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.
Highlights
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
While d0 early transition metal centers are not known to be directly oxidizable, we accidentally found that electrochemical oxidation of d0 early transition metal-oxo species in 68–98% H2SO4 yields cation a Electrophilic activation
As the tentative turnover-limiting step (TLS) uncommon for homogenous electrocatalysis, an electrochemical one-electron removal of 1 yields a cation radical (V2V,V +, 2) reactive towards CH4, while the catalytic cycle is fulfilled by additional electrochemical oxidation and cation radical regeneration
Summary
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. 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, earthabundant 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. As the tentative turnover-limiting step (TLS) uncommon for homogenous electrocatalysis, an electrochemical one-electron removal of 1 yields a cation radical (V2V,V +, 2) reactive towards CH4, while the catalytic cycle is fulfilled by additional electrochemical oxidation and cation radical regeneration
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