|FRIDAY 1st JULY 2022|
|15:00-16:00||Understanding and controlling zeolite synthesis, by Toru Wakihara, Institute of Engineering Innovation, The University of Tokyo, Tokyo, Japan|
|16:00-17:00||Predicting zeolite polymorphism from experimental and computational data, by Rafael Gómez-Bombarelli, Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, USA|
|17:30-18:30||Structure determination of microporous materials at the atomic scale using electron microscopy, by Tom Willhammar, Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden|
From molecules to frameworks: The reticular approach in the design and discovery of new materials, by Felipe Gándara, Materials Science Institute of Madrid (ICMM-CSIC), Madrid, Spain
|SATURDAY 2nd JULY 2022|
|9:00-10:00||Molecular simulation applied to porous materials, by Sofía Calero, Department of Applied Physics, Eindhoven University of Technology (TU/e), The Netherlands|
|10:00-11:00||Good practices in spectroscopic studies of Zeolites as catalysts, by Silvia Bordiga, Department of Chemistry, NIS Centre of Excellence, University of Torino, Italy|
|11:00-11:30||Coffee Break / Poster session|
|11:30-12:30||Zeolites and zeo-type materials for storage and conversion of CO2 to valuable products, by Girolamo Giordano, Department of Environmental and Chemical Engineering, University of Calabria, Italy|
|12:30-13:30||Zeolite Membranes, from Synthesis to Application- Basics and Emerging Trends, by Anne Julbe, Institut Européen des Membranes (IEM, UMR 5635 CNRS, ENCM, UM), Université de Montpellier, France|
|13:30-15:30||Lunch / Poster session|
|15:30-16:30||An industrial view on the role of zeolitic materials towards #decarbonizing the production of chemicals and fuels, by Juan S. Martínez-Espín, Biobased Chemicals R&D, Topsoe, Kongens Lyngby, Denmark|
|16:30-17:30||Insights into zeolite confinement effect on bifunctional catalysis by Filipa Ribeiro, CQE, Instituto Superior Técnico, Lisboa|
Understanding and controlling zeolite synthesis
Institute of Engineering Innovation, The University of Tokyo, Tokyo, JAPAN
Zeolites are artificially synthesized from silicon sources, aluminum sources, mineralizing agents and structure-directing agents in batch systems under hydrothermal conditions. To fulfill the wide industrial demands, efficient synthesis of zeolites with controllable crystallization kinetics is considered crucially important. It is believed that the amorphous aluminosilicate obtained by mixing raw materials first undergoes an induction stage, where its structure changes to a more stable amorphous state, and then a "crystal nucleus," the smallest entity that can be recognized as a crystalline phase, is formed. Thus, if the process of initial structural evolution of zeolites can be clarified and controlled, it will be possible to design and synthesize zeolites with controlled structure and composition in a rational manner. Furthermore, it is expected to make a significant contribution to the discovery of theoretical zeolites with unknown structure and composition. However, the multifaceted formation process of zeolites cannot be simply explained by the classical nucleation theory, in which monomers aggregate to reach a critical size. Furthermore, the aperiodic structure of the aluminosilicate precursor invalidates the conventional crystallographic characterization, and this amorphous-to-crystalline transition process is still a black box. This lecture will focus on the synthesis of zeolites, explaining how zeolites are formed in the hydrothermal synthesis process and how they can be controlled.
Predicting zeolite polymorphism from experimental and computational data
Department of Materials Science and Engineering, MIT, Cambridge, USA
Zeolites are nanoporous materials with many applications in separations and catalysis. Thanks to their topological diversity they are extremely versatile. Over 250 known polymorphs exist and thousands more are predicted to be possible. However, zeolite synthesis is a complex combinatorial problem with dozens of input variables, and it typically requires intensive trial and error in the lab. This results in challenges in controlling polymorphism (i.e. which phase will be formed under certain conditions) in a predictive fashion.
Machine learning tools can leverage large datasets to address high-dimensional design challenges. We have recently shown that big-data tools, combining atomistic simulations, and automated literature extraction with natural-language process can produce insights and quantitative predictions for controlling these phases. For instance, solid-state interzeolite transformations can be rationalized by quantifying the similarity in chemical connectivity between frameworks. For templated zeolite synthesis, we have used over a million atomistic simulations, validated with exhaustive literature data extracted from the literature, to rationalize and design molecular templates.
In this talk, we will provide a brief introduction to the discipline of machine learning, and delineate key concepts such as supervised vs. unsupervised learning, feature engineering vs. representation learning, training vs. test data, etc. Then, we will relate these foundational concepts in ML to successful applications in predicting zeolite synthesis.
Structure determination of microporous materials at the atomic scale using electron microscopy
Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, SWEDEN
Ordered microporous materials, such as zeolites and metal-organic frameworks, have been implemented in a large number of important industrial applications. Their unique properties are largely determined by their unique and well-defined structures with pores in the size range of small molecules. In order to understand their properties it is hence important to obtain insights into their structures at the atomic scale. Transmission electron microscopy provides two versatile tool for this task, three-dimensional electron diffraction (3D ED) and high-resolution (scanning) transmission electron microscopy ((S)TEM) imaging.
The synthesis of microporous materials often results in sub-micrometer-sized crystals. Earlier this hampered structure determination since this directed the process towards the more challenging powder X-ray diffraction data. With the advent of 3D ED a more straight-forward route for determination of the atomic crystal structure opened up. Using the 3D ED, crystals as small as 100 nm or less can now be considered single-crystals and their structures can be determined using ab-initio methods similar to the ones used for single-crystal X-ray diffraction.1
Materials containing defects and stacking disorder or low-dimensional materials however still remain a challenge. For these materials, atomic resolution imaging methods are of great importance in order to retrieve structural information. Recent developments of modern electron microscopes are now enabling several opportunities for real space examination of porous solids at the atomic scale. The aberration-correction makes it possible to obtain STEM images with sub-Ångström resolution and the traditional high resolution TEM (HRTEM) imaging can still be used to obtain images at the atomic scale. The recently developed integrated differential phase contrast (iDPC) technique opens up for STEM imaging with electron beam doses one order of magnitude lower than before. These methods all make it possible to study defects, structural disorder, non-periodic features, surface termination, low-dimensional structures2 etc. in zeolites and metal-organic frameworks.
Molecular Simulation Applied to Porous Materials
Department of Applied Physics, Eindhoven University of Technology, THE NETHERLANDS
Molecular simulation plays an important role in the field of porous materials. In recent years there has been a great improvement in methodology, force fields and software, which has allowed molecular simulation to be a powerful tool that complements the experiment and creates a perfect synergy with industry. Using molecular simulation we can predict not only the adsorption and separation performance of a given material, but also its stability against water, temperature and pressure. We can also suggest, based on these predictions, strategies to improve both performance and stability. We can even go further and propose new designs for separation processes, scaling them up for industrial application.
This presentation will focus on molecular simulation, discussing the state of the art, current work and what we foresee in the short and long term. In particular, I will discuss the software available for the study and visualisation of porous materials and the need to make good use of force fields and high-throughput methods. Only with all this will we be able to accurately calculate surface properties, as well as adsorption, transport and separation of gases and liquids in porous materials. I will show innovative approaches to assess the stability of materials and to identify and design new high-performance multifunctional porous structures. Finally, I will discuss how machine learning can play a key role in this field, indicating current advantages and limitations.
From molecules to frameworks: The reticular approach in the design and discovery of new materials.
Materials Science Institute of Madrid (ICMM-CSIC), Madrid, SPAIN
Reticular materials are built up by the linkage of molecular building blocks through strong bonds, forming extended, crystalline frameworks with predefined structural and topological features. The rise of reticular chemistry during the last two decades has endowed chemists and material scientists with new tools for the design and preparation of new functional materials with precise structural control. Metal-organic frameworks (MOFs), and covalent-organic frameworks (COFs) have thus emerged as versatile porous materials with interest and application in multiple fields, such as gas storage, drug delivery, catalysis, opto-electronics, etc. This lecture is intended to first give a general overview of the implementation of reticular chemistry principles in the obtaining of MOFs and COFs, followed by a discussion of the new avenues that have been opened to achieve materials with higher levels of complexity, always with consideration of synthetic, characterization, and application aspects.
Zeolites and zeo-type materials for storage and conversion of CO2 to valuable products
C.E.Ca.S.P. Lab., University of Calabria, Rende, ITALY
The increasing amount of anthropogenic carbon dioxide (CO2) emissions is a global concern. Since a correlation between the rise in global temperature and the increment of CO2 in atmosphere has been demonstrated, reducing the amount of CO2 concentration could mitigate the greenhouse effect. Scientists have been studying methods for reducing CO2 emissions for decades. Capturing CO2, either from flue gases of industrial processes or directly from the atmosphere, is one option known as carbon capture and storage (CCS). A second way is the so-called CCU (Carbon Capture and Utilization) in which CO2 is used as reactant for carbon-containing compounds. Catalytic conversion of CO2 can be achieved through different ways: electrocatalysis, photocatalysis, plasma and plasma-catalysis and thermo-catalysis and one of the more promising road is the carbon dioxide reduction via hydrogenation. This reaction can take place through two competing pathways: the modified Fischer–Tropsch (MFTS) synthesis (combining RWGS and FTS) and the methanol-mediated synthesis. In this lecture are reported the use of zeolite for CO2 valorization in MFTS reactions (with catalysts supported on zeo-type materials such as MOF, ZIF and SAPO) and in CO2 to DME using redox/acid catalytic function in which the acid function is due to the presence of zeolite catalysts. Finally, the performance on ZTC material (Zeolite Templating Carbon) in CO2 adsorption are reported and the high performance of Beta-ZTC are showed (adsorption of CO2 higher than 75% in weight).
Zeolite Membranes, from Synthesis to Application- Basics and Emerging Trends.
Institut Européen des Membranes, University of Montpellier, FRANCE
By coupling the unique properties of zeolites with the continuous separation capability of membrane processes, zeolite membranes demonstrated high efficiencies in separation operations that are not attainable by conventional methods. In fact, these inorganic membranes are able to operate angstrom-sharp separations, but also selective adsorption and catalytic reactions, with stable performance thanks to their good thermal resistance and stability in organic solvents. Since the beginning of the 1980s, significant progress has been made in zeolite membrane science, stimulated by their huge attractiveness for industrial applications such as gas separation, solvents de-watering, isomers separation and desalination. To make them a viable option for each specific application, improvements are needed, not only in reducing membrane defects and manufacturing costs, but also in enhancing reproducibility and operational stability. To date, large-scale application of these membranes in industry is limited to alcohol dehydration by pervaporation. Intensive academic and industrial research is still ongoing for the development of new generations of zeolite membranes with high competitiveness and performance at large-scale and in real operation conditions, e.g. for gas separation and process intensification in reactors.
The objective of this presentation is to provide students and young researchers with a general overview of the current state of the art in zeolite membrane science. It will include basics on zeolite membrane preparation, characterization and main applications, together with a focus on recent advances in the field. Finally, the large versatility offered by MOFs membranes, a metal-organic counterpart of zeolite membranes, will be briefly highlighted.
An industrial view on the role of zeolitic materials towards #decarbonizing the production of chemicals and fuels
Juan S. Martínez-Espín
Biobased Chemicals R&D, Topsoe, Kongens Lyngby, Denmark
In the last decade, pressing environmental concerns and policies are driving research and strategies to rely less on fossil-based fuels and chemicals. At this stage, we see a transformation of the industrial sector from within, and renewable fuels and biobased chemicals are steadily increasing their market presence. In this talk, we will go through the role of zeolitic materials in the valorization of different types of biomass resources into high quality fuels and chemicals.
Since biomass is a very different feedstock compared to fossils, new approaches to pre-treat those feeds and/or adjust the zeolitic catalysts are needed. In the fuels sector, we will look into sustainable processes with both build-up and crack-down approaches to produce gasoline, jet and diesel fuels. Generally, the zeolitic role in these processes can take advantage of the vast existing knowledge to transform already complex fossil feedstocks. Contrarily, the production of biobased chemicals over zeolites and zeotypes typically presents important challenges from often having to operate in aqueous liquid phase reactions and interact with very reactive compounds with high O/C ratios. In this regard, we will highlight the strategies developed to solve these challenges and make the use of zeolitic materials possible for the production of biobased chemicals.
Insights into zeolite confinement effect on bifunctional catalysis.
CQE, Instituto Superior Técnico, Lisboa
Zeolite based catalysts have been widely used since the 60’s and many of their main industrial applications are based on their unique porous characteristics and the resulting confinement effects which affect not only adsorption and diffusion of hydrocarbons but also the stability of reaction intermediates and the nature of active sites. Acid/basic sites and active metal species confined into microporous or hierarchical zeolites have a key role in bifunctional reactions, such as hydroisomerization or hydrocracking of long chain n-paraffins, which continue to attract considerable attention in the current challenging scenarios of transition to renewable energy.
The nature and characteristics of metal species depend, among other things, on their location and environment induced by micropores characteristics of the zeolite structure or by inter or intracrystalline mesopores generated on zeolites. The proximity between metal and acid sites has been claimed as a crucial parameter for the design of efficient bifunctional catalysts. Usually, the stabilization of metal nanoparticles inside zeolite pores is more difficult when they have mesopores, but many synthesis strategies are being developed to take advantage of the combination of the hierarchical structure, providing shorter diffusion path lengths for hydrocarbons, and of the neighborhood of acidic and metallic sites on the catalytic performances. Also, the use of nanocomposites or hybrid bifunctional catalysts, combining supported metal and different acid solids (micro/mesoporous zeolites, alumina, etc.) and the way they can provide cooperative effects can be extremely important to control the branched paraffins yield or the distribution of products obtained from the catalytic production of fuels via Fischer Tropsch synthesis.