Towards a deeper understanding of catalytic activity in supported precious metal catalysts

Lead Research Organisation: University College London
Department Name: Chemistry

Abstract

Supported heterogeneous catalysts comprising nano-sized metals/metal oxides such as Cr, Ni, Co, Au, Pd, Pt and Ag dispersed on an oxide support (i.e. SiO2/Al2O3), play a central role in an industry estimated to be worth ca. 1500 billion $US/annum. They are the principle protagonists in the conversion of fractions from natural oil and gas to produce, via core catalytic processes (i.e. polymerisation, isomerisation, reduction and oxidation), a wide variety of chemicals for everyday use. A combination of dwindling supply and increasing demand on these feedstocks means it is vital that catalysts and catalytic processes operate as efficiently as possible. Optimal efficiency is normally achieved by rationalisation of structure with function and forms the basis for much catalysis research. However the characterisation performed is often incomplete and rarely performed under reaction conditions leading to contrasting conclusions as to what makes a catalyst active. This project will develop more robust structure-activity relationships by correlating how parameters that influence catalyst performance i.e. nanoparticle size, shape, redox functionality and metal-support interactions, affect and evolve in core catalytic processes of hydrogenation and oxidation. The project adopts a novel approach drawing on skills in catalyst preparation and in situ catalyst characterisation to prepare size-controlled monometallic nanoparticles, deposited on a flat oxide supports and to characterise them in operando using simultaneous time-resolved grazing incidence X-ray scattering (GIXRS) techniques. In particular small angle/wide angle grazing incidence scattering methods (GISAXS/GIWAXS) will be used although attempts will also be made to extract pair distribution function ((GI)PDF) from the data to enable a more complete characterisation of the catalyst. Such a thorough characterisation has never been previously employed and will be used to determine the salient characteristics of catalytic nanoparticles in both two-phase (hydrogenation) and three-phase (oxidation) catalytic systems. It is expected that these measurements will prove invaluable for understanding what makes a supported nanoparticle tick and an important basis for future catalyst optimisation and design.

Planned Impact

Chemicals are one of the UK's chief exports and central to the success of this industry are heterogeneous catalysts. The catalysis industry therefore fulfills an important economic role and through the development of pharmaceuticals, hygiene products and emission control systems an important societal one too. Central to the success of this field in the UK has been the strong investment in R & D in both industrial and academic settings rendering it internationally competitive. Investment and growth in this area, particularly through the creation of research centres, is vitally important in order to not only maintain the status quo but also to strengthen it in light of growing, stiff international competition. At the heart of UK excellence in catalysis is the combination of a strong fundamental understanding applied to real catalytic problems; a research environment that is complementary to the approach adopted in this project and one very much in line with current UK Science policy. By utilising a targeted approach to tackle specific, industrially important applications of hydrogenation and oxidation it is expected that the results generated will be of direct interest to companies that operate such processes. As such even modest gains in their understanding could result in an immediate impact on current industrial practice in the UK and beyond, via the application of new, targeted preparation methods or else via the optimisation of catalytic processes. However, since these reactions are core catalytic processes used across the chemical industry, the findings in this project are also likely to be of interest to a wider audience. A more thorough understanding of these catalytic processes will also allow us to identify the key traits for activity so as to design and develop new, more efficient catalysts and catalytic processes altogether. Ultimately it is hoped that the information provided in this study/approach could provide the basis for tackling two major issues that we as a global society currently face, i.e. to find alternative, more sustainable fuel sources (i.e. biomass, fuel cells, etc) and to find alternatives to the scarce yet heavily-in-demand platinum group metals used in many catalytic processes (notably, emission control). Meanwhile the developments in the characterisation methodologies employed here will also result in an expansion in the catalysis scientist's toolbox, with these developments (and others) expected to demonstrate the benefits of locating the Catalysis Centre close to central measurement facilities and serving as a powerful magnet for attracting future investment from academic and industrial sources, nationally and internationally. This need not be limited to catalysis since such techniques can provide insight to scientific problems across a number of research areas where structure-activity relationships are valued such as nanotechnology, energy and cultural heritage where, for example, the study of nanoparticles present in artefacts and paintings under variable atmospheres is important in understanding aging. Finally by providing a combination of necessary skills set, research know how and innovation experience the project will ensure that the co-researchers on the project (post docs) obtain an excellent grounding for a career in catalysis, materials science or synchrotron radiation in an industrial or academic setting, so that they may continue to contribute to the knowledge economy of the UK. As such the benefits of this project could be very broad in both economic and societal terms in the short and longer term.

Publications

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Beale AM (2018) X-ray physico-chemical imaging during activation of cobalt-based Fischer-Tropsch synthesis catalysts. in Philosophical transactions. Series A, Mathematical, physical, and engineering sciences

 
Description Nanoparticles have been shown to evolve in structure and composition during reaction - this will help us understand how an active catalyst is formed.
Exploitation Route To help design new catalysts/materials for future applications
Sectors Chemicals,Education,Energy,Environment

 
Description A High Pressure Flow Reactor for the Operando Surface X-ray Scattering Analaysis
Amount £111,000 (GBP)
Organisation Diamond Light Source 
Sector Private
Country United Kingdom
Start 09/2019 
End 10/2023
 
Title Interlaced XRD-CT 
Description Method for collecting chemical tomography data in which the user can decide a posteriori whether to utilise time or spatially resolved information. 
Type Of Material Database/Collection of data 
Year Produced 2016 
Provided To Others? Yes  
Impact Too early to say since the work has only just been published. 
 
Title XRD-CT Multiple Outliers 
Description Developed the method of removal of artefacts from XRD-CT data. 
Type Of Material Data handling & control 
Year Produced 2015 
Provided To Others? Yes  
Impact Currently too early to say although this method outperforms current methods for such purposes. 
 
Description Hasselt University 
Organisation University of Hasselt
Department Institute for Materials Research
Country Belgium 
Sector Academic/University 
PI Contribution Analysis of samples using techniques such as Grazing Incidence X-ray Scattering techniques prepared by the Hasselt group.
Collaborator Contribution Preparation of specially constructed samples
Impact Paper submitted to Chemical Communications as of 10/3/2017
Start Year 2014
 
Description In Operando Study of Solid State Transformations of Catalysts 
Organisation BP (British Petroleum)
Country United Kingdom 
Sector Private 
PI Contribution Company's catalyst is provided to use and we characterise it under process conditions using newly developed imaging techniques
Collaborator Contribution Company provides catalyst
Impact N/A
Start Year 2014
 
Description Case study 
Form Of Engagement Activity Engagement focused website, blog or social media channel
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Case study on some recent research - based on the publication Senecal et al. ACS Catal., 2017, 7, pp 2284-2293
Year(s) Of Engagement Activity 2017
URL http://www.esrf.eu/cms/live/live/en/sites/www/home/Industry/applications-and-case-studies/catalysis-...
 
Description Diamond Light Source/UCL write-up/highlight of scientific paper 
Form Of Engagement Activity A press release, press conference or response to a media enquiry/interview
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact Our work is regularly featured as a highlight of how Diamond capability is yielding new insights into the behaviour of functional materials.
Year(s) Of Engagement Activity 2015,2017,2019
URL https://www.diamond.ac.uk/Home/News/LatestNews/2019/25-01-2019.html
 
Description Diamond light source open day 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Public/other audiences
Results and Impact Basically a repeat of the summer science exhibition some 3 weeks after the exhibition had finished.
Year(s) Of Engagement Activity 2017
URL https://www.pirbright.ac.uk/events/diamond-light-source-open-day-0
 
Description ESRF/DLS Annual Review 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Scientific highlight contribution overview of a piece of research carried out in the last academic year
Year(s) Of Engagement Activity 2013,2014,2015,2016,2017
 
Description Interview for promotional video for iCAR2015 Conference 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Promoting the impact of Diamond research for the automotive industry/associated industries and advertising the meeting.
Year(s) Of Engagement Activity 2015
URL http://www.diamond.ac.uk/ICAR2015.html
 
Description Royal Society Summer Science Exhibition 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Schools
Results and Impact The summer science exhibition runs every year at the royal society and for 7 days we manned a stall (jointly exhibited with Cardiff University) detailing how, with advanced characterisation techniques, we are developing new catalysts to tackle issues of the 21st century. Footfall at this sort of event is easily 100 visitors + per day and the team spent time encouraging participants to engage in activities and dialogue explaining the impacts of our research. The meetings with attendees resulted in 2 invitations to present at a local school and at a learned society at Cambridge university. Spoke to members of government advisory panels on the subject of emission control and was assured that our opinions regarding the potential for cleaner diesel engines/emission control systems could yet mean the technology has a not so bleak future.
Year(s) Of Engagement Activity 2017
URL https://royalsociety.org/science-events-and-lectures/2017/summer-science-exhibition/exhibits/zoom-fo...
 
Description Video broadcast describing our scientific research at Diamond Light Source 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact Video was shown/is being shown at various public events.
Year(s) Of Engagement Activity 2015
URL https://vimeo.com/134219909
 
Description Visit of UCL 4th Year Students to RAL 
Form Of Engagement Activity Participation in an open day or visit at my research institution
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Undergraduate students
Results and Impact Day visit of ~ 40 4th year students to DLS/ISIS for working visit.
Year(s) Of Engagement Activity 2014,2015,2016,2017