Periodic Reporting for period 1 - ZEOCATALYST (Development of Multifunctional Zeolites for the Amelioration of Biomass Catalysis by Measuring and Understanding Synergistic Effects of Catalytic Active Sites)
Période du rapport: 2019-03-01 au 2021-02-28
Custom manufacturing of fine chemicals such as fuels, solvents, additives and value-added functional materials is a vital part of modern industrial chemistry. Increasing demand for the production of such chemicals and materials necessitates the development of sustainable approaches. Biomass valorization is a potential solution to this problem; however, several challenges must be overcome to efficiently transform highly cross-linked biopolymers into desired chemicals using different valorization routes. The main goal of ZEOCATALYST project was to gain molecular level insight into the biomass valorization processes including zeolite based heterogenous catalysis and biomass derived functional materials. The other objectives of this project were to tackle the issues associated with the other valorizations routes including: (a) preparation of cationic and protonic functional zeolites using post-synthesis hydrothermal modification approaches, (b) measuring and understanding local compositions and structures of catalytic active sites on surfaces, (c) determination of catalytic activity of multifunctional zeolites for the conversion of biomass-derived compounds into fine chemicals, and (d) the amelioration of different biomass valorisation routes by investigating local compositions and structures using high field solid-state NMR spectroscopy. In doing so, we combined synthesis and multiscale characterization techniques from surface-to-bulk (electron microscopy, X-ray diffraction, porosity measurements using BET isotherms, 1D and 2D solid-state (ss)NMR techniques) in order to understand the catalytic activity and stability of zeolites under hydrothermal catalytic reactions. Apart from the scientific objectives, fostering the development of the fellow’s career prospects is also one of the project's key objectives. Project objectives were met: material design, multiscale characterization, new soft materials and ssNMR spectroscopy enabled the fundamental knowledge, which will obviously expedite the biomass conversion and valorization pathways. In the broader context, the scientific outcomes from the project will be of substantial interest to researchers in synthesis, catalysis, biomass pretreatment, functional materials, chemical engineering, and characterization chemistry, particularly with respect to understanding nanoscale structures that drive catalytic activity, reaction yields and functional properties. Therefore, this project enabled significant impact not only in the area of biomass, but also for energy and environmental materials, which is expected to stimulate further research in these areas for the years to come.
As part ZEOCATALYST project, we investigated the following biomass valorization routes:
1. Catalytic hydrothermal reactions on zeolites. Our work on transformative reactions in cationic and protonic zeolites under catalytic hydrothermal treatment is an outstanding investigation of the chemical behavior of zeolites under reaction conditions. In this study, we present a molecular level understanding of possible transformations and the impact of various parameters on the hydrothermal stability of zeolites, which could be extremely useful for the designing and developing new catalytic processes for biomass conversions. In the context of zeolite-mediated heterogeneous catalytic conversion of biomass for the production of platform chemicals and fuels, diffusion limitation arising from the microporous structure and hydrothermal stability remain as the two major bottlenecks. So far, there is no clear understanding of zeolite stability in catalytic hydrothermal reactions; thus, this work is expected to improve this understanding. Our methods and investigations pave the way towards the design of stable and efficient zeolites for the catalytic conversion of biomass derived compounds.
2. Environmental remediation materials based on lignocellulose biomass. In an alternative valorization route, we explored the boron chemistry to develop cellulose based environmental remediation materials. This study provides molecular-level insights into the boron-cellulose interactions at different length scales to tailor the materials for sorption and fire retardancy. These results and understandings offer recommendations to expedite the design strategies of new biomass derived materials and are expected to stimulate further work on the fundamental understanding of cellulose based boron chemistry to facilitate functional materials. The paper has received significant attention in the conference presentations and on social media with over 5k views/impressions from across materials, nanotechnology, chemicals, pharma and higher education sectors.
3. Cellulose based functional hydrogels. By introducing chemical or physical cross links, we have successfully made multifunctional hydrogels consisting of 3D polymeric networks that can absorb and retain large amounts of water because of their hydrophilic groups. In the first step, covalent cross links are introduced in carboxymethyl cellulose (CMC) by using various cross linkers such as epichlorohydrin, citric acid and boric acid that interact with the hydroxyl groups of CMCs. To enhance the mechanical strength and further tune the properties, multivalent metal cations such as Al3+ and Zn2+ are incorporated as those could interact with the carboxyl moieties present in the CMC structure. Since the presence of metal cations impart antimicrobial properties, sensing performance, high water retention capabilities and conductivity, such duel cross linked hydrogel systems could have a large number of potential applications such as drug delivery, wound healing, tissue engineering, flexible wearable devices, batteries, cosmetics and agriculture.
Overall, the project lead to 13 publications, with 3 more in preparation, 4 conference presentations, 2 MSc theses and 1 PhD (in progress) thesis, and received enormous attention on social media with over 40k views/impressions.
1. Catalytic hydrothermal reactions on zeolites. Our work on transformative reactions in cationic and protonic zeolites under catalytic hydrothermal treatment is an outstanding investigation of the chemical behavior of zeolites under reaction conditions. In this study, we present a molecular level understanding of possible transformations and the impact of various parameters on the hydrothermal stability of zeolites, which could be extremely useful for the designing and developing new catalytic processes for biomass conversions. In the context of zeolite-mediated heterogeneous catalytic conversion of biomass for the production of platform chemicals and fuels, diffusion limitation arising from the microporous structure and hydrothermal stability remain as the two major bottlenecks. So far, there is no clear understanding of zeolite stability in catalytic hydrothermal reactions; thus, this work is expected to improve this understanding. Our methods and investigations pave the way towards the design of stable and efficient zeolites for the catalytic conversion of biomass derived compounds.
2. Environmental remediation materials based on lignocellulose biomass. In an alternative valorization route, we explored the boron chemistry to develop cellulose based environmental remediation materials. This study provides molecular-level insights into the boron-cellulose interactions at different length scales to tailor the materials for sorption and fire retardancy. These results and understandings offer recommendations to expedite the design strategies of new biomass derived materials and are expected to stimulate further work on the fundamental understanding of cellulose based boron chemistry to facilitate functional materials. The paper has received significant attention in the conference presentations and on social media with over 5k views/impressions from across materials, nanotechnology, chemicals, pharma and higher education sectors.
3. Cellulose based functional hydrogels. By introducing chemical or physical cross links, we have successfully made multifunctional hydrogels consisting of 3D polymeric networks that can absorb and retain large amounts of water because of their hydrophilic groups. In the first step, covalent cross links are introduced in carboxymethyl cellulose (CMC) by using various cross linkers such as epichlorohydrin, citric acid and boric acid that interact with the hydroxyl groups of CMCs. To enhance the mechanical strength and further tune the properties, multivalent metal cations such as Al3+ and Zn2+ are incorporated as those could interact with the carboxyl moieties present in the CMC structure. Since the presence of metal cations impart antimicrobial properties, sensing performance, high water retention capabilities and conductivity, such duel cross linked hydrogel systems could have a large number of potential applications such as drug delivery, wound healing, tissue engineering, flexible wearable devices, batteries, cosmetics and agriculture.
Overall, the project lead to 13 publications, with 3 more in preparation, 4 conference presentations, 2 MSc theses and 1 PhD (in progress) thesis, and received enormous attention on social media with over 40k views/impressions.
This project has addressed the key challenges associated with understanding of chemical behavior of zeolites under catalytic hydrothermal reaction conditions for biomass conversion. One of the most significant advancements is understanding of transformative reactions on catalytic surfaces under hydrothermal reaction conditions, which are relevant for catalytic efficiency, recyclability and product yields. Several young researchers at the Masters and PhD level acquired skills in the synthesis and solid-state NMR characterization of these materials. This project was conducted at the UCCS Laboratory of University of Lille, which is among the leading laboratories for biomass valorization in north EU: FP7 Eurobioref project. By working at UCCS laboratory, the fellow has gained significant exposure to catalysis and biomass valorization groups as well as ssNMR characterization groups in France, EU and worldwide. Overall, the experience gained in MSCA has a profound impact on the career of the fellow. Building up on these fundamental results, the fellow has applied for habilitation à diriger des recherches (HDR), which allows to carry out independent research by leading a team of PhD students and postdocs.