Exploring cost-effective and efficient catalysts for oxygen reduction reaction(ORR)poses a significant challenge,espe-cially in the pursuit of alternatives to precious metals like platinum.Significant advancements hav...Exploring cost-effective and efficient catalysts for oxygen reduction reaction(ORR)poses a significant challenge,espe-cially in the pursuit of alternatives to precious metals like platinum.Significant advancements have driven electrochem-ists to develop efficient ORR catalysts using abundant materials,particularly iron(Fe)-based,known for their exceptional performance in ORR.While the crucial function of Fe in boosting ORR catalytic activity is recognized,the connection between material attributes and catalytic performance remains enigmatic.Understanding the dynamic processes involved in oxygen electrocatalysis is paramount for designing precious-metals-free ORR electrocatalysts.Mössbauer spectroscopy stands out as a powerful technique for deciphering the structural characteristics of Fe species in catalysis,facilitating the identification of active sites and the clarification of catalytic mechanisms.By showcasing noteworthy case studies within this review,we demonstrate the application of in-situ/operando 57Fe Mössbauer spectroscopy across diverse Fe-involved materials in ORR catalysis.This sheds light on various aspects of ORR catalysis,such as identifying active sites,assessing stability,and understanding the reaction mechanism.Our inquiry drives towards the opportunities and hurdles associ-ated with Mössbauer spectroscopy,unveiling potential breakthroughs and avenues for enhancement within this pivotal research realm.展开更多
The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-ass...The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-assembly method is used to fabricate controllable MOF-on-MOF multiscale heterostructures,where triangular host MOF(ZIF-67)nanosheets undergo in situ epitaxial growth to form uniform orthogonal vip MOF(CoFe PBA)nanosheets.Phosphorus(P)is further introduced in situ to fabricate CoP and Fe_(2)P heterostructured nanosheets(CoFe-P-NS),which exhibit excellent bifunctional electrocatalytic performance due to the enhancement of intrinsic electrocatalytic activity by p-d orbital hybridization.Specifically,the CoFe-P-NS requires low overpotential of 259 and 307 mV to reach 500 mA cm−2 for HER and OER,respectively.Remarkably,the assembled electrolysis cell maintained a large current density of 300 mA cm−2 for over 360 h with negligible voltage increase during alkaline seawater electrolysis.Experiments and theoretical calculations show that the synergistic catalytic activity of bimetallic phosphides arises from p-d orbital hybridization,where the CoP-P sites enhance HER by optimizing H*adsorption in the Volmer-Heyrovsky steps,while the Fe_(2)P-Fe sites accelerate OER by lowering the energy barrier of the rate-determining step from O*to OOH*.This study provides valuable insights into the design of a controllable MOF-on-MOF-based electrocatalyst toward alkaline seawater splitting.展开更多
Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparti...Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.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
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
High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-poly...High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.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
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
Advanced OER/HER electrocatalytic alternatives are crucial for the wide adaptation of green hydrogen energy.Herein,Ru/NiMnB spherical cluster pillar(SCP),denoted as Ru/NiMnB,is synthesized using a combination of elect...Advanced OER/HER electrocatalytic alternatives are crucial for the wide adaptation of green hydrogen energy.Herein,Ru/NiMnB spherical cluster pillar(SCP),denoted as Ru/NiMnB,is synthesized using a combination of electro-deposition and hydrothermal reaction.Systematic investigation of Ru doping in the NiMnB matrix revealed significant improvements in electrocatalytic performance.The Ru/NiMnB SCPs demonstrate superior OER/HER activity with low overpotentials of 150 and 103 mV at 50mA/cm^(2)in 1 M KOH,making them highly competitive with state-of-the-art electrocatalysts.Remarkably,the Ru/NiMnB SCPs exhibit a low 2-E cell voltage of 2.80 V at ultra-high current density of 2,000 m A/cm^(2)in 1 M KOH,outperforming the standard benchmark electrodes of RuO_(2)||Pt/C,thereby positioning Ru/NiMnB as one of the best bifunctional electrocatalysts.These SCPs exhibit exceptional high-current characteristics,stability and corrosion resistance,as evidenced by continuous operation at 1,000 mA/cm^(2)high-current density for over 150 h in 6 M KOH at elevated temperatures under harsh industrial conditions.Only a small amount of Ru incorporation significantly enhances the electrocatalytic performances of NiMnB,attributed to increased active sites and improved intrinsic properties such as conductivity,adsorption/desorption capability and reaction rates.Consequently,Ru/NiMnB SCPs present a promising bi-functional electrode concept for efficient green H_(2)production.展开更多
A high-activity and stable bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalyst is critical for seawater-based Zn-air batteries(ZABs).Herein,we report a wood-derived chainmail e...A high-activity and stable bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalyst is critical for seawater-based Zn-air batteries(ZABs).Herein,we report a wood-derived chainmail electrocatalyst containing defective nitrogen-doped carbon nanotubes encapsulating cobalt nanoparticles(Co@D-NCNT/CW)to enhance the ORR/OER activity and stability in seawater medium.During the preparation process,the introduction and removal of Zn increased the defect sites and pyridine N content in the carbon material,modulating charge distribution and influencing the adsorption and activation processes.The highly ordered open channels in Co@D-NCNT/CW promoted mass transfer of reactants and accelerated gas diffusion.The resultant chainmail electrocatalyst exhibited impressive bifunctional ORR and OER activities with an ultra-low gap of 0.67 V in sea water-based alkaline electrolyte.The Co@D-NCNT/CW-assembled seawater-based rechargeable liquid ZABs demonstrated a maximum power density of 245.3 mW cm^(-2)and a long-term cycling performance over 500 h.The seawater-based all-solid-state ZABs achieved the maximum power density of 48.2 mW cm^(-2)and stabilized over 30 h.Density functional theory revealed that the presence of defects and pyridine nitrogen in Co@D-NCNT/CW modulated the electronic structure of Co,optimizing the binding affinity of the Co sites with intermediates and weakening Cl^(-)adsorption.This work provides a new approach to preparing high-activity and stable ORR/OER electrocatalyst utilizing wood nanostructures,boosting the development of seawater-based ZABs.展开更多
Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree c...Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree control strategy was employed to fabricate nitrogen-doped carbon sphere(NCS)decorated with dual-phase Co/Co_(7)Fe_(3)heterojunctions(CoFe@NCS).The phase composition of materials has been adjusted by controlling the alloying degree.The optimal CoFe_(0.08)@NCS electrocatalyst displays a half-wave potential of 0.80 V for ORR and an overpotential of 283 mV at 10 mA·cm^(-2)for OER in an alkaline electrolyte.The intriguing bifunctional electrocatalytic activity and durability is attributed to the hierarchically porous structure and interfacial electron coupling of highly-active Co_(7)Fe_(3)alloy and metallic Co species.When the CoFe_(0.08)@NCS material is used as air-cathode catalyst of rechargeable liquid-state zinc-air battery(ZAB),the device shows a high peak power-density(157 mW·cm^(-2))and maintains a stable voltage gap over 150 h,outperforming those of the benchmark(Pt/C+RuO_(2))-based device.In particular,the as-fabricated solid-state flexible ZAB delivers a reliable compatibility under different bending conditions.Our work provides a promising strategy to develop metal/alloy-based electrocatalysts for the application in renewable energy conversion technologies.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
Electrides,in which anionic electrons are trapped in structural cavities,have garnered significant attention for exceptionalfunctionalities based on their low work function.In low-dimensional electrides,a strong quant...Electrides,in which anionic electrons are trapped in structural cavities,have garnered significant attention for exceptionalfunctionalities based on their low work function.In low-dimensional electrides,a strong quantum confinement of anionicelectrons leads to many interesting phenomena,but a severe chemical instability due to their open structures is one of the majordisadvantages for practical applications.Here we report that one-dimensional(1D)dititanium sulfide electride exhibits an ex-traordinary stability originating from the surface self-passivation and consequent durability in bifunctional electrocatalytic activity.Theoretical calculations identify the uniqueness of the 1D[Ti_(2)S]^(2+)·2e^(−)electride,where multiple cavities form two distinct channelstructures of anionic electrons.Combined surface structure analysis and in-situ work function measurement indicate that thenatural formation of amorphous titanium oxide surface layer in air is responsible for the remarkable inertness in water and pH-varied solutions.This makes the[Ti_(2)S]^(2+)·2e^(−)electride an ideal support for a heterogenous metal-electride hybrid catalyst,demonstrating the enhanced efficiency and superior durability in both the hydrogen evolution and oxygen reduction reactionscompared to commercial Pt/C catalysts.This study will stimulate further exploratory research for developing a chemically stableelectride in reactive conditions,evoking a strategy for a practical electrocatalyst for industrial energy conversions.展开更多
Red mud(RM)is a solid waste generated in the aluminum industry after the extraction of alumina oxide;its multiple elements and higher pH value likely pose a severe threat to the environment after treatment.However,RM&...Red mud(RM)is a solid waste generated in the aluminum industry after the extraction of alumina oxide;its multiple elements and higher pH value likely pose a severe threat to the environment after treatment.However,RM's higher concentrations of metal components,particularly Fe_(2)O_(3)and rare earth elements(REEs),render RM promising for catalytic application.Hence,this work showed an efficient high-speed RM to catalyze electrocatalytic nitrate-to-ammonia reduction reaction(NARR).RM calcined at 500℃(RM-500)exhibited excellent catalytic performance.Faradaic efficiency of ammonia(FENH_(3))in an electrolyte solution containing 1 mol·L^(-1)NO_(3)-achieved a maximum value of 92.3%at-0.8 V(vs.RHE).Additionally,24-h cycle testing and post-reaction PXRD and SEM indicated that the RM-500 electrocatalyst is stable during NARR.The RM-500 demonstrated a high FE of NH_(3)-to-NO_(3)-of 89.7%at 1.85 V(vs.RHE),showing great potential in the ammonia fuel cells technology and achieving the nitrogen cycle.展开更多
Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur(Li-S)batteries.This work provides a facile strategy to design an intimat...Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur(Li-S)batteries.This work provides a facile strategy to design an intimate heterostructure of MIL-88A@CdS as a sulfur electrocatalyst combining high sulfur adsorption and accelerated polysulfide conversion.The MIL-88A can give a region of high-ordered polysulfide adsorption,whereas the CdS is an effective nanoreactor for the sulfur reduction reaction(SRR).Notedly,the significant size difference between MIL-88A and CdS enables the unique heterostructure interactions.The largesize MIL-88A ensures a uniform distribution of CdS nanoparticles as a substrate.This configuration facilitates control of the initial polysulfide adsorption position relative to its final deposition site as lithium sulfide.The heterostructure also demonstrates rapid transport and efficient conversion of lithium polysulfides.Consequently,the Li-S battery with MIL-88A@CdS heterostructure modified separator delivers exceptional performance,achieving an areal capacity exceeding 6 mAh cm^(−2),an excellent rate capability of 980 mAh g^(−1) at 5 C,and notable cycling stability in a 2 Ah pouch cell over 100 cycles.This work is significant for elucidating the relationship between heterostructure and electrocatalytic performance,providing great insights for material design aimed at highly efficient future electrocatalysts in practical applications.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
The hydrogen evolution reaction(HER)in alkaline water electrolysis faces significant kinetic and thermodynamic challenges that hinder its efficiency and scalability for sustainable hydrogen production.Herein,we employ...The hydrogen evolution reaction(HER)in alkaline water electrolysis faces significant kinetic and thermodynamic challenges that hinder its efficiency and scalability for sustainable hydrogen production.Herein,we employed an in-situ synthesis strategy to incorporate H atoms into the PdRu alloy lattice to form H_(Inc)-PdRu electrocatalyst,thereby modulating its electronic structure and enhancing its alkaline HER performance.We demonstrate that the incorporation of H atoms significantly improves electrocatalytic activity,achieving a remarkably low overpotential of 25 mV at 10 mA cm^(-2)compared with the Pd,Ru and PdRu catalysts while maintaining robust catalyst stability.Operando spectroscopic analysis indicates that H insertion into the H_(Inc)-PdRu electrocatalyst enhances the availability of H_(2)O^(*)at the surface,promoting water dissociation at the active sites.Theoretical calculations proposed that the co-incorporating H and Ru atoms induces s-d orbital coupling within the Pd lattices,effectively weakening hydrogen adsorption strength and optimizing the alkaline HER energetics.This work presents a facile approach for the rational design of bimetallic electrocatalysts for efficient and stable alkaline water electrolysis for renewable hydrogen production.展开更多
The main challenge preventing the broad commercial use of polymer electrolyte membrane fuel cells(PEMFCs)is the dependence on noble metals,specifically electrocatalyst(EC)based on platinum(Pt)at the cathode,which is i...The main challenge preventing the broad commercial use of polymer electrolyte membrane fuel cells(PEMFCs)is the dependence on noble metals,specifically electrocatalyst(EC)based on platinum(Pt)at the cathode,which is indispensable for assisting the oxygen reduction reaction(ORR)in fuel cells(FCs).Research on EC-containing non-noble metal(NNM)has been considerable over the past few decades to minimize costs and reduce the excessive loading of EC based on Pt.This review is aimed at improving the reliability and stability of non-precious metal EC.To achieve a feasible ORR,Pt-based EC is crucial for the widespread commercial applications of PEMFCs.The review emphasizes improving ORR performance,stability,and cost-effectiveness in catalysts that are not precious metals.The article examines the advancements in non-precious nanomaterial-based EC,highlighting different types that have improved ORR efficiency.The review suggests future possibilities and directions for further improvement in designing and constructing EC with high efficiency and low costs for PEMFCs.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
基金financially supported by the National Natural Science Foundation of China (22350410386,W2412116,22375200,U22A202175,21961142006)。
文摘Exploring cost-effective and efficient catalysts for oxygen reduction reaction(ORR)poses a significant challenge,espe-cially in the pursuit of alternatives to precious metals like platinum.Significant advancements have driven electrochem-ists to develop efficient ORR catalysts using abundant materials,particularly iron(Fe)-based,known for their exceptional performance in ORR.While the crucial function of Fe in boosting ORR catalytic activity is recognized,the connection between material attributes and catalytic performance remains enigmatic.Understanding the dynamic processes involved in oxygen electrocatalysis is paramount for designing precious-metals-free ORR electrocatalysts.Mössbauer spectroscopy stands out as a powerful technique for deciphering the structural characteristics of Fe species in catalysis,facilitating the identification of active sites and the clarification of catalytic mechanisms.By showcasing noteworthy case studies within this review,we demonstrate the application of in-situ/operando 57Fe Mössbauer spectroscopy across diverse Fe-involved materials in ORR catalysis.This sheds light on various aspects of ORR catalysis,such as identifying active sites,assessing stability,and understanding the reaction mechanism.Our inquiry drives towards the opportunities and hurdles associ-ated with Mössbauer spectroscopy,unveiling potential breakthroughs and avenues for enhancement within this pivotal research realm.
基金financial support of the National Natural Science Foundation of China (21875247,21072221, 21172252)the Project of Talent Cultivation for Carbon Peak and Carbon Neutrality of the University of Chinese of Academy of Science
文摘The design and fabrication of ordered epitaxial MOF-on-MOF heterostructures as highly efficient electrocatalysts for water splitting is crucial but still challenging.In this study,a simple coordination-driven self-assembly method is used to fabricate controllable MOF-on-MOF multiscale heterostructures,where triangular host MOF(ZIF-67)nanosheets undergo in situ epitaxial growth to form uniform orthogonal vip MOF(CoFe PBA)nanosheets.Phosphorus(P)is further introduced in situ to fabricate CoP and Fe_(2)P heterostructured nanosheets(CoFe-P-NS),which exhibit excellent bifunctional electrocatalytic performance due to the enhancement of intrinsic electrocatalytic activity by p-d orbital hybridization.Specifically,the CoFe-P-NS requires low overpotential of 259 and 307 mV to reach 500 mA cm−2 for HER and OER,respectively.Remarkably,the assembled electrolysis cell maintained a large current density of 300 mA cm−2 for over 360 h with negligible voltage increase during alkaline seawater electrolysis.Experiments and theoretical calculations show that the synergistic catalytic activity of bimetallic phosphides arises from p-d orbital hybridization,where the CoP-P sites enhance HER by optimizing H*adsorption in the Volmer-Heyrovsky steps,while the Fe_(2)P-Fe sites accelerate OER by lowering the energy barrier of the rate-determining step from O*to OOH*.This study provides valuable insights into the design of a controllable MOF-on-MOF-based electrocatalyst toward alkaline seawater splitting.
基金supported by the National Natural Science Foundation of China(No.12205165)Hebei Province Innovation Ability Improvement Plan Project(No.225676111H).
文摘Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.
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 Fundamental Research Funds for the Central Universities(No.22120230104).
文摘High-entropy alloy(HEA)nanoparticles(NPs)have attracted great attention in electrocatalysis due to their tailorable complex compositions and unique properties.Herein,we introduce Fe,Co,Ni,Cr and Mn into the metal-polyphenol coordination system to prepare HEA NPs enclosed in N-doped carbon(FeCoNiCrMn)with great potential for catalyzing oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The unique high-entropy structural characteristics in FeCoNiCrMn facilitate effective interplay between metal species,leading to improved ORR(E_(1/2)=0.89 V)and OER(η=330 mV,j=10 mA·cm^(−2))activity.Additionally,FeCoNiCrMn exhibits excellent open-circuit voltage(1.523 V),power density(110 mW·cm^(−2))and long-term durability,outperforming Pt/C+IrO_(2) electrodes as a cathode catalyst in Zn-air batteries(ZABs).Such polyphenol-assisted alloying method broadens and simplifies the development of HEA electrocatalysts for high-performance ZABs.
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Core Research Institute Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(No.2018R1A6A1A03025242)in part by the research grant of Kwangwoon University in 2024。
文摘Advanced OER/HER electrocatalytic alternatives are crucial for the wide adaptation of green hydrogen energy.Herein,Ru/NiMnB spherical cluster pillar(SCP),denoted as Ru/NiMnB,is synthesized using a combination of electro-deposition and hydrothermal reaction.Systematic investigation of Ru doping in the NiMnB matrix revealed significant improvements in electrocatalytic performance.The Ru/NiMnB SCPs demonstrate superior OER/HER activity with low overpotentials of 150 and 103 mV at 50mA/cm^(2)in 1 M KOH,making them highly competitive with state-of-the-art electrocatalysts.Remarkably,the Ru/NiMnB SCPs exhibit a low 2-E cell voltage of 2.80 V at ultra-high current density of 2,000 m A/cm^(2)in 1 M KOH,outperforming the standard benchmark electrodes of RuO_(2)||Pt/C,thereby positioning Ru/NiMnB as one of the best bifunctional electrocatalysts.These SCPs exhibit exceptional high-current characteristics,stability and corrosion resistance,as evidenced by continuous operation at 1,000 mA/cm^(2)high-current density for over 150 h in 6 M KOH at elevated temperatures under harsh industrial conditions.Only a small amount of Ru incorporation significantly enhances the electrocatalytic performances of NiMnB,attributed to increased active sites and improved intrinsic properties such as conductivity,adsorption/desorption capability and reaction rates.Consequently,Ru/NiMnB SCPs present a promising bi-functional electrode concept for efficient green H_(2)production.
基金financial support by the Excellent Youth Foundation of Shandong Province(No.ZR2022YQ22)National Natural Science Foundation of China(No.32101451)Youth Innovation Team Project of Shandong Province(No.2022KJ303)。
文摘A high-activity and stable bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalyst is critical for seawater-based Zn-air batteries(ZABs).Herein,we report a wood-derived chainmail electrocatalyst containing defective nitrogen-doped carbon nanotubes encapsulating cobalt nanoparticles(Co@D-NCNT/CW)to enhance the ORR/OER activity and stability in seawater medium.During the preparation process,the introduction and removal of Zn increased the defect sites and pyridine N content in the carbon material,modulating charge distribution and influencing the adsorption and activation processes.The highly ordered open channels in Co@D-NCNT/CW promoted mass transfer of reactants and accelerated gas diffusion.The resultant chainmail electrocatalyst exhibited impressive bifunctional ORR and OER activities with an ultra-low gap of 0.67 V in sea water-based alkaline electrolyte.The Co@D-NCNT/CW-assembled seawater-based rechargeable liquid ZABs demonstrated a maximum power density of 245.3 mW cm^(-2)and a long-term cycling performance over 500 h.The seawater-based all-solid-state ZABs achieved the maximum power density of 48.2 mW cm^(-2)and stabilized over 30 h.Density functional theory revealed that the presence of defects and pyridine nitrogen in Co@D-NCNT/CW modulated the electronic structure of Co,optimizing the binding affinity of the Co sites with intermediates and weakening Cl^(-)adsorption.This work provides a new approach to preparing high-activity and stable ORR/OER electrocatalyst utilizing wood nanostructures,boosting the development of seawater-based ZABs.
基金financially supported by the National Natural Science Foundation of China(No.22279047)the Instrumental Analysis Center of Jiangsu University of Science and Technology。
文摘Exploring efficient and nonprecious metal electrocatalysts of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is crucial for developing rechargeable zinc-air batteries(ZABs).Herein,an alloying-degree control strategy was employed to fabricate nitrogen-doped carbon sphere(NCS)decorated with dual-phase Co/Co_(7)Fe_(3)heterojunctions(CoFe@NCS).The phase composition of materials has been adjusted by controlling the alloying degree.The optimal CoFe_(0.08)@NCS electrocatalyst displays a half-wave potential of 0.80 V for ORR and an overpotential of 283 mV at 10 mA·cm^(-2)for OER in an alkaline electrolyte.The intriguing bifunctional electrocatalytic activity and durability is attributed to the hierarchically porous structure and interfacial electron coupling of highly-active Co_(7)Fe_(3)alloy and metallic Co species.When the CoFe_(0.08)@NCS material is used as air-cathode catalyst of rechargeable liquid-state zinc-air battery(ZAB),the device shows a high peak power-density(157 mW·cm^(-2))and maintains a stable voltage gap over 150 h,outperforming those of the benchmark(Pt/C+RuO_(2))-based device.In particular,the as-fabricated solid-state flexible ZAB delivers a reliable compatibility under different bending conditions.Our work provides a promising strategy to develop metal/alloy-based electrocatalysts for the application in renewable energy conversion technologies.
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 Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(2022M3H4A1A01010832 and RS-2024-00449682)the Basic Science Research Program through the NRF funded by the Ministry of Education(2021R1A6A1A03039696)+1 种基金Computer time allocation has been provided by the US DOE INCITE program(DE-AC02-06CH11357)National ScienceFoundation ACCESS program(NSF-2138296)。
文摘Electrides,in which anionic electrons are trapped in structural cavities,have garnered significant attention for exceptionalfunctionalities based on their low work function.In low-dimensional electrides,a strong quantum confinement of anionicelectrons leads to many interesting phenomena,but a severe chemical instability due to their open structures is one of the majordisadvantages for practical applications.Here we report that one-dimensional(1D)dititanium sulfide electride exhibits an ex-traordinary stability originating from the surface self-passivation and consequent durability in bifunctional electrocatalytic activity.Theoretical calculations identify the uniqueness of the 1D[Ti_(2)S]^(2+)·2e^(−)electride,where multiple cavities form two distinct channelstructures of anionic electrons.Combined surface structure analysis and in-situ work function measurement indicate that thenatural formation of amorphous titanium oxide surface layer in air is responsible for the remarkable inertness in water and pH-varied solutions.This makes the[Ti_(2)S]^(2+)·2e^(−)electride an ideal support for a heterogenous metal-electride hybrid catalyst,demonstrating the enhanced efficiency and superior durability in both the hydrogen evolution and oxygen reduction reactionscompared to commercial Pt/C catalysts.This study will stimulate further exploratory research for developing a chemically stableelectride in reactive conditions,evoking a strategy for a practical electrocatalyst for industrial energy conversions.
基金supported by grants from the National Natural Science Foundation of China (22178339)2023 Innovation-driven Development Special Foundation of Guangxi(AA23023021)the Hundred Talents Program (A) of the Chinese Academy of Sciences
文摘Red mud(RM)is a solid waste generated in the aluminum industry after the extraction of alumina oxide;its multiple elements and higher pH value likely pose a severe threat to the environment after treatment.However,RM's higher concentrations of metal components,particularly Fe_(2)O_(3)and rare earth elements(REEs),render RM promising for catalytic application.Hence,this work showed an efficient high-speed RM to catalyze electrocatalytic nitrate-to-ammonia reduction reaction(NARR).RM calcined at 500℃(RM-500)exhibited excellent catalytic performance.Faradaic efficiency of ammonia(FENH_(3))in an electrolyte solution containing 1 mol·L^(-1)NO_(3)-achieved a maximum value of 92.3%at-0.8 V(vs.RHE).Additionally,24-h cycle testing and post-reaction PXRD and SEM indicated that the RM-500 electrocatalyst is stable during NARR.The RM-500 demonstrated a high FE of NH_(3)-to-NO_(3)-of 89.7%at 1.85 V(vs.RHE),showing great potential in the ammonia fuel cells technology and achieving the nitrogen cycle.
基金supported by the Natural Science Foundation of China(22309179)the Natural Science Foundation of China(12404049)+4 种基金Natural Science Foundation of Ningxia(2023AAC01003)Guangdong Basic and Applied Basic Research Foundation(2021A1515110156,2022A1515010724,2023A1515110521,2023B1515120095,2024A1515011260)Science and Technology Program of Guangzhou(No.2019050001)the Outstanding Youth Project of Guangdong Natural Science Foundation(2021B1515020051)Dalian Revitalization Talents Program(No.2022RG01).
文摘Developing electrocatalysts to inhibit polysulfide shuttling and expedite sulfur species conversion is vital for the evolution of Lithium-sulfur(Li-S)batteries.This work provides a facile strategy to design an intimate heterostructure of MIL-88A@CdS as a sulfur electrocatalyst combining high sulfur adsorption and accelerated polysulfide conversion.The MIL-88A can give a region of high-ordered polysulfide adsorption,whereas the CdS is an effective nanoreactor for the sulfur reduction reaction(SRR).Notedly,the significant size difference between MIL-88A and CdS enables the unique heterostructure interactions.The largesize MIL-88A ensures a uniform distribution of CdS nanoparticles as a substrate.This configuration facilitates control of the initial polysulfide adsorption position relative to its final deposition site as lithium sulfide.The heterostructure also demonstrates rapid transport and efficient conversion of lithium polysulfides.Consequently,the Li-S battery with MIL-88A@CdS heterostructure modified separator delivers exceptional performance,achieving an areal capacity exceeding 6 mAh cm^(−2),an excellent rate capability of 980 mAh g^(−1) at 5 C,and notable cycling stability in a 2 Ah pouch cell over 100 cycles.This work is significant for elucidating the relationship between heterostructure and electrocatalytic performance,providing great insights for material design aimed at highly efficient future electrocatalysts in practical applications.
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.
文摘The hydrogen evolution reaction(HER)in alkaline water electrolysis faces significant kinetic and thermodynamic challenges that hinder its efficiency and scalability for sustainable hydrogen production.Herein,we employed an in-situ synthesis strategy to incorporate H atoms into the PdRu alloy lattice to form H_(Inc)-PdRu electrocatalyst,thereby modulating its electronic structure and enhancing its alkaline HER performance.We demonstrate that the incorporation of H atoms significantly improves electrocatalytic activity,achieving a remarkably low overpotential of 25 mV at 10 mA cm^(-2)compared with the Pd,Ru and PdRu catalysts while maintaining robust catalyst stability.Operando spectroscopic analysis indicates that H insertion into the H_(Inc)-PdRu electrocatalyst enhances the availability of H_(2)O^(*)at the surface,promoting water dissociation at the active sites.Theoretical calculations proposed that the co-incorporating H and Ru atoms induces s-d orbital coupling within the Pd lattices,effectively weakening hydrogen adsorption strength and optimizing the alkaline HER energetics.This work presents a facile approach for the rational design of bimetallic electrocatalysts for efficient and stable alkaline water electrolysis for renewable hydrogen production.
文摘The main challenge preventing the broad commercial use of polymer electrolyte membrane fuel cells(PEMFCs)is the dependence on noble metals,specifically electrocatalyst(EC)based on platinum(Pt)at the cathode,which is indispensable for assisting the oxygen reduction reaction(ORR)in fuel cells(FCs).Research on EC-containing non-noble metal(NNM)has been considerable over the past few decades to minimize costs and reduce the excessive loading of EC based on Pt.This review is aimed at improving the reliability and stability of non-precious metal EC.To achieve a feasible ORR,Pt-based EC is crucial for the widespread commercial applications of PEMFCs.The review emphasizes improving ORR performance,stability,and cost-effectiveness in catalysts that are not precious metals.The article examines the advancements in non-precious nanomaterial-based EC,highlighting different types that have improved ORR efficiency.The review suggests future possibilities and directions for further improvement in designing and constructing EC with high efficiency and low costs for PEMFCs.
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.
