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Report

Teaser, summary, work performed and final results

Periodic Reporting for period 1 - MULTI2HYCAT (MULTI-site organic-inorganic HYbrid CATalysts for MULTI-step chemical processes)

Teaser

Summary

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 (Fig.1.1). 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.

Work performed

During the 18M period of the project, UPO, CAGE, CSIC, UoS, CNRS and SOL have started the research activity, while PNO-CTECH the dissemination and exploitation activity. The most suitable monomer precursors to act as active sites in the organic-inorganic hybrids have been identified considering the C-C bond forming transformations, coupling reactions, aldol condensation and Michael addition, rearrangements and stereo-selective reductions. Pd-Najera and Pd(DPPF)Cl2 complexes have been selected for Suzuki reactions and CBS (Corey-Bakshi-Shibata) organocatalysts for stereoselective reductions. These precursors have been synthesized by CAGE in WP2 with a spacer-linker moiety bearing a reactive functional group necessary to graft the organic moieties on the surface of the inorganic supports, synthesized by CSIC in WP3. Simultaneously, monofunctional and multifunctional hybrids with super-acid s and/or super-base functionalities supported on mesoporous silicas have been synthesized by CSIC in WP3. The synthetic activity was supported by experimental and computational physico-chemical characterization by UPO in WP4. The characterization provided information on surface features, density and type of silanols available for functionalization after activation at different temperatures. Such information is relevant for the planning of the grafting reactions as well as for the selection of the more suitable silica surface models employed in the computational studies. Hierarchical inorganic supports have also been synthesized by UPO and delivered to CSIC, UoS and CNRS. A detailed physico-chemical characterization has also been performed by UPO on hybrid catalysts synthesized by CSIC and UoS in order to get insight into the nature and strength of the active sites. The hybrids produced by CSIC and hierarchical porous acid catalysts produced by UPO were catalytically tested by UoS in WP5 at lab-scale and CNRS in WP6. Moreover, the hierarchical acid silicoaluminophosphates (HP-SAPO) materials synthesized by UPO were functionalized by CSIC in WP3 by grafting different base silyl-derivatives and by UoS in WP5 by grafting N-heterocyclic carbenes (NHC). These hybrid catalysts were tested by UoS and CNRS.

Final results

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.