Electrocatalytic Methane Functionalization with d0 Early Transition Metals Under Ambient Conditions

The undesirable loss of methane (CH4) at remote locations welcomes approaches that ambiently functionalize CH4 on-site without intense infrastructure investment. Recently, we found electrochemical oxidation vanadium(V)-oxo with bisulfate ligand leads to activation ambient conditions. key question is whether such an observation a one-off coincidence or general strategy for electrocatalyst design. Here, scheme electrocatalytic d0 early transition metals established. pre-catalysts’ molecular structure, kinetics, and mechanism were detailed titanium (IV), vanadium (V), chromium (VI) species as model systems. After turnover-limiting one-electron oxidation, the yielded ligand-centered cation radicals activate low energy high selectivity. reactivities are universal among from Period 4 6, trend different correlate their d orbital energies across periodic table. Our results offer new chemical insights towards developing advanced electrocatalysts natural gas.