Ionic-Liquid Surface Structure: Informing Applications through Dynamical Measurements

Lead Research Organisation: Heriot-Watt University
Department Name: Sch of Engineering and Physical Science

Abstract

US Collaborator: Prof T K Minton, Montana State University.
We aim to enhance the fundamental understanding of ionic-liquid (IL) surface structure and to relate this new insight to some key sustainable applications of ILs. Inelastic and reactive scattering of atoms and molecules from liquid surfaces will be developed as a new, chemically specific analytical probe. Two distinct and complementary experimental approaches will be pursued, based on laser-photolysis-laser-spectroscopic probing and molecular-beam scattering. The laser-based method is well matched to higher-throughput screening of surface composition of a range of samples, while molecular-beam scattering will provide additional information on surface structure for selected liquids. In combination, they will probe the degree of surface segregation in custom-synthesized, high-purity ILs of recognized practical interest. The research will proceed in stages of complexity and degree of risk. The first phase will address unanswered structural questions for pure ILs representative of important families of large organic cations combined with a range of anions. The second will investigate surface enrichment in IL mixtures. The third will explore the relationship between the surface structures of IL solutions and their applications in catalysis, through supporting measurements of kinetics and product state distributions. The final phase will enter the uncharted area of the surface properties of liquid-crystalline ILs. The interpretations will be supported throughout by molecular dynamics (MD) simulations and selected QM/MM scattering calculations.
The results will have scientific impact on several levels. We expect to directly influence the future programs of scientists already engaged in closely cognate studies of collision dynamics at liquid or related surfaces. Our results will also be of direct interest to a broader community who have been using other methods to analyze liquid surfaces, or characterizing them through MD simulations. Finally, and most broadly, the results will inform the very large research community working on the synthesis of new ILs and the development of their future applications.
The investigators represent a unique combination of established expertise in the chemical synthesis and catalytic applications of ILs (Slattery and Bruce; York, UK), experimental measurements of scattering dynamics using laser-based (McKendrick and Costen; Heriot-Watt, UK) or molecular-beam (Minton; Montana State, USA) methods, and theoretical modeling of gas-liquid interactions (Schatz; Northwestern, USA). The proposed program is founded on extensive exchanges of staff, broadening their experience and promoting exchanges of ideas and complementary technical expertise.
The fundamental new insight that we will generate is most likely to be exploited through its enabling role in the design and optimization of IL materials for numerous "environmentally friendly" applications. The most direct impact will be on processes involving transport through the gas-liquid interface, including various forms of catalysis. The staff employed will receive an exceptional and unusually diverse training in modern research methods. They will have ample opportunities to develop broader, transferable skills and enjoy the cultural benefits of international exchange, equipping them to contribute to the future growth or creation of high-technology companies. Outreach will be actively promoted through the creation of a new website, and associated YouTube Channels. These will promote both the results of the proposed on ILs and their broader uses in general. Downloadable objects will be suitable for tutorials and other teaching tools. The web site will be hosted at MSU.. It will be populated with material aimed at a number of levels, ranging from the specifically interested scientific experts, through a scientifically-inclined audience, to school (K-12) teachers and the lay public.

Planned Impact

The most direct link from our work to sustainable chemistry will be through informing the creation of new IL materials for "environmentally friendly" applications. ILs have already been used on an industrial scale in a number of sustainable processes, such as the BASIL process for the production of alkoxyphenylphosphines (BASF); isomerisation of 3,4-epoxybut-1-ene to 2,5-dihydrofuran (Eastman), or the dimerisation of alkenes (IFP). The proposed work is most likely to lead to societal and economic benefits on a longer timescale, but if direct commercial opportunities should arise they would be pursued via the HWU Research and Enterprise Services unit, York's Research Innovation Office, and/or through the Technology Transfer Office at MSU.
Our goal is to develop a highly integrated, multidisciplinary training program with shared mentorship aimed at creating new scientists whose expertise spans modern synthetic chemical methodology; forefront computational modeling; and laser, molecular-beam, vacuum, electronic-data capture and data-processing technologies. Students and post-docs in the individual groups at the participating institutions will receive individual instruction and guidance from their primary advisor and from other senior students and post-docs in the group. In addition, groups will hold regular meetings in which research plans and progress are discussed.Through the collaborative exchanges, all graduate students and post-docs will have an opportunity to be co-mentored by another senior investigator, broadening their perspective on research and ensuring the multidisciplinary nature of the training. Our educational program will provide these students and post-docs with a breadth of knowledge that will equip them for ongoing research and to go out as engaged scientists and educators able to contribute to scholarly activities at all levels. They will be ideally suited to contribute to the growth or creation of high-technology companies, enhancing innovative capacity and consequently increasing business revenues. The students at MSU and HWU and the PDRAs at HWU and York will be encouraged to engage in undergraduate teaching (within the contractual limits set by EPSRC) and we would continue to provide opportunities for UK undergraduate students to undertake compulsory research project work in these areas.
Outreach will be actively promoted through the creation of a new website, and associated YouTube Channels. These will promote both the results of the proposed research on ionic liquids and their broader uses in general, with the intent that downloadable objects will be suitable for tutorials and other teaching tools. It will be populated with material aimed at a number of levels, ranging from the specifically interested scientific experts, through a scientifically-inclined audience (e.g., undergraduates, college and university teachers, curious members of the educated public), to school teachers and the lay public.

Publications

10 25 50

publication icon
Purcell SM (2022) Surface Structure of Alkyl/Fluoroalkylimidazolium Ionic-Liquid Mixtures. in The journal of physical chemistry. B

 
Description We have established through experiments and realistic atomic-level simulations that;
- the surfaces of room-temperature ionic liquids made up of a single compound are increasingly dominated by the 'waxy' alkyl chains as the lengths of these chains get longer
- that the surfaces of ionic liquids with different cation types are very similar, with the cationic headgroups 'hidden; under the long alkyl chains
- that the steric bulk of the anion dominates how many cations and hence alkyl chains can be packed at the surface
- that the surface of mixtures of ionic liquids are dominated by the cation with the longer alkyl chain
- that the structure of the bulk of ionic liquids with liquid crystalline phases has little effect on the structure of the outer surface of the liquid
- that fluorinated alkyl chains are more surface-active than regular alkyl chains
- that the departure from stoichiometry of the surface composition has a general form
- the F atoms can be used as an effective reactive-atom probe, and give great insight when combined with site-selective isotopic substitution
Exploitation Route Our findings have potential uses in applications where gas phase molecules are taken up at the surfaces of ionic liquids, particularly multiphase catalysis and gas-sequestration
Sectors Chemicals,Environment

URL http://dynamics.eps.hw.ac.uk/Interface/Analytical_Applications.php
 
Description We have begun to collaborate with an applied chemical engineering group at University of Erlangen. They are investigating the capabilities of some of the liquid systems whose fundamental properties we have examined as stationary phases in real catalytic processes of industrial interest.
First Year Of Impact 2021
Sector Chemicals
Impact Types Economic

 
Description Ionic-Liquid Mixtures: from Surface Structure to Catalytic Performance
Amount £680,203 (GBP)
Funding ID EP/T03114X/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 07/2020 
End 08/2024
 
Description New Directions in Molecular Scattering
Amount £5,880,172 (GBP)
Funding ID EP/T021675/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 05/2020 
End 05/2025
 
Description Platform Grant
Amount £1,277,251 (GBP)
Funding ID EP/P001459/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 07/2016 
End 08/2021
 
Description Collaboration between York (Slattery and Bruce) and IST, Lisbon (Canongia Lopes) 
Organisation Technical University of Lisbon
Country Portugal 
Sector Academic/University 
PI Contribution We synthesise ionic liquids and undertake experimental measurements to try to understand their properties and applications. In the course of this we often encounter problems that are difficult to provide answers to through experimental studies alone. As such we collaborate with Canongia Lopes and his group, who are experts in atomistic MD simulations, to understand these systems better.
Collaborator Contribution Canongia Lopes and his group are experts in atomistic MD simulations, in particular in the area of ionic liquids. The collaboration between York and Lisbon has already provided a significant new insight into the systems that we are studying and several publications involving this work are being written up at the moment.
Impact Several publications involving this work are being written up at the moment. We have secured a Royal Society International Exchanges grant (£12,000) as part of the collaboration (running from Dec 2013 to Dec 2016).
Start Year 2012
 
Description Minton (MSU) on NSF/EPSRC jointly funded project 
Organisation Montana State University
Country United States 
Sector Academic/University 
PI Contribution Linked funding was obtained from NSF and EPSRC for a joint project between Minton (MSU, Montana, USA) and Slattery and Bruce (York) with Costen and McKendrick (HWU).
Collaborator Contribution Complementary experiments and theory at MSU. Chemical synthesis and complementary neutron, X-ray and physical prperty measurements at York.
Impact Outputs are linked to the award.
Start Year 2013
 
Description Minton (MSU) on NSF/EPSRC jointly funded project 
Organisation University of York
Department Department of Chemistry
Country United Kingdom 
Sector Academic/University 
PI Contribution Linked funding was obtained from NSF and EPSRC for a joint project between Minton (MSU, Montana, USA) and Slattery and Bruce (York) with Costen and McKendrick (HWU).
Collaborator Contribution Complementary experiments and theory at MSU. Chemical synthesis and complementary neutron, X-ray and physical prperty measurements at York.
Impact Outputs are linked to the award.
Start Year 2013
 
Description Chairman, International Symposium on Molecular Beams 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Organised the 28th edition of the recurrent conference series: International Symposium on Molecular Beams
Year(s) Of Engagement Activity 2019
URL http://ismbedinburgh2019.eps.hw.ac.uk/index.html
 
Description D'Andrea poster presentation at the 12th International Conference on Materials Chemistry (MC12) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Lucia D'Andrea gave a poster presentation at the 12th International Conference on Materials Chemistry (MC12) in York in 2015. There was significant interest in her poster and some useful discussions with other delegates.
Year(s) Of Engagement Activity 2015
URL http://www.rsc.org/ConferencesAndEvents/RSCConferences/MC12/
 
Description D'Andrea poster presentation at the 6th International Congress on Ionic Liquids (COIL-6) in Jeju, Korea 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Lucia D'Andrea gave a poster presentation on her work at the 6th International Congress on Ionic Liquids (COIL-6) in Jeju, Korea in 2015. This is the foremost international conference on ionic liquids and it was good for her to be able to engage with other members of the ionic liquids community during this conference and during her poster presentation.
Year(s) Of Engagement Activity 2015
 
Description D'Andrea poster presentation at the Molten Salts and Ionic Liquids XXV (EUCHEMS 2014) meeting in Tallinn (Estonia) 2014 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Lucia D'Andrea gave a poster presentation at the Molten Salts and Ionic Liquids XXV (EUCHEMS 2014) meeting in Tallinn (Estonia) 2014. This was a good opportunity to discuss her project with other researchers in the ionic liquids fields and to get some feedback that has helped to shape future projects.
Year(s) Of Engagement Activity 2014
 
Description D'Andrea presentation at the Molten Salts Discussion Group Christmas Meeting 2014 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Lucia D'Andrea gave a poster presentation at the Molten Salts Discussion Group Christmas Meeting 2014. The presentation was well received and she was able to discuss her work with other researchers in the field.
Year(s) Of Engagement Activity 2014
 
Description D'Andrea presentation at the Molten Salts Discussion Group Summer Meeting 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Lucia D'Andrea gave a presentation "Investigating nano-segregation and structuring in the bulk-phase and surface of ionic liquid mixtures" at the Molten Salts Discussion Group Summer Meeting in Cambridge, 2015. The work was well received and prompted some interesting discussion.
Year(s) Of Engagement Activity 2015
URL http://msdg.org.uk/
 
Description Invited participation in WE-Heraeus-Seminar: Surface and Interface of Ionic Liquids, Bad Honnef, Germany 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited participation by Dr Simon Purcell in WE-Heraeus-Seminar: Surface and Interface of Ionic Liquids, 4th to 6th Dec, 2017, Bad Honnef, Germany. Poster presentation and flash 1 minute talk.
Year(s) Of Engagement Activity 2017
URL http://www.we-heraeus-stiftung.de/index.php?option=com_icagenda&view=list&layout=event&id=238&Itemid...
 
Description Mini symposium on ionic liquids at the University of York 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Several experts in ionic liquid chemistry and related fields came to York to present their work to a mixed audience comprising academic staff, researchers and postgraduate students from York, Heriot Watt, Bath, Nottingham, Leicester, Imperial College and the IST in Lisbon, Portugal. Speakers are listed below. The purpose of the meeting was to disseminate results from recent work to others in the field and to host discussions with current and potential future collaborators. The talks were well received and there was a good discussion in the sessions and informally outside of these. Several new potential collaborative projects are likely to arise from the meeting.

Professor Tom Welton (Imperial College London)
Dr Matthew Costen (Heriot-Watt University)
Dr Lucia D'Andrea (University of York)
Professor José Nuno Canongia Lopes (IST & ITQB, Lisbon)
Dr Karen Edler (University of Bath)
Year(s) Of Engagement Activity 2016
 
Description Physical Chemistry Research seminar University of Edinburgh 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Research seminar - Studying collisions at liquid surfaces may be interesting, but is it useful?
Year(s) Of Engagement Activity 2017
 
Description School Visits 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact Multiple visits to schools across Northern England and Scotland, as part of the Public Understanding Outreach programme of the School of Engineering and Physical Sciences. Presentation to penultimate/final year school pupils, called 'How do Chemical Reactions Go?' which incorporates information on and results from our EPSRC funded projects. Question and answer sessions included, as well as discussion with the teaching staff present. Teaching staff generally report subsequent enthusiastic discussion about the topics raised.
Year(s) Of Engagement Activity 2012,2013,2014,2015,2016
 
Description Slattery presentation and poster at the 6th International Congress on Ionic Liquids (COIL-6) in Jeju, Korea 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Slattery presented a short talk and a poster on the surface and bulk structure of ionic liquid mixtures at the 6th International Congress on Ionic Liquids (COIL-6) in Jeju, Korea. This is the main international conference in the ionic liquids field and is well attended by a range of delegates from around the world. The presentations were well received and there were some good formal discussions with other delegates about the work that will help to refine our analysis of data from recent studies.
Year(s) Of Engagement Activity 2015
URL http://coil6.cjint.kr/