A DFT-based simulated annealing method for the optimization of global energy in zeolite framework systems

Application to natrolite, chabazite and clinoptilolite

Significance 

Zeolites are microporous solids of the aluminosilicate mineral family that are commonly used as commercial adsorbents. Typically, they confer interesting structural properties that tend to favor their application in industrial processes. In particular, their impact has been notorious in petrochemical and biochemical manufacture of fuels and feedstocks, adsorption and separation, as well as ion-exchange; especially in the case of zeolite-supported nanoscale zero-valent iron which has been suggested to have a great potential for treating water and soil multi-contaminated with heavy metals (As, Cd and Pb). Consequently, it is crucial to highlight the uses of zeolites in environmental care. To date, large modeling studies, focused on attaining crystallographic-quality description of the extra-framework structure of complex zeolites, have been conducted using interatomic potentials with much less space occupied by the expensive Density Functional Theory (DFT) based studies. Studies have shown that the sensitive properties of the zeolites show a remarkable dependence on the structural model, thereby calling for the necessity of more zeolite models to properly describe them. Moreover, previous research showed that such large exploration of the configurational space of complex zeolites using DFT approaches is challenging due to the inherent computational cost; therefore, alternative approaches ought to be sought.

To date, numerous approaches for solving optimization problems have been proposed. Among them, Simulated Annealing (SA) has emerged as one of the most versatile method. However, SA methods have not been applied to predict the structure of the extra-framework species in zeolites considering their inherent structural relaxation and flexibility. In this view, researchers from the University of Sevilla, Spain: Dr. Mohamed Abatal and Professor Norge Cruz Hernández, in collaboration with Dr. A. Rabdel Ruiz-Salvador at the Pablo de Olavide University demonstrated SAs’ usefulness in DFT-based calculation in zeolites bearing charge-compensating cations and polar molecules. Their work is currently published in the research journal, Microporous and Mesoporous Materials.

Basically, the SA idea is to perform a molecular dynamics (MD) by increasing the temperature step-by-step to overcome local energy minima; after that, by subsequent energy optimization, it is possible to move to a different local minimum. In their work, the researchers implemented the aforementioned procedure up to the temperatures of 300 and 400K. Further, MD, as well as, geometry optimization, were carried out in a periodic framework and dispersion corrected DFT calculation using VASP. Also, in their approach, they used three widely studied zeolites as model systems: i.e. natrolite, chabazite and clinoptilolite.

As such, the research team were able to obtain the global minimum energy by using SA in DFT-based calculation in zeolites including charge-compensating cations and polar molecules. Indeed, their results were able to show slight differences depending on the peak temperature of the rump up of SA, suggesting there that more than one simulation with different maximum temperature should be considered.

In summary, the study demonstrated the SA method as an efficient and relatively cheap approach to perform DFT studies of the zeolites structure including strongly interacting extra-framework species, when their structural relaxation and flexibility are considered. Remarkably, the reported method was able to explore multiple minima in the complex systems used, thus minimizing the chances of getting trapped in a local minimum. In a statement to Advances in Engineering, Professor Norge Cruz Hernández highlighted that their findings were in good agreement between their interaction energy results after performing SA and experimental/theoretical data available in literature.

A DFT-based simulated annealing method for the optimization of global energy in zeolite framework systems: Application to natrolite, chabazite and clinoptilolite - Advances in Engineering

About the author

Dr. A. Rabdel Ruiz-Salvador

He started doing research (1992/1995) on ionic conductivity in solids and electrical response of materials. In 1996 he moved to the area of porous solids, finishing his PhD Thesis (1999) on the development of computational methodologies for the study of the structure of zeolites in cooperation with The Royal Institution of Great Britain and University College London. This research was awarded as the most relevant work in the natural and exact sciences at the University of Havana and at the same time with a national prize of the Cuban Academy of Science. Since 1998, he has been also involved with experimental investigations of nanoporous solids. At the time, he started the structural modeling of hydrated zeolites and in 2000 he received a prestigious Visiting Research Grant from the Royal Society, Great Britain. In 2000 he was elected member of the Scientific Council of the Institute of Materials Science and Technology, of University of Havana, in 2002 elected a Young Associate of the Cuban Academy of Sciences and in 2004 a member of the Scientific Council of the University of Havana. In 2001 he started his own group combining modelling and experiment for studying zeolites and MOFs. In 2004 he pioneered the research on the automatic atomistic design of nanoporous solids based on topology, giving rise to the Tobunporous code. He acted as local leader of an ALFA-EU project in cooperation with four European and two Latin America partners, which was directed to the design, modeling and experimental studies of nanoporous solids for gas storage. In 2013 he moved to the Pablo de Olavide University, Seville, Spain, as a postdoc. Since September 2018 he returned to his own work as a professor at the Pablo de Olavide University.

His current research interests are: (a) development of methods and methodologies for the atomistic design of materials, in particular nanoporous, linkded to ToBuNPorouS (Topological Building of Nanoporous Solids) program and related; (b) development of methodologies to increase efficiency in atomistic modeling of the structure, adsorption and diffusion of materials, with focus on nanoporous solids using classical and quantum approximations; (c) development of ab-inito derived interatomic potentials to efficiently describe intra- and intermolecular interactions; (d) conceptual design of nanoporous materials, MOFs and zeolites, both from synthesis and postsynthetic modifications; (e)  structural analysis (connected to experimentation) of nanoporous materials, which includes development of theoretical-computational methodologies and algorithms for this purpose.

Url: https://scholar.google.com/citations?user=ZeXKD0YAAAAJ&hl
E-mail: [email protected]

About the author

Dr. Mohamed Abatal

His PhD degrees at National Autonomous University of Mexico (2001-2005). He received his Posdoct in the Department of Geochemistry of the Institute of Geology of the National Autonomous University of Mexico (August 2006-July 2008) and in the Department of Environmental Sciences of the National Institute for Nuclear Research (August 2008- July 2009). His PhD Bachelor’s degree in Science from the Hassan II University, 2001. In 2018–2019, he completed a sabbatical at Seville University with the supervision of Professor Norge Cruz Hernández.

Mohamed Abatal joined with Mechanical Engineering Group of Faculty of Engineering in Autonomous University of Carmen as a research professor at August 2009. He is a member of the National System of Researchers since January 2007 and of the Network of Nanosciences and Nanotechnology since 2017. His research interests include materials science, environmental engineering and computational chemistry. His research work have resulted in several research grants, 3 book chapters and more than 45 peer reviewed journal and conference publications.

ORCID: https://orcid.org/0000-0003-2479-8769
E-mail: [email protected]

About the author

Dr. Norge Cruz Hernández

He obtained his bachelor in Nuclear Physics at Higher Institute of Nuclear Sciences and Technology in Havana (ISCTN), Cuba, July 1996. In June 1998, he got the MSc degree in Nuclear Physics, also in the ISCTN. Next, on February 2002 he received his PhD Chemistry degree (Material Science) at Physical Chemistry Department at University of Seville. Now a day, he is associated Professor at the Applied Physics Department, in the Higher Polytechnic School at University of Seville. Moreover, he has completed stay of research at: Technische Universität München, Cornell University, University of Chile, University of Reding and Universidad Autónoma del Estado de Morelos.

His research interests include the molecular and materials simulation by using DFT periodic calculation, as well as, classical molecular dynamic simulations. The studied systems have been : heterogeneous catalysis (metal deposited on metal oxide), metal organic framework (MOF and ZIFs), zeolites systems and more recently biomolecules.

Url: https://personal.us.es/norge/
E-mail: [email protected]
ResearcherID: E-1067-2011

Reference

Mohamed Abatal, A. Rabdel Ruiz-Salvador, Norge Cruz Hernández. A DFT-based simulated annealing method for the optimization of global energy in zeolite framework systems: Application to natrolite, chabazite and clinoptilolite. Microporous and Mesoporous Materials, volume 294 (2020) 109885. DOI 10.1016/j.micromeso.2019.109885

Go To Microporous and Mesoporous Materials

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