Designed Synthesis of Zeolites for Environmental and Biorenewables Catalysis
Lead Research Organisation:
University of St Andrews
Department Name: Chemistry
Abstract
Heterogeneous catalysis plays a major role in the synthesis of commodity and fine chemicals, fuels and environmental protection for UK industry and aluminosilicate zeolites are the catalysts of choice for many important reactions in oil refining and petrochemical and automobile emission control. Uniquely among industrial solid catalysts, their performance is directly related to their bulk crystal structure, via important details of their pore structure and the chemical structure of their active sites, but synthesis of new materials has by and large relied on trial-and-error approaches. Our research hypothesis is that enough is now known about the synthesis of zeolites and their action as catalysts to plan and execute the preparation of novel active heterogeneous catalysts for selected expanding catalytic technologies.
This ambitious research program spans structural design, hydrothermal synthesis and catalytic performance testing of zeolite catalysts. It will be facilitated by crystallography, atomistic modelling and in situ spectroscopic methods to predict and elucidate details of the mechanisms of crystallisation and of catalysis over targeted zeolites. The program will build on our recent advances in the design of hypothetical zeolite structures and the targeted preparation of novel zeolites, and in the in situ monitoring by solid state NMR, Raman and X-ray spectroscopies of zeolite preparation and of their catalytic reactions. These reactions are important for hydrocarbon generation from oxygenates and for the selective catalytic reduction (SCR) of unwanted nitrogen oxides with ammonia.
The designed synthesis of new zeolites will target hypothetical frameworks that, under computational screening, show promise for SCR or for oxygenates-to-hydrocarbons. Initial studies will develop 'retrosynthetic', modelling-led, approaches to templating these structures, while extended studies will aim to extend these to devise upscalable, commercially viable approaches.
The work will be performed in close collaboration with the UK's leading commercial catalyst company and will not only prepare novel catalysts with potential advantages of performance and patentability over current materials, but will also develop a fully-connected methodology for the synthesis of new catalysts embedded in a computational and in situ experimental framework for the study of the relationship between structure and catalytic function.
This ambitious research program spans structural design, hydrothermal synthesis and catalytic performance testing of zeolite catalysts. It will be facilitated by crystallography, atomistic modelling and in situ spectroscopic methods to predict and elucidate details of the mechanisms of crystallisation and of catalysis over targeted zeolites. The program will build on our recent advances in the design of hypothetical zeolite structures and the targeted preparation of novel zeolites, and in the in situ monitoring by solid state NMR, Raman and X-ray spectroscopies of zeolite preparation and of their catalytic reactions. These reactions are important for hydrocarbon generation from oxygenates and for the selective catalytic reduction (SCR) of unwanted nitrogen oxides with ammonia.
The designed synthesis of new zeolites will target hypothetical frameworks that, under computational screening, show promise for SCR or for oxygenates-to-hydrocarbons. Initial studies will develop 'retrosynthetic', modelling-led, approaches to templating these structures, while extended studies will aim to extend these to devise upscalable, commercially viable approaches.
The work will be performed in close collaboration with the UK's leading commercial catalyst company and will not only prepare novel catalysts with potential advantages of performance and patentability over current materials, but will also develop a fully-connected methodology for the synthesis of new catalysts embedded in a computational and in situ experimental framework for the study of the relationship between structure and catalytic function.
Planned Impact
Heterogeneous catalysis plays a major global role in the synthesis of commodity and fine chemicals, the refinement of hydrocarbon fuels and in environmental protection, and therefore has widespread impact. This research aims to develop a new synthetic and cost-effective route to active and selective new microporous catalysts and to evaluate their performance under realistic conditions.
The new zeolite catalysts will have impact in two broad areas: the control of emissions from automobile and other exhausts and the efficient conversion of biorenewables to fuels and chemicals.
In emission control technologies, catalysts can continue to reduce the levels of toxic nitric oxide emissions from the range of diesel and hybrid diesel/electric vehicles that will be with us for decades. This will improve public health, particularly for inhabitants of heavily built-up urban areas.
The conversion of biomass to produce fuel and organic feedstock chemicals will reduce the need for fossil fuels by replacing them with a renewable resource. In particular, where the biomass comes from sources that are not competitive with food production, this can reduce our dependence on oil reserves.
More specifically, the designed synthesis of new zeolites and the development of cost-effective routes to them will give UK industry a technological advantage and so enhance its competitivity and profitability. Another impact will be to further encourage scientific and industrial careers in the area of heterogeneous catalysis.
The new zeolite catalysts will have impact in two broad areas: the control of emissions from automobile and other exhausts and the efficient conversion of biorenewables to fuels and chemicals.
In emission control technologies, catalysts can continue to reduce the levels of toxic nitric oxide emissions from the range of diesel and hybrid diesel/electric vehicles that will be with us for decades. This will improve public health, particularly for inhabitants of heavily built-up urban areas.
The conversion of biomass to produce fuel and organic feedstock chemicals will reduce the need for fossil fuels by replacing them with a renewable resource. In particular, where the biomass comes from sources that are not competitive with food production, this can reduce our dependence on oil reserves.
More specifically, the designed synthesis of new zeolites and the development of cost-effective routes to them will give UK industry a technological advantage and so enhance its competitivity and profitability. Another impact will be to further encourage scientific and industrial careers in the area of heterogeneous catalysis.
Publications
Watts AE
(2020)
Site-Specific Iron Substitution in STA-28, a Large Pore Aluminophosphate Zeotype Prepared by Using 1,10-Phenanthrolines as Framework-Bound Templates.
in Angewandte Chemie (International ed. in English)
Lozinska MM
(2022)
Understanding the Anion-Templated, OSDA-Free, Interzeolite Conversion Synthesis of High Silica Zeolite ZK-5.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Chitac R
(2021)
Designed Synthesis of STA-30: A Small-Pore Zeolite Catalyst with Topology Type SWY
in Chemistry of Materials
Description | So far, we have developed optimised routes to the preparation of zeolites using metal complexes as templates, and we have worked on raising the Si/Al ratio of existing zeolites, including ZK-5, to make them more stable. This latter investigation has highlighted a new synthesis mechanism (anion templating) that we have published and disseminated. The synthesis and detailed structure of the novel templated large pore zeotype STA-28 has been established collaboratively by modelling and experiment, and published. The rational synthesis approach has been used successfully to prepare a novel small pore zeolite, STA-30(SWY), and its activity for NH3 SCR of NO has been measured. This work has been published, and follow up studies are underway in which its methanol-to-olefins catalytic performance has been measured. Further work on this material has revealed that under suitable conditions a hierarchically porous solid is prepared, with addition extra large micropores being produced (published in J Am Chem Soc, 2023). We have investigated the role of organic templating in preparing a known small pore zeolite with an enhanced Si/Al ratio. In this study we have demonstrated the use of polymeric additives to inhibit competitive crystallisation and in situ transformations of amines to the final template. We continued this in a 6-month follow up project and are writing the full paper, which reveals organic templates can be prepared in situ. |
Exploitation Route | Using methodology to prepare new microporous solids Developing new catalysts for clean air catalysis for diesel exhausts Developing catalysts for the methanol-to-olefins conversion |
Sectors | Chemicals Energy Transport |
Description | Findings have been taken forward in a patent application which has now been granted. The principles of template design for zeolites that we have established have attracted interest from a commercial company who have funded further research in this area in the last year (2023-2024) and will provide future employment. (Details confidential at this stage) |
First Year Of Impact | 2023 |
Sector | Chemicals |
Impact Types | Economic |
Description | Designed Synthesis of Novel Zeolite Catalysts |
Amount | £120,000 (GBP) |
Organisation | Johnson Matthey |
Sector | Private |
Country | United Kingdom |
Start | 02/2024 |
End | 01/2028 |
Description | Enhancing the Industrial Impact of Fundamental Zeolite Science |
Amount | £178,753 (GBP) |
Funding ID | INF\R2\192052 |
Organisation | The Royal Society |
Sector | Charity/Non Profit |
Country | United Kingdom |
Start | 01/2020 |
End | 12/2023 |
Title | Designed Synthesis of STA-30: A Small Pore Zeolite Catalyst with Topology Type SWY (dataset) |
Description | Raw data deposition on the paper of the same name, with powder diffraction data, solid state NMR data, adsorption data and catalytic data. This corresponds to figures and analyses described in the manuscript or in the Supporting Information. |
Type Of Material | Database/Collection of data |
Year Produced | 2021 |
Provided To Others? | Yes |
Impact | None |
URL | https://risweb.st-andrews.ac.uk/portal/en/datasets/designed-synthesis-of-sta30-a-small-pore-zeolite-... |
Title | Site-Specific Iron Substitution in STA-28, a Large Pore Aluminophosphate Zeotype prepared using 1,10-Phenanthrolines as Framework-Bound Structure Directing Agents (dataset) |
Description | Raw data for Publication |
Type Of Material | Database/Collection of data |
Year Produced | 2021 |
Provided To Others? | Yes |
Impact | patent published on this material |
Title | Site-Specific Iron Substitution in STA-28, a Large Pore Aluminophosphate Zeotype prepared using 1,10-Phenanthrolines as Framework-Bound Structure Directing Agents (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2020 |
Provided To Others? | Yes |
URL | https://risweb.st-andrews.ac.uk:443/portal/en/datasets/sitespecific-iron-substitution-in-sta28-a-lar... |
Title | Understanding the Anion-Templated, OSDA-Free, Interzeolite Conversion Synthesis of High Silica ZK-5 (dataset) |
Description | Raw data associated with the publication, including diffraction patterns, cif files, adsorption iostherms and spectra |
Type Of Material | Database/Collection of data |
Year Produced | 2022 |
Provided To Others? | Yes |
Impact | none |
URL | https://risweb.st-andrews.ac.uk/portal/en/datasets/understanding-the-aniontemplated-osdafree-interze... |
Description | Computational Chemistry for Rational Design of Zeolite Catalysts |
Organisation | University of Portsmouth |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | The joint project includes theoretical crystallography and atomistic simulations, materials synthesis and characterisation, in situ monitoring by lasers, X-rays and NMR spectroscopy, and industrial input of resources (materials, testing) Our contribution is materials synthesis and characterisation, and will also include catalytic testing as new materials arise. |
Collaborator Contribution | Portsmouth University (Paul Cox, Mervyn Shannon, James Mattock) are performing the theoretical crystallography and atomistic simulations. Mervyn Shannon has an extensive database of hypothetical zeolite structures that are being encoded. These are being/will then be searched as targets for synthesis on the basis of their expected stability and catalytic potential by Paul Cox and James Mattock. For the most promising, potential organic templates will be screened by modelling and suggestions passed to Johnson Matthey for their preparation. These organics are passed to us for assessment in synthetic structures. In parallel, the catalytic potential of zeolites is being assessed computationally at Portsmouth in terms of potential actives sites and the stability of intermediates estimated from modelling. |
Impact | We have jointly published 'Site-specific Iron Substitution in STA-28, a Large Pore Aluminophosphate Zeotype prepared using 1,10-Phenanthrolines as Framework-Bound Structure Directing Agents ' in Angew. Chem. Our work has been in the synthesis and characterisation, which has been aided by computational modelling at Portsmouth. We have two papers in preparation, one on new templates for STA-7 zeotype, the other on understanding the crystallisation of TNU-9, both combining synthesis, characterisation and modelling. |
Start Year | 2019 |
Description | In situ characterisation of designer zeolites |
Organisation | University College London |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | We design synthetic routes to zeolites, including new structures, and assess their catalytic activity. |
Collaborator Contribution | In situ characterisation and monitoring of synthesis of zeolites and of catalysis taking place over zeolites by laser spectroscopy and X-ray diffraction and spectroscopy. |
Impact | Early stage of collaboration. UCL have looked at some of our zeolites by laser spectroscopy and are analysing the results.. |
Start Year | 2019 |
Description | Partnership and project management of rational design of zeolite catalysts |
Organisation | Johnson Matthey |
Department | Johnson Matthey Technology Centre |
Country | United Kingdom |
Sector | Private |
PI Contribution | In this project, my team works on preparing novel zeolites, or developing and understanding novel routes to zeolites, with specific catalytic reactions in view. |
Collaborator Contribution | Johnson Matthey's role in the project is to manage it, as well as preparing and supplying organic template molecules chosen by another partner, Portsmouth, as being promising for the synthesis of zeolite structures according to computational predictions. Also JM will test promising catalysts on an industrial scale. |
Impact | While this particular project dates from 2018, when the proposal was written, my group has had a partnership with JM since 2010, including 5 PhD studentships and several short projects. The outcomes overall have included many research papers, PhD theses and several patents. I was awarded a Royal Society Industry Fellowship, covering one-half my salary for 4 years, to work at JMTC. (2020-2023) This is built on the relationship established over the last decade. Most recently I have been awarded a PhD studentship (started Feb 2024) to continue studies in this area. |
Start Year | 2019 |
Description | Understanding the coordination of Al in zeolites |
Organisation | Johnson Matthey |
Department | Johnson Matthey Technology Centre |
Country | United Kingdom |
Sector | Private |
PI Contribution | We have prepared novel zeolites. A patent application has been published on one of these, while another is under discussion. We have identified novel structural features (hierarchical porosity in the extra large micropore range) and characterised them. We have identified new routes to the synthesis of zeolites (e.g. anion templating of zeolite ZK-5). |
Collaborator Contribution | JM have provided synthesis, characterisation and catalytic testing facilities, in addition to ongoing helpful scientific input/discussions via weekly meetings. |
Impact | Many publications (2 this year) plus 1 patent application |
Title | STA-30, A NEW MEMBER OF THE SWY FAMILY OF MOLECULAR SIEVES, METHODS OF PREPARATION AND USE |
Description | The present invention is directed to a method of preparing a molecular sieve of SWY framework type, denominated STA-30. STA-30 is synthesized using 1,4-diazabicyclo[2.2.2]octane, 1-azabicyclo[2.2.2]octane derivates and combinations thereof as structure directing agents. The resulting molecular sieve is useful as catalysts, particularly when used in combination with exchanged transition metal(s) for the Selective Catalytic Reduction (SCR) of NO |
IP Reference | US2022333519 |
Protection | Patent / Patent application |
Year Protection Granted | 2022 |
Licensed | No |
Impact | Further research in this area to prepare a related zeolite |