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Thermodynamic Considerations for Optimizing Selective CO₂ Reduction by Molecular Catalysts.

ABSTRACT: Energetically efficient electrocatalysts with high product selectivity are desirable targets for sustainable chemical fuel generation using renewable electricity. Recycling CO₂ by reduction to more energy dense products would support a carbon-neutral cycle that mitigates the intermittency of renewable energy sources. Conversion of CO₂ to more saturated products typically requires proton equivalents. Complications with product selectivity stem from competitive reactions between H⁺ or CO₂ at shared intermediates. We describe generalized catalytic cycles for H₂, CO, and HCO₂ ^- formation that are commonly proposed in inorganic molecular catalysts. Thermodynamic considerations and trends for the reactions of H⁺ or CO₂ at key intermediates are outlined. A quantitative understanding of intermediate catalytic steps is key to designing systems that display high selectivity while promoting energetically efficient catalysis by minimizing the overall energy landscape. For CO₂ reduction to CO, we describe how an enzymatic active site motif facilitates efficient and selective catalysis and highlight relevant examples from synthetic systems.

SUBMITTER: Barlow JM

PROVIDER: S-EPMC6487447 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Thermodynamic Considerations for Optimizing Selective CO2 Reduction by Molecular Catalysts.

Barlow Jeffrey M JM Yang Jenny Y JY

ACS central science 20190312 4

Energetically efficient electrocatalysts with high product selectivity are desirable targets for sustainable chemical fuel generation using renewable electricity. Recycling CO2 by reduction to more energy dense products would support a carbon-neutral cycle that mitigates the intermittency of renewable energy sources. Conversion of CO2 to more saturated products typically requires proton equivalents. Complications with product selectivity stem from competitive reactions betw ...[more]

PMID: 31041377

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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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Thermodynamic Considerations for Optimizing Selective CO₂ Reduction by Molecular Catalysts.

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Thermodynamic Considerations for Optimizing Selective CO<sub>2</sub> Reduction by Molecular Catalysts.

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