Dr Mark Symes

Senior Lecturer (School of Chemistry)

telephone: (+44) (0)141 330 4416
email: Mark.Symes@glasgow.ac.uk

ORCID iD https://orcid.org/0000-0001-8067-5240

Research interests

The Symes group is interested in all aspects of energy conversion in chemical systems. In the first instance, this means using electrical, photochemical and sonochemical inputs to drive chemical reactions that might not happen otherwise. A cornerstone of our approach is using renewable (or potentially renewable) energy sources to drive unfavourable or slow chemical reactions to deliver fuels and other high-commodity substances.

Renewable routes to nitrogen fixation

A primary target of our investigations is the fixation of nitrogen to ammonia. Ammonia is used mainly for fertilisers but is also important in the manufacture of pharmaceuticals, explosives and plastics. Beyond these existing uses, it is also conceivable that dinitrogen-reduction products such as ammonia and hydrazine might one day be used as fuels, where the end products of combustion are simply nitrogen and water. Hence a green energy storage cycle would be possible if the hydrogen that was originally used to reduce the nitrogen was obtained from water using renewable energy inputs (e.g. solar-driven electrochemical or photoelectrochemical water splitting).

Ammonia reaction scheme

In effect, the nitrogen would be used as a carrier for the hydrogen produced from water splitting in much the same way as CO₂ would do in an anthropogenic carbon cycle. A key advantage of using N₂ for this purpose over CO₂ is that there is significantly more N₂ available in the atmosphere for this fixation. Moreover, thermodynamically speaking, the energy required to reduce N₂ to NH₃ compares favourably with that required to reduce CO₂ to its most easily obtained fuel, formic acid. However, the activation energy for nitrogen reduction is prohibitively large and methods for generating NH₃ are generally sluggish. Our research program looks at new ways to overcome this energy barrier to nitrogen fixation, using scalable electrochemical, photochemical and sonochemical methods.

More recently, we have also begun to explore nitrogen fixation by the oxidation of nitrogen to nitrite. This allows much more mild conditions to be employed than with nitrogen reduction to ammonia (open to air and water and at room temperature and pressure). Once nitrite is produced, its central position in the nitrogen cycle allows its ready conversion to nitrogen species in other oxidation states. We use synthetic metal-ligand coordination complexes to achieve these nitrogen oxide interconversions, a topic we recently reviewed.

Selected publications

“Efficient Electrocatalytic Water Oxidation at Neutral and High pH by Adventitious Nickel at Nanomolar Concentrations.” I. Roger and M. D. Symes J. Am. Chem. Soc. 2015, 137, DOI: 10.1021/jacs.5b08139.
“Converting Between the Oxides of Nitrogen Using Metal-Ligand Coordination Complexes.” A. J. Timmons and M. D. Symes Chem. Soc. Rev. 2015, 44, 6708-6722.
“Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting.” B. Rausch, M. D. Symes, G. Chisholm and L. Cronin Science 2014, 345, 1326-1330.
“Decoupling Hydrogen and Oxygen Evolution During Water Splitting Using a Proton-Coupled-Electron Buffer.” M. D. Symes and L. Cronin Nature Chem. 2013, 5, 403-409.
“Bidirectional and Unidirectional PCET in a Molecular Model of a Cobalt-Based Oxygen-Evolving Catalyst.” M. D. Symes, Y. Surendranath, D. A. Lutterman and D. G. Nocera J. Am. Chem. Soc. 2011, 133, 5174-5177.

Selected publications

Lydon, C., Sabi, M.M., Symes, M.D. , Long, D.L. , Murrie, M. , Yoshii, S., Nojiri, H. and Cronin, L. (2012) Directed assembly of nanoscale Co(II)-substituted {Co9[P2W15]3} and {Co14[P2W15]4} polyoxometalates. Chemical Communications, 48(79), pp. 9819-9821. (doi:10.1039/c2cc34865a)

Barran, P.E., Cole, H.L., Goldup, S.M., Leigh, D.A., McGonigal, P.R., Symes, M.D. , Wu, J. and Zengerle, M. (2011) Active-metal template synthesis of a molecular trefoil knot. Angewandte Chemie (International Edition), 50(51), pp. 12280-12284. (doi:10.1002/anie.201105012)

Bloor, L. G., Solarska, R., Bienkowski, K., Kulesza, P. J., Augustynski, J., Symes, M. D. and Cronin, L. (2016) Solar-driven water oxidation and decoupled hydrogen production mediated by an electron-coupled-proton buffer. Journal of the American Chemical Society, 138(21), pp. 6707-6710. (doi:10.1021/jacs.6b03187) (PMID:27159121) (PMCID:PMC5033397)

Symes, M.D. , Surendranath, Y., Lutterman, D.A. and Nocera, D.G. (2011) Bidirectional and unidirectional PCET in a molecular model of a cobalt-based oxygen-evolving catalyst. Journal of the American Chemical Society, 133(14), pp. 5174-5177. (doi:10.1021/ja110908v)

Cioncoloni, G., Senn, H. M. , Sproules, S. , Wilson, C. and Symes, M. (2016) The electronic and solvatochromic properties of [Co(L)(bipyridine)2]+ (L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study. Dalton Transactions, 45(39), pp. 15575-15585. (doi:10.1039/C6DT02807A)

Symes, M.D. and Cronin, L. (2011) The crystal computer - computing with inorganic cellular frameworks and nets. International Journal of Nanotechnology and Molecular Computation, 3(1), pp. 24-34. (doi:10.4018/jnmc.2011010103)

Shipman, M. A. and Symes, M. D. (2017) Recent progress towards the electrosynthesis of ammonia from sustainable resources. Catalysis Today, 286, pp. 57-68. (doi:10.1016/j.cattod.2016.05.008)

Symes, M. D. , Lutterman, D. A., Teets, T. S., Anderson, B. L., Breen, J. J. and Nocera, D. G. (2013) Photo-active cobalt cubane model of an oxygen-evolving catalyst. Chemsuschem, 6(1), pp. 65-69. (doi:10.1002/cssc.201200682)

Roger, I. and Symes, M. D. (2017) Silver leakage from Ag/AgCl reference electrodes as a potential cause of interference in the electrocatalytic hydrogen evolution reaction. ACS Applied Materials and Interfaces, 9(1), pp. 472-478. (doi:10.1021/acsami.6b13438) (PMID:27996241)

Musumeci, C., Rosnes, M.H., Giannazzo, F., Symes, M.D. , Cronin, L. and Pignataro, B. (2011) Smart high-κ nanodielectrics using solid supported polyoxometalate-rich nanostructures. ACS Nano, 5(12), pp. 9992-9999. (doi:10.1021/nn2037797)

Nemeth, B., Symes, M. D. , Boulay, A. G., Busche, C., Cooper, G. J. T. , Cumming, D. R. S. and Cronin, L. (2012) Real-time ion-flux imaging in the growth of micrometer-scale structures and membranes. Advanced Materials, 24(9), pp. 1238-1242. (doi:10.1002/adma.201104345)

Bloor, L.G., Molina-Sanchez, P.I., Symes, M. and Cronin, L. (2014) Low pH electrolytic water splitting using earth abundant metastable catalysts that self-assemble in situ. Journal of the American Chemical Society, 136(8), pp. 3304-3311. (doi:10.1021/ja5003197)

Thiel, J., Molina-Sanchez, P.I., Symes, M.D. and Cronin, L. (2012) Insights into the self-assembly mechanism of the modular polyoxometalate "Keggin-Net" family of framework materials and their electronic properties. Crystal Growth and Design, 12(2), pp. 902-908. (doi:10.1021/cg201342z)

Anamimoghadam, O., Symes, M. D. , Long, D. L. , Sproules, S. , Cronin, L. and Bucher, G. (2015) Electronically stabilized nonplanar phenalenyl radical and its planar isomer. Journal of the American Chemical Society, 137(47), pp. 14944-14951. (doi:10.1021/jacs.5b07959) (PMID:26526672)

Symes, M.D. and Cronin, L. (2013) Decoupling hydrogen and oxygen evolution during electrolytic water splitting using an electron-coupled-proton buffer. Nature Chemistry, 5, pp. 403-409. (doi:10.1038/nchem.1621)

Chen, J.-J., Symes, M. D. , Fan, S.-C., Zheng, M.-S., Miras, H. N. , Dong, Q.-F. and Cronin, L. (2015) High performance polyoxometalate-based cathode materials for rechargeable lithium ion batteries. Advanced Materials, 27(31), pp. 4649-4654. (doi:10.1002/adma.201501088) (PMID:26177828)

Crowley, J.D., Leigh, D.A., Lusby, P.J., McBurney, R.T., Perret-Aebi, L., Petzold, C., Slawin, A.M.Z. and Symes, M.D. (2007) A switchable palladium-complexed molecular shuttle and its metastable positional isomers. Journal of the American Chemical Society, 129(48), pp. 15085-15090. (doi:10.1021/ja076570h)

Rausch, B., Symes, M.D. and Cronin, L. (2013) A bio-inspired, small molecule electron-coupled-proton buffer for decoupling the half-reactions of electrolytic water splitting. Journal of the American Chemical Society, 135(37), pp. 13656-13659. (doi:10.1021/ja4071893)

Roger, I. and Symes, M. D. (2016) First row transition metal catalysts for solar-driven water oxidation produced by electrodeposition. Journal of Materials Chemistry A, 4(18), pp. 6724-6741. (doi:10.1039/C5TA09423B)

Berna, J., Goldup, S.M., Lee, A., Leigh, D.A., Symes, M.D. , Teobaldi, G. and Zerbetto, F. (2008) Cadiot-Chodkiewicz active template synthesis of rotaxanes and switchable molecular shuttles with weak intercomponent interactions. Angewandte Chemie (International Edition), 47(23), pp. 4392-4396. (doi:10.1002/anie.200800891)

Kitson, P. J., Symes, M. D. , Dragone, V. and Cronin, L. (2013) Combining 3D printing and liquid handling to produce user-friendly reactionware for chemical synthesis and purification. Chemical Science, 4(8), pp. 3099-3103. (doi:10.1039/C3SC51253C)

Mathieson, J. S., Cooper, G. J.T. , Symes, M. and Cronin, L. (2014) Quantification of ion binding using electrospray mass spectrometry. Inorganic Chemistry Frontiers, 1, pp. 49-52. (doi:10.1039/C3QI00037K)

Beves, J.E., Blanco, V., Blight, B.A., Carrillo, R., D'Souza, D.M., Howgego, D., Leigh, D.A., Slawin, A.M.Z. and Symes, M.D. (2014) Toward metal complexes that can directionally walk along tracks: controlled stepping of a molecular biped with a palladium(II). Journal of the American Chemical Society, 136(5), pp. 2094-2100. (doi:10.1021/ja4123973)

Roger, I., Moca, R., Miras, H. , Crawford, K. G., Moran, D. A.J. , Ganin, A. Y. and Symes, M. D. (2017) The direct hydrothermal deposition of cobalt-doped MoS2 onto fluorine-doped SnO2 substrates for catalysis of the electrochemical hydrogen evolution reaction. Journal of Materials Chemistry A, 5(4), pp. 1472-1480. (doi:10.1039/C6TA08287D)

Timmons, A. J. and Symes, M. D. (2015) Converting between the oxides of nitrogen using metal–ligand coordination complexes. Chemical Society Reviews, 44(19), pp. 6708-6722. (doi:10.1039/C5CS00269A) (PMID:26158348)

Martinez-Cuezva, A., Pastor, A., Cioncoloni, G., Orenes, R.-A., Alajarin, M., Symes, M. D. and Berna, J. (2015) Versatile control of the submolecular motion of di(acylamino)pyridine-based [2]rotaxanes. Chemical Science, 6(5), pp. 3087-3094. (doi:10.1039/C5SC00790A) (PMID:28706682) (PMCID:PMC5490047)

Symes, M.D., Kitson, P.J., Yan, J., Richmond, C.J., Cooper, G.J.T., Bowman, R.W., Vilbrandt, T. and Cronin, L. (2012) Integrated 3D-printed reactionware for chemical synthesis and analysis. Nature Chemistry, 4, pp. 349-354. (doi:10.1038/nchem.1313)

Goldup, S.M., Leigh, D.A., Long, T., McGonigal, P.R., Symes, M.D. and Wu, J. (2009) Active metal template synthesis of [2]catenanes. Journal of the American Chemical Society, 131(43), pp. 15924-15929. (doi:10.1021/ja9070317)

Symes, M. D. and Cronin, L. (2012) Materials for water splitting. In: Letcher, T. M. and Scott, J. L. (eds.) Materials for a Sustainable Future. Royal Society of Chemistry: Cambridge, pp. 592-616. ISBN 9781849734073

Symes, M.D. , Kitson, P.J., Yan, J., Richmond, C., Cooper, G.J.T. , Bowman, R.W., Vilbrandt, T. and Cronin, L. (2012) Integrated 3D-printed reactionware for chemical synthesis and analysis. Nature Chemistry, 4, pp. 349-354. (doi:10.1038/nchem.1313)

Cereda, A., Hitchcock, A., Symes, M. D. , Cronin, L. , Bibby, T. S. and Jones, A. K. (2014) A bioelectrochemical approach to characterize extracellular electron transfer by Synechocystis sp. PCC6803. PLoS ONE, 9(3), e91484. (doi:10.1371/journal.pone.0091484) (PMID:24637387) (PMCID:PMC3956611)

Leigh, D.A., Lusby, P., McBurney, R.T. and Symes, M.D. (2010) Improved dynamics and positional bias with a second generation palladium(II)-complexed molecular shuttle. Chemical Communications, 46(14), pp. 2382-2384. (doi:10.1039/C001697G)

Roger, I. and Symes, M. D. (2015) Efficient electrocatalytic water oxidation at neutral and high pH by adventitious nickel at nanomolar concentrations. Journal of the American Chemical Society, 137(43), pp. 13980-13988. (doi:10.1021/jacs.5b08139) (PMID:26477432)

Symes, M.D. and Cronin, L. (2012) Patterned metal oxide films for solar energy. Nano Energy, 1(3), pp. 340-341. (doi:10.1016/j.nanoen.2012.02.002)

Rausch, B., Symes, M. D. , Chisholm, G. and Cronin, L. (2014) Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting. Science, 345(6202), pp. 1326-1330. (doi:10.1126/science.1257443)

Symes, M.D. , Cogdell, R.J. and Cronin, L. (2013) Designing artificial photosynthetic devices using hybrid organic-inorganic modules based on polyoxometalates. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 371(1996), p. 20110411. (doi:10.1098/rsta.2011.0411)

Anamimoghadam, O., Symes, M. D. , Busche, C., Long, D.-L. , Caldwell, S. T., Flors, C., Nonell, S., Cronin, L. and Bucher, G. (2013) Naphthoxanthenyl, a new stable phenalenyl type radical stabilized by electronic effects. Organic Letters, 15(12), pp. 2970-2973. (doi:10.1021/ol401117g)

Grants

Lord Kelvin Adam Smith Research Fellowship (University of Glasgow), 10 K per annum.
MDS is currently a Co-I on an EPSRC-funded grant related to the use of Electron-Coupled-Proton Buffers (ECPBs) in water splitting applications (Reference PEB 61602, FEC £455,000).
MDS was a named Co-I on the University of Glasgow College of Science and Engineering’s successful Small Equipment bid in late 2012 (EPSRC reference 62131). This allowed MDS to purchase £30,000 of necessary equipment for his group.

Teaching

“S4 – Electrochemistry for a sustainable future”

Additional information

Selected recent talks

7. Low pH Electrolytic Water Splitting Using Earth-Abundant Metastable Catalysts That Self-Assemble in Situ, Electrochem2014, Loughborough, UK, September 2014.

6. Low pH Electrolytic Water Splitting Using Earth-Abundant Metastable Catalysts That Self-Assemble in Situ, 65th annual meeting of the International Electrochemical Society, Lausanne, Switzerland, August 2014.

5. Low pH electrocatalytic water splitting with first row transition metals, 2014 RSC Scottish Dalton Meeting, St. Andrews University, UK, March 2014.

4. Electron-Coupled Proton Buffers for electrolytic water splitting, ECOST meeting CM1202, University of Ulm, Ulm, Germany, December 2013.

3. Catalysis and mediation in electrolytic water splitting, Lorentz Center, University of Leiden, Netherlands, October 2013.

2. Decoupling Hydrogen and Oxygen Evolution During Water Splitting Using a Proton-Electron Buffer, RSC Macrocyclic and Supramolecular Conference 2012 (MASC2012), QMUL, London, UK, December 2012.

1. Decoupling Hydrogen and Oxygen Evolution During Water Splitting Using a Proton-Electron Buffer, Frontiers in Metal Oxide Cluster Science 2012, Lanzarote, Spain, November 2012.

Recent Outreach

4. Does powering the planet have to cost us the Earth? The Glasgow Skeptics Society, Glasgow, August 2014 (public lecture and question-and-answer session).

3. Reliable Renewable Fuels - storing renewable energy, Dunkeld and Pitlochry Cafe Scientifique, Dunkeld, October 2013 (public lecture and question-and-answer session).

2. Reliable Renewable Fuels, Glasgow Cafe Scientifique, Glasgow, November 2012 (public lecture and question-and-answer session).

1. The Physics of Solar Fuels, Institute of Physics 38th Stirling Physics Meeting, University of Stirling, Stirling, May 2012.