Asymmetric Electron Redistribution in Niobic‐Oxygen Vacancy Associates to Tune Noncovalent Interaction in CO<sub>2</sub> Photoreduction
Jun Di, Chao Chen, Yao Wu, Hao Chen, Jun Xiong, Ran Long, Shuzhou Li, Li Song, Wei Jiang, Zheng Liu
Abstract
Abstract The role of vacancy associates in photocatalytic CO 2 reduction is an open question. Herein, the Nb─O vacancy associates (V Nb─O ) are engineered into niobic acid (NA) atomic layers to tailor the CO 2 photoreduction performance. The intrinsic charge compensation from O to Nb around Nb─O vacancy associates can manipulate the active electronic states, leading to the asymmetric electron redistribution. These local symmetry breaking sites show a charge density gradient, forming a localized polarization field to polarize nonpolar CO 2 molecules and tune the noncovalent interaction of reaction intermediates. This unique configuration contributes to the 9.3 times increased activity for photocatalytic CO 2 reduction. Meantime, this V Nb─O NA also shows excellent photocatalytic activity for NO 3 − –NH 4 + synthesis, with NH 4 + formation rate up to 3442 µmol g −1 h −1 . This work supplies fresh insights into the vacancy associate design for electron redistribution and noncovalent interaction tuning in photocatalysis.