D. Esquivel

Facile synthesis of cooperative acid-base catalysts by clicking cysteine and cysteamine on an ethylene-bridged periodic mesoporous organosilica

J. Ouwehand, J. Lauwaert, D. Esquivel, K. Hendrickx, V. Van Speybroeck, J.W. Thybaut, P. Van der Voort
European Journal of Inorganic Chemistry
2016, 13-14, 2144-2151


A Periodic Mesoporous Organosilica (PMO) containing ethylene bridges was functionalized in order to obtain a series of cooperative acid-base catalysts. A straightforward, single-step procedure was devised to immobilize cysteine and cysteamine on the support material via a photoinitiated thiol-ene click reaction. Likewise, PMO materials capped with hexamethyldisilazane (HMDS) were used to support both compounds. This resulted in different materials, where the amine site was promoted by carboxylic acid groups, surface silanol groups or both. The catalysts were tested in the aldol reaction of 4-nitrobenzaldehyde and acetone. It was found that silanol groups have a stronger promoting effect on the amine than the carboxylic acid group. The highest turnover frequency (TOF) was obtained for an amine functionalized material which only contained silanol promoting sites. The loading of the active sites also has a significant effect on the activity of the catalysts, which was rationalized based on a computational study.

Au@UiO-66: a base free oxidation catalyst

K. Leus, P. Concepcion, M. Vandichel, M. Meledina, A. Grirrane, D. Esquivel, S. Turner, D. Poelman, M. Waroquier, V. Van Speybroeck, G. Van Tendeloo, H. Garcia, P. Van der Voort
RSC Advances
5 (29), 22334–22342


We present the in situ synthesis of Au nanoparticles within the Zr based Metal Organic Framework, UiO-66. The resulting Au@UiO-66 materials were characterized by means of N2 sorption, XRPD, UV-Vis, XRF, XPS and TEM analysis. The Au nanoparticles (NP) are homogeneously distributed along the UiO-66 host matrix when using NaBH4 or H2 as reducing agents. The Au@UiO-66 materials were evaluated as catalysts in the oxidation of benzyl alcohol and benzyl amine employing O2 as oxidant. The Au@MOF materials exhibit a very high selectivity towards the ketone (up to 100 %). Regenerability and stability tests demonstrate that the Au@UiO-66 catalyst can be recycled with a negligible loss of Au species and no loss of crystallinity. In situ IR measurements of UiO-66 and Au@UiO-66-NaBH4, before and after treatment with alcohol, showed an increase in IR bands that can be assigned to a combination of physisorbed and chemisorbed alcohol species. This was confirmed by velocity power spectra obtained from the molecular dynamics simulations. Active peroxo and oxo species on Au could be visualized with Raman analysis.

Open Access version available at UGent repository
Subscribe to RSS - D. Esquivel