Tuning the electronic properties of nanocatalysts via doping with monodispersed hetero-metal atoms is an effective method used to enhance catalytic properties. Doping CuO nanoparticles with monodispersed Co atoms using different reductants affords catalysts (CoBCu/Al2O3 and CoHCu/Al2O3) with strikingly different electronic structures. Compared to CoHCu/Al2O3, the CuO nanoparticles in CoBCu/Al2O3 have longer and weaker Cu-O bonds, with a lower 1s → 4pz antibonding transition and higher 4p → 1s bonding transition (as demonstrated from HERFD-XANES and valence-to-core X-ray emission spectroscopy). The weaker Cu-O bonds in CoBCu/Al2O3 lead to superior redox activity of the CuO nanoparticles, evidenced from operando XAFS and in-situ near ambient pressure-near edge X-ray absorption fine structures studies. Such superior redox properties of CuO in CoBCu/Al2O3 result in a much reduced activation energy of CoBCu/Al2O3 compared to CoHCu/Al2O3 (40.0 vs. 63.5 kJ/mol), thus leading to an enhancement in catalytic performance in the selective catalytic oxidation of NH3 to N2.
