Pub Date : 2026-03-01Epub Date: 2025-12-17DOI: 10.1016/j.micromeso.2025.114002
Yiting Peng , Qianqian Zhou , Lei Wang , Pengcheng Wang , Shenghu Zhou
Olefins generated from semi-hydrogenations of alkynes are important intermediates for the synthesis of spices, pharmaceuticals, pesticides and polymers. However, semi-hydrogenations of alkynes remain challenging to achieve both high catalytic activity and selectivity under mild conditions due to the easy over-hydrogenation. In this study, we report the synthesis of PdCu alloy nanoparticles encapsulated in hollow porous silica nanospheres (PdCu@HPSNs) for semi-hydrogenations of alkynes. The mentioned materials were synthesized by a templating method in a reverse microemulsion system, and feature small PdCu nanoparticles inside hollow cavities. Under mild conditions and a substrate/Pd molar ratio of 1000/1, the optimized Pd1Cu0.5@HPSNs achieved complete conversion of 2-methyl-3-butyn-2-ol at 18 min with 2-methyl-3-buten-2-ol selectivity of up to 96.7 %. In addition, the catalysts are recyclable, and show much better performance for semi-hydrogenations of a series of alkynes than their monometallic analogues. The enhancement can be ascribed to the formation of PdCu alloy inside hollow silica nanospheres, where the Pd-Cu interaction improves the semi-hydrogenation performance, and the silica shells protect inner nanoparticles to increase their stability.
{"title":"PdCu alloy nanoparticles confined in hollow porous silica nanospheres for alkyne semi-hydrogenation","authors":"Yiting Peng , Qianqian Zhou , Lei Wang , Pengcheng Wang , Shenghu Zhou","doi":"10.1016/j.micromeso.2025.114002","DOIUrl":"10.1016/j.micromeso.2025.114002","url":null,"abstract":"<div><div>Olefins generated from semi-hydrogenations of alkynes are important intermediates for the synthesis of spices, pharmaceuticals, pesticides and polymers. However, semi-hydrogenations of alkynes remain challenging to achieve both high catalytic activity and selectivity under mild conditions due to the easy over-hydrogenation. In this study, we report the synthesis of PdCu alloy nanoparticles encapsulated in hollow porous silica nanospheres (PdCu@HPSNs) for semi-hydrogenations of alkynes. The mentioned materials were synthesized by a templating method in a reverse microemulsion system, and feature small PdCu nanoparticles inside hollow cavities. Under mild conditions and a substrate/Pd molar ratio of 1000/1, the optimized Pd<sub>1</sub>Cu<sub>0.5</sub>@HPSNs achieved complete conversion of 2-methyl-3-butyn-2-ol at 18 min with 2-methyl-3-buten-2-ol selectivity of up to 96.7 %. In addition, the catalysts are recyclable, and show much better performance for semi-hydrogenations of a series of alkynes than their monometallic analogues. The enhancement can be ascribed to the formation of PdCu alloy inside hollow silica nanospheres, where the Pd-Cu interaction improves the semi-hydrogenation performance, and the silica shells protect inner nanoparticles to increase their stability.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114002"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145789878","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 : 2026-03-01Epub Date: 2025-12-19DOI: 10.1016/j.micromeso.2025.113981
Nikola Jakupec , Erik Uran , Magdalena Jabłońska , Krunoslav Užarević , Ana Palčić
Thermally-controllable mechanochemistry has shown great potential in fast and energy-efficient solid-state interzeolite conversion. In this work, a broader search of effects on mechanochemical interzeolite conversion reactions by variation of temperature, time of reaction, the amount of water in the system, and the seeds present is performed and correlated to reference experiments conducted in the oven without mechanical agitation. The results presented herein indicate an increased tendency for amorphization and desilication in thermo-mechanochemically treated samples, as well as accelerated interzeolite conversion at higher temperatures.
{"title":"Thermo-mechanochemical interzeolite conversion in water-deficient systems","authors":"Nikola Jakupec , Erik Uran , Magdalena Jabłońska , Krunoslav Užarević , Ana Palčić","doi":"10.1016/j.micromeso.2025.113981","DOIUrl":"10.1016/j.micromeso.2025.113981","url":null,"abstract":"<div><div>Thermally-controllable mechanochemistry has shown great potential in fast and energy-efficient solid-state interzeolite conversion. In this work, a broader search of effects on mechanochemical interzeolite conversion reactions by variation of temperature, time of reaction, the amount of water in the system, and the seeds present is performed and correlated to reference experiments conducted in the oven without mechanical agitation. The results presented herein indicate an increased tendency for amorphization and desilication in thermo-mechanochemically treated samples, as well as accelerated interzeolite conversion at higher temperatures.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 113981"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145789880","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 : 2026-03-01Epub Date: 2026-01-02DOI: 10.1016/j.micromeso.2026.114027
Yangyu Liu , Ke Ren , Jiuyue Wang , Arman Peyravi , Zaher Hashisho , Yuping Tong , Xiao Wang , Xi Chen , Jinggan Shao , Jinyong Wu , Ruqin Gao
In this study, CoFe2O4 nanoparticles were anchored onto natural Opoka-derived MCM-41 (denoted as CFMCM) using a facile citrate combustion method, resulting in a composite with excellent performance and stability. Systematic characterization and peroxymonosulfate (PMS) activation experiments were conducted to evaluate tetracycline (TC) degradation performance. Compared to bare CoFe2O4, CFMCM exhibited greatly enhanced specific surface area and pore volume. The MCM-41 support facilitated multidirectional crystallization of CoFe2O4 nanoparticles, resulting in reduced grain size and lower crystallinity, thereby providing abundant active sites for PMS activation. The CFMCM composite demonstrated superior PMS activation capability with a degradation rate constant that was 3.3 times higher than bare CoFe2O4. The uniform anchoring of highly dispersed CoFe2O4 nanoparticles on MCM-41 effectively prevented metal leaching, ensuring excellent reusability. Radical quenching tests and electron paramagnetic resonance (EPR) analysis revealed that reactive oxygen species (•OH, SO4•-, and 1O2) participated in the degradation process, with SO4•- and 1O2 being the dominant species. These reactive species were generated through the redox cycling between Co2+/Co3+ and Fe2+/Fe3+ pairs. Furthermore, possible TC degradation pathways were proposed based on intermediates identification. This work provides new insights into developing high-efficiency PMS-activating catalysts derived from natural minerals for wastewater treatment.
{"title":"CoFe2O4 nanoparticles supported on MCM-41 as highly efficient peroxymonosulfate catalyst for tetracycline degradation","authors":"Yangyu Liu , Ke Ren , Jiuyue Wang , Arman Peyravi , Zaher Hashisho , Yuping Tong , Xiao Wang , Xi Chen , Jinggan Shao , Jinyong Wu , Ruqin Gao","doi":"10.1016/j.micromeso.2026.114027","DOIUrl":"10.1016/j.micromeso.2026.114027","url":null,"abstract":"<div><div>In this study, CoFe<sub>2</sub>O<sub>4</sub> nanoparticles were anchored onto natural Opoka-derived MCM-41 (denoted as CFMCM) using a facile citrate combustion method, resulting in a composite with excellent performance and stability. Systematic characterization and peroxymonosulfate (PMS) activation experiments were conducted to evaluate tetracycline (TC) degradation performance. Compared to bare CoFe<sub>2</sub>O<sub>4</sub>, CFMCM exhibited greatly enhanced specific surface area and pore volume. The MCM-41 support facilitated multidirectional crystallization of CoFe<sub>2</sub>O<sub>4</sub> nanoparticles, resulting in reduced grain size and lower crystallinity, thereby providing abundant active sites for PMS activation. The CFMCM composite demonstrated superior PMS activation capability with a degradation rate constant that was 3.3 times higher than bare CoFe<sub>2</sub>O<sub>4</sub>. The uniform anchoring of highly dispersed CoFe<sub>2</sub>O<sub>4</sub> nanoparticles on MCM-41 effectively prevented metal leaching, ensuring excellent reusability. Radical quenching tests and electron paramagnetic resonance (EPR) analysis revealed that reactive oxygen species (•OH, SO<sub>4</sub>•<sup>-</sup>, and <sup>1</sup>O<sub>2</sub>) participated in the degradation process, with SO<sub>4</sub>•<sup>-</sup> and <sup>1</sup>O<sub>2</sub> being the dominant species. These reactive species were generated through the redox cycling between Co<sup>2+</sup>/Co<sup>3+</sup> and Fe<sup>2+</sup>/Fe<sup>3+</sup> pairs. Furthermore, possible TC degradation pathways were proposed based on intermediates identification. This work provides new insights into developing high-efficiency PMS-activating catalysts derived from natural minerals for wastewater treatment.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114027"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921898","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, Cu-based hydrotalcite-zeolite (CuHT-ZSM-5) composites were synthesized and characterized to explore their potential as catalyst precursors. The hydrotalcite phase was successfully formed on ZSM-5 zeolite supports with different Si/Al ratios under standard co-precipitation conditions (pH = 10, T = 65 °C). Structural analysis confirmed that the zeolite framework remained intact during synthesis, with only minor acidity modifications observed for Al-containing ZSM-5. The hydrotalcite layers were composed of copper, magnesium and aluminium cations, while the carbonate anions were used as interlayer anions.
Thermal decomposition of the CuHT phase resulted in in-situ generation of highly dispersed mixed metal oxides (MMOs). Textural characterization revealed that optimal calcination temperatures (500–600 °C) allow to obtain materials with high specific surface areas, while excessive heating (≥800 °C) led to partial collapse of the porous structure and formation of new MgSiO3 phases.
The study demonstrates that CuHT-ZSM-5 composites are structurally stable, thermally resistant, and exhibit tuneable acidity – key properties for catalytic applications. These findings open new possibilities for optimizing MMO-zeolite catalysts, particularly for NH3-SCO reactions.
本研究合成了cu基水滑石-沸石（CuHT-ZSM-5）复合材料，并对其进行了表征，以探索其作为催化剂前驱体的潜力。在标准共沉淀条件下（pH = 10, T = 65℃），在不同Si/Al比的ZSM-5沸石载体上成功形成水滑石相。结构分析证实，分子筛框架在合成过程中保持完整，仅观察到含al的ZSM-5有轻微的酸性修饰。水滑石层由铜、镁、铝阳离子组成，碳酸盐阴离子作为层间阴离子。CuHT相的热分解导致原位生成高度分散的混合金属氧化物（MMOs）。结构表征表明，最佳的煅烧温度（500-600℃）可以获得高比表面积的材料，而过度加热（≥800℃）会导致多孔结构的部分坍塌并形成新的MgSiO3相。研究表明，CuHT-ZSM-5复合材料结构稳定，耐热，并具有可调的酸度-催化应用的关键性能。这些发现为优化mmo -沸石催化剂，特别是NH3-SCO反应开辟了新的可能性。
{"title":"Hydrotalcite-zeolite composites as precursors for catalysis: Synthesis, transformation and structural stability","authors":"Sylwia Górecka , Kateřina Pacultová , Kateřina Karásková , Kamil Górecki , Kateřina Kupková , Eva Kinnertová , Antonio Eduardo Palomares Gimeno , Lucie Obalová","doi":"10.1016/j.micromeso.2026.114031","DOIUrl":"10.1016/j.micromeso.2026.114031","url":null,"abstract":"<div><div>In this study, Cu-based hydrotalcite-zeolite (CuHT-ZSM-5) composites were synthesized and characterized to explore their potential as catalyst precursors. The hydrotalcite phase was successfully formed on ZSM-5 zeolite supports with different Si/Al ratios under standard co-precipitation conditions (pH = 10, T = 65 °C). Structural analysis confirmed that the zeolite framework remained intact during synthesis, with only minor acidity modifications observed for Al-containing ZSM-5. The hydrotalcite layers were composed of copper, magnesium and aluminium cations, while the carbonate anions were used as interlayer anions.</div><div>Thermal decomposition of the CuHT phase resulted in in-situ generation of highly dispersed mixed metal oxides (MMOs). Textural characterization revealed that optimal calcination temperatures (500–600 °C) allow to obtain materials with high specific surface areas, while excessive heating (≥800 °C) led to partial collapse of the porous structure and formation of new MgSiO<sub>3</sub> phases.</div><div>The study demonstrates that CuHT-ZSM-5 composites are structurally stable, thermally resistant, and exhibit tuneable acidity – key properties for catalytic applications. These findings open new possibilities for optimizing MMO-zeolite catalysts, particularly for NH<sub>3</sub>-SCO reactions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114031"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921908","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}
Organic pollutants, including synthetic dyes, phenolic compounds, and pesticide residues commonly found in wastewater, pose persistent threats to aquatic ecosystem protection. In this study, a mixed-ligand strategy was employed to synthesize MIL-101(Cr) with enhanced adsorption performance toward structurally diverse pollutants, namely methyl orange (MO), 2-naphthol, and carbaryl. The mixed-ligand MIL-101(Cr)-NH2 was tailored by varying the molar ratio between 1,4-benzenedicarboxylic acid (H2BDC) and 2-amino-1,4-benzenedicarboxylic acid (NH2BDC), while nitric acid (HNO3) was used as a safer, non-toxic alternative to hydrofluoric acid (HF) as the modulator in the hydrothermal synthesis. Notably, the MOF prepared with 75 % NH2BDC (MILCr75 %) exhibited a significantly higher specific surface area (1754.7 m2/g) compared to pristine MIL-101(Cr) (1094.5 m2/g). Adsorption kinetics followed the pseudo-second-order model, with maximum adsorption capacities of 410.55 mg/g for MO, 67.48 mg/g for 2-naphthol, and 36.31 mg/g for carbaryl. The corresponding rate constants (k2) were 0.0135 g/mg·min, 0.0119 g/mg·min, and 0.109 g/mg·min, respectively. To complement the experimental results, density functional theory (DFT) calculations were performed to elucidate the electronic properties of the pollutants and their adsorption interactions with the MOF. Furthermore, MILCr75 % demonstrated superior chemical and water stability, retaining removal efficiencies of 77 % for MO and 68 % for 2-naphthol even after five adsorption–desorption cycles. This work highlights the synergistic benefits of mixed-ligand engineering and computational insights in designing robust MOFs for ionic and non-ionic pollutant remediation.
{"title":"Tailoring MIL-101(Cr) via a mixed-ligand strategy for enhanced adsorption of phenolic, pesticide, and dye pollutants: Experimental and DFT insight","authors":"Nuhaa Faaizatunnisa , Ratna Ediati , Enis Nadia Md Yusof , Arif Fadlan , Muhammad Naufal Ariesta , Desindy Ramadhani Putri","doi":"10.1016/j.micromeso.2025.113997","DOIUrl":"10.1016/j.micromeso.2025.113997","url":null,"abstract":"<div><div>Organic pollutants, including synthetic dyes, phenolic compounds, and pesticide residues commonly found in wastewater, pose persistent threats to aquatic ecosystem protection. In this study, a mixed-ligand strategy was employed to synthesize MIL-101(Cr) with enhanced adsorption performance toward structurally diverse pollutants, namely methyl orange (MO), 2-naphthol, and carbaryl. The mixed-ligand MIL-101(Cr)-NH<sub>2</sub> was tailored by varying the molar ratio between 1,4-benzenedicarboxylic acid (H<sub>2</sub>BDC) and 2-amino-1,4-benzenedicarboxylic acid (NH<sub>2</sub>BDC), while nitric acid (HNO<sub>3</sub>) was used as a safer, non-toxic alternative to hydrofluoric acid (HF) as the modulator in the hydrothermal synthesis. Notably, the MOF prepared with 75 % NH<sub>2</sub>BDC (MILCr75 %) exhibited a significantly higher specific surface area (1754.7 m<sup>2</sup>/g) compared to pristine MIL-101(Cr) (1094.5 m<sup>2</sup>/g). Adsorption kinetics followed the pseudo-second-order model, with maximum adsorption capacities of 410.55 mg/g for MO, 67.48 mg/g for 2-naphthol, and 36.31 mg/g for carbaryl. The corresponding rate constants (k<sub>2</sub>) were 0.0135 g/mg·min, 0.0119 g/mg·min, and 0.109 g/mg·min, respectively. To complement the experimental results, density functional theory (DFT) calculations were performed to elucidate the electronic properties of the pollutants and their adsorption interactions with the MOF. Furthermore, MILCr75 % demonstrated superior chemical and water stability, retaining removal efficiencies of 77 % for MO and 68 % for 2-naphthol even after five adsorption–desorption cycles. This work highlights the synergistic benefits of mixed-ligand engineering and computational insights in designing robust MOFs for ionic and non-ionic pollutant remediation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 113997"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838952","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 recent years, MOF-templated pyrolysis has emerged as a novel strategy for the synthesis of composite transition metal oxides with unique structures. Herein, binary metal oxides composites MnOx/CeO2 derived from MOF were successfully synthesized and applied for the selective oxidation of alkenes. The results indicate that the reaction pathway is critically determined by the employment of solvent. The selective epoxidation of alkenes was achieved with this catalyst in organic solvents, whereas the oxidation of alkenes to the corresponding carbonyl compounds was achieved in aqueous media. A series of characterization techniques on the catalyst revealed that the excellent catalytic performance is attributed to the synergy of Ce-Mn bimetallic oxides, the Mn3+/Ce4+ → Mn4+/Ce3+ redox cycle, and abundant oxygen vacancies. Furthermore, the catalyst demonstrated excellent structural stability and reusability performance, maintaining its catalytic activity over ten consecutive reaction cycles. Additionally, mechanistic investigations revealed the involvement of a radical pathway in the catalytic reactions.
{"title":"From controlled doping to efficient catalysis: MOF-derived Ce-Mn oxides for selective alkene oxidation","authors":"Wenwen Li, Zhigang Zhang, Yuntao Hu, Guangbing Zheng, Hongyan Xu, Huaiqing Zhao","doi":"10.1016/j.micromeso.2025.113999","DOIUrl":"10.1016/j.micromeso.2025.113999","url":null,"abstract":"<div><div>In recent years, MOF-templated pyrolysis has emerged as a novel strategy for the synthesis of composite transition metal oxides with unique structures. Herein, binary metal oxides composites MnO<sub>x</sub>/CeO<sub>2</sub> derived from MOF were successfully synthesized and applied for the selective oxidation of alkenes. The results indicate that the reaction pathway is critically determined by the employment of solvent. The selective epoxidation of alkenes was achieved with this catalyst in organic solvents, whereas the oxidation of alkenes to the corresponding carbonyl compounds was achieved in aqueous media. A series of characterization techniques on the catalyst revealed that the excellent catalytic performance is attributed to the synergy of Ce-Mn bimetallic oxides, the Mn<sup>3+</sup>/Ce<sup>4+</sup> → Mn<sup>4+</sup>/Ce<sup>3+</sup> redox cycle, and abundant oxygen vacancies. Furthermore, the catalyst demonstrated excellent structural stability and reusability performance, maintaining its catalytic activity over ten consecutive reaction cycles. Additionally, mechanistic investigations revealed the involvement of a radical pathway in the catalytic reactions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 113999"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838951","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 : 2026-03-01Epub Date: 2025-12-22DOI: 10.1016/j.micromeso.2025.114013
Mon Bryan Z. Gili , Mark Laurence V. Cabahug , Gina B. Abrera , Vina B. Argayosa , Shah Qasim Jan , Manh-Huong Phan , Jirawat Assawakhajornsak , Hideki Nakajima , Marlon T. Conato , Marienette M. Vega
A green gamma radiolytic method was utilized to synthesize silver-zeolite nanocomposites (Ag/ZeoNCs) using Philippine natural zeolite (PNZ) and synthetic Zeolite 4A, with ι-carrageenan as the food-grade reducing agent. (Ag/ZeoNCs) were irradiated at 5, 10, and 15 kGy doses, facilitating in-situ reduction of Ag+ to Ag0 without toxic reducing agents or inert gas purging. XRD confirmed the retention of zeolite crystallinity post-irradiation, while TEM revealed bimodal AgNP size distributions (∼2 nm and ∼13 nm), localized primarily on zeolite surfaces. XPS analysis detected both Ag+ and Ag0 species, with increasing Ag0 signal intensity at higher doses, confirming partial reduction. The Ag content in Zeolite 4A samples ranged from 0.0413 to 0.0445 at. %. Antimicrobial indices (AI) for irradiated samples ranged from 0.55 to 0.64 depending on dose and bacterial strain, exceeding that of Ag+-exchanged controls (AI = 0.54–0.60). The AI increased with silver nitrate loading, reaching a plateau at 208 μL of 0.2 M AgNO3 solution, indicating a saturation point for optimal antibacterial efficacy. Over a 5-month period, long-term tests showed an increase in AI from an initial 0.18 to peaks of 0.32 (E. coli) and 0.30 (S. aureus), followed by slight decline while remaining above baseline. These results demonstrate that gamma-radiolytically synthesized Ag/Zeo4ANCs maintain strong, durable antibacterial activity with minimal silver loading (0.0445 at. %), offering a sustainable and effective antimicrobial platform.
{"title":"Radiolytic synthesis of silver-zeolite nanocomposites for long-term antibacterial activity","authors":"Mon Bryan Z. Gili , Mark Laurence V. Cabahug , Gina B. Abrera , Vina B. Argayosa , Shah Qasim Jan , Manh-Huong Phan , Jirawat Assawakhajornsak , Hideki Nakajima , Marlon T. Conato , Marienette M. Vega","doi":"10.1016/j.micromeso.2025.114013","DOIUrl":"10.1016/j.micromeso.2025.114013","url":null,"abstract":"<div><div>A green gamma radiolytic method was utilized to synthesize silver-zeolite nanocomposites (Ag/ZeoNCs) using Philippine natural zeolite (PNZ) and synthetic Zeolite 4A, with ι-carrageenan as the food-grade reducing agent. (Ag/ZeoNCs) were irradiated at 5, 10, and 15 kGy doses, facilitating in-situ reduction of Ag<sup>+</sup> to Ag<sup>0</sup> without toxic reducing agents or inert gas purging. XRD confirmed the retention of zeolite crystallinity post-irradiation, while TEM revealed bimodal AgNP size distributions (∼2 nm and ∼13 nm), localized primarily on zeolite surfaces. XPS analysis detected both Ag<sup>+</sup> and Ag<sup>0</sup> species, with increasing Ag<sup>0</sup> signal intensity at higher doses, confirming partial reduction. The Ag content in Zeolite 4A samples ranged from 0.0413 to 0.0445 at. %. Antimicrobial indices (AI) for irradiated samples ranged from 0.55 to 0.64 depending on dose and bacterial strain, exceeding that of Ag<sup>+</sup>-exchanged controls (AI = 0.54–0.60). The AI increased with silver nitrate loading, reaching a plateau at 208 μL of 0.2 M AgNO<sub>3</sub> solution, indicating a saturation point for optimal antibacterial efficacy. Over a 5-month period, long-term tests showed an increase in AI from an initial 0.18 to peaks of 0.32 (<em>E. coli</em>) and 0.30 (<em>S. aureus</em>), followed by slight decline while remaining above baseline. These results demonstrate that gamma-radiolytically synthesized Ag/Zeo4ANCs maintain strong, durable antibacterial activity with minimal silver loading (0.0445 at. %), offering a sustainable and effective antimicrobial platform.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114013"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838956","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 : 2026-03-01Epub Date: 2025-12-18DOI: 10.1016/j.micromeso.2025.113975
Hongyu Liu , Yufan Wang , Tongguang Xu , Haoyu Bu , Qian Kong , Huatong Li , Haixiao Sun , Zhaoshuo Yuan , Linglong Yao , Xuelian Zhang , Xin Zhang
Nicotine, being the highly toxic, strongly addictive, and poorly biodegradable alkaloid, posing dual threats to human health and ecological systems. However, current nicotine adsorbents are plagued by issues such as high costs, limited adsorption capacity, and restricted environmental adaptability. In this study, through pre-treatment and persulfate ammonium oxidation modification methods, oxidized activated carbon (AC-A-APS) was successfully synthesized. Aqueous-phase adsorption experiments demonstrated that modified activated carbon (AC-A-APS) achieved an equilibrium adsorption capacity (qe) of 151.4 mg g−1 based on the Langmuir model for nicotine, representing a 59 % enhancement compared to the original activated carbon (AC, 95.2 mg g−1). In laboratory simulation device testing and smoking machine trials, AC-A-APS exhibited nicotine aerosol retention efficiencies of 90.1 % and 84.7 %, respectively. This study significantly increased the specific surface area of activated carbon and enriched oxygen-containing groups through acid washing and ammonium persulfate oxidation treatment demonstrated by N2 adsorption-desorption, NH3-TPD characterizations. By modulating the pore structure and surface acidic functional groups, the adsorption and capture efficiency of nicotine in both aqueous solution and gaseous states can be synergistically enhanced. The study provides key theoretical and technical support for developing high-performance, renewable adsorbents for wastewater treatment and cigarette filters.
尼古丁是剧毒、成瘾性强、可生物降解性差的生物碱，对人类健康和生态系统构成双重威胁。然而，目前的尼古丁吸附剂存在成本高、吸附能力有限、环境适应性受限等问题。本研究通过预处理和过硫酸盐铵氧化改性的方法，成功合成了氧化活性炭（AC-A-APS）。水相吸附实验表明，基于Langmuir模型，改性活性炭（AC- a - aps）对尼古丁的平衡吸附量（qe）为151.4 mg g - 1，与原活性炭（AC, 95.2 mg g - 1）相比，提高了59%。在实验室模拟装置测试和吸烟机试验中，AC-A-APS的尼古丁气溶胶保留效率分别为90.1%和84.7%。通过N2吸附-脱附、NH3-TPD表征，表明通过酸洗和过硫酸铵氧化处理可以显著提高活性炭的比表面积，并富集含氧基团。通过调节孔结构和表面酸性官能团，可以协同提高烟碱在水溶液和气态的吸附和捕获效率。该研究为开发高性能、可再生的废水处理吸附剂和香烟过滤嘴提供了关键的理论和技术支持。
{"title":"Dual-phase nicotine adsorption by phenolic hydroxyl-enriched activated carbon","authors":"Hongyu Liu , Yufan Wang , Tongguang Xu , Haoyu Bu , Qian Kong , Huatong Li , Haixiao Sun , Zhaoshuo Yuan , Linglong Yao , Xuelian Zhang , Xin Zhang","doi":"10.1016/j.micromeso.2025.113975","DOIUrl":"10.1016/j.micromeso.2025.113975","url":null,"abstract":"<div><div>Nicotine, being the highly toxic, strongly addictive, and poorly biodegradable alkaloid, posing dual threats to human health and ecological systems. However, current nicotine adsorbents are plagued by issues such as high costs, limited adsorption capacity, and restricted environmental adaptability. In this study, through pre-treatment and persulfate ammonium oxidation modification methods, oxidized activated carbon (AC-A-APS) was successfully synthesized. Aqueous-phase adsorption experiments demonstrated that modified activated carbon (AC-A-APS) achieved an equilibrium adsorption capacity (q<sub>e</sub>) of 151.4 mg g<sup>−1</sup> based on the Langmuir model for nicotine, representing a 59 % enhancement compared to the original activated carbon (AC, 95.2 mg g<sup>−1</sup>). In laboratory simulation device testing and smoking machine trials, AC-A-APS exhibited nicotine aerosol retention efficiencies of 90.1 % and 84.7 %, respectively. This study significantly increased the specific surface area of activated carbon and enriched oxygen-containing groups through acid washing and ammonium persulfate oxidation treatment demonstrated by N<sub>2</sub> adsorption-desorption, NH<sub>3</sub>-TPD characterizations. By modulating the pore structure and surface acidic functional groups, the adsorption and capture efficiency of nicotine in both aqueous solution and gaseous states can be synergistically enhanced. The study provides key theoretical and technical support for developing high-performance, renewable adsorbents for wastewater treatment and cigarette filters.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 113975"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145789879","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}
Carbon capture, utilization, storage (CCUS), particularly post-combustion CO2 capture, relies heavily on efficient gas separation materials. Zeolites have shown great potential as adsorbents due to their tunable structures and adsorption properties. In this work, Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations were employed to investigate the competitive adsorption and diffusion behaviors of CO2 and N2 in M-ZSM-5 (M = Li, Na, K) under flue gas conditions. It was notably found that although the adsorption of pure N2 increases with pressure in these zeolites, N2 uptake becomes negligible in competitive flue gas mixtures, while CO2 adsorption remains largely unaffected. This behavior leads to a significant enhancement in CO2/N2 selectivity. Among all samples, Li-ZSM-5 exhibited the highest performance, with a CO2 uptake of 2.41 mol/kg and a selectivity of 640 for CO2 over N2 at 303 K and 1 bar, which is attributed to the strong electrostatic interactions introduced by cation modification. These findings highlight the promising application of cation-exchanged ZSM-5 zeolites for efficient CO2 separation from flue gas.
{"title":"Competitive adsorption and diffusion of CO2/N2 in M-ZSM-5 for post-combustion capture: A molecular simulation insight","authors":"Ziyi Zhao, Weixin Qian, Hongfang Ma, Weiyong Ying, Haitao Zhang, Peiqing Yuan","doi":"10.1016/j.micromeso.2025.114024","DOIUrl":"10.1016/j.micromeso.2025.114024","url":null,"abstract":"<div><div>Carbon capture, utilization, storage (CCUS), particularly post-combustion CO<sub>2</sub> capture, relies heavily on efficient gas separation materials. Zeolites have shown great potential as adsorbents due to their tunable structures and adsorption properties. In this work, Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations were employed to investigate the competitive adsorption and diffusion behaviors of CO<sub>2</sub> and N<sub>2</sub> in M-ZSM-5 (M = Li, Na, K) under flue gas conditions. It was notably found that although the adsorption of pure N<sub>2</sub> increases with pressure in these zeolites, N<sub>2</sub> uptake becomes negligible in competitive flue gas mixtures, while CO<sub>2</sub> adsorption remains largely unaffected. This behavior leads to a significant enhancement in CO<sub>2</sub>/N<sub>2</sub> selectivity. Among all samples, Li-ZSM-5 exhibited the highest performance, with a CO<sub>2</sub> uptake of 2.41 mol/kg and a selectivity of 640 for CO<sub>2</sub> over N<sub>2</sub> at 303 K and 1 bar, which is attributed to the strong electrostatic interactions introduced by cation modification. These findings highlight the promising application of cation-exchanged ZSM-5 zeolites for efficient CO<sub>2</sub> separation from flue gas.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114024"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921896","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 : 2026-03-01Epub Date: 2025-12-17DOI: 10.1016/j.micromeso.2025.114000
Rong Lei, Rutong Zhang, Xiaolei Fu, Lu Li, Yuhuan Nie, Qibin Chen
Despite the significant progress in the synthesis of hypercrosslinked polymers (HCPs), the precise construction of HCPs with unique nano- and microstructures without using template remains a great challenge. In this study, a uniquely nanotubular HCP had been synthesized via an ortho-substitution strategy activated by electron-donating groups introduced, using 4,4′-biphenyldiol (BPD) and p-dichloroxylene (DCX) as building block and crosslinker, respectively. More strikingly, nanotubular HCPs derived from achiral BPD and DCX afford the enantioselective recognition ability to some extent, hereafter denoted as chiral HCP (CHCP). All CHCPs tend to spontaneously form the ultra-thin sheet at the first stage, subsequently roll-up and self-assemble into nanotubes. In order to further improve the enantioselectivity, a certain amount of D- or L-phenylalanine (D- or L-Phe) was used as chiral selector to improve the chiral environment, affording the corresponding nanotubular D- and L-CHCPs. Moreover, the combination of the nanotubular CHCP with the chiral selector can exert a significant synergic effect on improving the enantioselectivity, according to the differential pulse voltammetry (DPV). Our findings suggest that the ortho-substitution strategy proposed in this work represents a fundamentally new approach that opens significant opportunities for the manipulation of HCP structures and the enhancement in the specifically functional property of new materials.
{"title":"Chiral tubular hypercrosslinked polymers from orientational rolling-up of nanosheet directed by ortho-position substitution","authors":"Rong Lei, Rutong Zhang, Xiaolei Fu, Lu Li, Yuhuan Nie, Qibin Chen","doi":"10.1016/j.micromeso.2025.114000","DOIUrl":"10.1016/j.micromeso.2025.114000","url":null,"abstract":"<div><div>Despite the significant progress in the synthesis of hypercrosslinked polymers (HCPs), the precise construction of HCPs with unique nano- and microstructures without using template remains a great challenge. In this study, a uniquely nanotubular HCP had been synthesized via an ortho-substitution strategy activated by electron-donating groups introduced, using 4,4′-biphenyldiol (BPD) and <em>p</em>-dichloroxylene (DCX) as building block and crosslinker, respectively. More strikingly, nanotubular HCPs derived from achiral BPD and DCX afford the enantioselective recognition ability to some extent, hereafter denoted as chiral HCP (CHCP). All CHCPs tend to spontaneously form the ultra-thin sheet at the first stage, subsequently roll-up and self-assemble into nanotubes. In order to further improve the enantioselectivity, a certain amount of <em>D-</em> or <em>L</em>-phenylalanine (<em>D-</em> or <em>L</em>-Phe) was used as chiral selector to improve the chiral environment, affording the corresponding nanotubular <em>D</em>- and <em>L</em>-CHCPs. Moreover, the combination of the nanotubular CHCP with the chiral selector can exert a significant synergic effect on improving the enantioselectivity, according to the differential pulse voltammetry (DPV). Our findings suggest that the ortho-substitution strategy proposed in this work represents a fundamentally new approach that opens significant opportunities for the manipulation of HCP structures and the enhancement in the specifically functional property of new materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114000"},"PeriodicalIF":4.7,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145789881","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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