Ren, WenhaoTan, XinYang, WanfengJia, ChenXu, ShumaoWang, KaixueSmith, Sean C.Zhao, Chuan2025-03-302025-03-30researchoutputwizard:u5786633xPUB829Scopus:85064697824WOS:WOS:000476423300023https://dspace-test.anu.edu.au/handle/1885/733747439Polynary single-atom structures can combine the advantages of homogeneous and heterogeneous catalysts while providing synergistic functions based on different molecules and their interfaces. However, the fabrication and identification of such an active-site prototype remain elusive. Here we report isolated diatomic Ni-Fe sites anchored on nitrogenated carbon as an efficient electrocatalyst for CO2 reduction. The catalyst exhibits high selectivity with CO Faradaic efficiency above 90 % over a wide potential range from −0.5 to −0.9 V (98 % at −0.7 V), and robust durability, retaining 99 % of its initial selectivity after 30 hours of electrolysis. Density functional theory studies reveal that the neighboring Ni-Fe centers not only function in synergy to decrease the reaction barrier for the formation of COOH* and desorption of CO, but also undergo distinct structural evolution into a CO-adsorbed moiety upon CO2 uptake.We thank UNSW Mark Wainwright Analytical Center for providing access to their XRD, SEM, XPS, Raman, NMR and facilities. This research was undertaken with the assistance of resources provided by the National Computing 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 LE160100051 (Maintaining and enhancing merit-based access to the NCI National Facility, 2016–2018). This work was supported by the Australian Research Council (DP160103107, FT170100224).5EnglishPublisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimCO reductionelectrocatalystsmetal centerssingle-atom catalysts2019-05-2010.1002/anie.201901575http://www.scopus.com/inward/record.url?scp=85064697824&partnerID=8YFLogxK