Electrocatalytic reduction of nitrate(NO_(3)^(−))is a promising approach to achieving sustainable and green ammonia synthesis and environmental denitrification.Here,click chemistry is extended to fabricate dynamic sin...Electrocatalytic reduction of nitrate(NO_(3)^(−))is a promising approach to achieving sustainable and green ammonia synthesis and environmental denitrification.Here,click chemistry is extended to fabricate dynamic singlesite metal catalysts for NO3−electroreduction.Specifically,Co^(2+)-coordinated molecular units are covalently clicked into a stable Th-metal–organic framework,confining and dispersing single-site metals that exhibit the asymmetrical Co–N2Cl2 coordination configuration.The obtained CoN2Cl2@Th-BPDC electrocatalyst achieves an outstanding ammonia production rate of 770.3μmol h^(−1) cm^(−2)(5135.3 mmol gcat^(−1) h^(−1))at−0.4 V versus RHE,which is approximately 25.7 times higher than that of the Haber–Bosch process(<200 mmol gcat^(−1) h^(−1))and outperforms the most recently reported electrocatalysts.Theoretical calculations reveal that single-site Co2+exhibits strong bidentate adsorption toward NO_(3)^(−)due to the suitable geometric space provided by the rotation of Co-coordinated Cl atoms(a dynamic feature),which promotes NO_(3)^(−)activation and decreases the reaction barrier,resulting in excellent catalytic activity.This study describes an innovative strategy for fabricating dynamic asymmetrical single-site metal electrocatalysts and may inspire new methodologies for the precise synthesis of advanced catalytic materials.展开更多
Carbon-based materials with tunable properties have emerged as promising candidates to replace Pt-based catalysts for accelerating oxygen reduction reaction(ORR)in fuel cells or metal-air batteries.In this work,we con...Carbon-based materials with tunable properties have emerged as promising candidates to replace Pt-based catalysts for accelerating oxygen reduction reaction(ORR)in fuel cells or metal-air batteries.In this work,we constructed a carbon hybrid which consists of one-dimensional(1D)carbon nanotubes and flake-like carbons by pyrolysis of leaf-like metal-organic frameworks.The optimal hybrid electrocatalyst of Fe_(7%)-L-CNT-900 possesses the desired features for ORR,including active Fe species,high degree of graphitization,large specific surface area,and hierarchical porous structures.Consequently,Fe_(7%)-L-CNT900 performs a high electrocatalytic activity for ORR with a half-wave potential of 0.88 V,which is comparable to that of Pt/C(20 wt.%).This strategy provides an insight into the investigation of highly efficient and low-cost composite electrocatalyst for oxygen reduction reaction.展开更多
基金support from NationalNatural Science Foundation of China (grant nos.22368002 and 52300195)Young Elite Scientists SponsorshipProgram by Jiangxi Association for Science andTechnology (JXAST) (grant no.2023QT10)+5 种基金JiangxiProvincial Natural Science Foundation (grant nos.20224BAB203003 and 20232BAB203021)OpeningProject of Project of National Key Laboratory of UraniumResources Exploration-Mining and Nuclear RemoteSensing (grant no.2024QZ-KF-06)Jiangxi ProvinceKey Laboratory of Polymer Micro/Nano Manufacturingand Devices (grant no.PMND202204)Japan Scienceand Technology Agency (JST)- Exploratory Research forAdvanced Technology (ERATO) Yamauchi Materials Space-Tectonics Project (grant no.JPMJER2003)theAustralian Research Council (ARC) Laureate Fellowship(grant no.FL230100095)Science and TechnologyResearch Program of Chongqing Municipal EducationCommission (grant no.KJQN202201308)。
文摘Electrocatalytic reduction of nitrate(NO_(3)^(−))is a promising approach to achieving sustainable and green ammonia synthesis and environmental denitrification.Here,click chemistry is extended to fabricate dynamic singlesite metal catalysts for NO3−electroreduction.Specifically,Co^(2+)-coordinated molecular units are covalently clicked into a stable Th-metal–organic framework,confining and dispersing single-site metals that exhibit the asymmetrical Co–N2Cl2 coordination configuration.The obtained CoN2Cl2@Th-BPDC electrocatalyst achieves an outstanding ammonia production rate of 770.3μmol h^(−1) cm^(−2)(5135.3 mmol gcat^(−1) h^(−1))at−0.4 V versus RHE,which is approximately 25.7 times higher than that of the Haber–Bosch process(<200 mmol gcat^(−1) h^(−1))and outperforms the most recently reported electrocatalysts.Theoretical calculations reveal that single-site Co2+exhibits strong bidentate adsorption toward NO_(3)^(−)due to the suitable geometric space provided by the rotation of Co-coordinated Cl atoms(a dynamic feature),which promotes NO_(3)^(−)activation and decreases the reaction barrier,resulting in excellent catalytic activity.This study describes an innovative strategy for fabricating dynamic asymmetrical single-site metal electrocatalysts and may inspire new methodologies for the precise synthesis of advanced catalytic materials.
基金The authors acknowledge the financial support from the National Natural Science Foundation of China(No.22005099)sponsored by Shanghai Pujiang Program(No.19PJ1402500)and Fundamental Research Funds for the Central Universities.
文摘Carbon-based materials with tunable properties have emerged as promising candidates to replace Pt-based catalysts for accelerating oxygen reduction reaction(ORR)in fuel cells or metal-air batteries.In this work,we constructed a carbon hybrid which consists of one-dimensional(1D)carbon nanotubes and flake-like carbons by pyrolysis of leaf-like metal-organic frameworks.The optimal hybrid electrocatalyst of Fe_(7%)-L-CNT-900 possesses the desired features for ORR,including active Fe species,high degree of graphitization,large specific surface area,and hierarchical porous structures.Consequently,Fe_(7%)-L-CNT900 performs a high electrocatalytic activity for ORR with a half-wave potential of 0.88 V,which is comparable to that of Pt/C(20 wt.%).This strategy provides an insight into the investigation of highly efficient and low-cost composite electrocatalyst for oxygen reduction reaction.
