Our world is facing global warming and feedstock shortage, both of which can be potentially solvable through carbon dioxide reduction reactions (CO2RR). Electrocatalysis is one strategy to overcome the potential energy barrier. Quantum mechanical modeling is indispensable to decipher structural and energetic details of CO2RR at the atomistic level and to interpret distributions of final products, because in-situ experimental measurements for intermediates and transition states are infeasible due to their low abundance. In addition, it is urgent to design alternative electrocatalysts for CO2RR because conventional pristine copper (Cu) surfaces do not present sufficient selectivity towards specific products. In this work, we proposed a Cu-doped two-dimensional material as an alternative electrocatalyst exhibiting a very different selectivity. Combining quantum mechanics and statistical mechanics, we modeled reaction pathways leading to important one-carbon (C1) and two-carbon (C2) products, including methanol (CH3OH), methane (CH4), ethanol (CH3CH2OH), and ethylene (CH2=CH2), and evaluated Gibbs free energy profiles for corresponding intermediates and transition states. Our results will provide the community with important hints for measurable C1 and C2 intermediates and products on the two-dimensional electrocatalyst in question, as well as new ideas to design and optimize alternative electrocatalysts.

Quantum mechanical modeling of electrocatalytic carbon dioxide reduction reactions on copper-doped two-dimensional materials

ACS Spring 2022

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