Pub Date : 2025-11-13DOI: 10.1016/j.micromeso.2025.113938
Kristoffer Vorm , Chrysoula Stathaki , Pedro L. Oseliero Filho , Hery Mitsutake , Tereza S. Martins , Nikolay Kardjilov , Luis C. Cides-da-Silva , Márcia C.A. Fantini , François B. Lauze , Heloisa N. Bordallo
Ordered Mesoporous Silica (OMS) materials, particularly SBA-15, are widely used in drug delivery due to their structural stability and high porosity. However, the role of macroporosity (pores >50 nm) in influencing protein adsorption and spatial distribution remains poorly understood. In this study, three SBA-15 variants were produced by changing the synthesis temperature and stirring speed, and combined evolved gas analysis (EGA), Raman imaging, and X-ray micro-computed tomography (micro-CT) were used to investigate the adsorption and distribution of lysozyme, a model protein, in the samples. While thermal analysis showed comparable overall protein uptake across all variants, Raman imaging and micro-CT demonstrated that SBA-15 with the larger macropore distribution exhibited a less uniform lysozyme distribution. These observations suggest that macroporosity affects protein localization within SBA-15, which is critical for optimizing antigen delivery and release. Our results advance understanding of how OMS morphology impacts biomolecule encapsulation, offering insights valuable for the design of advanced drug delivery systems and oral vaccines.
{"title":"Protein distribution in SBA-15: Insights from thermal decomposition and advanced imaging","authors":"Kristoffer Vorm , Chrysoula Stathaki , Pedro L. Oseliero Filho , Hery Mitsutake , Tereza S. Martins , Nikolay Kardjilov , Luis C. Cides-da-Silva , Márcia C.A. Fantini , François B. Lauze , Heloisa N. Bordallo","doi":"10.1016/j.micromeso.2025.113938","DOIUrl":"10.1016/j.micromeso.2025.113938","url":null,"abstract":"<div><div>Ordered Mesoporous Silica (OMS) materials, particularly SBA-15, are widely used in drug delivery due to their structural stability and high porosity. However, the role of macroporosity (pores >50 nm) in influencing protein adsorption and spatial distribution remains poorly understood. In this study, three SBA-15 variants were produced by changing the synthesis temperature and stirring speed, and combined evolved gas analysis (EGA), Raman imaging, and X-ray micro-computed tomography (micro-CT) were used to investigate the adsorption and distribution of lysozyme, a model protein, in the samples. While thermal analysis showed comparable overall protein uptake across all variants, Raman imaging and micro-CT demonstrated that SBA-15 with the larger macropore distribution exhibited a less uniform lysozyme distribution. These observations suggest that macroporosity affects protein localization within SBA-15, which is critical for optimizing antigen delivery and release. Our results advance understanding of how OMS morphology impacts biomolecule encapsulation, offering insights valuable for the design of advanced drug delivery systems and oral vaccines.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113938"},"PeriodicalIF":4.7,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145569431","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}
A series of UiO-PY-66-based metal-organic frameworks (MOFs) were synthesized via trifluoroacetic acid (TFA) modulation, thermal activation, and post-synthetic functionalization with 1-bromopropane, aiming to enhance catalytic activity for CO2 cycloaddition with epoxides to form cyclic carbonates. TFA modulation effectively introduced structural defects, thereby increasing the density of acidic sites and increasing overall porosity. Subsequent thermal activation removed residual TFA and guest solvent molecules, further enhancing textural properties and surface acidity. Post-synthetic functionalization introduced pyridinium cations and bromide ions, providing nucleophilic sites for CO2 activation and epoxide ring-opening. The resulting materials were characterized using powder X-ray diffraction, nitrogen sorption analysis, ammonia temperature-programmed desorption, and X-ray photoelectron spectroscopy. Among the synthesized materials, the acid-modulated, thermally activated, and functionalized MOF (PY-FO-Br) exhibited the highest catalytic activity. This enhanced performance is attributed to the synergistic combination of increased acidity, hierarchical porosity with enhanced mesoporosity, and the presence of nucleophilic bromide ions. Under optimized co-catalyst and solvent-free conditions, PY-FO-Br achieved a 78 % yield of styrene carbonate. The catalyst demonstrated good reusability over three cycles and broad substrate scope across various epoxides. This work presents a modular approach to tailoring UiO-66-based MOFs for CO2 fixation, offering a promising route toward sustainable cyclic carbonate synthesis under mild conditions.
{"title":"Hierarchical pore engineering in pyridine-based MOFs for enhanced CO2 cycloaddition","authors":"Parinya Meejaiyen , Pawnprapa Pitakjakpipop , Kyriakos C. Stylianou , Wipark Anutrasakda","doi":"10.1016/j.micromeso.2025.113941","DOIUrl":"10.1016/j.micromeso.2025.113941","url":null,"abstract":"<div><div>A series of UiO-PY-66-based metal-organic frameworks (MOFs) were synthesized via trifluoroacetic acid (TFA) modulation, thermal activation, and post-synthetic functionalization with 1-bromopropane, aiming to enhance catalytic activity for CO<sub>2</sub> cycloaddition with epoxides to form cyclic carbonates. TFA modulation effectively introduced structural defects, thereby increasing the density of acidic sites and increasing overall porosity. Subsequent thermal activation removed residual TFA and guest solvent molecules, further enhancing textural properties and surface acidity. Post-synthetic functionalization introduced pyridinium cations and bromide ions, providing nucleophilic sites for CO<sub>2</sub> activation and epoxide ring-opening. The resulting materials were characterized using powder X-ray diffraction, nitrogen sorption analysis, ammonia temperature-programmed desorption, and X-ray photoelectron spectroscopy. Among the synthesized materials, the acid-modulated, thermally activated, and functionalized MOF (PY-FO-Br) exhibited the highest catalytic activity. This enhanced performance is attributed to the synergistic combination of increased acidity, hierarchical porosity with enhanced mesoporosity, and the presence of nucleophilic bromide ions. Under optimized co-catalyst and solvent-free conditions, PY-FO-Br achieved a 78 % yield of styrene carbonate. The catalyst demonstrated good reusability over three cycles and broad substrate scope across various epoxides. This work presents a modular approach to tailoring UiO-66-based MOFs for CO<sub>2</sub> fixation, offering a promising route toward sustainable cyclic carbonate synthesis under mild conditions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113941"},"PeriodicalIF":4.7,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145518365","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 : 2025-11-12DOI: 10.1016/j.micromeso.2025.113944
Hassan Amasha , Aqeel Ahmad , Othman Charles S. Al Hamouz
This work reports the synergistic effect of tuning the structure and functionality of triptycene-heteroaromatic porous organic polymers toward selective CO2 capture. The polymers were constructed by a rapid and energy-efficient microwave-assisted Friedel-Crafts polymerization of triptycene with heteroaromatic units of pyrrole, furan, and thiophene using dimethoxymethane (DMM) as a linker and FeCl3 as a catalyst. The resulting materials exhibit robust thermal stability and high BET surface areas, reaching up to 1316 m2/g. Gas sorption studies confirmed the polymers' potential, demonstrating significant CO2 uptake (up to 2.81 mmol g−1 at 273 K) and high selectivity for CO2 over N2 and CH4, reaching a selectivity of CO2/N2 up to 238 and a selectivity of CO2/CH4 up to 24. The research establishes that the incorporation of different heteroatoms (N, O, S) provides an effective strategy for tuning the polymers' adsorption properties, highlighting the synergistic effect of triptycene's space-generating structure and the electronic functionalities and loading of the heteroaromatic units on the overall structure and performance of the polymer.
{"title":"Effect of structure and functionality on the performance of triptycene-heteroaromatic porous polymers for selective CO2 capture","authors":"Hassan Amasha , Aqeel Ahmad , Othman Charles S. Al Hamouz","doi":"10.1016/j.micromeso.2025.113944","DOIUrl":"10.1016/j.micromeso.2025.113944","url":null,"abstract":"<div><div>This work reports the synergistic effect of tuning the structure and functionality of triptycene-heteroaromatic porous organic polymers toward selective CO<sub>2</sub> capture. The polymers were constructed by a rapid and energy-efficient microwave-assisted Friedel-Crafts polymerization of triptycene with heteroaromatic units of pyrrole, furan, and thiophene using dimethoxymethane (DMM) as a linker and FeCl<sub>3</sub> as a catalyst. The resulting materials exhibit robust thermal stability and high BET surface areas, reaching up to 1316 m<sup>2</sup>/g. Gas sorption studies confirmed the polymers' potential, demonstrating significant CO<sub>2</sub> uptake (up to 2.81 mmol g<sup>−1</sup> at 273 K) and high selectivity for CO<sub>2</sub> over N<sub>2</sub> and CH<sub>4</sub>, reaching a selectivity of CO<sub>2</sub>/N<sub>2</sub> up to 238 and a selectivity of CO<sub>2</sub>/CH<sub>4</sub> up to 24. The research establishes that the incorporation of different heteroatoms (N, O, S) provides an effective strategy for tuning the polymers' adsorption properties, highlighting the synergistic effect of triptycene's space-generating structure and the electronic functionalities and loading of the heteroaromatic units on the overall structure and performance of the polymer.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113944"},"PeriodicalIF":4.7,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145518366","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 : 2025-11-11DOI: 10.1016/j.micromeso.2025.113940
Ilya V. Yakovlev , Aleksandr V. Toktarev , Evgeniy S. Papulovskiy , Natalia E. Cherepanova , Aleksandr A. Shubin , Olga B. Lapina
Microporous silicoaluminophosphates (SAPO-n) attract much interest in the field of heterogeneous catalysis as acidic catalysts and catalyst supports that provide steric constraints on the reactants. The acidic properties of SAPO-n depend on the distribution of Si sites in the framework (e.g. isolated Si sites, Si patches), which remains a highly discussed topic. In this work, we use solid-state NMR spectroscopy of 29Si-enriched SAPO-5 and SAPO-11 in combination with DFT calculations to determine the location of Si sites in the corresponding frameworks and characterize the associated Brønsted acid sites. Using a probabilistic approach, we find the preferred sites for Si substitution and the preferred directions of the OH bonds in the hydroxy groups.
{"title":"Distribution of Si sites in silicoaluminophosphates SAPO-5 and SAPO-11 according to solid-state NMR spectroscopy and DFT calculations","authors":"Ilya V. Yakovlev , Aleksandr V. Toktarev , Evgeniy S. Papulovskiy , Natalia E. Cherepanova , Aleksandr A. Shubin , Olga B. Lapina","doi":"10.1016/j.micromeso.2025.113940","DOIUrl":"10.1016/j.micromeso.2025.113940","url":null,"abstract":"<div><div>Microporous silicoaluminophosphates (SAPO-n) attract much interest in the field of heterogeneous catalysis as acidic catalysts and catalyst supports that provide steric constraints on the reactants. The acidic properties of SAPO-n depend on the distribution of Si sites in the framework (e.g. isolated Si sites, Si patches), which remains a highly discussed topic. In this work, we use solid-state NMR spectroscopy of <sup>29</sup>Si-enriched SAPO-5 and SAPO-11 in combination with DFT calculations to determine the location of Si sites in the corresponding frameworks and characterize the associated Brønsted acid sites. Using a probabilistic approach, we find the preferred sites for Si substitution and the preferred directions of the OH bonds in the hydroxy groups.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113940"},"PeriodicalIF":4.7,"publicationDate":"2025-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145518362","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}
In this study, to modulate the properties of mesostructured alumina synthetized by combining the sol-gel process and the surfactant templating mechanism, the introduction of fluorine has been carried out through a one step process using ammonium fluoride as fluorinating agent.
Small angle x-ray scattering, X-ray diffraction, 19F, 27Al NMR and manometry nitrogen adsorption-desorption analyses show that even after heating at 500 °C, amorphous mesostructured aluminum (hydr)oxyfluoride with an intrinsic mesoporosity are obtained for NH4F concentration in water lower than 112.5 g L−1.
With the increase in the fluorine content, the mesostructuration is lost. For materials recovered after removal of the porogen agent (Pluronic P123) by Soxhlet extraction, aluminum (hydr)oxyfluoride hydrate Al2(OH)2.76F3.24(H2O) and ammonium fluoroaluminates, are detected by XRD. When the extracted materials are calcined at 500 °C, ammonium fluoroaluminates are decomposed into AlF3 and AlF1.96(OH)1.04 is also detected. Because of the presence of the crystalline phases, the intrinsic porosity vanishes and the mesoporosity is mainly inter-aggregates.
Adsorption of pyridine followed by infrared spectroscopy reveals that whatever the fluorine content, no Brønsted acid site is present. The concentration of the Lewis acid sites first increases to reach a maximum value around 0.8 μmol m−2 for a NH4F concentration in water of 112.5 g L−1, then it reaches a plateau.
本研究以氟化铵为氟化剂，通过一步法引入氟，对溶胶-凝胶法制备的介结构氧化铝的性能进行调控。小角x射线散射、x射线衍射、19F、27Al核磁共振和测压法氮吸附-解吸分析表明，当水中NH4F浓度低于112.5 g L−1时，即使在500℃加热后，也能得到具有本征介孔的无定形介孔结构氟化铝（氢氧）。随着氟含量的增加，介观结构丧失。对索氏萃取法去除多孔剂（Pluronic P123）后回收的材料，用x射线衍射仪（XRD）检测了氢化氟氧铝Al2(OH)2.76F3.24（H2O）和氟铝酸铵。提取的物料在500℃下煅烧，氟铝酸铵分解为AlF3，同时检测到AlF1.96(OH)1.04。由于结晶相的存在，本征孔隙消失，介孔主要为团聚体间孔隙。对吡啶的吸附和红外光谱分析表明，无论氟含量如何，都没有Brønsted酸位存在。当NH4F浓度为112.5 g L−1时，Lewis酸位点的浓度先升高，在0.8 μmol m−2左右达到最大值，然后趋于平稳。
{"title":"Tailoring of mesostructured alumina properties by the one pot incorporation of fluorine","authors":"Jean-Luc Blin , Sylvette Brunet , Laure Michelin , Séverinne Rigolet , Jean Dominique Comparot , Bénédicte Lebeau","doi":"10.1016/j.micromeso.2025.113937","DOIUrl":"10.1016/j.micromeso.2025.113937","url":null,"abstract":"<div><div>In this study, to modulate the properties of mesostructured alumina synthetized by combining the sol-gel process and the surfactant templating mechanism, the introduction of fluorine has been carried out through a one step process using ammonium fluoride as fluorinating agent.</div><div>Small angle x-ray scattering, X-ray diffraction, <sup>19</sup>F, <sup>27</sup>Al NMR and manometry nitrogen adsorption-desorption analyses show that even after heating at 500 °C, amorphous mesostructured aluminum (hydr)oxyfluoride with an intrinsic mesoporosity are obtained for NH<sub>4</sub>F concentration in water lower than 112.5 g L<sup>−1</sup>.</div><div>With the increase in the fluorine content, the mesostructuration is lost. For materials recovered after removal of the porogen agent (Pluronic P123) by Soxhlet extraction, aluminum (hydr)oxyfluoride hydrate Al<sub>2</sub>(OH)<sub>2.76</sub>F<sub>3.24</sub>(H<sub>2</sub>O) and ammonium fluoroaluminates, are detected by XRD. When the extracted materials are calcined at 500 °C, ammonium fluoroaluminates are decomposed into AlF<sub>3</sub> and AlF<sub>1.96</sub>(OH)<sub>1.04</sub> is also detected. Because of the presence of the crystalline phases, the intrinsic porosity vanishes and the mesoporosity is mainly inter-aggregates.</div><div>Adsorption of pyridine followed by infrared spectroscopy reveals that whatever the fluorine content, no Brønsted acid site is present. The concentration of the Lewis acid sites first increases to reach a maximum value around 0.8 μmol m<sup>−2</sup> for a NH<sub>4</sub>F concentration in water of 112.5 g L<sup>−1</sup>, then it reaches a plateau.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113937"},"PeriodicalIF":4.7,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145518361","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 : 2025-11-06DOI: 10.1016/j.micromeso.2025.113936
Hídila Souza Teixeira da Silva, Diogo Pimentel de Sa da Silva, Ricardo Reis Soares
This study systematically investigates the influence of structure-directing agents (urea, PVP, and F127), crystallization time (24, 36, and 48 h), and calcination temperature (400, 500, and 600 °C) on the structural, textural, and acidic properties of mesoporous niobium pentoxide (meso-Nb2O5). The synthesized materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, nitrogen adsorption–desorption, thermogravimetric analysis (TG/DTG), scanning electron microscopy (SEM), and zeta potential measurements. Urea was identified as the most effective structure-directing agent, yielding a well-developed meso-Nb2O5 with a high surface area (195 m2 g−1) and enhanced total acidity (58 μmol g−1). The crystallization time significantly affected the structural organization, with 36 h favoring the formation of the pseudo-hexagonal TT-Nb2O5 phase and improved textural properties. The calcination temperature played a key role in phase transitions, with 500 °C being the optimal condition to balance crystallinity and mesoporosity. Catalytic performance was evaluated in Fischer–Tropsch synthesis (FTS). The Co catalyst supported on meso-Nb2O5 (10Co/Meso-Nb2O5) exhibited higher CO conversion (23 %) than its conventional Nb2O5 counterpart (10Co/Conv-Nb2O5), which reached 12 %, as well as greater selectivity toward medium-chain hydrocarbons (C5–C12, 44.1 % vs. 28.1 %) and lower methane formation (10.4 % vs. 17.1 %). These results demonstrate that the mesoporous Nb2O5 structure enhances cobalt dispersion and metal–support interactions. Overall, tuning the synthesis parameters effectively tailors Nb2O5 properties for advanced applications in heterogeneous catalysis.
{"title":"Optimized synthesis of mesoporous niobium pentoxide: influence of structure-directing agents, crystallization time, and calcination temperature","authors":"Hídila Souza Teixeira da Silva, Diogo Pimentel de Sa da Silva, Ricardo Reis Soares","doi":"10.1016/j.micromeso.2025.113936","DOIUrl":"10.1016/j.micromeso.2025.113936","url":null,"abstract":"<div><div>This study systematically investigates the influence of structure-directing agents (urea, PVP, and F127), crystallization time (24, 36, and 48 h), and calcination temperature (400, 500, and 600 °C) on the structural, textural, and acidic properties of mesoporous niobium pentoxide (meso-Nb<sub>2</sub>O<sub>5</sub>). The synthesized materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, nitrogen adsorption–desorption, thermogravimetric analysis (TG/DTG), scanning electron microscopy (SEM), and zeta potential measurements. Urea was identified as the most effective structure-directing agent, yielding a well-developed meso-Nb<sub>2</sub>O<sub>5</sub> with a high surface area (195 m<sup>2</sup> g<sup>−1</sup>) and enhanced total acidity (58 μmol g<sup>−1</sup>). The crystallization time significantly affected the structural organization, with 36 h favoring the formation of the pseudo-hexagonal TT-Nb<sub>2</sub>O<sub>5</sub> phase and improved textural properties. The calcination temperature played a key role in phase transitions, with 500 °C being the optimal condition to balance crystallinity and mesoporosity. Catalytic performance was evaluated in Fischer–Tropsch synthesis (FTS). The Co catalyst supported on meso-Nb<sub>2</sub>O<sub>5</sub> (10Co/Meso-Nb<sub>2</sub>O<sub>5</sub>) exhibited higher CO conversion (23 %) than its conventional Nb<sub>2</sub>O<sub>5</sub> counterpart (10Co/Conv-Nb<sub>2</sub>O<sub>5</sub>), which reached 12 %, as well as greater selectivity toward medium-chain hydrocarbons (C<sub>5</sub>–C<sub>12</sub>, 44.1 % vs. 28.1 %) and lower methane formation (10.4 % vs. 17.1 %). These results demonstrate that the mesoporous Nb<sub>2</sub>O<sub>5</sub> structure enhances cobalt dispersion and metal–support interactions. Overall, tuning the synthesis parameters effectively tailors Nb<sub>2</sub>O<sub>5</sub> properties for advanced applications in heterogeneous catalysis.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113936"},"PeriodicalIF":4.7,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145518363","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 : 2025-11-04DOI: 10.1016/j.micromeso.2025.113932
Yi Hu , Zhirui Chen , Xue Qiao , Guoliang Wu , Yunfeng Hu , Qiang Bao , Jian Zhang , Zhenlu Wang
Three distinct Si/Al ratios of RHO zeolites were synthesized via hydrothermal technique, yielding K-RHO zeolites with Si/Al ratios of 1.5, 3.4, and 5.9 after K+ exchange. XRD, SEM, ICP, and N2 adsorption-desorption characterization analyses were conducted simultaneously. The single-component adsorption isotherms of N2 and CH4 for the three samples were assessed at 298 K. The results indicate that the Si/Al ratio affects both the cation quantity and, more importantly, modifies the pore sizes of the zeolites, which play a key role in the shape-selective adsorption separation of N2/CH4. Among them, K-RHO (3.4) exhibits remarkable shape-selective adsorption of N2, with an adsorbent selection parameter (S parameter) of 38.38. Cation occupancy, N2 adsorption sites, and N2 adsorption isotherms for the K-RHO zeolites with varying Si/Al ratios were simulated using Materials Studio 2020 software. It is shown that changes in the Si/Al ratio alter the positions of the cations and either increase or decrease the adsorption sites for N2 on the adsorbent. Moreover, the results of adsorption kinetics research indicate that changes in the Si/Al ratio cause the adsorption kinetic mechanism of K-RHO zeolites for N2 to transition from surface diffusion to pore diffusion, leading to shape-selective adsorption of N2. The IAST analysis results indicate that the K-RHO (3.4) zeolite is suitable for removing N2 in natural gas industrial applications.
采用水热法合成了三种不同Si/Al比的RHO沸石，经K+交换后得到Si/Al比分别为1.5、3.4和5.9的K-RHO沸石。同时进行了XRD、SEM、ICP和N2吸附-脱附表征分析。测定了3种样品在298 K下对N2和CH4的单组分吸附等温线。结果表明，Si/Al比不仅影响阳离子的数量，更重要的是改变分子筛的孔径，这对N2/CH4的形状选择性吸附分离起关键作用。其中K-RHO（3.4）对N2表现出显著的形状选择性吸附，吸附剂选择参数（S参数）为38.38。利用Materials Studio 2020软件模拟了不同Si/Al比下K-RHO沸石的阳离子占据率、N2吸附位点和N2吸附等温线。结果表明，Si/Al比的变化改变了阳离子的位置，增加或减少了吸附剂对N2的吸附位点。此外，吸附动力学研究结果表明，Si/Al比的变化导致K-RHO沸石对N2的吸附动力学机制由表面扩散向孔扩散转变，导致N2的形状选择性吸附。IAST分析结果表明，K-RHO（3.4）分子筛适合用于天然气工业中N2的脱氮。
{"title":"Variation of adsorption mechanism with Si/al ratio in RHO zeolites for nitrogen/methane separation","authors":"Yi Hu , Zhirui Chen , Xue Qiao , Guoliang Wu , Yunfeng Hu , Qiang Bao , Jian Zhang , Zhenlu Wang","doi":"10.1016/j.micromeso.2025.113932","DOIUrl":"10.1016/j.micromeso.2025.113932","url":null,"abstract":"<div><div>Three distinct Si/Al ratios of RHO zeolites were synthesized via hydrothermal technique, yielding K-RHO zeolites with Si/Al ratios of 1.5, 3.4, and 5.9 after K<sup>+</sup> exchange. XRD, SEM, ICP, and N<sub>2</sub> adsorption-desorption characterization analyses were conducted simultaneously. The single-component adsorption isotherms of N<sub>2</sub> and CH<sub>4</sub> for the three samples were assessed at 298 K. The results indicate that the Si/Al ratio affects both the cation quantity and, more importantly, modifies the pore sizes of the zeolites, which play a key role in the shape-selective adsorption separation of N<sub>2</sub>/CH<sub>4</sub>. Among them, K-RHO (3.4) exhibits remarkable shape-selective adsorption of N<sub>2</sub>, with an adsorbent selection parameter (<em>S</em> parameter) of 38.38. Cation occupancy, N<sub>2</sub> adsorption sites, and N<sub>2</sub> adsorption isotherms for the K-RHO zeolites with varying Si/Al ratios were simulated using Materials Studio 2020 software. It is shown that changes in the Si/Al ratio alter the positions of the cations and either increase or decrease the adsorption sites for N<sub>2</sub> on the adsorbent. Moreover, the results of adsorption kinetics research indicate that changes in the Si/Al ratio cause the adsorption kinetic mechanism of K-RHO zeolites for N<sub>2</sub> to transition from surface diffusion to pore diffusion, leading to shape-selective adsorption of N<sub>2</sub>. The IAST analysis results indicate that the K-RHO (3.4) zeolite is suitable for removing N<sub>2</sub> in natural gas industrial applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113932"},"PeriodicalIF":4.7,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464610","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 : 2025-11-04DOI: 10.1016/j.micromeso.2025.113923
Rui G. Faria , O. Salomé G.P. Soares , Pedro L. Almeida , Salete S. Balula , Luís Cunha-Silva
A straightforward innovative strategy to improve the reusability of a polyoxometalate/porous metal-organic framework (POM/MOF) heterogeneous catalysts based in suitable structural modification by thermal treatment is reported in this manuscript for the first time. The incorporation of the active Keggin-type phosphomolybdate anion ([PMo12O40]3-, PMo12) into the porous Zeolitic Imidazolate Framework (ZIF-8) led to the formation of the composite material PMo12@ZIF-8. This material exhibited catalytic activity during the first use but could not be reused in subsequent oxidative desulfurization (ODS) cycles of a multicomponent model diesel (2000 ppm S). Remarkably, an appropriate post-synthetic thermal treatment at temperatures slightly below the structural collapse point (400 °C and 500 °C), as well as at 550 °C, enabled efficient reutilization of the material. This modified material was reutilized for at least five consecutive ODS cycles without any observable loss in catalytic performance. These results confirm the integrity and durability of the heterogeneous catalyst. The methodology here developed is a reference that can be adapted to improve the robustness of active POM@MOF based catalyst, increasing the viability of these highly active materials for industrial application.
{"title":"Straightforward approach to promote an efficient reutilization of POM@MOF catalysts in oxidative desulfurization processes","authors":"Rui G. Faria , O. Salomé G.P. Soares , Pedro L. Almeida , Salete S. Balula , Luís Cunha-Silva","doi":"10.1016/j.micromeso.2025.113923","DOIUrl":"10.1016/j.micromeso.2025.113923","url":null,"abstract":"<div><div>A straightforward innovative strategy to improve the reusability of a polyoxometalate/porous metal-organic framework (POM/MOF) heterogeneous catalysts based in suitable structural modification by thermal treatment is reported in this manuscript for the first time. The incorporation of the active Keggin-type phosphomolybdate anion ([PMo<sub>12</sub>O<sub>40</sub>]<sup>3-</sup>, PMo<sub>12</sub>) into the porous Zeolitic Imidazolate Framework (ZIF-8) led to the formation of the composite material PMo<sub>12</sub>@ZIF-8. This material exhibited catalytic activity during the first use but could not be reused in subsequent oxidative desulfurization (ODS) cycles of a multicomponent model diesel (2000 ppm S). Remarkably, an appropriate post-synthetic thermal treatment at temperatures slightly below the structural collapse point (400 °C and 500 °C), as well as at 550 °C, enabled efficient reutilization of the material. This modified material was reutilized for at least five consecutive ODS cycles without any observable loss in catalytic performance. These results confirm the integrity and durability of the heterogeneous catalyst. The methodology here developed is a reference that can be adapted to improve the robustness of active POM@MOF based catalyst, increasing the viability of these highly active materials for industrial application.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113923"},"PeriodicalIF":4.7,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145518364","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 : 2025-11-04DOI: 10.1016/j.micromeso.2025.113924
Aojing Deng , Ruizhen Zhang , Jiamin Li , Yifei Pan , Danxue Zhang , Kai Zong
Amine-free synthesis of high-silica ZSM-5 (SAR ≥200) remained a significant challenge due to the instability of the silica-rich framework under alkaline conditions. In this study, a facile and efficient synthetic route for high-silica ZSM-5 (SAR = 300) was developed with the assistance of silicalite-1 seed and short-chain alcohol. Firstly, high-crystalline ZSM-5 (80 % relative crystallinity) with hexagonal prism morphology and the size of 850–1500 nm was successfully synthesized by systematically optimizing the solvent composition (EtOH/SiO2 = 4–8, H2O/SiO2 = 15–25) and alkalinity (Na2O/SiO2 = 0.03–0.04). Then, replacing ethanol with butanol further enhanced the crystallinity (>95 %) and reduced crystal size (750–1300 nm), attributed to the fact that water-butanol mixture had a lower dielectric constant than water-ethanol mixture, which could more effectively weaken the solvent's charge-shielding capability and improve the electrostatic interaction between Na+ and negatively charged species, thereby promoting the nucleation and the assembly of MFI skeleton. In summary, this work provided a concise process for the synthesis of high-silica ZSM-5 with the assistance of alcohol and silicalite-1 seed, which enabled the cost-effective, eco-friendly production of high-silica ZSM-5 with high crystallinity in the amine-free system.
{"title":"Influence of solvent effect on the amine-free synthesis of high-silica ZSM-5 with the investigation of mechanism","authors":"Aojing Deng , Ruizhen Zhang , Jiamin Li , Yifei Pan , Danxue Zhang , Kai Zong","doi":"10.1016/j.micromeso.2025.113924","DOIUrl":"10.1016/j.micromeso.2025.113924","url":null,"abstract":"<div><div>Amine-free synthesis of high-silica ZSM-5 (SAR ≥200) remained a significant challenge due to the instability of the silica-rich framework under alkaline conditions. In this study, a facile and efficient synthetic route for high-silica ZSM-5 (SAR = 300) was developed with the assistance of silicalite-1 seed and short-chain alcohol. Firstly, high-crystalline ZSM-5 (80 % relative crystallinity) with hexagonal prism morphology and the size of 850–1500 nm was successfully synthesized by systematically optimizing the solvent composition (EtOH/SiO<sub>2</sub> = 4–8, H<sub>2</sub>O/SiO<sub>2</sub> = 15–25) and alkalinity (Na<sub>2</sub>O/SiO<sub>2</sub> = 0.03–0.04). Then, replacing ethanol with butanol further enhanced the crystallinity (>95 %) and reduced crystal size (750–1300 nm), attributed to the fact that water-butanol mixture had a lower dielectric constant than water-ethanol mixture, which could more effectively weaken the solvent's charge-shielding capability and improve the electrostatic interaction between Na<sup>+</sup> and negatively charged species, thereby promoting the nucleation and the assembly of MFI skeleton. In summary, this work provided a concise process for the synthesis of high-silica ZSM-5 with the assistance of alcohol and silicalite-1 seed, which enabled the cost-effective, eco-friendly production of high-silica ZSM-5 with high crystallinity in the amine-free system.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113924"},"PeriodicalIF":4.7,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787310","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 : 2025-11-04DOI: 10.1016/j.micromeso.2025.113935
Sofya A. Dogadaeva, Lubov A. Antina, Mikhail B. Berezin, Elena V. Antina
In the present work, BODIPY@ZIF-8 nanocomposites different synthesis strategies comparative study was carried out by hydrophobic BODIPY photosensitizers encapsulation into metal-organic framework ZIF-8. The BODIPY@ZIF-8s powders were synthesized via different methods: a simple one-step method (in situ) in the process of framework synthesis in a solution of various solvents or mechanochemically in the solvent absence; ZIF-8 post-synthetic modification method (ex situ) by impregnating it with a BODIPY luminophore solution. Solvent nature has a deep impact on the characteristics of both the ZIF-8 carriers themselves and BODIPY@ZIF-8 nanocomposites, as well as on the luminophore loading efficiency. The optimal conditions for BODIPY@ZIF-8 nanocomposites synthesis with the highest specific dye loading and optimal textural characteristics were selected. In addition, BODIPY@ZIF-8 powders demonstrating intense fluorescence obtaining conditions have been selected, which can be used to obtain solid-state fluorescent materials.
{"title":"Structural and fluorescent characteristics of BODIPY@ZIF-8 nanocomposites: a comparative study of different synthesis strategies","authors":"Sofya A. Dogadaeva, Lubov A. Antina, Mikhail B. Berezin, Elena V. Antina","doi":"10.1016/j.micromeso.2025.113935","DOIUrl":"10.1016/j.micromeso.2025.113935","url":null,"abstract":"<div><div>In the present work, BODIPY@ZIF-8 nanocomposites different synthesis strategies comparative study was carried out by hydrophobic BODIPY photosensitizers encapsulation into metal-organic framework ZIF-8. The BODIPY@ZIF-8s powders were synthesized <em>via</em> different methods: a simple one-step method (<em>in situ</em>) in the process of framework synthesis in a solution of various solvents or mechanochemically in the solvent absence; ZIF-8 post-synthetic modification method (<em>ex situ</em>) by impregnating it with a BODIPY luminophore solution. Solvent nature has a deep impact on the characteristics of both the ZIF-8 carriers themselves and BODIPY@ZIF-8 nanocomposites, as well as on the luminophore loading efficiency. The optimal conditions for BODIPY@ZIF-8 nanocomposites synthesis with the highest specific dye loading and optimal textural characteristics were selected. In addition, BODIPY@ZIF-8 powders demonstrating intense fluorescence obtaining conditions have been selected, which can be used to obtain solid-state fluorescent materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113935"},"PeriodicalIF":4.7,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145465012","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}
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