Professor David Willock

Professor of Computational and Physical Chemistry

: WillockDJ@cardiff.ac.uk
: +44 29208 74779

: Available for postgraduate supervision

David Willock's research group is concerned with the use of computer simulation to understand materials with a particular focus on catalysis and related areas.

Heterogeneous catalysis depends on the adsorption and reaction of molecules at a surface. The main materials of interest are metals, oxides, microporous structures and supported metal nanoparticles with calculations aimed at understanding the properties of these systems and the reactions that are catalysed on their surfaces.

Simulation of structure and properties at the molecular level is carried out using a combination of quantum chemical and atomic forcefield methodology. The development of Monte Carlo simulation for host/guest systems has allowed us to explore templating and shape selectivity in zeolites and to generate new models of the pore structure of polymer materials. Periodic DFT has been applied to the adsorption and isomerisation of ketones on Pt surfaces and the reactions of molecules at defects on oxides.

In most cases collaboration with colleagues in spectroscopy, surface science and catalysis has been used to gain insight into the accuracy of the modelling protocols and provide a more rounded description of the "real world" system.

Links

Personal Web Sites: CCI

2023

Guadix-Montero, S. et al. 2023. Ruthenium ion catalysed C–C bond activation in lignin model compounds – towards lignin depolymerisation. Catalysis Science & Technology 13, pp. 5912-5923. (10.1039/d3cy00076a)
Carter, J. H. et al. 2023. The selective oxidation of methane to methanol using in situ generated H 2 O 2 over palladium-based bimetallic catalysts †. Catalysis Science & Technology (10.1039/d3cy00116d)
Dummer, N. F. et al. 2023. Methane oxidation to methanol. Chemical Reviews 9, pp. 6359-6411. (10.1021/acs.chemrev.2c00439)
Willock, D. 2023. Crystal binding (interatomic forces): Metallic bonding and crystals. In: Reference Module in Materials Science and Materials Engineering. Elsevier, (10.1016/B978-0-323-90800-9.00193-1)
Damoyi, N. E., Friedrich, H. B., Kruger, G. H. and Willock, D. J. 2023. A DFT study of the catalytic ODH of n-hexane over a cluster model of vanadium oxide. Molecular Catalysis 541, article number: 113078. (10.1016/j.mcat.2023.113078)
Lombard, C. J., van Sittert, C. G. C. E., Mugo, J. N., Perry, C. and Willock, D. 2023. Computational investigation of α-SiO 2 surfaces as a support for Pd †. Physical Chemistry Chemical Physics (10.1039/d2cp04722e)

2022

Smith, L. R., Douthwaite, M., Mugford, K., Dummer, N. F., Willock, D. J., Hutchings, G. J. and Taylor, S. H. 2022. Recent advances on the valorization of glycerol into alcohols. Energies 15(17), article number: e6250. (10.3390/en15176250)
Taylor, S., Carter, J., Dummer, N., Nasrallah, A., Willock, D. and Hutchings, G. 2022. Selective oxidation of methane to oxygenates using heterogeneous catalysts. In: Li, L. and Hargreaves, J. eds. Heterogeneous Catalysis for Sustainable Energy. Weinheim: Wiley, pp. 183-203.
Mandal, S., Nanavati, S. P., Willock, D. J. and Ananthakrishnan, R. 2022. Band gap engineering of amine functionalized Ag(I)-based coordination polymers and their plasmonic Ag0 coupled novel visible light driven photo-redox system for selective oxidation of benzyl alcohol. Applied Catalysis B: Environmental 303, article number: 120821. (10.1016/j.apcatb.2021.120821)
Douthwaite, M., Zhang, B., Iqbal, S., Miedziak, P. J., Bartley, J. K., Willock, D. J. and Hutchings, G. J. 2022. Transfer hydrogenation of methyl levulinate with methanol to gamma valerolactone over Cu-ZrO2: A sustainable approach to liquid fuels. Catalysis Communications 164, article number: 106430. (10.1016/j.catcom.2022.106430)
Qi, G. et al. 2022. Au-ZSM-5 catalyses the selective oxidation of CH4 to CH3OH and CH3COOH using O2. Nature Catalysis 5 (10.1038/s41929-021-00725-8)

2021

Bowden, B., Davies-Jones, J. A., Davies, M., Davies, P. R., Morgan, D. J., Sainna, M. A. and Willock, D. J. 2021. Investigating the effects of surface adsorbates on gold and palladium deposition on carbon. Topics in Catalysis 64, pp. 1041-1051. (10.1007/s11244-021-01423-2)
Agarwal, N. et al. 2021. The direct synthesis of hydrogen peroxide over Au and Pd nanoparticles: A DFT study. Catalysis Today 381, pp. 76-85. (10.1016/j.cattod.2020.09.001)
Nasrallah, A., Engel, J., Catlow, C. R. A. and Willock, D. J. 2021. Density functional theory study of the partial oxidation of methane to methanol on Au and Pd surfaces. Journal of Physical Chemistry C 125(34), pp. 18770–18785. (10.1021/acs.jpcc.1c06206)
Nowicka, E. et al. 2021. Controlled reduction of aromaticity of alkylated polyaromatic compounds by selective oxidation using H2WO4, H3PO4 and H2O2: A route for upgrading heavy oil fractions. New Journal of Chemistry 45(31), pp. 13885-13892. (10.1039/D1NJ01986D)
Freakley, S. J., Dimitratos, N., Willock, D. J., Taylor, S. H., Kiely, C. J. and Hutchings, G. J. 2021. Methane oxidation to methanol in water. Accounts of Chemical Research 54(11), pp. 2614–2623. (10.1021/acs.accounts.1c00129)
Sainna, M. et al. 2021. A combined periodic DFT and QM/MM approach to understand the radical mechanism of the catalytic production of methanol from glycerol. Faraday Discussions 229, pp. 108-130. (10.1039/D0FD00005A)
Guan, S. et al. 2021. The interaction of CO with a copper(ii) chloride oxy-chlorination catalyst. Faraday Discussions 229, pp. 318-340. (10.1039/D0FD00014K)
Smith, L. R. et al. 2021. Gas phase clycerol valorization over ceria nanostructures with well-defined morphologies. ACS Catalysis 11, pp. 4893-4907. (10.1021/acscatal.0c05606)

2020

Devlia, J., Smith, L., Douthwaite, M., Taylor, S. H., Willock, D. J., Hutchings, G. J. and Dummer, N. F. 2020. The formation of methanol from glycerol bio-waste over doped ceria based catalysts. Philosophical Transactions A: Mathematical, Physical and Engineering Sciences 378(2176), article number: 20200059. (10.1098/rsta.2020.0059)
Meenakshisundaram, S. et al. 2020. Role of the support in gold-containing nanoparticles as heterogeneous catalysts. Chemical Reviews 120(8), pp. 3890-3938. (10.1021/acs.chemrev.9b00662)
Campisi, S. et al. 2020. DFT-assisted spectroscopic studies on the coordination of small ligands to palladium: from isolated ions to nanoparticles. Journal of Physical Chemistry C 124(8), pp. 4781-4790. (10.1021/acs.jpcc.9b09791)

2011

Thetford, A., Hutchings, G. J., Taylor, S. H. and Willock, D. J. 2011. The decomposition of H2O2 over the components of Au/TiO2 catalysts. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences 467(2131), pp. 1885-1899. (10.1098/rspa.2010.0561)
Lopez-Sanchez, J. A. et al. 2011. Hydrocarbon selective oxidation with heterogeneous gold catalysts. Patent WO 2011051642 [Patent].
Carley, A. F. et al. 2011. CO bond cleavage on supported nano-gold during low temperature oxidation. Physical Chemistry Chemical Physics 13(7), pp. 2528-2538. (10.1039/c0cp01852j)
Murphy, D. M. et al. 2011. Visualizing diastereomeric interactions of chiral amine-chiral copper salen adducts by EPR spectroscopy and DFT. Inorganic Chemistry 50(15), pp. 6944-6955. (10.1021/ic200113u)
Taylor, R. J., Jiang, Y. X., Rees, N. V., Attard, G. A., Jeffery, E. L. and Willock, D. J. 2011. Enantioselective hydrogenation of α-ketoesters: an in situ surface-enhanced Raman spectroscopy (SERS) study. Journal of Physical Chemistry C 115(43), pp. 21363-21372. (10.1021/jp208403g)
Jones, J. T. A. et al. 2011. On-off porosity switching in a molecular organic solid. Angewandte Chemie. International Edition 50(3), pp. 749-753. (10.1002/anie.201006030)
Howard, K. L. and Willock, D. J. 2011. A periodic DFT study of the activation of O2 by Au nanoparticles on a-Fe2O3. Faraday Discussions 152, pp. 135-151. (10.1039/c1fd00026h)

2010

Carter, E., Fallis, I. A., Murphy, D. M., Willock, D. J., Van Doorslaer, S. and Vinck, E. 2010. Probing the role of weak outer sphere interactions (H-bonds) in VO(3,5-tBu2-salophen) – Epoxide adducts by EPR, ENDOR and HYSCORE. Chemical Physics Letters 486(1-3), pp. 74-79. (10.1016/j.cplett.2009.12.066)
Bartley, J. K., Hargreaves, J. S. J., Hutchings, G. J., Rico, J. L., Taylor, S. H., Wells, R. . P. K. and Willock, D. J. 2010. Metal oxides. In: Horvath, I. T. ed. Encyclopedia of Catalysis. New York: John Wiley & Sons, (10.1002/0471227617.eoc139.pub2)

2009

Murphy, D. M., Fallis, I. A., Carter, E., Willock, D. J., Landon, J., Van Doorslaer, S. and Vinck, E. 2009. Enantioselective binding of structural epoxide isomers by a chiral vanadyl salen complex: a pulsed EPR, cw-ENDOR and DFT investigation. Physical Chemistry Chemical Physics 11(31), pp. 6757-6769. (10.1039/b907807j)
Willock, D. J. 2009. Molecular symmetry. Chichester: Wiley. (10.1002/9780470747414)

2008

Coombs, N. D., Clegg, W., Thompson, A. L., Willock, D. J. and Aldridge, S. 2008. A group 13/group 17 analogue of CO and N2: coordinative trapping of the gal molecule. Journal of the American Chemical Society 130(16), pp. 5449-5451. (10.1021/ja800876k)
Coombs, N. D. et al. 2008. Cationic Terminal Gallylene Complexes by Halide Abstraction: Coordination Chemistry of a Valence Isoelectronic Analogue of CO and N-2. Journal of the American Chemical Society 130(47), pp. 16111-16124. (10.1021/ja806655f)
Coquet, R., Howard, K. and Willock, D. J. 2008. Theory and simulation in heterogeneous gold catalysis. Chemical Society Reviews 37(9), pp. 2046-2076. (10.1039/b707385m)
Murphy, D. M., Fallis, I. A., Willock, D. J., Landon, J. H., Carter, E. and Vinck, E. 2008. Discrimination of geometrical epoxide isomers by ENDOR spectroscopy and DFT calculations: the role of hydrogen bonds. Angewandte Chemie. International Edition 47(8), pp. 1414-1416. (10.1002/anie.200703537)
Trewin, A., Willock, D. J. and Cooper, A. I. 2008. Atomistic simulation of micropore structure, surface area, and gas sorption properties for amorphous microporous polymer networks. Journal of Physical Chemistry. C 112(51), pp. 20549-20559. (10.1021/jp806397f)

2007

Conte, M. et al. 2007. Hydrochlorination of acetylene using a supported gold catalyst: A study of the reaction mechanism. Journal of Catalysis 250(2), pp. 231-239. (10.1016/j.jcat.2007.06.018)

2006

Coquet, R., Hutchings, G. J., Taylor, S. H. and Willock, D. J. 2006. Calculations on the adsorption of Au to MgO surfaces using SIESTA. Journal of Materials Chemistry 16(20), pp. 1978-1988. (10.1039/b601213b)
Hayes, R. A., Watson, G. W. and Willock, D. J. 2006. Simulation of the structure of organosilane film coatings. Molecular Simulation 32(12-13), pp. 1095-1101. (10.1080/08927020601052898)

2005

Coquet, R. and Willock, D. J. 2005. The (010) surface of α-MoO3, a DFT + U study. Physical chemistry chemical physics 7(22), pp. 3819-3828. (10.1039/b511044k)
Beutler, A., Davies, C. D., Elliott, M. C., Galea, N., Long, M. S., Willock, D. J. and Wood, J. L. 2005. Diastereoselective Dimerisation of Alkenylthiazolines: A Combined Synthetic and Computational Study. European Journal of Organic Chemistry 2005(17), pp. 3791-3800. (10.1002/ejoc.200500360)
Jeffery, E. L., Mann, R. K., Hutchings, G. J., Taylor, S. H. and Willock, D. J. 2005. A density functional theory study of the adsorption of acetone to the (111) surface of Pt: Implications for hydrogenation catalysis. Catalysis Today 105(1), pp. 85-92. (10.1016/j.cattod.2005.04.013)

2004

Fallis, I. A., Murphy, D. M., Willock, D. J., Tucker, R. J., Farley, R. D., Jenkins, R. L. and Strevens, R. R. 2004. Direct Observation of Enantiomer Discrimination of Epoxides by Chiral Salen Complexes Using ENDOR. Journal of the American Chemical Society 126(48), pp. 15660-15661. (10.1021/ja045491s)
Griffiths, P. C. et al. 2004. The Structure of Metallomicelles. Chemistry - A European Journal 10(8), pp. 2022-2028. (10.1002/chem.200305670)
Li, X. et al. 2004. Enantioselective hydrogenation using cinchona-modified Pt/γ-Al 2O3 catalysts: Comparison of the reaction of ethyl pyruvate and buta-2,3-dione. Catalysis Letters 96(3-4), pp. 147-151. (10.1023/B:CATL.0000030112.70608.a0)

2003

Tucker, R. J., Fallis, I. A., Farley, R. D., Murphy, D. M. and Willock, D. J. 2003. An ENDOR and DFT analysis of 'solvatochromic' effects in an oxovanadium (IV) complex. Chemical Physics Letters 380(5-6), pp. 758-766. (10.1016/j.cplett.2003.09.077)
Hammond, C. R., Hutchings, G. J., Willock, D. J. and Taylor, S. H. 2003. A study of methane activation by modified gallium- and zinc-based catalysts. Research on Chemical Intermediates 29(7-9), pp. 911-920. (10.1163/156856703322601906)

2002

Murphy, D. M., Fallis, I. A., Farley, R. D., Tucker, R. J., Avery, K. L. and Willock, D. J. 2002. Conformational changes of an oxovanadium complex probed by ENDOR spectroscopy and DFT calculations. Physical Chemistry Chemical Physics 4(20), pp. 4937-4943. (10.1039/b204564h)
Dickinson, A. A., Willock, D. J., Calder, R. J. and Aldridge, S. 2002. Analysis of Bonding in Cyclopentadienyl Transition-Metal Boryl Complexes. Organometallics 21(6), pp. 1146-1157. (10.1021/om0105122)

2001

Elliott, M. C., Kruiswijk, E. and Willock, D. J. 2001. Asymmetric hetero-Diels-Alder reactions. Reactions of oxazolo[3,2-c]pyrimidines. Tetrahedron 57(51), pp. 10139-10146. (10.1016/S0040-4020(01)01032-8)
Cooper, C. A., Hammond, C. R., Hutchings, G. J., Taylor, S. H., Willock, D. J. and Tabata, K. 2001. A combined experimental and theoretical approach to the study of methane activation over oxide catalysts. Catalysis Today 71(1-2), pp. 3-10. (10.1016/S0920-5861(01)00446-1)
Elliott, M. C., Galea, N., Long, M. S. and Willock, D. J. 2001. Highly diastereoselective dimerisation of alkenylthiazolines. Tetrahedron Letters 42(29), pp. 4937-4939. (10.1016/S0040-4039(01)00886-3)
Cooper, C. A., Hammond, C. R., Hutchings, G. J., Taylor, S. H., Willock, D. J. and Tabata, K. 2001. The role of gallium oxide in methane partial oxidation catalysts: an experimental and theoretical study. Studies in Surface Science and Catalysis 136, pp. 319-324.

1998

Elliott, M. C., Kruiswijk, E. and Willock, D. J. 1998. Asymmetric hetero-Diels-Alder reactions. Mechanism of the reaction of alkenyloxazolines with isocyanates. Tetrahedron Letters 39(48), pp. 8911-8914. (10.1016/S0040-4039(98)01949-2)

Our interest in periodic DFT calculations for surfaces important in catalysis is exemplified by the images below on MoO₃. This important oxidation catalyst is known to form as a defective (sub-stoichiometric) material with surface oxygen defects. Some oxidation processes also involve the use of lattice oxygen following the Mars-van Krevelen mechanism. The exchange of oxygen with the surface then becomes key to understand the oxygen supply.

Formally, the removal of oxygen from the MoO₃ surface shown below involves a reduction of a single Mo centre from Mo⁶⁺ to Mo⁴⁺. GGA-DFT fails to reproduce this effect since the electrons left behind after O is removed delocalise through the conduction band of the material. We have used the Hubbard U parameter extension of DFT to consider this system, which increases the band gap (closer to the experimental) and gives localised states at the Mo centre. The spin density shows a triplet ground state for this defect.

Molecular oxygen will adsorb at this defect site, donate an electron to the Mo centre and produce a surface superoxo (O₂^-) species. The superoxo itself may play a role in oxidation catalysis, or go on to heal the defect.

CH3204 Symmetry, Spectroscopy and Quantum Mechanics

CH3304 Advanced Physical Chemistry

CH3406 Theoretical Methods

CHT232 Key skills for Postgraduate Chemists

CHT401 Advanced Heterogeneous Catalysis

Details of modules can be found in course finder.

PhD, Queen Mary and Westfield College, London., Dept. Physics, (1991, E.G. Wilson), PDRAs UCL (S.L.Price), Royal Institution (C.R.A.Catlow), Daresbury Labs. (M.Leslie), Leverhulme Centre, Liverpool (G.J.Hutchings). Appointed Lecturer in Cardiff (1998) promoted to Senior Lecturer (2003) and Professor (2022).

Member of RSC (CChem), IOP (CPhys), SCI, ACS.

Computational Chemistry
Periodic DFT
Catalytic mechanism
Heterogeneous Catalysis.

Current supervision

Eimear McCarthy

Research student

Cornelius Lombard

Research student

Past projects

DFT Simulation of the glycerol to methanol reaction.
Simulation of methane oxidation over AuPd catalysts.
Combining Computational Modelling and Interrogative Kenetics.
Simulation of Heterogeneous Au Catalysis.
DFT simulation of catalysis for platform molecules from renewable resources.

Celebrating the International Year of the Periodic Table

21 January 2019

Cardiff science on show at annual Royal Society exhibition

03 July 2017

External profiles

ORCID