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.

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 agricuture 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.

Publications

10 25 50
 
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 10/2013 
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 10/2015 
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 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 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