Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer
Journal
Nature Communications
Journal Volume
11
Journal Issue
1
Date Issued
2020
Author(s)
Abstract
The abundant yet widely distributed methane resources require efficient conversion of methane into liquid chemicals, whereas an ambient selective process with minimal infrastructure support remains to be demonstrated. Here we report selective electrochemical oxidation of CH4 to methyl bisulfate (CH3OSO3H) at ambient pressure and room temperature with a molecular catalyst of vanadium (V)-oxo dimer. This water-tolerant, earth-abundant catalyst possesses a low activation energy (10.8 kcal mol?1) and a high turnover frequency (483 and 1336 hr?1 at 1-bar and 3-bar pure CH4, respectively). The catalytic system electrochemically converts natural gas mixture into liquid products under ambient conditions over 240 h with a Faradaic efficiency of 90% and turnover numbers exceeding 100,000. This tentatively proposed mechanism is applicable to other d0 early transition metal species and represents a new scalable approach that helps mitigate the flaring or direct emission of natural gas at remote locations. ? 2020, The Author(s).
Subjects
glycine; methane; natural gas; vanadium; activation energy; catalyst; electrochemistry; methane; molecular analysis; natural gas; oxidation; transition element; vanadium; Article; bioinformatics; carbon nuclear magnetic resonance; catalysis; catalyst; crystallization; density functional theory; electrochemical analysis; electrochemistry; electrolysis; electron transport; environmental temperature; freeze drying; gas chromatography; impedance spectroscopy; kinetics; mass fragmentography; nuclear magnetic resonance spectroscopy; oxidation; photoelectron spectroscopy; proton nuclear magnetic resonance; quantum chemistry; Raman spectrometry; refraction index; room temperature; scanning electron microscopy; size exclusion chromatography; solvent extraction; thin layer chromatography; transmission electron microscopy; turnover number; ultraviolet visible spectroscopy; X ray absorption spectroscopy; X ray diffraction
SDGs
Type
journal article