Cu Catalysts Doped with a Heteroatom into the Subsurface: Unraveling the Role of Subsurface Chemistry in Tuning the Catalytic Performance of CH Selective Hydrogenation.

Heteroatoms doped into the subsurface of transition metals play a vital role in heterogeneous catalysis via either expressing surface structures or even directly participating in the reaction. Herein, DFT calculations and microkinetic modeling are implemented to examine CH selective hydrogenation over heteroatom (H, B, C, N, or P)-doped Cu(111) and Cu(211) subsurfaces, which are compared with pure Cu(111) and Cu(211) to unravel the role of subsurface chemistry in tuning the surface structure and further regulating catalytic performance. Our results indicate that the catalytic performance toward CH selective hydrogenation is closely related to the type of doped subsurface heteroatom and the Cu surface coordination environment, which can be attributed to the simultaneous change of Cu surface geometric and electronic structures. Catalytic performance improvement over the heteroatom-doped Cu(111) is generally better than that over the doped Cu(211); especially, B- or N-doped Cu(111) has excellent CH activity and selectivity and greatly inhibits green oil. For the heteroatom-doped Cu(211), better performance is only obtained on P-Cu(211), which is still lower than the B- and N-doped Cu(111). The subsurface heteroatom doping should focus on high-coordination Cu(111) instead of low-coordination Cu(211). AIMD simulations verified the thermal stability of B-Cu(111) and N-Cu(111); both were screened out to be the most suitable catalysts toward CH hydrogenation. This work clearly unravels the role of subsurface chemistry in heterogeneous catalysis and contributes to the rational design of high-performance metal catalysts by tuning surface structures with the heteroatom into the subsurface.