Comprehensive Mechanisms of Electrocatalytic CO2 Reduction by [Ir(bip)(ppy)(CH3CN)](PF6)2

Manbeck, Gerald F.; Polyansky, Dmitry E.; Fujita, Etsuko

doi:10.1021/acscatal.9b04371

Title: Comprehensive Mechanisms of Electrocatalytic CO₂ Reduction by [Ir(bip)(ppy)(CH₃CN)](PF₆)₂

Journal Article · Wed May 27 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b04371· OSTI ID:1637482

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Brookhaven National Lab. (BNL), Upton, NY (United States)

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).

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1637482

Report Number(s):: BNL-216111-2020-JAAM

Journal Information:: ACS Catalysis, Vol. 10, Issue 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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