Deng JLin S.-CFuller J.TIII, Zandkarimi BZandkarimi BIIIHAO MING CHENAlexandrova A.NLiu C.2022-04-252022-04-25202114337851https://www.scopus.com/inward/record.uri?eid=2-s2.0-85118806134&doi=10.1002%2fanie.202107720&partnerID=40&md5=5ea51d1a910f675a34022535b3870928https://scholars.lib.ntu.edu.tw/handle/123456789/606875The undesirable loss of methane (CH4) at remote locations welcomes approaches that ambiently functionalize CH4 on-site without intense infrastructure investment. Recently, we found that electrochemical oxidation of vanadium(V)-oxo with bisulfate ligand leads to CH4 activation at ambient conditions. The key question is whether such an observation is a one-off coincidence or a general strategy for electrocatalyst design. Here, a general scheme of electrocatalytic CH4 activation with d0 early transition metals is established. The pre-catalysts’ molecular structure, electrocatalytic kinetics, and mechanism were detailed for titanium (IV), vanadium (V), and chromium (VI) species as model systems. After a turnover-limiting one-electron electrochemical oxidation, the yielded ligand-centered cation radicals activate CH4 with low activation energy and high selectivity. The reactivities are universal among early transition metals from Period 4 to 6, and the reactivities trend for different early transition metals correlate with their d orbital energies across periodic table. Our results offer new chemical insights towards developing advanced ambient electrocatalysts of natural gas. ? 2021 Wiley-VCH GmbHambient conditionsd0 electronic structureearly transition metalselectrocatalysismethane functionalizationActivation energyChromium compoundsElectrocatalysisElectrocatalystsInvestmentsLigandsMethaneTitanium compoundsTransition metalsAmbient conditionsCH 4D0 electronic structureEarly-transition metalsElectrocatalyticElectronic.structureInfrastructure investmentMethane functionalizationPrecatalystsRemote locationElectronic structure[SDGs]SDG9journal article10.1002/anie.202107720346066782-s2.0-85118806134