splitting,has emerged as a highly promising photoanode material.This review begins by introducing the history and fundamental characteristics of Ta_(3)N_(5),emphasizing both its advantages and challenges.It then explores methods to improve light absorption efficiency,charge separation and transfer efficiency,surface reaction rate,and the stability of Ta_(3)N_(5) photoanodes.Additionally,the review discusses the progress of research on tandem PEC cells incorporating Ta_(3)N_(5) photoanodes.Finally,it looks ahead to future research directions for Ta_(3)N_(5) photoanodes.The strategic approach outlined in this review can also be applied to other photoelectrode materials,providing guidance for their development.
基金supported by National Natural Science Foundation of China (No. 22006120)the Fundamental Research Funds for the Central Universities (No. SWU-XDJH202314)+1 种基金the Program for Innovation Team Building at Institutions of Higher Education in Chongqing (No. CXTDX201601011)Chongqing Municipal Natural Science Foundation (No. cstc2018jcyj AX0625)。
文摘Exploring the intrinsic reasons for the dynamic reconstruction of catalysts during electrocatalytic reactions and their impact on activity enhancement still face severe challenges. Herein, the bifunctional catalyst Ru/V-Co O/CP with doping strategy and heterostructure was synthesized for overall water splitting.The Ru/V-Co O exhibits excellent activity for HER and OER with low overpotentials of 49, 147 m V at a current density of 10 m A/cm^(2) in 1.0 mol/L KOH, respectively. The assembled electrolytic cell just needs voltages of 1.47 and 1.71 V to achieve 10 and 350 m A/cm^(2)current density under the same conditions and delivers an outstanding stability for over 100 h, which is far superior to the commercial Ru O_(2)||Pt/C cell. Experimental and theoretical results indicate that the doping of V species and the formation of heterostructures lead to charge redistribution. More importantly, the leaching of V species induces electron transfer form Co to O and then Ru through the Co-O-Ru electron bridge, optimizes the adsorption strength of the key intermediate, thereby reducing the free energy barrier of the rate-determining step and improving catalytic activity. This work proposes an effective strategy of using cation dissolution to induce electron transfer through the electron bridge and thus regulate the electronic structure of catalysts,providing new ideas for the design and development of efficient and stable electrocatalysts.
基金financially supported by the Yancheng Polytechnic College School-Level Scientific Research, China (No. ygy1903)the National Natural Science Foundation of China (Nos. 52001163, 52075237, and 52371157)+2 种基金the Open Project of Taihu Laboratory of Deep-Sea Technology Science, Key Research and Development Plan of Jiangsu Province, China (No. BE2019119)supported by the Priority Academic Program Development of Jiangsu Higher Education Institution (PAPD), Chinathe research funding for the Jiangsu Specially-Appointed Professor Program, China。
文摘Recent advancements in electrocatalysis have highlighted the exceptional application value of amorphous electrocatalysts. Withtheir unique atomic configurations, these electrocatalysts exhibit superior catalytic performance compared to that of their crystalline coun-terparts. Transition metal(TM) amorphous ribbon-shaped electrocatalysts have recently emerged as a new frontier in the catalysis field.Dealloying is widely considered a fascinating method for enhancing the electrocatalyst performance. In this review, we comprehensivelyexamine the principles of water electrolysis, discuss the prevalent methods for fabricating ribbon-configured electrocatalysts, and providean overview of amorphous alloys. Furthermore, we discuss binary, ternary, and high-entropy amorphous TM-based electrocatalysts,which satisfy the requirements necessary for effective water electrolysis. We also propose strategies to enhance the activity of amorphousTM-based ribbons, including morphology control, defect engineering, composition optimization, and heterostructure creation in differentelectrolytes. Our focus extends to the latest developments in the design of heterogeneous micro/nanostructures, management of prepara-tion techniques, and synthesis of different compositions. Finally, we address the ongoing challenges and provide a perspective on the fu-ture development of broadly applicable, self-supporting TM ribbon-shaped electrocatalysts.
基金support of the Natural Science Foundation of Shaanxi Province(2023-JC-QN-0415)the Special Project on Functional Materials from Shaanxi Provincial Department of Finance(0801YC2305)+1 种基金the Talent Project from Northwest Institute for Non-ferrous Metal Research(YK2310)the National Natural Science Foundation of China(52225606 and 52304334).
文摘Rational interface engineering via regulating the anchoring groups between molecular catalysts and light-absorbing semiconductors is essential and emergent to stabilize the semiconductor/molecular complex interaction and facilitate the photocarriers transport,thus realizing highly active and stable photoelectrochemical(PEC)water splitting.In this mini review,following a showcasing of the fundamental details of hybrid PEC systems containing semiconductor photoelectrodes and molecular catalysts for water splitting,the state-of-the-art progress of anchoring group regulation at semiconductor/molecular complex interface for efficient and stable PEC water splitting,as well as its effect on charge transfer kinetics,are comprehensively reviewed.Finally,potential research directions aimed at building high-efficiency hybrid PEC water splitting systems are summarized.
基金supported by the National Natural Science Foundation of China(No.61804039)the University Natural Sciences Research Project of Anhui Province(No.2022AH010096)+1 种基金the Talent Research Fund of Hefei University(No.20RC35)the Natural Science Foundation of Anhui Higher Education Institution of China(No.2023AH040160).
文摘CuBi_(2)O_(4)is identified as a promising photocathode in photoelectrochemical(PEC)water splitting systems.However,the PEC performance of CuBi_(2)O_(4)is far from expected due to the limited separation and transport efficiency of photogenerated carriers.To address the above issues,a cost-effective ternary Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode was designed.Firstly,a thin Cu:NiO_(X)film was inserted between CuBi_(2)O_(4)and FTO conducting substrate as a hole-selective layer,which promotes the transmission of photogenerated holes to the FTO substrate effectively.Furthermore,the modification of CuO film on the CuBi_(2)O_(4)electrode not only increases the absorption of sunlight and generates more photogenerated carriers,but also constitutes a heterojunction with CuBi_(2)O_(4),creating a built-in electric field,which facilitates the separation of electrons and holes,and accelerates the electrons transfer to electrode–electrolyte interface.The fabricated Cu:NiO_(X)/CuBi_(2)O_(4)/CuO composite photocathode exhibits a surprisingly high photocurrent density of−1.51 mA·cm^(−2)at 0.4 V versus RHE,which is 2.6 times that of the pristine CuBi_(2)O_(4)photocathode.The improved PEC performance is attributed to the synergy effect of the Cu:NiO_(X)hole-selective layer and the CuBi_(2)O_(4)/CuO heterojunction.Moreover,the combination with the BiVO_(4)/CoS,an unbiased overall water splitting was achieved,which has a photocurrent of 0.193 mA·cm^(−2).
基金the financial support from National Natural Science Foundation of China (No. 21503097)Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX23_3905)。
文摘Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.
基金the National Natural Science Foundation of China(Nos.52488201,52376209)the Fundamental Research Funds for the Central Universities.Zhenxiong Huang thanks the Key Project of Jiangxi Academy of Science(No.2022YYB05)the Science and Technology Innovation Project for Carbon Peak and Neutrality of Jiangxi Carbon Neutralization Research Center(2022JXST02).
文摘Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and cost-effectiveness.Polymeric carbon nitride(PCN)represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability.Nevertheless,limited by rapid charge recombination and insufficient oxidative capability,little success has been achieved on pristine PCN photocatalyst in POWS.In this context,recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance.Based on the fundamental principles of photocatalysis,this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems.With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems,modification strategies including crystallinity engineering,supramolecular precursor design,cocatalyst modulation,and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years.Future perspectives for PCN-based photocatalysts are proposed,aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.
基金supported by the National Natural Science Foundation of China(No.22469018)the Natural Science Basic Research Program of Department of Science and Technology of Shaanxi Province(Nos.2023-JC-ZD-22 and 2023-JC-YB-404)the Scientific Research Startup Program for Introduced Talents of Shaanxi University of Technology(Nos.SLGRCQD2303 and SLGRCQD2306).
文摘Transition metal selenides(TMSs)are effective pre-electrocatalysts and are commonly used in electrochemical processes.During the electrocatalytic oxygen evolution reaction(OER),metal cations in TMSs are in-situ reconstructed and converted into high-valence metal oxyhydroxides.However,a limited understanding of the effects of electro-oxidation and anion leaching has resulted in insufficient theoretical guidance for the rational design of efficient catalysts.Herein,FeSe@NiSe nanorods were fabricated for the OER using a facile hydrothermal selenization method supported on FeNi foam.In-situ Raman spectroscopy and multiple characterization techniques were employed to elucidate the mechanism of FeSe@NiSe surface evolution.Metal cations on the catalyst surface were reconstructed and converted into OER-active species Fe/NiOOH at low potential.As the applied potential increased,electro-oxidation and leaching of Se occurred,resulting in SeO_(4)^(2−)adsorption on the catalyst surface,which further enhanced catalytic activity.As a result,the reconstructed FeSe@NiSe/iron-nickel foam(INF)exhibited exceptional catalytic activity for OER,achieving an ultralow overpotential of 283 mV at a current density of 100 mA·cm^(−2).Notably,the bifunctional FeSe@NiSe/INF electrode facilitated overall water splitting,affording a current density of 10 mA·cm^(−2) only at 1.53 V,even superior to the noble RuO_(2)(+)||Pt/C(−).This work offers valuable insights into the surface evolution and electrocatalytic mechanisms of TMSs.
