Abstract
AbstractThe 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.
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