caa a22 4500 606173242 CHVBK 20210128100732.0 cr unu---uuuuu 210128e20150201xx s 000 0 eng 10.1007/s11244-014-0340-2 doi (NATIONALLICENCE)springer-10.1007/s11244-014-0340-2 Electrochemical Reduction of Aqueous Imidazolium on Pt(111) by Proton Coupled Electron Transfer [Elektronische Daten] [Kuo Liao, Mikhail Askerka, Elizabeth Zeitler, Andrew Bocarsly, Victor Batista] Recent electrochemical studies have reported aqueous CO2 reduction to formic acid, formaldehyde and methanol at potentials of ca. −600mV versus SCE, when using a Pt working electrode in acidic pyridine solutions. In those experiments, pyridinium is thought to function as a one-electron shuttle for the underlying multielectron reduction of CO2. DFT studies proposed that the critical step of the underlying reaction mechanism is the one-electron reduction of pyridinium at the Pt surface through proton coupled electron transfer. Such reaction forms a H adsorbate that is subsequently transferred to CO2 as a hydride, through a proton coupled hydride transfer mechanism where pyridinium functions as a Brønsted acid. Here, we find that imidazolium exhibits an electrochemical behavior analogous to pyridinium, as characterized by the experimental and theoretical analysis of the initial reduction on Pt. A cathodic wave, with a cyclic voltammetric half wave potential of ca. −680mV versus SCE, is consistent with the theoretical prediction based on the recently proposed reaction mechanism suggesting that positively charged Brønsted acids could serve as electrocatalytic one-electron shuttle species for multielectron CO2 reduction. Springer Science+Business Media New York, 2014 Imidazolium nationallicence DFT nationallicence CO2 reduction nationallicence Electrocatalysis nationallicence PCET nationallicence Liao Kuo Department of Chemistry, Princeton University, 08544, Princeton, NJ, USA aut Askerka Mikhail Department of Chemistry, Yale University, P.O. Box 208107, 06520, New Haven, CT, USA aut Zeitler Elizabeth Department of Chemistry, Princeton University, 08544, Princeton, NJ, USA aut Bocarsly Andrew Department of Chemistry, Princeton University, 08544, Princeton, NJ, USA aut Batista Victor Department of Chemistry, Yale University, P.O. Box 208107, 06520, New Haven, CT, USA aut Topics in Catalysis Springer US; http://www.springer-ny.com 58/1(2015-02-01), 23-29 1022-5528 58:1<23 2015 58 11244 https://doi.org/10.1007/s11244-014-0340-2 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s11244-014-0340-2 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Liao Kuo Department of Chemistry, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Askerka Mikhail Department of Chemistry, Yale University, P.O. Box 208107, 06520, New Haven, CT, USA aut NATIONALLICENCE 700 1- Zeitler Elizabeth Department of Chemistry, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Bocarsly Andrew Department of Chemistry, Princeton University, 08544, Princeton, NJ, USA aut NATIONALLICENCE 700 1- Batista Victor Department of Chemistry, Yale University, P.O. Box 208107, 06520, New Haven, CT, USA aut NATIONALLICENCE 773 0- Topics in Catalysis Springer US; http://www.springer-ny.com 58/1(2015-02-01), 23-29 1022-5528 58:1<23 2015 58 11244