Electrocatalytic Methane Functionalization with d 0 Early Transition Metals Under Ambient Conditions

Autor: Borna Zandkarimi, Hao Ming Chen, Sheng-Chih Lin, Jack T. Fuller, Anastassia N. Alexandrova, Jiao Deng, Chong Liu
Rok vydání: 2021
Předmět:
Zdroj: Angewandte Chemie International Edition. 60:26630-26638
ISSN: 1521-3773
1433-7851
DOI: 10.1002/anie.202107720
Popis: 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.
Databáze: OpenAIRE
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