@article{Dong2026, 
author = {Shuming Dong and Xinyuan Huang and Chaoxiu Qin and Kun Wang and Xinyu Wu and Anyang Tang and Ximeng Lv and Huibin Zhang and Huazhen Cao and Guoqu Zheng and Zhengzheng Liu},
title = {Enhanced electron delocalization induced by p-p-d orbital coupling for high-rate formic acid electrosynthesis},
year = {2026},
journal = {Nano Research},
keywords = {CO2 electroreduction, bismuth-based catalysts, orbital coupling, electron delocalization, formic acid},
url = {https://www.sciopen.com/article/10.26599/NR.2026.94909081},
doi = {10.26599/NR.2026.94909081},
abstract = {The electroreduction of carbon dioxide (CO2RR) to high-value-added formic acid (HCOOH) is of great significance for closing the anthropogenic CO2 cycle. Bismuth oxide (Bi2O3) possesses Biδ+ sites that is favorable for oxygenate intermediate (i.e. *OCHO) adsorption, while the competitive hydrogen evolution reaction is also facilitated, inhibiting broad-range high selectivity. In this work, we propose to build an ultrathin Bi2WO6 nanosheets (NSs) with Aurivillius-phase for enhancing electronic delocalization of Biδ+ by 5d (Bi)−2p (O)−6p (W) orbital coupling. The delocalized Biδ+ sites could boost the coupling between the O 2p orbital of *OCHO and the Bi 6p orbital that promotes *OCHO adsorption and electron transfer from Biδ+ to the *OCHO intermediate, thereby improving the CO2RR performance and maintaining structure. In situ Raman spectroscopy and theoretical calculations demonstrated that delocalized Biδ+ could optimize the structure of interfacial water and decrease the *H coverage for restraining by-product H2 production. As a result, these advantages endowed the Bi2WO6 NSs with high HCOOH selectivity of 97.8% and peak partial current density of 877 mA cm–2, superior to pristine Bi2O3 and Aurivillius-phase bismuth molybdate NSs.}
}