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Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes

DuChene, Joseph S. and Tagliabue, Giulia and Welch, Alex J. and Li, Xueqian and Cheng, Wen-Hui and Atwater, Harry A. (2020) Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes. Nano Letters, 20 (4). pp. 2348-2358. ISSN 1530-6984. doi:10.1021/acs.nanolett.9b04895.

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We report the light-induced modification of catalytic selectivity for photoelectrochemical CO₂ reduction in aqueous media using copper (Cu) nanoparticles dispersed onto p-type nickel oxide (p-NiO) photocathodes. Optical excitation of Cu nanoparticles generates hot electrons available for driving CO₂ reduction on the Cu surface, while charge separation is accomplished by hot-hole injection from the Cu nanoparticles into the underlying p-NiO support. Photoelectrochemical studies demonstrate that optical excitation of plasmonic Cu/p-NiO photocathodes imparts increased selectivity for CO₂ reduction over hydrogen evolution in aqueous electrolytes. Specifically, we observed that plasmon-driven CO₂ reduction increased the production of carbon monoxide and formate, while simultaneously reducing the evolution of hydrogen. Our results demonstrate an optical route toward steering the selectivity of artificial photosynthetic systems with plasmon-driven photocathodes for photoelectrochemical CO₂ reduction in aqueous media.

Item Type:Article
Related URLs:
URLURL TypeDescription
DuChene, Joseph S.0000-0002-7145-323X
Tagliabue, Giulia0000-0003-4587-728X
Welch, Alex J.0000-0003-2132-9617
Li, Xueqian0000-0002-1197-3743
Cheng, Wen-Hui0000-0003-3233-4606
Atwater, Harry A.0000-0001-9435-0201
Additional Information:© 2020 American Chemical Society. Received: November 25, 2019; Revised: March 3, 2020; Published: March 5, 2020. This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DE-SC0004993. G.T. acknowledges support from the Swiss National Science Foundation through the Early Postdoc Mobility Fellowship, grant no. P2EZP2_159101, and the Advanced Mobility Fellowship, grant no. P300P2_171417. A.J.W. acknowledges support from the Resnick Sustainability Institute at the California Institute of Technology and the National Science Foundation (NSF) Graduate Research Fellowship Program under Base Award No. 1745301. We thank Professor Brian McCloskey for sharing the design of the photoelectrochemical cell for temperature-controlled CO₂ reduction experiments. We also thank Dr. Matthias Richter for XPS characterization of p-type NiO and Cu/p-NiO films, which was performed at the Molecular Materials Research Center in the Beckman Institute of the California Institute of Technology. Author Contributions: J.S.D. and H.A.A. conceived the idea, designed the experiments, and wrote the manuscript. J.S.D. performed all photoelectrochemical experiments with assistance from A.J.W. and X.L. J.S.D., G.T., A.J.W., and X.L. fabricated and characterized devices. W.-H.C. performed optical characterization of materials and assisted with calibration and maintenance of gas chromatography equipment. H.A.A. supervised the project. All authors have given approval to the final version of the manuscript. The authors declare no competing financial interest.
Group:JCAP, Resnick Sustainability Institute
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Swiss National Science Foundation (SNSF)P2EZP2_159101
Swiss National Science Foundation (SNSF)P300P2_171417
Resnick Sustainability InstituteUNSPECIFIED
NSF Graduate Research FellowshipDGE-1745301
Subject Keywords:artificial photosynthesis, photoelectrochemistry, hot holes, plasmonic photocathode, CO2 reduction
Issue or Number:4
Record Number:CaltechAUTHORS:20200305-145718553
Persistent URL:
Official Citation:Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO2 Reduction in Aqueous Electrolytes. Joseph S. DuChene, Giulia Tagliabue, Alex J. Welch, Xueqian Li, Wen-Hui Cheng, and Harry A. Atwater. Nano Letters 2020 20 (4), 2348-2358; DOI: 10.1021/acs.nanolett.9b04895
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:101732
Deposited By: Tony Diaz
Deposited On:05 Mar 2020 23:10
Last Modified:16 Nov 2021 18:05

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