L. Joos

Flexibility versus rigidity: what determines the stability of zeolite frameworks? A case study

E. Verheyen, L. Joos, C. Martineau, C.J. Dawson, C. Weidenthaler, W. Schmidt, R. Yuan, E. Breynaerts, V. Van Speybroeck, M. Waroquier, F. Taulelle, M.M.J. Treacy, J.A. Martens, C. Kirschhock
Materials Horizons
Vol. 1 , 582 - 587


All silica COK-14/-COK-14 with OKO topology is the first case of a zeolite which reversibly transforms from a systematically interrupted to a fully connected state and back. Analysis of the opening/closing behavior allowed the study of entropy and framework flexibility as determinants for the stability of zeolite topologies, which, until now, has been experimentally inaccessible. Interconversion of the all-silica COK-14 zeolite with fully connected OKO topology and its -COK-14 variant with systematic framework interruption was investigated using high-temperature XRD, thermogravimetric analysis, Si-29 MAS NMR, nitrogen adsorption and a range of modelling techniques. Specific framework bonds in the OKO framework can be reversibly hydrolyzed and condensed. Structural silanols of the parent -COK-14, prepared by degermanation of the IM-12 zeolite, were condensed by heating at 923 K, and hydrolyzed again to the initial state by contacting the zeolite with warm water. Molecular modelling revealed an inversion of the relative stabilities for both variants depending on temperature and hydration. Condensation of the structural silanols in -COK-14 to COK-14 is entropy driven, mainly resulting from the release of water molecules. Framework reopening in the presence of water is spontaneous due to the high rigidity of the fully connected OKO framework. Isomorphous substitution was demonstrated as a viable option for stabilization of the fully connected OKO framework as this renders the closed framework flexible.

Molecular Simulation Study of the Competitive Adsorption of H2O and CO2 in Zeolite 13X

L. Joos, J.A. Swisher, B. Smit, A. Bruder
29 (48), 14743-14747


Surfactants exhibit maxima in their critical micelle concentrations upon application of hydrostatic pressure, which is attributable to changes in their volumes of micellization from positive to negative values with increasing pressure. We present a direct molecular simulation analysis of the volumes of micellization of an anionic, cationic, and nonionic surfactant in aqueous solution at pressures up to 2500 bar. Excellent agreement with experiment is observed. A Kirkwood-Buff theory analysis based on proximal solvent distributions permits the breakdown of the volumes of micellization into constituent surfactant headgroup and tailgroup contributions. Although the micellization volume crossover is analogous to the transfer of an alkane from water to its pure liquid, significant differences are observed, including lower compressibilities of micelle volumes compared to that of the alkane liquid, negative partial compressibilites for anionic sulfated surfactant monomers, and large nonionic ethoxy headgroup contributions to the micellization volume.

Reactivity of CO on carbon covered cobalt surfaces in Fischer-Tropsch Synthesis

L. Joos, I. Filot, S. Cottenier, E. Hensen, M. Waroquier, V. Van Speybroeck, R.A. van Santen
Journal of Physical Chemistry C
118 (10), 5317–5327


Fischer–Tropsch synthesis is an attractive process to convert alternative carbon sources, such as biomass, natural gas, or coal, to fuels and chemicals. Deactivation of the catalyst is obviously undesirable, and for a commercial plant it is of high importance to keep the catalyst active as long as possible during operating conditions. In this study, the reactivity of CO on carbon-covered cobalt surfaces has been investigated by means of density functional theory (DFT). An attempt is made to provide insight into the role of carbon deposition on the deactivation of two cobalt surfaces: the closed-packed Co(0001) surface and the corrugated Co(112̅1) surface. We also analyzed the adsorption and diffusion of carbon atoms on both surfaces and compared the mobility. Finally, the results for Co(0001) and Co(112̅1) are compared, and the influence of the surface topology is assessed.

Entropy-Driven Chemisorption of NOx on Phosphotungstic Acid

S. Heylen, L. Joos, V. Van Speybroeck, C. Kirschhock, J.A. Martens
Angewandte Chemie int. Ed.
51 (44), 11010-11013


Nitrogen oxides, NOx, are formed in combustion engines. They contribute to acid rain and the formation of ozone and are hazardous for men and environment. In this article, a process was investigated that can 'capture' the NOx from the exhaust gases using heteropoly acids and can later release them for processing. One of the main conclusions is that the mobility of the captured and released molecules is the key to control the reaction. This can now be used to optimize and commercialize the technology.

Stikstofoxiden, aangeduid als NOx, worden gevormd in verbrandingsmotoren. Ze dragen bij tot zure regen, de vorming van ozon en zijn dus schadelijk voor mens en milieu. In dit artikel werd een proces onderzocht dat de NOx kan ‘vangen’ uit de uitlaatgassen aan de hand van heteropolyzuren en later terug kan vrijgeven voor verdere verwerking. Een van de belangrijkste vaststellingen is dat de mobiliteit van de opgeslagen en vrijgegeven moleculen de sleutel is voor het controleren van het proces. De conclusies van het onderzoek kunnen nu verder gebruikt worden voor de optimalisering en commercialisering van het proces.


NOx adsorption on Phosphotungstic acid is entropy-driven due to the watermolecules that are released.

Computational Study of the Reversible Opening and Closing of the COK-14 zeolite


Conference / event / venue 

WATOC 2014 Satellite Meeting on Large Condensed and Biological Systems
Concepción, Chili
Monday, 13 October, 2014 to Tuesday, 14 October, 2014


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