Oxygen reduction reaction(ORR) occurs at the cathode of fuel cells and metal-air batteries,but usually suffers from sluggish kinetics.To solve this issue,efficient electrocatalysts are highly desired.Palladium(Pd)-bas...Oxygen reduction reaction(ORR) occurs at the cathode of fuel cells and metal-air batteries,but usually suffers from sluggish kinetics.To solve this issue,efficient electrocatalysts are highly desired.Palladium(Pd)-based nanomaterials,as the most promising substitute of platinum(Pt),exhibit superior activity and stability in ORR electrocatalysis.The delicate regulation of the structure and/or composition shows great potential in improving the electrocatalytic ORR performance of Pd-based nanomaterials.In this review,we retrospect the recent advance of Pdbased ORR electrocatalysts,and analyses the relationship between nanostructure and catalytic performance.We start with the ORR mechanism and indicators of ORR performance in both alkaline and acidic media,followed by the synthetic methods for Pd-based nanoparticles.Then,we emphasize the design strategies of efficient Pd-based ORR catalysts from the perspective of composition,crystal phase,morphology,and support effects.Last but not least,we conclude with possible opportunities and outlook on Pd-based nanomaterials toward ORR.展开更多
Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt...Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.展开更多
Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen ba...Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen batteries(LOBs)due to their poor OER performance,resulting from poor electrical conductivity and overly strong intermediate adsorption.In this work,fancy double heterojunctions on 1T/2H-MoS_(2)@Co_(3)S_(4)(1T/2H-MCS)were constructed derived from the charge donation from Co to Mo ions,thus inducing the phase transformation of Mo S_(2)from 2H to 1T.The unique features of these double heterojunctions endow the1T/2H-MCS with complementary catalysis during charging and discharging processes.It is worth noting that 1T-Mo S2@Co3S4could provide fast Co-S-Mo electron transport channels to promote ORR/OER kinetics,and 2H-MoS_(2)@Co_(3)S_(4)contributed to enabling moderate egorbital occupancy when adsorbed with oxygen-containing intermediates.On the basis,the Li_(2)O_(2)nucleation route was changed to solution and surface dual pathways,improving reversible deposition and decomposition kinetics.As a result,1T/2H-MCS cathodes exhibit an improved electrocatalytic performance compared with those of Co_(3)S_(4)and Mo S2cathodes.This innovative heterostructure design provides a reliable strategy to construct efficient transition metal sulfide catalysts by improving electrical conductivity and modulating adsorption toward oxygenated intermediates for LOBs.展开更多
Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a...Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a series of Schreibersite-type intermetallic compounds,particularly Mo_(2)Fe_(0.8)Ru_(0.2)P,are synthesized through high-temperature solid-phase synthesis.Experimental results demonstrate that the integration of Ru significantly improves the kinetics of proton adsorption and desorption during the hydrogen evolution reaction(HER).Additionally,density functional theory(DFT)calculations and X-ray absorption near edge structure(XANES)analyses effectively corroborate the pronounced d-orbital hybridization of Fe within the structure,which facilitates the transfer of hydroxide ions and the maintenance of material durability during alkaline HER processes.Remarkably,Mo_(2)Fe_(0.8)Ru_(0.2)P exhibits superior alkaline HER activity,characterized by an overpotential of merely 48 mV at a current density of 10 mA cm^(-2).After prolonged operation of 1000 h at high current densities(1.1 A cm^(-2)),the activity decline remains minimal,under 4%(with overpotential increasing from 258 mV to 268 mV).These results demonstrate the potential of strategically combining metallic elements to design high-performance industrial-grade electrocatalysts.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
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
Inspired by molecular catalysts,researchers developed atomically precise nitrogen-coordinated single or dual metal sites imbedded in graphitized carbon(M-N-C)to fully utilize metallic sites for 02activation.These cata...Inspired by molecular catalysts,researchers developed atomically precise nitrogen-coordinated single or dual metal sites imbedded in graphitized carbon(M-N-C)to fully utilize metallic sites for 02activation.These catalysts performed remarkably well in the electrocatalytic oxygen reduction reaction(ORR)due to their distinct coordination and electrical structures,Nonetheless,their maximum efficacy in practical applications has yet to be achieved.This agenda identifies tailoring the coordination environment,spin states,intersite distance,and metal-metal interaction as innovative approaches to regulate the ORR performance of these catalysts.However,it is necessary to undertake a precise assessment of these methodologies and the knowledge obtained to be implemented in the design of future M-N-C catalysts for ORR.Therefore,this review aims to analyze recent progress in M-N-C ORR catalysts,emphasizing their innovative engineering with aspects such as alteration in intersite distance,metal-metal interaction,coordination environment,and spin states.Additionally,we critically discuss how to logically monitor the atomic structure,local coordination,spin,and electronic states of M-N-C catalysts to modulate their ORR activity.We have also highlighted the challenges associated with M-N-C catalysts and proposed suggestions for their future design and fabrication.展开更多
Electrochemical water splitting is a highly promising approach for producing carbon-neutral hydrogen.The development of efficient electrocatalysts for the hydrogen evolution reaction(HER)is crucial to lowering the ene...Electrochemical water splitting is a highly promising approach for producing carbon-neutral hydrogen.The development of efficient electrocatalysts for the hydrogen evolution reaction(HER)is crucial to lowering the energy barriers and enhancing hydrogen production.This drives the search for HER electrocatalysts that are not only cost-effective and abundant but also exhibit high activity and long-term stability.In this review,we provide an in-depth analysis of recent progress in the application of ruthenium phosphides as HER electrocatalysts,offering key insights into their design and performance.Meanwhile,we explore various strategies to enhance their catalytic efficiency,such as increasing the availability of active sites and optimizing their electronic structure.Finally,we outline the key challenges and future directions for developing the next generation of ruthenium phosphide-based HER electrocatalysts.展开更多
The realization of practical solar hydrogen production relies on the development of efficient devices with nontoxic and low-cost materials.Since the predominant contributors for the performance and cost are the cataly...The realization of practical solar hydrogen production relies on the development of efficient devices with nontoxic and low-cost materials.Since the predominant contributors for the performance and cost are the catalyst and the light absorber,it is imperative to develop cost-effective catalysts and absorbers that are compatible with each other for achieving high performance.In this study,a 10%efficient solar-to-hydrogen conversion device was developed through the meticulous integration of low-cost Ni Heazlewoodite-based catalysts for the hydrogen evolution reaction(HER)and ternary bulk heterojunction organic semiconductor(OS)-based light absorbers.Se-incorporated Ni_(3)S_(2)was synthesized using a simple one-step hydrothermal method,which demonstrated a low overpotential and Tafel slope,indicating superior HER activity compared to Ni_(3)S_(2).The theoretical calculation results validate the enhanced HER performance of the Se-incorporated Ni_(3)S_(2)catalyst in alkaline electrolytes.The ternary phase organic light absorber is designed to generate tailored photovoltage and maximized photocurrent,resulting in a photocurrent density of 8.24 mA cm^(-2)under unbiased conditions,which corresponds to 10%solar to hydrogen conversion.Low-temperature photoluminescence spectroscopy results revealed that the enhanced photocurrent density originates from a reduction in both phonon-and vibration-induced inter-and intramolecular non-radiative decay.Our results establish a new benchmark for the emerging OS-based efficient solar hydrogen production based on nontoxic and cost-effective materials.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
The oxygen evolution reaction(OER),a critical half-reaction in water electrolysis,has garnered significant attention.However,sluggish OER kinetics has emerged as a major impediment to efficient electrochemical energy c...The oxygen evolution reaction(OER),a critical half-reaction in water electrolysis,has garnered significant attention.However,sluggish OER kinetics has emerged as a major impediment to efficient electrochemical energy conversion.There is an urgent need to design novel electrocatalysts with optimized OER kinetics and enhanced intrinsic activity to improve overall OER performance.Herein,one-dimensional(1D)nanocomposites with high electrocatalytic activity were developed through the deposition of CoFePBA nanocubes onto the surface of MnO_(2) nanowires.The electronic structure of the nanocomposite surface was modified,and the synergistic effects between transition metals were leveraged to enhance catalytic activity through the deposition of Prussian blue analog(PBA)nanocubes on manganese dioxide nanowires.Specifically,CoFePBA featured an open crystal structure that offiered numerous electrochemical active sites and efficient charge transfer pathways.Additionally,the synergistic interactions between Co and Fe significantly reduced the OER overpotential.Additionally,the 1D rigid MnO_(2) acted as protective armor,ensuring the stability of active sites within CoFePBA during the OER.The synthesized MnO_(2)@CoFePBA achieved an overpotential of 1.614 V at 10 mA/cm^(2) and a small Tafel slope of 94 mV/dec and demonstrated stable performance for over 200 h.This work offers new insights into the rational design of various PBA-based nanocomposites with high activity and stability.展开更多
As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind en...As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind energy,is the most promising and viable option,with the advantages of celerity,high efficiency,cleanliness,and sustainability.However,this process necessitates a highly active and durable hydrogen evolution reaction(HER)catalyst to enhance the overall reaction efficiency.This article thoroughly reviews the recent development of electrocatalysts exhibiting high-performance HER.In particular,a comprehensive look at noble metals platinum(Pt),ruthenium(Ru),iridium(Ir),and non-noble metals,including sulfides,carbides,nitrides and phosphides is taken.Synthesis strategies,methods for enhancing performance,and the correlation between structure,composition,and catalytic performance are discussed.We also pay particular attention to density functional theory(DFT)calculations to reveal the mechanisms behind the improvement of HER performance.Finally,the critical challenges associated with electrochemical water splitting and propose coping strategies are presented.展开更多
Water electrolysis using renewable electricity is a promising strategy for high-purity hydrogen production.To realize the practical application of water electrolysis,an electrocatalyst with high redox properties and l...Water electrolysis using renewable electricity is a promising strategy for high-purity hydrogen production.To realize the practical application of water electrolysis,an electrocatalyst with high redox properties and low cost is essential for enhancing the sluggish oxygen evolution reaction.Herein,we fabricated Fe-doped nickel oxalate(Fe-NiC_(2)O_(4))directly grown on nickel(Ni)foam as an efficient electrocatalyst for the alkaline oxygen evolution reaction using a facile one-step hydrothermal method.Fe-NiC_(2)O_(4) served as a precursor for obtaining highly active Fe-doped Ni oxyhydroxide(Fe-NiOOH)via in situ electrochemical oxidation.Consequently,0.75Fe-NiOOH was demonstrated to be the optimal electrocatalyst,exhibiting outstanding oxygen evolution reaction activity with a low overpotential of 220 mV at a current density of 100 mA cm^(-2) and a Tafel slope of 20.5 mV dec^(-1).Furthermore,Fe-NiOOH maintained its oxygen evolution reaction activity without performance decay during long-term electrochemical measurements,owing to the phase transformation from nickel oxyhydroxide(NiOOH)toγ-NiOOH(gamma nickel oxyhydroxide).These performances significantly surpass those of recently reported transition-metal-based electrocatalysts.展开更多
Metal-free electrocatalysts for the oxygen evolution reaction(OER)are gaining attention for their low cost,high conductivity,and moderate catalytic performance.While trace metal interference in assynthesized catalysts...Metal-free electrocatalysts for the oxygen evolution reaction(OER)are gaining attention for their low cost,high conductivity,and moderate catalytic performance.While trace metal interference in assynthesized catalysts has been ruled out,the impact of trace metal contamination during electrochemical activation remains unexplored.This study demonstrates that anodic pretreatment in alkaline electrolytes enhances the catalytic performance of carbon cloth.Specifically,carbon cloth activated in 8 mol/L Na OH achieves a current density of 10 m A/cm^(2)with an overpotential of only 338 m V,comparable to metalbased OER catalysts.Electrochemical and spectroscopic analyses show the deposition of Fe Ni O_(x)H_(y)oxyhydroxides(0.19±0.06μg/cm^(2))on specific sites of the carbon substrate during activation.These nanoparticles contribute significantly to the catalytic activity,with a synergistic effect between Fe Ni O_(x)H_(y)and the carbon substrate.The turnover frequency(TOF)for Fe correlates with the amount of C=O groups on the carbon substrate,providing evidence for an interfacial synergistic effect.This work emphasizes the importance of considering trace metal effects in metal-free catalyst evaluation and offers insights for the design of more efficient carbon-based hybrid OER catalysts.展开更多
The exsolution method has garnered significant attention owing to its high efficacy in developing highly efficient and stable metal nanocatalysts.Herein,a versatile exsolution approach is developed to embed size-tunab...The exsolution method has garnered significant attention owing to its high efficacy in developing highly efficient and stable metal nanocatalysts.Herein,a versatile exsolution approach is developed to embed size-tunable metal nanocatalysts within a conductive metal pnictogenide matrix.The gas-phase reaction of Ru-substituted Ni-Fe-layered-double-hydroxide(Ni_(2)Fe_(1-x)Ru_(x)-LDH)with pnictogenation reagents leads to the exsolution of Ru metal nanocatalysts and a phase transformation into metal pnictogenide.The variation in reactivity of pnictogenation reagents allows for control over the size of the exsolved metal nanocatalysts(i.e.,nanoclusters for nitridation and single atoms for phosphidation),underscoring the effectiveness of the pnictogenation-driven exsolution strategy in stabilizing size-tunable metal nanocatalysts.The Ru-exsolved nickel-iron nitride/phosphide demonstrates outstanding electrocatalyst activity for the hydrogen evolution reaction,exhibiting a smaller overpotential and higher stability than Ru-deposited homologs.The high efficacy of pnictogenation-assisted exsolution in optimizing the performance and stability of Ru metal nanocatalysts is ascribed to the efficient interfacial electronic interaction between Ru metals and nitride/phosphide ions assisted by the inner sphere mechanism.In situ spectroscopic analyses highlight that exsolved Ru single atoms facilitate more efficient electron transfer to the reactants than the exsolved Ru nanoclusters,which is primarily responsible for the superior impact of the phosphidation-driven exsolution approach.展开更多
High entropy materials(HEMs)show great potential as electrocatalysts for oxygen evolution reaction(OER)thanks to their interesting four-core effect.This paper presents the first systematic summary of the key factors i...High entropy materials(HEMs)show great potential as electrocatalysts for oxygen evolution reaction(OER)thanks to their interesting four-core effect.This paper presents the first systematic summary of the key factors in the synthetic methods and their influence on the structure and OER properties of HEMs(including complexing agent,synthetic temperature,and calcination atmosphere).Optimizing the components of high entropy alloys and compounds by introducing heteroatoms(such as O,S,P,N,C,and B)can enhance the chemical configurations of active sites and thus enhance the intrinsic OER kinetics.In addition,this paper emphasizes the importance of the electrocatalytic influence mechanism of the four-core effects(including the high entropy effect,lattice distortion effect,cocktail effect and sluggish diffusion effect)on catalyst structure and their OER performance.Finally,we outline the current challenges and future development directions,aiming to offer crucial insights for creating economical and efficient HEM-based electrocatalysts in the OER field.展开更多
Direct formic acid fuel cells are promising energy devices with advantages of low working temperature and high safety in fuel storage and transport.They have been expected to be a future power source for portable elec...Direct formic acid fuel cells are promising energy devices with advantages of low working temperature and high safety in fuel storage and transport.They have been expected to be a future power source for portable electronic devices.The technology has been developed rapidly to overcome the high cost and low power performance that hinder its practical application,which mainly originated from the slow reaction kinetics of the formic acid oxidation and complex mass transfer within the fuel cell electrodes.Here,we provide a comprehensive review of the progress around this technology,in particular for addressing multiscale challenges from catalytic mechanism understanding at the atomic scale,to catalyst design at the nanoscale,electrode structure at the micro scale and design at the millimeter scale,and finally to device fabrication at the meter scale.The gap between the highly active electrocatalysts and the poor electrode performance in practical devices is highlighted.Finally,perspectives and opportunities are proposed to potentially bridge this gap for further development of this technology.展开更多
Electrocatalysts are an effective strategy to mitigate the shuttling effect of lithium polysulfides(LiPSs)and accelerate the redox kinetics of LiPSs in lithium-sulfur(Li-S)batteries.However,traditional electrocatalyst...Electrocatalysts are an effective strategy to mitigate the shuttling effect of lithium polysulfides(LiPSs)and accelerate the redox kinetics of LiPSs in lithium-sulfur(Li-S)batteries.However,traditional electrocatalysts only have a single active site and often undergo structural collapse and aggregation during charging and discharging,resulting in reduced catalytic performance.Herein,the two-dimensional(2D)polar high-entropy La_(0.71)Sr_(0.29)Co_(0.21)Ni_(0.20)Fe_(0.19)Cr_(0.20)Cu_(0.20)O_(3)(LCO-HEO)nanosheets were rationally designed and successfully synthesized to address this issue.The distinct functional polar sites in LCOHEOs were formed by the d-d orbital hybridization between spatially coupling adjacent transition metals,which can strengthen the dipole-dipole interaction between polar LCO-HEOs and polar LiPSs.2D polar LCO-HEO nanosheets can efficiently capture and trigger the tandem catalysis of polar LiPSs during their sequential conversion.The S/LCO-HEO composite cathode exhibits a high specific capacity of 1161.1 mA h g^(-1)at 1.0 C,with an ultralow capacity attenuation rate of 0.036%per cycle over 1200 cycles,and achieves stable cycling for 1500 cycles even at 8.0 C.Furthermore,even with a high sulfur loading(5.5 mg cm^(-2))and a low electrolyte/sulfur(E/S)ratio(4.0μL mg^(-1)),the S/LCO-HEO composite cathode shows desirable sulfur utilization and good cycle stability.This work demonstrates the feasibility of high entropy-driven multiple distinct functional polar sites for high-rate and long-cycle Li-S batteries.展开更多
Electrochemical CO_(2) reduction(ECR)driven by intermittent renewable energy sources is an emerging technology to achieve net-zero CO_(2) emissions.Tandem electrochemical CO_(2) reduction(T-ECR),employs tandem catalys...Electrochemical CO_(2) reduction(ECR)driven by intermittent renewable energy sources is an emerging technology to achieve net-zero CO_(2) emissions.Tandem electrochemical CO_(2) reduction(T-ECR),employs tandem catalysts with synergistic or complementary functions to efficiently convert CO_(2) into multi-carbon(C^(2+))products in a succession of reactions within single or sequentially coupled reactors.However,the lack of clear interpretation and systematic understanding of T-ECR mechanisms has resulted in suboptimal current outcomes.This review presents new perspectives and summarizes recent advancements in efficient T-ECR across various scales,including synergistic tandem catalysis at the microscopic scale,relay tandem catalysis at the mesoscopic scale,and tandem reactors at the macroscopic scale.We begin by outlining the principle of tandem catalysis,followed by discuss on tandem catalyst design,the electrode construction,and reactor configuration.Additionally,we address the challenges and prospects of tandem strategies,emphasizing the integration of machine learning,theoretical calculations,and advanced characterization techniques for developing industry-scale CO_(2) valorization.展开更多
基金financially supported by the National Natural Science Foundation of China (No.52172058)。
文摘Oxygen reduction reaction(ORR) occurs at the cathode of fuel cells and metal-air batteries,but usually suffers from sluggish kinetics.To solve this issue,efficient electrocatalysts are highly desired.Palladium(Pd)-based nanomaterials,as the most promising substitute of platinum(Pt),exhibit superior activity and stability in ORR electrocatalysis.The delicate regulation of the structure and/or composition shows great potential in improving the electrocatalytic ORR performance of Pd-based nanomaterials.In this review,we retrospect the recent advance of Pdbased ORR electrocatalysts,and analyses the relationship between nanostructure and catalytic performance.We start with the ORR mechanism and indicators of ORR performance in both alkaline and acidic media,followed by the synthetic methods for Pd-based nanoparticles.Then,we emphasize the design strategies of efficient Pd-based ORR catalysts from the perspective of composition,crystal phase,morphology,and support effects.Last but not least,we conclude with possible opportunities and outlook on Pd-based nanomaterials toward ORR.
基金supported by the National Natural Science Foundation of China(Grant Nos.:21825201,52401244 and 52201227)Henan Province Key Research and Development and Promotion Program(Scientific and Technological Breakthrough Project:232102240088 and 252102230078)+3 种基金the Key Research&Development and Promotion of Special Project(Scientific Problem Tackling)of Henan Province(252102230078)Doctoral Research Startup Fund Project of Henan Open University(BSJH-2025-04)Zhejiang Provincial Natural Science Foundation of China(LQ24B020005,LQ23B030001)China Postdoctoral Science Foundation(2024M762442).
文摘Electrocatalytic nitrate-to-ammonia conversion offers dual environmental and sustainable synthesis benefits,but achieving high efficiency with low-cost catalysts remains a major challenge.This review focuses on cobalt-based electrocatalysts,emphasizing their structural engineering for enhanced the performance of electrocatalytic nitrate reduction reaction(NO3RR)through dimensional control,compositional tuning,and coordination microenvironment modulation.Notably,by critically analyzing metallic cobalt,cobalt alloys,cobalt compounds,cobalt single atom and molecular catalyst configurations,we firstly establish correlations between atomic-scale structural features and catalytic performance in a coordination environment perspective for NO3RR,including the dynamic reconstruction during operation and its impact on active site.Synergizing experimental breakthroughs with computational modeling,we decode mechanisms underlying competitive hydrogen evolution suppression,intermediate adsorption-energy optimization,and durability enhancement in complex aqueous environments.The development of cobalt-based catalysts was summarized and prospected,and the emerging opportunities of machine learning in accelerating the research and development of high-performance catalysts and the configuration of series reactors for scalable nitrate-to-ammonia systems were also introduced.Bridging surface science and applications,it outlines a framework for designing multifunctional electrocatalysts to restore nitrogen cycle balance sustainably.
基金financially supported by the National Natural Science Foundation of China(U21A20311,U24A2040,52171141,52272117)the Natural Science Foundation of Shandong Province(ZR2022JQ19)+3 种基金the Key Technology Research Project of Shandong Province(2023CXGC010202)the Taishan Industrial Experts Program(TSCX202306142)the Core Facility Sharing Platform of Shandong Universitythe Foundation of Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),Nankai University。
文摘Co_(3)S_(4)electrocatalysts with mixed valences of Co ions and excellent structural stability possess favorable oxygen evolution reaction(OER)activity,yet challenges remain in fabricating rechargeable lithiumoxygen batteries(LOBs)due to their poor OER performance,resulting from poor electrical conductivity and overly strong intermediate adsorption.In this work,fancy double heterojunctions on 1T/2H-MoS_(2)@Co_(3)S_(4)(1T/2H-MCS)were constructed derived from the charge donation from Co to Mo ions,thus inducing the phase transformation of Mo S_(2)from 2H to 1T.The unique features of these double heterojunctions endow the1T/2H-MCS with complementary catalysis during charging and discharging processes.It is worth noting that 1T-Mo S2@Co3S4could provide fast Co-S-Mo electron transport channels to promote ORR/OER kinetics,and 2H-MoS_(2)@Co_(3)S_(4)contributed to enabling moderate egorbital occupancy when adsorbed with oxygen-containing intermediates.On the basis,the Li_(2)O_(2)nucleation route was changed to solution and surface dual pathways,improving reversible deposition and decomposition kinetics.As a result,1T/2H-MCS cathodes exhibit an improved electrocatalytic performance compared with those of Co_(3)S_(4)and Mo S2cathodes.This innovative heterostructure design provides a reliable strategy to construct efficient transition metal sulfide catalysts by improving electrical conductivity and modulating adsorption toward oxygenated intermediates for LOBs.
基金supported by Research Grants of the NRF(2023R1A2C2003823,RS-2024-00405818)funded by the National Research Foundation under the Ministry of Science,ICT&Future,Korea。
文摘Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a series of Schreibersite-type intermetallic compounds,particularly Mo_(2)Fe_(0.8)Ru_(0.2)P,are synthesized through high-temperature solid-phase synthesis.Experimental results demonstrate that the integration of Ru significantly improves the kinetics of proton adsorption and desorption during the hydrogen evolution reaction(HER).Additionally,density functional theory(DFT)calculations and X-ray absorption near edge structure(XANES)analyses effectively corroborate the pronounced d-orbital hybridization of Fe within the structure,which facilitates the transfer of hydroxide ions and the maintenance of material durability during alkaline HER processes.Remarkably,Mo_(2)Fe_(0.8)Ru_(0.2)P exhibits superior alkaline HER activity,characterized by an overpotential of merely 48 mV at a current density of 10 mA cm^(-2).After prolonged operation of 1000 h at high current densities(1.1 A cm^(-2)),the activity decline remains minimal,under 4%(with overpotential increasing from 258 mV to 268 mV).These results demonstrate the potential of strategically combining metallic elements to design high-performance industrial-grade electrocatalysts.
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 Research Fund for International Scientists(RFIS-Grant numbers:52150410410)National Natural Science Foundation of Chinathe Deanship of Scientific Research and Graduate Studies at King Khalid University for funding this research work through Large Research Project under the grant number RGP2/121/1445.
文摘Inspired by molecular catalysts,researchers developed atomically precise nitrogen-coordinated single or dual metal sites imbedded in graphitized carbon(M-N-C)to fully utilize metallic sites for 02activation.These catalysts performed remarkably well in the electrocatalytic oxygen reduction reaction(ORR)due to their distinct coordination and electrical structures,Nonetheless,their maximum efficacy in practical applications has yet to be achieved.This agenda identifies tailoring the coordination environment,spin states,intersite distance,and metal-metal interaction as innovative approaches to regulate the ORR performance of these catalysts.However,it is necessary to undertake a precise assessment of these methodologies and the knowledge obtained to be implemented in the design of future M-N-C catalysts for ORR.Therefore,this review aims to analyze recent progress in M-N-C ORR catalysts,emphasizing their innovative engineering with aspects such as alteration in intersite distance,metal-metal interaction,coordination environment,and spin states.Additionally,we critically discuss how to logically monitor the atomic structure,local coordination,spin,and electronic states of M-N-C catalysts to modulate their ORR activity.We have also highlighted the challenges associated with M-N-C catalysts and proposed suggestions for their future design and fabrication.
基金supported by the Frontier Exploration Projects of Longmen Laboratory(No.LMQYTSKT008)the Program for Science and Technology Innovation Talents in Universities of Henan Province(Nos.22HASTIT008 and 24HASTIT006)+2 种基金the Natural Science Foundations of Henan Province(Nos.222300420502 and 242300420045)the Programs for Science and Technology Development of Henan Province(No.242102240066)the Key Scientific Research Projects of University in Henan Province(No.23B430002)。
文摘Electrochemical water splitting is a highly promising approach for producing carbon-neutral hydrogen.The development of efficient electrocatalysts for the hydrogen evolution reaction(HER)is crucial to lowering the energy barriers and enhancing hydrogen production.This drives the search for HER electrocatalysts that are not only cost-effective and abundant but also exhibit high activity and long-term stability.In this review,we provide an in-depth analysis of recent progress in the application of ruthenium phosphides as HER electrocatalysts,offering key insights into their design and performance.Meanwhile,we explore various strategies to enhance their catalytic efficiency,such as increasing the availability of active sites and optimizing their electronic structure.Finally,we outline the key challenges and future directions for developing the next generation of ruthenium phosphide-based HER electrocatalysts.
基金supported by the National R&D Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(Grant No.RS-2023-0025177 and 2021R1A2B5B01002879)The technology Innovation Program funded by the Ministry of Trade Industry and Energy(MOTIE,Korea)(Grant No.RS-2024-00435432)。
文摘The realization of practical solar hydrogen production relies on the development of efficient devices with nontoxic and low-cost materials.Since the predominant contributors for the performance and cost are the catalyst and the light absorber,it is imperative to develop cost-effective catalysts and absorbers that are compatible with each other for achieving high performance.In this study,a 10%efficient solar-to-hydrogen conversion device was developed through the meticulous integration of low-cost Ni Heazlewoodite-based catalysts for the hydrogen evolution reaction(HER)and ternary bulk heterojunction organic semiconductor(OS)-based light absorbers.Se-incorporated Ni_(3)S_(2)was synthesized using a simple one-step hydrothermal method,which demonstrated a low overpotential and Tafel slope,indicating superior HER activity compared to Ni_(3)S_(2).The theoretical calculation results validate the enhanced HER performance of the Se-incorporated Ni_(3)S_(2)catalyst in alkaline electrolytes.The ternary phase organic light absorber is designed to generate tailored photovoltage and maximized photocurrent,resulting in a photocurrent density of 8.24 mA cm^(-2)under unbiased conditions,which corresponds to 10%solar to hydrogen conversion.Low-temperature photoluminescence spectroscopy results revealed that the enhanced photocurrent density originates from a reduction in both phonon-and vibration-induced inter-and intramolecular non-radiative decay.Our results establish a new benchmark for the emerging OS-based efficient solar hydrogen production based on nontoxic and cost-effective materials.
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supported by the National Natural Science Foundation of China(No.52371240)the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘The oxygen evolution reaction(OER),a critical half-reaction in water electrolysis,has garnered significant attention.However,sluggish OER kinetics has emerged as a major impediment to efficient electrochemical energy conversion.There is an urgent need to design novel electrocatalysts with optimized OER kinetics and enhanced intrinsic activity to improve overall OER performance.Herein,one-dimensional(1D)nanocomposites with high electrocatalytic activity were developed through the deposition of CoFePBA nanocubes onto the surface of MnO_(2) nanowires.The electronic structure of the nanocomposite surface was modified,and the synergistic effects between transition metals were leveraged to enhance catalytic activity through the deposition of Prussian blue analog(PBA)nanocubes on manganese dioxide nanowires.Specifically,CoFePBA featured an open crystal structure that offiered numerous electrochemical active sites and efficient charge transfer pathways.Additionally,the synergistic interactions between Co and Fe significantly reduced the OER overpotential.Additionally,the 1D rigid MnO_(2) acted as protective armor,ensuring the stability of active sites within CoFePBA during the OER.The synthesized MnO_(2)@CoFePBA achieved an overpotential of 1.614 V at 10 mA/cm^(2) and a small Tafel slope of 94 mV/dec and demonstrated stable performance for over 200 h.This work offers new insights into the rational design of various PBA-based nanocomposites with high activity and stability.
基金supported by the National Natural Science Foundation of China(No.52102470)。
文摘As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind energy,is the most promising and viable option,with the advantages of celerity,high efficiency,cleanliness,and sustainability.However,this process necessitates a highly active and durable hydrogen evolution reaction(HER)catalyst to enhance the overall reaction efficiency.This article thoroughly reviews the recent development of electrocatalysts exhibiting high-performance HER.In particular,a comprehensive look at noble metals platinum(Pt),ruthenium(Ru),iridium(Ir),and non-noble metals,including sulfides,carbides,nitrides and phosphides is taken.Synthesis strategies,methods for enhancing performance,and the correlation between structure,composition,and catalytic performance are discussed.We also pay particular attention to density functional theory(DFT)calculations to reveal the mechanisms behind the improvement of HER performance.Finally,the critical challenges associated with electrochemical water splitting and propose coping strategies are presented.
基金supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)(No.20213030040590)the Korea Institute for Advancement of Technology(KIAT)and the Ministry of Trade,Industry&Energy(MOTIE),Republic of Korea(No.P0022130)Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education(2021R1A6C101A404)。
文摘Water electrolysis using renewable electricity is a promising strategy for high-purity hydrogen production.To realize the practical application of water electrolysis,an electrocatalyst with high redox properties and low cost is essential for enhancing the sluggish oxygen evolution reaction.Herein,we fabricated Fe-doped nickel oxalate(Fe-NiC_(2)O_(4))directly grown on nickel(Ni)foam as an efficient electrocatalyst for the alkaline oxygen evolution reaction using a facile one-step hydrothermal method.Fe-NiC_(2)O_(4) served as a precursor for obtaining highly active Fe-doped Ni oxyhydroxide(Fe-NiOOH)via in situ electrochemical oxidation.Consequently,0.75Fe-NiOOH was demonstrated to be the optimal electrocatalyst,exhibiting outstanding oxygen evolution reaction activity with a low overpotential of 220 mV at a current density of 100 mA cm^(-2) and a Tafel slope of 20.5 mV dec^(-1).Furthermore,Fe-NiOOH maintained its oxygen evolution reaction activity without performance decay during long-term electrochemical measurements,owing to the phase transformation from nickel oxyhydroxide(NiOOH)toγ-NiOOH(gamma nickel oxyhydroxide).These performances significantly surpass those of recently reported transition-metal-based electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(No.22479097)the Shanghai Science and Technology Committee(Nos.23ZR1433000 and 22511100400)+1 种基金the National High-Level Talent Program for Young Scholarsthe Start-up Fund(F.Song)from Shanghai Jiao Tong University。
文摘Metal-free electrocatalysts for the oxygen evolution reaction(OER)are gaining attention for their low cost,high conductivity,and moderate catalytic performance.While trace metal interference in assynthesized catalysts has been ruled out,the impact of trace metal contamination during electrochemical activation remains unexplored.This study demonstrates that anodic pretreatment in alkaline electrolytes enhances the catalytic performance of carbon cloth.Specifically,carbon cloth activated in 8 mol/L Na OH achieves a current density of 10 m A/cm^(2)with an overpotential of only 338 m V,comparable to metalbased OER catalysts.Electrochemical and spectroscopic analyses show the deposition of Fe Ni O_(x)H_(y)oxyhydroxides(0.19±0.06μg/cm^(2))on specific sites of the carbon substrate during activation.These nanoparticles contribute significantly to the catalytic activity,with a synergistic effect between Fe Ni O_(x)H_(y)and the carbon substrate.The turnover frequency(TOF)for Fe correlates with the amount of C=O groups on the carbon substrate,providing evidence for an interfacial synergistic effect.This work emphasizes the importance of considering trace metal effects in metal-free catalyst evaluation and offers insights for the design of more efficient carbon-based hybrid OER catalysts.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(RS-2023-00208355,RS-2024-00439825,and 2022M3H4A408610313)supported by the Global Science Research Center Program(RS-2024-00411134)+1 种基金funded by the National Research Foundation of KoreaThe experiments at PAL were supported in part by MOST and POSTECH。
文摘The exsolution method has garnered significant attention owing to its high efficacy in developing highly efficient and stable metal nanocatalysts.Herein,a versatile exsolution approach is developed to embed size-tunable metal nanocatalysts within a conductive metal pnictogenide matrix.The gas-phase reaction of Ru-substituted Ni-Fe-layered-double-hydroxide(Ni_(2)Fe_(1-x)Ru_(x)-LDH)with pnictogenation reagents leads to the exsolution of Ru metal nanocatalysts and a phase transformation into metal pnictogenide.The variation in reactivity of pnictogenation reagents allows for control over the size of the exsolved metal nanocatalysts(i.e.,nanoclusters for nitridation and single atoms for phosphidation),underscoring the effectiveness of the pnictogenation-driven exsolution strategy in stabilizing size-tunable metal nanocatalysts.The Ru-exsolved nickel-iron nitride/phosphide demonstrates outstanding electrocatalyst activity for the hydrogen evolution reaction,exhibiting a smaller overpotential and higher stability than Ru-deposited homologs.The high efficacy of pnictogenation-assisted exsolution in optimizing the performance and stability of Ru metal nanocatalysts is ascribed to the efficient interfacial electronic interaction between Ru metals and nitride/phosphide ions assisted by the inner sphere mechanism.In situ spectroscopic analyses highlight that exsolved Ru single atoms facilitate more efficient electron transfer to the reactants than the exsolved Ru nanoclusters,which is primarily responsible for the superior impact of the phosphidation-driven exsolution approach.
基金supported by the National Natural Science Foundation of China(52103342 and 22209032)the Scientific Research Fund of Zhejiang Provincial Education Department(Y202456353)。
文摘High entropy materials(HEMs)show great potential as electrocatalysts for oxygen evolution reaction(OER)thanks to their interesting four-core effect.This paper presents the first systematic summary of the key factors in the synthetic methods and their influence on the structure and OER properties of HEMs(including complexing agent,synthetic temperature,and calcination atmosphere).Optimizing the components of high entropy alloys and compounds by introducing heteroatoms(such as O,S,P,N,C,and B)can enhance the chemical configurations of active sites and thus enhance the intrinsic OER kinetics.In addition,this paper emphasizes the importance of the electrocatalytic influence mechanism of the four-core effects(including the high entropy effect,lattice distortion effect,cocktail effect and sluggish diffusion effect)on catalyst structure and their OER performance.Finally,we outline the current challenges and future development directions,aiming to offer crucial insights for creating economical and efficient HEM-based electrocatalysts in the OER field.
基金sponsored by a PhD Scholarship from the School of Chemical Engineering at the University of Birminghamsupported by EU H2020-MSCAIF-2019 project EconCell 898486
文摘Direct formic acid fuel cells are promising energy devices with advantages of low working temperature and high safety in fuel storage and transport.They have been expected to be a future power source for portable electronic devices.The technology has been developed rapidly to overcome the high cost and low power performance that hinder its practical application,which mainly originated from the slow reaction kinetics of the formic acid oxidation and complex mass transfer within the fuel cell electrodes.Here,we provide a comprehensive review of the progress around this technology,in particular for addressing multiscale challenges from catalytic mechanism understanding at the atomic scale,to catalyst design at the nanoscale,electrode structure at the micro scale and design at the millimeter scale,and finally to device fabrication at the meter scale.The gap between the highly active electrocatalysts and the poor electrode performance in practical devices is highlighted.Finally,perspectives and opportunities are proposed to potentially bridge this gap for further development of this technology.
基金supported by grants from the National Natural Science Foundation of China(52072099)Team program of the Natural Science Foundation of Heilongjiang Province,China(No.TD2021E005)Joint Guidance Project of the Natural Science Foundation of Heilongjiang Province,China(No.LH2022E093)。
文摘Electrocatalysts are an effective strategy to mitigate the shuttling effect of lithium polysulfides(LiPSs)and accelerate the redox kinetics of LiPSs in lithium-sulfur(Li-S)batteries.However,traditional electrocatalysts only have a single active site and often undergo structural collapse and aggregation during charging and discharging,resulting in reduced catalytic performance.Herein,the two-dimensional(2D)polar high-entropy La_(0.71)Sr_(0.29)Co_(0.21)Ni_(0.20)Fe_(0.19)Cr_(0.20)Cu_(0.20)O_(3)(LCO-HEO)nanosheets were rationally designed and successfully synthesized to address this issue.The distinct functional polar sites in LCOHEOs were formed by the d-d orbital hybridization between spatially coupling adjacent transition metals,which can strengthen the dipole-dipole interaction between polar LCO-HEOs and polar LiPSs.2D polar LCO-HEO nanosheets can efficiently capture and trigger the tandem catalysis of polar LiPSs during their sequential conversion.The S/LCO-HEO composite cathode exhibits a high specific capacity of 1161.1 mA h g^(-1)at 1.0 C,with an ultralow capacity attenuation rate of 0.036%per cycle over 1200 cycles,and achieves stable cycling for 1500 cycles even at 8.0 C.Furthermore,even with a high sulfur loading(5.5 mg cm^(-2))and a low electrolyte/sulfur(E/S)ratio(4.0μL mg^(-1)),the S/LCO-HEO composite cathode shows desirable sulfur utilization and good cycle stability.This work demonstrates the feasibility of high entropy-driven multiple distinct functional polar sites for high-rate and long-cycle Li-S batteries.
文摘Electrochemical CO_(2) reduction(ECR)driven by intermittent renewable energy sources is an emerging technology to achieve net-zero CO_(2) emissions.Tandem electrochemical CO_(2) reduction(T-ECR),employs tandem catalysts with synergistic or complementary functions to efficiently convert CO_(2) into multi-carbon(C^(2+))products in a succession of reactions within single or sequentially coupled reactors.However,the lack of clear interpretation and systematic understanding of T-ECR mechanisms has resulted in suboptimal current outcomes.This review presents new perspectives and summarizes recent advancements in efficient T-ECR across various scales,including synergistic tandem catalysis at the microscopic scale,relay tandem catalysis at the mesoscopic scale,and tandem reactors at the macroscopic scale.We begin by outlining the principle of tandem catalysis,followed by discuss on tandem catalyst design,the electrode construction,and reactor configuration.Additionally,we address the challenges and prospects of tandem strategies,emphasizing the integration of machine learning,theoretical calculations,and advanced characterization techniques for developing industry-scale CO_(2) valorization.
