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Carbon Dioxide Dimer Radical Anion as Surface Intermediate of Photoinduced CO2 Reduction at Aqueous Cu and CdSe Nanoparticle Catalysts by Rapid-Scan FT-IR Spectroscopy

Authors
Sheng, HuaOh, Myoung HwanOsowiecki, Wojciech T.Kim, WooyulAlivisatos, A. PaulFrei, Heinz
Issue Date
Mar-2018
Publisher
AMER CHEMICAL SOC
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.140, no.12, pp 4363 - 4371
Pages
9
Journal Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume
140
Number
12
Start Page
4363
End Page
4371
URI
https://scholarworks.sookmyung.ac.kr/handle/2020.sw.sookmyung/4615
DOI
10.1021/jacs.8b00271
ISSN
0002-7863
1520-5126
Abstract
Monitoring of visible light sensitized reduction of CO2 at Cu nanoparticles in aqueous solution by rapid-scan ATR FT-IR spectroscopy on the time scale of seconds allowed structural identification of a one-electron intermediate and demonstrated its kinetic relevancy for the first time. Isotopic labeling (C-12: 1632, 1358, 1346 cm(-1); C-13: 1588, 1326, 1316 cm(-1)) revealed a species of carbon dioxide dimer radical anion structure, most likely bound to the catalyst surface through carbon. Intermediacy of Cu-C(=O)OCO2- surface species is in agreement with a recently proposed mechanism for electrocatalytic CO2 reduction at Cu metal nanoparticles based on Tafel slope analysis. Spontaneous decrease of the intermediate after termination of the photosensitization pulse (Sn porphyrin excited at 405 nm) was accompanied by the growth of HCO3-. CO was produced as well, but sensitive detection required photolysis for tens of minutes. A direct kinetic link between a C2O4- surface intermediate and the CO product was also demonstrated for photocatalyzed CO2 reduction at aqueous CdSe nanoparticles, where first order growth of a Cd-C(=O)OCO2- species was accompanied by rise of CO (monitored by a fast Ni complex trap) and HCO3- showing a distinct induction period. The detection of the one-electron surface intermediate and confirmation of its catalytic relevancy was enabled by the delivery of electrons one-by-one by the photosensitization method. The observation of carbon dioxide dimer radical anion points to approaches for rate enhancements of heterogeneous CO2 reduction by creating catalytic environments that favor formation of this intermediate.
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