期刊
TOPICS IN CATALYSIS
卷 58, 期 1, 页码 23-29出版社
SPRINGER/PLENUM PUBLISHERS
DOI: 10.1007/s11244-014-0340-2
关键词
Imidazolium; DFT; CO2 reduction; Electrocatalysis; PCET
资金
- AFOSR [FA9550-13-1-0020]
- Air Force Office of Scientific Research through the MURI program under AFOSR [FA9550-10-1-0572]
- NSF [CHE-1308652]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1308652] Funding Source: National Science Foundation
Recent electrochemical studies have reported aqueous CO2 reduction to formic acid, formaldehyde and methanol at potentials of ca. -600 mV 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 Bronsted 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. -680 mV versus SCE, is consistent with the theoretical prediction based on the recently proposed reaction mechanism suggesting that positively charged Bronsted acids could serve as electrocatalytic one-electron shuttle species for multielectron CO2 reduction.
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