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 (...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.展开更多
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)+3 种基金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 Universityallocated 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).
文摘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.
