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Issue 34, 2020, Issue in Progress
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Mechanochemical defect engineering of HKUST-1 and impact of the resulting defects on carbon dioxide sorption and catalytic cyclopropanation

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Abstract

Metal–organic frameworks (MOFs) are recognized as ideal candidates for many applications such as gas sorption and catalysis. For a long time the properties of these materials were thought to essentially arise from their well-defined crystal structures. It is only recently that the importance of structural defects for the properties of MOFs has been evidenced. In this work, salt-assisted and liquid-assisted grinding were used to introduce defects in a copper-based MOF, namely HKUST-1. Different milling times and post-synthetic treatments with alcohols allow introduction of defects in the form of free carboxylic acid groups or reduced copper(I) sites. The nature and the amount of defects were evaluated by spectroscopic methods (FTIR, XPS) as well as TGA and NH3 temperature-programmed desorption experiments. The negative impact of free –COOH groups on the catalytic cyclopropanation reaction of ethyl diazoacetate with styrene, as well as on the gravimetric CO2 sorption capacities of the materials, was demonstrated. The improvement of the catalytic activity of carboxylic acid containing materials by the presence of CuI sites was also evidenced.

Graphical abstract: Mechanochemical defect engineering of HKUST-1 and impact of the resulting defects on carbon dioxide sorption and catalytic cyclopropanation

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Supplementary files

Article information


Submitted
11 Dec 2019
Accepted
06 May 2020
First published
27 May 2020

This article is Open Access

RSC Adv., 2020,10, 19822-19831
Article type
Paper

Mechanochemical defect engineering of HKUST-1 and impact of the resulting defects on carbon dioxide sorption and catalytic cyclopropanation

T. Steenhaut, N. Grégoire, G. Barozzino-Consiglio, Y. Filinchuk and S. Hermans, RSC Adv., 2020, 10, 19822
DOI: 10.1039/C9RA10412G

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