The p‐Orbital Delocalization of Main‐Group Metals to Boost CO2 Electroreduction. Issue 49 (8th November 2018)

• Record Type: Journal Article
• Authors: He, Sisi; Ni, Fenglou; Ji, Yujin; Wang, Lie; Wen, Yunzhou; Bai, Haipeng; Liu, Gejun; Zhang, Ye; Li, Youyong; Zhang, Bo; Peng, Huisheng
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 49(2018)
• Page Start: 16114
• Page End: 16119
• Publication Date: 2018-11-08
• Subjects: bismuth -- CO2 electroreduction -- delocalization -- formate -- heterogeneous catalysis; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201810538
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Enhancing the p‐orbital delocalization of a Bi catalyst (termed as POD‐Bi) via layer coupling of the short inter‐layer Bi−Bi bond facilitates the adsorption of intermediate *OCHO of CO2 and thus boosts the CO2 reduction reaction (CO2 RR) rate to formate. X‐ray absorption fine spectroscopy shows that the POD‐Bi catalyst has a shortened inter‐layer bond after the catalysts are electrochemically reduced in situ from original BiOCl nanosheets. The catalyst on a glassy carbon electrode exhibits a record current density of 57 mA cm −2 (twice the state‐of‐the‐art catalyst) at −1.16 V vs. RHE with an excellent formate Faradic efficiency (FE) of 95 %. The catalyst has a record half‐cell formate power conversion efficiency of 79 % at a current density of 100 mA cm −2 with 93 % formate FE when applied in a flow‐cell system. The highest rate of the CO2 RR production reported (391 mg h −1 cm 2 ) was achieved at a current density of 500 mA cm −2 with formate FE of 91 % at high CO2 pressure. Abstract : A bismuth catalyst with p‐orbital delocalization exhibits the highest rate of CO2 reduction reaction ever reported (391 mg h −1 cm 2 at a current density of 500 mA cm −2 with formate Faradaic efficiency of 91 %), which is twice the state‐of‐the‐art synthesized catalysts. Simulations reveal that the p‐orbital localization facilitates adsorption of intermediate *OCHO of CO2 and hence the formation of formate.