Dataset Information

Tuning the Proton-Coupled Electron-Transfer Rate by Ligand Modification in Catalyst-Dye Supramolecular Complexes for Photocatalytic Water Splitting.

ABSTRACT: In view of the considerably high activation energy barrier of the O-O bond formation photocatalytic step in water oxidation, it is essential to understand if and how nonadiabatic factors can accelerate the proton-coupled electron transfer (PCET) rate in this process to find rational design strategies facilitating this step. Herein, constrained ab initio molecular dynamics simulations are performed to investigate this rate-limiting step in a series of catalyst-dye supramolecular complexes functionalized with different alkyl groups on the catalyst component. These structural modifications lead to tunable thermodynamic driving forces, PCET rates, and vibronic coupling with specific resonant torsional modes. These results reveal that such resonant coupling between electronic and nuclear motions contributes to crossing catalytic barriers in PCET reactions by enabling semiclassical coherent conversion of a reactant into a product. Our results provide insight on how to engineer efficient catalyst-dye supramolecular complexes by functionalization with steric substituents for high-performance dye-sensitized photoelectrochemical cells.

SUBMITTER: Yang

PROVIDER: S-EPMC7821158 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

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Publications

Tuning the Proton-Coupled Electron-Transfer Rate by Ligand Modification in Catalyst-Dye Supramolecular Complexes for Photocatalytic Water Splitting.

Yang de Groot Huub J M HJM Buda Francesco F

ChemSusChem 20200915 1

In view of the considerably high activation energy barrier of the O-O bond formation photocatalytic step in water oxidation, it is essential to understand if and how nonadiabatic factors can accelerate the proton-coupled electron transfer (PCET) rate in this process to find rational design strategies facilitating this step. Herein, constrained ab initio molecular dynamics simulations are performed to investigate this rate-limiting step in a series of catalyst-dye supramolecular complexes functio ...[more]

PMID: 32871047

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Project description:Designing molecular platforms for controlling proton and electron movement in artificial photosynthetic systems is crucial to efficient catalysis and solar energy conversion. The transfer of both protons and electrons during a reaction is known as proton-coupled electron transfer (PCET) and is used by nature in myriad ways to provide low overpotential pathways for redox reactions and redox leveling, as well as to generate bioenergetic proton currents. Herein, we describe theoretical and electrochemical studies of a series of bioinspired benzimidazole-phenol (BIP) derivatives and a series of dibenzimidazole-phenol (BI2P) analogs with each series bearing the same set of terminal proton-accepting (TPA) groups. The set of TPAs spans more than 6 pK a units. These compounds have been designed to explore the role of the bridging benzimidazole(s) in a one-electron oxidation process coupled to intramolecular proton translocation across either two (the BIP series) or three (the BI2P series) acid/base sites. These molecular constructs feature an electrochemically active phenol connected to the TPA group through a benzimidazole-based bridge, which together with the phenol and TPA group form a covalent framework supporting a Grotthuss-type hydrogen-bonded network. Infrared spectroelectrochemistry demonstrates that upon oxidation of the phenol, protons translocate across this well-defined hydrogen-bonded network to a TPA group. The experimental data show the benzimidazole bridges are non-innocent participants in the PCET process in that the addition of each benzimidazole unit lowers the redox potential of the phenoxyl radical/phenol couple by 60 mV, regardless of the nature of the TPA group. Using a series of hypothetical thermodynamic steps, density functional theory calculations correctly predicted the dependence of the redox potential of the phenoxyl radical/phenol couple on the nature of the final protonated species and provided insight into the thermodynamic role of dibenzimidazole units in the PCET process. This information is crucial for developing molecular "dry proton wires" with these moieties, which can transfer protons via a Grotthuss-type mechanism over long distances without the intervention of water molecules.

Dataset Information

Tuning the Proton-Coupled Electron-Transfer Rate by Ligand Modification in Catalyst-Dye Supramolecular Complexes for Photocatalytic Water Splitting.

Publications

Tuning the Proton-Coupled Electron-Transfer Rate by Ligand Modification in Catalyst-Dye Supramolecular Complexes for Photocatalytic Water Splitting.

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