Boosting room-temperature conversion of methane via confining Cu atoms in ultrathin Ru nanosheets

Abstract

Designing active centers for CH4 activation under mild conditions is pivotal for the low-energy conversion of natural gas, which is still a great challenge owing to the chemical inertness of CH4 and the difficulties in tuning coordination environments of active centers. Herein, we report that highly efficient room-temperature CH4 conversion to liquid C1 oxygenates is achieved over ultrathin Ru nanosheets with confined Cu atoms. Compared with previously reported catalysts, it delivers a superior performance of up to 1,533 mmol g−1Cu(surf.) h−1 productivity and 97.3 h−1 TOF with over 99% selectivity for C1 oxygenates, and the optimized CH4 conversion reaches 0.05% at 25°C. Multiple spectroscopic analysis and first-principles calculations reveal that bi-coordinated bridge-site oxygen species generated on the Ru edge-confined Cu sites can dissociate the C–H bond of CH4 with a moderately low energy barrier and thus enable the CH4 conversion at room temperature via a free radical mechanism.