Microporous and Mesoporous Materials最新文献_第8页

The notable features of mesoporous aluminosilicates as catalytic supports for hydrodearomatization and hydrodesulfurization of fuels

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-13 DOI: 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}

引用次数: 0

Naproxen-loaded mesoporous silica nanoparticles: How can the process of incorporation affect drug placement, drug release and the in vitro naproxen irritant potential?

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-13 DOI: 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}

引用次数: 0

Green synthesis of functionalized sodalite ZIFs through mechanochemistry and their performance in CO2 capture

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-11 DOI: 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}

引用次数: 0

Microwave synthesis of UiO-66 with encapsulated caffeine: Liquor mother reuse and release from polyamide composites

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-11 DOI: 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}

引用次数: 0

Enhanced adsorption of Fe(II) from synthetic wastewater using modified bentonite: Isotherms, kinetics, thermodynamics, and adsorption mechanisms

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-11 DOI: 10.1016/j.micromeso.2024.113451

Davron Abdikodirovich Khandamov , Tonni Agustiono Kurniawan , Akbarbek Shukhratovich Bekmirzayev , Fatima Batool , Dilnoza Khandamova , Shavkat Nurullayev , Sevara Kholikova , Zebo Babakhanova , Md Munir Hayet Khan

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 (q_max) 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}

引用次数: 0

Efficient synthesis of MSE-type zeolite using a highly effective organic structure-directing agent and excellent catalytic performance of its derived titanosilicate

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-11 DOI: 10.1016/j.micromeso.2024.113452

Shengxiang Zhang, Yuko Nishi, Kaisei Nakamura, Kai Okubo, Fumiya Takaoka, Issei Saita, Satoshi Inagaki, Yoshihiro Kubota

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 (MSE_CHDMP/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}

引用次数: 0

Theoretical insights on the adsorption of sulfur compounds over a CuCl2-loaded Metal–Organic Framework

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-11 DOI: 10.1016/j.micromeso.2024.113444

Amanda C. Marques , Carla V. Soares , Alexandre A. Leitão

First principles calculations based on density functional theory were performed to examine the adsorption behavior of H₂O, EtOH, CO₂, and a series of sulfur compounds (H₂S, COS, Et-SH, Et-S-Met and DMDS) within the UiO-66(Zr) metal–organic framework (MOF) and the CuCl₂-loaded UiO-66 (CuCl₂@UiO-66). Electronic structure analyses were conducted to characterize the material properties and guide the adsorption site selection within the MOFs pores. Adsorption energies were computed for the guests molecules in their gaseous states, revealing a significant enhancement with CuCl₂ loaded in UiO-66. Thermodynamic analysis were also conducted for the adsorption of the guests on CuCl₂@UiO-66, revealing that all process are spontaneous and exothermic under standard temperature and pressure conditions. The findings suggest that both UiO-66 and CuCl₂@UiO-66 are promising desulfurization adsorbents for Et-SH, DMDS and Et-S-Met in the presence of CO₂ and water vapor, with CuCl₂@UiO-66 showing superior performance due to favorable interactions between Cu and sulfur.

{"title":"Theoretical insights on the adsorption of sulfur compounds over a CuCl2-loaded Metal–Organic Framework","authors":"Amanda C. Marques , Carla V. Soares , Alexandre A. Leitão","doi":"10.1016/j.micromeso.2024.113444","DOIUrl":"10.1016/j.micromeso.2024.113444","url":null,"abstract":"<div><div>First principles calculations based on density functional theory were performed to examine the adsorption behavior of H<sub>2</sub>O, EtOH, CO<sub>2</sub>, and a series of sulfur compounds (H<sub>2</sub>S, COS, Et-SH, Et-S-Met and DMDS) within the UiO-66(Zr) metal–organic framework (MOF) and the CuCl<sub>2</sub>-loaded UiO-66 (CuCl<sub>2</sub>@UiO-66). Electronic structure analyses were conducted to characterize the material properties and guide the adsorption site selection within the MOFs pores. Adsorption energies were computed for the guests molecules in their gaseous states, revealing a significant enhancement with CuCl<sub>2</sub> loaded in UiO-66. Thermodynamic analysis were also conducted for the adsorption of the guests on CuCl<sub>2</sub>@UiO-66, revealing that all process are spontaneous and exothermic under standard temperature and pressure conditions. The findings suggest that both UiO-66 and CuCl<sub>2</sub>@UiO-66 are promising desulfurization adsorbents for Et-SH, DMDS and Et-S-Met in the presence of CO<sub>2</sub> and water vapor, with CuCl<sub>2</sub>@UiO-66 showing superior performance due to favorable interactions between Cu and sulfur.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113444"},"PeriodicalIF":4.8,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100627","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}

引用次数: 0

The pursuit of framework zinc affirmation in zincosilicate zeolites: Clues from conventional and spectroscopic characterization

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-10 DOI: 10.1016/j.micromeso.2024.113449

Gleb Ivanushkin , Ibrahim Khalil , Mostafa Torka Beydokhti , Aram Bugaev , Juna Bae , Thibaut Donckels , Michiel Dusselier

Fine-tuning of active sites in zeolites makes it possible to achieve targeted catalytic activity for many industrial processes. Incorporation of zinc into aluminum-free zeolites grants Lewis acidity while simultaneously creating divalent cation exchange positions. Unfortunately, verification and quantification of zinc sites in zeolites is particularly arduous because metal insertion is accompanied by the formation of extra-framework zinc (hydr)oxide phases, which does not offer the desired properties but also carry some Lewis acidity, leading to difficulty in distinguishing between the two. Here, we present a rigorous characterization of (supposedly) Zn-substituted MFI zeolites. For this, two series of Zn-MFI zeolites were prepared, one via classic batch and the other via the recently invented Electro-Assisted Synthesis (EAS) approach, and these were further benchmarked against Zn-impregnated samples. A suite of analytical techniques was used, among which divalent cation capacity (DCC), infrared spectroscopy (FT-IR), and X-ray absorption spectroscopy (XAS) were proven to be the most efficient. Particularly, DCC highlights the framework Zn stability and ability towards exchange of divalent ions. FT-IR spectroscopy demonstrates the healing of silanol nests upon Zn incorporation into the framework. Additionally, a consistent band at around 525 cm⁻¹ was assigned to framework Zn-MFI vibrations. Furthermore, pyridine adsorption followed by FT-IR revealed a shift in the position of Lewis acid sites peak, when comparing Zn- and Al-MFI, while confirming the absence of Lewis acidity for zinc (hydr)oxide phases. Eventually, XAS complemented our findings by distinguishing two types of Zn^II species among prepared zeolites.

{"title":"The pursuit of framework zinc affirmation in zincosilicate zeolites: Clues from conventional and spectroscopic characterization","authors":"Gleb Ivanushkin , Ibrahim Khalil , Mostafa Torka Beydokhti , Aram Bugaev , Juna Bae , Thibaut Donckels , Michiel Dusselier","doi":"10.1016/j.micromeso.2024.113449","DOIUrl":"10.1016/j.micromeso.2024.113449","url":null,"abstract":"<div><div>Fine-tuning of active sites in zeolites makes it possible to achieve targeted catalytic activity for many industrial processes. Incorporation of zinc into aluminum-free zeolites grants Lewis acidity while simultaneously creating divalent cation exchange positions. Unfortunately, verification and quantification of zinc sites in zeolites is particularly arduous because metal insertion is accompanied by the formation of extra-framework zinc (hydr)oxide phases, which does not offer the desired properties but also carry some Lewis acidity, leading to difficulty in distinguishing between the two. Here, we present a rigorous characterization of (supposedly) Zn-substituted MFI zeolites. For this, two series of Zn-MFI zeolites were prepared, one via classic batch and the other via the recently invented Electro-Assisted Synthesis (EAS) approach, and these were further benchmarked against Zn-impregnated samples. A suite of analytical techniques was used, among which divalent cation capacity (DCC), infrared spectroscopy (FT-IR), and X-ray absorption spectroscopy (XAS) were proven to be the most efficient. Particularly, DCC highlights the framework Zn stability and ability towards exchange of divalent ions. FT-IR spectroscopy demonstrates the healing of silanol nests upon Zn incorporation into the framework. Additionally, a consistent band at around 525 cm<sup>−1</sup> was assigned to framework Zn-MFI vibrations. Furthermore, pyridine adsorption followed by FT-IR revealed a shift in the position of Lewis acid sites peak, when comparing Zn- and Al-MFI, while confirming the absence of Lewis acidity for zinc (hydr)oxide phases. Eventually, XAS complemented our findings by distinguishing two types of Zn<sup>II</sup> species among prepared zeolites.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"387 ","pages":"Article 113449"},"PeriodicalIF":4.8,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143454539","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}

引用次数: 0

Performance of catalytic dehydration of ethanol to ethylene using SUZ–4 zeolite synthesized from rice husk ash in a packed–bed reactor

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-09 DOI: 10.1016/j.micromeso.2024.113446

Tanongsak Sukkasem, Thitipob Sirisoontornpanit, Supunnee Junpirom

This work aimed to study the development of ethylene production through the catalytic dehydration of ethanol using SUZ‒4 zeolitesynthesized from rice husk ash. The optimal conditions for zeolite synthesis, which were tested in the catalytic dehydration process, included a molar ratio of 50 R:50 S and a hydrothermal temperature of 150 °C for 4 days. Under these conditions, the SUZ‒4 zeolite exhibited high crystallinity (97.4 %) and a well‒distributed microporous structure on the catalytic surface, with a pore volume of 0.137 cm³/g and pore sizes ranging from 4.33 to 7.65 Å. The multichannel porous structure further enhanced the selectivity of reactant and product molecules. The zeolite also exhibited a high concentration of weak acid sites (0.787 mmol/g), which are crucial for catalyzing the reaction. Additionally, an investigation into a W/F ratio of 4.45–4.96 g_cat./mmol_EtOH·min⁻¹ showed that this range was optimal for efficiency, highlighting the importance of balancing the catalyst amount with ethanol molecules for effective catalysis at 300 °C. Ethanol conversion reached 99.75 %, and the ethylene yield was 81.28 %. Over a 33‒hour period, the stability of the SUZ‒4 zeolite maintained the ethanol percentage above 90 %. After coke formation on the SUZ‒4 catalyst surface, the zeolite was regenerated, and the ethylene yield remained between 70 and 80 % over 4 regeneration cycles, demonstrating the catalyst's reuse efficiency. Finally, under the optimal conditions for SUZ‒4 zeolite synthesis and catalytic dehydration, a scale‒up experiment was conducted using a packed‒bed reactor 250 times the original size. The results showed that both ethylene yield and ethanol conversion remained consistent.

{"title":"Performance of catalytic dehydration of ethanol to ethylene using SUZ–4 zeolite synthesized from rice husk ash in a packed–bed reactor","authors":"Tanongsak Sukkasem, Thitipob Sirisoontornpanit, Supunnee Junpirom","doi":"10.1016/j.micromeso.2024.113446","DOIUrl":"10.1016/j.micromeso.2024.113446","url":null,"abstract":"<div><div>This work aimed to study the development of ethylene production through the catalytic dehydration of ethanol using SUZ‒4 zeolitesynthesized from rice husk ash. The optimal conditions for zeolite synthesis, which were tested in the catalytic dehydration process, included a molar ratio of 50 R:50 S and a hydrothermal temperature of 150 °C for 4 days. Under these conditions, the SUZ‒4 zeolite exhibited high crystallinity (97.4 %) and a well‒distributed microporous structure on the catalytic surface, with a pore volume of 0.137 cm<sup>3</sup>/g and pore sizes ranging from 4.33 to 7.65 Å. The multichannel porous structure further enhanced the selectivity of reactant and product molecules. The zeolite also exhibited a high concentration of weak acid sites (0.787 mmol/g), which are crucial for catalyzing the reaction. Additionally, an investigation into a W/F ratio of 4.45–4.96 g<sub>cat.</sub>/mmol<sub>EtOH</sub>·min⁻<sup>1</sup> showed that this range was optimal for efficiency, highlighting the importance of balancing the catalyst amount with ethanol molecules for effective catalysis at 300 °C. Ethanol conversion reached 99.75 %, and the ethylene yield was 81.28 %. Over a 33‒hour period, the stability of the SUZ‒4 zeolite maintained the ethanol percentage above 90 %. After coke formation on the SUZ‒4 catalyst surface, the zeolite was regenerated, and the ethylene yield remained between 70 and 80 % over 4 regeneration cycles, demonstrating the catalyst's reuse efficiency. Finally, under the optimal conditions for SUZ‒4 zeolite synthesis and catalytic dehydration, a scale‒up experiment was conducted using a packed‒bed reactor 250 times the original size. The results showed that both ethylene yield and ethanol conversion remained consistent.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113446"},"PeriodicalIF":4.8,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100171","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}

引用次数: 0

Boosting the uranium adsorption capacity of UiO-66 (Ce) by incorporation of amino groups: Experimental and theoretical perspective

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-12-09 DOI: 10.1016/j.micromeso.2024.113450

Nitin Gumber , Rajesh V. Pai , Anil Boda , S.K. Musharaf Ali

In pursuit of clean energy, nuclear field is growing at a rapid pace. To obtain sustainable power production, a large amount of uranium is required which makes it imperative to recover uranium present from different aqueous streams. Thus, this manuscript focuses on the synthesis of UiO-66 (Ce)-NH₂ MOF at ambient conditions and the uranium adsorption studies from aqueous solution. The MOF was thoroughly characterized using different conventional techniques as described in the manuscript. The γ-radiation stability revealed it to be stable up to 1000 kGy of dose. The synthesized MOF exhibited high surface area of 677 m² g⁻¹ and displayed a remarkable uptake of uranium. The stability of synthesized MOF was evaluated under different pH conditions and solvents as mentioned in the manuscript. The adsorption characteristics were evaluated by varying the pH from 2 to 8, time of adsorption, initial concentration of uranium (25–400 mg/L) etc. pH 5 was observed to be ideal with equilibration time of 4 h and followed Pseduo Second Order model implying chemisorption as the main driving force. The Maximum adsorption capacity of ∼321 mg/g was observed using Langmuir isotherm model which is higher than many other reported adsorbents as described in the main text. Adsorption capacity was independent of ionic strength which suggests inner sphere complexation. Further, the reusability studies showed the potential of MOF to be utilized atleast 3 times without any much loss in the adsorption capacity. The selectivity studies towards U in presence of different metal ions like Ni, Cu, K, Co, Fe, La showed MOF to be fairly selective towards U under experimental conditions and plausible mechanism of adsorption are also reported. Additionally, some insights regarding selective adsorption among different metal ions through computational methodology are depicted. Finally, a plausible mechanism of adsorption was deciphered through use of different techniques such as XRD, FT-IR and XPS which elucidated that the adsorption was governed mainly through chelation of NH₂ groups. Thus, the state of art in the field of MOFs is growing exponentially which could use be used to develop more advanced materials with superior adsorption characteristics.

{"title":"Boosting the uranium adsorption capacity of UiO-66 (Ce) by incorporation of amino groups: Experimental and theoretical perspective","authors":"Nitin Gumber , Rajesh V. Pai , Anil Boda , S.K. Musharaf Ali","doi":"10.1016/j.micromeso.2024.113450","DOIUrl":"10.1016/j.micromeso.2024.113450","url":null,"abstract":"<div><div>In pursuit of clean energy, nuclear field is growing at a rapid pace. To obtain sustainable power production, a large amount of uranium is required which makes it imperative to recover uranium present from different aqueous streams. Thus, this manuscript focuses on the synthesis of UiO-66 (Ce)-NH<sub>2</sub> MOF at ambient conditions and the uranium adsorption studies from aqueous solution. The MOF was thoroughly characterized using different conventional techniques as described in the manuscript. The γ-radiation stability revealed it to be stable up to 1000 kGy of dose. The synthesized MOF exhibited high surface area of 677 m<sup>2</sup> g<sup>−1</sup> and displayed a remarkable uptake of uranium. The stability of synthesized MOF was evaluated under different pH conditions and solvents as mentioned in the manuscript. The adsorption characteristics were evaluated by varying the pH from 2 to 8, time of adsorption, initial concentration of uranium (25–400 mg/L) etc. pH 5 was observed to be ideal with equilibration time of 4 h and followed Pseduo Second Order model implying chemisorption as the main driving force. The Maximum adsorption capacity of ∼321 mg/g was observed using Langmuir isotherm model which is higher than many other reported adsorbents as described in the main text. Adsorption capacity was independent of ionic strength which suggests inner sphere complexation. Further, the reusability studies showed the potential of MOF to be utilized atleast 3 times without any much loss in the adsorption capacity. The selectivity studies towards U in presence of different metal ions like Ni, Cu, K, Co, Fe, La showed MOF to be fairly selective towards U under experimental conditions and plausible mechanism of adsorption are also reported. Additionally, some insights regarding selective adsorption among different metal ions through computational methodology are depicted. Finally, a plausible mechanism of adsorption was deciphered through use of different techniques such as XRD, FT-IR and XPS which elucidated that the adsorption was governed mainly through chelation of NH<sub>2</sub> groups. Thus, the state of art in the field of MOFs is growing exponentially which could use be used to develop more advanced materials with superior adsorption characteristics.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"384 ","pages":"Article 113450"},"PeriodicalIF":4.8,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100124","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}

引用次数: 0