Integrated Computational Solutions for Catalysis

Lead Research Organisation: Cardiff University
Department Name: Chemistry

Abstract

The aim of this Platform grant is to initiate a new protocol for catalytic modelling where the different components relating to synthesis and growth; crystal, surface and active site structure; reactivity and deactivation; are fully integrated to achieve a comprehensive description of catalytic processes at the molecular level.
The platform funding will be used first, to stabilise and strengthen the joint programmes of the applicants in catalytic science and surface chemistry; key areas of computational materials science that have developed strongly over the last five years with EPSRC support. Secondly, the platform grant will be used to facilitate the development of our programme in new directions of strategic priority to EPSRC and high potential impact to the UK economy and Society in general.
The investigators have collaborated for more than ten years, initially in the field of computational mineralogy, followed by work on eScience technologies, and more recently in surface and catalytic science. They have joint publications and joint research grants and have co-supervised a number of doctoral students and postdoctoral research fellows. Most recently, they have initiated a computational programme on surface processes in interplanetary space, in collaboration with experimental groups in UCL and Arizona. The applicants' teams are firmly embedded in the large UCL materials modelling community and have strong interactions with industry and experimental groups within UCL and elsewhere in the UK and abroad.
The Platform grant is people-centric and will be used to provide flexible, underpinning support to allow strategic planning of our research programme. Although there will be a number of related sub-themes, the platform will be run as a whole thus promoting the maximum synergy between its different components and staff. The Platform funding will be used first to allow a coherent and strategic approach in those areas where our team has currently a very high profile (catalysis, surface science and reactivity); secondly to allow us to develop in new directions which respond to EPSRC priority themes and have the potential for high impact, eg. materials for energy applications (solid oxide fuel cells, hydrogen storage, photo-catalysis) and the environment (biomass utilisation, carbon capture and conversion); and thirdly to foster long-term international collaborations.
Staff funded by the grant will be assigned to themes and projects and not to individual investigators, thereby enhancing the strategic nature of the platform support. The flexibility of the Platform grant will be used to appoint a critical mass of key people to carry out research which best uses their particular skills, but applied to a number of topical applications areas. This approach will encourage the PDRAs to work effectively as a team and to take a broader view of research issues beyond individual projects. In addition, the Platform programme will seek to enhance the PDRAs' professional development by encouraging research independence and the initiation of scientific collaborations, in preparation for applications for competitive lectureships/fellowships or positions in industry.
In summary, the Platform grant will allow us the flexibility to (i) draw together our team into an integrated predictive computational research programme on "Total Catalysis"; (ii) carry out feasibility studies in new and strategic areas of catalytic science; (iii) initiate overseas collaborations and recruit promising researchers from abroad; (iv) retain key staff with unique expertise between relevant project funding, (v) carry through successful research that is close to commercial implementation beyond the duration of an individual project, and (v) assist in career development of the staff.

Planned Impact

Catalysis is the lynchpin of a large number of industrial processes, which are instrumental in maintaining global wealth and health, as well as playing a key role in developing processes that are both environmentally and economically sustainable. This project and its outcomes will therefore impact on:

* Society, by developing effective and more benign catalysts to allow the use of sustainable alternatives to fossil fuels, thus assisting in maintaining our quality of life;
* The Economy, through the design of new catalysts for alternative routes to important products. Catalysis is at the heart of the chemical industry - an immensely successful and important part of the overall UK economy, generating in excess of £50 billion per annum.
* Knowledge, both academic and commercial, as the new computational models will deliver significant advances in catalyst design and optimisation and more widely in materials (nano-)science;
* People, through the technical expertise developed by the researchers during the project, the training received by them in societal and ethical issues and the transferable skills developed in engagement with the media, the general public, policy makers and legislators.

In addition to the obvious benefits to academic researchers in the field (see Academic Beneficiaries section), the research will benefit in particular (i) ) the UK and global commercial sector, but also (ii) the general public, (iii) the public sector, and, more speculatively (iv) voluntary workers and charities.

(i) Commercial sector
Many industrially crucial processes, e.g. the water-gas shift reaction, still take place under extreme conditions of pressure and temperature, thus making them environmentally unsustainable in the long term. Furthermore, existing catalysts often depend on the use of expensive noble metals (Pt, Pd, Au) and transition metal compounds (e.g. ceria), which are often only available from limited sources and countries, or toxic elements, such as chromium in iron-oxide catalysts, whose use is increasingly limited by EU legislation. The development of novel catalysts, which operature under milder conditions and can utilise sustainable alternatives to fossil fuels, will clearly benefit both the catalyst manufacturing industry and the companies employing these catalysts in their production processes, e.g. pharmaceuticals and fine chemicals manufacturers, oil refineries and energy industries generally.

(ii) The general public
Everyone, whether living in highly industrialised countries or, increasingly, in the developing world, is dependent on products produced by catalytic processes. Moreover, catalytic science will be vital in developing technologies for CO2 conversion and the utilisation of agricultural residues for bio-energy production, which is of particular benefit to primarily agricultural societies, such as those in West Africa. Underpinning research on catalytic science therefore has very broad economic and societal benefits.

(iii) Government/Public Sector
With ever more stringent legislation put in place to guarantee a cascade of international agreements to reduce CO2 and other greenhouse gases to acceptable levels, viable routes to reduction in CO2 generation are clearly of prime importance to policy makers and legislators. As biomass is currently the only truly sustainable alternative source of energy, and with lingering public opposition to nuclear energy and more (off-shore) wind farms, bio-energy is clearly of interest.

(iv) Third Sector
More speculative beneficiaries of this research are charities and voluntary organisations. Catalytic science is of key importance in environmental remediation and energy technologies. With the consequences of environmental degradation and rising energy costs leading to increased disruption and hardship, the call on voluntary aid organisations is growing rapidly and alternative energy sources would alleviate this burden to sustainable levels.

Publications

10 25 50

Related Projects

Project Reference Relationship Related To Start End Award Value
EP/K009567/1 15/09/2013 31/12/2014 £1,215,346
EP/K009567/2 Transfer EP/K009567/1 01/04/2015 30/11/2019 £1,019,445
 
Description The aim of this Platform grant is to initiate a new protocol for catalytic modelling where the different components relating to synthesis and growth; crystal, surface and active site structure; reactivity and deactivation; are fully integrated to achieve a comprehensive description of catalytic processes at the molecular level.

The aim of the platform funding is to stabilise and strengthen our research programmes in catalytic science and surface chemistry; key areas of computational materials science that have developed strongly over the last five years. Secondly, the platform grant aims to facilitate the development of our programme in new directions of strategic priority to EPSRC and high potential impact to the UK economy and Society in general.

The Platform grant is people-centric and used to provide flexible, underpinning support to allow strategic planning of our research programme. Although there are a number of related sub-themes, the platform will be run as a whole thus promoting the maximum synergy between its different components and staff. The Platform funding will be used first to allow a coherent and strategic approach in those areas where our team has currently a very high profile (catalysis, surface science and reactivity); secondly to allow us to develop in new directions which respond to EPSRC priority themes and have the potential for high impact, eg. materials for energy applications (solid oxide fuel cells, hydrogen storage, photo-catalysis) and the environment (biomass utilisation, carbon capture and conversion); and thirdly to foster long-term international collaborations.

Thus far, we have made excellent progress in a number of fields:

1. We have identified the major surface structures and properties of molybdenum carbide, a promising material for catalytic applications;

2. Our calculations have shown the activity of the reactive iron sulfide mackinawite towards the catalytic conversion of exhaust gases NO and NO2;

3. Potential homogeneous catalysts based on base metal iron, rather than more expensive noble metals, as well as reactive doped zeolite sheets, have been investigated for their activity towards the conversion of biomass to fuels and chemicals.

4. Work on oxysulfides have shown that the presence of sulfide in the catalyst surface is crucial to enhance the catalytic activity.
Exploitation Route Catalysis is a cornerstone of the chemical industry and our computational investigations, identifying catalytic pathways and mechanisms and suggesting new catalysts could be taken forward by industrial catalysts manufacturers to improve existing catalytic systems or design new procedures.
Sectors Chemicals,Energy,Environment

 
Description Peer-reviewed scientific publications, presentations at international conferences, exchange visits with overseas research groups
First Year Of Impact 2015
Sector Chemicals,Energy,Environment
Impact Types Cultural,Societal,Economic

 
Description Energy X
Geographic Reach Europe 
Policy Influence Type Participation in a national consultation
 
Description Bath programme
Amount £3,333,000 (GBP)
Funding ID EP/K016288/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 11/2013 
End 11/2018
 
Description Bio-inspired 2
Amount £1,100,000 (GBP)
Funding ID EP/K035355/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 11/2013 
End 10/2016
 
Title Density Functional Theory Modelling of the Zeolite-mediated Tautomerization of Phenol and Catechol 
Description We have performed an analysis of the possible tautomerization of phenol and catechol by the Lewis acid sites at the external (010) surface of zeolite MFI using computational chemistry tools. The dataset is described by four excel files, which contain the data presented in the main publication. The first excel file, titled "3.1_Slab_model_and_Al_distribution.xlsx", presents the relative stability of the aluminium substitution in each T-site, and the pore distortion provoked by the aluminium substitution in each T-site. The distortion is measured by the variation of the separation between the T-sites T7 and T1, and T12 and T6, from the pure-silica zeolite to the aluminium substituted zeolite. This distortion is reported as a percentage. The second excel file, titled "3.2_Reaction_barriers_Phenol_adsorption_473K.xlsx", presents the energy values along the tautomerization pathway of phenol. The first set labelled "Using internal energies without zero-point energy and entropic corrections (kJ/mol)" uses the internal energies at 0.0 K to calculate the energy barriers. The second set labelled "Using internal energies with zero-point energy and entropic corrections (Free energy at 473 K) (kJ/mol)" uses the free energies calculated at 473.0 K to calculate the energy barriers. The third excel file, titled "3.3_Reaction_barriers_Cathecol_adsorption_473K.xlsx", presents the energy values along the tautomerization pathway of catechol. The first set labelled "Using internal energies without zero-point energy and entropic corrections (kJ/mol)" uses the internal energies at 0.0 K to calculate the energy barriers. The second set labelled "Using internal energies with zero-point energy and entropic corrections (Free energy at 473 K) (kJ/mol)" uses the free energies calculated at 473.0 K to calculate the energy barriers. The fourth and last excel file, titled "Bader_charge_Phenol.xlsx", presents the calculated charges of Bader after the dissociation of the O-H bond of phenol for both the non-planar and co-planar adsorptions. The column "Atoms" lists the different atoms of the system. The column "Valence (e-)" lists the number of electrons in the valence states for each atom. The column "Charge (e-)" lists the charge of each atom by subtracting the initial number of valence electrons from the final one. 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
 
Title Mixing thermodynamics and electronic structure of the Pt1??Ni? (0 = x = 1) bimetallic alloy 
Description The Pt1-xNix solid solution has been investigated using density functional theory (DFT) calculations. Pt-based bimetallic alloys are currently used as alternative bifunctional electrode materials for the electro-catalytic oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) underpinning the technology required for regenerative fuel cells. The work involved studying the mixing thermodynamics and electronic structure of the solid solution with Pt and Ni as end members. The data described here are ASCII files containing the data for the configurational entropy and the mixing enthalpy as function of composition; the probability distribution of energies for the equilibrium composition at room temperature and for the fully disordered system; the density of states for the end members of the solid solution; as well as the electronic band structure along the atomic charges and magnetic moments for the two major configurations of the equilibrium composition. Calculations were carried out using the Vienna Ab-initio Simulation Package (VASP). 
Type Of Material Database/Collection of data 
Year Produced 2019 
Provided To Others? Yes  
 
Title Substitutional doping with Ag of the zinc oxide ZnO(10-10) surfaces - data 
Description The substitutional doping with Ag of the two non-polar terminations of the zinc oxide ZnO(10-10) surface has been investigated using density functional theory (DFT) calculations. Wurtzite ZnO is one of the major components for chemical sensors used to discriminate and detect volatile organic compounds (VOCs) in hazardous environments. The novel surface functionalisation approach followed here included using both transition metal dopant atoms and noble bimetallic alloy nanoparticles to reduce the detection limit of VOCs. The data described here are the ASCII files containing the atomic charges, displacements and spin moments of the Ag-doped ZnO(10-10) surfaces. Calculations were carried out using the Vienna Ab-initio Simulation Package (VASP). 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
URL https://research.cardiff.ac.uk/converis/portal/detail/Dataset/81500252?auxfun=&lang=en_GB
 
Title The electronic and magnetic structures and the thermodynamics of cation distribution in the LiMn2O4 spinel 
Description The electronic and magnetic structures and the inversion thermodynamics of bulk lithium manganese oxide (LiMn2O4) has been investigated using density functional theory (DFT) calculations. The spinel structured LiMn2O4 is a candidate material for the cathode of secondary lithium-ion batteries with good lithium diffusion properties and less toxicity than currently commercialised counterparts. This work involved studying the inversion thermodynamics and the electronic and magnetic properties of the completely normal and fully inverse LiMn2O4. The data described here are ASCII files containing the density of states, atomic charges and spin moments of the extreme cation distributions. Calculations were carried out using the Vienna Ab-initio Simulation Package (VASP). 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
 
Title Thermodynamic properties of FeS polymorphs 
Description The dataset was generated during a density functional theory study of the thermodynamics properties of the FeS polymorphs based on the quasi-harmonic theory of lattice vibrations. FeS polymorphs are of significant relevance to condensed matter physics and planetary science. In particular, they are thought to form the cores of Earth and Mars, which is suggested by their presence in many meteorites. Data are plain text files containing the relative volume expansion, molar heat capacity and molar entropy of the FeS phases at different pressures as a function of temperature. 
Type Of Material Database/Collection of data 
Year Produced 2017 
Provided To Others? Yes  
 
Description IIT Madras 
Organisation Indian Institute of Technology Madras
Country India 
Sector Academic/University 
PI Contribution Collaboration with Professor P. Selvam at IIT Madras, India, who has visited my research group and hosted the postdoctoral researcher engaged in this project. The IIT Madras team is expert in the synthesis of tailored zeolites and testing of their catalytic properties.
Collaborator Contribution They will synthesise zeolites as pure counterparts to the clay-based materials from Ghana and test all materials for their catalytic properties. Translation will be possible as well, as Engineering colleagues in IIT Madras are developing a low-cost portable water filter for rural communities in India.
Impact Paper submitted
Start Year 2019
 
Description Johnson Matthey Technology Centre 
Organisation Johnson Matthey
Country United Kingdom 
Sector Private 
Start Year 2005
 
Description Limpopo 
Organisation University of Limpopo
Department School of Medicine
Country South Africa 
Sector Academic/University 
PI Contribution Collaboration on modelling minerals and energy materials, such as battery materials. One of my postdocs has spent 3 months in Limpopo, having been awarded a UK Postdoctoral fellowship by the SA National Research Foundation, helping to supervise 2 of their PhD students. Two of my PhD students have spent time in Limpopo to carry out collaborative research.
Collaborator Contribution Professor Phuti Ngoepe is the SA PI on the ESRC Newton award and coordinates the SA side of the exchange and collaboration programme. A number of PhD students have been engaged in collaborative research with my research group and will be visiting Cardiff later this year.
Impact Student exchanges: 1 PDRA and 2 PhD students from UK to SA
Start Year 2016
 
Description North-West University SA 
Organisation North-West University
Country South Africa 
Sector Academic/University 
PI Contribution New collaboration with Professor Cornie Van Sittard at Northwest University in South Africa. Direct result of ESRC UK-SA PhD partnership grant. We have hosted PhD students from Northwest University to learn computational catalysis techniques and carry out collaborative research.
Collaborator Contribution SA partners have provided experimental information on catalytic processes of importance to SA industry and they have sent PhD students to the UK to learn computational techniques and carry out collaborative research.
Impact No outputs as yet, but publications are in preparation
Start Year 2017
 
Description UCL 
Organisation University College London
Department Chemical Engineering
Country United Kingdom 
Sector Academic/University 
PI Contribution Collaboration with relevant colleagues in UCL Chemistry and UCL Chemical Engineering
Collaborator Contribution Experimental research to be guided by and validate computational research
Impact Joint grant applications and joint publications
Start Year 2015
 
Description University of Cape Town 
Organisation University of Cape Town
Department Centre for Infectious Disease Epidemiology and Research
Country South Africa 
Sector Academic/University 
PI Contribution Collaboration on catalytic properties of cobalt materials, linking our computational research with their experimental investigations. Exchange of students and joint Royal Society award.
Collaborator Contribution Collaboration on catalytic properties of cobalt materials, linking our computational research with their experimental investigations. Exchange of students and joint Royal Society award.
Impact Student exchange: One student from UCT has visited Cardiff University and will return in the spring of 2017. One Cardiff student has visited UCT in January 2017.
Start Year 2016