Catalysis By Design

The aim of the Catalyst By Design (Design) theme is to develop Fundamental knowledge of structure and mechanism promoting innovation. This theme focusses on i) Computational Modelling. ii) Use of cutting edge Facilities including synchrotrons such as Diamond Light source, neutron sources including ISIS and Laser facilities and iii)Multi scale and multi-technique approach: from nano- to macro.thise theme will be primarily hosted at the RCaH hub and will interact with all other themes.


- Project 1:  Developments in neutron scattering to characterise adsorbed species

This project seeks to develop the use of neutron diffraction techniques available at ISIS (eg NIMROD) to study adsorbed overlayers on catalyst surfaces in real time. One of the primary areas of work will be to investigate the poorly understood nature of catalyst deactivation and the formation of adsorbed carbonaceous material.


- Project 2:  Technical developments for probing the nature of the active site and catalytic mechanisms

This area of work focuses on one of the key benefits of the RCaH – its location and access to facilities on the RAL campus (Diamond, ISIS and the Central Laser Facility). The project will develop the techniques required for understanding the fundamental processes in catalysis; the nature of the active site at the atomic and molecular level, mechanistic pathways for enhancing catalytic synergy and deactivation.


- Project 3:  Active-Site Design for Effecting and Affecting Catalysis at the Nano-scale

The aim is to (i) design novel stable monodispersed and multimetallic nanoparticles and clusters by controlling the crucial parameters of size, shape and morphology (ii) to understand the parameters for controlling final morphology and (iii) to study the effect of metal-support interactions.


- Project 4:  Microporous and Hierarchical Architectures with Multifunctional Active Sites

A wide-range of microporous and hybrid hierarchical architectures containing a diverse array of active sites will be rationally designed. The main objectives are (i) understanding the fundamental principles associated with the design of active sites with atomic precision within molecular frameworks; (ii) probing the electronic and structural environment, at the molecular level, and (iii) eliciting catalytic synergies with controlled pore-apertures for maximising shape-selective, regiospecific and enantioselective catalytic transformations.


- Project 5:  Multiscale modelling of catalytic pathways and kinetics

The project aims to develop a multiscale modelling framework for catalyst and reactor design, ranging from the molecular to the reactor-scale. The framework will employ first-principles methodologies at the nano-scale, kinetic Monte Carlo (KMC) at the micro-scale, micro-kinetic models at the meso-scale, and CFD and reactor models at the macro-scale.


- Project 6:  Hierarchically Structured Porous Catalysts with Superior Performance due to Nano-confinement and Multiscale Optimisation of the Pore Space

This project provides a platform (i) to steer nano-confinement effects (of homogeneous complexes, enzymes and nanoparticles) to enhance intrinsic catalytic activity, selectivity and stability, and (ii) to utilize the intrinsic catalytic performance (as realized at the nanoscale) up to macroscopic scales by optimal engineering and synthesis of the 3D hierarchical pore network architecture and active site location.


Environmental Catalysis

The Environmental Catalysis theme aims to Use catalysis to make the world a better place. The theme will combine heterogeneous, homogeneous and bio catalysis together with experimental and theoretical approaches to attack key problems including i) Improved atom efficiency – eradicating waste. ii) Environmental cleanup – dealing with waste. iii) New green applications – catalysis in new domains. And iv) Use of bio-renewable resources – CO2


- Project 1:  New advances in redox catalysis

The aim is to design new redox catalysts based on supported bimetallic nanoparticles where the properties will be fine tuned by (a) control of the composition and morphology of the nanoparticles, (b) control of the nature of the support-metal interface.


- Project 2:  Towards closing the chlorine cycle in large-scale chemical manufacturing

The central theme of the workplan is to investigate the oxy-chlorination of CO to produce phosgene via the application of supported copper catalysts Realization of this goal will provide the opportunity for the expanding isocyanate manufacturing industry to significantly reduce the large quantities of HCl waste streams currently generated. A combination of surface science coupled with theory will be used to predict favourable catalyst formulations, which will then be tested in a newly constructed facility.


- Project 3:  Selective oxidation of alkanes

In this project we will explore new catalytic methodologies exhibiting ultimate efficiency and specificity, which is highly relevant to the ‘environmental theme’ but has also strong links with the ‘catalyst design’ and ‘chemical transformations’ themes. The major targets of this project comprise redesigning enzyme active sites for atom economic catalysis. The chosen approach dovetails transition metal based homogeneous and heterogeneous catalysis with biocatalysis. The enzymes Methane MonoOxygenase and Butane MonoOxygenase are multiprotein complexes containing redox cofactors rendering them unsuited for real catalytic applications. Therefore we plan to immobilize robust iron and manganese based oxidation catalysts in well-defined protein scaffolds. In addition powerful computational methods will be employed for de-novo enzyme design.


- Project 4:  Water treatment – combined hydrocarbon and nitrate removal

The aim is to design new photo active catalysts based on supported bimetallic nanoparticles aimed at the photodegradation of pollutants in water. In the longer term this project aims to be the precursor for a major effort on water purification, which can be a key theme for catalysis research at the UK Catalysis Hub. The photocatalytic properties will be fine tuned by (a) selections and control of the composition and morphology of the nanoparticles, (b) control of the nature of the support-metal interface and selection and preparation of the support matrix.


- Project 5:  Particulate destruction

The problem of catalysing immobilised carbon particulate by activating gas-phase oxidants will be addressed through an iterative study, starting from single-component catalytic materials and progressing to structured catalysts. Initial screening will be followed by in-situ testing of the most promising candidates, before integration into a reactor that will trap and oxidise the particulate in one step. It is based on the type of holistic approach favoured by industry, to solve a multiphase catalytic challenge posed by a pressing environmental issue.


- Project 6:  Autonomous Damage Repair

We are seeking to embed new types of catalyst within lightweight composite structures for advanced functionality, such as autonomous damage repair. A critical aspect of this project in the context of the wider hub is that it will engage with collaborators, and in particular end-user communities, who are not traditional users of catalysis. The project has strong technical links to the Chemical Transformations theme, in particular the polymerization catalysis project within this theme; knowledge and materials exchange between these projects is planned, and polymer characterization expertise and equipment will be shared. The project could also be badged as ‘Energy’ research in the sense that composite materials are used to manufacture off-shore wind turbine blades (where damage detection and repair is a particular concern) and the fuel savings which lighter composite materials yield are a significant reason for their use in aerospace. The ‘Catalyst Design’ theme is likely to underpin every project but it is noteworthy that we are seeking to heterogenise and activate catalysts in a new way which is biologically inspired – so links across all three catalysis areas are important. This is a project which aims to redefine and broaden what catalysis can do – an aim which is an aspiration for the Catalysis Hub.


- Project 7:  Direct fixation of CO2

This proposal relates to one of the most important problems facing humanity at the present time, namely global warming and the over-use of fossil fuels. So here we explore possibilities for using CO2 for making chemicals, and in particular, we will use novel catalysts (including photocatalysts and electrocatalysts) in an attempt to make simple, but critical intermediate products such as methanol and formic acid, which are currently made from fossil fuels (mainly methane).


- Project 8:  Functionalising C-H bonds with CO2

The project addresses true Grand Challenges in catalysis – in fact it addresses two: C-H functionalisation and the constructive use of CO2 in chemicals synthesis. The programme takes advantage of our unique expertise in homogeneous and heterogeneous catalysis in a synergistic holistic approach. Indeed it will be the pooling of this expertise that can be achieved with hub funding.


Chemical Transformations

The Chemical Transformations theme aims to promote the prosperity of the UK manufacturing base in fine and bulk chemicals, polymers and pharmaceuticals areas of research include : i) Enhancing selectivity and sustainability of existing processes, ii) Pharmaceutical process chemistry; synthesis gas conversion; renewable polymers, iii) New catalytic approaches to transformations including Catalysis in confined environments; transition metal free catalysis; biocatalysis for new chemical transformations and iv) Combination of biocatalysis, homogeneous and heterogeneous, organo- and metal-based catalysis


- Project 1:  Activation and Reaction of sp3 Centres

The project involves a collaboration of academics that are internationally recognised for their work in chemo- and bio- catalytic hydrogen transfer reactions and mechanism, together with representatives of key Pharma, Agrochem and Fine Chemical end-user companies. There are links we wish to exploit with other sub-projects: support from Catalyst Design in modelling ligand/metal/substrate/product interactions and catalytic cycles; other projects within Chemical Transformations such as Biocatalysis for High Value Transformations and Catalysis within Confined Environments (cf. our use of immobilised and encapsulated catalysts). There is a link with Energy Catalysis through our transformations involving low energy redox reactions for low energy processing; the catalysts will generate hydrogen from formic acid and C1-C3 alcohols. The project also has synergies with Environmental Catalysis, indeed the collaborating companies demand this, for example: improved atom efficiency of catalytic hydrogen transfer over traditional reduction and oxidation reagents (eg NaBH4,); the catalysts work in sustainable solvents and would be expected to do so here; the methodology we develop should be applicable to renewable starting materials to enable green chemistry methods for making heterocycles (eg use of glycols, hydroxy and amino acids). A key aspect of this project is to develop industrially useful methods which necessitate efficient catalytic processes.


- Project 2:  Selective Synthesis Gas Conversion

The project is in the ‘Chemical Transformations’ theme since our initial focus will be on the fundamental chemistry which underpins the conversion of synthesis gas. However, there are strong links to all of the other themes – we are basically trying to achieve homogeneous Fischer-Tropsch, so the link to Energy is clear (also as downstream technology for the reforming exemplar project). The production of CO/H2 via gasification of (waste) biomass is linked to Environmental catalysis. The ‘Catalyst Design’ theme is likely to underpin every project but this project specifically tries to build bridges between homogeneous and heterogeneous catalysis, as is clear from the project team. There are also potential links to projects within the theme – cooperative effects are a common thread in a number of projects (e.g. metal-free catalysis), and the exchange of expertise and material can be envisaged.


- Project 3:  New Catalysts and Processes for Oxygenated Polymers.

This collaboration brings together expertise in catalysis spanning homogeneous and heterogeneous catalysis, reactor engineering and process engineering. Thus, it addresses many of the fundamental aspects of catalysis. The findings from this project would also be highly complementary to, and could benefit and feed into, the project in the Environmental sub-theme (Autonomous Damage Repair). We have discussed a collaboration with projects in the Catalyst Design sub-theme whereby completely new bio-catalysts and heterogeneous catalysts could be trialed in these polymerizations. There are also overlaps/complementarity with projects in the Energy theme (auto-reforming). There is an interesting processing link to the oxidation catalysts, developed by Hutchings et al (Cardiff), as the monomer used (epoxide) could, in future, be produced using clean oxidation catalysis, which would substantially further improve the sustainability of the process. There are clear links to the facilities at Harwell (RAL), including using EXAFS to analyse catalyst structures in situ, in solvents and at temperatures 25-150 ° C, and XRD, particularly under high gas pressures.


- Project 4:  Catalysis in Confined Environments – Homogeneous Organometallic Chemistry in the Solid–State

Homogeneous organometallic transition metal catalysts use carefully tailored organic ligands to control the function of a metal centre (i.e., reactivity, selectivity, overall rate, decomposition pathways). They are well characterised by solution spectroscopic methods and their mechanisms can be studied in detail both experimentally and computationally. By contrast, heterogeneous catalysts are typically compositionally simple solids that allow easy separation of the substrates but also provide the potential for selectivity in catalysis through spatial control in cavities in the material (e.g. zeolites). However the limitations of experimental techniques and computational methods make it difficult to define and probe the catalytic site, which in turn means that options for tuning activity and selectivity of heterogeneous catalysts based on mechanistic understanding are limited. We propose a new set of materials which combine the benefits of single–site homogeneous species with the benefits of heterogeneous materials, by the synthesis of well–defined but, importantly, highly reactive low-coordinate organometallic species protected by the confined molecular environments of platform materials such as MOFs and polymer composites. It is an approach that takes the fields of both heterogeneous catalysis and homogeneous catalysis in a new and exciting direction. We will demonstrate the ambition of our methodology by applying and developing these systems in fundamentally challenging chemical transformations that also have real-world applications. The upgrading of alkanes (C–H activation followed by C–C bond formation) of abundant chemical feedstocks (primarily shale gas: methane and ethane) to higher value alkanes is one area that we will initially target. Such technology requires the development of suitably highly–reactive transition metal centres that also offer control over product distributions, confined environment platform technologies that incorporate these active centres (i.e. MOFs), mechanism (kinetics) and gas/solid reactivity (membranes). The project, will develop a program of innovation and development in the Catalysts for Chemical Transformations theme, and will have particular synergy with the sub-themes of “C–X activation” and “selective syn gas conversion” . It will also have significant bearing on other themes, in particular: Energy (production of energy–dense materials from abundant resources, e.g., reforming technologies) and Catalyst design. In this last theme the “Hybrid and hierarchical solids” and “Nanoconfinement” programs have close synergy with ours, in addition to use of inoperando methods based at Harwell.


- Project 5:  Transition Metal-Free Catalysis

The collaboration we propose will impact on other key areas supported by the Hub within the ‘Chemical Transformations’ theme; there is the potential for profitable overlap with ‘Catalytic Process Chemistry and C-X Activation’, and we envisage synergy with ‘Biocatalysis’ through the development of complementary high-value transformations. Our focus on catalyst efficiency and transition-metal free reactions also makes us natural partners for researchers within the ‘Environmental Catalysis’ theme. Thus, the development of controlled C-H activation chemistry by carbenoid systems (based on our exciting preliminary results in this area), for example, offers overlap with a number of projects within this theme. Key collaborative interactions within the Harwell based Hub itself are outlined below.


- Project 6:  Biocatalysis for High Value Transformations that Chemical Catalysis Struggles To Perform

This project will have huge breadth as a function of its use of exploitation and design of biological catalysis for application to unique transformations. It will encompass use of natural and unnatural moieties and so bridge the gap between homo and bio.


Catalysis for Energy

The catalysis for energy theme aims to use fundamental science & engineering to develop innovative & practical solutions for current and future energy needs including i) Gas to liquid transformation, ii)Synthesis and utilisation of biofuels, iii) Process integration and intensification for efficient energy usage and storage, and iv) Photocatalytic water splitting.


- Project 1:  Fuel Cells beyond methanol and ethanol – 3rd generation direct fuel cells using oxygenates as fuels

The project brings together groups spanning materials synthesis, electrocatalysis, photocatalysis, engineering with the aim to develop new fuel cell technology to use of oxygenates (>C2) as fuels. It will combine the design of the new anode catalysts with the investigation of alternative oxidants and finally the production of a demonstrator unit based on the best technology developed within the project. It spans both the catalysis by design theme (DFT modeling and synchrotron/neutron source usage) and the energy theme. It requires a multidisciplinary approach and encompasses theory/experiment and science/engineering.


- Project 2:  New Approaches to Reforming

Three related aspects of reforming will be examined requiring process engineering, catalysts/nanoparticle synthesis, photocatalysis, gas phase heterogeneous catalysis and materials characterization. The aim is to develop reforming technology which will be much more energy efficient than current technology through combined heat management via new heat transfer media, storage and release of energy through looping technology and combining thermal and photo initiated gas phase catalytic reactions. The project spans the catalysis by design, energy and environmental themes. Materials developed in activating CO2 and characterizing materials will be developed for dry reforming technology, for example. The project is at the interface between science and engineering and success is dependent on strong collaborations between the groups involved.


- Project 3:  Biofuels

The project brings together groups with expertise spanning materials synthesis, kinetic & mechanistic analysis, homogeneous catalysis, Ionic Liquids (IL), reactor engineering and modelling/fluid dynamics to develop improved catalytic processes for biofuels synthesis. New catalytic materials will be developed possessing improved hydrothermal stability and pore structures to minimize internal mass transport for biofuels synthesis via aqueous phase reforming (APR) and hydrodeoxygenation (HDO) of pyrolysis oil, with process optimization aided by modeling and fluid dynamic studies. Novel routes to bio-butanol will also be investigated using immobilized homogeneous complexes. The project spans both the catalysis by design, chemical transformations and the energy theme and requires a multidisciplinary approach encompassing theory/experiment and science/engineering.


- Project 4:  Integrated system assessment

This project brings together groups across the entire Catalysis Hub to provide an over-arching sustainability assessment of the technological developments undertaken across the catalysis by design, energy and environmental themes. The assessment will integrate Life Cycle Analysis with Energy analysis and advanced optimization methods to assess the performance of different disciplinary theme projects, their environmental hot spots, material utilization and energy resource utilisation against benchmarked baseline cases. The project will start with the development of the LCA framework for the benchmarked baseline cases while new technology developments are being investigated within the Hub and new results become available to feed into a comparative analysis. The project is at the interface between science and engineering, it links the experimental/theoretical developments undertaken within the Hub to a process system engineering approach, and its success is dependent on strong collaborations between the groups involved.