Preparation of novel hybrid catalyst with an hierarchical micro-/mesoporous structure by direct growth of the HKUST-1 nanoparticles inside mesoporous silica matrix (MMS)

• Published in: Microporous and mesoporous materials Vol. 300; p. 110136
• Main Authors: Isaeva, V.I., Chernyshev, V.V., Fomkin, A.A., Shkolin, A.V., Veselovsky, V.V., Kapustin, G.I., Sokolova, N.A., Kustov, L.M.
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 15.06.2020
• Subjects: Catalysis; Condensation reaction; Hierarchical porous structure; Hybrid materials; Mesoporous silica matrix; MOF NPs; Condensation reaction; Catalysis; Hierarchical porous structure; Hybrid materials; MOF NPs; Mesoporous silica matrix
• ISSN: 1387-1811; 1873-3093
• DOI: 10.1016/j.micromeso.2020.110136

A novel hybrid material was prepared by the direct growth technique starting from metal-organic framework HKUST-1 (Cu3(BTC)2, BTC = benzene-1,3,5-tricarboxylate) and mesoporous silica matrix (MMS). MMS acts as a structure-directing agent, which assists to the formation of very small HKUST-1 nanoparticles (4–8 nm) are dispersed homogeneously in the silica matrix. To evaluate the field of the potential exploitation of HKUST-1@MMS hybrid, it was examined as a heterogeneous catalyst with Lewis and Brønsted acid sites in demanding organic transformations widely used for fine chemicals production, i.e. in the Friedlӓnder reaction between 2-amino-5-chlorobenzophenone and acetylacetone and Henry reaction (nitroaldol condensation) between nitromethane and 4-nitrobenzaldehyde. The cooperative effect between Lewis acid sites as Cu2+ ions in the HKUST-1 framework and acid sites of MMs silica in the HKUST-1@MMS catalytic material relevant to the Henry reaction between 4-nitrobenzaldehyde and nitromethane was found for the first time. According to adsorption tests, the novel hybrid features an hierarchical micro-/mesoporous structure and can also find application as an adsorbent with molecular-sieving properties. [Display omitted] •Novel HKUST-1@MMS hybrid material was synthesized in-situ using mesoporous silica.•Very small MOF nanoparticles (4–8 nm) were encapsulated in the MMS matrix.•Hierarchical micro/mesoporous structure of the novel HKUST-1@MMS hybrid is revealed.•The hybrid catalyzes selectively the Friedlӓnder and Henry reactions.