Efficient ammonia production over e_(g)-occupancy-optimized perovskite electrocatalysts  

作　　者：Mingfa Chen Yu Zhang Fulong Liu Zhenbao Zhang Yuming Dong Yongfa Zhu Heqing Jiang Jiawei Zhu 

机构地区：[1]Key Laboratory of Synthetic and Biological Colloids,Ministry of Education,School of Chemical and Material Engineering,Jiangnan University,Wuxi 214122,China [2]Qingdao Institute of Bioenergy and Bioprocess Technology,Chinese Academy of Sciences,Qingdao 266101,China [3]School of Chemistry and Chemical Engineering,Linyi University,Linyi 276005,China [4]Department of Chemistry,Tsinghua University,Beijing 100084,China

出　　处：《Nano Research》2024年第6期4682-4686,共5页纳米研究（英文版）

基　　金：the National Natural Science Foundation of China(No.52102258);the Taishan Scholars Program(No.tsqn202306309);Natural Science Foundation of Shandong Province(No.ZR2023YQ012);Natural Science Foundation of Jiangsu Province(No.BK20210447);the Special Fund Project of Jiangsu Province for Scientific and Technological Innovation in Carbon Peaking and Carbon Neutrality(No.BK20220023).

摘　　要：Renewable-energy-driven nitrate(NO_(3)^(−))electroreduction to ammonia(NH_(3))(NERA)has been an attractive technology for decarbonizing NH_(3)production and wastewater treatment.Improving NERA efficiency requires electrocatalysts that are earth-abundant and show fantastic performance.Here we report a semiempirical activity descriptor of eg occupancy(of surface B-site cations)for identifying inexpensive perovskite oxides with extremely high efficacy toward NERA.We establish the descriptor by systematic investigations of more than 10 perovskite oxides.These investigations demonstrate that their intrinsic NERA activities display a volcano-shaped dependence on eg occupancy and the optimized intrinsic activities are accessible at near-1 eg occupancies.This could plausibly be attributed to the favorable overlaps between surface adsorbates and vertically-oriented eg orbitals.More importantly,utilizing this descriptor,we predict a highly active,selective,and durable NERA electrocatalyst with a composition of Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3−δ)(BSCF).Because of its close-to-1 e_(g)occupancy(i.e.~1.2),the BSCF features a superior NH_(3)production rate of 0.12 g·h^(−1)·mg_(cat.)^(−1)(Faradaic efficiency of 97.8%)that is at top of the volcano plot,and substantially outperforms most NERA electrocatalysts reported in literature.

关 键 词：perovskite oxide nitrate electroreduction ammonia electrosynthesis eg occupancy 

分 类 号：O643.36[理学—物理化学]