Dataset Information

Assembly of a Metal-Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO₂ Reduction.

ABSTRACT: Electrochemically active Metal-Organic Frameworks (MOFs) have been progressively recognized for their use in solar fuel production schemes. Typically, they are utilized as platforms for heterogeneous tethering of exceptionally large concentration of molecular electrocatalysts onto electrodes. Yet so far, the potential influence of their extraordinary chemical modularity on electrocatalysis has been overlooked. Herein, we demonstrate that, when assembled on a solid Ag CO₂ reduction electrocatalyst, a non-catalytic UiO-66 MOF acts as a porous membrane that systematically tunes the active site's immediate chemical environment, leading to a drastic enhancement of electrocatalytic activity and selectivity. Electrochemical analysis shows that the MOF membrane improves catalytic performance through physical and electrostatic regulation of reactants delivery towards the catalytic sites. The MOF also stabilizes catalytic intermediates via modulation of active site's secondary coordination sphere. This concept can be expanded to a wide range of proton-coupled electrochemical reactions, providing new means for precise, molecular-level manipulation of heterogeneous solar fuels systems.

SUBMITTER: Mukhopadhyay S

PROVIDER: S-EPMC8251703 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

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Publications

Assembly of a Metal-Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO<sub>2</sub> Reduction.

Mukhopadhyay Subhabrata S Shimoni Ran R Liberman Itamar I Ifraemov Raya R Rozenberg Illya I Hod Idan I

Angewandte Chemie (International ed. in English) 20210505 24

Electrochemically active Metal-Organic Frameworks (MOFs) have been progressively recognized for their use in solar fuel production schemes. Typically, they are utilized as platforms for heterogeneous tethering of exceptionally large concentration of molecular electrocatalysts onto electrodes. Yet so far, the potential influence of their extraordinary chemical modularity on electrocatalysis has been overlooked. Herein, we demonstrate that, when assembled on a solid Ag CO<sub>2</sub> reduction ele ...[more]

PMID: 33755294

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Project description:Several thousands of metal organic frameworks (MOFs) have been reported to date, but the information on H2/N2 separation performances of MOF membranes is currently very limited in the literature. We report the first large-scale computational screening study that combines state-of-the-art molecular simulations, grand canonical Monte Carlo (GCMC) and molecular dynamics (MD), to predict H2 permeability and H2/N2 selectivity of 3765 different types of MOF membranes. Results showed that MOF membranes offer very high H2 permeabilities, 2.5 × 103 to 1.7 × 106 Barrer, and moderate H2/N2 membrane selectivities up to 7. The top 20 MOF membranes that exceed the polymeric membranes' upper bound for H2/N2 separation were identified based on the results of initial screening performed at infinite dilution condition. Molecular simulations were then carried out considering binary H2/N2 and quaternary H2/N2/CO2/CO mixtures to evaluate the separation performance of MOF membranes under industrial operating conditions. Lower H2 permeabilities and higher N2 permeabilities were obtained at binary mixture conditions compared to the ones obtained at infinite dilution due to the absence of multicomponent mixture effects in the latter. Structure-performance relations of MOFs were also explored to provide molecular-level insights into the development of new MOF membranes that can offer both high H2 permeability and high H2/N2 selectivity. Results showed that the most promising MOF membranes generally have large pore sizes (>6 Å) as well as high surface areas (>3500 m2/g) and high pore volumes (>1 cm3/g). We finally examined H2/N2 separation potentials of the mixed matrix membranes (MMMs) in which the best MOF materials identified from our high-throughput screening were used as fillers in various polymers. Results showed that incorporation of MOFs into polymers almost doubles H2 permeabilities and slightly enhances H2/N2 selectivities of polymer membranes, which can advance the current membrane technology for efficient H2 purification.

Dataset Information

Assembly of a Metal-Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO₂ Reduction.

Publications

Assembly of a Metal-Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO<sub>2</sub> Reduction.

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Dataset Information

Assembly of a Metal-Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO2 Reduction.

Publications

Assembly of a Metal-Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO<sub>2</sub> Reduction.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Assembly of a Metal-Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular-Level Control Over Heterogeneous CO₂ Reduction.