@article{1d5990750b2741f3802cfefd0734aea0,
title = "Switching of electrochemical selectivity due to plasmonic field-induced dissociation",
abstract = "Electrochemical reactivity is known to be dictated by the structure and composition of the electrocatalyst–electrolyte interface. Here, we show that optically generated electric fields at this interface can influence electrochemical reactivity insofar as to completely switch reaction selectivity. We study an electrocatalyst composed of gold–copper alloy nanoparticles known to be active toward the reduction of CO2 to CO. However, under the action of highly localized electric fields generated by plasmonic excitation of the gold–copper alloy nanoparticles, water splitting becomes favored at the expense of CO2 reduction. Real-time time-dependent density functional tight binding calculations indicate that optically generated electric fields promote transient-hole-transfer-driven dissociation of the O–H bond of water preferentially over transient-electron-driven dissociation of the C–O bond of CO2. These results highlight the potential of optically generated electric fields for modulating pathways, switching reactivity on/off, and even directing outcomes.",
keywords = "catalysis, electric field, energy, hot electron, plasmon",
author = "Alcorn, {Francis M.} and Giri, {Sajal Kumar} and Maya Chattoraj and Rachel Nixon and Schatz, {George C.} and Jain, {Prashant K.}",
note = "ACKNOWLEDGMENTS. This material is based on work supported by the NSF under Grant No. CHE-2304910 awarded to P.K.J. S.K.G. and G.C.S. (theory work) were supported by the Department of Energy, Office of Basic Energy Sciences, under grant DE-SC0004752. Funding for this work was provided in part (support for F.M.A.) by the Robert C. and Carolyn J. Springborn Endowment and the Future Interdisciplinary Research Explorations (FIRE) Grant from the UIUC College of Agricultural, Consumer, and Environmental Sciences. M.C. was supported by the Clare Boothe Luce Program. R.N. was supported by a Link Foundation Energy Fellowship.The work was carried out in part at the Materials Research Laboratory Central Research Facilities, University of Illinois. We acknowledge Dr. Alexander Ulanov of the Metabolomics Core Facility at the Roy.J Carver Biotechnology Center (CBC) for assistance with gas chromatography\u2013mass spectrometry. This material is based on work supported by the NSF under Grant No. CHE-2304910 awarded to P.K.J. S.K.G. and G.C.S. (theory work) were supported by the Department of Energy, Office of Basic Energy Sciences, under grant DE-SC0004752. Funding for this work was provided in part (support for F.M.A.) by the Robert C. and Carolyn J. Springborn Endowment and the Future Interdisciplinary Research Explorations (FIRE) Grant from the UIUC College of Agricultural, Consumer, and Environmental Sciences. M.C. was supported by the Clare Boothe Luce Program. R.N. was supported by a Link Foundation Energy Fellowship. The work was carried out in part at the Materials Research Laboratory Central Research Facilities, University of Illinois. We acknowledge Dr. Alexander Ulanov of the Metabolomics Core Facility at the Roy. J Carver Biotechnology Center (CBC) for assistance with gas chromatography\u2013mass spectrometry.",
year = "2024",
month = oct,
day = "8",
doi = "10.1073/pnas.2404433121",
language = "English (US)",
volume = "121",
journal = "Proceedings of the National Academy of Sciences of the United States of America",
issn = "0027-8424",
publisher = "National Academy of Sciences",
number = "41",
}