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Pre-equilibrium reactions involving pendent relays improve CO reduction mediated by molecular Cr-based electrocatalysts. | LitMetric

AI Article Synopsis

  • - The development of earth-abundant transition-metal electrocatalysts for CO2 reduction aims to reduce harmful CO emissions by creating valuable chemical products.
  • - Previous studies revealed that the efficiency of Cr-centered bipyridine-based complexes is limited by a slow proton-transfer step during carbon-oxygen bond breakdown.
  • - Introducing a methoxy group in the catalyst's structure enhances its activity and selectivity in converting CO2 to CO, especially when paired with a cationic acid, indicating that optimizing the secondary coordination sphere can improve catalytic performance.

Article Abstract

Homogeneous earth abundant transition-metal electrocatalysts capable of carbon dioxide (CO) reduction to generate value-added chemical products are a possible strategy to minimize rising anthropogenic CO emissions. Previously, it was determined that Cr-centered bipyridine-based NO complexes for CO reduction are kinetically limited by a proton-transfer step during C-OH bond cleavage. Therefore, it was hypothesized that the inclusion of pendent relay groups in the secondary coordination sphere of these molecular catalysts could increase their catalytic activity. Here, it is shown that the introduction of a pendent methoxy group favorably impacts a pre-equilibrium protonation prior to the catalytic resting state, resulting in a significant increase in catalytic activity without a loss of product selectivity for generating carbon monoxide (CO) from CO. Interestingly, combining the pendent methoxy group with a cationic acid causes a positive shift of the catalytic reduction potential of the system, while maintaining increased activity and quantitative selectivity. This work suggests that tuning the secondary coordination sphere with respect to cationic proton sources can result in activity improvements by modifying the kinetic and thermodynamic aspects of proton transfer in the catalytic cycle.

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Source
http://dx.doi.org/10.1039/d4dt01981dDOI Listing

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