Role of Bimetallic Interactions in the Enhancement of Catalytic CO2 Reduction by a Macrocyclic Cobalt Catalyst

Polyansky, Dmitry E.; Grills, David C.; Ertem, Mehmed Z.; Ngo, Ken T.; Fujita, Etsuko

doi:10.1021/acscatal.1c05043

Role of Bimetallic Interactions in the Enhancement of Catalytic CO₂ Reduction by a Macrocyclic Cobalt Catalyst

Journal Article · Fri Jan 14 04:00:00 EST 2022 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.1c05043· OSTI ID:1844567

^[1]; ^[1]; ^[1]; Ngo, Ken T. ^[2]; Fujita, Etsuko ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)
Univ. of Massachusetts, Boston, MA (United States)

The use of two metal centers in a CO₂ reduction catalyst that work together synergistically, with similar or complementary functions, can potentially lead to a significant reduction in overpotential, enhance catalytic activity and/or selectivity, and/or enable access to cascade strategies where each metal center catalyzes a different step in the conversion of CO₂ to a fuel. Here, the bimetallic reactivity of two metal centers has been identified as the primary route for the reduction of CO₂ to CO promoted by the macrocycle, [Co(HMD)]²⁺ (HMD = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene), based on the experimental characterization of all major steps of the proposed catalytic cycle using pulse radiolysis time-resolved IR (PR-TRIR) spectroscopy, corroborated by density functional theory (DFT) calculations and IR spectroelectrochemistry (IR-SEC). A bimetallic intermediate is formed in situ from two singly reduced [Co(HMD)]⁺ species bridged by a CO₂ molecule, and the presence of a coordinating species, e.g., formate anion, appears to assist in the formation of such an intermediate. In this work, it has been demonstrated that this reactivity enables access to elementary steps with lower energy requirements, resulting in overall catalysis being kinetically more facile compared to the mononuclear pathway. A two-step approach that combines chemical reduction followed by PR-TRIR has been successfully used for probing the structure and reactivity of reactive intermediates involved in the advanced stages of a catalytic cycle, which are rarely interrogated using experimental techniques.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). Laser-Electron Accelerator Facility (LEAF)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1844567

Report Number(s):: BNL-222709-2022-JAAM

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 3 Vol. 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Role of Bimetallic Interactions in the Enhancement of Catalytic CO2 Reduction by a Macrocyclic Cobalt Catalyst

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References (46)

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