Periodic Reporting for period 1 - ZEOLIghT (Dual challenges in the discovery and sustainability of nanozeolites: controlling defect sites and structural flexibility)
Reporting period: 2022-10-01 to 2025-03-31
Zeolites are a class of nanoporous crystalline inorganic materials that rank among the most versatile catalysts, facilitating the development of sustainable chemistry, separation technologies, and emerging processes.
The aim of ZEOLIghT is to understand the fundamental molecular-level interactions that drive the crystallization of nanozeolites and use this knowledge to tailor their properties. The main objective of the project is to investigate the growth kinetics of zeolites in colloidal and high-solid precursors, leading to frameworks with controlled defects and enhanced flexibility. Key achievements include a deeper understanding of nanozeolite properties by elucidating the role of defects and structural flexibility.
The project focused on several key goals, including developing new methods for nanozeolite synthesis, advancing techniques to characterize their properties at atomic resolution, and improving their performance by controlling structural defects and framework flexibility. One of the main challenges was enhancing the efficiency of these materials by reducing structural defects that limit their performance.
Using advanced synthesis techniques and high-throughput robotics, we synthesized various types of zeolites with fewer defect sites, resulting in materials that are more hydrophobic, structurally stable, and efficient as catalysts. Another significant achievement was improving the flexibility of nanozeolites by modifying their chemical composition, extra-framework cations, framework structure, and intergrowth stages. This enabled the design of materials that selectively adsorb CO2 over other gases such as N2, CH₄, and H2O, making them highly effective for carbon capture and gas separation. Additionally, ultra-thin zeolites with nanosheet morphology and high thermal stability were developed, opening new possibilities for gas drying and membrane technologies. To address the challenge of methane conversion, we designed ultra-stable metal containing catalysts with engineered porosity, reducing the formation of carbon deposits (coke) and significantly extending the catalysts' lifespan compared to traditional ones.
This interdisciplinary project involved close collaboration with industry partners. The team also integrated cutting-edge tools such as robotic synthesis, real-time in situ characterization, and computational modeling to accelerate the discovery of novel nanozeolites with precise structures and properties.
The aim of ZEOLIghT is to understand the fundamental molecular-level interactions that drive the crystallization of nanozeolites and use this knowledge to tailor their properties. The main objective of the project is to investigate the growth kinetics of zeolites in colloidal and high-solid precursors, leading to frameworks with controlled defects and enhanced flexibility. Key achievements include a deeper understanding of nanozeolite properties by elucidating the role of defects and structural flexibility.
The project focused on several key goals, including developing new methods for nanozeolite synthesis, advancing techniques to characterize their properties at atomic resolution, and improving their performance by controlling structural defects and framework flexibility. One of the main challenges was enhancing the efficiency of these materials by reducing structural defects that limit their performance.
Using advanced synthesis techniques and high-throughput robotics, we synthesized various types of zeolites with fewer defect sites, resulting in materials that are more hydrophobic, structurally stable, and efficient as catalysts. Another significant achievement was improving the flexibility of nanozeolites by modifying their chemical composition, extra-framework cations, framework structure, and intergrowth stages. This enabled the design of materials that selectively adsorb CO2 over other gases such as N2, CH₄, and H2O, making them highly effective for carbon capture and gas separation. Additionally, ultra-thin zeolites with nanosheet morphology and high thermal stability were developed, opening new possibilities for gas drying and membrane technologies. To address the challenge of methane conversion, we designed ultra-stable metal containing catalysts with engineered porosity, reducing the formation of carbon deposits (coke) and significantly extending the catalysts' lifespan compared to traditional ones.
This interdisciplinary project involved close collaboration with industry partners. The team also integrated cutting-edge tools such as robotic synthesis, real-time in situ characterization, and computational modeling to accelerate the discovery of novel nanozeolites with precise structures and properties.
The developments within the ZEOLIghT project focus on the discovery aof nanozeolites by controlling defect sites and structural flexibility. The activities are structured according to three main objectives: fundamental understanding of defects in nanozeolites, studying their flexibility, and engineering zeolites with novel properties for applications where flexibility and defects influence performance.
The synthesis of nanozeolites with tailored properties was achieved through systematic investigations of hydrolysis, condensation, nucleation, and growth processes. This optimization enabled the synthesis of zeolites with various framework structures, using modified precursor suspensions. Both high-solid and highly diluted precursors were employed for the synthesis of pure silica, aluminosilicates, and metal silicates. Metal incorporation into zeolite frameworks demonstrated outstanding stability and catalytic performance in lean methane combustion. A novel Ge-containing zeolite with extreme hydrophobicity and high germanium content (14% Ge) was synthesized, free of defects and no fluorine ions. This resulted in a double-bridge configuration of Ge pairs in zeolites, giving rise to exceptional material stability. Additionally, the impact of template charge density on defect distribution and hydrophilicity of aluminophosphates was demonstrated.
Beyond direct synthesis approaches, post-synthesis treatments highlighted the role of metals in healing silanol defect sites in zeolites. The reactivity of silanol defects was exemplified in Zn-MFI type zeolites, which enhanced hydroxyl radical formation for methane conversion.
In alignment with the second objective, the flexibility of nanozeolites was evaluated by varying alkali cations, intergrowth levels, Al content, and crystal size. The substantial effect of alkali cations (Na⁺, K⁺, Cs⁺) on the flexibility of zeolites was examined, emphasizing their impact on silanol distribution and structural dynamics. These materials showed high efficiency in CO2 separation due to their framework flexibility and controlled particle size, which is critical for diffusion. In addition the amount and distribution of Al within the zeolite framework were found to be crucial for controlled CO2 adsorption. Further attention was given to controlling crystal size and morphology, exemplified by the synthesis of ultra-thin zeolite nanosheets with exceptional water adsorption capacity and mesoporosity, offering excellent flexibility and thermal stability.
The engineered nanozeolites with controlled defect sites and flexibility were tested in various gas separation processes and catalytic applications, particularly those requiring stability under harsh conditions. Zeolites with macropores exhibited reduced coke deposition, enhancing catalyst stability. The simultaneous synthesis, advanced in situ characterization, and application studies facilitated rapid optimization through dynamic feedback loops.
The synthesis of nanozeolites with tailored properties was achieved through systematic investigations of hydrolysis, condensation, nucleation, and growth processes. This optimization enabled the synthesis of zeolites with various framework structures, using modified precursor suspensions. Both high-solid and highly diluted precursors were employed for the synthesis of pure silica, aluminosilicates, and metal silicates. Metal incorporation into zeolite frameworks demonstrated outstanding stability and catalytic performance in lean methane combustion. A novel Ge-containing zeolite with extreme hydrophobicity and high germanium content (14% Ge) was synthesized, free of defects and no fluorine ions. This resulted in a double-bridge configuration of Ge pairs in zeolites, giving rise to exceptional material stability. Additionally, the impact of template charge density on defect distribution and hydrophilicity of aluminophosphates was demonstrated.
Beyond direct synthesis approaches, post-synthesis treatments highlighted the role of metals in healing silanol defect sites in zeolites. The reactivity of silanol defects was exemplified in Zn-MFI type zeolites, which enhanced hydroxyl radical formation for methane conversion.
In alignment with the second objective, the flexibility of nanozeolites was evaluated by varying alkali cations, intergrowth levels, Al content, and crystal size. The substantial effect of alkali cations (Na⁺, K⁺, Cs⁺) on the flexibility of zeolites was examined, emphasizing their impact on silanol distribution and structural dynamics. These materials showed high efficiency in CO2 separation due to their framework flexibility and controlled particle size, which is critical for diffusion. In addition the amount and distribution of Al within the zeolite framework were found to be crucial for controlled CO2 adsorption. Further attention was given to controlling crystal size and morphology, exemplified by the synthesis of ultra-thin zeolite nanosheets with exceptional water adsorption capacity and mesoporosity, offering excellent flexibility and thermal stability.
The engineered nanozeolites with controlled defect sites and flexibility were tested in various gas separation processes and catalytic applications, particularly those requiring stability under harsh conditions. Zeolites with macropores exhibited reduced coke deposition, enhancing catalyst stability. The simultaneous synthesis, advanced in situ characterization, and application studies facilitated rapid optimization through dynamic feedback loops.
The ZEOLIghT project has made significant advances in zeolite synthesis, characterization, and application, surpassing existing methodologies and expanding their industrial relevance. In situ visualization of nanozeolite flexibility was achieved, revealing their dynamic response to external stimuli such as CO2 adsorption under elevated temperatures. Nanozeolites with precisely controlled defects demonstrate superior catalytic performance, reducing coke deposition and extending catalyst lifetime. Flexible nanozeolites have exhibited unmatched efficiency in CO2 capture, presenting viable solutions for industrial carbon capture.
Industry collaborations with Total Energies and Petro China underscore the commercial potential of ZEOLIghT’s innovations.
To ensure the full impact and market adoption of ZEOLIghT’s breakthroughs, the following steps are crucial:
Scaling up promising nanomaterials via high-throughput robotic synthesis and exploring new catalytic applications.
Transitioning from laboratory - to – large scale production, including start-up creation and strengthened industry partnerships.
Securing intellectual property rights (IPR) and aligning with regulatory frameworks to accelerate market adoption. Patents already have been filed on the synthesis of nanozeolites for CO2 and H2O adsorption/separation.
The CLEAR Center for Zeolites and Nanoporous Materials, where the ZEOLIghT project is developed provides a strategic platform for advancing these efforts.
Summary of Key Achievements
Publications: 16 published papers in high-impact journals.
Presentations: 14 plenary/keynote lectures, 30 oral contributions by students and postdocs.
Awards: 2024 Les Étoiles de l'Europe, 2024 Flanigen Lecture Award, 2023 GFZ Honorary Award, 2024 Paris Olympics Torchbearer.
The ZEOLIghT project has redefined nanozeolite research with advancements in synthesis, characterization, and applications.
Industry collaborations with Total Energies and Petro China underscore the commercial potential of ZEOLIghT’s innovations.
To ensure the full impact and market adoption of ZEOLIghT’s breakthroughs, the following steps are crucial:
Scaling up promising nanomaterials via high-throughput robotic synthesis and exploring new catalytic applications.
Transitioning from laboratory - to – large scale production, including start-up creation and strengthened industry partnerships.
Securing intellectual property rights (IPR) and aligning with regulatory frameworks to accelerate market adoption. Patents already have been filed on the synthesis of nanozeolites for CO2 and H2O adsorption/separation.
The CLEAR Center for Zeolites and Nanoporous Materials, where the ZEOLIghT project is developed provides a strategic platform for advancing these efforts.
Summary of Key Achievements
Publications: 16 published papers in high-impact journals.
Presentations: 14 plenary/keynote lectures, 30 oral contributions by students and postdocs.
Awards: 2024 Les Étoiles de l'Europe, 2024 Flanigen Lecture Award, 2023 GFZ Honorary Award, 2024 Paris Olympics Torchbearer.
The ZEOLIghT project has redefined nanozeolite research with advancements in synthesis, characterization, and applications.