Boosting the activity of Fe–N_x moieties in Fe–N–C electrocatalysts via phosphorus doping for oxygen reduction reaction  

P掺杂提高Fe–N–C催化剂中Fe–Nx活性基团的氧还原催化活性

作　　者：Jin-Cheng Li Hong Zhong Mingjie Xu Tao Li Liguang Wang Qiurong Shi Shuo Feng Zhaoyuan Lyu Dong Liu Dan D u Scott PBeckman Xiaoqing Pan Yuehe Lin Minhua Shao 李金成;钟泓;徐明杰;李涛;王利光;石秋容;冯硕;吕昭媛;刘栋;杜丹;Scott PBeckman;潘晓晴;林跃河;邵敏华(School of Mechanical and Materials Engineering,Washington State University,Pullman,WA 99164,USA;Fok Ying Tung Research Institute,Hong Kong University of Science and Technology,Guangzhou 511458,China;Department of Chemical Engineering and Materials Science,University of California Irvine,Irvine,CA 92697,USA;Department of Chemistry and Biochemistry,Northern Illinois University,1425 W.Lincoln Hwy.,DeKalb,IL 60115,USA;X-ray Science Division,Argonne National Laboratory,9700 South Cass Avenue,Lemont,Illinois 60439,USA;Department of Chemical and Biological Engineering,Hong Kong University of Science and Technology,Clear Water Bay,Kowloon,Hong Kong,China)

机构地区：[1]School of Mechanical and Materials Engineering,Washington State University,Pullman,WA 99164,USA [2]Fok Ying Tung Research Institute,Hong Kong University of Science and Technology,Guangzhou 511458,China [3]Department of Chemical Engineering and Materials Science,University of California Irvine,Irvine,CA 92697,USA [4]Department of Chemistry and Biochemistry,Northern Illinois University,1425 W.Lincoln Hwy.,DeKalb,IL 60115,USA [5]X-ray Science Division,Argonne National Laboratory,9700 South Cass Avenue,Lemont,Illinois 60439,USA [6]Department of Chemical and Biological Engineering,Hong Kong University of Science and Technology,Clear Water Bay,Kowloon,Hong Kong,China

出　　处：《Science China Materials》2020年第6期965-971,共7页中国科学（材料科学（英文版）

基　　金：This work was supported by the National Key R&D Program of China(2017YFB0102900);the Research Grant Council(N一HKUST610/17)of Hong Kong Special Administrative Region.It used resources of the Advanced Photon Source,Office of Science user facilities,supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences(DE-AC02-06CH11357).

摘　　要：The Fe–N–C material is a promising non-noblemetal electrocatalyst for oxygen reduction reaction(ORR).Further improvement on the ORR activity is highly desired in order to replace Pt/C in acidic media.Herein,we developed a new-type of single-atom Fe–N–C electrocatalyst,in which Fe–Nxactive sites were modified by P atoms.The half-wave potential of the optimized material reached 0.858 V,which is 23 mV higher than that of the pristine one in a 0.1 mol L-1 HClO4 solution.Density functional theory(DFT)calculations revealed that P-doping can reduce the thermodynamic overpotential of the rate determining step and consequently improve the ORR activity.Fe–N–C材料是一类有前景的非贵金属氧还原催化剂.为了在酸性介质中取代Pt/C催化剂,需要大幅度地改善其氧还原催化活性.本文提出一种通过P原子掺杂的方法来调节单原子Fe–N–C材料中Fe–Nx活性位点的活性.优化得到的材料在0.1 mol L-1HClO4溶液中表现出优异的氧还原性能,其半波电位为0.858 V(比没有P掺杂的Fe–N–C材料高23 mV).密度泛函理论计算表明,P掺杂能降低限制步骤的热力学过电位,从而提高其氧还原催化活性.

关 键 词：P-DOPING single-atom catalysts oxygen reduction 

分 类 号：O643.36[理学—物理化学]