Charge-orbital synergistic engineering of TM@Ti3C2O1-xBx for highly selective CO2 electrochemical reduction.

Abstract

Inspired by MXene nanosheets and their regulation of surface functional groups, a series of Ti3C2-MXene-based single TM atom electrocatalysts with a doped boron (B) atom (TM@Ti3C2O2-xBx, TM is V, Cr, Mn, Fe, Co or Ni, x = 0.11) are proposed for achieving a high performance catalytic CO2 reduction reaction (CO2RR). The results reveal that the doped B atom involves in the adsorption reaction of CO2 molecules and CO intermediates in the CO2RR. The TM-to-C and B-to-C π-back bonding contribute to the activation of the CO2 molecules and CO intermediates in the CO2RR. Enough electrons from the single TM atom and B atom occupied orbitals can be injected into the CO2 molecules and *CO intermediates through direct bonding interactions, which effectively alleviates the difficulty of the first hydrogenation reaction step and further helps CO reduction towards CH4. The calculated values of ΔG for the first hydrogenation reaction and the formation of *CHO on Ti3C2O2-xBx are significantly smaller than those of other single-atom catalysts (SACs). Fe@Ti3C2O2-xBx is found to have the highest electrocatalytic activity with a limiting potential of ∼0.40 V and exhibits a high selectivity for obtaining CH4 through the CO2RR compared with the hydrogen evolution reaction. This work is expected to open a research path for engineering the charge-orbital state of the innate atoms of a substrate based on mechanistic insights, which guides the rational design of highly selective MXene-based CO2RR electrocatalysts.