Defect‐Enhanced CO2 Reduction Catalytic Performance in O‐Terminated MXenes

Abstract Electrochemical carbon dioxide reduction reaction (CO 2 RR) represents a promising way to generate fuels and chemical feedstock sustainably. Recently, studies have shown that two‐dimensional metal carbides and nitrides (MXenes) can be promising CO 2 RR electrocatalysts due to the alternating −C and −H coordination with intermediates that decouples scaling relations seen on transition metal catalysts. However, further by tuning the electronic and surface structure of MXenes it should still be possible to reach higher turnover number and selectivities. To this end, defect engineering of MXenes for electrochemical CO 2 RR has not been investigated to date. In this work, first‐principles modelling simulations are employed to systematically investigate CO 2 RR on M 2 XO 2 ‐type MXenes with transition metal and carbon/nitrogen vacancies. We found that the −C‐coordinated intermediates take the form of fragments (e. g., *COOH, *CHO) whereas the −H‐coordinated intermediates form a complete molecule (e. g., *HCOOH, *H 2 CO). Interestingly, the fragment‐type intermediates become more strongly bound when transition‐metal vacancies are present on most MXenes, while the molecule‐type intermediates are largely unaffected, allowing the CO 2 RR overpotential to be tuned. The most promising defective MXene is Hf 2 NO 2 containing Hf vacancies, with a low overpotential of 0.45 V. More importantly, through electronic structure analysis it could be observed that the Fermi level of the MXene changes significantly in the presence of vacancies, indicating that the Fermi level shift can be used as an ideal descriptor to rapidly predict the catalytic performance of defective MXenes. Such an evaluation strategy is applicable to other catalysts beyond MXenes, which could enhance high throughput screening efforts for accelerated catalyst discovery.