Despite the intense research efforts directed to electrocatalytic nitrogen reduction reaction(eNRR),the NH_(3) yield and selectivity are still not up to the standard of practical application.Here,high-entropy perovski...Despite the intense research efforts directed to electrocatalytic nitrogen reduction reaction(eNRR),the NH_(3) yield and selectivity are still not up to the standard of practical application.Here,high-entropy perovskite oxides with composition Bax(FeCoNiZrY)_(0.2)O_(3−δ)(Bx(FCNZY)_(0.2)(x=0.9,1)are reported as eNRR catalysts.The eNRR activity of high-entropy perovskite oxide is enhanced by changing the nonstoichiometric metal elements at the A-site,thus generating additional oxygen vacancies.The NH_(3) yield and Faraday efficiency for B_(0.9)(FCNZY)_(0.2) are 1.51 and 1.95 times higher than those for B(FCNZY)_(0.2),respectively.The d-band center theory is used to theoretically predict the catalytically active center at the B-site,and as a result,nickel was identified as the catalytic site.The free energy values of the intermediate states in the optimal distal pathway show that the third protonation step(*NNH_(2)→*NNH_(3))is the rate-determining step and that the increase in oxygen vacancies in the high-entropy perovskite contributes to nitrogen adsorption and reduction.This work provides a framework for applying high-entropy structures with active site diversity for electrocatalytic nitrogen fixation.展开更多
基金supported by the National Natural Science Foundation of China (52161135302, 21674019, and 51801075)the Research Foundation Flanders (G0F2322N)+8 种基金Shanghai Scientific and Technological Innovation Project (18JC1410600)the Program of the Shanghai Academic Research Leader (17XD1400100)the financial support from the Flemish Government through the Moonshot cSBO project P2C (HBC.2019.0108)the Long-term Structural Funding (Methusalem CASAS2, Meth/15/04)Interne Fondsen KU Leuven through project C3/20/067the support from the Research Foundation-Flanders (FWO) in the form of a doctoral fellowship (1SA3321N)the financial support from China Scholarship Council in the form of a visiting Ph.D. Student (File No. 202106790090)the LvLiang Cloud Computing Center of China, and the calculations were performed on a TianHe-2 systemthe characterizations supported by the Central Laboratory, School of Chemical and Material Engineering, Jiangnan University。
文摘Despite the intense research efforts directed to electrocatalytic nitrogen reduction reaction(eNRR),the NH_(3) yield and selectivity are still not up to the standard of practical application.Here,high-entropy perovskite oxides with composition Bax(FeCoNiZrY)_(0.2)O_(3−δ)(Bx(FCNZY)_(0.2)(x=0.9,1)are reported as eNRR catalysts.The eNRR activity of high-entropy perovskite oxide is enhanced by changing the nonstoichiometric metal elements at the A-site,thus generating additional oxygen vacancies.The NH_(3) yield and Faraday efficiency for B_(0.9)(FCNZY)_(0.2) are 1.51 and 1.95 times higher than those for B(FCNZY)_(0.2),respectively.The d-band center theory is used to theoretically predict the catalytically active center at the B-site,and as a result,nickel was identified as the catalytic site.The free energy values of the intermediate states in the optimal distal pathway show that the third protonation step(*NNH_(2)→*NNH_(3))is the rate-determining step and that the increase in oxygen vacancies in the high-entropy perovskite contributes to nitrogen adsorption and reduction.This work provides a framework for applying high-entropy structures with active site diversity for electrocatalytic nitrogen fixation.
