MULTI-site organic-inorganic HYbrid CATalysts for MULTI-step chemical processes

Informations projet

MULTI2HYCAT

N° de convention de subvention: 720783

DOI

10.3030/720783

Projet clôturé

Date de signature de la CE 22 Novembre 2016

Date de début 1 Janvier 2017

Date de fin 30 Juin 2021

Financé au titre de

• INDUSTRIAL LEADERSHIP - Leadership in enabling and industrial technologies - Advanced materials

Coût total

€ 5 346 957,50

Contribution de l’UE

€ 5 346 957,50

Coordonné par

UNIVERSITA DEGLI STUDI DEL PIEMONTE ORIENTALE AMEDEO AVOGADRO
Italy

Periodic Reporting for period 3 - MULTI2HYCAT (MULTI-site organic-inorganic HYbrid CATalysts for MULTI-step chemical processes)

Période du rapport: 2020-01-01 au 2021-06-30

Résumé du contexte et des objectifs généraux du projet

The main objective of MULTI2HYCAT is to design, obtain proof of concept (2 gr.), upscale and obtain industrial validation in a pre-pilot reactor (20-50 gr.) of a new class of hierarchically porous organic-inorganic hybrids to be used as catalysts to carry out multi-step asymmetric catalytic processes with predominantly high conversions (up to 90%) and selectivity (in the range of 80- 90%) towards the desired products. The project promises to solve the limits of current organosiliceous solids, while at the same time improving the flexibility and versatility and reducing catalyst costs, making them attractive for a wide range of industrial applications. These novel catalysts will be demonstrated for pharmaceutical and intermediate chemistry applications, as a concrete prime-mover for subsequent replication. The development of efficient catalytic processes, where different individual steps are involved, is an important challenge for the current industry to obtain valuable chemical products with high economic rentability, following environmentally friendly production routes.
MULTI2HYCAT will contribute to the implementation of the EU policies and Directives on competitiveness and sustainability through the validation of novel concepts in hybrid materials design for heterogeneous catalysis. This includes the preparation and validation of innovative organic-inorganic hybrids with several active sites perfectly located in specific structural positions in their framework which will be used as single-solid reusable catalysts to carry out multi-step catalytic processes with high conversions and selectivities towards the desired products. The new materials will allow avoiding the extra-efforts associated with isolation of intermediate products, wastes and solvents elimination and purification processes thus enabling more efficient and sustainable catalytic routes from the economic, energetic as well as the environmental points of view.

Travail effectué depuis le début du projet jusqu’à la fin de la période considérée dans le rapport et principaux résultats atteints jusqu’à présent

At the beginning (M1-M18), the most suitable monomer precursors as active sites in the organic-inorganic hybrids were identified considering the C-C bond forming transformations, coupling reactions, aldol condensation, rearrangements and(stereo)selective reductions.
During the second period (M19-M36), the research was focused in the development of multi-site hybrid catalysts. Several synthetic strategies were explored to produce a multi-site platforms to be anchored on inorganic supports. The catalytic results evidenced that the 2nd generation platforms based on BAM-BINAP showed potential application in tandem reactions. In fact, as two primary amines are included in BAM-BINAP, one of them could act as a reactive group for the linking to the surface of the inorganic support, while the other operates as an active site for base-catalysed reactions, along with the diphosphine, once the latter is coordinated to a Pd or Ru. Simultaneously, the research continued on the development of mono-functional Pd-based hybrids, in particular Pd(DPPF)Cl2 was anchored on silicas to catalyse a Suzuki reaction of interest for ALM. Pd-based hybrid catalysts evidenced good catalytic performances in Suzuki reaction and good recyclability.
During the third period (M37-M54), all partners were working on the optimization of multi-functional hybrids for tandem reactions combining basic or acid active sites with metals, despite the impact of the COVID-19 outbreak. Some good results have been obtained with the multi-site Pd-BAM-BINAP-MCM-41 in Suzuki/Aldol condensation tandem reaction with 100% conversion and good recyclability and with multi-site Pd-NH2-MCM-41 in Aldol condensation/Hydrogenation tandem reaction. In parallel, an hybrid catalyst (Pd-NHC-Silica) for Suzuki coupling of ALM’s target reaction has also been tested by ALM with an excellent yield (>90%), good recyclability, and very low Pd residue compared to the commercial homogeneous catalyst used for this reaction. Different types of asymmetric hybrid catalysts were also synthesised and tested in asymmetric reaction during the last period, in particular secondary amine anchored on silica surfaces have shown promising result in cyclopropanation reactions.

Progrès au-delà de l’état des connaissances et impact potentiel prévu (y compris l’impact socio-économique et les conséquences sociétales plus larges du projet jusqu’à présent)

The main innovations of the project with respect to the State of the art are:
1. Design of novel multi-functional hybrid catalysts from innovative organosiloxane precursors with unique catalytic properties.
2. Validation of advanced methodologies to obtain a broad variety of multi-functional catalysts with a precise and tunable distribution of accessible sites affording complex cascade reactions for the synthesis of high value fine chemicals and pharmaceutical products.
3. In silico design of catalyst precursors to rationalise the level of synergy between nearby sites for carrying out cascade reactions.
4. Probing confinement effects by combining smart experiments with refined characterisation analyses and simulations to establish structure-property correlations.
5. Design of catalysts with adjustable hydrophilic/hydrophobic balance (HLB) properties near the catalytic sites, with high potential for running solvent-free biphasic reactions.
6. Comparison of concerted and multifunctional catalysis using a design-application approach.
7. Possibility to design and realise intensified and greener processes affording a reduction of the carbon footprint and eco-toxicity by reducing the energy demand, use of solvents, water consumption and salt generation.
8. Capacity of achieving a high level of standarisation of catalytic preparation protocols, reaction products and intermediates, and catalytic processes.
In line with the Europe 2020 strategy, MULTI2HYCAT envisions a transition towards a green, low carbon, energy and resource-efficient circular economy as essential to achieve smart, sustainable, and inclusive growth.
The MULTI2HYCAT solutions will bring relevant impacts at different levels:
- Innovation and Advance of Knowledge: the novel hybrids are the result of the combination of breakthrough innovations in multisite catalyst design, computational modelling, overall process intensification and optimisation, through the concerted collaboration among top players of the EU scientific community and industry with a sound multidisciplinary and inter-sectorial approach.
- Global markets & competitiveness: the MULTI2HYCAT project aims at boosting green and sustainable economic growth, which constitutes a key driver for new business, investment and competitiveness in Europe during the next 30 years. The project will impact the pharmaceutical and intermediate chemical industries in the whole value chain. MULTI2HYCAT will offer a platform for delivering innovations from academia to the markets via a coherent strategy led by a multidisciplinary team of prime scientific actors and business experts.
- Environment and resource efficiency: MULTI2HYCAT intends to impact the carbon footprint and the eco-toxicity of several current industrial processes where catalysts play a role, including large parts of the pharmaceutical and chemical industries, via either a smart redesign or the eco-conception of new processes involving cascade reactions.
- Policies and Directives: MULTI2HYCAT is fully in line and will contribute to a better implementation of the main EU strategic policies and Directives for environmental protection and transition to a green, low-carbon, energy and resource-efficient economy and will contribute to their implementation.

Figure 1.1: Multifunctional hybrid materials as multisite catalysts for consecutive or cascade react