Pub Date : 2024-12-15DOI: 10.1016/j.micromeso.2024.113461
Cléophée Gourmand , Luis Bartolomé , Eder Amayuelas , Juan Miguel López del Amo , Elena Palomo del Barrio , Simone Meloni , Yaroslav Grosu
Wetting of a porous solid by a fluid is of significant interest to many industrial processes. However, at the nanoscale, this process is complex, and little is known about its temperature dependance. In this work, we explored the intrusion-extrusion of water for a heterogeneous lyophobic system composed of a hydrophobic mesoporous silica gel and water over a wide 25–250 °C temperature range. The intrusion pressure was found to have a classical negative temperature dependance in the whole 25–250 °C temperature range. However, an unexpected non-monotonic temperature dependance was observed for the extrusion pressure. In particular, it became temperature independent above 200 °C. This observation suggests that dewetting of nanopores at high temperature is more complex than previously thought of and serves as experimental grounds for further theoretical exploration.
{"title":"Intrusion-extrusion of water into-from hydrophobic nanopores at high temperature: Unexpected dependence of dewetting pressure above 200 °C","authors":"Cléophée Gourmand , Luis Bartolomé , Eder Amayuelas , Juan Miguel López del Amo , Elena Palomo del Barrio , Simone Meloni , Yaroslav Grosu","doi":"10.1016/j.micromeso.2024.113461","DOIUrl":"10.1016/j.micromeso.2024.113461","url":null,"abstract":"<div><div>Wetting of a porous solid by a fluid is of significant interest to many industrial processes. However, at the nanoscale, this process is complex, and little is known about its temperature dependance. In this work, we explored the intrusion-extrusion of water for a heterogeneous lyophobic system composed of a hydrophobic mesoporous silica gel and water over a wide 25–250 °C temperature range. The intrusion pressure was found to have a classical negative temperature dependance in the whole 25–250 °C temperature range. However, an unexpected non-monotonic temperature dependance was observed for the extrusion pressure. In particular, it became temperature independent above 200 °C. This observation suggests that dewetting of nanopores at high temperature is more complex than previously thought of and serves as experimental grounds for further theoretical exploration.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113461"},"PeriodicalIF":4.8,"publicationDate":"2024-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
All-silica, boron and boron-aluminium substituted MFI-type zeolites were prepared. Different amounts of boron were added to the starting reaction mixtures to investigate their influence on the properties of the obtained zeolites. A comprehensive characterization of the materials was conducted using various techniques: X-ray Diffraction (XRD), nitrogen physisorption, Scanning Electron Microscopy (SEM), infrared (IR), Nuclear Magnetic Resonance (NMR) spectroscopy, thermogravimetric analysis (TGA) as well as microcalorimetry. The MFI topology and crystallinity is preserved regardless the amount of heteroatoms that occupied different local environments, while the morphology of the crystals, their thermal stability, and their acidity differ considerably. For instance, boron assuming both tetrahedral and trigonal coordination, affect the interactions of the framework with both the organic structure directing agents (OSDA) and ammonia species giving rise to detectable differences in acidity.
{"title":"Boron's role in altering MFI-type zeolite","authors":"Vladislav Rac , Vesna Rakić , Ana Palčić , Eddy Dib , Georgeta Postole , Ljiljana Damjanović-Vasilić , Vladimir Pavlović , Steva Lević , Sanja Bosnar","doi":"10.1016/j.micromeso.2024.113454","DOIUrl":"10.1016/j.micromeso.2024.113454","url":null,"abstract":"<div><div>All-silica, boron and boron-aluminium substituted MFI-type zeolites were prepared. Different amounts of boron were added to the starting reaction mixtures to investigate their influence on the properties of the obtained zeolites. A comprehensive characterization of the materials was conducted using various techniques: X-ray Diffraction (XRD), nitrogen physisorption, Scanning Electron Microscopy (SEM), infrared (IR), Nuclear Magnetic Resonance (NMR) spectroscopy, thermogravimetric analysis (TGA) as well as microcalorimetry. The MFI topology and crystallinity is preserved regardless the amount of heteroatoms that occupied different local environments, while the morphology of the crystals, their thermal stability, and their acidity differ considerably. For instance, boron assuming both tetrahedral and trigonal coordination, affect the interactions of the framework with both the organic structure directing agents (OSDA) and ammonia species giving rise to detectable differences in acidity.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113454"},"PeriodicalIF":4.8,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-14DOI: 10.1016/j.micromeso.2024.113456
Liang Zhao , Yong Wang , Peipei Xiao , Hiroto Toyoda , Qi Li , Yuqin Sun , Bekhti Samya , Hermann Gies , Toshiyuki Yokoi
The distribution of acid sites, which are derived from tetrahedrally coordinated aluminum (Al) atoms within zeolite framework plays a critical role in the acidic catalyzed reactions, is strongly influenced by electrostatic interactions between cationic structure-directing agents (SDAs) and anionic charges. Herein, we synthesized various ZSM-5 zeolites without OSDAs and conducted an in-situ analysis to investigate the impact of anionic species from various Al sources on the crystallization and acid site localization in the framework. The results demonstrated that when Al(NO3)3 is used as the Al source (denoted as Z5-N), the electronic environment influenced by NO3⁻ alters the framework formation pathway, leading to the creation of distorted, tetracoordinated Al intermediates. This process enhances Al atoms incorporation during the early stages of crystallization, resulting in partially bonded framework Al due to lower polarization ability on Na+. In contrast, using Al(OH)₃ as the Al source (denoted as Z5-H) accelerates the nucleation process and leads to the formation of smaller particle size. Notably, the 2⁷Al multiple quantum magic angle spinning nuclear magnetic resonance (MQMAS NMR) results revealed that pure OH⁻ ions facilitate the preferential localization of Al atoms at T11 sites within the ZSM-5 framework, where the acid strength is reduced due to the larger Si-O-Al bond angle. The unique Al distributions are attributed to the strong polarization ability induced by the electrostatic attraction of OH⁻ ions to Na⁺. This study enhances our understanding of how different anionic environments influence Al placement, enabling more targeted design and synthesis of zeolite materials with tailored catalytic properties.
{"title":"Impact of anionic species on the crystallization and aluminum localization in the zeolite framework","authors":"Liang Zhao , Yong Wang , Peipei Xiao , Hiroto Toyoda , Qi Li , Yuqin Sun , Bekhti Samya , Hermann Gies , Toshiyuki Yokoi","doi":"10.1016/j.micromeso.2024.113456","DOIUrl":"10.1016/j.micromeso.2024.113456","url":null,"abstract":"<div><div>The distribution of acid sites, which are derived from tetrahedrally coordinated aluminum (Al) atoms within zeolite framework plays a critical role in the acidic catalyzed reactions, is strongly influenced by electrostatic interactions between cationic structure-directing agents (SDAs) and anionic charges. Herein, we synthesized various ZSM-5 zeolites without OSDAs and conducted an in-situ analysis to investigate the impact of anionic species from various Al sources on the crystallization and acid site localization in the framework. The results demonstrated that when Al(NO<sub>3</sub>)<sub>3</sub> is used as the Al source (denoted as Z5-N), the electronic environment influenced by NO<sub>3</sub>⁻ alters the framework formation pathway, leading to the creation of distorted, tetracoordinated Al intermediates. This process enhances Al atoms incorporation during the early stages of crystallization, resulting in partially bonded framework Al due to lower polarization ability on Na<sup>+</sup>. In contrast, using Al(OH)₃ as the Al source (denoted as Z5-H) accelerates the nucleation process and leads to the formation of smaller particle size. Notably, the <sup>2</sup>⁷Al multiple quantum magic angle spinning nuclear magnetic resonance (MQMAS NMR) results revealed that pure OH⁻ ions facilitate the preferential localization of Al atoms at T11 sites within the ZSM-5 framework, where the acid strength is reduced due to the larger Si-O-Al bond angle. The unique Al distributions are attributed to the strong polarization ability induced by the electrostatic attraction of OH⁻ ions to Na⁺. This study enhances our understanding of how different anionic environments influence Al placement, enabling more targeted design and synthesis of zeolite materials with tailored catalytic properties.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113456"},"PeriodicalIF":4.8,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-14DOI: 10.1016/j.micromeso.2024.113459
Chaehoon Kim , Seunghyuck Chi , Hyeonsuk Yoo , Yongjin Lee , Minkee Choi
Zeolite-templated carbons (ZTCs) are a unique class of carbon materials characterized by ordered microporous structures, large surface areas, and substantial micropore volumes. ZTCs are synthesized by replicating the microporous structures of zeolite templates with carbon. Typically, zeolites with three-dimensional (3D) micropore connectivity have been used as templates for carbon deposition, producing ZTCs with 3D microporous channels and framework structures. In this study, we extend the synthesis of ZTCs using zeolite templates with two-dimensional (2D) micropore connectivity, which enables the production of 2D ZTCs—carbon nanosheets with vertically aligned ordered micropores. By studying 2D zeolites with various structures (UTL, IWV, MWW, and FER) and chemical compositions as templates, we identified key factors that govern the faithful replication of zeolite micropores with a carbon framework. Zeolite structures with large micropore apertures (≥12-membered rings), such as UTL and IWV, and a high density of acid sites (B or Al) were found to be beneficial for accurate carbon replication. The use of NaOH aqueous solution for template etching proved more effective in producing high-quality 2D ZTCs without inorganic residue, compared to the conventionally used HCl/HF aqueous solutions. Negative surface charges generated at carbon surfaces in highly alkaline NaOH solutions inhibited rapid stacking of carbon nanosheets via π-π interaction, which can cause the trapping of inorganic residues. We believe that the resulting 2D ZTCs hold significant promise for the fabrication of advanced membranes and energy storage devices.
{"title":"Synthesis of Two-Dimensional Zeolite-Templated Carbons with Ordered Micropores","authors":"Chaehoon Kim , Seunghyuck Chi , Hyeonsuk Yoo , Yongjin Lee , Minkee Choi","doi":"10.1016/j.micromeso.2024.113459","DOIUrl":"10.1016/j.micromeso.2024.113459","url":null,"abstract":"<div><div>Zeolite-templated carbons (ZTCs) are a unique class of carbon materials characterized by ordered microporous structures, large surface areas, and substantial micropore volumes. ZTCs are synthesized by replicating the microporous structures of zeolite templates with carbon. Typically, zeolites with three-dimensional (3D) micropore connectivity have been used as templates for carbon deposition, producing ZTCs with 3D microporous channels and framework structures. In this study, we extend the synthesis of ZTCs using zeolite templates with two-dimensional (2D) micropore connectivity, which enables the production of 2D ZTCs—carbon nanosheets with vertically aligned ordered micropores. By studying 2D zeolites with various structures (UTL, IWV, MWW, and FER) and chemical compositions as templates, we identified key factors that govern the faithful replication of zeolite micropores with a carbon framework. Zeolite structures with large micropore apertures (≥12-membered rings), such as UTL and IWV, and a high density of acid sites (B or Al) were found to be beneficial for accurate carbon replication. The use of NaOH aqueous solution for template etching proved more effective in producing high-quality 2D ZTCs without inorganic residue, compared to the conventionally used HCl/HF aqueous solutions. Negative surface charges generated at carbon surfaces in highly alkaline NaOH solutions inhibited rapid stacking of carbon nanosheets via π-π interaction, which can cause the trapping of inorganic residues. We believe that the resulting 2D ZTCs hold significant promise for the fabrication of advanced membranes and energy storage devices.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113459"},"PeriodicalIF":4.8,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100133","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-13DOI: 10.1016/j.micromeso.2024.113457
A. Abdrassilova , G. Vassilina , K. Abdildina , L. Briones , A. Peral , J.M. Escola
Despite being discovered more than 25 years ago, mesoporous aluminosilicates are still very relevant materials, considering the huge number of publications appearing every year harnessing them. Their notable features such as high BET surface area, accessible mesopore size, mild acidity and tunable pore wall thickness have resulted in different successful catalytic applications. Additionally, different kinds of mesoporous aluminosilicates may be found in literature (MCM-41, MCM-48, HMS, SBA-15, SBA-16, etc.) that allow to tailor to certain extent some physicochemical properties such as the spatial group, mesopore size and dimension, the pore wall thickness and consequently the hydrothermal stability, for the wanted catalytic application. This review is focused on discussing the main characteristics of the most common mesoporous aluminosilicates and exploring their reported performance in literature as supports of bifunctional catalysts for the hydrodearomatization (HDA) and desulfurization (HDS) of fuels. Although their hydrothermal stability has always been questioned by their lack of crystallinity, several successful applications of both MCM-41 and SBA-15 as supports of bifunctional catalysts for HDA/HDS of model compounds such as dibenzothiophene (DBT) can be found in literature, which in some cases interestingly also point out the prolonged stability of the catalyst, leading towards high yields of fuels by its mild acidity. Additionally, supported metal catalysts over mesoporous aluminosilicates might be the basis for the preparation of advanced bulk metal hydroprocessing catalysts, by application of different etching strategies. Therefore, this review will show these promising catalytic outcomes that opens up the application of mesoporous aluminosilicates as supports of bifunctional catalysts devoted to HDA/HDS of not only model sulfur/aromatic compounds but true fuels as well such as those proceeding from Kazakhstan oil.
{"title":"The notable features of mesoporous aluminosilicates as catalytic supports for hydrodearomatization and hydrodesulfurization of fuels","authors":"A. Abdrassilova , G. Vassilina , K. Abdildina , L. Briones , A. Peral , J.M. Escola","doi":"10.1016/j.micromeso.2024.113457","DOIUrl":"10.1016/j.micromeso.2024.113457","url":null,"abstract":"<div><div>Despite being discovered more than 25 years ago, mesoporous aluminosilicates are still very relevant materials, considering the huge number of publications appearing every year harnessing them. Their notable features such as high BET surface area, accessible mesopore size, mild acidity and tunable pore wall thickness have resulted in different successful catalytic applications. Additionally, different kinds of mesoporous aluminosilicates may be found in literature (MCM-41, MCM-48, HMS, SBA-15, SBA-16, etc.) that allow to tailor to certain extent some physicochemical properties such as the spatial group, mesopore size and dimension, the pore wall thickness and consequently the hydrothermal stability, for the wanted catalytic application. This review is focused on discussing the main characteristics of the most common mesoporous aluminosilicates and exploring their reported performance in literature as supports of bifunctional catalysts for the hydrodearomatization (HDA) and desulfurization (HDS) of fuels. Although their hydrothermal stability has always been questioned by their lack of crystallinity, several successful applications of both MCM-41 and SBA-15 as supports of bifunctional catalysts for HDA/HDS of model compounds such as dibenzothiophene (DBT) can be found in literature, which in some cases interestingly also point out the prolonged stability of the catalyst, leading towards high yields of fuels by its mild acidity. Additionally, supported metal catalysts over mesoporous aluminosilicates might be the basis for the preparation of advanced bulk metal hydroprocessing catalysts, by application of different etching strategies. Therefore, this review will show these promising catalytic outcomes that opens up the application of mesoporous aluminosilicates as supports of bifunctional catalysts devoted to HDA/HDS of not only model sulfur/aromatic compounds but true fuels as well such as those proceeding from Kazakhstan oil.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113457"},"PeriodicalIF":4.8,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143164112","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-13DOI: 10.1016/j.micromeso.2024.113458
Nadine Lysyk Funk , Flávia Carvalho Tavaniello , Juliana Dos Santos , Edilson Valmir Benvenutti , Silvio Buchner , Karina Paese , Monique Deon , Ruy Carlos Ruver Beck
Mesoporous silica nanoparticles (MSN) serve as versatile drug nanocarriers to avoid the interaction of highly irritant drugs with stomach mucosa, such as nonsteroidal anti-inflammatory drugs (NSAIDs). In this study, spherical and nanometric particles (181 ± 11 nm) with long-channel nanopores (∼2.5 nm in diameter) hexagonally arranged were synthesised. The NSAID naproxen (NPX) was incorporated into MSN by using the incipient wetness method. NPX ethanolic solutions of 30 mg mL−1 (NPX-ES-30) and 40 mg mL−1 (NPX-ES-40) were employed to obtain MSN-NPX30-1 and MSN-NPX40-1, corresponding to 8.26 % and 10.12 % (w/w) NPX loading, respectively. A second incorporation was performed to produced MSN-NPX30-2 and MSN-NPX40-2, with 13.45 % and 16.78 % (w/w) NPX loading, respectively. A reduction in surface area and pore volume was observed for all drug-loaded formulations compared to bare MSN. Notably, formulations prepared with NPX-ES-40 exhibited a less pronounced reduction, indicating that a portion of the drug was likely positioned outside the MSN pores. In contrast, NPX-ES-30 formulations showed efficient internalization of NPX into the mesopores, resulting in a more significant reduction in surface area and pore volume following drug incorporation. The enhanced silica–drug interaction in these formulations resulted in a slower NPX release rate compared with the NPX-ES-40 formulations, and a lower in vitro irritation score for the hen's eggs test on chorioallantoic membrane. In conclusion, the concentration of the NPX solution influenced the drug placement within MSN pores and, therefore, the NPX drug release rate and in vitro irritant potential.
{"title":"Naproxen-loaded mesoporous silica nanoparticles: How can the process of incorporation affect drug placement, drug release and the in vitro naproxen irritant potential?","authors":"Nadine Lysyk Funk , Flávia Carvalho Tavaniello , Juliana Dos Santos , Edilson Valmir Benvenutti , Silvio Buchner , Karina Paese , Monique Deon , Ruy Carlos Ruver Beck","doi":"10.1016/j.micromeso.2024.113458","DOIUrl":"10.1016/j.micromeso.2024.113458","url":null,"abstract":"<div><div>Mesoporous silica nanoparticles (MSN) serve as versatile drug nanocarriers to avoid the interaction of highly irritant drugs with stomach mucosa, such as nonsteroidal anti-inflammatory drugs (NSAIDs). In this study, spherical and nanometric particles (181 ± 11 nm) with long-channel nanopores (∼2.5 nm in diameter) hexagonally arranged were synthesised. The NSAID naproxen (NPX) was incorporated into MSN by using the incipient wetness method. NPX ethanolic solutions of 30 mg mL<sup>−1</sup> (NPX-ES-30) and 40 mg mL<sup>−1</sup> (NPX-ES-40) were employed to obtain MSN-NPX30-1 and MSN-NPX40-1, corresponding to 8.26 % and 10.12 % (w/w) NPX loading, respectively. A second incorporation was performed to produced MSN-NPX30-2 and MSN-NPX40-2, with 13.45 % and 16.78 % (w/w) NPX loading, respectively. A reduction in surface area and pore volume was observed for all drug-loaded formulations compared to bare MSN. Notably, formulations prepared with NPX-ES-40 exhibited a less pronounced reduction, indicating that a portion of the drug was likely positioned outside the MSN pores. In contrast, NPX-ES-30 formulations showed efficient internalization of NPX into the mesopores, resulting in a more significant reduction in surface area and pore volume following drug incorporation. The enhanced silica–drug interaction in these formulations resulted in a slower NPX release rate compared with the NPX-ES-40 formulations, and a lower <em>in vitro</em> irritation score for the hen's eggs test on chorioallantoic membrane. In conclusion, the concentration of the NPX solution influenced the drug placement within MSN pores and, therefore, the NPX drug release rate and <em>in vitro</em> irritant potential.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113458"},"PeriodicalIF":4.8,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100635","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-11DOI: 10.1016/j.micromeso.2024.113453
Aljaž Škrjanc , Amalija Golobič , Matjaž Mazaj , Matej Huš , Blaž Likozar , Nataša Zabukovec Logar
Mechanochemical synthesis of Zeolitic imidazolate frameworks (ZIFs) has emerged as a compelling and environmetally conscious alternative to conventional solvothermal methods, especially when they rely on the use of toxic formamide-based solvents and excess of metal precursors or linkers. In this study, a facile liquid assisted grinding synthesis achieving high product yields with short synthesis times, have been introduced for a series of ZIFs with SOD topology featuring both single and mixed ligands with diverse functional groups. The phase pure and crystalline products with even particle size distribution and retained sorption performance confirmed the efficiency of mechanochemical synthesis as sustainable and viable approach for the optimisation and the design of a new ZIF archetypes. Deeper insights into the structural and CO2 sorption capabilities was gained by a comparative quantum chemical calculations between a benchmark ZIF-8 and a newly synthesized isostructural analogue NICS-23, featuring an ester-functionalized imidazole ligand. The analysis revealed distinctive sorption characteristics of NICS-23, showcasing also its potential for gas separation processes with wet CO2 involved. Findings highlight the advatages of mechanochemical synthesis in ZIF production as a facile green synthesis method over the longer solvothermal procedure, potentially allowing also for faster screening of functional materials.
{"title":"Green synthesis of functionalized sodalite ZIFs through mechanochemistry and their performance in CO2 capture","authors":"Aljaž Škrjanc , Amalija Golobič , Matjaž Mazaj , Matej Huš , Blaž Likozar , Nataša Zabukovec Logar","doi":"10.1016/j.micromeso.2024.113453","DOIUrl":"10.1016/j.micromeso.2024.113453","url":null,"abstract":"<div><div>Mechanochemical synthesis of Zeolitic imidazolate frameworks (ZIFs) has emerged as a compelling and environmetally conscious alternative to conventional solvothermal methods, especially when they rely on the use of toxic formamide-based solvents and excess of metal precursors or linkers. In this study, a facile liquid assisted grinding synthesis achieving high product yields with short synthesis times, have been introduced for a series of ZIFs with SOD topology featuring both single and mixed ligands with diverse functional groups. The phase pure and crystalline products with even particle size distribution and retained sorption performance confirmed the efficiency of mechanochemical synthesis as sustainable and viable approach for the optimisation and the design of a new ZIF archetypes. Deeper insights into the structural and CO<sub>2</sub> sorption capabilities was gained by a comparative quantum chemical calculations between a benchmark ZIF-8 and a newly synthesized isostructural analogue NICS-23, featuring an ester-functionalized imidazole ligand. The analysis revealed distinctive sorption characteristics of NICS-23, showcasing also its potential for gas separation processes with wet CO<sub>2</sub> involved. Findings highlight the advatages of mechanochemical synthesis in ZIF production as a facile green synthesis method over the longer solvothermal procedure, potentially allowing also for faster screening of functional materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113453"},"PeriodicalIF":4.8,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100168","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-11DOI: 10.1016/j.micromeso.2024.113455
Cristina Pina-Vidal , Gabriela A. Ortega-Moreno , Luis A. Lozano , Elena Piera , Miguel A. Caballero , Juan M. Zamaro , Carlos Téllez
In this study, UiO-66 was in-situ synthesized with encapsulated caffeine (CAF@UiO-66) following a one-pot DMF-free microwave-assisted method. The microwave-assisted approach allowed for an efficient and fast encapsulation of caffeine within the metal-organic framework in a single step thus achieving a more environmentally friendly process. It was shown that the CAF@UiO-66 solid was capable of gradually dosing caffeine into aqueous media over a long period. Moreover, the recovered synthesis solution containing residual caffeine and solvent was successfully reused in several encapsulation cycles, giving capsules that showed good caffeine release properties. In addition, CAF@UiO-66 solids were incorporated into polyamide 6 (PA6) fibers through an extrusion process without altering their physicochemical properties. These composites showed a gradual and sustained release of caffeine, extending the dosage time and shelf life of the additive which made it potentially useful for its application in functional textile products. Finally, the release of caffeine from the capsules was fitted to a Fickian model while that from the polymeric composites was adjusted to the semi-empirical Korsmeyer-Peppas model.
{"title":"Microwave synthesis of UiO-66 with encapsulated caffeine: Liquor mother reuse and release from polyamide composites","authors":"Cristina Pina-Vidal , Gabriela A. Ortega-Moreno , Luis A. Lozano , Elena Piera , Miguel A. Caballero , Juan M. Zamaro , Carlos Téllez","doi":"10.1016/j.micromeso.2024.113455","DOIUrl":"10.1016/j.micromeso.2024.113455","url":null,"abstract":"<div><div>In this study, UiO-66 was in-situ synthesized with encapsulated caffeine (CAF@UiO-66) following a one-pot DMF-free microwave-assisted method. The microwave-assisted approach allowed for an efficient and fast encapsulation of caffeine within the metal-organic framework in a single step thus achieving a more environmentally friendly process. It was shown that the CAF@UiO-66 solid was capable of gradually dosing caffeine into aqueous media over a long period. Moreover, the recovered synthesis solution containing residual caffeine and solvent was successfully reused in several encapsulation cycles, giving capsules that showed good caffeine release properties. In addition, CAF@UiO-66 solids were incorporated into polyamide 6 (PA6) fibers through an extrusion process without altering their physicochemical properties. These composites showed a gradual and sustained release of caffeine, extending the dosage time and shelf life of the additive which made it potentially useful for its application in functional textile products. Finally, the release of caffeine from the capsules was fitted to a Fickian model while that from the polymeric composites was adjusted to the semi-empirical Korsmeyer-Peppas model.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113455"},"PeriodicalIF":4.8,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100169","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The introduction of Fe2⁺ ions into water systems poses significant environmental risks globally. This study investigates the adsorption efficiency of bentonite from the Kongyrtog deposit in Uzbekistan and its modified forms for Fe2⁺ removal from contaminated water. Batch adsorption experiments were conducted with Fe2⁺ concentrations of 2.0–20 mg/L, at pH 7.0, an adsorbent dose of 1 g/L, and temperatures between 288 and 308 K. The bentonites were named MED (modified with ethylenediammoniumdihydrochloride) and MGD (modified with hexamethylenediammonium dihydrochloride), while NKB refers to natural bentonite. Multiple linear regression (MLR) modeling validated the adsorption process, with high R2 correlation coefficients supporting the Langmuir model. Optimal adsorption conditions included a dose of 1 g/L, pH 5.2, a contact time of 40 min, and a temperature of 308 K, with the adsorption kinetics fitting a pseudo-second-order model. Using the Langmuir isotherm model, the maximum adsorption capacities (qmax) were determined as 8.47 mg/g for NKB, 8.51 mg/g for MGD, and 10.84 mg/g for MED. Among the modified bentonites, Fe2⁺ adsorption followed the activity sequence MED > MGD > NKB, with intraparticle diffusion modeling suggesting a two-stage adsorption process. The negative Gibbs free energy values (ΔG°) confirmed the process was spontaneous and endothermic. These modified bentonites offer a cost-effective alternative to activated carbon with the ability to regenerate up to four times. Initial regeneration efficiencies were 78 % for NKB, 83 % for MGD, and 86 % for MED. This study demonstrates the potential of modified bentonites as sustainable adsorbents for Fe2⁺ removal, contributing to advancements in eco-friendly water treatment technologies.
{"title":"Enhanced adsorption of Fe(II) from synthetic wastewater using modified bentonite: Isotherms, kinetics, thermodynamics, and adsorption mechanisms","authors":"Davron Abdikodirovich Khandamov , Tonni Agustiono Kurniawan , Akbarbek Shukhratovich Bekmirzayev , Fatima Batool , Dilnoza Khandamova , Shavkat Nurullayev , Sevara Kholikova , Zebo Babakhanova , Md Munir Hayet Khan","doi":"10.1016/j.micromeso.2024.113451","DOIUrl":"10.1016/j.micromeso.2024.113451","url":null,"abstract":"<div><div>The introduction of Fe<sup>2</sup>⁺ ions into water systems poses significant environmental risks globally. This study investigates the adsorption efficiency of bentonite from the Kongyrtog deposit in Uzbekistan and its modified forms for Fe<sup>2</sup>⁺ removal from contaminated water. Batch adsorption experiments were conducted with Fe<sup>2</sup>⁺ concentrations of 2.0–20 mg/L, at pH 7.0, an adsorbent dose of 1 g/L, and temperatures between 288 and 308 K. The bentonites were named MED (modified with ethylenediammoniumdihydrochloride) and MGD (modified with hexamethylenediammonium dihydrochloride), while NKB refers to natural bentonite. Multiple linear regression (MLR) modeling validated the adsorption process, with high <em>R</em><sup>2</sup> correlation coefficients supporting the Langmuir model. Optimal adsorption conditions included a dose of 1 g/L, pH 5.2, a contact time of 40 min, and a temperature of 308 K, with the adsorption kinetics fitting a pseudo-second-order model. Using the Langmuir isotherm model, the maximum adsorption capacities (<u>q</u><sub><em>max</em></sub>) were determined as 8.47 mg/g for NKB, 8.51 mg/g for MGD, and 10.84 mg/g for MED. Among the modified bentonites, Fe<sup>2</sup>⁺ adsorption followed the activity sequence MED > MGD > NKB, with intraparticle diffusion modeling suggesting a two-stage adsorption process. The negative Gibbs free energy values (ΔG°) confirmed the process was spontaneous and endothermic. These modified bentonites offer a cost-effective alternative to activated carbon with the ability to regenerate up to four times. Initial regeneration efficiencies were 78 % for NKB, 83 % for MGD, and 86 % for MED. This study demonstrates the potential of modified bentonites as sustainable adsorbents for Fe<sup>2</sup>⁺ removal, contributing to advancements in eco-friendly water treatment technologies.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113451"},"PeriodicalIF":4.8,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The use of organic structure-directing agents (OSDAs) is effective in constructing zeolite frameworks with high hydrophobicity and thermal stability. Since OSDAs are guest molecules that stabilize cyclic hosts, designing guest molecules and realizing strong host-guest interactions is one of the reasonable strategies for controlling the structure of zeolites. A very powerful OSDA for the synthesis of MSE-type zeolite was designed and successfully prepared. When using conventional OSDA, TEBOP2+, more than 10 d of crystallization time was necessary to give the conventional MSE-type zeolite (=MCM-68), whereas the use of the new type of OSDA, CHDMP2+, gave another MSE-type zeolite (MSECHDMP/STZ-1) within only 32 h of crystallization time. The computed values of stabilization energy showed that CHDMP2+-MSE composite was thermodynamically more stable than TEBOP2+-MSE composite, indicating the stronger host-guest interaction was realized by the CHDMP2+. Since CHDMP2+ has a suitable C/N+ value for the synthesis of high-silica zeolites, the strong host-guest interaction from the viewpoints of both geometry and hydrophobicity could cause frequent nucleation, giving the MSE-type zeolite with smaller crystals, i.e. STZ-1. The STZ-1 was thoroughly dealuminated and Ti atoms were introduced to the defect sites. Thus-obtained titanosilicate, Ti-STZ-1, was found to be an excellent catalyst for the phenol oxidation reaction. In particular, the total product yield and the para-selectivity were up to 92.2 % and 95.9 % in the presence of ethanol, respectively. Superior activity of Ti-STZ-1 to conventional Ti-MCM-68 was ascribed to smaller particle size caused by the stronger host-guest interaction between CHDMP2+ and MSE framework.
{"title":"Efficient synthesis of MSE-type zeolite using a highly effective organic structure-directing agent and excellent catalytic performance of its derived titanosilicate","authors":"Shengxiang Zhang, Yuko Nishi, Kaisei Nakamura, Kai Okubo, Fumiya Takaoka, Issei Saita, Satoshi Inagaki, Yoshihiro Kubota","doi":"10.1016/j.micromeso.2024.113452","DOIUrl":"10.1016/j.micromeso.2024.113452","url":null,"abstract":"<div><div>The use of organic structure-directing agents (OSDAs) is effective in constructing zeolite frameworks with high hydrophobicity and thermal stability. Since OSDAs are guest molecules that stabilize cyclic hosts, designing guest molecules and realizing strong host-guest interactions is one of the reasonable strategies for controlling the structure of zeolites. A very powerful OSDA for the synthesis of <strong>MSE</strong>-type zeolite was designed and successfully prepared. When using conventional OSDA, TEBOP<sup>2+</sup>, more than 10 d of crystallization time was necessary to give the conventional <strong>MSE</strong>-type zeolite (=MCM-68), whereas the use of the new type of OSDA, CHDMP<sup>2+</sup>, gave another <strong>MSE</strong>-type zeolite (MSE<sub>CHDMP</sub>/STZ-1) within only 32 h of crystallization time. The computed values of stabilization energy showed that CHDMP<sup>2+</sup>-<strong>MSE</strong> composite was thermodynamically more stable than TEBOP<sup>2+</sup>-<strong>MSE</strong> composite, indicating the stronger host-guest interaction was realized by the CHDMP<sup>2+</sup>. Since CHDMP<sup>2+</sup> has a suitable C/N<sup>+</sup> value for the synthesis of high-silica zeolites, the strong host-guest interaction from the viewpoints of both geometry and hydrophobicity could cause frequent nucleation, giving the <strong>MSE</strong>-type zeolite with smaller crystals, i.e. STZ-1. The STZ-1 was thoroughly dealuminated and Ti atoms were introduced to the defect sites. Thus-obtained titanosilicate, Ti-STZ-1, was found to be an excellent catalyst for the phenol oxidation reaction. In particular, the total product yield and the <em>para</em>-selectivity were up to 92.2 % and 95.9 % in the presence of ethanol, respectively. Superior activity of Ti-STZ-1 to conventional Ti-MCM-68 was ascribed to smaller particle size caused by the stronger host-guest interaction between CHDMP<sup>2+</sup> and <strong>MSE</strong> framework.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113452"},"PeriodicalIF":4.8,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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