Prediction of C2N-Supported Double-Atom Catalysts with Individual/Integrated Descriptors for Electrochemical and Thermochemical CO2 Reduction

Electrochemical/thermochemical CO2 reduction reactions (CO2RR) on double-atom catalysts (DACs) have emerged as a novel frontier in energy and environmental catalysis. However, the lack of investigation of the underlying structure-property relationship greatly limits the rational design and practical application of related catalysts. Herein, we carried out a comprehensive theoretical study on CO2RR catalyzed by a series of C2N-supported transition metals to shed light on this issue. We demonstrate that the activity of DAC can be obviously improved by judicious manipulation of metal type, and CoNi with the highest reactivity and excellent selectivity is identified as the most promising candidate for both electroreduction and thermoreduction processes. Then, based on systemically electronic and structural analysis, various quantitative structure-property relationships are established. The results reveal that key interaction and reaction properties of elementary steps can be quantitatively determined directly from individual descriptors, including key species, charge transfer, d-orbital center, bond length, spectroscopic signals, etc, while for total reaction, the integrated descriptors designed by a novel and effective three-step strategy have much better performance. The proposed ability of quantitative prediction of the catalytic property utilizing physically interpretable parameters can significantly broaden the applicability of catalytic descriptors for materials design, thus leading to indispensable guidelines for related DACs.