Comprehensive Mechanisms of Electrocatalytic CO2 Reduction by [Ir(bip)(ppy)(CH3CN)](PF6)2
Abstract
Examples of transition metal complexes capable of the dual roles of light harvesting and catalysis of CO2 reduction are rare. This self-sensitized approach simplifies systems and efficiencies; therefore complete understanding of mechanistic principles is essential for improving catalysts. Here we present a comprehensive study of dark reactions using electrochemical techniques to understand the multiple pathways for the selective reduction of CO2 to CO by an example self-sensitized photocatalyst: [Ir(bip)(ppy)(CH3CN)]2+. (bip = 2,6-bis(benzimidazole)pyridine, ppy = 2-phenylpyridine). Cyclic voltammetry (CV) in acetonitrile under anhydrous conditions reveals electrocatalysis by a two electron cycle at -1.7 V vs Fc+/0 (denoted the cat-1 region) in which the metallocarboxylate formed by binding of Ir(I) to CO2 is cleaved by CO2 as the oxide acceptor. At -1.9 V (denoted the cat-2 region) the Ir(CO2) intermediate is reduced and catalysis is accelerated. In the presence of water, the Ir(CO2) is protonated to Ir(CO2H) which is reduced at a potential less negative than -1.7 V and then the oxide acceptor is either CO2 to form HCO3- or protons to release H2O and the conjugate base of the acid source. Further reduction of Ir(CO2H) at cat-2 again accelerates catalysis. Rates vary widely in these various regimes with the minimum kobsmore »
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1637482
- Report Number(s):
- BNL-216111-2020-JAAM
Journal ID: ISSN 2155-5435
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 11; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Citation Formats
Manbeck, Gerald F., Polyansky, Dmitry E., and Fujita, Etsuko. Comprehensive Mechanisms of Electrocatalytic CO2 Reduction by [Ir(bip)(ppy)(CH3CN)](PF6)2. United States: N. p., 2020.
Web. doi:10.1021/acscatal.9b04371.
Manbeck, Gerald F., Polyansky, Dmitry E., & Fujita, Etsuko. Comprehensive Mechanisms of Electrocatalytic CO2 Reduction by [Ir(bip)(ppy)(CH3CN)](PF6)2. United States. https://doi.org/10.1021/acscatal.9b04371
Manbeck, Gerald F., Polyansky, Dmitry E., and Fujita, Etsuko. Wed .
"Comprehensive Mechanisms of Electrocatalytic CO2 Reduction by [Ir(bip)(ppy)(CH3CN)](PF6)2". United States. https://doi.org/10.1021/acscatal.9b04371. https://www.osti.gov/servlets/purl/1637482.
@article{osti_1637482,
title = {Comprehensive Mechanisms of Electrocatalytic CO2 Reduction by [Ir(bip)(ppy)(CH3CN)](PF6)2},
author = {Manbeck, Gerald F. and Polyansky, Dmitry E. and Fujita, Etsuko},
abstractNote = {Examples of transition metal complexes capable of the dual roles of light harvesting and catalysis of CO2 reduction are rare. This self-sensitized approach simplifies systems and efficiencies; therefore complete understanding of mechanistic principles is essential for improving catalysts. Here we present a comprehensive study of dark reactions using electrochemical techniques to understand the multiple pathways for the selective reduction of CO2 to CO by an example self-sensitized photocatalyst: [Ir(bip)(ppy)(CH3CN)]2+. (bip = 2,6-bis(benzimidazole)pyridine, ppy = 2-phenylpyridine). Cyclic voltammetry (CV) in acetonitrile under anhydrous conditions reveals electrocatalysis by a two electron cycle at -1.7 V vs Fc+/0 (denoted the cat-1 region) in which the metallocarboxylate formed by binding of Ir(I) to CO2 is cleaved by CO2 as the oxide acceptor. At -1.9 V (denoted the cat-2 region) the Ir(CO2) intermediate is reduced and catalysis is accelerated. In the presence of water, the Ir(CO2) is protonated to Ir(CO2H) which is reduced at a potential less negative than -1.7 V and then the oxide acceptor is either CO2 to form HCO3- or protons to release H2O and the conjugate base of the acid source. Further reduction of Ir(CO2H) at cat-2 again accelerates catalysis. Rates vary widely in these various regimes with the minimum kobs of 0.3 s-1 for anhydrous cat-1 to a maximum cat-2 rate of 2100 s-1 with 1% water. Competitive deactivation pathways were discovered as Ir-Ir dimerization without reacting with CO2 or the formation of a hydride-bridged dinuclear complex during extended electrolysis at high water concentration. The Ir-Ir dimer was characterized by high-resolution mass spectrometry and X-ray absorption spectroscopy (XAS).},
doi = {10.1021/acscatal.9b04371},
journal = {ACS Catalysis},
number = 11,
volume = 10,
place = {United States},
year = {Wed May 27 00:00:00 EDT 2020},
month = {Wed May 27 00:00:00 EDT 2020}
}
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