Electrochemical reduction reactions,including the oxygen reduction reaction(ORR),hydrogen evolution reaction(HER),carbon dioxide reduction reaction(CRR),and nitrate reduction reaction(NRR),hold promise for energy conv...Electrochemical reduction reactions,including the oxygen reduction reaction(ORR),hydrogen evolution reaction(HER),carbon dioxide reduction reaction(CRR),and nitrate reduction reaction(NRR),hold promise for energy conversion and storage.However,electrocatalysts exhibit slow kinetics and inactivation effects,resulting in inadequate energy efficiency and poor stability.To address these challenges,the groupⅧelement-based single-atom electrocatalysts(GVSAEs)were endowed with tunable electronic structures and porous carbon substrates to reduce intermediate adsorption and desorption energy barriers,which can accelerate electrochemical kinetics.This mini review summarises the recent achievements in GVSAEs with electronic structure and porous substrate engineering discussions.Furthermore,these GVSAEs are divided into non-noble iron series element(Fe,Co,and Ni)single-atom electrocatalysts and noble platinum series elements(Ru,Rh,Pd,Os,Ir,and Pt)based single-atom electrocatalysts for the ORR,HER,CRR,and NRR,where the porous substrate structure,electronic structure,and catalytic activity are discussed.Finally,conclusions and perspectives relating to future challenges and potential opportunities are provided for electrocatalysis with better performance.展开更多
Metal-organic frameworks(MOFs) have been widely used in oxygen reduction reaction(ORR) of fuel cells and metal-air batteries, attributed to their unique structures and compositions. Recently, the preparation of transi...Metal-organic frameworks(MOFs) have been widely used in oxygen reduction reaction(ORR) of fuel cells and metal-air batteries, attributed to their unique structures and compositions. Recently, the preparation of transition-metallic single-atom electrocatalysts(TM-SACs) using MOFs as precursors or templates has made great progress. Herein, the development history of SACs prepared based on MOFs and their characterization are overviewed firstly, and then several strategies are summarized for preparing TM-SACs using MOFs and further modification. Finally, the challenges and opportunities confronted by TM-SACs are fully discussed. Consequently, our work can guide the realization of TM-SACs abundant with high activity, high loading and high stability.展开更多
Lithium-sulfur batteries(LSBs)have been regarded as one of the promising candidates for the next-generation“lithium-ion battery beyond”owing to their high energy density and due to the low cost of sulfur.However,the...Lithium-sulfur batteries(LSBs)have been regarded as one of the promising candidates for the next-generation“lithium-ion battery beyond”owing to their high energy density and due to the low cost of sulfur.However,the main obstacles encountered in the commercial implementation of LSBs are the notorious shuttle effect,retarded sulfur redox kinetics,and uncontrolled dendrite growth.Accordingly,single-atom catalysts(SACs),which have ultrahigh catalytic efficiency,tunable coordination configuration,and light weight,have shown huge potential in the field of LSBs to date.This review summarizes the recent research progress of SACs applied as multifunctional components in LSBs.The design principles and typical synthetic strategies of SACs toward effective Li–S chemistry as well as the working mechanism promoting sulfur conversion reactions,inhibiting the lithium polysulfide shuttle effect,and regulating Li+nucleation are comprehensively illustrated.Potential future directions in terms of research on SACs for the realization of commercially viable LSBs are also outlined.展开更多
Efficient and robust single-atom catalysts(SACs)based on cheap and earth-abundant elements are highly desirable for electrochemical reduction of nitrogen to ammonia(NRR)under ambient conditions.Herein,for the first ti...Efficient and robust single-atom catalysts(SACs)based on cheap and earth-abundant elements are highly desirable for electrochemical reduction of nitrogen to ammonia(NRR)under ambient conditions.Herein,for the first time,a Mn-N-C SAC consisting of isolated manganese atomic sites on ultrathin carbon nanosheets is developed via a template-free folic acid self-assembly strategy.The spontaneous molecular partial dissociation enables a facile fabrication process without being plagued by metal atom aggregation.Thanks to well-exposed atomic Mn active sites anchored on two-dimensional conductive carbon matrix,the catalyst exhibits excellent activity for NRR with high activity and selectivity,achieving a high Faradaic efficiency of 32.02%for ammonia synthesis at−0.45 V versus reversible hydrogen electrode.Density functional theory calculations unveil the crucial role of atomic Mn sites in promoting N_(2) adsorption,activation and selective reduction to NH_(3) by the distal mechanism.This work provides a simple synthesis process for Mn-N-C SAC and a good platform for understanding the structure-activity relationship of atomic Mn sites.展开更多
Developing efficient electrocatalysts for converting dinitrogen to ammonia through electrocatalysis is of significance to the decentralized ammonia production. Here, through high-throughput density functional theory c...Developing efficient electrocatalysts for converting dinitrogen to ammonia through electrocatalysis is of significance to the decentralized ammonia production. Here, through high-throughput density functional theory calculations, we demonstrated that the interfacial modulation of hexagonal boron nitride/graphene(hBN-graphene) could sufficiently improve the catalytic activity of the single transition metal atom catalysts for nitrogen reduction reaction(NRR). It was revealed that Re@hBN-graphene and Os@hBN-graphene possessed remarkable NRR catalytic activity with low limiting potentials of 0.29 V and 0.33 V, respectively. Furthermore, the mechanism of the enhanced catalytic activity was investigated based on various descriptors of the adsorption energies of intermediates, where the synergistic effect of hBN and graphene in the hybrid substrate was found to play a key role. Motivated by the synergistic effect of hybrid substrate in single-atom catalysts, a novel strategy was proposed to efficiently design dual-atom catalysts by integrating the merits of both metal components. The as-designed dual-atom catalyst Fe-Mo@hBN exhibited more excellent NRR catalytic performance with a limiting potential of 0.17 V, manifesting the solidity of the design strategy. Our findings open new avenues for the search of heterostructure substrates for single-atom catalysts and the efficient design of dualatom catalysts for NRR.展开更多
Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Here...Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.展开更多
Aluminum-sulfur(Al-S)batteries are regarded as a desirable candidate for large-scale energy storage be-cause of their high energy density and abundant natural resources of electrode materials.To address the critical i...Aluminum-sulfur(Al-S)batteries are regarded as a desirable candidate for large-scale energy storage be-cause of their high energy density and abundant natural resources of electrode materials.To address the critical issues of low discharge voltage and rapid capacity decay in Al-S batteries,here an electrocatalyst-assisted gel-polymer electrolyte(GPE)-based Al-S battery is fabricated using platinum nanoparticles deco-rated platinum/nitrogen co-doped graphene(PtNG)as sulfur host for positive electrode and metal-organic frameworks(MOF)filled GPE(MOF@GPE)as solid electrolyte.Pt-based active sites derived from Pt nan-oclusters’surface and atomically dispersed Pt-N_(2) chemical bonds in PtNG can catalyze the decomposition of sulfur and polysulfides in the electrochemical process,greatly accelerating the sulfur redox kinetics.Furthermore,the MOF fillers in MOF@GPE electrolyte significantly inhibit the shuttle effect of polysul-fides,efficiently improving the utilization of sulfur.Consequently,the established Al-S battery delivers a specific capacity of 1009 mAh g^(−1) with a discharge plateau of∼0.95 V,along with a capacity retention of 65% after 300 cycles,revealing ultrahigh energy density and long cycle life.Such a strategy of combin-ing electrocatalyst and MOF-based gel electrolyte affords a fresh plateau for promoting the rechargeable ability of Al-S batteries,advancing remarkable routes for achieving efficient and stable energy storage devices.展开更多
The strategic manipulation of the interaction between a central metal atom and its coordinating environment in single-atom catalysts(SACs)is crucial for catalyzing the CO_(2)reduction reaction(CO_(2)RR).However,it rem...The strategic manipulation of the interaction between a central metal atom and its coordinating environment in single-atom catalysts(SACs)is crucial for catalyzing the CO_(2)reduction reaction(CO_(2)RR).However,it remains a major challenge.While density-functional theory calculations serve as a powerful tool for catalyst screening,their time-consuming nature poses limitations.This paper presents a machine learning(ML)model based on easily accessible intrinsic descriptors to enable rapid,cost-effective,and high-throughput screening of efficient SACs in complex systems.Our ML model comprehensively captures the influences of interactions between 3 and 5d metal centers and 8 C,N-based coordination environments on CO_(2)RR activity and selectivity.We reveal the electronic origin of the different activity trends observed in early and late transition metals during coordination with N atoms.The extreme gradient boosting regression model shows optimal performance in predicting binding energy and limiting potential for both HCOOH and CO production.We confirm that the product of the electronegativity and the valence electron number of metals,the radius of metals,and the average electronegativity of neighboring coordination atoms are the critical intrinsic factors determining CO_(2)RR activity.Our developed ML models successfully predict several high-performance SACs beyond the existing database,demonstrating their potential applicability to other systems.This work provides insights into the low-cost and rational design of high-performance SACs.展开更多
With the development of advanced catalysts,the assessment of emerging single-atom-based electrochemical catalysts(SAECs)has significantly increased owing to their similarity to natural enzymes.They hold substantial po...With the development of advanced catalysts,the assessment of emerging single-atom-based electrochemical catalysts(SAECs)has significantly increased owing to their similarity to natural enzymes.They hold substantial potential for the design and construction of electrochemical sensing platforms.The fabrication of single-atombased electrodes revealed their potential for sensitive and selective analyses.Among various nanomaterials,transition metal element-based single-atom,bimetallic single-atom,and metal-free single-atom,each with welldefined active sites,exhibit enhanced catalytic activity,selectivity,and stability.The rational construction of the composition,size,and the strategic development of single-atom electrocatalysts on carbon platforms to enable them to function effectively in complex environments and demonstrate their efficiency between the active sites and electrode construction strategies.Unlike traditional catalysts,SAECs are considered to potential substitutes for natural enzymes.This perspective has been described in a mini-review that highlights recent developments in transition metal elements-based single/bimetallic single atoms and metal-free single atoms anchored on carbon nanostructures.Additionally,there has been a rise in the fabrication of printed electrodes as sensing platforms for biomedical,environmental,and food toxin detection.The challenges and prospects for SAECs in multiple sensing applications are also concisely elaborated.展开更多
Oxygen reduction reaction(ORR)in neutral electrolyte is urgently needed in various areas,such as metalair batteries.However,the N-coordinated transition-metal single-atom electrocatalysts confront sluggish catalytic k...Oxygen reduction reaction(ORR)in neutral electrolyte is urgently needed in various areas,such as metalair batteries.However,the N-coordinated transition-metal single-atom electrocatalysts confront sluggish catalytic kinetics due to the inappropriate electronic structure and the as-resulted unreasonable adsorption strength towards oxygen-containing intermediates.In this work,we develop a strategy to tune the Fe d-orbital spin state by introducing inert Si atom into the first coordination sphere of Fe-N_(4)moieties.The experimental and theoretical results suggest that Si atom generates the coordination field distortion of Fe and induces the Fe d-orbital spin state transforming from low to medium spin state.The optimized spin-electron filled state(t2g^(4)eg^(1))of Fe sites weakens the adsorption strength to intermediates and reduces the energy barrier of^(∗)OH desorption.Consequently,Fe-Si/NC catalyst exhibits superior ORR performance compared with that of Fe-NC and commercial Pt/C,showing a more positive half-wave potential of 0.753 V(vs.RHE)in 0.1 mol/L phosphate buffered saline.In addition,Fe-Si/NC-based neutral zinc-air batteries show a maximum power density of 108.9 mW cm^(−2)and long-term stability for 200 h.This work represents the possibility of constructing distorted coordination configurations of single-atom catalysts to modulate electronic structure and enhance ORR activity in neutral electrolyte.展开更多
Development of high-efficiency bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalysts is vital for the widespread application of zinc-air batteries(ZABs).However,it still remains...Development of high-efficiency bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalysts is vital for the widespread application of zinc-air batteries(ZABs).However,it still remains a great challenge to avoid the inhomogeneous distribution and aggregation of metal single-atomic active centers in the construction of bifunctional electrocatalysts with atomically dispersed multimetallic sites because of the common calcination method.Herein,we report a novel catalyst with phthalocyanine-assembled Fe-Co-Ni single-atomic triple sites dispersed on sulfur-doped graphene using a simple ultrasonic procedure without calcination,and X-ray absorption fine structure(XAFS),aberration-corrected scanning transmission electron microscopy(AC-STEM),and other detailed characterizations are performed to demonstrate the successful synthesis.The novel catalyst shows extraordinary bifunctional ORR/OER activities with a fairly low potential difference(ΔE=0.621 V)between the OER overpotential(Ej10=315 mV at 10 m A cm^(-2))and the ORR half-wave potential(Ehalf-wave=0.924 V).Moreover,the above catalyst shows excellent ZAB performance,with an outstanding specific capacity(786 mAh g^(-1)),noteworthy maximum power density(139 mW cm^(-2)),and extraordinary rechargeability(discharged and charged at 5 mA cm^(-2) for more than 1000 h).Theoretical calculations reveal the vital importance of the preferable synergetic coupling effect between adjacent active sites in the Fe-Co-Ni trimetallic single-atomic sites during the ORR/OER processes.This study provides a new avenue for the investigation of bifunctional electrocatalysts with atomically dispersed trimetallic sites,which is intended for enhancing the ORR/OER performance in ZABs.展开更多
Atomically dispersed single-atom catalysts(SACs)supported on graphene provide a ladder of opportunity for achieving the electrocatalytic CO_(2)reduction to value-added chemicals,where the efficient combinations of act...Atomically dispersed single-atom catalysts(SACs)supported on graphene provide a ladder of opportunity for achieving the electrocatalytic CO_(2)reduction to value-added chemicals,where the efficient combinations of active sites and coordination environments are a powerful approach to optimize both activity and selectivity.Nevertheless,the understanding of the underlying mechanism about how the catalytic performance varies via active sites and coordination environments is very limited.Herein,we successfully constructed the activity trend of SACs with different coordination environments(MXnY4−n X,Y=N,S,P,and M=19 transition metals)for CO_(2)reduction to CH_(4),using easily obtainable parameters.Based on the entire reaction free energy over 110 stable SACs,the binding strength of*OCHO intermediate(ΔE*OCHO)is identified as an initial activity indicator towards CO_(2)reduction to CH_(4).With the help of multi-task symbolic regression,a simple active descriptor consisting of intrinsic properties(valence-electron number and electronegativity of metal atoms and coordination atoms)is further constructed,which can well describe the variation ofΔE*OCHO and the onset potential for CH_(4).Importantly,this active descriptor enables rapid evaluation on the activity of SACs without DFT computations.This work is instructive for the rational design of other CO_(2)electrocatalysts and establishing more multiplex descriptors through decoupling the factors and handling them separately.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
Single-atom catalysts(SACs)have become one of the most considered research directions today,owing to their maximum atom utilization and simple structures,to investigate structure-activity relationships.In the field of...Single-atom catalysts(SACs)have become one of the most considered research directions today,owing to their maximum atom utilization and simple structures,to investigate structure-activity relationships.In the field of non-precious-metal electrocatalysts,atomically dispersed Fe-N4 active sites have been proven to possess the best oxygen reduction activity.Yet the majority of preparation methods remains complex and costly with unsatisfying controllability.Herein,we have designed a surface-grafting strategy to directly synthesize an atomically dispersed Fe-NVC electrocatalyst applied to the oxygen reduction reaction(ORR).Through an esterification process in organic solution,metal-containing precursors were anchored on the surface of carbon substrates.The covalent bonding effect could suppress the formation of aggregated particles during heat treatment.Melamine was further introduced as both a cost-effective nitrogen resource and blocking agent retarding the migration of metal atoms.The optimized catalyst has proven to have abundant atomically dispersed Fe-N4 active sites with enhanced ORR catalytic performance in acid condition.This method has provided new feasible ideas for the synthesis of SACs.展开更多
Single-atom catalysts(SACs)have been widely used in heterogeneous catalysis owing to the maximum utilization of metal-active sites with controlled structures and well-defined locations.Upon tailored coordination with ...Single-atom catalysts(SACs)have been widely used in heterogeneous catalysis owing to the maximum utilization of metal-active sites with controlled structures and well-defined locations.Upon tailored coordination with nitrogen atom,the metal-nitrogen(M-N)-based SACs have demonstrated interesting physical,optical and electronic properties and have become intense in photocatalysis and electrocatalysis in the past decade.Despite substantial efforts in constructing various M–N-based SACs,the principles for modulating the intrinsic photocatalytic and electrocatalytic performance of their active sites and catalytic mechanism have not been sufficiently studied.Herein,the present review intends to shed some light on recent research made in studying the correlation between intrinsic electronic structure,catalytic mechanism,single-metal atom(SMA)confinement and their photocatalytic and electrocatalytic activities(conversion,selectivity,stability and etc).Based on the analysis of fundamentals of M–N-based SACs,theoretical calculations and experimental investigations,including synthetic methods and characterization techniques,are both included to provide an integral understanding of the underlying mechanisms behind improved coordination structure and observed activity.Finally,the challenges and perspectives for constructing highly active M–N based photocatalysis and electrocatalysis SACs are provided.In particular,extensive technical and mechanism aspects are thoroughly discussed,summarized and analyzed for promoting further advancement of M-N-based SACs in photocatalysis and electrocatalysis.展开更多
Fe-N-C endowed with inexpensiveness,high activity,and excellent anti-poisoning power have emerged as promising candidate catalysts for oxygen reduction reaction(ORR).Single-atom Fe-N-C electrocatalysts derived from Fe...Fe-N-C endowed with inexpensiveness,high activity,and excellent anti-poisoning power have emerged as promising candidate catalysts for oxygen reduction reaction(ORR).Single-atom Fe-N-C electrocatalysts derived from Fe-doped ZIF-8 represent the top-level ORR performance.However,the current fabrication of Fe-doped ZIF-8 relies on heavy consumption of time,energy,cost and organic solvents.Herein,we develop a rapid and solvent-free method to produce Fe-doped ZIF-8 under microwave irradiation,which can be easily amplified in combination with ball-milling.After rational pyrolysis,Fe-N-C catalysts with atomic FeN4 sites well dispersed on the hierarchically porous carbon matrix are obtained,which exhibit exceptional ORR performance with a half-wave potential of 0.782 V(vs.reversible hydrogen electrode(RHE))and brilliant methanol tolerance.The assembled direct methanol fuel cells(DMFCs)endow a peak power density of 61 mW cm^(-2) and extraordinary stability,highlighting the application perspective of this strategy.展开更多
The discovery of single-atom catalysts(SACs)represents a groundbreaking advancement in the field of catalysis over the past decades.With the in-depth exploration of relevant structure-activity relationships,the metal−...The discovery of single-atom catalysts(SACs)represents a groundbreaking advancement in the field of catalysis over the past decades.With the in-depth exploration of relevant structure-activity relationships,the metal−support interaction(MSI)is widely adopted to elucidate variations in electronic structure and coordination configuration of atomic active sites on various kinds of supports.Herein,we briefly summarize the metal oxide supports for SACs fabrication,including the distinctive characteristics of metal oxide supports,enlightening advancements in metal oxide support-based SACs(MO-SACs),feasible preparation methods for MO-SACs and effective regulation strategies of MSI effect in MO-SACs.In addition,we present our viewpoints and outlook in this field to stimulate rational design and construction of novel MO-SACs applied in diverse renewable energy devices,while some universal suggestions are sincerely given to provoke thoughtful considerations during the research process.展开更多
Ongoing efforts to develop single-atom catalysts(SACs) for the oxygen reduction reaction(ORR) typically focus on SACs with cationic metal centers,while SACs with anionic metal centers(anionic SACs) have been generally...Ongoing efforts to develop single-atom catalysts(SACs) for the oxygen reduction reaction(ORR) typically focus on SACs with cationic metal centers,while SACs with anionic metal centers(anionic SACs) have been generally neglected.However,anionic SACs may offer excellent active sites for ORR,since anionic metal centers could facilitate the activation of O_(2) by back donating electrons to the antibonding orbitals of O_(2).In this work,we propose a simple guideline for designing anionic SACs:the metal centers should have larger electronegativity than the surrounding atoms in the substrate on which the metal atoms are supported.By means of density functional theory(DFT) simulations,we identified 13 anionic metal centers(Co,Ni,Cu,Ru,Rh,Pd,Ag,Re,Os,Ir,Pt,Au,and Hg) dispersed on pristine or defective antimonene substrates as new anionic SACs,among which anionic Au and Co metal centers exhibit limiting potentials comparable to,or even better than,conventional Pt-based catalysts towards ORR.We also found that anionic Os and Re metal centers on the defective antimonene can electrochemically catalyze the nitrogen reduction reaction(NRR) with a limiting potential close to that of stepped Ru(0001).Overall,our work shows promise towards the rational design of anionic SACs and their utility for applications as electrocatalysts for ORR and other important electrochemical reactions.展开更多
High-performance bifunctional oxygen electrocatalysts that simultaneously boost the sluggish oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)need to be developed for advanced rechargeable Znair battery...High-performance bifunctional oxygen electrocatalysts that simultaneously boost the sluggish oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)need to be developed for advanced rechargeable Znair battery applications.In this work,a zeolitic imidazolate framework(ZIF)-phase conversion associated with a subsequent thermal fixing strategy was developed to fabricate bimetallic CoFe single atoms/clusters embedded in N-doped carbon(denoted as CoFe-N-C)nanorods,which can serve as efficient bifunctional ORR/OER electrocatalysts.Microstructural observation and X-ray absorption spectroscopy analysis confirm the co-existence of highly active Co/Fe-N_(x) dual sites and CoFe alloy nanoclusters.X-ray photoelectron spectroscopy(XPS)results prove that implanting secondary Fe atoms into Co-N-C matrix nanorods can induce electronic redistribution of atomic Co/Fe active sites and generate synergistic effects,which would optimize the adsorption energy of the reaction intermediates and thus enhance the bifunctional ORR/OER activity.The bimetallic CoFe-N-C nanorods exhibit significantly enhanced bifunctional ORR/OER activity and stability than the monometallic Co/Fe-N-C nanorods in alkaline electrolytes in terms of a very positive half-wave potential of 0.90 V(vs.reversible hydrogen electrode(RHE))for ORR,and an overpotential of 440 mV to reach current density of 10 mA·cm^(-2)for OER,yielding a small overpotential gap of 0.77 V.Furthermore,the rechargeable Zn-air batteries using bimetallic CoFe-N-C nanorods as air-cathode catalyst demonstrates peak power density of200.7 mW·cm^(-2)and robust cycling stability of up to200 h,corresponding to 1200 discharge-charge cycles.展开更多
Superior bifunctional electrocatalysts with ultra-high stability and excellent efficiency are crucial to boost the oxygen evolution reaction(OER) and the hydrogen evolution reduction(HER) in the overall water splittin...Superior bifunctional electrocatalysts with ultra-high stability and excellent efficiency are crucial to boost the oxygen evolution reaction(OER) and the hydrogen evolution reduction(HER) in the overall water splitting(OWS) for the sustainable production of clean fuels. Herein, comprehensive density functional theory(DFT) computations were performed to explore the potential of several single transition metal(TM) atoms anchored on various S-doped black phosphorenes(TM/Snx-BP) for bifunctional OWS electrocatalysis. The results revealed that these candidates display good stability, excellent electrical conductivity, and diverse spin moments. Furthermore, the Rh/S12-BP catalyst was identified as an eligible bifunctional catalyst for OWS process due to the low overpotentials for OER(0.43 V) and HER(0.02 V), in which Rh and its adjacent P atoms were identified as the active sites. Based on the computed Gibbs free energies of OH~*, O~*, OOH~* and H~*, the corresponding volcano plots for OER and HER were established.Interestingly, the spin moments and the charge distribution of the active sites determine the catalytic trends of OER and HER. Our findings not only propose a promising bifunctional catalyst for OWS, but also widen the potential application of BP in electrocatalysis.展开更多
基金supported by the National Natural Science Foundation of China-Yunnan Joint Fund(No.U2002213)the Science and Technology Talent and Platform Program of Yunnan Provincial Science and Technology Department(No.202305AM070001)+1 种基金Open Foundation of Guangxi Key Laboratory of Processing for Non-Ferrous Metals and Featured Materials(No.2022GXYSOF10)Double First University Plan(No.C176220100042)
文摘Electrochemical reduction reactions,including the oxygen reduction reaction(ORR),hydrogen evolution reaction(HER),carbon dioxide reduction reaction(CRR),and nitrate reduction reaction(NRR),hold promise for energy conversion and storage.However,electrocatalysts exhibit slow kinetics and inactivation effects,resulting in inadequate energy efficiency and poor stability.To address these challenges,the groupⅧelement-based single-atom electrocatalysts(GVSAEs)were endowed with tunable electronic structures and porous carbon substrates to reduce intermediate adsorption and desorption energy barriers,which can accelerate electrochemical kinetics.This mini review summarises the recent achievements in GVSAEs with electronic structure and porous substrate engineering discussions.Furthermore,these GVSAEs are divided into non-noble iron series element(Fe,Co,and Ni)single-atom electrocatalysts and noble platinum series elements(Ru,Rh,Pd,Os,Ir,and Pt)based single-atom electrocatalysts for the ORR,HER,CRR,and NRR,where the porous substrate structure,electronic structure,and catalytic activity are discussed.Finally,conclusions and perspectives relating to future challenges and potential opportunities are provided for electrocatalysis with better performance.
基金supported by the National Natural Science Foundation of China(51872115,51932003)the 2020 International Cooperation Project of the Department of Science and Technology of Jilin Province(20200801001GH)+3 种基金the Program for the Development of Science and Technology of Jilin Province(20190201309JC)the Jilin Province/Jilin University coConstruction Project-Funds for New Materials(SXGJSF2017-3,Branch-2/440050316A36)the Project for Self-innovation Capability Construction of Jilin Province Development and Reform Commission(2021C026)the Fundamental Research Funds for the Central Universities JLU,and “Double-First Class”Discipline for Materials Science&Engineering。
文摘Metal-organic frameworks(MOFs) have been widely used in oxygen reduction reaction(ORR) of fuel cells and metal-air batteries, attributed to their unique structures and compositions. Recently, the preparation of transition-metallic single-atom electrocatalysts(TM-SACs) using MOFs as precursors or templates has made great progress. Herein, the development history of SACs prepared based on MOFs and their characterization are overviewed firstly, and then several strategies are summarized for preparing TM-SACs using MOFs and further modification. Finally, the challenges and opportunities confronted by TM-SACs are fully discussed. Consequently, our work can guide the realization of TM-SACs abundant with high activity, high loading and high stability.
基金Science and Technology Innovation Program of Hunan Province,Grant/Award Number:2021RC3021Project of State Key Laboratory of Environment‐Friendly Energy Materials,Grant/Award Numbers:18ZD320304,21fksy24+2 种基金Natural Science Foundation of Hunan Province,Grant/Award Number:2021JJ40780National Natural Science Foundation of China,Grant/Award Numbers:51902346,52172239Start‐up Funding of Yangtze Region Institute(Huzhou),University of Electronic Science and Technology,Grant/Award Number:U03220102。
文摘Lithium-sulfur batteries(LSBs)have been regarded as one of the promising candidates for the next-generation“lithium-ion battery beyond”owing to their high energy density and due to the low cost of sulfur.However,the main obstacles encountered in the commercial implementation of LSBs are the notorious shuttle effect,retarded sulfur redox kinetics,and uncontrolled dendrite growth.Accordingly,single-atom catalysts(SACs),which have ultrahigh catalytic efficiency,tunable coordination configuration,and light weight,have shown huge potential in the field of LSBs to date.This review summarizes the recent research progress of SACs applied as multifunctional components in LSBs.The design principles and typical synthetic strategies of SACs toward effective Li–S chemistry as well as the working mechanism promoting sulfur conversion reactions,inhibiting the lithium polysulfide shuttle effect,and regulating Li+nucleation are comprehensively illustrated.Potential future directions in terms of research on SACs for the realization of commercially viable LSBs are also outlined.
基金The authors thank the financial support from the National Natural Science Foundation of China(No.51902204,52001214,21975163)Bureau of Industry and Information Technology of Shenzhen(No.201901171518)Shenzhen Science and Technology Program(KQTD20190929173914967).
文摘Efficient and robust single-atom catalysts(SACs)based on cheap and earth-abundant elements are highly desirable for electrochemical reduction of nitrogen to ammonia(NRR)under ambient conditions.Herein,for the first time,a Mn-N-C SAC consisting of isolated manganese atomic sites on ultrathin carbon nanosheets is developed via a template-free folic acid self-assembly strategy.The spontaneous molecular partial dissociation enables a facile fabrication process without being plagued by metal atom aggregation.Thanks to well-exposed atomic Mn active sites anchored on two-dimensional conductive carbon matrix,the catalyst exhibits excellent activity for NRR with high activity and selectivity,achieving a high Faradaic efficiency of 32.02%for ammonia synthesis at−0.45 V versus reversible hydrogen electrode.Density functional theory calculations unveil the crucial role of atomic Mn sites in promoting N_(2) adsorption,activation and selective reduction to NH_(3) by the distal mechanism.This work provides a simple synthesis process for Mn-N-C SAC and a good platform for understanding the structure-activity relationship of atomic Mn sites.
基金the financial support from the National Natural Science Foundation of China (52076045)the Ministry of Science and Technology of China (2019YFC1906700, 2018YFC1902600)the support from “Zhishan Scholar” of Southeast University。
文摘Developing efficient electrocatalysts for converting dinitrogen to ammonia through electrocatalysis is of significance to the decentralized ammonia production. Here, through high-throughput density functional theory calculations, we demonstrated that the interfacial modulation of hexagonal boron nitride/graphene(hBN-graphene) could sufficiently improve the catalytic activity of the single transition metal atom catalysts for nitrogen reduction reaction(NRR). It was revealed that Re@hBN-graphene and Os@hBN-graphene possessed remarkable NRR catalytic activity with low limiting potentials of 0.29 V and 0.33 V, respectively. Furthermore, the mechanism of the enhanced catalytic activity was investigated based on various descriptors of the adsorption energies of intermediates, where the synergistic effect of hBN and graphene in the hybrid substrate was found to play a key role. Motivated by the synergistic effect of hybrid substrate in single-atom catalysts, a novel strategy was proposed to efficiently design dual-atom catalysts by integrating the merits of both metal components. The as-designed dual-atom catalyst Fe-Mo@hBN exhibited more excellent NRR catalytic performance with a limiting potential of 0.17 V, manifesting the solidity of the design strategy. Our findings open new avenues for the search of heterostructure substrates for single-atom catalysts and the efficient design of dualatom catalysts for NRR.
文摘Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.51725401 and 51874019)the Fundamental Research Funds for the Central Universities(No.FRF-TP-17-002C2)。
文摘Aluminum-sulfur(Al-S)batteries are regarded as a desirable candidate for large-scale energy storage be-cause of their high energy density and abundant natural resources of electrode materials.To address the critical issues of low discharge voltage and rapid capacity decay in Al-S batteries,here an electrocatalyst-assisted gel-polymer electrolyte(GPE)-based Al-S battery is fabricated using platinum nanoparticles deco-rated platinum/nitrogen co-doped graphene(PtNG)as sulfur host for positive electrode and metal-organic frameworks(MOF)filled GPE(MOF@GPE)as solid electrolyte.Pt-based active sites derived from Pt nan-oclusters’surface and atomically dispersed Pt-N_(2) chemical bonds in PtNG can catalyze the decomposition of sulfur and polysulfides in the electrochemical process,greatly accelerating the sulfur redox kinetics.Furthermore,the MOF fillers in MOF@GPE electrolyte significantly inhibit the shuttle effect of polysul-fides,efficiently improving the utilization of sulfur.Consequently,the established Al-S battery delivers a specific capacity of 1009 mAh g^(−1) with a discharge plateau of∼0.95 V,along with a capacity retention of 65% after 300 cycles,revealing ultrahigh energy density and long cycle life.Such a strategy of combin-ing electrocatalyst and MOF-based gel electrolyte affords a fresh plateau for promoting the rechargeable ability of Al-S batteries,advancing remarkable routes for achieving efficient and stable energy storage devices.
基金the National Key R&D Program of China(No.2022YFE0102000)the National Natural Science Foundation of China(Nos.22121004,U22A20409,22250008,and 22108197)+2 种基金the Haihe Laboratory of Sustainable Chemical Transformations,the Natural Science Foundation of Tianjin City(No.21JCZXJC00060)the Program of Introducing Talents of Discipline to Universities(No.BP0618007)the XPLORER PRIZE for financial support。
文摘The strategic manipulation of the interaction between a central metal atom and its coordinating environment in single-atom catalysts(SACs)is crucial for catalyzing the CO_(2)reduction reaction(CO_(2)RR).However,it remains a major challenge.While density-functional theory calculations serve as a powerful tool for catalyst screening,their time-consuming nature poses limitations.This paper presents a machine learning(ML)model based on easily accessible intrinsic descriptors to enable rapid,cost-effective,and high-throughput screening of efficient SACs in complex systems.Our ML model comprehensively captures the influences of interactions between 3 and 5d metal centers and 8 C,N-based coordination environments on CO_(2)RR activity and selectivity.We reveal the electronic origin of the different activity trends observed in early and late transition metals during coordination with N atoms.The extreme gradient boosting regression model shows optimal performance in predicting binding energy and limiting potential for both HCOOH and CO production.We confirm that the product of the electronegativity and the valence electron number of metals,the radius of metals,and the average electronegativity of neighboring coordination atoms are the critical intrinsic factors determining CO_(2)RR activity.Our developed ML models successfully predict several high-performance SACs beyond the existing database,demonstrating their potential applicability to other systems.This work provides insights into the low-cost and rational design of high-performance SACs.
基金supported by National Research Foundation of Korea(NRF-2020M3A9E4104385,2023R1A2C1003669)Korea Environment Industry&Technology Institute(KEITI)through"Technology Development Project for Biological Hazards Management in Indoor Air"Project,funded by Korea Ministry of Environment(MOE)(G232021010381).
文摘With the development of advanced catalysts,the assessment of emerging single-atom-based electrochemical catalysts(SAECs)has significantly increased owing to their similarity to natural enzymes.They hold substantial potential for the design and construction of electrochemical sensing platforms.The fabrication of single-atombased electrodes revealed their potential for sensitive and selective analyses.Among various nanomaterials,transition metal element-based single-atom,bimetallic single-atom,and metal-free single-atom,each with welldefined active sites,exhibit enhanced catalytic activity,selectivity,and stability.The rational construction of the composition,size,and the strategic development of single-atom electrocatalysts on carbon platforms to enable them to function effectively in complex environments and demonstrate their efficiency between the active sites and electrode construction strategies.Unlike traditional catalysts,SAECs are considered to potential substitutes for natural enzymes.This perspective has been described in a mini-review that highlights recent developments in transition metal elements-based single/bimetallic single atoms and metal-free single atoms anchored on carbon nanostructures.Additionally,there has been a rise in the fabrication of printed electrodes as sensing platforms for biomedical,environmental,and food toxin detection.The challenges and prospects for SAECs in multiple sensing applications are also concisely elaborated.
基金financially supported by the National Natural Science Foundation of China(Nos.52422314,U23A20687,and 52231008)the International Science&Technology Cooperation Program of Hainan Province(No.GHYF2023007).
文摘Oxygen reduction reaction(ORR)in neutral electrolyte is urgently needed in various areas,such as metalair batteries.However,the N-coordinated transition-metal single-atom electrocatalysts confront sluggish catalytic kinetics due to the inappropriate electronic structure and the as-resulted unreasonable adsorption strength towards oxygen-containing intermediates.In this work,we develop a strategy to tune the Fe d-orbital spin state by introducing inert Si atom into the first coordination sphere of Fe-N_(4)moieties.The experimental and theoretical results suggest that Si atom generates the coordination field distortion of Fe and induces the Fe d-orbital spin state transforming from low to medium spin state.The optimized spin-electron filled state(t2g^(4)eg^(1))of Fe sites weakens the adsorption strength to intermediates and reduces the energy barrier of^(∗)OH desorption.Consequently,Fe-Si/NC catalyst exhibits superior ORR performance compared with that of Fe-NC and commercial Pt/C,showing a more positive half-wave potential of 0.753 V(vs.RHE)in 0.1 mol/L phosphate buffered saline.In addition,Fe-Si/NC-based neutral zinc-air batteries show a maximum power density of 108.9 mW cm^(−2)and long-term stability for 200 h.This work represents the possibility of constructing distorted coordination configurations of single-atom catalysts to modulate electronic structure and enhance ORR activity in neutral electrolyte.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22305071,52472200,52271176,and52072114)the 111 Project(Grant No.D17007)+3 种基金Henan Center for Outstanding Overseas Scientists(Grant No.GZS2022017)the China Postdoctoral Science Foundation(Grant No.2022M721049)the Henan Province Key Research and Development Project(Grant No.231111520500)the Natural Science Foundation of Henan Province(Grant No.252300421556)。
文摘Development of high-efficiency bifunctional oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)electrocatalysts is vital for the widespread application of zinc-air batteries(ZABs).However,it still remains a great challenge to avoid the inhomogeneous distribution and aggregation of metal single-atomic active centers in the construction of bifunctional electrocatalysts with atomically dispersed multimetallic sites because of the common calcination method.Herein,we report a novel catalyst with phthalocyanine-assembled Fe-Co-Ni single-atomic triple sites dispersed on sulfur-doped graphene using a simple ultrasonic procedure without calcination,and X-ray absorption fine structure(XAFS),aberration-corrected scanning transmission electron microscopy(AC-STEM),and other detailed characterizations are performed to demonstrate the successful synthesis.The novel catalyst shows extraordinary bifunctional ORR/OER activities with a fairly low potential difference(ΔE=0.621 V)between the OER overpotential(Ej10=315 mV at 10 m A cm^(-2))and the ORR half-wave potential(Ehalf-wave=0.924 V).Moreover,the above catalyst shows excellent ZAB performance,with an outstanding specific capacity(786 mAh g^(-1)),noteworthy maximum power density(139 mW cm^(-2)),and extraordinary rechargeability(discharged and charged at 5 mA cm^(-2) for more than 1000 h).Theoretical calculations reveal the vital importance of the preferable synergetic coupling effect between adjacent active sites in the Fe-Co-Ni trimetallic single-atomic sites during the ORR/OER processes.This study provides a new avenue for the investigation of bifunctional electrocatalysts with atomically dispersed trimetallic sites,which is intended for enhancing the ORR/OER performance in ZABs.
基金the National Natural Science Foundation of China(22403014,21673036)the Youth Development Foundation of Jilin Province(20230508183RC)+1 种基金the China Postdoctoral Science Foundation(2023M730539,2024T170121)the Fundamental Research Funds for the Central Universities(2412022ZD050,2412023QD012)。
文摘Atomically dispersed single-atom catalysts(SACs)supported on graphene provide a ladder of opportunity for achieving the electrocatalytic CO_(2)reduction to value-added chemicals,where the efficient combinations of active sites and coordination environments are a powerful approach to optimize both activity and selectivity.Nevertheless,the understanding of the underlying mechanism about how the catalytic performance varies via active sites and coordination environments is very limited.Herein,we successfully constructed the activity trend of SACs with different coordination environments(MXnY4−n X,Y=N,S,P,and M=19 transition metals)for CO_(2)reduction to CH_(4),using easily obtainable parameters.Based on the entire reaction free energy over 110 stable SACs,the binding strength of*OCHO intermediate(ΔE*OCHO)is identified as an initial activity indicator towards CO_(2)reduction to CH_(4).With the help of multi-task symbolic regression,a simple active descriptor consisting of intrinsic properties(valence-electron number and electronegativity of metal atoms and coordination atoms)is further constructed,which can well describe the variation ofΔE*OCHO and the onset potential for CH_(4).Importantly,this active descriptor enables rapid evaluation on the activity of SACs without DFT computations.This work is instructive for the rational design of other CO_(2)electrocatalysts and establishing more multiplex descriptors through decoupling the factors and handling them separately.
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This work was partially supported by National Key R&D Plan of China(No.2016YFB0101308)the National Natural Science Foundation of China(Nos.21802069,21676135,and U1508202)+1 种基金China Postdoctoral Science Foundation(No.2018M642213)“333”project of Jiangsu Province(No.BRA2018007).
文摘Single-atom catalysts(SACs)have become one of the most considered research directions today,owing to their maximum atom utilization and simple structures,to investigate structure-activity relationships.In the field of non-precious-metal electrocatalysts,atomically dispersed Fe-N4 active sites have been proven to possess the best oxygen reduction activity.Yet the majority of preparation methods remains complex and costly with unsatisfying controllability.Herein,we have designed a surface-grafting strategy to directly synthesize an atomically dispersed Fe-NVC electrocatalyst applied to the oxygen reduction reaction(ORR).Through an esterification process in organic solution,metal-containing precursors were anchored on the surface of carbon substrates.The covalent bonding effect could suppress the formation of aggregated particles during heat treatment.Melamine was further introduced as both a cost-effective nitrogen resource and blocking agent retarding the migration of metal atoms.The optimized catalyst has proven to have abundant atomically dispersed Fe-N4 active sites with enhanced ORR catalytic performance in acid condition.This method has provided new feasible ideas for the synthesis of SACs.
文摘Single-atom catalysts(SACs)have been widely used in heterogeneous catalysis owing to the maximum utilization of metal-active sites with controlled structures and well-defined locations.Upon tailored coordination with nitrogen atom,the metal-nitrogen(M-N)-based SACs have demonstrated interesting physical,optical and electronic properties and have become intense in photocatalysis and electrocatalysis in the past decade.Despite substantial efforts in constructing various M–N-based SACs,the principles for modulating the intrinsic photocatalytic and electrocatalytic performance of their active sites and catalytic mechanism have not been sufficiently studied.Herein,the present review intends to shed some light on recent research made in studying the correlation between intrinsic electronic structure,catalytic mechanism,single-metal atom(SMA)confinement and their photocatalytic and electrocatalytic activities(conversion,selectivity,stability and etc).Based on the analysis of fundamentals of M–N-based SACs,theoretical calculations and experimental investigations,including synthetic methods and characterization techniques,are both included to provide an integral understanding of the underlying mechanisms behind improved coordination structure and observed activity.Finally,the challenges and perspectives for constructing highly active M–N based photocatalysis and electrocatalysis SACs are provided.In particular,extensive technical and mechanism aspects are thoroughly discussed,summarized and analyzed for promoting further advancement of M-N-based SACs in photocatalysis and electrocatalysis.
基金financially supported by the Key Program of the Chinese Academy of Sciences(KFZD-SW-419),Chinathe Major Research Plan of the National Natural Science Foundation of China(91834301),China。
文摘Fe-N-C endowed with inexpensiveness,high activity,and excellent anti-poisoning power have emerged as promising candidate catalysts for oxygen reduction reaction(ORR).Single-atom Fe-N-C electrocatalysts derived from Fe-doped ZIF-8 represent the top-level ORR performance.However,the current fabrication of Fe-doped ZIF-8 relies on heavy consumption of time,energy,cost and organic solvents.Herein,we develop a rapid and solvent-free method to produce Fe-doped ZIF-8 under microwave irradiation,which can be easily amplified in combination with ball-milling.After rational pyrolysis,Fe-N-C catalysts with atomic FeN4 sites well dispersed on the hierarchically porous carbon matrix are obtained,which exhibit exceptional ORR performance with a half-wave potential of 0.782 V(vs.reversible hydrogen electrode(RHE))and brilliant methanol tolerance.The assembled direct methanol fuel cells(DMFCs)endow a peak power density of 61 mW cm^(-2) and extraordinary stability,highlighting the application perspective of this strategy.
基金The authors are grateful to the financial support from the Key Research and Development Program sponsored by the Ministry of Science and Technology(MOST)(2022YFA1203400)the National Natural Science Foundation of China(22102172,22372155,22072145,22005294,21925205,21721003)the authors also thank the ZEROVISION company for providing assistance in creating figures for this manuscript.
文摘The discovery of single-atom catalysts(SACs)represents a groundbreaking advancement in the field of catalysis over the past decades.With the in-depth exploration of relevant structure-activity relationships,the metal−support interaction(MSI)is widely adopted to elucidate variations in electronic structure and coordination configuration of atomic active sites on various kinds of supports.Herein,we briefly summarize the metal oxide supports for SACs fabrication,including the distinctive characteristics of metal oxide supports,enlightening advancements in metal oxide support-based SACs(MO-SACs),feasible preparation methods for MO-SACs and effective regulation strategies of MSI effect in MO-SACs.In addition,we present our viewpoints and outlook in this field to stimulate rational design and construction of novel MO-SACs applied in diverse renewable energy devices,while some universal suggestions are sincerely given to provoke thoughtful considerations during the research process.
基金financially supported by the National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation,Research and Education in Environmental Nanotechnology (CIRE2N) (Grant No.HRD-1736093)the NSF Center for the Advancement of Wearable Technologies (Grant No.1849243)National Energy Research Scientific Computing Center,which is supported by the Office of Science of the U.S.DOE under Contract No.DE-AC02-05CH11231。
文摘Ongoing efforts to develop single-atom catalysts(SACs) for the oxygen reduction reaction(ORR) typically focus on SACs with cationic metal centers,while SACs with anionic metal centers(anionic SACs) have been generally neglected.However,anionic SACs may offer excellent active sites for ORR,since anionic metal centers could facilitate the activation of O_(2) by back donating electrons to the antibonding orbitals of O_(2).In this work,we propose a simple guideline for designing anionic SACs:the metal centers should have larger electronegativity than the surrounding atoms in the substrate on which the metal atoms are supported.By means of density functional theory(DFT) simulations,we identified 13 anionic metal centers(Co,Ni,Cu,Ru,Rh,Pd,Ag,Re,Os,Ir,Pt,Au,and Hg) dispersed on pristine or defective antimonene substrates as new anionic SACs,among which anionic Au and Co metal centers exhibit limiting potentials comparable to,or even better than,conventional Pt-based catalysts towards ORR.We also found that anionic Os and Re metal centers on the defective antimonene can electrochemically catalyze the nitrogen reduction reaction(NRR) with a limiting potential close to that of stepped Ru(0001).Overall,our work shows promise towards the rational design of anionic SACs and their utility for applications as electrocatalysts for ORR and other important electrochemical reactions.
基金financially supported by the National Natural Science Foundation of China(No.52302233)Shenzhen Science and Technology Innovation Committee(No.JCYJ20200109113212238)+1 种基金Guangdong Basic and Applied Basic Research Foundation(No.2021A1515111154)Talent Recruitment Project of Guangdong Province(No.2021QN02C900)。
文摘High-performance bifunctional oxygen electrocatalysts that simultaneously boost the sluggish oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)need to be developed for advanced rechargeable Znair battery applications.In this work,a zeolitic imidazolate framework(ZIF)-phase conversion associated with a subsequent thermal fixing strategy was developed to fabricate bimetallic CoFe single atoms/clusters embedded in N-doped carbon(denoted as CoFe-N-C)nanorods,which can serve as efficient bifunctional ORR/OER electrocatalysts.Microstructural observation and X-ray absorption spectroscopy analysis confirm the co-existence of highly active Co/Fe-N_(x) dual sites and CoFe alloy nanoclusters.X-ray photoelectron spectroscopy(XPS)results prove that implanting secondary Fe atoms into Co-N-C matrix nanorods can induce electronic redistribution of atomic Co/Fe active sites and generate synergistic effects,which would optimize the adsorption energy of the reaction intermediates and thus enhance the bifunctional ORR/OER activity.The bimetallic CoFe-N-C nanorods exhibit significantly enhanced bifunctional ORR/OER activity and stability than the monometallic Co/Fe-N-C nanorods in alkaline electrolytes in terms of a very positive half-wave potential of 0.90 V(vs.reversible hydrogen electrode(RHE))for ORR,and an overpotential of 440 mV to reach current density of 10 mA·cm^(-2)for OER,yielding a small overpotential gap of 0.77 V.Furthermore,the rechargeable Zn-air batteries using bimetallic CoFe-N-C nanorods as air-cathode catalyst demonstrates peak power density of200.7 mW·cm^(-2)and robust cycling stability of up to200 h,corresponding to 1200 discharge-charge cycles.
基金financially supported by the Natural Science Funds (NSF) for Distinguished Young Scholar of Heilongjiang Province (No. JC2018004)。
文摘Superior bifunctional electrocatalysts with ultra-high stability and excellent efficiency are crucial to boost the oxygen evolution reaction(OER) and the hydrogen evolution reduction(HER) in the overall water splitting(OWS) for the sustainable production of clean fuels. Herein, comprehensive density functional theory(DFT) computations were performed to explore the potential of several single transition metal(TM) atoms anchored on various S-doped black phosphorenes(TM/Snx-BP) for bifunctional OWS electrocatalysis. The results revealed that these candidates display good stability, excellent electrical conductivity, and diverse spin moments. Furthermore, the Rh/S12-BP catalyst was identified as an eligible bifunctional catalyst for OWS process due to the low overpotentials for OER(0.43 V) and HER(0.02 V), in which Rh and its adjacent P atoms were identified as the active sites. Based on the computed Gibbs free energies of OH~*, O~*, OOH~* and H~*, the corresponding volcano plots for OER and HER were established.Interestingly, the spin moments and the charge distribution of the active sites determine the catalytic trends of OER and HER. Our findings not only propose a promising bifunctional catalyst for OWS, but also widen the potential application of BP in electrocatalysis.
