Mechanochemical defect engineering of HKUST-1 and impact of the resulting defects on carbon dioxide sorption and catalytic cyclopropanation. Issue 34 (27th May 2020)

• Record Type: Journal Article
• Authors: Steenhaut, Timothy; Grégoire, Nicolas; Barozzino-Consiglio, Gabriella; Filinchuk, Yaroslav; Hermans, Sophie
• Is Part Of: RSC advances. Volume 10:Issue 34(2020)
• Page Start: 19822
• Page End: 19831
• Publication Date: 2020-05-27
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c9ra10412g
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : Defective HKUST-1 was prepared by salt- or liquid-assisted grinding with post-synthetic treatments with alcohols. The defects identified as free carboxylic acid groups or reduced Cu(i ) sites influence strongly gas storage and catalytic properties. 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 Cu I sites was also evidenced.