Issue 28, 2020
From the journal:

Chemical Science

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

Ben A. Johnson ORCID logo *a  and  Sascha Ott ORCID logo *a  

* Corresponding authors

a Department of Chemistry, Ångström Laboratory, Uppsala University, Box 523, 751 20 Uppsala, Sweden
E-mail: ben.johnson@kemi.uu.se, sascha.ott@kemi.uu.se

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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Article information

DOI
https://doi.org/10.1039/D0SC02601H
Article type
Edge Article
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
Creative Commons BY-NC license

Chem. Sci., 2020,11, 7468-7478

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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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