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Title: pH effects on the electrochemical reduction of CO (2) towards C 2 products on stepped copper

Abstract

Here, we present a microkinetic model for CO (2) reduction (CO (2)R) on Cu(211) towards C 2 products, based on energetics estimated from an explicit solvent model. We show that the differences in both Tafel slopes and pH dependence for C 1 vs C 2 activity arise from differences in their multi-step mechanisms. We find the depletion in C 2 products observed at high overpotential and high pH to arise from the 2nd order dependence of C-C coupling on CO coverage, which decreases due to competition from the C 1 pathway. We further demonstrate that CO (2) reduction at a fixed pH yield similar activities, due to the facile kinetics for CO 2 reduction to CO on Cu, which suggests C 2 products to be favored for CO 2R under alkaline conditions. The mechanistic insights of this work elucidate how reaction conditions can lead to significant enhancements in selectivity and activity towards higher value C 2 products.

Authors:
 [1];  [1];  [2];  [3];  [1];  [1];  [1];  [1];  [1];  [1];  [4];  [1];  [5];  [6]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); Westlake Univ., Hangzhou (China)
  3. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Guangzhou Univ., Guangzhou (China)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1487380
Alternate Identifier(s):
OSTI ID: 1529394
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Xianyan, Schlexer, Philomena, Xiao, Jianping, Ji, Yongfei, Wang, Lei, Sandberg, Robert B., Tang, Michael, Brown, Kris, Peng, Hongjie, Ringe, Stefan, Hahn, Christopher, Jaramillo, Thomas F., Norskov, Jens K., and Chan, Karen. pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper. United States: N. p., 2019. Web. doi:10.1038/s41467-018-07970-9.
Liu, Xianyan, Schlexer, Philomena, Xiao, Jianping, Ji, Yongfei, Wang, Lei, Sandberg, Robert B., Tang, Michael, Brown, Kris, Peng, Hongjie, Ringe, Stefan, Hahn, Christopher, Jaramillo, Thomas F., Norskov, Jens K., & Chan, Karen. pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper. United States. doi:10.1038/s41467-018-07970-9.
Liu, Xianyan, Schlexer, Philomena, Xiao, Jianping, Ji, Yongfei, Wang, Lei, Sandberg, Robert B., Tang, Michael, Brown, Kris, Peng, Hongjie, Ringe, Stefan, Hahn, Christopher, Jaramillo, Thomas F., Norskov, Jens K., and Chan, Karen. Thu . "pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper". United States. doi:10.1038/s41467-018-07970-9. https://www.osti.gov/servlets/purl/1487380.
@article{osti_1487380,
title = {pH effects on the electrochemical reduction of CO(2) towards C2 products on stepped copper},
author = {Liu, Xianyan and Schlexer, Philomena and Xiao, Jianping and Ji, Yongfei and Wang, Lei and Sandberg, Robert B. and Tang, Michael and Brown, Kris and Peng, Hongjie and Ringe, Stefan and Hahn, Christopher and Jaramillo, Thomas F. and Norskov, Jens K. and Chan, Karen},
abstractNote = {Here, we present a microkinetic model for CO(2) reduction (CO(2)R) on Cu(211) towards C2 products, based on energetics estimated from an explicit solvent model. We show that the differences in both Tafel slopes and pH dependence for C1 vs C2 activity arise from differences in their multi-step mechanisms. We find the depletion in C2 products observed at high overpotential and high pH to arise from the 2nd order dependence of C-C coupling on CO coverage, which decreases due to competition from the C1 pathway. We further demonstrate that CO(2) reduction at a fixed pH yield similar activities, due to the facile kinetics for CO2 reduction to CO on Cu, which suggests C2 products to be favored for CO2R under alkaline conditions. The mechanistic insights of this work elucidate how reaction conditions can lead to significant enhancements in selectivity and activity towards higher value C2 products.},
doi = {10.1038/s41467-018-07970-9},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {1}
}

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Cited by: 15 works
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Figures / Tables:

Figure 1 Figure 1: Reaction schemes of major pathways considered for CO reduction towards C1 and C2+ products.The green path denotes C2 production via OC-CHO coupling; the blue and red path represents C2 production via protonation of OCCO to form OCCHO and OCCOH, respectively; the yellow path represents C2 production via OC-CHOHmore » coupling. The black path denotes C1 production via CHOH and the dashed CH2O.« less

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    Works referencing / citing this record:

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