Efficient Photoreduction of Diluted CO2to Tunable Syngas by Ni−Co Dual Sites through d‐band Center Manipulation

Abstract Photocatalytic conversion of CO 2 into syngas is a promising way to address the energy and environmental challenges. Here we report the integration of Ni−Co dual sites on Ni doped Co 3 O 4 ultrathin nanosheets assembled double‐hollow nanotube (Ni−Co 3 O 4 NSDHN) for efficient photoreduction of low‐concentration CO 2 . Quasi in situ spectra and density functional theory calculations demonstrate that the declining of d ‐band center of Ni−Co dual sites enables the electrons accumulation in the d xz / d yz ‐2π* and d z2 ‐ 5 σ orbitals. As a result, the binding strength of *CO is weakened and the *H adsorption site is modulated from metal sites to an oxygen site. Remarkably, Ni−Co 3 O 4 NSDHN exhibits superior diluted CO 2 photoconversion activity and controllable selectivity under the irradiation of visible light or even natural sunlight. A syngas evolution rate of 170.0 mmol g −1 h −1 with an apparent quantum yield of 3.7 % and continuously adjustable CO/H 2 ratios from 1 : 10 to 10 : 1 are achieved.