Electrocatalytic Methane Functionalization with d0 Early Transition Metals Under Ambient Conditions
Journal
Angewandte Chemie - International Edition
Journal Volume
60
Journal Issue
51
Pages
26630-26638
Date Issued
2021
Author(s)
Abstract
The 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 GmbH
Subjects
ambient conditions
d0 electronic structure
early transition metals
electrocatalysis
methane functionalization
Activation energy
Chromium compounds
Electrocatalysis
Electrocatalysts
Investments
Ligands
Methane
Titanium compounds
Transition metals
Ambient conditions
CH 4
D0 electronic structure
Early-transition metals
Electrocatalytic
Electronic.structure
Infrastructure investment
Methane functionalization
Precatalysts
Remote location
Electronic structure
SDGs
Type
journal article