Asymmetric Electron Redistribution in Niobic-Oxygen Vacancy Associates to Tune Noncovalent Interaction in CO2 Photoreduction

Jun Di; Chao Chen; Yao Wu; Hao Chen; Jun Xiong; Ran Long; Shuzhou Li; Li Song; Wei Jiang; Zheng Liu

doi:10.1002/adma.202401914

Asymmetric Electron Redistribution in Niobic-Oxygen Vacancy Associates to Tune Noncovalent Interaction in CO₂ Photoreduction

Adv Mater. 2024 Mar 4:e2401914. doi: 10.1002/adma.202401914. Online ahead of print.

Authors

Jun Di¹, Chao Chen^{2

3}, Yao Wu², Hao Chen⁴, Jun Xiong⁵, Ran Long⁴, Shuzhou Li², Li Song⁴, Wei Jiang¹, Zheng Liu²

Affiliations

¹ School of Chemistry and Chemical Engineering, National Special Superfine Powder Engineering Research Center, Nanjing University of Science and Technology, Nanjing, 210094, China.
² School of Materials Science & Engineering, Nanyang Technological University, Singapore, 639798, Singapore.
³ Xi'an Key Laboratory of Liquid Crystal and Organic Photovoltaic Materials, Xi'an Modern Chemistry Research Institute, Xi'an, 710065, P. R. China.
⁴ National Synchrotron Radiation Laboratory, State Key Laboratory of Particle Detection and Electronics, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
⁵ Institute for Energy Research, Jiangsu University, Zhenjiang, 212013, P. R. China.

PMID: 38436110
DOI: 10.1002/adma.202401914

Abstract

The role of vacancy associates in photocatalytic CO₂ 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 CO₂ 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 CO₂ molecules and tune the noncovalent interaction of reaction intermediates. This unique configuration contributes to the 9.3 times increased activity for photocatalytic CO₂ reduction. Meantime, this V_Nb─O NA also shows excellent photocatalytic activity for NO₃ ^- -NH₄ ⁺ synthesis, with NH₄ ⁺ 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.

Keywords: Nb─O vacancy associates; asymmetric electron redistribution; noncovalent interaction; photocatalytic CO2 reduction.

Abstract

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