Carbon Dioxide Dimer Radical Anion as Surface Intermediate of Photoinduced CO 2 Reduction at Aqueous Cu and CdSe Nanoparticle Catalysts by Rapid-Scan FT-IR Spectroscopy.

التفاصيل البيبلوغرافية
العنوان:	Carbon Dioxide Dimer Radical Anion as Surface Intermediate of Photoinduced CO 2 Reduction at Aqueous Cu and CdSe Nanoparticle Catalysts by Rapid-Scan FT-IR Spectroscopy.
المؤلفون:	Sheng H; Molecular Biophysics and Integrated Bioimaging Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States., Oh MH; Materials Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.; Department of Chemistry , University of California , Berkeley , California 94720 , United States., Osowiecki WT; Materials Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.; Department of Chemistry , University of California , Berkeley , California 94720 , United States., Kim W; Molecular Biophysics and Integrated Bioimaging Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States., Alivisatos AP; Materials Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.; Department of Chemistry , University of California , Berkeley , California 94720 , United States.; Department of Materials Science and Engineering , University of California , Berkeley , California 94720 , United States.; Kavli Energy NanoScience Institute , Berkeley , California 94720 , United States., Frei H; Molecular Biophysics and Integrated Bioimaging Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.
المصدر:	Journal of the American Chemical Society [J Am Chem Soc] 2018 Mar 28; Vol. 140 (12), pp. 4363-4371. Date of Electronic Publication: 2018 Mar 15.
نوع المنشور:	Journal Article; Research Support, U.S. Gov't, Non-P.H.S.
اللغة:	English
بيانات الدورية:	Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: PubMed not MEDLINE
أسماء مطبوعة:	Publication: Washington, DC : American Chemical Society Original Publication: Easton, Pa. [etc.]
مستخلص:	Monitoring of visible light sensitized reduction of CO 2 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 ( ¹² C: 1632, 1358, 1346 cm ^-1 ; ¹³ C: 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)OCO 2 ^- surface species is in agreement with a recently proposed mechanism for electrocatalytic CO 2 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 HCO 3 ^- . CO was produced as well, but sensitive detection required photolysis for tens of minutes. A direct kinetic link between a C 2 O 4 ^- surface intermediate and the CO product was also demonstrated for photocatalyzed CO 2 reduction at aqueous CdSe nanoparticles, where first order growth of a Cd-C(═O)OCO 2 ^- species was accompanied by rise of CO (monitored by a fast Ni complex trap) and HCO 3 ^- 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 CO 2 reduction by creating catalytic environments that favor formation of this intermediate.
تواريخ الأحداث:	Date Created: 20180310 Date Completed: 20180608 Latest Revision: 20180608
رمز التحديث:	20240829
DOI:	10.1021/jacs.8b00271
PMID:	29522319
قاعدة البيانات:	MEDLINE

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الوصف
تدمد:	1520-5126
DOI:	10.1021/jacs.8b00271