To address the challenge of removing heavy metal ions from industrial effluents, chitosan-based adsorbent materials have been extensively reported, particularly in terms of composite materials and the introduction of groups. In this paper, β-cyclodextrin (β-CD) and amidoxime (AO) were simultaneously chemically cross-linked with chitosan (CTS) for the first time, resulting in amidoxime functionalized chitosan/β-cyclodextrin composite (CTS-g-AO-β-CD) which was primarily applied to remove toxic metal ions. The adsorption capacities of CTS-g-AO-β-CD were 35.66, 31.28, 16.46 mg/g for Cu2+, Pb2+ and Zn2+. The adsorption of Cu2+ and Pb2+ followed the pseudo-second-order kinetic and the Langmuir isotherm model, whereas the adsorption of Zn2+ adhered to the pseudo-second-order kinetic and Freundlich isotherm model more closely. After five regeneration cycles, CTS-g-AO-β-CD still retained a certain adsorption performance, demonstrating its potential for application as a novel adsorbent.
{"title":"Amidoxime functionalized chitosan/β-cyclodextrin composite for removal of Cu2+, Pb2+, and Zn2+","authors":"Jing Zhang , Yifei Pu , Baichuan Zhuang , Jifei Zhuo , Xiaoli Xie , Shuang Xie , Tengfei Qu , Guangjun Gou","doi":"10.1016/j.micromeso.2025.113987","DOIUrl":"10.1016/j.micromeso.2025.113987","url":null,"abstract":"<div><div>To address the challenge of removing heavy metal ions from industrial effluents, chitosan-based adsorbent materials have been extensively reported, particularly in terms of composite materials and the introduction of groups. In this paper, <em>β-</em>cyclodextrin (<em>β</em>-CD) and amidoxime (AO) were simultaneously chemically cross-linked with chitosan (CTS) for the first time, resulting in amidoxime functionalized chitosan/<em>β-</em>cyclodextrin composite (CTS-g-AO-<em>β</em>-CD) which was primarily applied to remove toxic metal ions. The adsorption capacities of CTS-g-AO-<em>β</em>-CD were 35.66, 31.28, 16.46 mg/g for Cu<sup>2+</sup>, Pb<sup>2+</sup> and Zn<sup>2+</sup>. The adsorption of Cu<sup>2+</sup> and Pb<sup>2+</sup> followed the pseudo-second-order kinetic and the Langmuir isotherm model, whereas the adsorption of Zn<sup>2+</sup> adhered to the pseudo-second-order kinetic and Freundlich isotherm model more closely. After five regeneration cycles, CTS-g-AO-<em>β</em>-CD still retained a certain adsorption performance, demonstrating its potential for application as a novel adsorbent.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113987"},"PeriodicalIF":4.7,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734048","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 : 2026-02-15Epub Date: 2025-12-11DOI: 10.1016/j.micromeso.2025.113995
Fatma Yelda Ünlü , Melih Beşir Arvas , Hadi Jahangiri , Hasan Gökçe , Nilüfer Koçyiğit , İbrahim Özçeşmeci , Caner Ünlü
Simple, in situ routes to tune ZIF-8 particle size, interfacial chemistry, and redox functionality—without post-processing—remain limited. In this work, we present a single-step, in situ phthalocyanine (Pc) additive strategy that modulates ZIF-8 crystallization. Without carbonization or extra processing, the approach reduces particle size, adjusts surface/near-surface chemistry, and—when metalated Pc is used—yields a persistent interfacial redox signature. Under identical activation, N2 sorption retained the microporous ZIF-8 response while developing a hierarchical-like texture consistent with slit-like/interaggregate voids. Detailed surface analysis indicated that Pc was located at or near interfaces with preservation of the sodalite framework. Electrochemical measurements under identical conditions indicated an enhanced interfacial response relative to pristine ZIF-8. Overall, phthalocyanine-guided growth offers a practical, modular handle to tune particle size, interfacial chemistry, and interfacial redox in ZIF-8 using a simple drop-in molecular additive, relevant to adsorption and other transport-limited applications.
{"title":"Molecular additive control of MOF crystallization: effect of phthalocyanine on size and interfacial redox response of ZIF-8","authors":"Fatma Yelda Ünlü , Melih Beşir Arvas , Hadi Jahangiri , Hasan Gökçe , Nilüfer Koçyiğit , İbrahim Özçeşmeci , Caner Ünlü","doi":"10.1016/j.micromeso.2025.113995","DOIUrl":"10.1016/j.micromeso.2025.113995","url":null,"abstract":"<div><div>Simple, in situ routes to tune ZIF-8 particle size, interfacial chemistry, and redox functionality—without post-processing—remain limited. In this work, we present a single-step, in situ phthalocyanine (Pc) additive strategy that modulates ZIF-8 crystallization. Without carbonization or extra processing, the approach reduces particle size, adjusts surface/near-surface chemistry, and—when metalated Pc is used—yields a persistent interfacial redox signature. Under identical activation, N<sub>2</sub> sorption retained the microporous ZIF-8 response while developing a hierarchical-like texture consistent with slit-like/interaggregate voids. Detailed surface analysis indicated that Pc was located at or near interfaces with preservation of the sodalite framework. Electrochemical measurements under identical conditions indicated an enhanced interfacial response relative to pristine ZIF-8. Overall, phthalocyanine-guided growth offers a practical, modular handle to tune particle size, interfacial chemistry, and interfacial redox in ZIF-8 using a simple drop-in molecular additive, relevant to adsorption and other transport-limited applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113995"},"PeriodicalIF":4.7,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734047","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 : 2026-02-15Epub 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":"2026-02-15","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 : 2026-02-15Epub Date: 2025-12-09DOI: 10.1016/j.micromeso.2025.113984
Guilherme P. Campos, Heloise O. Pastore
The risks associated with the presence of recalcitrant contaminants in water and the difficulty in identification promoted the investigation and application of complementary methods for their removal. The present study shows the results of the use of three zeolitic structures (LTA, FAU and MFI) loaded with iron to photodegrade eriochrome black T dye as a mimic for contaminant molecules. The materials were active in this reaction however Fe-ZSM-5 3.2 % (MFI) achieved a faster color removal in 60 min and promoted 90 % of dye degradation, while Fe-X 3.6 % (FAU) led to similar results within a longer reaction time. The LTA zeolite presented the smallest activity and lost its structural organization upon the dye degradation reaction. Fe-X was the best material examined and kept its activity over 5 cycles of reuse without any treatment between the reactions. Almost no iron leached from Fe-zeolites during the reactions.
水中顽固污染物存在的风险和难以识别的问题促使人们研究和应用去除这些污染物的补充方法。本研究展示了负载铁的三种沸石结构（LTA， FAU和MFI）作为污染物分子的模拟物光降解erichrome black T染料的结果。这些材料在该反应中具有活性，但Fe-ZSM-5 3.2% （MFI）在60分钟内实现了更快的脱色，并促进了90%的染料降解，而Fe-X 3.6% （FAU）在更长的反应时间内取得了类似的结果。LTA沸石在染料降解反应中活性最小，失去了结构组织。Fe-X是测试的最佳材料，在重复使用5次循环中保持其活性，而无需在反应之间进行任何处理。在反应过程中，铁沸石中几乎没有铁浸出。
{"title":"Eriochrome black T degradation by photo-Fenton process in heterogeneous Fe-zeolite synthesized from bauxite mining waste","authors":"Guilherme P. Campos, Heloise O. Pastore","doi":"10.1016/j.micromeso.2025.113984","DOIUrl":"10.1016/j.micromeso.2025.113984","url":null,"abstract":"<div><div>The risks associated with the presence of recalcitrant contaminants in water and the difficulty in identification promoted the investigation and application of complementary methods for their removal. The present study shows the results of the use of three zeolitic structures (LTA, FAU and MFI) loaded with iron to photodegrade eriochrome black T dye as a mimic for contaminant molecules. The materials were active in this reaction however Fe-ZSM-5 3.2 % (MFI) achieved a faster color removal in 60 min and promoted 90 % of dye degradation, while Fe-X 3.6 % (FAU) led to similar results within a longer reaction time. The LTA zeolite presented the smallest activity and lost its structural organization upon the dye degradation reaction. Fe-X was the best material examined and kept its activity over 5 cycles of reuse without any treatment between the reactions. Almost no iron leached from Fe-zeolites during the reactions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113984"},"PeriodicalIF":4.7,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734104","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 : 2026-02-15Epub Date: 2025-12-09DOI: 10.1016/j.micromeso.2025.113986
Qingsong Zeng , Lidong Yi , Yunjie Feng , Zhiwei Wang , Danni Jiang , YiQiang Wu
Cellulose extracted from TEMPO-treated agriculture and forestry waste was employed as a carrier for the in-situ growth of ZIF-8, significantly enhancing the latter's loading capacity and dispersibility. Coordination modulator PVP regulates the coordination interaction between metal sites and ligands, inducing the formation of defect sites. When used as a photocatalyst, this composite material exhibits remarkably improved tetracycline degradation efficiency compared to unmodified ZIF-8 nanoparticles, with the efficiency increasing from 50.1 % to 90.1 %. Mechanistic studies reveal that the PVP-regulated defect sites possess a stronger O2 adsorption energy (−0.42 eV) than pristine ZIF-8 (−0.36 eV). Furthermore, PVP modulation exposes more Zn2+ active sites on the material surface. These Zn2+ ions combine with adsorbed oxygen in an aqueous environment to form the [Zn(H2O)6·O2]2+ intermediate, which captures photoexcited electrons (e−) to generate reactive oxygen species (ROS), effectively promoting the separation of photogenerated carriers. Under light irradiation, electrons are transferred from the lowest unoccupied molecular orbital (LUMO) of the ligand to the highest occupied molecular orbital (HOMO) of the metal center via the ligand-to-metal charge transfer (LMCT) pathway. This LMCT process accelerates electron transfer and improves light utilization efficiency, ultimately enhancing the overall photocatalytic performance.
{"title":"The mechanism of photocatalytic degradation of tetracycline by agriculture and forestry waste-based MOFs composites","authors":"Qingsong Zeng , Lidong Yi , Yunjie Feng , Zhiwei Wang , Danni Jiang , YiQiang Wu","doi":"10.1016/j.micromeso.2025.113986","DOIUrl":"10.1016/j.micromeso.2025.113986","url":null,"abstract":"<div><div>Cellulose extracted from TEMPO-treated agriculture and forestry waste was employed as a carrier for the in-situ growth of ZIF-8, significantly enhancing the latter's loading capacity and dispersibility. Coordination modulator PVP regulates the coordination interaction between metal sites and ligands, inducing the formation of defect sites. When used as a photocatalyst, this composite material exhibits remarkably improved tetracycline degradation efficiency compared to unmodified ZIF-8 nanoparticles, with the efficiency increasing from 50.1 % to 90.1 %. Mechanistic studies reveal that the PVP-regulated defect sites possess a stronger O<sub>2</sub> adsorption energy (−0.42 eV) than pristine ZIF-8 (−0.36 eV). Furthermore, PVP modulation exposes more Zn<sup>2+</sup> active sites on the material surface. These Zn<sup>2+</sup> ions combine with adsorbed oxygen in an aqueous environment to form the [Zn(H<sub>2</sub>O)<sub>6</sub>·O<sub>2</sub>]<sup>2+</sup> intermediate, which captures photoexcited electrons (e<sup>−</sup>) to generate reactive oxygen species (ROS), effectively promoting the separation of photogenerated carriers. Under light irradiation, electrons are transferred from the lowest unoccupied molecular orbital (LUMO) of the ligand to the highest occupied molecular orbital (HOMO) of the metal center via the ligand-to-metal charge transfer (LMCT) pathway. This LMCT process accelerates electron transfer and improves light utilization efficiency, ultimately enhancing the overall photocatalytic performance.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113986"},"PeriodicalIF":4.7,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787309","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 : 2026-02-15Epub Date: 2025-11-24DOI: 10.1016/j.micromeso.2025.113961
Laura Premet , Emmanuel Oheix , Gérald Chaplais , Eliane Bou Orm , Habiba Nouali , Laure Michelin , Ludovic Josien , T. Jean Daou , Laurent Pieuchot
Microporous materials are widely explored as carriers for the controlled release of antimicrobial agents, yet their practical application requires the development of scalable and adaptable shaping processes. Metal-organic frameworks (MOFs) have the potential to exert antimicrobial effects through the release of either inorganic nodes, organic linkers, encapsulated antimicrobial agents or their combinations. In this study, the preparation and antimicrobial study of polymer-based composite films containing zeolitic imidazolate frameworks (ZIFs) on a pilot-scale are reported. Such materials are intended to be shaped for applications in food packaging. To fulfill our aim, ZIF materials have been synthesized on a large scale (>200 g scale) and fully characterized (X-Ray Diffraction, Scanning Electronic Microscopy/coupled to Energy-Dispersive X-Ray spectroscopy, thermogravimetry, low-temperature nitrogen physisorption). Structural and morphological analyses are consistent with the coexistence of two polymorphs in the large scale samples (35 wt.% ZIF-8 and 65 wt..% ZIF-dia(Zn)). Nevertheless, complementary and initial study involving pure ZIF-8 and ZIF-dia solids highlights similar antimicrobial activity for the two MOFs. Large scale samples were subsequently used for the preparation of polymer-based composite films, containing 5, 10 and 30 wt.% of ZIF-8/ZIF-dia(Zn), which were fully characterized and compared to MOF-free film. The antimicrobial disinfection studies indicate that the film with 30 wt.% MOF display significantly higher ability to inhibit Escherichia Coli growth compared to 5, 10 wt.% MOF and MOF-free formulations. Importantly, the pilot-scale process developed here is readily translatable to industrial-scale production, offering a viable route for the integration of MOF-based antimicrobial materials into commercial food packaging solutions.
{"title":"Fabrication of ZIF-loaded polymer composites with antimicrobial properties towards food packaging solutions","authors":"Laura Premet , Emmanuel Oheix , Gérald Chaplais , Eliane Bou Orm , Habiba Nouali , Laure Michelin , Ludovic Josien , T. Jean Daou , Laurent Pieuchot","doi":"10.1016/j.micromeso.2025.113961","DOIUrl":"10.1016/j.micromeso.2025.113961","url":null,"abstract":"<div><div>Microporous materials are widely explored as carriers for the controlled release of antimicrobial agents, yet their practical application requires the development of scalable and adaptable shaping processes. Metal-organic frameworks (MOFs) have the potential to exert antimicrobial effects through the release of either inorganic nodes, organic linkers, encapsulated antimicrobial agents or their combinations. In this study, the preparation and antimicrobial study of polymer-based composite films containing zeolitic imidazolate frameworks (ZIFs) on a pilot-scale are reported. Such materials are intended to be shaped for applications in food packaging. To fulfill our aim, ZIF materials have been synthesized on a large scale (>200 g scale) and fully characterized (X-Ray Diffraction, Scanning Electronic Microscopy/coupled to Energy-Dispersive X-Ray spectroscopy, thermogravimetry, low-temperature nitrogen physisorption). Structural and morphological analyses are consistent with the coexistence of two polymorphs in the large scale samples (35 wt.% ZIF-8 and 65 wt..% ZIF-dia(Zn)). Nevertheless, complementary and initial study involving pure ZIF-8 and ZIF-dia solids highlights similar antimicrobial activity for the two MOFs. Large scale samples were subsequently used for the preparation of polymer-based composite films, containing 5, 10 and 30 wt.% of ZIF-8/ZIF-dia(Zn), which were fully characterized and compared to MOF-free film. The antimicrobial disinfection studies indicate that the film with 30 wt.% MOF display significantly higher ability to inhibit <em>Escherichia Coli</em> growth compared to 5, 10 wt.% MOF and MOF-free formulations. Importantly, the pilot-scale process developed here is readily translatable to industrial-scale production, offering a viable route for the integration of MOF-based antimicrobial materials into commercial food packaging solutions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113961"},"PeriodicalIF":4.7,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734102","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}
Efficient co-oxidation of volatile organic compounds (VOCs) and carbon monoxide (CO) remains challenging in environmental catalysis due to the coexistence of multiple pollutants and the difficulty in controlling catalyst interfaces. In this work, sodalite (SOD) zeolites were synthesized from fly ash as the Si-Al source, and sodium silicate was introduced to regulate crystal growth and surface electronic structure. Pt nanoparticles were subsequently supported on these zeolites to obtain a series of Pt/SOD catalysts. Structural characterizations revealed that sodium silicate addition transformed the morphology from aggregated nanoparticles into nanosheet-assembled spheres and significantly modulated the Pt-support interaction, surface-active oxygen concentration, and Lewis acidity. Among them, Pt/SOD0 exhibited the highest fraction and accessibility of metallic Pt0 species and the richest surface-adsorbed oxygen, achieving superior synergistic oxidation performance (T90(toluene) = 171.3 °C; T90(CO) = 131.2 °C). In situ DRIFTS analysis confirmed a dual “promotion-competition” relationship between the two reactants, where CO accelerated toluene oxidation (C6H5CH2OH → C6H5CHO → C6H5COOH) while toluene suppressed CO oxidation at low temperatures. This work provides a cost-effective route for converting fly ash into durable Pt/zeolite catalysts and offers mechanistic insight for designing efficient VOC-CO co-oxidation systems.
{"title":"Sodium-silicate-modulated Pt/sodalite interfaces for synergistic VOC-CO co-oxidation: Balancing SMSI and acid-metal synergy","authors":"Xirui Wang, Mingyuan Zhang, Shuaiqi Liu, Liping Wang, Chentao Hou","doi":"10.1016/j.micromeso.2025.113974","DOIUrl":"10.1016/j.micromeso.2025.113974","url":null,"abstract":"<div><div>Efficient co-oxidation of volatile organic compounds (VOCs) and carbon monoxide (CO) remains challenging in environmental catalysis due to the coexistence of multiple pollutants and the difficulty in controlling catalyst interfaces. In this work, sodalite (SOD) zeolites were synthesized from fly ash as the Si-Al source, and sodium silicate was introduced to regulate crystal growth and surface electronic structure. Pt nanoparticles were subsequently supported on these zeolites to obtain a series of Pt/SOD catalysts. Structural characterizations revealed that sodium silicate addition transformed the morphology from aggregated nanoparticles into nanosheet-assembled spheres and significantly modulated the Pt-support interaction, surface-active oxygen concentration, and Lewis acidity. Among them, Pt/SOD0 exhibited the highest fraction and accessibility of metallic Pt<sup>0</sup> species and the richest surface-adsorbed oxygen, achieving superior synergistic oxidation performance (T<sub>90</sub>(toluene) = 171.3 °C; T<sub>90</sub>(CO) = 131.2 °C). In situ DRIFTS analysis confirmed a dual “promotion-competition” relationship between the two reactants, where CO accelerated toluene oxidation (C<sub>6</sub>H<sub>5</sub>CH<sub>2</sub>OH → C<sub>6</sub>H<sub>5</sub>CHO → C<sub>6</sub>H<sub>5</sub>COOH) while toluene suppressed CO oxidation at low temperatures. This work provides a cost-effective route for converting fly ash into durable Pt/zeolite catalysts and offers mechanistic insight for designing efficient VOC-CO co-oxidation systems.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113974"},"PeriodicalIF":4.7,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734107","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 : 2026-02-15Epub Date: 2025-12-03DOI: 10.1016/j.micromeso.2025.113979
Yi-Fan Wang , Lanying Xu , Bingshan Zhao, Zhiyou Tan, Tao Long
Water pollution is undoubtedly one of the key issues of global concern, and photocatalytic technology is considered to be a promising and innovative strategy to solve this problem. TiO2 aerogel combines the advantages of TiO2 and aerogel, including high catalytic activity, nontoxicity, chemical stability, high specific surface area and porosity, which means a great practical application potential. Herein, using acetic acid to control the hydrolysis and polycondensation of titanium alkoxide, we successfully prepared monolithic anatase TiO2 aerogels with microscale macropores and nanoscale mesopores by simple one-step hydrolysis under atmospheric pressure. The method developed had the advantages of low cost, simple operation and mild reaction condition, and the monolithic material with hierarchically porous could be obtained directly by this way. The TiO2 aerogel prepared had high porosity (95.7 %), small density (0.169 g/cm3), macropores with a maximum size of 20 μm and mesopore with an average size of 10.01 nm. Thanks to its large specific surface area and anatase crystal type, the monolithic TiO2 aerogel showed excellent photocatalytic degradation performance for methylene blue, which was mainly attributed to the ·OH and ·O2− produced under ultraviolet light. Moreover, TiO2 aerogel obtained was easy to separate and recycle due to it was monolithic and had satisfactory mechanical strength, suggesting the environmental and economic sustainability of the present approach.
{"title":"Fabrication of monolithic titania TiO2 aerogels with hierarchical pores and their recyclable photocatalytic application","authors":"Yi-Fan Wang , Lanying Xu , Bingshan Zhao, Zhiyou Tan, Tao Long","doi":"10.1016/j.micromeso.2025.113979","DOIUrl":"10.1016/j.micromeso.2025.113979","url":null,"abstract":"<div><div>Water pollution is undoubtedly one of the key issues of global concern, and photocatalytic technology is considered to be a promising and innovative strategy to solve this problem. TiO<sub>2</sub> aerogel combines the advantages of TiO<sub>2</sub> and aerogel, including high catalytic activity, nontoxicity, chemical stability, high specific surface area and porosity, which means a great practical application potential. Herein, using acetic acid to control the hydrolysis and polycondensation of titanium alkoxide, we successfully prepared monolithic anatase TiO<sub>2</sub> aerogels with microscale macropores and nanoscale mesopores by simple one-step hydrolysis under atmospheric pressure. The method developed had the advantages of low cost, simple operation and mild reaction condition, and the monolithic material with hierarchically porous could be obtained directly by this way. The TiO<sub>2</sub> aerogel prepared had high porosity (95.7 %), small density (0.169 g/cm<sup>3</sup>), macropores with a maximum size of 20 μm and mesopore with an average size of 10.01 nm. Thanks to its large specific surface area and anatase crystal type, the monolithic TiO<sub>2</sub> aerogel showed excellent photocatalytic degradation performance for methylene blue, which was mainly attributed to the ·OH and ·O<sub>2</sub><sup>−</sup> produced under ultraviolet light. Moreover, TiO<sub>2</sub> aerogel obtained was easy to separate and recycle due to it was monolithic and had satisfactory mechanical strength, suggesting the environmental and economic sustainability of the present approach.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113979"},"PeriodicalIF":4.7,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787308","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 : 2026-02-15Epub Date: 2025-12-13DOI: 10.1016/j.micromeso.2025.113998
Yongjin Wang , Ran Hou , Xiaoxia Zhang , Tuanyuan Hou , Junjie Liao , Weiren Bao , Liping Chang
The application of blast furnace gas for combined heat and power generation is constrained by SO2 emissions produced from the combustion of its hydrogen sulfide (H2S) content, requiring deep desulfurization to comply with stringent environmental regulations. Among various desulfurization materials, faujasite (FAU) zeolites exhibit distinct advantages owing to their stable framework and tunable acid-base properties. However, systematic studies on the key factors affecting their H2S adsorption performance are still lacking, especially regarding the structure–activity relationship between framework composition and active sites. To address the aforementioned challenges, in this work, a series of FAU zeolites with systematically varied SiO2/Al2O3 ratios were employed as sorbents for H2S removal. FAU2.7 and FAU5.0 are low-SiO2/Al2O3, Na-type FAU zeolites with high framework Al content. FAU5.4 is obtained via ion exchange of FAU5.0 to the H-type, and high-silica Na-free zeolite sorbents (FAU7.4–FAU111.4) are prepared by steam dealumination of FAU5.0, using breakthrough experiments, XRD, Py-FTIR, NH3-TPD, CO2-TPD, and in situ FTIR to analyze desulfurization behavior from the perspectives of Lewis acid site (LAS) density, thermal stability, and dissociative chemisorption mechanism. The results indicate that zeolites with a low SiO2/Al2O3 ratio, such as FAU2.7, which possess high Al framework content and abundant thermally stable LAS, can achieve dissociative adsorption of H2S into HS− and H+. These species are then chemically fixed through acid–base synergism, yielding a breakthrough sulfur capacity (QBSC) of up to 836 mg S/100 g. In contrast, high SiO2/Al2O3 zeolites suffer from severe framework dealumination and drastically reduced acid site density, relying primarily on weak physisorption and failing to stabilize sulfur species, with a significantly reduced QBSC of 7 mg S/100 g. A positive correlation was established between the LAS and the QBSC value. This study reveals the intrinsic relationship between the acidic site configuration of FAU zeolites and the dissociative adsorption of H2S, providing theoretical guidance for the rational design of high-performance desulfurization sorbents.
{"title":"SiO2/Al2O3 ratio modulated Lewis acidity governs H2S adsorption on FAU zeolites","authors":"Yongjin Wang , Ran Hou , Xiaoxia Zhang , Tuanyuan Hou , Junjie Liao , Weiren Bao , Liping Chang","doi":"10.1016/j.micromeso.2025.113998","DOIUrl":"10.1016/j.micromeso.2025.113998","url":null,"abstract":"<div><div>The application of blast furnace gas for combined heat and power generation is constrained by SO<sub>2</sub> emissions produced from the combustion of its hydrogen sulfide (H<sub>2</sub>S) content, requiring deep desulfurization to comply with stringent environmental regulations. Among various desulfurization materials, faujasite (FAU) zeolites exhibit distinct advantages owing to their stable framework and tunable acid-base properties. However, systematic studies on the key factors affecting their H<sub>2</sub>S adsorption performance are still lacking, especially regarding the structure–activity relationship between framework composition and active sites. To address the aforementioned challenges, in this work, a series of FAU zeolites with systematically varied SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratios were employed as sorbents for H<sub>2</sub>S removal. FAU<sub>2.7</sub> and FAU<sub>5.0</sub> are low-SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub>, Na-type FAU zeolites with high framework Al content. FAU<sub>5.4</sub> is obtained via ion exchange of FAU<sub>5.0</sub> to the H-type, and high-silica Na-free zeolite sorbents (FAU<sub>7.4</sub>–FAU<sub>111.4</sub>) are prepared by steam dealumination of FAU<sub>5.0</sub>, using breakthrough experiments, XRD, Py-FTIR, NH<sub>3</sub>-TPD, CO<sub>2</sub>-TPD, and in situ FTIR to analyze desulfurization behavior from the perspectives of Lewis acid site (LAS) density, thermal stability, and dissociative chemisorption mechanism. The results indicate that zeolites with a low SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratio, such as FAU<sub>2.7</sub>, which possess high Al framework content and abundant thermally stable LAS, can achieve dissociative adsorption of H<sub>2</sub>S into HS<sup>−</sup> and H<sup>+</sup>. These species are then chemically fixed through acid–base synergism, yielding a breakthrough sulfur capacity (Q<sub>BSC</sub>) of up to 836 mg S/100 g. In contrast, high SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> zeolites suffer from severe framework dealumination and drastically reduced acid site density, relying primarily on weak physisorption and failing to stabilize sulfur species, with a significantly reduced Q<sub>BSC</sub> of 7 mg S/100 g. A positive correlation was established between the LAS and the Q<sub>BSC</sub> value. This study reveals the intrinsic relationship between the acidic site configuration of FAU zeolites and the dissociative adsorption of H<sub>2</sub>S, providing theoretical guidance for the rational design of high-performance desulfurization sorbents.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113998"},"PeriodicalIF":4.7,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787341","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 : 2026-02-15Epub Date: 2025-12-11DOI: 10.1016/j.micromeso.2025.113989
Yajuan Tu , Yuxin Hou , Xinyang He , Ming Ouyang , Ruoyi Chen , Xiang Wang , Xingyun Guan , Peng Liu , Mingli Fu , Steven L. Suib , Pingxiao Wu , Daiqi Ye
Natural nanofibrous palygorskite with micropores, nanotubular halloysite with mesopores, and disc-shaped diatomite with macropores exhibit distinct advantages in dispersing metal oxide particles due to their regular porosity, mechanical adhesion, and thermal stability. Three natural porous minerals with typical morphology were employed as supports for Cu-Co oxides in the catalytic oxidation of butyl acetate. XRD and Raman reveal that spinel-structured Cu0.72Co2.28O4 and tenorite-structured CuO are main phases on three supports, while SEM and TEM suggest that halloysite and palygorskite are better than diatomite in dispersing Cu-Co oxide particles. Due to high dispersion, superior reducibility, and moderate Co3+-O2-, the halloysite-supported Cu-Co oxides exhibit the lowest T50 of butyl acetate conversion at 232 °C among three supported catalysts. Natural porous supports modulate the spinel lattice, improve the adsorption of butyl acetate, provide surface hydroxyls in oxidation, and enhance the thermal stability of Cu-Co oxides. The gaseous O2 supplements the surface chemisorbed oxygen and lattice oxygen, which participate in the complete oxidation of butyl acetate. Above results indicate that natural porous minerals are potential supports to transition metal oxides for VOCs oxidation.
{"title":"Cu-Co oxides supported on porous minerals for catalytic oxidation of butyl acetate: Particle dispersion, catalytic performance, and oxidation mechanism","authors":"Yajuan Tu , Yuxin Hou , Xinyang He , Ming Ouyang , Ruoyi Chen , Xiang Wang , Xingyun Guan , Peng Liu , Mingli Fu , Steven L. Suib , Pingxiao Wu , Daiqi Ye","doi":"10.1016/j.micromeso.2025.113989","DOIUrl":"10.1016/j.micromeso.2025.113989","url":null,"abstract":"<div><div>Natural nanofibrous palygorskite with micropores, nanotubular halloysite with mesopores, and disc-shaped diatomite with macropores exhibit distinct advantages in dispersing metal oxide particles due to their regular porosity, mechanical adhesion, and thermal stability. Three natural porous minerals with typical morphology were employed as supports for Cu-Co oxides in the catalytic oxidation of butyl acetate. XRD and Raman reveal that spinel-structured Cu<sub>0.72</sub>Co<sub>2.28</sub>O<sub>4</sub> and tenorite-structured CuO are main phases on three supports, while SEM and TEM suggest that halloysite and palygorskite are better than diatomite in dispersing Cu-Co oxide particles. Due to high dispersion, superior reducibility, and moderate Co<sup>3+</sup>-O<sup>2-</sup>, the halloysite-supported Cu-Co oxides exhibit the lowest T<sub>50</sub> of butyl acetate conversion at 232 °C among three supported catalysts. Natural porous supports modulate the spinel lattice, improve the adsorption of butyl acetate, provide surface hydroxyls in oxidation, and enhance the thermal stability of Cu-Co oxides. The gaseous O<sub>2</sub> supplements the surface chemisorbed oxygen and lattice oxygen, which participate in the complete oxidation of butyl acetate. Above results indicate that natural porous minerals are potential supports to transition metal oxides for VOCs oxidation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"402 ","pages":"Article 113989"},"PeriodicalIF":4.7,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734049","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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