Pub Date : 2025-12-02DOI: 10.1016/j.micromeso.2025.113963
Yanxia Zheng , Na Zhao , Shanshan Liu , Mingliang Ding , Yuchao Li , Ming Wang , Rui Xu , Cuncun Zuo , Haofei Huang , Yansong Zhao , Qian Wang
Hydrotreatment of lubrication oil waste can effectively remove sulfur and some other impurities, which can benefit resource regeneration and result in positive environmental and economic impact. A dual-template strategy employing PMMA microspheres and CTAB was adopted to synthesize porous Y-type zeolites with tunable macropore dimensions. The resulting Y-type zeolite framework exhibited an ordered system of mesopores and interconnected macropores, which was subsequently loaded with NiMo active metals for the hydrogen desulfurization (HDS) of benzothiophene during waste lubricating oil treatment. Effect of various macropore size on benzothiophene hydrogenation performance was investigated. The results showed that macropore size variation played a crucial role in the HDS process. The macroporous structure also helps reduce excessive growth of MoS2 nanosheets, maintaining a high number of stacked layers and short sheet lengths. This promotes the formation of highly dispersed MoS2 nanosheet structures, thereby facilitating the development of the active NiMoS phase. Furthermore, catalyst with the largest macropore size achieved a benzothiophene HDS conversion of up to 99.6 %, with an activation energy of 29.85 kJ/mol.
{"title":"Preparation of macro-mesoporous composite Y-type zeolite via guided synthesis to enhance hydrodesulfurization performance of waste lubricating oil","authors":"Yanxia Zheng , Na Zhao , Shanshan Liu , Mingliang Ding , Yuchao Li , Ming Wang , Rui Xu , Cuncun Zuo , Haofei Huang , Yansong Zhao , Qian Wang","doi":"10.1016/j.micromeso.2025.113963","DOIUrl":"10.1016/j.micromeso.2025.113963","url":null,"abstract":"<div><div>Hydrotreatment of lubrication oil waste can effectively remove sulfur and some other impurities, which can benefit resource regeneration and result in positive environmental and economic impact. A dual-template strategy employing PMMA microspheres and CTAB was adopted to synthesize porous Y-type zeolites with tunable macropore dimensions. The resulting Y-type zeolite framework exhibited an ordered system of mesopores and interconnected macropores, which was subsequently loaded with NiMo active metals for the hydrogen desulfurization (HDS) of benzothiophene during waste lubricating oil treatment. Effect of various macropore size on benzothiophene hydrogenation performance was investigated. The results showed that macropore size variation played a crucial role in the HDS process. The macroporous structure also helps reduce excessive growth of MoS<sub>2</sub> nanosheets, maintaining a high number of stacked layers and short sheet lengths. This promotes the formation of highly dispersed MoS<sub>2</sub> nanosheet structures, thereby facilitating the development of the active NiMoS phase. Furthermore, catalyst with the largest macropore size achieved a benzothiophene HDS conversion of up to 99.6 %, with an activation energy of 29.85 kJ/mol.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 113963"},"PeriodicalIF":4.7,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145789882","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 biomass extracted in water after ultrasonic treatment of red pepper powder contributes to the liquid exfoliation of solids such as graphite, hematite, magnetite and silicon and the formation of two-dimensional nanostructures. Afterwards, the amphiphilic biomass acting as a gelator, contributes to the formation of soft hydrogels and the corresponding ultralight monolithic aerogels based on the graphene, hematene, magnetene and silicene nanosheets resulting from the liquid exfoliation. Depending on the basic chemical element of the nanostructures, these novel aerogels exhibited extremely low densities, between 4.22 mg cm−3 with silicene and 14.35 mg cm−3 with magnetene and porosities exceeding 99.7 %. The monolithic ultralight graphene, hematene and magnetene aerogels were fully sustainable as they are derived from natural materials such as minerals hematite, magnetite and graphite, a natural product such as red pepper and water as solvent. Energy consumption for the basic aerogel formation process was also limited compared to other techniques due to the use of short-duration ultrasound.
超声波处理后的红椒粉在水中提取的生物质有助于石墨、赤铁矿、磁铁矿和硅等固体物质的液体剥落，形成二维纳米结构。然后，两亲性生物质作为凝胶剂，以液体剥离产生的石墨烯、血红素、磁烯和硅烯纳米片为基础，形成软水凝胶和相应的超轻单片气凝胶。根据纳米结构的基本化学元素，这些新型气凝胶表现出极低的密度，在含硅的4.22 mg cm - 3和含磁烯的14.35 mg cm - 3之间，孔隙率超过99.7%。单片超轻石墨烯、赤铁矿和磁烯气凝胶是完全可持续的，因为它们是从天然材料中提取的，如矿物赤铁矿、磁铁矿和石墨，一种天然产物，如红辣椒和水作为溶剂。由于使用短时间超声，与其他技术相比，基本气凝胶形成过程的能耗也很有限。
{"title":"Biomass based ultralight monolithic aerogels of two-dimensional nanostructures","authors":"Apostolos Koutsioukis , Christina Rista , Eleni Tegkelidi , Christos Priovolos , Dimitris Manolis , Konstantina Goumenou , Elli Bellou , Argyris Kolokithas Ntoukas , Konstantinos Ar Papageorgiou , Vasilios I. Georgakilas","doi":"10.1016/j.micromeso.2025.113978","DOIUrl":"10.1016/j.micromeso.2025.113978","url":null,"abstract":"<div><div>The biomass extracted in water after ultrasonic treatment of red pepper powder contributes to the liquid exfoliation of solids such as graphite, hematite, magnetite and silicon and the formation of two-dimensional nanostructures. Afterwards, the amphiphilic biomass acting as a gelator, contributes to the formation of soft hydrogels and the corresponding ultralight monolithic aerogels based on the graphene, hematene, magnetene and silicene nanosheets resulting from the liquid exfoliation. Depending on the basic chemical element of the nanostructures, these novel aerogels exhibited extremely low densities, between 4.22 mg cm<sup>−3</sup> with silicene and 14.35 mg cm<sup>−3</sup> with magnetene and porosities exceeding 99.7 %. The monolithic ultralight graphene, hematene and magnetene aerogels were fully sustainable as they are derived from natural materials such as minerals hematite, magnetite and graphite, a natural product such as red pepper and water as solvent. Energy consumption for the basic aerogel formation process was also limited compared to other techniques due to the use of short-duration ultrasound.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113978"},"PeriodicalIF":4.7,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682635","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 : 2025-12-01DOI: 10.1016/j.micromeso.2025.113976
Alaa Bin Shuqayr , Sadeem Bin Tuwaym , Mostafa Zeama , Rawan AL Natour , Osama Shekhah , Mohamed Eddaoudi , Zeid A. Alothman , Kareem Y. Mahmoud
The separation of light alkane/alkene mixtures remains a central challenge in petrochemical processing, especially under mild conditions where traditional energy-intensive approaches such as cryogenic distillation are impractical. Here, we report a mixed-matrix monolithic composite (MMMo) comprising only 0.5 wt% MOF-801 nanoparticles embedded in a divinylbenzene (DVB) matrix, synthesized via in situ capillary polymerization. Despite the trace MOF loading, the composite exhibits an unusual and dual thermodynamic selectivity for ethane over ethylene (α = 1.49, Rs = 0.87 at 0 °C) and propane over propylene (α = 1.19, Rs = 0.40 at 25 °C)—a rare feature among porous materials.
Using inverse gas chromatography (IGC), we quantified the thermodynamic parameters governing gas–solid interactions, revealing stronger adsorption enthalpies for alkanes (up to 49.6 kJ mol−1 for propane) and a clear enthalpy–entropy compensation across the alkane series. Polar probe analysis revealed a mildly basic surface character and dominant dispersive interactions, further supporting the preference for alkanes. Importantly, the composite retained excellent structural integrity and selectivity under extended operation and increasing gas concentrations, confirming its robustness.
These findings position the MOF-801@DVB MMMo as a scalable and energy-efficient platform for selective gas separations, offering rare dual selectivity within a monolithic architecture and opening new avenues for low-pressure, thermodynamically governed hydrocarbon purification.
{"title":"Trace-loaded MOF-801 mixed-matrix monolith for selective adsorption of alkane over alkene in binary gas mixtures","authors":"Alaa Bin Shuqayr , Sadeem Bin Tuwaym , Mostafa Zeama , Rawan AL Natour , Osama Shekhah , Mohamed Eddaoudi , Zeid A. Alothman , Kareem Y. Mahmoud","doi":"10.1016/j.micromeso.2025.113976","DOIUrl":"10.1016/j.micromeso.2025.113976","url":null,"abstract":"<div><div>The separation of light alkane/alkene mixtures remains a central challenge in petrochemical processing, especially under mild conditions where traditional energy-intensive approaches such as cryogenic distillation are impractical. Here, we report a mixed-matrix monolithic composite (MMMo) comprising only 0.5 wt% MOF-801 nanoparticles embedded in a divinylbenzene (DVB) matrix, synthesized via in situ capillary polymerization. Despite the trace MOF loading, the composite exhibits an unusual and dual thermodynamic selectivity for ethane over ethylene (α = 1.49, R<sub>s</sub> = 0.87 at 0 °C) and propane over propylene (α = 1.19, R<sub>s</sub> = 0.40 at 25 °C)—a rare feature among porous materials.</div><div>Using inverse gas chromatography (IGC), we quantified the thermodynamic parameters governing gas–solid interactions, revealing stronger adsorption enthalpies for alkanes (up to 49.6 kJ mol<sup>−1</sup> for propane) and a clear enthalpy–entropy compensation across the alkane series. Polar probe analysis revealed a mildly basic surface character and dominant dispersive interactions, further supporting the preference for alkanes. Importantly, the composite retained excellent structural integrity and selectivity under extended operation and increasing gas concentrations, confirming its robustness.</div><div>These findings position the MOF-801@DVB MMMo as a scalable and energy-efficient platform for selective gas separations, offering rare dual selectivity within a monolithic architecture and opening new avenues for low-pressure, thermodynamically governed hydrocarbon purification.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113976"},"PeriodicalIF":4.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682705","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 : 2025-12-01DOI: 10.1016/j.micromeso.2025.113973
Xiaosan Song , Po Zhao , Xuan Zhang
1,4-Dioxane (1.4-DX) as an emerging organic pollutant poses a serious threat to human health and the ecological environment. However, effective removal is still a challenge in wastewater treatment. In this study, we successfully synthesized Fe-ZSM-5 zeolite and employed it as an adsorbent/catalyst for the removal of 1,4-DX. The characterization results of SEM, XRD and N2 adsorption-desorption exhibited a large surface and good textural properties of Fe-ZSM-5 zeolite, implying excellent adsorption performance and high catalytic efficiency for 1,4-DX. The adsorption equilibrium of 1,4-DX on Fe-ZSM-5 zeolite can be reached a maximum adsorbed amount of 43.15 mg/g within 5 min, and experimental adsorption data were fitted well with the Langmuir isotherms and pseudo-second-order kinetics. The optimum removal efficiency of 1,4-DX, i.e. 90.3 % for 180 min of treatment, was observed at pH of 3.0–5.0, anode of Ti/pt, catalyst dosage of 1 g/L, current density of 20 mA/cm2, and initial target pollutant concentration of 10 mg/L. Moreover, Fe-ZSM-5 zeolite showed an exhibited excellent stability and reusability, with little change in removal efficiency over five cycles. Degradation product analysis speculated possible oxidative degradation pathways. Quenching experiments indicated that .OH and O2.- formed by the oxidation reaction of Fe-ZSM-5 zeolite with hydrogen peroxide produced by electrochemical in-situ oxidation were the main reactive oxygen species for the oxidative degradation of 1,4-DX. This study demonstrated that the three-dimensional heterogeneous electro-Fenton with traditional Fe-zeolites may be a promising technology for organic wastewater.
{"title":"Three-dimensional heterogeneous electro-Fenton with traditional Fe-zeolites for the efficient removal of 1,4-dioxane","authors":"Xiaosan Song , Po Zhao , Xuan Zhang","doi":"10.1016/j.micromeso.2025.113973","DOIUrl":"10.1016/j.micromeso.2025.113973","url":null,"abstract":"<div><div>1,4-Dioxane (1.4-DX) as an emerging organic pollutant poses a serious threat to human health and the ecological environment. However, effective removal is still a challenge in wastewater treatment. In this study, we successfully synthesized Fe-ZSM-5 zeolite and employed it as an adsorbent/catalyst for the removal of 1,4-DX. The characterization results of SEM, XRD and N<sub>2</sub> adsorption-desorption exhibited a large surface and good textural properties of Fe-ZSM-5 zeolite, implying excellent adsorption performance and high catalytic efficiency for 1,4-DX. The adsorption equilibrium of 1,4-DX on Fe-ZSM-5 zeolite can be reached a maximum adsorbed amount of 43.15 mg/g within 5 min, and experimental adsorption data were fitted well with the Langmuir isotherms and pseudo-second-order kinetics. The optimum removal efficiency of 1,4-DX, i.e. 90.3 % for 180 min of treatment, was observed at pH of 3.0–5.0, anode of Ti/pt, catalyst dosage of 1 g/L, current density of 20 mA/cm<sup>2</sup>, and initial target pollutant concentration of 10 mg/L. Moreover, Fe-ZSM-5 zeolite showed an exhibited excellent stability and reusability, with little change in removal efficiency over five cycles. Degradation product analysis speculated possible oxidative degradation pathways. Quenching experiments indicated that <strong><sup>.</sup></strong>OH and O<sub>2</sub><strong><sup>.</sup></strong><sup>-</sup> formed by the oxidation reaction of Fe-ZSM-5 zeolite with hydrogen peroxide produced by electrochemical in-situ oxidation were the main reactive oxygen species for the oxidative degradation of 1,4-DX. This study demonstrated that the three-dimensional heterogeneous electro-Fenton with traditional Fe-zeolites may be a promising technology for organic wastewater.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113973"},"PeriodicalIF":4.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682636","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 : 2025-12-01DOI: 10.1016/j.micromeso.2025.113962
Federico Schipani , David Smirnoff , Fernando P. Cometto , Rodrigo Parra , Carla di Luca
This study investigates the synthesis and gas-sensing performance of SnO2- mesoporous alumina, focusing on the influence of pore ordering and calcination temperature on sensing response. Two sol-gel routes based on the Evaporation-Induced Self-Assembly (EISA) strategy were employed: Method M, which produced ordered mesoporous structures, and Method C, which led to disordered porosity. Both methods yielded materials with high surface areas (∼250 m2/g) and uniform tin dispersion within an amorphous alumina matrix after heat-treatment at 400 °C. The samples were thoroughly characterized by TEM, FESEM-EDS, N2 physisorption, XPS, and XRD, confirming the development of well-defined mesostructures. Gas-sensing tests revealed that the disordered sample (Method C) exhibited markedly higher sensitivity, up to a 230-fold increase in conductivity and faster response times (∼4 s) when exposed to CO2, NO2, and H2, compared to the ordered counterpart. Furthermore, increasing the heat-treatment temperature to 900 °C induced structural collapse and phase segregation, significantly worsening sensor performance. In agreement with the insulating nature of the host matrix, electrical conductivity arises primarily via thermally activated electron hopping. These results reveal that structural disorder enhances surface reactivity and electrical conductivity. These findings underscore the potential of tin dioxide-mesoporous alumina composite as a robust and efficient material for gas detection applications.
{"title":"Influence of mesostructural order on the gas-sensing performance of tin dioxide-mesoporous alumina composite","authors":"Federico Schipani , David Smirnoff , Fernando P. Cometto , Rodrigo Parra , Carla di Luca","doi":"10.1016/j.micromeso.2025.113962","DOIUrl":"10.1016/j.micromeso.2025.113962","url":null,"abstract":"<div><div>This study investigates the synthesis and gas-sensing performance of SnO<sub>2</sub>- mesoporous alumina, focusing on the influence of pore ordering and calcination temperature on sensing response. Two sol-gel routes based on the Evaporation-Induced Self-Assembly (EISA) strategy were employed: Method M, which produced ordered mesoporous structures, and Method C, which led to disordered porosity. Both methods yielded materials with high surface areas (∼250 m<sup>2</sup>/g) and uniform tin dispersion within an amorphous alumina matrix after heat-treatment at 400 °C. The samples were thoroughly characterized by TEM, FESEM-EDS, N<sub>2</sub> physisorption, XPS, and XRD, confirming the development of well-defined mesostructures. Gas-sensing tests revealed that the disordered sample (Method C) exhibited markedly higher sensitivity, up to a 230-fold increase in conductivity and faster response times (∼4 s) when exposed to CO<sub>2</sub>, NO<sub>2</sub>, and H<sub>2</sub>, compared to the ordered counterpart. Furthermore, increasing the heat-treatment temperature to 900 °C induced structural collapse and phase segregation, significantly worsening sensor performance. In agreement with the insulating nature of the host matrix, electrical conductivity arises primarily via thermally activated electron hopping. These results reveal that structural disorder enhances surface reactivity and electrical conductivity. These findings underscore the potential of tin dioxide-mesoporous alumina composite as a robust and efficient material for gas detection applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113962"},"PeriodicalIF":4.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682704","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 : 2025-12-01DOI: 10.1016/j.micromeso.2025.113977
Adrià Pérez-Calm , Claudia Müller-Sánchez , Anna Maria Piña Cañaveras , Eva Berteloot , Santiago Grijalvo , Soraia P.S. Fernandes , Yury V. Kolen'ko , Oleg Lebedev , Jordi Esquena , Manuel Reina , Carlos Rodríguez-Abreu
Lyotropic chromonic liquid crystals (LCLC) enable the templating of silica fibers with aligned porous structures and tunable pore size, properties that hold significant potential for applications like controlled drug delivery. LCLC guide the synthesis of microporous and mesoporous silicas through sol-gel reactions in the presence of silicon alkoxides, such as tetraethyl orthosilicate (TEOS), typically producing fibers with long, aligned pores and specific surface areas around 200–300 m2/g. Here, we develop micro/mesoporous silica materials using a cationic chromonic perylene diimide as template, combined with a porogenic silica precursor, hexadecyl trimethoxysilane (HDTMS), to achieve increased specific surface areas and larger pore sizes compared to conventional TEOS-based chromonic-templated silicas. The resulting silica materials can be fabricated as macroscopic, centimeter-sized monoliths with tunable porosity, composed of entangled silica nanofibers forming a networked structure. These highly porous monoliths were evaluated as carriers of small drugs (ibuprofen), and demonstrated high encapsulation efficiencies, as well as sustained drug release in a simulated body fluid (SBF, pH = 7.4), achieving complete release within 24 h. In contrast, powdered silica samples of the same composition showed poorer encapsulation efficiencies and faster release rates, highlighting the advantages of monolithic structures for drug delivery. Furthermore, hydroxyapatite (HAp) was deposited onto the silica monoliths to produce robust composite scaffolds, whose degradation products did not affect HEK293 cell viability.
{"title":"Chromonic-liquid-crystal-templated synthesis of powdered and monolithic silica materials: mechanism, textural properties and drug delivery","authors":"Adrià Pérez-Calm , Claudia Müller-Sánchez , Anna Maria Piña Cañaveras , Eva Berteloot , Santiago Grijalvo , Soraia P.S. Fernandes , Yury V. Kolen'ko , Oleg Lebedev , Jordi Esquena , Manuel Reina , Carlos Rodríguez-Abreu","doi":"10.1016/j.micromeso.2025.113977","DOIUrl":"10.1016/j.micromeso.2025.113977","url":null,"abstract":"<div><div>Lyotropic chromonic liquid crystals (LCLC) enable the templating of silica fibers with aligned porous structures and tunable pore size, properties that hold significant potential for applications like controlled drug delivery. LCLC guide the synthesis of microporous and mesoporous silicas through sol-gel reactions in the presence of silicon alkoxides, such as tetraethyl orthosilicate (TEOS), typically producing fibers with long, aligned pores and specific surface areas around 200–300 m<sup>2</sup>/g. Here, we develop micro/mesoporous silica materials using a cationic chromonic perylene diimide as template, combined with a porogenic silica precursor, hexadecyl trimethoxysilane (HDTMS), to achieve increased specific surface areas and larger pore sizes compared to conventional TEOS-based chromonic-templated silicas. The resulting silica materials can be fabricated as macroscopic, centimeter-sized monoliths with tunable porosity, composed of entangled silica nanofibers forming a networked structure. These highly porous monoliths were evaluated as carriers of small drugs (ibuprofen), and demonstrated high encapsulation efficiencies, as well as sustained drug release in a simulated body fluid (SBF, pH = 7.4), achieving complete release within 24 h. In contrast, powdered silica samples of the same composition showed poorer encapsulation efficiencies and faster release rates, highlighting the advantages of monolithic structures for drug delivery. Furthermore, hydroxyapatite (HAp) was deposited onto the silica monoliths to produce robust composite scaffolds, whose degradation products did not affect HEK293 cell viability.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113977"},"PeriodicalIF":4.7,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682638","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 : 2025-11-27DOI: 10.1016/j.micromeso.2025.113945
Sneh Lata , Nasreen Ghazi Ansari
Water is vital to flourishing life on Earth, and it has been facing severe issues due to various contaminants in water bodies. The emergence of globalization and industrialization in the future highlights the need for creative and effective wastewater cleanup solutions. Metal-organic frameworks are emerging as a promising solution because of their unique properties and adaptability. Furthermore, the availability of iron through natural and biological means makes it a more economical, sustainable, and less toxic alternative to other metals for MOF design. Moreover, metal-organic framework with Fe as a metallic node show excellent tunability, high porosity, functionality, and diverse topologies, making them ideal for wastewater remediation. Their structural characteristics are customized to showcase their applicability in several thorough assessments. This primer thoroughly explains the synthesis process, structural properties with topological identifiers, the adsorption mechanism, and applications. Nonetheless, this comprehensive discussion considers the limitations of the structural integrity of Fe-MOF and the possibility of large-scale commercialisation by evaluating their safety assessment and disposal plan. This review article also offers a complete approach to quantum mechanics and molecular modelling for a thorough understanding of Fe-MOF design, which forecasts corrective steps for commercialisation and industrial applications. In a nutshell, Fe-MOF's potential in wastewater remediation offers hope for a cleaner environment.
{"title":"Iron-based Metal–Organic Frameworks as efficient adsorbents for wastewater remediation: Insight into mechanistic, ecotoxicological and disposal concerns","authors":"Sneh Lata , Nasreen Ghazi Ansari","doi":"10.1016/j.micromeso.2025.113945","DOIUrl":"10.1016/j.micromeso.2025.113945","url":null,"abstract":"<div><div>Water is vital to flourishing life on Earth, and it has been facing severe issues due to various contaminants in water bodies. The emergence of globalization and industrialization in the future highlights the need for creative and effective wastewater cleanup solutions. Metal-organic frameworks are emerging as a promising solution because of their unique properties and adaptability. Furthermore, the availability of iron through natural and biological means makes it a more economical, sustainable, and less toxic alternative to other metals for MOF design. Moreover, metal-organic framework with Fe as a metallic node show excellent tunability, high porosity, functionality, and diverse topologies, making them ideal for wastewater remediation. Their structural characteristics are customized to showcase their applicability in several thorough assessments. This primer thoroughly explains the synthesis process, structural properties with topological identifiers, the adsorption mechanism, and applications. Nonetheless, this comprehensive discussion considers the limitations of the structural integrity of Fe-MOF and the possibility of large-scale commercialisation by evaluating their safety assessment and disposal plan. This review article also offers a complete approach to quantum mechanics and molecular modelling for a thorough understanding of Fe-MOF design, which forecasts corrective steps for commercialisation and industrial applications. In a nutshell, Fe-MOF's potential in wastewater remediation offers hope for a cleaner environment.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113945"},"PeriodicalIF":4.7,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682701","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 : 2025-11-27DOI: 10.1016/j.micromeso.2025.113965
Ziyang Xu, Zicheng Yang, Jiale Ni, Yi Feng, Jianfeng Yao
The functionalization of metal organic frameworks (MOFs) with tailored ligands offers a promising pathway for enhancing their catalytic performance in CO2 fixation. This work systematically explores the impact of ligand engineering in MIL-101(Cr) through carboxyl (–COOH) and amino (–NH2) functionalization for the CO2 cycloaddition reaction. Comprehensive characterizations of pristine MIL-101 and functionalized MILs involving MIL-101-COOH, MIL-101-NH2, and MIL-101-COOH/NH2 reveal that –COOH functionalization significantly enhances the surface area (2717 m2/g) and reduces the activation energy (17.1 kJ/mol vs. 23.1 kJ/mol for pristine MIL-101), whereas –NH2 groups improve the CO2 binding strength but compromise the crystallinity and surface area (532 m2/g). Under mild conditions (80 °C and 0.1 MPa CO2), MIL-101-COOH achieves >99 % yield for CO2 cycloaddition with epichlorohydrin at 8 h and maintains stability over ten cycles, outperforming other MILs (72–82.5 % yields). This work establishes ligand engineering, especially –COOH functionalization, as a critical strategy to optimize MILs for CO2 fixation to produce cyclic carbonates.
{"title":"Ligand engineering in MIL-101(Cr) for enhanced CO2 cycloaddition: the dominant role of carboxyl over amino functionalization","authors":"Ziyang Xu, Zicheng Yang, Jiale Ni, Yi Feng, Jianfeng Yao","doi":"10.1016/j.micromeso.2025.113965","DOIUrl":"10.1016/j.micromeso.2025.113965","url":null,"abstract":"<div><div>The functionalization of metal organic frameworks (MOFs) with tailored ligands offers a promising pathway for enhancing their catalytic performance in CO<sub>2</sub> fixation. This work systematically explores the impact of ligand engineering in MIL-101(Cr) through carboxyl (–COOH) and amino (–NH<sub>2</sub>) functionalization for the CO<sub>2</sub> cycloaddition reaction. Comprehensive characterizations of pristine MIL-101 and functionalized MILs involving MIL-101-COOH, MIL-101-NH<sub>2</sub>, and MIL-101-COOH/NH<sub>2</sub> reveal that –COOH functionalization significantly enhances the surface area (2717 m<sup>2</sup>/g) and reduces the activation energy (17.1 kJ/mol vs. 23.1 kJ/mol for pristine MIL-101), whereas –NH<sub>2</sub> groups improve the CO<sub>2</sub> binding strength but compromise the crystallinity and surface area (532 m<sup>2</sup>/g). Under mild conditions (80 °C and 0.1 MPa CO<sub>2</sub>), MIL-101-COOH achieves >99 % yield for CO<sub>2</sub> cycloaddition with epichlorohydrin at 8 h and maintains stability over ten cycles, outperforming other MILs (72–82.5 % yields). This work establishes ligand engineering, especially –COOH functionalization, as a critical strategy to optimize MILs for CO<sub>2</sub> fixation to produce cyclic carbonates.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113965"},"PeriodicalIF":4.7,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145617185","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 : 2025-11-27DOI: 10.1016/j.micromeso.2025.113964
Julien Schmitt , Emilie Molina , Javier Pérez , Patrick Lacroix-Desmazes , Corine Gérardin , Nathalie Marcotte
Polyion complex (PIC) micelles are highly efficient agents for directing the structure of silica. They are particularly attractive because they enable the direct preparation of functional mesostructured materials by anchoring one of the two micellar constituents in the silica network, while allowing the other one to be released for recycling or for use in specific applications. Notably, the formation of these hybrid materials proceeds in a one-pot process under moderately acidic conditions. Despite their versatility and broad range of potential applications, their formation mechanisms have not yet been elucidated. In this work, we used in situ SAXS experiments to monitor the formation kinetics of a mesoPIC material formed from a polyion complex composed of poly(ethylene oxide)-b-poly(acrylic acid) (PEO-b-PAA) as a double hydrophilic block copolymer (DHBC) and neomycin (NM) as a micellizing agent. The results were benchmarked against the well-known SBA-15 silica material made with P123 copolymer, due to the similarity of the neutral poly(ethylene oxide) chain interacting with silica. The mechanisms of formation of the mesoPIC material resembles those already reported, involving the growth of silica oligomers and their integration into the micelle corona, followed by the formation of a 2D-hexagonal hybrid mesophase. Interestingly, a transient signal was detected during the kinetics, attributed to the formation of poorly organized packed silica-rich micelles present in large grain mesostructured material. The well-ordered final mesostructure together with the emergence and disappearance of the transient signal highlight the ability of the PIC system to reorganize dynamically into highly ordered mesostructured materials.
{"title":"In situ saxs investigation of the formation of mesostructured materials structured from polyion complex micelles","authors":"Julien Schmitt , Emilie Molina , Javier Pérez , Patrick Lacroix-Desmazes , Corine Gérardin , Nathalie Marcotte","doi":"10.1016/j.micromeso.2025.113964","DOIUrl":"10.1016/j.micromeso.2025.113964","url":null,"abstract":"<div><div>Polyion complex (PIC) micelles are highly efficient agents for directing the structure of silica. They are particularly attractive because they enable the direct preparation of functional mesostructured materials by anchoring one of the two micellar constituents in the silica network, while allowing the other one to be released for recycling or for use in specific applications. Notably, the formation of these hybrid materials proceeds in a one-pot process under moderately acidic conditions. Despite their versatility and broad range of potential applications, their formation mechanisms have not yet been elucidated. In this work, we used <em>in situ</em> SAXS experiments to monitor the formation kinetics of a mesoPIC material formed from a polyion complex composed of poly(ethylene oxide)-<em>b</em>-poly(acrylic acid) (PEO-<em>b</em>-PAA) as a double hydrophilic block copolymer (DHBC) and neomycin (NM) as a micellizing agent. The results were benchmarked against the well-known SBA-15 silica material made with P123 copolymer, due to the similarity of the neutral poly(ethylene oxide) chain interacting with silica. The mechanisms of formation of the mesoPIC material resembles those already reported, involving the growth of silica oligomers and their integration into the micelle corona, followed by the formation of a 2D-hexagonal hybrid mesophase. Interestingly, a transient signal was detected during the kinetics, attributed to the formation of poorly organized packed silica-rich micelles present in large grain mesostructured material. The well-ordered final mesostructure together with the emergence and disappearance of the transient signal highlight the ability of the PIC system to reorganize dynamically into highly ordered mesostructured materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113964"},"PeriodicalIF":4.7,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682634","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 : 2025-11-26DOI: 10.1016/j.micromeso.2025.113960
Janina Carolin Höner , Andreas Schaate , Andreas M. Schneider , Jonas Blaser , Hubert Koller , Yaşar Krysiak , Peter Behrens
While alkylammonium salts or organic amines are commonly used as structure-directing agents (SDAs) to synthesize zeolites, metal complexes can also serve this purpose. In this study, we present a novel interrupted framework, which can be regarded as a precursor of the CHA framework type with a pure-silica composition. The polycrystalline yellow powder was synthesized using a cobalt (III)-triazacyclononane complex [Co(tacn)2]3+. Structure determination via 3D electron diffraction revealed details of the [Si–O⋅⋅⋅H⋅⋅⋅O–Si]– hydrogen bonds, which are periodically ordered. They connect the D6R units of the CHA precursor-type structure. Upon calcination, the organic component is removed, yielding a blue material, resulting in the fully connected chabazite structure. The blue color is characteristic for tetrahedrally coordinated Co2+, which is most likely located in the chabazite cage and coordinated to the 6-rings of the framework. Temperature-dependent powder diffraction analysis was used to investigate the structural transformation and the discontinuous decrease in the constants a and c of the hexagonal lattice. Finally, spectroscopic and sorption measurements were conducted to characterize the properties of the material.
{"title":"Novel zeolite framework LMU-2: unveiling of CHA-related structure with active sites by Co-complex structure-directing agent","authors":"Janina Carolin Höner , Andreas Schaate , Andreas M. Schneider , Jonas Blaser , Hubert Koller , Yaşar Krysiak , Peter Behrens","doi":"10.1016/j.micromeso.2025.113960","DOIUrl":"10.1016/j.micromeso.2025.113960","url":null,"abstract":"<div><div>While alkylammonium salts or organic amines are commonly used as structure-directing agents (SDAs) to synthesize zeolites, metal complexes can also serve this purpose. In this study, we present a novel interrupted framework, which can be regarded as a precursor of the CHA framework type with a pure-silica composition. The polycrystalline yellow powder was synthesized using a cobalt (III)-triazacyclononane complex [Co(<em>tacn</em>)<sub>2</sub>]<sup>3+</sup>. Structure determination via 3D electron diffraction revealed details of the [Si–O⋅⋅⋅H⋅⋅⋅O–Si]<sup>–</sup> hydrogen bonds, which are periodically ordered. They connect the D6R units of the CHA precursor-type structure. Upon calcination, the organic component is removed, yielding a blue material, resulting in the fully connected chabazite structure. The blue color is characteristic for tetrahedrally coordinated Co<sup>2+</sup>, which is most likely located in the chabazite cage and coordinated to the 6-rings of the framework. Temperature-dependent powder diffraction analysis was used to investigate the structural transformation and the discontinuous decrease in the constants <em>a</em> and <em>c</em> of the hexagonal lattice. Finally, spectroscopic and sorption measurements were conducted to characterize the properties of the material.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113960"},"PeriodicalIF":4.7,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682637","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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