Photocatalytic CO<sub>2</sub> Reduction to Ethanol by ZnCo<sub>2</sub>O<sub>4</sub>/ZnO Janus Hollow Nanofibers
Hongyu Ma, Xi Wu, Xinghua Li, Jie Liu, Haipeng Dong, Yu Liu, Luyao Niu, Fang Zhang, Wenbo Wang, Changlu Shao, Xiaowei Li, Yichun Liu
Abstract
Photocatalytic carbon dioxide (CO 2 ) reduction for high-value hydrocarbon fuel production is a promising strategy to tackle global energy demand and climate change. However, this technology faces formidable challenges, primarily stemming from low yield and poor selectivity of C2 products of the desired hydrocarbon fuels. This study reported ZnO/ZnCo 2 O 4 Janus hollow nanofibers (ZnO/ZCO JHNFs) prepared by electrospinning and atomic layer deposition. Photocatalytic tests revealed an ethanol yield of 4.99 μmol g –1 h –1 for ZnO/ZnCo 2 O 4 JHNFs, surpassing mixed ZnO/ZnCo 2 O 4 nanofibers (ZnO/ZCO NFs) by 4.35 times and pure ZnO by 12.7 times. The selectivity of 58.8% is 2.38 and 4.49 times higher than those of ZnO/ZnCo 2 O 4 NFs and ZnO, respectively. These enhancements are attributed to efficient carrier separation facilitated by the ordered internal electric field of the Z-scheme heterojunction interface, validated by the energy band evaluations from experimentation and density functional theory (DFT) simulations and charge separation characterizations of photocurrent, impedance, and photoluminescence spectra. The Janus structure also effectively exposes the surface of ZnCo 2 O 4 to CO 2 molecules, increasing the active site availability, as confirmed by BET nitrogen adsorption/desorption, temperature-programmed desorption tests, and DFT adsorption energy calculations. This study proposes a novel approach for efficient photocatalytic hydrocarbon fuel production, with potential applications in energy and climate crisis mitigation.