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Issue 28, 2020
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Diagnosing surface versus bulk reactivity for molecular catalysis within metal–organic frameworks using a quantitative kinetic model

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Abstract

Metal–organic frameworks (MOFs) are becoming increasingly popular as heterogenous support matrices for molecular catalysts. Given that reactants, or potentially holes/electrons, need to diffuse into the porous framework as the reaction proceeds, the reaction can possibly take place within the bulk of the particle or be confined to a thin layer at the surface due to transport limitations. Herein, a simple steady-state reaction-diffusion kinetic model is developed to diagnose these two mutually exclusive behaviors in MOF-based systems. The oxygen evolution reaction (OER) driven by a chemical oxidant is presented as an example mechanism. Quantitative metrics for assigning either bulk or surface reactivity are delineated over a wide variety of conditions, and numerical simulations are employed to verify these results. For each case, expressions for the turnover frequency (TOF) are outlined, and it is shown that surface reactivity can influence measured TOFs. Importantly, this report shows how to transition from surface to bulk reactivity and thus identifies which experimental parameters to target for optimizing the efficiency of MOF-based molecular catalyst systems.

Graphical abstract: Diagnosing surface versus bulk reactivity for molecular catalysis within metal–organic frameworks using a quantitative kinetic model

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Supplementary files

Article information


Submitted
07 May 2020
Accepted
25 Jun 2020
First published
26 Jun 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 7468-7478
Article type
Edge Article

Diagnosing surface versus bulk reactivity for molecular catalysis within metal–organic frameworks using a quantitative kinetic model

B. A. Johnson and S. Ott, Chem. Sci., 2020, 11, 7468
DOI: 10.1039/D0SC02601H

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