Theory-guided construction of electron-deficient sites via removal of lattice oxygen for the boosted electrocatalytic synthesis of ammonia  

作　　者：Li Zhang Shilong Jiao Xin Tan Yuliang Yuan Yu Xiang Yu-Jia Zeng Jingyi Qiu Ping Peng Sean C.Smith Hongwen Huang 

机构地区：[1]College of Materials Science and Engineering,Hunan University,Changsha,410082,China [2]College of Physics and Optoelectronic Engineering,Shenzhen University,Shenzhen,518061,China [3]Integrated Materials Design Laboratory,Department of Applied Mathematics,Research School of Physics,The Australian National University,Canberra,ACT,2601,Australia [4]Research Institute of Chemical Defense,Beijing,100191,China

出　　处：《Nano Research》2021年第5期1457-1464,共8页纳米研究（英文版）

基　　金：This work was supported by the National Natural Science Foundation of China (No. 21603208);Shenzhen Science and Technology Project (Nos. JCYJ20170412105400428 and JCYJ20180507182246321);Shenzhen Peacock Technological Innovation Project (No. KQJSCX20170727101208249);Fundamental Research Funds for the Central Universities, the Open Project Program of the State Key Laboratory of Silicon Materials, Zhejiang University, and China Postdoctoral Science Foundation (No. 2019M663058);This research was undertaken with the assistance of resources provided by the National Computational Infrastructure (NCI) facility at the Australian National University;allocated through both the National Computational Merit Allocation Scheme supported by the Australian Government and the Australian Research Council grant LE190100021 (Sustaining and strengthening merit-based access at NCI, 2019–2021).

摘　　要：Rational design of catalytic sites to activate the inert N≡N bond is of paramount importance to advance N2 electroreduction. Here, guided by the theoretical predictions, we construct a NiFe layered double hydroxide (NiFe-LDH) nanosheet catalyst with a high density of electron-deficient sites, which were achieved by introducing oxygen vacancies in NiFe-LDH. Density functional theory calculations indicate that the electron-deficient sites show a much lower energy barrier (0.76 eV) for the potential determining step compared with that of the pristine NiFe-LDH (2.02 eV). Benefiting from this, the NiFe-LDH with oxygen vacancies exhibits the greatly improved electrocatalytic activity, presenting a high NH3 yield rate of 19.44 µg·h−1·mgcat−1, Faradaic efficiency of 19.41% at −0.20 V vs. reversible hydrogen electrode (RHE) in 0.1 M KOH electrolyte, as well as the outstanding stability. The present work not only provides an active electrocatalyst toward N2 reduction but also offers a facile strategy to boost the N2 reduction.

关 键 词：nitrogen reduction density functional theory oxygen vacancies electron-deficient sites 

分 类 号：O643.3[理学—物理化学]