High Spec Raman Spectrometer Regional Facility

Lead Research Organisation: University of Surrey
Department Name: Chemistry

Abstract

The most common spectroscopic methods for providing chemical fingerprints of molecules and materials are Raman and Infra-red (IR) spectroscopy. Raman and IR spectroscopy are complementary techniques; generally when a material is Raman active it is IR inactive and vice versa. Advantages of using Raman over IR include the minimal sample preparation required, the increased spatial resolution achieved and the fact that analysis of wet samples is possible since water is not significantly Raman active but water features are dominant in IR when present.

Commonly available Raman spectrometers consist generally of one or two laser lines, restricting the type of characterisation that can be carried out. The instrument proposed here will provide a Raman microscope-spectrometer with lasers that cover the spectrum from the deep UV into the Infra-red. This allows the widest range of sample materials to be analysed. Additional features of the proposed system will allow temperature controlled studies, and high speed Raman chemical imaging of large area samples.

By providing chemical fingerprints of materials, Raman spectroscopy, can offer sample identification down to submicron spatial resolutions. Information on sample composition, interactions between materials, distributions within composites, and charge distribution can be provided non-invasively. The programme of work enabled by the proposed facility spans the areas of: energy conversion technologies such as reverse electrodialysis and fuel cells, energy storage (e.g. batteries and supercapacitors), electrocatalysts, nuclear fuel recycling, heterogeneous catalysis, CO2 conversion, forensic analysis, sensors, and biochemistry.

Planned Impact

This proposal supports research in applications ranging from energy and electronics through the aerospace and automotive industries. It underpins developments in forensics, smart cities and health. The fields of energy and biotechnology are estimated to contribute nearly £30 billion per annum to the UK, while forensics can act as a crime deterrent and help to reduce the estimated £36 billion (annual) economic cost of crime against individuals and households. The establishment of the proposed Raman facility would enable academia and industry to work on new technologies in the above-mentioned areas. With the demise of the UK Forensic Science Service (FSS), research enabled by this proposal is of interest to the Home Office and UK police forces.

It is envisaged that society will be beneficially impacted by research carried out on materials for energy, which are central to electric vehicles. Electric vehicles offer promise in terms of sustainability and lowering of the carbon footprint. The associated positive environmental impact will be of both economic and societal benefit. The societal impact associated with smart phone technology and proposed health benefits of wearable technologies for health, have all been enabled by research into materials for electronics. Advanced electronic materials provide faster and smaller computing and communications systems are transforming how society lives and works.

The UK electrochemical industry [e.g. Nexeon (developing advanced electrodes for lithium-ion batteries) and Johnson Matthey PLC (developing fuel cell electrodes and battery materials)] would profit from the availability of this facility. In the similar way, a Raman facility such as the one proposed could offer services to UK-based materials manufacturers [such as Haydale Ltd. (plasma functionalised carbons) and Thomas Swan (providing niche advanced materials for emerging technologies in composite, energy and water applications)].

The skills and facilities will be made open for use by other academics and industrial researchers, helping to ensure that the UK stays at the forefront of Raman microscopy research. The associated facilities will be seen and recognised as a valuable resource. Public interaction is key to realising the full impact of the research proposed here; it will increase awareness of the challenges and progress in the applications of Raman spectro-microscopy as well as the wider materials field.

Publications

10 25 50

 
Description This facility has allowed characterisation to be carried out that was previously not possible at Surrey.It has allowed my group to map the cross-section of a pH responsive coated cotton thread to characterise the location of particular materials in the coating. In positive discovery in particular is, and perhaps something not originally envisaged, that having access to a 457 nm laser coupled to a Raman microscope has allowed better polymer characterisation. This is particularly relevant for mapping the uniformity of polymer modification when trialling these polymers used in fuel cells, with record performance recently reported by Varcoe et al at Surrey. Research by Keddie et al at Surrey on stratification in colloidal films (for application in layered films as adhesives, inks, and coatings) has been possible thanks to this 457 nm laser and the depth profiling available on the Raman system to look at the distinct polymer layers.
This system has also helped a local company (TISICS) to characterise their silicon carbide filaments better (that are used in high performance composited in aviation and space) and to help explain changes in processes during the filament formation.
The fact that this spectrometer has a 244 nm UV laser and a temperature controlled stage is being put to use in the near future by a Royal Society University Research Fellow in Catalysis Engineering at Cardiff University.
Exploitation Route The results and papers generated can show the breadth of analysis possible using this instrument. They can also help to highlight the capability of micro-Raman analysis to a broader community of researchers. These findings can be used for promotional material to advertise the facility more widely and leverage further funding.
Sectors Aerospace, Defence and Marine,Chemicals,Energy,Environment,Culture, Heritage, Museums and Collections,Pharmaceuticals and Medical Biotechnology

 
Description TISICS is an SME based in Farnborough, Hampshire, and is the only European silicon carbide mono-filament production plant. They make mono-filament reinforced metal matrix composites, based on aluminium and titanium matrix alloys as components for civil aerospace; brakes and landing gear. The Raman spectrometer funded by this award has made it possible to better characterise the mono-filaments and explain changes in the production process. The spectrometer provided by the grant has allowed novel paint research to be conducted, which was sponsored by a European-based industrial partner specialising in coatings. When particles of different sizes are used in paint, they can dry into distinct layers so that a specific surface finish is achieved that is different from the bulk. This spectrometer has been used to verify and optimise mathematical models of the drying process.
Sector Aerospace, Defence and Marine,Chemicals,Manufacturing, including Industrial Biotechology
Impact Types Economic

 
Description EPSRC Strategic Equipment
Amount £513,000 (GBP)
Funding ID EP/P001440/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 11/2016 
End 10/2019
 
Description Next generation anion-exchange membranes (AEM) with covalently-bound antiradical functions for enhanced durability
Amount £674,000 (GBP)
Funding ID EP/T009233/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 04/2020 
End 11/2023
 
Description REDAEM: Anion-Exchange Membranes for Reverse Electrodialysis
Amount £779,015 (GBP)
Funding ID EP/R044163/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 09/2018 
End 09/2021
 
Description SELECTCO2: selective Electrochemical Reduction of CO2 to High Value Chemicals
Amount € 3,971,832 (EUR)
Funding ID 851441 
Organisation European Commission 
Sector Public
Country European Union (EU)
Start 01/2020 
End 12/2022
 
Description University Global Partnership Network (UGPN)
Amount £14,760 (GBP)
Organisation UGPN 
Sector Academic/University
Start 07/2017 
End 07/2018
 
Description Ana-Laura Biancolli (FAPESP) 
Organisation Universidade de São Paulo
Department Institute of Chemistry
Country Brazil 
Sector Academic/University 
PI Contribution Hosted Ana-Laura Biancolli as a visiting research student (PhD) at Surrey (Department of Chemistry).
Collaborator Contribution FAPESP provided the funds to allow the visit.
Impact Paper published: A. L. Gonçalves Biancolli, D. Herranz, L. Wang, G. Stehlikova, R. Bance-Soualhi, J. Ponce-Gonzalez, P. Ocon, E. A. Ticianelli, D. K. Whelligan, J. R. Varcoe, E. I. Santiago, "ETFE-based anion-exchange membrane ionomer powders for alkaline membrane fuel cells: a first performance comparison of head-group chemistry", J. Mater. Chem. A, 6, 24330 (2018).
Start Year 2016
 
Description Collaboration between Dr Carol Crean and Prof E. Vallés (University of Barcelona) 
Organisation University of Barcelona
Country Spain 
Sector Academic/University 
PI Contribution Making conducting fibres at Surrey and testing fibres that have been modified in Barcelona using Raman spectroscopy at Surrey.
Collaborator Contribution Involves the University of Barcelona modifying conducting fibres made at Surrey with magnetic materials, and testing these modified fibres for electrochemical and magnetic properties
Impact There is a paper in final draft that will be submitted shortly to Journal of Materials Chemistry C
Start Year 2016
 
Description Collaboration between University of Wollongong (2017 - present) 
Organisation University of Wollongong
Country Australia 
Sector Academic/University 
PI Contribution Advanced Raman mapping of flexible electrode surfaces coupled with in-situ electrochemical characterisation.
Collaborator Contribution Advanced Raman mapping of flexible electrode surfaces coupled with in-situ electrochemical characterisation.
Impact Research report
Start Year 2017
 
Description Collaboration with ICCOM at CNR (Italy) 
Organisation National Research Council
Country Italy 
Sector Public 
PI Contribution Supplied anion-exchange membranes and ionomer powders to ICCOM
Collaborator Contribution Supply of anode and cathode catalysts (developed at ICCOM) to test in Surrey Alkali Membrane Fuel Cells
Impact Led to a Royal Society - CNR International Exchange programme grant award in Jan 2018 (grant IES\R3\170134). Joint papers published: M. Bellini, M. V. Pagliaro, A. Lenarda, P. Fornasiero, M. Marelli, C. Evangelisti, M. Innocenti, Q. Jia, S. Mukerjee, J. Jankovic, L. Wang, J. R. Varcoe, C. B. Krishnamurthy, I. Grinberg, E. Davydova, D. R. Dekel, H. A. Miller, F. Vizza, "Palladium-Ceria Catalysts with Enhanced Alkaline Hydrogen Oxidation Activity for Anion Exchange Membrane Fuel Cells", ACS Appl. Energy Mater., 2, 4999 (2019). R Ren, S Zhang, HA Miller, F Vizza, JR Varcoe, Q He, "Facile preparation of novel cardo Poly (oxindolebiphenylylene) with pendent quaternary ammonium by superacid-catalysed polyhydroxyalkylation reaction for anion exchange membranes", Journal of Membrane Science, 591, 117320 (2019). L. Wang, M. Bellini, H. A. Miller, J. R. Varcoe, "A high conductivity ultrathin anion-exchange membrane with 500+ h alkali stability for use in alkaline membrane fuel cells that can achieve 2 W per square cm at 80 degC", J. Mater. Chem. A, 6, 15404 (2018). Research exchanges 2018-2020. More joint papers planeed.
Start Year 2017
 
Description Collaboration with Prof Dekel (Technion) 
Organisation Technion - Israel Institute of Technology
Department The Wolfson Department of Chemical Engineering
Country Israel 
Sector Academic/University 
PI Contribution Supply of anion-exchange membranes and ionomer powders to Technion.
Collaborator Contribution Testing of Surrey materials in Technion systems (including humidity controlled degradation set-up).
Impact Joint papers published: J. Muller, A. Zhegur, U. Krewer, J. R. Varcoe, D. R. Dekel, "A practical ex-situ technique to measure the chemical stability of anion-exchange membranes under conditions simulating fuel cell environment", ACS Mater. Lett., 2, 168 (2020). Y. Zheng, U. Ash, R. P. Pandey, A. G. Ozioko, J. Ponce-González, M. Handl, T. Weissbach, J. R. Varcoe, S. Holdcroft, M. W. Liberatore, R. Hiesgen, D. R. Dekel, "Water Uptake Study of Anion Exchange Membranes", Macromolecules, 51, 3264 (2018).
Start Year 2016
 
Description Collaboration with Prof Nasef (UTM) 
Organisation University of Technology, Malaysia
Country Malaysia 
Sector Academic/University 
PI Contribution Scientific discussion on Radiation-grafted. Testing of UTM materials in Surrey's fuel cells and Raman Instrument. Hosted Prof Nasef at Surrey (see outputs)
Collaborator Contribution Discussion of Surrey results and input into a paper on Surrey's materials.
Impact L. Wang, E. Magliocca, E. L. Cunningham, W. E. Mustain, S. D. Poynton, R. Escudero-Cid, M. M. Nasef, J. Ponce-Gonzalez, R. Bance-Souahli, R. C. T. Slade, D. K. Whelligan, J. R. Varcoe, "An optimised synthesis of high performance radiation-grafted anion-exchange membranes", Green Chem., 19, 831-843 (2017). Prof Nasef being awarded a RAEng Distinguished Visting Fellowship in May 2016 for his 1 month research visit to Surrey in Aug 2016.
Start Year 2016
 
Description Collaboration with Universidad Autónoma de Madrid  
Organisation Autonomous University of Madrid
Department Department of Applied Physical Chemistry
Country Spain 
Sector Academic/University 
PI Contribution Hosted UAM students and postdocs for joint reserch projects at Surrey.
Collaborator Contribution Paid for some of the costs for student and postdoc visits to Surrey.
Impact A. L. Gonçalves Biancolli, D. Herranz, L. Wang, G. Stehlikova, R. Bance-Soualhi, J. Ponce-Gonzalez, P. Ocon, E. A. Ticianelli, D. K. Whelligan, J. R. Varcoe, E. I. Santiago, "ETFE-based anion-exchange membrane ionomer powders for alkaline membrane fuel cells: a first performance comparison of head-group chemistry", J. Mater. Chem. A, 6, 24330 (2018). L. Wang, E. Magliocca, E. L. Cunningham, W. E. Mustain, S. D. Poynton, R. Escudero-Cid, M. M. Nasef, J. Ponce-Gonzalez, R. Bance-Souahli, R. C. T. Slade, D. K. Whelligan, J. R. Varcoe, "An optimised synthesis of high performance radiation-grafted anion-exchange membranes", Green Chem., 19, 831-843 (2017). S. D. Poynton, R. C. T. Slade, T. Omasta, W. E. Mustain, R. Escudero Cid, P. Ocón, J. R. Varcoe, "Preparation of radiation-grafted powders for use as anion exchange ionomers in alkaline polymer electrolyte fuel cells", J. Mater. Chem. A, 2, 5124 (2014).
Start Year 2014
 
Description Elisabete Santiago FAPESP 
Organisation Institute of Nuclear and Energy Research (IPEN)
Country Brazil 
Sector Academic/University 
PI Contribution Hosted Dr Elisabete Santiago as visiting postdoc for 1 year research visit at Surrey (Department of Chemistry)
Collaborator Contribution FAPESP provided the funds to allow the research visit.
Impact Paper published: A. L. Gonçalves Biancolli, D. Herranz, L. Wang, G. Stehlikova, R. Bance-Soualhi, J. Ponce-Gonzalez, P. Ocon, E. A. Ticianelli, D. K. Whelligan, J. R. Varcoe, E. I. Santiago, "ETFE-based anion-exchange membrane ionomer powders for alkaline membrane fuel cells: a first performance comparison of head-group chemistry", J. Mater. Chem. A, 6, 24330 (2018).
Start Year 2016
 
Description Exploratory Analysis of Wind Turbine Blades with Raman Spectroscopy 
Organisation Aerotrope Limited
Country United Kingdom 
Sector Private 
PI Contribution Analysed failed wind turbine blades to examine failure mechanism and assess Raman spectroscopy as a method of analysis.
Collaborator Contribution Aerotrope provided samples and expertise in microscopy, mechanical failure and material composition.
Impact Analysis report to blade manufacturer
Start Year 2020
 
Description NREL collaboration 
Organisation U.S. Department of Energy
Department National Renewable Energy Laboratory (NREL)
Country United States 
Sector Public 
PI Contribution Supply of anion-exchange membranes and ionomers powders.
Collaborator Contribution NREL is conducting some performance and durability testing on Surrey materials.
Impact John Varcoe visit to NREL April 2019. Joint paper being planned.
Start Year 2017
 
Description Surrey - Birmingham fuel cell catalyst collaboration 
Organisation University of Birmingham
Country United Kingdom 
Sector Academic/University 
PI Contribution Tested Birmingham's fuel cell catalyst in our fuel cells with Surrey's alkaline membrane electrode assemblies. We also provided some Raman data.
Collaborator Contribution Supply of non-PGM cathode catalyst.
Impact Paper: M. Wang, H. Zhang, G. Thirunavukkarasu, I. Salam, J. R. Varcoe, P. Mardle, X. Li, S. Mu, S. Du, "Ionic liquid-modified microporous ZnCoNC-based electrocatalysts for polymer electrolyte fuel cells", ACS Energy Lett., 4, 2104 (2019).
Start Year 2018
 
Description Surrey - Max Plank 
Organisation Max Planck Society
Department Max Planck Institute for Solid State Research
Country Germany 
Sector Academic/University 
PI Contribution Surrey supplied anion exchange membranes and ionomers
Collaborator Contribution MPI conducted ion-exchange capacity titrations and alkali stability measurements.
Impact Joint paper (with NREL) submitted.
Start Year 2018
 
Description University of Surrey - University of Science and Technology of China (Hefei, PR China) 
Organisation University of Science and Technology of China USTC
Country China 
Sector Academic/University 
PI Contribution Developing new membrane chemistries for alkaline anion-exchange membrane fuel cells. Exchange of materials. Testing of USTC Hefei membranes in Surrey Fuel Cell Test Stations
Collaborator Contribution Supply of USTC Hefei membranes to test in Surrey Fuel Cell Test Stations
Impact NSFC joint grant awarded (NSFC grant 21720102003). Joint papers published: X. Liang, M. A. Shehzad, Y. Zhu, L. Wang, X. Ge, J. Zhang, Z. Yang, L. Wu, J. R. Varcoe, T. Xu, "Ionomer Cross-linking Immobilization of Catalyst Nanoparticles for High Performance Alkaline Membrane Fuel Cell", Chemistry of Materials, 31, 7812 (2019). L. Wu, Q. Pan, J. R. Varcoe, D. Zhou, J. Ran, Z. Yang, T. Xu, "Thermal Crosslinking of an Alkaline Anion Exchange Membrane Bearing Unsaturated Side Chains", J. Membr. Sci., 490, 1 (2015). Y. Zhu, L. Ding, X. Liang, M. A. Shehzad, L. Wang, X. Ge, Y. He, L. Wu, J. R. Varcoe, T. Xu, "Beneficial use of rotatable-spacer side-chains in alkaline anion exchange membrane fuel cells" Energy Environ. Sci., 11, 3472 (2018). X. Lin, X. Liang, S. D. Poynton, J. R. Varcoe, A. Ong, J. Ran, Y. Li, Q. Li, T. Xu, "Alkaline anion exchange membranes containing pendant benzimidazolium groups for alkaline fuel cells", J. Membr. Sci., 443, 193 (2013). X. Lin, J. R. Varcoe, S. D. Poynton, X. Liang, A. Ong, J. Ran, Y. Li, T. Xu, "Alkaline polymer electrolytes containing pendant dimethylimidazolium groups for alkaline membrane fuel cells", J. Mater. Chem. A, 1, 7262 (2013). X. Lin, Y. Liu, S. D. Poynton, A. Ong, J. R. Varcoe, L. Wu, Y. Li, X. Liang, Q. Li, T. Xu, "Cross-linked anion exchange membranes for alkaline fuel cells synthesized using a solvent free strategy", J. Power Sources, 233, 259 (2013). Z. Zhang, L. Wu, J. Varcoe, C. Li, A. Ong, S. Poynton, T. Xu, "Aromatic polyelectrolytes via polyacylation of pre-quaternized monomers for alkaline fuel cells.", J. Mater. Chem. A, 1, 2595 (2013). X. Lin, L. Wu, Y. Liu, A. L. Ong, S. D. Poynton, J. R. Varcoe, T. Xu, "Alkali resistant and conductive guanidinium-based anion-exchange membranes for alkaline polymer electrolyte fuel cells", J. Power Sources, 217, 373 (2012). J. Ran, L. Wu, J. R. Varcoe, A. L. Ong, S. D. Poynton, T. Xu, "Development of imidazolium-type alkaline anion exchange membranes for fuel cell application", J. Membr. Sci., 415-416, 242 (2012). Y. Wu, C. Wu, J. R. Varcoe, S. D. Poynton, T. Xu, Y. Fu, "Novel silica/poly(2,6-dimethyl-1,4-phenylene oxide) hybrid anion exchange membranes for alkaline fuel cells: effect of silica content and the single cell performance", J. Power Sources, 195, 3069 (2010).
Start Year 2010
 
Description University of Surrey - University of South Carolina (USA) 
Organisation University of South Carolina
Department Department of Physics and Astronomy
Country United States 
Sector Academic/University 
PI Contribution Surrey has supplied anion-exchange membranes and powder ionomers for Prof William Mustain's group at USC to evaluate performance and durability in alkaline membarne fuel cells.
Collaborator Contribution Produced durability data that cannot be done at Surrey.
Impact Several joint papers have been produced and several more planned for 2019/2020: Published to date: L. Wang, X. Peng, W. E. Mustain, J. R. Varcoe, "Radiation-grafted anion-exchange membranes: the switch from low- to high-density polyethylene leads to remarkably enhanced fuel cell performance", Energy Environ. Sci., 12, 1575 (2019). [Raw data (CC-BY) is available at DOI: 10.15126/surreydata.8050274] Y. Zheng, T. J. Omasta, X. Peng, L. Wang, J. R. Varcoe, B. S. Pivovar, W. E. Mustain, "Quantifying and elucidating the effect of CO2 on the thermodynamics, kinetics and charge transport of AEMFCs", Energy Environ. Sci., 12, 2806 (2019). X. Peng, T. J. Omasta, E. Magliocca, L. Wang, J. R. Varcoe, W. E. Mustain, "N-doped Carbon CoOx Nanohybrids: The First Precious Metal Free Cathode to Achieve 1.0 W/cm2 Peak Power and 100 h Life in Anion-Exchange Membrane Fuel Cells" Angew. Chem. Intl. Ed., 58, 1046 (2019). T. J. Omasta, A. M. Park, J. M. LaManna, Y. Zhang, X. Peng, L. Wang, D. L. Jacobson, J. R. Varcoe, D. S. Hussey, B. S. Pivovar, W. E. Mustain, "Beyond Catalysis and Membranes: Visualizing and Solving the Challenge of Electrode Water Accumulation and Flooding in AEMFCs", Energy Environ. Sci., 11, 551 (2018). T. J. Omasta, L. Wang, X. Peng, C. A. Lewis, J. R. Varcoe, W. E. Mustain, "Importance of balancing membrane and electrode water in anion exchange membrane fuel cells", J. Power Sources, 375, 205 (2018). Travis J. Omasta, Yufeng Zhang, Andrew M. Park, Xiong Peng, Bryan Pivovar, John R. Varcoe,4 and William E. Mustain, "Strategies for Reducing the PGM Loading in High Power AEMFC Anodes", Journal of the Electrochemical Society, 165, F710 (2018). Travis J. Omasta, Xiong Peng, Hamish A. Miller, Francesco Vizza, Lianqin Wang, John R. Varcoe, Dario R. Dekel, and William E. Mustain, "Beyond 1.0Wcm-2 Performance without Platinum: The Beginning of a New Era in Anion Exchange Membrane Fuel Cells", Journal of Electrochemical Society, 165, J3039 (2018).
Start Year 2017