Computational screening of M/Cu core/shell nanoparticles and their applications for the electro-chemical reduction of CO2 and CO

To improve the catalytic activity of copper nanoparticles (Cu NPs) in the electro-chemical catalysis of the CO2 reduction reactions (CO(2)RRs), the formation and use of core/shell nanoparticles (CSNPs) with Cu as the shell composite may be an effective way. Using Cu-79 NP as the representative, we performed computational screening and confirmed four M-x@Cu79-x CSNPs that can stably exist. Then, the catalytic performance of the screened CSNPs was tested through first-principles calculations. The free energy profiles indicate that Fe-19@Cu-60 is more desirable for CO2RR catalysis due to its high selectivity for CO rather than HCOOH at a low potential. Moreover, when it electro-catalyzes CO2 into CH4, the Fe-19@Cu-60 CSNP exhibits much lower limiting potential (-0.58 V) compared with pure Cu-79 NP (-0.86 V) or the Cu (211) surface (-0.70 V). Taking the cost into consideration, the Fe-19@Cu-60 CSNP is highly recommended as a promising electro-catalyst for CO(2)RRs. In addition, when CO is taken as the initial reactant to be reduced, all the screened CSNPs exhibit lower limiting potentials than Cu-79 NP. From the view of material design, the significant weakening of CO binding originating from the change in the d-band center could be the reason why the formation of a core/shell structure will enhance the catalytic performance of Cu NPs in CO reduction.