jp7b07081_si_001.pdf (267.37 kB)
Strain and Ligand Effects on CO2 Reduction Reactions over Cu–Metal Heterostructure Catalysts
journal contribution
posted on 2017-09-20, 00:00 authored by Fuzhu Liu, Chao Wu, Shengchun YangThe
strain and ligand effects on the adsorption energies of key
intermediates (*COOH, *CO, *CHO, and *COH) in CO2 reduction
reactions on the Cu–M(111) (M = Ni, Co, Cu, Rh, Ir, Pd, Pt)
heterolayered catalysts have been quantitatively separated using first-principles
calculations. Contrary to the common belief that strain is always
the leading factor influencing catalytic performance of the core–shell
type heterostructure catalysts, the ligand effect due to the underlying
hetero elements should not be ignored and may become dominant for
strain-insensitive adsorbates (*CO and *COH). Moreover, the models
of Cu(2 ML/3 ML)–M(111) (M = Ir, Rh, Pt, Pd) have been shown
to be better catalysts for CO2 reduction, as they require
lower overpotential to drive the reaction than the Cu(111) slab. Particularly,
the overpotential is predicted to be lowered by 0.17 V for Cu(3 ML)–Ir(111)
model catalyst. Thus, both effects should be considered in heterostructure
catalyst design.