A series of core–shell catalysts aiming at CO oxidative coupling to dimethyl oxalate (DMO) were constructed, and effects of the second metal doping and surface structures on the reaction activity and favorable reaction path were investigated by using the density functional theory (DFT) method. Pd13, Al@Pd12, and Ag@Pd12 were first studied to find the proper doping metal. Our results showed that the activity of CO oxidative coupling to DMO follows the order of Al@Pd12 > Pd13 > Ag@Pd12, and the same result was also obtained via the electronic analysis. In addition, Al6@Pd32 and Al13@Pd42 catalysts with higher doping ratio and lower cost than that of Al@Pd12 were selected to examine the influence of surface structure on the reaction activity. It showed that CO + CH3O → COOCH3 + CO → OCCOOCH3 + CH3O → DMO is the favorable pathway on the (100) surface of Al6@Pd32 catalyst, while CO + CH3O → CO + CH3O (COOCH3) → COOCH3 + COOCH3 → DMO is the optimal pathway on the (111) surface of Al@Pd12 and Al13@Pd42, which indicated that the surface structure of catalysts affected the preferable pathway of DMO formation. Moreover, activities of CO oxidative coupling to DMO on AlPd core–shell catalysts followed the order of Al@Pd12 > Al13@Pd42 > Al6@Pd32. In addition, Al13@Pd42 also exhibited a good selectivity between DMO and DMC. Thus, Al13@Pd42 is a proper catalyst with high activity, high selectivity, and low cost because of high Al:Pd ratio.

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The formation of dimethyl oxalate (DMO) via CO catalytic coupling on a series of catalysts including Pdn (n = 1, 2, 3, 4 and 6) clusters loaded on TiO2-V has been explored by density functional theory (DFT) calculation.