CO2 activation on bimetallic CuNi nanoparticles

Density functional theory calculations have been performed to investigate the structural, electronic, and CO2 adsorption properties of 55-atom bimetallic CuNi nanoparticles (NPs) in core-shell and decorated architectures, as well as of their monometallic counterparts. Our results revealed that with respect to the monometallic Cu55 and Ni55 parents, the formation of decorated Cu12Ni43 and core-shell Cu42Ni13 are energetically favorable. We found that CO2 chemisorbs on monometallic Ni55, core-shell Cu13Ni42, and decorated Cu12Ni43 and Cu43Ni12, whereas, it physisorbs on monometallic Cu55 and core-shell Cu42Ni13. The presence of surface Ni on the NPs is key in strongly adsorbing and activating the CO2 molecule (linear to bent transition and elongation of C˭O bonds). This activation occurs through a charge transfer from the NPs to the CO2 molecule, where the local metal d-orbital density localization on surface Ni plays a pivotal role. This work identifies insightful structure-property relationships for CO2 activation and highlights the importance of keeping a balance between NP stability and CO2 adsorption behavior in designing catalytic bimetallic NPs that activate CO2.