Effects of crystallinity and different amines on the acid-base catalytic properties of amine-grafted H-aluminosilicates

• Grant number: 21/08326-9
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate
• Start date: December 01, 2021
• End date: November 30, 2022
• Field of knowledge: Engineering - Chemical Engineering - Chemical Technology
• Principal Investigator: Dilson Cardoso
• Grantee: Iago William Zapelini
• Supervisor: Svetlana Mintova
• Host Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil
• Institution abroad: École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), France
• Associated to the scholarship: 18/21136-1 - Embryonic zeolites: a novel catalyst for cascade reactions, BP.DR

Abstract

Zeolites are aluminosilicates that can show Brønsted acidity when in protonic form. As the microporous structure of the zeolite is formed, its total acidity becomes greater. However, in parallel, there is a confinement of acidic sites inside the zeolite structure, reducing its accessibility. In this sense, less crystallized materials can present, in various reactions, greater catalytic activity. This class of partially formed aluminosilicates has received particular attention in recent years as a promising class of catalysts for reactions involving bulky molecules. These zeolitic precursors also have many surface silanols, which can be used for anchoring functional groups, such as amines derived from silanes, adding basic properties to protonic aluminosilicates. In this proposal, we intend to evaluate the use of partially crystallized acidic aluminosilicates to the functionalization with amino silanes, producing acid-base catalysts, focusing on reducing diffusion limitation for applications in reactions with bulky molecules. H-ZSM-5 zeolites and their precursors with different crystallinities and Si/Al ratios will be prepared and functionalized with (3-Aminopropyl)-trimethoxy silane (APTMS), Trimethoxy[3-(methylamino)propyl] silane (MAPTMS), or (N,N-Dimethylaminopropyl)trimethoxy silane (DMAPTS). These solids will be used as catalysts in acid deacetalization of benzaldehyde dimethyl acetal, followed by Knoevenagel condensation with ethyl cyanoacetate, a model reaction for evaluating acid-base catalysts. This proposal for international collaboration will allow the evaluation of the physicochemical properties of zeolite precursors with advanced characterization techniques, mainly aimed at the study of acidic and basic sites with probe molecules, allowing the development of new materials for series reactions with bulky molecules. (AU)

Scientific publications

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

LIMA, DIEGO S. D.; SILVA, LAURA L. L.; ZAPELINI, IAGO W. W.; MINTOVA, SVETLANA; MARTINS, LEANDRO. Tailoring the accessibility and amphiphilicity of MWW zeolites for two-phase glycerol ketalization. INORGANIC CHEMISTRY FRONTIERS, v. 10, n. 19, p. 13-pg., 2023-08-23. (17/21965-5, 22/01789-6, 21/08326-9, 18/01258-5, 19/12486-1)

ZAPELINI, IAGO WILLIAM; DA SILVA, LAURA LORENA; MINTOVA, SVETLANA; CARDOSO, DILSON. Amine-grafted H-MFI zeolite precursors as acidic-basic catalysts for deacetalization-Knoevenagel condensation. Microporous and Mesoporous Materials, v. 362, p. 8-pg., 2023-09-01. (18/21136-1, 21/08326-9)