Clean catalysis for sustainable development
Lead Research Organisation:
University of St Andrews
Department Name: Chemistry
Abstract
A sustainable society requires the efficient use of energy and renewable matter. It consequently demands selective new methodologies for the preparation of advanced materials. In this context and as resources based on fossil reserves are rapidly depleting, there are two requirements: first, a change from traditional stoichiometric, high energy methods that produce huge amounts of chemical waste to mild and clean catalytic processes; second, a major step change in chemicals production with fossil fuels being replaced by renewable resources as chemical starter units.
The long term aim and vision of catalysis research at EaStCHEM and of this Critical Mass proposal in particular is to develop all-catalytic routes to useful chemicals from renewable resources. We will provide a research environment that both improves and expands the wide range of catalytic processes used in the chemical and pharmaceutical industries. To do this we will exploit renewable and alternative feedstocks including CO2, lignocellulose and other feedstocks formed on multimillion tonnes scale as waste products from agriculture and wood processing.
This proposed change in how we access our essential chemicals requires a new generation of catalysts. The challenge is even larger because the renewable substrates are not only difficult to activate (CO2, lignin) but are often available not as pure substrates but as components of a very diverse crude mixtures (e.g. methyl oleate in tall oil). Therefore, novel robust catalysts are required which are capable of combining high activity with superb selectivity and substrate compatibility. The required selectivity resulting in high atom economy, efficiency and environmental factor will only be feasible through the development of new scientific and technological tools. To achieve this challenging objective, existing catalysts must undergo major improvements and new catalysts must be designed for as yet uncatalyzed reactions. As we believe homogenous catalysts offer the unique combination of unprecedented activities and high selectivity, it is timely to combine EaStCHEM's strengths in homogeneous catalysis in this critical mass program to develop sustainable production methods by changing to all-catalytic conversions of renewable feedstocks.
The switch to a society which relies on chemical production from all-renewable resources is a challenge of GRAND proportions, and a roadmap for this change must be broken down into smaller components with suitable experts addressing achievable goals. In this proposal we have assessed the strengths in catalysis across EaStCHEM and have designed projects at a variety of risk levels that will significantly impact on the overall change necessary in the challenging move "from oil to biomass". We will:
1. use CO2 as an ever abundant C1 building block in chemical processes that exploit newly developed state-of-the-art catalytic transformations for C-H activation/carboxylation, polymer formation, as well as electro- and chemical reduction processes.
2. We will develop optimal catalysts for ether cleavage in 'real life samples' of lignin for maximising the potential of lignocellulose as a source of fuels and fine chemicals. By combining our expertise in ligand design and computational methods we will develop efficient catalyst based on N-heterocyclic carbenes, wide bite angle phosphines and oxidative enzymes and chemocatalysts.
3. We will develop novel catalytic methods to convert renewable and waste feedstocks to important products such as fuels, chemicals and polymers.
As we anticipate that this combined effort will include the de-novo development of new catalyst we will also create a ligand and catalyst synthesis and discovery centre which will support the catalyst development process of all the workpackages for the full duration of the project and thereafter. By focusing our experience and skills in catalysis, we will contribute to a post-fossil fuels world.
The long term aim and vision of catalysis research at EaStCHEM and of this Critical Mass proposal in particular is to develop all-catalytic routes to useful chemicals from renewable resources. We will provide a research environment that both improves and expands the wide range of catalytic processes used in the chemical and pharmaceutical industries. To do this we will exploit renewable and alternative feedstocks including CO2, lignocellulose and other feedstocks formed on multimillion tonnes scale as waste products from agriculture and wood processing.
This proposed change in how we access our essential chemicals requires a new generation of catalysts. The challenge is even larger because the renewable substrates are not only difficult to activate (CO2, lignin) but are often available not as pure substrates but as components of a very diverse crude mixtures (e.g. methyl oleate in tall oil). Therefore, novel robust catalysts are required which are capable of combining high activity with superb selectivity and substrate compatibility. The required selectivity resulting in high atom economy, efficiency and environmental factor will only be feasible through the development of new scientific and technological tools. To achieve this challenging objective, existing catalysts must undergo major improvements and new catalysts must be designed for as yet uncatalyzed reactions. As we believe homogenous catalysts offer the unique combination of unprecedented activities and high selectivity, it is timely to combine EaStCHEM's strengths in homogeneous catalysis in this critical mass program to develop sustainable production methods by changing to all-catalytic conversions of renewable feedstocks.
The switch to a society which relies on chemical production from all-renewable resources is a challenge of GRAND proportions, and a roadmap for this change must be broken down into smaller components with suitable experts addressing achievable goals. In this proposal we have assessed the strengths in catalysis across EaStCHEM and have designed projects at a variety of risk levels that will significantly impact on the overall change necessary in the challenging move "from oil to biomass". We will:
1. use CO2 as an ever abundant C1 building block in chemical processes that exploit newly developed state-of-the-art catalytic transformations for C-H activation/carboxylation, polymer formation, as well as electro- and chemical reduction processes.
2. We will develop optimal catalysts for ether cleavage in 'real life samples' of lignin for maximising the potential of lignocellulose as a source of fuels and fine chemicals. By combining our expertise in ligand design and computational methods we will develop efficient catalyst based on N-heterocyclic carbenes, wide bite angle phosphines and oxidative enzymes and chemocatalysts.
3. We will develop novel catalytic methods to convert renewable and waste feedstocks to important products such as fuels, chemicals and polymers.
As we anticipate that this combined effort will include the de-novo development of new catalyst we will also create a ligand and catalyst synthesis and discovery centre which will support the catalyst development process of all the workpackages for the full duration of the project and thereafter. By focusing our experience and skills in catalysis, we will contribute to a post-fossil fuels world.
Planned Impact
"The UK's "upstream" chemicals industry and "downstream" chemistry-using sector contributed a combined total of £258 billion in value added in 2007 equivalent to 21% of UK GDP and supported over 6 million UK jobs" (taken from the EPSRC/RSC jointly commissioned independent report on the UK Chemical Industry in 2010).
The societal and economic impact of the UK's chemical industry is clear. However, the industryis at a turning point as environmental issues race up the World agenda. Whilst there seems likely to be numerous solutions to the low carbon energy problem, the chemicals and materials which impact on every aspect of our life will continue to be carbon based - the question therefore becomes where does the carbon come from in a post-fossil resources world? Whilst the current chemical industry is hit hard by this reality it is also uniquely placed to solve many of the challenges. However, if this solution is to come fromthe vast resources encapsulated in biomass without competing with food, a new "chemistry toolkit" must be invented. This toolkit will drive the transition from oil to biomass, make possible the production of "old molecules" from "new feedstocks"andthe generation of products that meet an already defined need but that are made from a renewable resource.
The commonly held view is that the best economic solution is to use a "biorefinery" which converts biomass into a mixture of chemicals, fuels and energy. The chemical transformations necessary can of course be achieved biochemically, chemically and thermally. We contend that chemical transformations via homogeneous catalysis offer the correct mixture of resource efficiency (low temperature, high selectivity), versatility and very importantly familiarity within the industry makingthem the technology of choice provided that sufficient investment is made to develop them. To tackle some of the many challenges inherent in this vision we have assembled a unique team of academics, industrialists and agriculture experts. This team has expertise across homogeneous catalysis, computational chemistry, high-throughput technologies, the chemistry of carbon dioxide and agriculture. The involvement of two global chemical and energy companies in this project will ensure that industrial issues are considered from this early stage. Outside of this the excellent connections of the project team with fine chemical and pharmaceutical industries will complete this pathway to exploitation. The upstream part of the value chain will be covered by representatives from the crop science and forestry sectors including representation from the Forestry Commission.
In addition to developing a toolkit for biomass use, we are also very aware that carbon dioxide can be viewed as an increasingly abundant chemical starter unit. In order to take advantage of this resource we have assembled a team of experts on the chemical functionalisation of carbon dioxide. This work will be led by researchers from EaStCHEM and the Joseph Black Laboratory for CO2 Chemistry.
In summary - to ensure a sustainable chemical industry we need to develop a new "chemistry toolkit". This is what our proposal is about and we believe the economic and societal impact it will have is huge.
The societal and economic impact of the UK's chemical industry is clear. However, the industryis at a turning point as environmental issues race up the World agenda. Whilst there seems likely to be numerous solutions to the low carbon energy problem, the chemicals and materials which impact on every aspect of our life will continue to be carbon based - the question therefore becomes where does the carbon come from in a post-fossil resources world? Whilst the current chemical industry is hit hard by this reality it is also uniquely placed to solve many of the challenges. However, if this solution is to come fromthe vast resources encapsulated in biomass without competing with food, a new "chemistry toolkit" must be invented. This toolkit will drive the transition from oil to biomass, make possible the production of "old molecules" from "new feedstocks"andthe generation of products that meet an already defined need but that are made from a renewable resource.
The commonly held view is that the best economic solution is to use a "biorefinery" which converts biomass into a mixture of chemicals, fuels and energy. The chemical transformations necessary can of course be achieved biochemically, chemically and thermally. We contend that chemical transformations via homogeneous catalysis offer the correct mixture of resource efficiency (low temperature, high selectivity), versatility and very importantly familiarity within the industry makingthem the technology of choice provided that sufficient investment is made to develop them. To tackle some of the many challenges inherent in this vision we have assembled a unique team of academics, industrialists and agriculture experts. This team has expertise across homogeneous catalysis, computational chemistry, high-throughput technologies, the chemistry of carbon dioxide and agriculture. The involvement of two global chemical and energy companies in this project will ensure that industrial issues are considered from this early stage. Outside of this the excellent connections of the project team with fine chemical and pharmaceutical industries will complete this pathway to exploitation. The upstream part of the value chain will be covered by representatives from the crop science and forestry sectors including representation from the Forestry Commission.
In addition to developing a toolkit for biomass use, we are also very aware that carbon dioxide can be viewed as an increasingly abundant chemical starter unit. In order to take advantage of this resource we have assembled a team of experts on the chemical functionalisation of carbon dioxide. This work will be led by researchers from EaStCHEM and the Joseph Black Laboratory for CO2 Chemistry.
In summary - to ensure a sustainable chemical industry we need to develop a new "chemistry toolkit". This is what our proposal is about and we believe the economic and societal impact it will have is huge.
Organisations
- University of St Andrews (Lead Research Organisation)
- UNIVERSITY OF EDINBURGH (Collaboration)
- Engineering and Physical Sciences Research Council (EPSRC) (Collaboration)
- Heriot-Watt University (Collaboration)
- Leibniz Association (Collaboration)
- RWTH Aachen University (Collaboration)
- University of Groningen (Collaboration)
- Utrecht University (Collaboration)
- Sasol Technology Research Laboratory (Project Partner)
Publications

Arnold P
(2017)
Carbon oxygenate transformations by actinide compounds and catalysts
in Nature Reviews Chemistry

Arnold PL
(2021)
Instantaneous and Phosphine-Catalyzed Arene Binding and Reduction by U(III) Complexes.
in Inorganic chemistry

Arnold PL
(2019)
Applications of boroxide ligands in supporting small molecule activation by U(iii) and U(iv) complexes.
in Dalton transactions (Cambridge, England : 2003)

Arnold PL
(2018)
Selective and catalytic carbon dioxide and heteroallene activation mediated by cerium N-heterocyclic carbene complexes.
in Chemical science

Arokianathar J
(2018)
Isothiourea-Catalyzed Enantioselective Addition of 4-Nitrophenyl Esters to Iminium Ions
in ACS Catalysis

Bouxin F
(2015)
Catalytic depolymerisation of isolated lignins to fine chemicals using a Pt/alumina catalyst: part 1-impact of the lignin structure
in Green Chemistry

Boyce GR
(2022)
Arylboronic Acid-Catalyzed Racemization of Secondary and Tertiary Alcohols.
in The Journal of organic chemistry

Castro L
(2014)
Calculations of One-Electron Redox Potentials of Oxoiron(IV) Porphyrin Complexes.
in Journal of chemical theory and computation

Castro L
(2016)
Insights into structure and redox potential of lignin peroxidase from QM/MM calculations.
in Organic & biomolecular chemistry

Czauderna C
(2015)
Chiral Wide-Bite-Angle Diphosphine Ligands: Synthesis, Coordination Chemistry, and Application in Pd-Catalyzed Allylic Alkylation
in Organometallics
Description | We have actually identified the key step in Ru catalysed ether cleavage opening new routes to valorization of lignin as renewable feedstock for the production of aromatic chemicals. Developed novel analytical tools for identifying the actual cleavage of the diverse ether linkages in lignin by using advanced model compounds. |
Exploitation Route | Our findings have already been picked up by other international research groups via our reports in literature and on international conferences. |
Sectors | Chemicals |
URL | http://www.subicat.org |
Description | EU Marie Curie ITN |
Amount | € 1,480,245 (EUR) |
Organisation | European Commission |
Sector | Public |
Country | European Union (EU) |
Start | 09/2013 |
End | 09/2017 |
Description | Marie Sklodowska-Curie Individual Fellowships |
Amount | € 200,000 (EUR) |
Funding ID | H2020-MSCA-IF-2014-657755 |
Organisation | European Commission H2020 |
Sector | Public |
Country | Belgium |
Start | 09/2015 |
End | 09/2017 |
Title | CCDC 1046834: Experimental Crystal Structure Determination |
Description | Related Article: Siobhan R. Smith, Charlene Fallan, James E. Taylor, Ross McLennan, David S. B. Daniels, Louis C. Morrill, Alexandra M. Z. Slawin, Andrew D. Smith|2015|Chem.-Eur.J.|21|10530|doi:10.1002/chem.201501271 |
Type Of Material | Database/Collection of data |
Year Produced | 2015 |
Provided To Others? | Yes |
Title | Data undeprinning "Enantioselective isothiourea catalysed Michael-Michael-Lactonisation cascade; synthesis of d-lactones and 1,2,3,4-substituted cyclopentanes" |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Title | Data underpinning "Aryloxide-Facilitated Catalyst Turnover in Enantioselective a,ß-Unsaturated Acyl Ammonium Catalysis" |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Title | Data underpinning "Laccase Redox Potentials: pH Dependence and Mutants - A QM/MM Study" |
Description | Raw computational data and metadata (inputs and outputs) |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Title | Data underpinning - Enantioselective Stereodivergent Nucleophile-Dependent Isothiourea-Catalyzed Domino Reactions |
Description | All FID of 1H and 13C NMR spectra, HPLC data and other analytical data for compounds produced in this manuscript |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Title | Data underpinning - Insights into Structure and Redox Potential of Lignin Peroxidase from QM/MM Calculations |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Title | Data underpinning - Two-dimensional self-assembly of benzotriazole on an inert substrate |
Description | The ultra-high vacuum (UHV) room temperature adsorption of benzotriazole (BTAH), a well-known corrosion inhibitor for copper, has been investigated on the pristine Au(111) surface using a combination of surface sensitive techniques. The dimensionality of the molecule is reduced from the 3D crystal structure to a 2-dimensional surface confinement, which induces the formation of hydrogen bonded, 1-dimensional molecular chains consisting of alternating pro-S and pro-R enantiomers mainly. The 0-dimensional system is characteristic of gas-phase BTAH, which undergoes a tautomeric equilibrium, with consequences for the resulting adsorbed species. The balance between hydrogen bonding, inter-chain van der Waals interactions and surface-molecule interactions, and the correlation with the dimensionality of the system, are discussed in the light of the experimental results and a computational description of the observed features. |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Title | Data underpinning: N- to C-Sulfonyl Photoisomerisation of Dihydropyridinones: A Synthetic and Mechanistic Study |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Title | Data underpinning: Nickel nanocatalyst exsolution from (La,Sr)(Cr,M, Ni)O3 (M=Mn, Fe) perovskites for the fuel oxidation layer of Oxygen Transport Membranes |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2015 |
Provided To Others? | Yes |
Title | Data underpinning: Role of coal characteristics in the electrochemical behaviour of hybrid direct carbon fuel cells |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Title | Direct organocatalytic enantioselective functionalization of SiOx surfaces (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2018 |
Provided To Others? | Yes |
Title | Enzyme Activity by Design: An Artificial Rhodium Hydroformylase for Linear Aldehyes |
Description | Data files relating to the paper ' Enzyme Activity by Design: An Artificial Rhodium Hydroformylase for Linear Aldehyes' published in Angew. Chem. Int. Ed. |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Title | Grafting of Technical Lignins through Regioselective Triazole Formation on ß-O-4 Linkages (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Title | Isothiourea-Catalysed Acylative Kinetic Resolution of Aryl-Alkenyl (sp2 vs sp2) Substituted Secondary Alcohols |
Description | aryl-alkenyl (sp2 vs sp2) substituted secondary alcohols is described, with effective enantiodiscrimination achieved using the isothiourea organocatalyst HyperBTM (1 mol%) and isobutyric anhydride. The kinetic resolution of a wide range of aryl-alkenyl substituted alcohols has been evaluated, with either electron-rich or naphthyl aryl substituents in combination with an unsubstituted vinyl substituent providing the highest selectivity (S = 2-1980). The demonstration of this protocol for the gram-scale (2.5 g) kinetic resolution of a model aryl-vinyl (sp2 vs sp2) substituted secondary alcohol is demonstrated, giving access to >1 g of each of the product enantiomers both in 99:1 er. |
Type Of Material | Database/Collection of data |
Year Produced | 2016 |
Provided To Others? | Yes |
Title | Isothiourea-catalyzed enantioselective addition of 4-nitrophenyl esters to iminium ions (dataset) |
Description | |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Title | Less hindered ligands give improved catalysts for the nickel catalysed Grignard cross-coupling of aromatic ethers (dataset) |
Description | NMR spectra of substrates and products. Crystal data for Ni complexes. |
Type Of Material | Database/Collection of data |
Year Produced | 2017 |
Provided To Others? | Yes |
Description | Criticat |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Country | United Kingdom |
Sector | Public |
PI Contribution | I took the initiative to join forces in catalysis research in St Andrews and Edinburgh Universities to start an EPSRC funded critical mass program on 'Clean catalysis for sustainable development'. This was taken up and expanded with Heriot Watt University which has led to the EPSRC funded CDT 'Criticat' |
Collaborator Contribution | Similar as above as we initiated this as equal partners |
Impact | New case studentships with Sasol Technology UK Ltd |
Start Year | 2013 |
Description | Criticat |
Organisation | Heriot-Watt University |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | I took the initiative to join forces in catalysis research in St Andrews and Edinburgh Universities to start an EPSRC funded critical mass program on 'Clean catalysis for sustainable development'. This was taken up and expanded with Heriot Watt University which has led to the EPSRC funded CDT 'Criticat' |
Collaborator Contribution | Similar as above as we initiated this as equal partners |
Impact | New case studentships with Sasol Technology UK Ltd |
Start Year | 2013 |
Description | Criticat |
Organisation | University of Edinburgh |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | I took the initiative to join forces in catalysis research in St Andrews and Edinburgh Universities to start an EPSRC funded critical mass program on 'Clean catalysis for sustainable development'. This was taken up and expanded with Heriot Watt University which has led to the EPSRC funded CDT 'Criticat' |
Collaborator Contribution | Similar as above as we initiated this as equal partners |
Impact | New case studentships with Sasol Technology UK Ltd |
Start Year | 2013 |
Description | SuBiCat |
Organisation | Leibniz Association |
Department | Leibniz Institute for Catalysis |
Country | Germany |
Sector | Academic/University |
PI Contribution | I am coordinator/PI of this Marie Curie ITN |
Collaborator Contribution | Assembling a team of world-leading researchers in catalytic biomass conversions |
Impact | We have organised several international symposia and have several joint papers |
Start Year | 2013 |
Description | SuBiCat |
Organisation | RWTH Aachen University |
Country | Germany |
Sector | Academic/University |
PI Contribution | I am coordinator/PI of this Marie Curie ITN |
Collaborator Contribution | Assembling a team of world-leading researchers in catalytic biomass conversions |
Impact | We have organised several international symposia and have several joint papers |
Start Year | 2013 |
Description | SuBiCat |
Organisation | University of Groningen |
Department | Stratingh Institute for Chemistry |
Country | Netherlands |
Sector | Academic/University |
PI Contribution | I am coordinator/PI of this Marie Curie ITN |
Collaborator Contribution | Assembling a team of world-leading researchers in catalytic biomass conversions |
Impact | We have organised several international symposia and have several joint papers |
Start Year | 2013 |
Description | SuBiCat |
Organisation | Utrecht University |
Department | Debye Institute for NanoMaterials Science |
Country | Netherlands |
Sector | Academic/University |
PI Contribution | I am coordinator/PI of this Marie Curie ITN |
Collaborator Contribution | Assembling a team of world-leading researchers in catalytic biomass conversions |
Impact | We have organised several international symposia and have several joint papers |
Start Year | 2013 |
Description | UK Catalysis Conference (Loughborough) |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Postgraduate students |
Results and Impact | Oral presentation to an academic community at the UK Catalysis Conference. |
Year(s) Of Engagement Activity | 2017 |