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Electrocatalytic CO 2 reduction is an attractive strategy to mitigate the continuous rise in atmospheric CO 2 concentrations and generate value-added chemical products. A possible strategy to increase the activity of molecular systems for these reactions is the co-catalytic use of redox mediators (RMs), which direct reducing equivalents from the electrode surface to the active site. Recently, we demonstrated that a sulfone-based RM could trigger co-electrocatalytic CO 2 reduction via an inner-sphere mechanism under aprotic conditions. Here, we provide support for inner-sphere cooperativity under protic conditions by synthetically modulating the mediator to increase activity at lower overpotentials (inverse potential scaling). Furthermore, we show that both the intrinsic and co-catalytic performance of the Cr-centered catalyst can be enhanced by ligand design. By tuning both the Cr-centered catalyst and RM appropriately, an optimized co-electrocatalytic system with quantitative selectivity for CO at an overpotential ( η ) of 280 mV and turnover frequency (TOF) of 194 s −1 is obtained, representing a three-fold increase in co-catalytic activity at 130 mV lower overpotential than our original report. Importantly, this work lays the foundation of a powerful tool for developing co-catalytic systems for homogeneous electrochemical reactions.
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This content will become publicly available on February 1, 2026
Engineered metallobiocatalysts for energy–relevant reactions
Engineering metallobiocatalysts is a promising approach to addressing challenges in energy-relevant electrocatalysis and photocatalysis. The design freedom provided by semisynthetic and fully synthetic approaches to catalyst design allows researchers to demonstrate how structural modifications can improve selectivity and activity of biocatalysts. Furthermore, the provision of a superstructure in many metallobiocatalysts facilitates active-site microenvironment engineering. Recurring themes include the role of the biomolecular scaffold in enhancing reactivity in water and catalyst robustness, the impact of the outer sphere on reactivity, and the importance of tuning system components in full system optimization. In this perspective, recent strategies to design and modify novel biocatalysts, understand proton and electron transfer mechanisms, and tune system activity by modifying catalysts and system conditions are highlighted within the field of energy-related catalysis. Opportunities in this field include developing robust structure-function relationships to support approaches to engineering second-sphere interactions and identifying ways to enhance biocatalyst activity over time.
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- Award ID(s):
- 2108219
- PAR ID:
- 10656339
- Publisher / Repository:
- Elsevier, Current Opinion in Chemical Biology
- Date Published:
- Journal Name:
- Current Opinion in Chemical Biology
- Volume:
- 84
- ISSN:
- 1367-5931
- Page Range / eLocation ID:
- 102545
- Subject(s) / Keyword(s):
- Artificial enzyme hydrogen evolution carbon dioxide reduction de novo design semisynthetic protein engineered biocatalyst
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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