Ren, WenhaoTan, XinJia, ChenKrammer, AnnaSun, QianQu, JiangtaoSmith, Sean C.Schueler, AndreasHu, XileZhao, Chuan2022-05-092022-09-222022-05-092022-04-2710.1002/anie.202203335https://infoscience.epfl.ch/handle/20.500.14299/187740WOS:000787986000001Modulating the electronic structure of atomically dispersed active sites is promising to boost catalytic activity but is challenging to achieve. Here we show a cooperative Ni single-atom-on-nanoparticle catalyst (NiSA/NP) prepared via direct solid-state pyrolysis, where Ni nanoparticles donate electrons to Ni(i)-N-C sites via a network of carbon nanotubes, achieving a high CO current density of 346 mA cm(-2) at -0.5 V vs RHE in an alkaline flow cell. When coupled with a NiFe-based anode in a zero-gap membrane electrolyzer, the catalyst delivers an industrially relevant CO current density of 310 mA cm(-2) at a low cell voltage of -2.3 V, corresponding to an overall energy efficiency of 57 %. The superior CO2 electroreduction performance is attributed to the enhanced adsorption of key intermediate COOH* on the electron-rich Ni single atoms, as well as a high density of active sites.Chemistry, MultidisciplinaryChemistryco2 reductioncooperative single-atom catalystelectrocatalystelectronic regulationmetal-nitrogen-carbonsitesreductionmetalelectrocatalystsidentificationcatalysiscoppertext::journal::journal article::research article