Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates

Wang, Zhijiang; Wu, Lina; Sun, Kun; Chen, Ting; Jiang, Zhaohua; Cheng, Tao; Goddard, III, William A.

doi:10.1021/acs.jpclett.8b00959

Title: Surface Ligand Promotion of Carbon Dioxide Reduction through Stabilizing Chemisorbed Reactive Intermediates

Journal Article · Tue May 22 00:00:00 EDT 2018 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.8b00959· OSTI ID:1467603

^[1]; Wu, Lina ^[2];

^[1]; Chen, Ting ^[3]; Jiang, Zhaohua ^[1];

^[4];

^[4]

Harbin Inst. of Technology (China)
Harbin Medical Univ. (China)
Univ. of Oxford (United Kingdom)
California Inst. of Technology (CalTech), Pasadena, CA (United States)

We have explored functionalizing metal catalysts with surface ligands as an approach to facilitate electrochemical carbon dioxide reduction reaction (CO₂RR). To provide a molecular level understanding of the mechanism by which this enhancement occurs, we combine in situ spectroscopy analysis with an interpretation based on quantum mechanics (QM) calculations. We find that a surface ligand can play a critical role in stabilizing the chemisorbed CO₂, which facilitates CO₂ activation and leads to a 0.3 V decrease in the overpotential for carbon monoxide (CO) formation. Moreover, the presence of the surface ligand leads to nearly exclusive CO production. At -0.6 V (versus reversible hydrogen electrode, RHE), CO is the only significant product with a faradic efficiency of 93% and a current density of 1.9 mA cm^–2. This improvement corresponds to 53-fold enhancement in turnover frequency compared with the Ag nanoparticles (NPs) without surface ligands.

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Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0004993

OSTI ID:: 1467603

Journal Information:: Journal of Physical Chemistry Letters, Vol. 9, Issue 11; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 39 works

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Understanding the role of functional groups of thiolate ligands in electrochemical CO ₂ reduction over Au(111) from first-principles Li, Fuhua; Tang, Qing Journal of Materials Chemistry A, Vol. 7, Issue 34 https://doi.org/10.1039/c9ta06851a	journal	January 2019
Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO 2 Reduction Cao, Zhi; Zacate, Samson B.; Sun, Xiaodong Angewandte Chemie, Vol. 130, Issue 39 https://doi.org/10.1002/ange.201805696	journal	August 2018
Tuning Structural and Compositional Effects in Pd-Au Nanowires for Highly Selective and Active CO ₂ Electrochemical Reduction Reaction Zhu, Shangqian; Wang, Qi; Qin, Xueping Advanced Energy Materials, Vol. 8, Issue 32 https://doi.org/10.1002/aenm.201802238	journal	October 2018
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Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO 2 Reduction Cao, Zhi; Zacate, Samson B.; Sun, Xiaodong Angewandte Chemie International Edition, Vol. 57, Issue 39 https://doi.org/10.1002/anie.201805696	journal	August 2018

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