Enhanced dissociation activation of CO2 on the Bi/Cu(1 1 1) interface by the synergistic effect

•The Bi/Cu(111) interface shows enhanced activity towards CO2 activation with the synergetic effect as compared to Cu(111)•The interfacial structure is demonstrated to be important for the CO2 dissociation by forming the Bi-O-Cu heterostructure.•Further formation of Cu+ induced by the defective oxygen from the decomposition of Bi oxide promotes the dissociation of CO2.