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Title: Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials

Abstract

Here, electrochemical CO2 reduction to formate provides an avenue to reduce globally accelerating CO2 emissions and produce value-added products. Unfortunately, high selectivity in formate electrosynthesis has thus far only been achieved at highly cathodic potentials. Here we use density functional theory to investigate the effect of alloying Cu and Sn on the activity and selectivity towards formate. A theoretical thermodynamic analysis of the reaction energetics suggests that the incorporation of copper into tin could suppress hydrogen evolution and CO production, thus favouring formate generation. Consistent with theoretical trends, the designed CuSn3 catalysts by co-electrodeposition exhibit a Faradaic efficiency of 95% towards formate generation at –0.5 V versus RHE. Furthermore, the catalysts show no degradation over 50 h of operation. In situ Sn L3-edge and Cu K-edge X-ray absorption spectroscopy indicate electron donation from Sn to Cu, which indicates positive oxidation states of Sn in CuSn3 under operating conditions.

Authors:
ORCiD logo [1];  [2];  [1];  [1];  [1];  [3];  [2];  [1];  [3]; ORCiD logo [3];  [2]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1493352
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 2; Journal Issue: 1; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zheng, Xueli, Ji, Yongfei, Tang, Jing, Wang, Jiangyan, Liu, Bofei, Steinrück, Hans-Georg, Lim, Kipil, Li, Yuzhang, Toney, Michael F., Chan, Karen, and Cui, Yi. Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials. United States: N. p., 2018. Web. doi:10.1038/s41929-018-0200-8.
Zheng, Xueli, Ji, Yongfei, Tang, Jing, Wang, Jiangyan, Liu, Bofei, Steinrück, Hans-Georg, Lim, Kipil, Li, Yuzhang, Toney, Michael F., Chan, Karen, & Cui, Yi. Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials. United States. doi:10.1038/s41929-018-0200-8.
Zheng, Xueli, Ji, Yongfei, Tang, Jing, Wang, Jiangyan, Liu, Bofei, Steinrück, Hans-Georg, Lim, Kipil, Li, Yuzhang, Toney, Michael F., Chan, Karen, and Cui, Yi. Mon . "Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials". United States. doi:10.1038/s41929-018-0200-8. https://www.osti.gov/servlets/purl/1493352.
@article{osti_1493352,
title = {Theory-guided Sn/Cu alloying for efficient CO2 electroreduction at low overpotentials},
author = {Zheng, Xueli and Ji, Yongfei and Tang, Jing and Wang, Jiangyan and Liu, Bofei and Steinrück, Hans-Georg and Lim, Kipil and Li, Yuzhang and Toney, Michael F. and Chan, Karen and Cui, Yi},
abstractNote = {Here, electrochemical CO2 reduction to formate provides an avenue to reduce globally accelerating CO2 emissions and produce value-added products. Unfortunately, high selectivity in formate electrosynthesis has thus far only been achieved at highly cathodic potentials. Here we use density functional theory to investigate the effect of alloying Cu and Sn on the activity and selectivity towards formate. A theoretical thermodynamic analysis of the reaction energetics suggests that the incorporation of copper into tin could suppress hydrogen evolution and CO production, thus favouring formate generation. Consistent with theoretical trends, the designed CuSn3 catalysts by co-electrodeposition exhibit a Faradaic efficiency of 95% towards formate generation at –0.5 V versus RHE. Furthermore, the catalysts show no degradation over 50 h of operation. In situ Sn L3-edge and Cu K-edge X-ray absorption spectroscopy indicate electron donation from Sn to Cu, which indicates positive oxidation states of Sn in CuSn3 under operating conditions.},
doi = {10.1038/s41929-018-0200-8},
journal = {Nature Catalysis},
number = 1,
volume = 2,
place = {United States},
year = {2018},
month = {12}
}

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