Engineering the axial coordination of cobalt single atom catalysts for efficient photocatalytic hydrogen evolution  

作　　者：Ning Kang Lingwen Liao Xue Zhang Zhen He Binlu Yu Jiahong Wang Yongquan Qu Paul KChu Seeram Ramakrishna Xue-Feng Yu Xin Wang Licheng Bai 

机构地区：[1]Materials Interfaces Center,Shenzhen Institute of Advanced Technology,Chinese Academy of Sciences(CAS),Shenzhen 518055,China [2]Key Laboratory of Materials Physics,Anhui Key Laboratory of Nanomaterials and Nanotechnology,CAS Center for Excellence in Nanoscience,Institute of Solid State Physics,Chinese Academy of Sciences,Hefei 230031,China [3]Department of Chemistry,City University of Hong Kong,Kowloon,Hong Kong 999077,China [4]Hong Kong Branch of National Precious Metals Material Engineering Research Center(NPMM),City University of Hong Kong,Kowloon,Hong Kong 999077,China [5]Key Laboratory of Special Functional and Smart Polymer Materials of Ministry of Industry and Information Technology,School of Chemistry and Chemical Engineering,Northwestern Polytechnical University,Xi’an 710072,China [6]Department of Physics and Department of Materials Science and Engineering,City University of Hong Kong,Kowloon,Hong Kong 999077,China [7]National University of Singapore(NUS)Centre for Nanofibers and Nanotechnology,Department of Mechanical Engineering,National University of Singapore,Singapore 117542,Singapore

出　　处：《Nano Research》2024年第6期5114-5121,共8页纳米研究（英文版）

基　　金：National Natural Science Foundation of China(No.22008251);Guangdong Basic and Applied Basic Research Foundation(No.2022A1515010318);Shenzhen Science and Technology Program(No.JCYJ20220531095813031).

摘　　要：Improving the catalytic activity of non-noble metal single atom catalysts(SACs)has attracted considerable attention in materials science.Although optimizing the local electronic structure of single atom can greatly improve their catalytic activity,it often involves in-plane modulation and requires high temperatures.Herein,we report a novel strategy to manipulate the local electronic structure of SACs via the modulation of axial Co-S bond anchored onto graphitic carbon nitride(C_(3)N_(4))at room temperature(RT).Each Co atom is bonded to four N atoms and one S atom(Co-(N,S)/C_(3)N_(4)).Owing to the greater electronegativity of S in the Co-S bond,the local electronic structure of the Co atoms is available to be controlled at a relatively moderate level.Consequently,when employed for the photocatalytic hydrogen evolution reaction,the adsorption energy of intermediate hydrogen(H*)on the Co atoms is remarkably low.In the presence of the Co-(N,S)/C_(3)N_(4)SACs,the hydrogen evolution rates reach up to 10 mmol/(g·h),which is nearly 10 and 2.5 times greater than the rates in the presence of previously reported transition metal/C_(3)N_(4)and noble platinum nanoparticles(PtNPs)/C_(3)N_(4)catalysts,respectively.Attributed to the tailorable axial Co-S bond in the SAC,the local electronic structure of the Co atoms can be further optimized for other photocatalytic reactions.This axial coordination engineering strategy is universal in catalyst designing and can be used for a variety of photocatalytic applications.

关 键 词：transition metal single-atom local electronic structure photocatalytic hydrogen evolution graphitic carbon nitride axial coordination environment 

分 类 号：O64[理学—物理化学]