ERC - First principle molecular dynamics simulations for complex chemical transformations in nanoporous materials (DYNPOR)

Chemical transformations in nanoporous materials are vital in many application domains, such as catalysis, molecular separations, sustainable chemistry,... Model-guided design is indispensable to tailoring materials at the nanometer scale level.

At real operating conditions, chemical transformations taking place at the nanometer scale have a very complex nature, due to the interplay of several factors such as the number of particles present in the pores of the material, framework flexibility, competitive pathways, entropy effects,… The textbook concept of a single transition state is far too simplistic in such cases. A restricted number of configurations of the potential energy surface is not sufficient to capture the complexity of the transformation.

Within the DYNPOR project, we will simulate complex chemical transformations in nanoporous materials using first principle molecular dynamics methods at real operating conditions, capturing the full complexity of the free energy surface. To achieve these goals advanced sampling methods will be used to explore the interesting regions of the free energy surface. The number of guest molecules at real operating conditions will be derived and the diffusion of small molecules through pores with blocking molecules will be studied. New theoretical models will be developed to keep track of both the framework flexibility and entropy of the lattice.

The selected applications are timely and rely on an extensive network with prominent experimental partners. The applications will encompass contemporary catalytic conversions in zeolites, active site engineering in metal organic frameworks and structural transitions in nanoporous materials, and the expected outcomes will have the potential to yield groundbreaking new insights.

The results are expected to have impact far beyond the horizon of the current project as they will contribute to the transition from static to dynamically based modeling tools within heterogeneous catalysis.

A1 publications

Methane Adsorption in Zr-Based MOFs: Comparison and Critical Evaluation of Force Fields, S. Vandenbrande, T. Verstraelen, J. J. Gutierrez-Sevillano, M. Waroquier, V. Van Speybroeck, Journal of Physical Chemistry C, 121 (45), 25309-25322, 2017
Hydrogen transfer versus methylation: on the genesis of aromatics formation in the Methanol-To-Hydrocarbons over H-ZSM-5 , J. S. Martínez-Espín, K. De Wispelaere, T. V. Janssens, S. Svelle, K. P. Lillerud, P. Beato, V. Van Speybroeck, U. Olsbye, ACS Catalysis, 7, 5773–5780, 2017
Nature of active sites on UiO-66 and beneficial influence of water in the catalysis of Fischer esterification, C. Caratelli, J. Hajek, F. G. Cirujano, M. Waroquier, F. X. Llabres i Xamena, V. Van Speybroeck, Journal of Catalysis, 352, 401-414, 2017
Mechanical properties of a gallium fumarate metal-organic framework: a joint experimental-modelling exploration, P. Ramaswamy, J. Wieme, E. Alvarez, L. Vanduyfhuys, J.-P. Itié, P. Fabry, V. Van Speybroeck, C. Serre, P.G. Yot, G. Maurin, Journal of Materials Chemistry A, 5 (22), 11047-11054, 2017
The remarkable amphoteric nature of defective UiO-66 in catalytic reactions, J. Hajek, B. Bueken, M. Waroquier, D. De Vos, V. Van Speybroeck, ChemCatChem, 9 (12), 2203-2210, 2017
Metal-organic and covalent organic frameworks as single-site catalysts, S.M.J. Rogge, A. Bavykina, J. Hajek, H. Garcia, A.I. Olivos-Suarez, A. Sepúlveda-Escribano, A. Vimont, G. Clet, P. Bazin, F. Kapteijn, M. Daturi, E.V. Ramos-Fernandez, F.X. Llabres i Xamena, V. Van Speybroeck, J. Gascon, Chemical Society Reviews, 46 (11), 3134-3184, 2017
Benzene co-reaction with methanol and dimethyl ether over zeolite and zeotype catalysts: Evidence of parallel reaction paths to toluene and diphenylmethane, J. S. Martínez-Espín, K. De Wispelaere, M. Westgård Erichsen, S. Svelle, T. V. Janssens, V. Van Speybroeck, P. Beato, U. Olsbye, Journal of Catalysis, 349, 136-148, 2017
Missing linkers: an alternative pathway to UiO-66 electronic structure engineering, A. De Vos, K. Hendrickx, P. Van der Voort, V. Van Speybroeck, K. Lejaeghere, Chemistry of Materials, 29 (7), 3006–3019, 2017
The Monomer Electron Density Force Field (MEDFF): A Physically Inspired Model for Non-Covalent Interactions, S. Vandenbrande, M. Waroquier, V. Van Speybroeck, T. Verstraelen, Journal of Chemical Theory and Computation (JCTC), 13 (1), 161–179, 2017
Effect of temperature and branching on the nature and stability of alkene cracking intermediates in H-ZSM-5, P. Cnudde, K. De Wispelaere, J. Van der Mynsbrugge, M. Waroquier, V. Van Speybroeck, Journal of Catalysis, 345, 53-69, 2017
Acidity constant (pKa) calculation of large solvated dye molecules: evaluation of two advanced molecular dynamics methods, T. De Meyer, B. Ensing, S.M.J. Rogge, K. De Clerck, E.J. Meijer, V. Van Speybroeck, ChemPhysChem, 17 (21), 3447–3459, 2016
Suppression of the Aromatic Cycle in Methanol-to-Olefins Reaction over ZSM-5 by Post-Synthetic Modification Using Calcium, I. Yarulina, S. Bailleul, A. Pustovarenko, J. Ruiz-Martinez, K. De Wispelaere, J. Hajek, B.M. Weckhuysen, K. Houben, M. Baldus, V. Van Speybroeck, F. Kapteijn, J. Gascon, ChemCatChem, 8 (19) 3057–3063, 2016
Thermodynamic Insight in the High-Pressure Behavior of UiO-66: Effect of Linker Defects and Linker Expansion, S.M.J. Rogge, J. Wieme, L. Vanduyfhuys, S. Vandenbrande, G. Maurin, T. Verstraelen, M. Waroquier, V. Van Speybroeck, Chemistry of Materials, 28 (16), 5721-5732, 2016
Exploring the flexibility of MIL-47(V)-type materials using force field molecular dynamics simulations, J. Wieme, L. Vanduyfhuys, S.M.J. Rogge, M. Waroquier, V. Van Speybroeck, Journal of Physical Chemistry C, 120 (27), 14934-14947, 2016
Water coordination and dehydration processes in defective UiO-66 type metal organic frameworks, M. Vandichel, J. Hajek, A. Ghysels, A. De Vos, M. Waroquier, V. Van Speybroeck, CrystEngComm, 18 (37), 7056-7069 , 2016
Towards metal–organic framework based field effect chemical sensors: UiO-66-NH2 for nerve agent detection, L. Stassen, B. Bueken, H. Reinsch, J.F.M. Oudenhoven, D. Wouters, J. Hajek, V. Van Speybroeck, N. Stock, P.M. Vereecken, R. Van Schajik, D. De Vos, R. Ameloot, Chemical Science, 7, 5827-5832 , 2016
Minimal Basis Iterative Stockholder: Atoms-in-Molecules for Force-Field Development, T. Verstraelen, S. Vandenbrande, F. Heidar-Zadeh, L. Vanduyfhuys, V. Van Speybroeck, M. Waroquier, P.W. Ayers, Journal of Chemical Theory and Computation (JCTC), 12(8), 3894-3912, 2016
On the stability and nature of adsorbed pentene in Brønsted acid zeolite H-ZSM-5 at 323 K, J. Hajek, J. Van der Mynsbrugge, K. De Wispelaere, P. Cnudde, L. Vanduyfhuys, M. Waroquier, V. Van Speybroeck, Journal of Catalysis, 340, 227 - 235, 2016
Is the error on first-principles volume predictions absolute or relative?, K. Lejaeghere, L. Vanduyfhuys, T. Verstraelen, V. Van Speybroeck, S. Cottenier, Computational Materials Science, 117, 390-396, 2016
Towards molecular control of elementary reactions in zeolite catalysis by advanced molecular simulations mimicking operating conditions, K. De Wispelaere, S. Bailleul, V. Van Speybroeck, Catalysis Science & Technology, 6, 2686 – 2705, 2016
Cutting the cost of carbon capture: a case for carbon capture and utilization, L. Joos, J. Huck, V. Van Speybroeck, B. Smit, Faraday Discussions, 192, 391-414 , 2016
Vibrational fingerprint of the absorption properties of UiO-type MOF materials, A. Van Yperen-De Deyne, K. Hendrickx, L. Vanduyfhuys, G. Sastre, P. Van der Voort, V. Van Speybroeck, K. Hemelsoet, Theoretical Chemistry Accounts, 135, 4, 102, 2016
A breathing zirconium metal-organic framework with reversible loss of crystallinity by correlated nanodomain formation, B. Bueken, F. Vermoortele, M.J. Cliffe, M.T. Wharmby, D. Foucher, J. Wieme, L. Vanduyfhuys, C. Martineau, N. Stock, F. Taulelle, V. Van Speybroeck, A.L. Goodwin, D. De Vos, Chemistry - A European Journal, 2016, 22, 1-5, 2016
Insight into the Effect of Water on the Methanol-to-Olefins Conversion in H-SAPO-34 from Molecular Simulations and in Situ Microspectroscopy, K. De Wispelaere, C.S. Wondergem, B. Ensing, K. Hemelsoet, E.J. Meijer, B.M. Weckhuysen, V. Van Speybroeck, J. Ruiz-Martinez, ACS Catalysis, 6, 1991-2002, 2016
Mechanical energy storage performance of an aluminum fumarate metal-organic framework, P.G. Yot, L. Vanduyfhuys, E. Alvarez, J. Rodriguez, J.-P. Itié, P. Fabry, N. Guillou, T. Devic, P.L. Llewellyn, V. Van Speybroeck, C. Serre, G. Maurin, Chemical Science, 7, 446-450, 2016
A comparison of barostats for the mechanical characterization of metal-organic frameworks, S.M.J. Rogge, L. Vanduyfhuys, A. Ghysels, M. Waroquier, T. Verstraelen, G. Maurin, V. Van Speybroeck, Journal of Chemical Theory and Computation (JCTC), 11 (12), 5583-5597, 2015
Shape-selective diffusion of olefins in 8-ring solid acid microporous zeolites, A. Ghysels, S.L. Moors, K. Hemelsoet, K. De Wispelaere, M. Waroquier, G. Sastre, V. Van Speybroeck, Journal of Physical Chemistry C, 119, 41, 23721-23734, 2015
Mechanistic studies of aldol condensations in UiO-66 and UiO-66-NH2 metal organic frameworks, J. Hajek, M. Vandichel, B. Van de Voorde, B. Bueken, D. De Vos, M. Waroquier, V. Van Speybroeck, Journal of Catalysis, 331, 1-12, 2015
Mechanical properties from periodic plane wave QM codes: the challenge of the flexible nanoporous MIL-47 (V) framework , D.E.P. Vanpoucke, K. Lejaeghere, V. Van Speybroeck, M. Waroquier, A. Ghysels, Journal of Physical Chemistry C, 119, 23752-23766, 2015
Advances in theory and their application within the field of zeolite chemistry, V. Van Speybroeck, K. Hemelsoet, L. Joos, M. Waroquier, R.G. Bell, C.R.A. Catlow, Chemical Society Reviews, Vol. 44 , 7044-7111, 2015
Complex reaction environments and competing reaction mechanisms in zeolite catalysis: insights from advanced molecular dynamics, K. De Wispelaere, B. Ensing, A. Ghysels, E.J. Meijer, V. Van Speybroeck, Chemistry - A European Journal, 21 (26), 9385-9396, 2015