Periodic　density　functional　theory　calculations　have　been　performed　to　investigate　the　CO2　activation　on　a　series　of　TM/Cu　surface　alloys　that　are　built　by　dispersing　individual　later　3d　TM　atoms　(TM　=　Fe,　Co　and　Ni)　on　the　Cu(1　0　0),　Cu(1　1　0)　and　Cu(1　1　1)　surfaces.　The　most　stable　structure　with　bent　CO23-　configurations　on　the　different　TM/Cu　surfaces　are　determined,　and　the　results　show　that　among　the　late　3d-metals,　cobalt　is　potentially　a　good　dopant　to　activate　CO2　on　copper　surfaces.　Using　the　simple　d-band　model　that　treats　all　five　d　orbitals　of　surface　TM　atom　as　a　whole,　a　poor　correlation　between　adsorption　energy　and　the　d-band　center　is　observed.　To　obtain　a　deep　understanding　of　the　adsorption　property,　the　bonding　characteristics　of　the　TM-C　and　TM-O　adsorption　bonds　are　carefully　examined　by　the　crystal　orbital　Hamilton　population　technique,　which　reveals　that　the　TM　atom　primarily　provides　d　orbitals　with　z-component,　namely　C1.72,　d　and　dyz　orbitals　to　interact　with　the　CO2.　Based　on　this　result,　we　propose　a　modified　d-band　model　that　only　considers　the　contributions　of　those　d　orbitals　with　zcomponent,　and　by　employing　this　approach　a　good　linear　relationship　between　adsorption　energy　and　the　revised　d-band　center　can　be　established.　(C)　2015　Elsevier　B.V.　All　rights　reserved.