Atomically dispersed Sn modified with trace sulfur species derived from organosulfide complex for electroreduction of CO2

• Published in: Applied catalysis. B, Environmental Vol. 304; p. 120936
• Main Authors: Wang, Xin, Li, Fengli, Yin, Wen-Jin, Si, Yubing, Miao, Ming, Wang, Xiaoming, Fu, Yongzhu
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.05.2022; Elsevier BV
• Subjects: Benzene; Bis(benzene-1,2-dithiolato) complex; Carbon cycle; Carbon dioxide; Catalysts; CO2 electroreduction; Dispersion; Electrocatalysts; Electrochemistry; Electrowinning; Flow stability; Nanoclusters; Selectivity; Structure-activity relationship; Sulfur; Sulfur species dopant; Tin; Tin; CO2 electroreduction; Bis(benzene-1,2-dithiolato) complex; Structure-activity relationship; Sulfur species dopant
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2021.120936

Electrochemical CO2 conversion into fuels is highly desirable to achieve carbon artificial cycles. Among electrocatalyst candidates, earth-abundant tin is subject to unsatisfied efficiency and selectivity. In this work, atomically-dispersed Sn nanoclusters modified with the trace of sulfur doping are proposed to efficiently electroreduce CO2 to C1 chemicals. This electrocatalyst is in situ derived from bis(benzene-1,2-dithiolato). It exhibits a high Faradaic efficiency (90%) for carbonaceous products at a moderate overpotential (0.75 V). Importantly, it is exploited for the formate formation with unprecedented partial current density (90 mA cm−2) and long-term stability (50 h) using the flow cell, better than most Sn-based catalysts. Electrochemical experiments and theoretical calculations manifest the promoting effect of trace sulfur on Sn nanoclusters, which stabilizes the *HCOOH intermediate and favors CO2 electroreduction. Hence, it emphasizes the importance of dopants and charge modulating for performance enhancement. This work unfolds a promising candidate for Sn electrocatalysts towards CO2 electroreduction. The atomically dispersed Sn nanoclusters modified with the trace of sulfur doping are synthisized by in situ electrochemical production of organosulfide. And Sn NC:S is proposed to efficiently electroreduce CO2 to C1 chemicals, which is contributed by the promotion effect of trace sulfur species confirmed by the theoretical calculation. [Display omitted] •Atomically dispersed Sn nanoclusters with sulfur doping are prepared by in situ deriving from organosulfide complex.•This electrocatalyst converts CO2 to C1 chemicals with high FE (90%) and formate partial current density (90 mA cm−2).•Experiments and calculations manifest the promoting effect of trace sulfur on the Sn catalyst towards CO2RR process.