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Energy-efficient CO₂/CO interconversion by homogeneous copper-based molecular catalysts.

ABSTRACT: Facile conversion of CO₂ to commercially viable carbon feedstocks offer a unique way to adopt a net-zero carbon scenario. Synthetic CO₂-reducing catalysts have rarely exhibited energy-efficient and selective CO₂ conversion. Here, the carbon monoxide dehydrogenase (CODH) enzyme blueprint is imitated by a molecular copper complex coordinated by redox-active ligands. This strategy has unveiled one of the rarest examples of synthetic molecular complex-driven reversible CO₂ reduction/CO oxidation catalysis under regulated conditions, a hallmark of natural enzymes. The inclusion of a proton-exchanging amine groups in the periphery of the copper complex provides the leeway to modulate the biases of catalysts toward CO₂ reduction and CO oxidation in organic and aqueous media. The detailed spectroelectrochemical analysis confirms the synchronous participation of copper and redox-active ligands along with the peripheral amines during this energy-efficient CO₂ reduction/CO oxidation. This finding can be vital in abating the carbon footprint-free in multiple industrial processes.

SUBMITTER: Guria S

PROVIDER: S-EPMC10611766 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature

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Energy-efficient CO2/CO interconversion by homogeneous copper-based molecular catalysts.

Guria Somnath S Dolui Dependu D Das Chandan C Ghorai Santanu S Vishal Vikram V Maiti Debabrata D Lahiri Goutam Kumar GK Dutta Arnab A

Nature communications 20231027 1

Facile conversion of CO2 to commercially viable carbon feedstocks offer a unique way to adopt a net-zero carbon scenario. Synthetic CO2-reducing catalysts have rarely exhibited energy-efficient and selective CO2 conversion. Here, the carbon monoxide dehydrogenase (CODH) enzyme blueprint is imitated by a molecular copper complex coordinated by redox-active ligands. This strategy has unveiled one of the rarest examples of synthetic molecular complex-driven reversib ...[more]

PMID: 37891216

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Project description:To facilitate computational investigation of intermolecular interactions in the solution phase, we report the development of ALMO-EDA(solv), a scheme that allows the application of continuum solvent models within the framework of energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs). In this scheme, all the quantum mechanical states involved in the variational EDA procedure are computed with the presence of solvent environment so that solvation effects are incorporated in the evaluation of all its energy components. After validation on several model complexes, we employ ALMO-EDA(solv) to investigate substituent effects on two classes of complexes that are related to molecular CO2 reduction catalysis. For [FeTPP(CO2-κC)]2- (TPP = tetraphenylporphyrin), we reveal that two ortho substituents which yield most favorable CO2 binding, -N(CH3)3 + (TMA) and -OH, stabilize the complex via through-structure and through-space mechanisms, respectively. The coulombic interaction between the positively charged TMA group and activated CO2 is found to be largely attenuated by the polar solvent. Furthermore, we also provide computational support for the design strategy of utilizing bulky, flexible ligands to stabilize activated CO2 via long-range Coulomb interactions, which creates biomimetic solvent-inaccessible "pockets" in that electrostatics is unscreened. For the reactant and product complexes associated with the electron transfer from the p-terphenyl radical anion to CO2, we demonstrate that the double terminal substitution of p-terphenyl by electron-withdrawing groups considerably strengthens the binding in the product state while moderately weakens that in the reactant state, which are both dominated by the substituent tuning of the electrostatics component. These applications illustrate that this new extension of ALMO-EDA provides a valuable means to unravel the nature of intermolecular interactions and quantify their impacts on chemical reactivity in solution.

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Energy-efficient CO₂/CO interconversion by homogeneous copper-based molecular catalysts.

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Energy-efficient CO<sub>2</sub>/CO interconversion by homogeneous copper-based molecular catalysts.

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