Elevating the p-band centre of SnO nanosheets through W incorporation for promoting CO electroreduction

• Published in: Dalton transactions : an international journal of inorganic chemistry 2022-01, Vol.51 (2), p.541-552
• Main Authors: Fang, Dong, Zhang, Linlin, Niu, Yongjian, Wang, Yuanyuan, Su, Qingxiao, Wang, Jiao, Wang, Cheng
• Format: Article
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d1dt03152j

SnO 2 is one of the most promising catalysts for CO 2 electroreduction. However, the intrinsic low electrical conductivity and weak CO 2 adsorption and activation capability have rendered the reaction kinetically sluggish and inefficient. To surmount these hurdles, herein, W was incorporated into SnO 2 nanosheets to modulate the electronic structures. Compared with pristine SnO 2 , the p-band centre of W-doped SnO 2 was elevated towards the Fermi level, accompanied by the reduction in the band gap and work function. As a result, both the CO 2 adsorption and the electron transfer process were promoted, thus lowering the activation energy barrier for CO 2 reduction. Benefitting from these, a maximum faradaic efficiency of 87.8% was achieved for HCOOH at −0.9 V vs. the RHE. Meanwhile, the current density and energy efficiency approached 20.92 mA cm −2 and 60%, respectively. Such performances could sustain for 14 h without obvious fading and exceeded pristine SnO 2 and most reported Sn-based catalysts. Tafel slope and reaction order analyses further suggested that the reaction proceeded following a stepwise electron-proton transfer pathway with the formation of CO 2 &z.rad; − as the rate determining step. This work demonstrated the effectiveness of electronic structure tuning in promoting the catalytic performances of p-block metal oxides and contributed to the development of efficient catalysts for sustainable energy conversion and carbon neutrality. The p-band center of SnO 2 nanosheets was elevated through W incorporation. As a result, the CO 2 adsorption capability was enhanced and the activation energy barrier was lowered, hence promoting CO 2 electroreduction to HCOOH.