Pub Date : 2026-04-01Epub Date: 2026-02-05DOI: 10.1016/j.micromeso.2026.114048
Yogesh Kumar , Ajay Dixit , Suraj Bharati , Prabhat Garg , Sanjay Upadhyay , Vikas B. Thakare , G. Ravi Raju , Shaibal Banerjee
Chemical warfare agents (CWAs) pose severe environmental risks due to their high toxicity, immediate physiological effects, and persistence in air, soil, and water. Removal strategies have primarily focused on containment or capture, whereas the combined approach of capture and decontamination has not been thoroughly investigated. Here, we investigate the modulation of Lewis acidity and basicity in hexanuclear Zr(IV) cluster-based metal-organic frameworks, including Ce/Zr/Ti-UiO-66 and Ce/Zr-UiO-66-NH2, possessing high surface areas (1217 and 1102 m2 g−1) and pore volumes (0.580 and 0.475 cm3 g−1), respectively, as catalysts to explore how different node composition and linker functionality influence the binding and subsequent hydrolysis of CWAs. Both catalysts efficiently hydrolyze sulfur mustard (HD) and organophosphorous nerve agent, sarin (GB). Ti-incorporated Ce/Zr-UiO-66 enables rapid and complete hydrolysis of GB within 3 min, whereas amine-functionalized Ce-Zr-UiO-66 exhibits enhanced hydrolysis of HD with a half-life of 98 min. These results establish a node- and linker-engineered UiO-66 platform that enables agent-selective and rapid hydrolytic decontamination of both nerve and mustard agents within a single porous framework.
{"title":"Rational design of bimetallic and trimetallic UiO-66 based metal-organic frameworks towards efficient hydrolysis of toxic chemicals","authors":"Yogesh Kumar , Ajay Dixit , Suraj Bharati , Prabhat Garg , Sanjay Upadhyay , Vikas B. Thakare , G. Ravi Raju , Shaibal Banerjee","doi":"10.1016/j.micromeso.2026.114048","DOIUrl":"10.1016/j.micromeso.2026.114048","url":null,"abstract":"<div><div>Chemical warfare agents (CWAs) pose severe environmental risks due to their high toxicity, immediate physiological effects, and persistence in air, soil, and water. Removal strategies have primarily focused on containment or capture, whereas the combined approach of capture and decontamination has not been thoroughly investigated. Here, we investigate the modulation of Lewis acidity and basicity in hexanuclear Zr(IV) cluster-based metal-organic frameworks, including Ce/Zr/Ti-UiO-66 and Ce/Zr-UiO-66-NH<sub>2</sub>, possessing high surface areas (1217 and 1102 m<sup>2</sup> g<sup>−1</sup>) and pore volumes (0.580 and 0.475 cm<sup>3</sup> g<sup>−1</sup>), respectively, as catalysts to explore how different node composition and linker functionality influence the binding and subsequent hydrolysis of CWAs. Both catalysts efficiently hydrolyze sulfur mustard (HD) and organophosphorous nerve agent, sarin (GB). Ti-incorporated Ce/Zr-UiO-66 enables rapid and complete hydrolysis of GB within 3 min, whereas amine-functionalized Ce-Zr-UiO-66 exhibits enhanced hydrolysis of HD with a half-life of 98 min. These results establish a node- and linker-engineered UiO-66 platform that enables agent-selective and rapid hydrolytic decontamination of both nerve and mustard agents within a single porous framework.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114048"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186163","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 : 2026-04-01Epub Date: 2026-01-30DOI: 10.1016/j.micromeso.2026.114062
Yi Wang, Zhaoteng Xue, Tao Meng, Lei Wang, Hongyan Xue, Jun Yu, Dongsen Mao
A highly selective bifunctional catalyst for the direct conversion of syngas to light olefins was constructed by combining ZnZrOx with a carefully engineered SAPO-5 zeolite. The SAPO-5 component was synthesized via hydrothermal crystallization using hexamethyleneimine (HMI) as the structure-directing agent. A systematic investigation revealed that the HMI/Al ratio was critical for obtaining the pure SAPO-5 phase, while crystallization time and Si/Al ratio significantly tuned its morphology, crystallinity, pore texture, and acidity. The optimally synthesized zeolite (HMI/Al = 1.0, Si/Al = 0.1, 12 h crystallization), denoted SP5-1.0-12-0.1, was physically mixed with ZnZrOx. In the syngas-to-olefins reaction, this composite catalyst exhibited a CO conversion of 33.6 % with a C2-C4= selectivity of 73.8 % under conditions of 400 °C, 3.0 MPa, and a GHSV of 3600 mL g−1 h−1. Remarkably, operating at a slightly lower temperature of 380 °C boosted the olefin selectivity to 81.2 %, with C4 olefins consistently accounting for over 80 % of the total olefin products. This exceptional selectivity toward C4 olefins is attributed to the distinctive 12-membered ring (12 MR) pore architecture of the SAPO-5 zeolite, which promotes the formation and retention of longer-chain intermediates. This study highlights the crucial role of precisely synthesizing zeolites in adjusting the acidic properties and pore structure to control the product distribution in complex catalytic series reactions, providing clear design principles for the efficient utilization of syngas.
{"title":"From controlled synthesis to performance optimization: Engineering SAPO-5 zeolite for direct, high-efficiency syngas conversion to light olefins with predominant C4 formation","authors":"Yi Wang, Zhaoteng Xue, Tao Meng, Lei Wang, Hongyan Xue, Jun Yu, Dongsen Mao","doi":"10.1016/j.micromeso.2026.114062","DOIUrl":"10.1016/j.micromeso.2026.114062","url":null,"abstract":"<div><div>A highly selective bifunctional catalyst for the direct conversion of syngas to light olefins was constructed by combining ZnZrO<sub>x</sub> with a carefully engineered SAPO-5 zeolite. The SAPO-5 component was synthesized via hydrothermal crystallization using hexamethyleneimine (HMI) as the structure-directing agent. A systematic investigation revealed that the HMI/Al ratio was critical for obtaining the pure SAPO-5 phase, while crystallization time and Si/Al ratio significantly tuned its morphology, crystallinity, pore texture, and acidity. The optimally synthesized zeolite (HMI/Al = 1.0, Si/Al = 0.1, 12 h crystallization), denoted SP5-1.0-12-0.1, was physically mixed with ZnZrO<sub>x</sub>. In the syngas-to-olefins reaction, this composite catalyst exhibited a CO conversion of 33.6 % with a C<sub>2</sub>-C<sub>4</sub><sup>=</sup> selectivity of 73.8 % under conditions of 400 °C, 3.0 MPa, and a GHSV of 3600 mL g<sup>−1</sup> h<sup>−1</sup>. Remarkably, operating at a slightly lower temperature of 380 °C boosted the olefin selectivity to 81.2 %, with C<sub>4</sub> olefins consistently accounting for over 80 % of the total olefin products. This exceptional selectivity toward C<sub>4</sub> olefins is attributed to the distinctive 12-membered ring (12 MR) pore architecture of the SAPO-5 zeolite, which promotes the formation and retention of longer-chain intermediates. This study highlights the crucial role of precisely synthesizing zeolites in adjusting the acidic properties and pore structure to control the product distribution in complex catalytic series reactions, providing clear design principles for the efficient utilization of syngas.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114062"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186165","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 : 2026-04-01Epub Date: 2026-02-09DOI: 10.1016/j.micromeso.2026.114058
Wenli Hao , Chang Sun , Yutong Han, Na Xu, Zhong Zhang, Xiaohui Li, Xiuli Wang
The precise regulation of the valence states of metal ions in polyoxometalates (POMs) is crucial for the rational design of highly active catalysts. Herein, hierarchical TS-1 zeolite (H-TS-1) was employed as a carrier to support and disperse Keggin-type nickel phosphomolybdate (NiPMo). The resulting NiPMo/H-TS-1 exhibited outstanding catalytic activity and recyclability in the selective oxidation of sulfides. This can be attributed to the fact that the incorporation of NiPMo into H-TS-1 can induce electron transfer from NiPMo into H-TS-1 and promote the formation of MoV, thus enhancing catalytic performance. Comprehensive spectroscopic analyses manifested that the Brønsted acid sites of zeolite are essential for electron transfer and generation of MoV. This work first reveals the critical role of Brønsted acid sites of zeolite in tuning the states of metals in POMs, offering a strategy for designing high-performance POM/zeolite catalysts via valence state modulation.
{"title":"The critical role of zeolite Brønsted acid sites in valence modulation of polyoxometalate-based composite NiPMo/H-TS-1 for enhanced catalytic oxidation of sulfides","authors":"Wenli Hao , Chang Sun , Yutong Han, Na Xu, Zhong Zhang, Xiaohui Li, Xiuli Wang","doi":"10.1016/j.micromeso.2026.114058","DOIUrl":"10.1016/j.micromeso.2026.114058","url":null,"abstract":"<div><div>The precise regulation of the valence states of metal ions in polyoxometalates (POMs) is crucial for the rational design of highly active catalysts. Herein, hierarchical TS-1 zeolite (H-TS-1) was employed as a carrier to support and disperse Keggin-type nickel phosphomolybdate (NiPMo). The resulting NiPMo/H-TS-1 exhibited outstanding catalytic activity and recyclability in the selective oxidation of sulfides. This can be attributed to the fact that the incorporation of NiPMo into H-TS-1 can induce electron transfer from NiPMo into H-TS-1 and promote the formation of Mo<sup>V</sup>, thus enhancing catalytic performance. Comprehensive spectroscopic analyses manifested that the Brønsted acid sites of zeolite are essential for electron transfer and generation of Mo<sup>V</sup>. This work first reveals the critical role of Brønsted acid sites of zeolite in tuning the states of metals in POMs, offering a strategy for designing high-performance POM/zeolite catalysts <em>via</em> valence state modulation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114058"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186194","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 : 2026-04-01Epub Date: 2026-02-07DOI: 10.1016/j.micromeso.2026.114075
Stefano Magliocco , Reza K. Abasabadi , Francesco D'Amico , Joachim D. Bjerregaard , Anastasia Yu Molokova , Henrik Grönbeck , Ton V.W. Janssens , Gloria Berlier
In this work, we have followed by in situ IR spectroscopy the stepwise formation of the [CuII2(NH3)4O2]2+ peroxo complex in Cu-CHA zeolites with different Cu loading and Si/Al ratios. Unexpected changes were observed while oxidizing the [CuI(NH3)2]+ complexes formed by reaction of Cu-CHA with an NO/NH3 mixture. Namely, this process, causes a decrease in the intensity of physisorbed NH3 (bending mode at 1620 cm−1) and of its protonated form, NH4+ (bending mode at 1434 cm−1). These changes are correlated with the increase of a band at 900 cm−1, which is coherent with the growth of framework coordinated Z2CuII sites, where Z represent a negative charge on the framework, as confirmed by DFT calculations. The process can be described as an ion exchange between NH4+ and CuII ions during the oxidation, with formation of H2O and removal of protons. More CuII ions are replacing NH4+ at high Cu loading and low Si/Al ratio, in agreement with the current understanding of the effect of these parameters on ions diffusion, which in turns affect the efficiency of the oxidation and reduction half cycles of Cu-CHA in the low temperature NH3-SCR reaction.
{"title":"Unexpected ion exchange between NH4+ and CuII ions in Cu-CHA zeolites upon formation of the [CuII2(NH3)4O2]2+ peroxo complex","authors":"Stefano Magliocco , Reza K. Abasabadi , Francesco D'Amico , Joachim D. Bjerregaard , Anastasia Yu Molokova , Henrik Grönbeck , Ton V.W. Janssens , Gloria Berlier","doi":"10.1016/j.micromeso.2026.114075","DOIUrl":"10.1016/j.micromeso.2026.114075","url":null,"abstract":"<div><div>In this work, we have followed by <em>in situ</em> IR spectroscopy the stepwise formation of the [Cu<sup>II</sup><sub>2</sub>(NH<sub>3</sub>)<sub>4</sub>O<sub>2</sub>]<sup>2+</sup> peroxo complex in Cu-CHA zeolites with different Cu loading and Si/Al ratios. Unexpected changes were observed while oxidizing the [Cu<sup>I</sup>(NH<sub>3</sub>)<sub>2</sub>]<sup>+</sup> complexes formed by reaction of Cu-CHA with an NO/NH<sub>3</sub> mixture. Namely, this process, causes a decrease in the intensity of physisorbed NH<sub>3</sub> (bending mode at 1620 cm<sup>−1</sup>) and of its protonated form, NH<sub>4</sub><sup>+</sup> (bending mode at 1434 cm<sup>−1</sup>). These changes are correlated with the increase of a band at 900 cm<sup>−1</sup>, which is coherent with the growth of framework coordinated Z<sub>2</sub>Cu<sup>II</sup> sites, where Z represent a negative charge on the framework, as confirmed by DFT calculations. The process can be described as an ion exchange between NH<sub>4</sub><sup>+</sup> and Cu<sup>II</sup> ions during the oxidation, with formation of H<sub>2</sub>O and removal of protons. More Cu<sup>II</sup> ions are replacing NH<sub>4</sub><sup>+</sup> at high Cu loading and low Si/Al ratio, in agreement with the current understanding of the effect of these parameters on ions diffusion, which in turns affect the efficiency of the oxidation and reduction half cycles of Cu-CHA in the low temperature NH<sub>3</sub>-SCR reaction.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114075"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186159","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}
Urea-assisted precipitation could be a promising alternative to usual ammonia precipitation for preparing sepiolite–zirconium oxide/hydroxide composites with improved properties for removing phosphate from water. This study investigates the effects of synthesis temperature and duration on the properties of composites obtained by urea-assisted precipitation and their phosphate adsorption performance at pH 4 and 8. Urea-assisted precipitation was carried out at 95, 120, and 180 °C for 3 and 18 h, while ammonia precipitation was performed at room temperature. The results showed that the highest temperature and longest synthesis time (180 °C, 18 h) led to the most homogeneous distribution of ZrO2 particles; however, the increase in solution pH (∼8.5) and the formation of crystalline particles negatively affected the adsorption capacity. Lowering the synthesis temperature and duration slowed down urea hydrolysis, reduced both the solution pH and the point of zero charge of the composites, and decreased the tendency towards ZrO2 crystallization, which was favorable for phosphate adsorption. Nevertheless, urea-assisted syntheses did not significantly enhance the adsorption capacity compared to conventional precipitation at pH ∼12, most likely due to the stronger condensation of Zr–OH groups at elevated temperatures.
XPS analysis confirmed the involvement of both inner- and outer-sphere complexes in the adsorption mechanism at pH 4. The ATR-FTIR analysis supported the formation of inner-sphere complexes during phosphate adsorption at both pH 4 and pH 8. Desorption experiments indicated slow phosphate release, supporting the presence of strong interactions between phosphate ions and surface functional groups. These findings provide valuable insights into the control of structure and adsorption performance of sepiolite–ZrO2 composites through optimization of the urea-assisted precipitation process.
{"title":"Urea-assisted vs. conventional precipitation for the synthesis of sepiolite-zirconium oxide/hydroxide composites: Influence on the physicochemical properties and phosphate adsorption","authors":"Željka Milovanović , Slavica Lazarević , Ivona Janković-Častvan , Dejan Pjević , Slobodan Cvetković , Đorđe Janaćković , Rada Petrović","doi":"10.1016/j.micromeso.2026.114054","DOIUrl":"10.1016/j.micromeso.2026.114054","url":null,"abstract":"<div><div>Urea-assisted precipitation could be a promising alternative to usual ammonia precipitation for preparing sepiolite–zirconium oxide/hydroxide composites with improved properties for removing phosphate from water. This study investigates the effects of synthesis temperature and duration on the properties of composites obtained by urea-assisted precipitation and their phosphate adsorption performance at pH 4 and 8. Urea-assisted precipitation was carried out at 95, 120, and 180 °C for 3 and 18 h, while ammonia precipitation was performed at room temperature. The results showed that the highest temperature and longest synthesis time (180 °C, 18 h) led to the most homogeneous distribution of ZrO<sub>2</sub> particles; however, the increase in solution pH (∼8.5) and the formation of crystalline particles negatively affected the adsorption capacity. Lowering the synthesis temperature and duration slowed down urea hydrolysis, reduced both the solution pH and the point of zero charge of the composites, and decreased the tendency towards ZrO<sub>2</sub> crystallization, which was favorable for phosphate adsorption. Nevertheless, urea-assisted syntheses did not significantly enhance the adsorption capacity compared to conventional precipitation at pH ∼12, most likely due to the stronger condensation of Zr–OH groups at elevated temperatures.</div><div>XPS analysis confirmed the involvement of both inner- and outer-sphere complexes in the adsorption mechanism at pH 4. The ATR-FTIR analysis supported the formation of inner-sphere complexes during phosphate adsorption at both pH 4 and pH 8. Desorption experiments indicated slow phosphate release, supporting the presence of strong interactions between phosphate ions and surface functional groups. These findings provide valuable insights into the control of structure and adsorption performance of sepiolite–ZrO<sub>2</sub> composites through optimization of the urea-assisted precipitation process.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114054"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146096096","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 : 2026-03-15Epub Date: 2026-01-08DOI: 10.1016/j.micromeso.2026.114033
Joaquín Martínez-Ortigosa , J. Alejandro Vidal-Moya , Reisel Millán , Vincent Sarou-Kanian , Fernando Rey , Teresa Blasco
Host-guest interactions in pure silica MFI zeolites synthesized in fluoride media using a range of organic structure-directing agents (OSDAs) (TEA, TPA, TPMA, TBA and TBMA) were investigated with emphasis on the influence of OSDA symmetry. Solid-state NMR techniques, notably bidimensional 1H–19F heteronuclear correlation (1H–19F HMQC) and the Rotational Echo Double Resonance (REDOR) were employed. Fluoride bonds silicon at the Si9 site and, depending on the OSDA, also to the Si12 giving rise to characteristic 19F NMR signals at −65 ppm and −80 ppm, respectively. Bulky OSDAs reduces fluoride incorporation and promotes bonding at Si12 site along with the formation of siloxy-silanol defects. Triple Quantum-Single Quamtum (TQ-SQ) 1H NMR spectra confirm the involvement of three neighboring silanol groups in the siloxy-silanol defects. 1H–13C HMQC spectra revealed that these defects are located near the terminal methyl groups of the longer OSDA chains and are distributed along both straight and sinusoidal channels of the MFI structure. REDOR experiments demonstrated that in MFI zeolites synthesized with asymmetric trialkyl methyl ammonium OSDAs, fluoride at the Si9 site is closer to the N–CH3 group, as confirmed by theoretical calculations. These findings highlight the critical role of OSDA structure in directing charge distribution and defect formation during zeolite crystallization. The study showcases the power of advanced solid-state NMR methods for probing framework–OSDA interactions, which are essential for tailoring zeolite properties for different applications.
{"title":"Framework–OSDA interactions and charge compensation in pure silica MFI zeolites revealed by solid-state NMR","authors":"Joaquín Martínez-Ortigosa , J. Alejandro Vidal-Moya , Reisel Millán , Vincent Sarou-Kanian , Fernando Rey , Teresa Blasco","doi":"10.1016/j.micromeso.2026.114033","DOIUrl":"10.1016/j.micromeso.2026.114033","url":null,"abstract":"<div><div>Host-guest interactions in pure silica MFI zeolites synthesized in fluoride media using a range of organic structure-directing agents (OSDAs) (TEA, TPA, TPMA, TBA and TBMA) were investigated with emphasis on the influence of OSDA symmetry. Solid-state NMR techniques, notably bidimensional <sup>1</sup>H–<sup>19</sup>F heteronuclear correlation (<sup>1</sup>H–<sup>19</sup>F HMQC) and the Rotational Echo Double Resonance <strong>(</strong>REDOR) were employed. Fluoride bonds silicon at the Si9 site and, depending on the OSDA, also to the Si12 giving rise to characteristic <sup>19</sup>F NMR signals at −65 ppm and −80 ppm, respectively. Bulky OSDAs reduces fluoride incorporation and promotes bonding at Si12 site along with the formation of siloxy-silanol defects. Triple Quantum-Single Quamtum (TQ-SQ) <sup>1</sup>H NMR spectra confirm the involvement of three neighboring silanol groups in the siloxy-silanol defects. <sup>1</sup>H–<sup>13</sup>C HMQC spectra revealed that these defects are located near the terminal methyl groups of the longer OSDA chains and are distributed along both straight and sinusoidal channels of the MFI structure. REDOR experiments demonstrated that in MFI zeolites synthesized with asymmetric trialkyl methyl ammonium OSDAs, fluoride at the Si9 site is closer to the N–CH<sub>3</sub> group, as confirmed by theoretical calculations. These findings highlight the critical role of OSDA structure in directing charge distribution and defect formation during zeolite crystallization. The study showcases the power of advanced solid-state NMR methods for probing framework–OSDA interactions, which are essential for tailoring zeolite properties for different applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114033"},"PeriodicalIF":4.7,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950096","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 : 2026-03-15Epub Date: 2026-01-17DOI: 10.1016/j.micromeso.2026.114047
Andressa Vieira Hilário , Katia Bernardo-Gusmão , Christian Wittee Lopes
The synthesis of zeolites with tailored structures and properties is of paramount importance for their application in catalysis, adsorption, and separation processes. In this work, we explore the use of four novel organic structure-directing agents (OSDAs) containing phenyl or biphenyl spacers between two cationic sites for the fluoride-mediated synthesis of purely siliceous zeolites. The OSDAs were systematically synthesized and characterized before being employed in hydrothermal syntheses at 150 °C under varying conditions of water-to-silica ratio and crystallization time. X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirmed the successful formation of crystalline zeolites for specific OSDA compositions. The OSDA-I1 and OSDA-A1 species, containing single phenyl spacers and differing in cationic nature (imidazolium vs. ammonium), led to the formation of the MTW and ∗STO zeolite phases, respectively. Thermogravimetric analysis (TGA) and solid-state nuclear magnetic resonance (NMR) provided further insights into the structural properties of the synthesized materials. These findings contribute to the ongoing efforts to design novel OSDAs for targeted zeolite synthesis and highlight the role of phenyl-based spacers in directing framework topology.
{"title":"Synthesis of pure silica large-pore MTW and ∗STO zeolites using phenyl-containing dicationic OSDAs","authors":"Andressa Vieira Hilário , Katia Bernardo-Gusmão , Christian Wittee Lopes","doi":"10.1016/j.micromeso.2026.114047","DOIUrl":"10.1016/j.micromeso.2026.114047","url":null,"abstract":"<div><div>The synthesis of zeolites with tailored structures and properties is of paramount importance for their application in catalysis, adsorption, and separation processes. In this work, we explore the use of four novel organic structure-directing agents (OSDAs) containing phenyl or biphenyl spacers between two cationic sites for the fluoride-mediated synthesis of purely siliceous zeolites. The OSDAs were systematically synthesized and characterized before being employed in hydrothermal syntheses at 150 °C under varying conditions of water-to-silica ratio and crystallization time. X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirmed the successful formation of crystalline zeolites for specific OSDA compositions. The <strong>OSDA-I1</strong> and <strong>OSDA-A1</strong> species, containing single phenyl spacers and differing in cationic nature (imidazolium <em>vs.</em> ammonium), led to the formation of the <strong>MTW</strong> and <strong>∗STO</strong> zeolite phases, respectively. Thermogravimetric analysis (TGA) and solid-state nuclear magnetic resonance (NMR) provided further insights into the structural properties of the synthesized materials. These findings contribute to the ongoing efforts to design novel OSDAs for targeted zeolite synthesis and highlight the role of phenyl-based spacers in directing framework topology.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114047"},"PeriodicalIF":4.7,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035908","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 : 2026-03-15Epub Date: 2026-01-23DOI: 10.1016/j.micromeso.2026.114052
Huazhang Zeng , Ying Huang , Jiapan Huang , Jiajun Liu , Guangfu Yin , Zhongbing Huang , Xiaoming Liao , Ximing Pu , Shunze Cao , Boxuan Li , Juan Wang
Breast cancer is the primary threat to the health of women worldwide. Traditional treatment methods are limited by their toxic side effects and insufficient efficacy against metastatic tumors, and thus, there is an urgent need for breakthroughs. In this study, we designed a multifunctional nanotherapeutic platform that integrates targeted drug delivery with synergistic chemo-photothermal therapy, providing an effective paradigm for the combination of chemotherapy and photothermal therapy (PTT) for breast cancer. The nanosystem has a mesoporous silica nanoparticle (MSN) core loaded with the chemotherapeutic drug doxorubicin hydrochloride (Dox), which is encapsulated by a polydopamine (PDA) shell that enables near-infrared (NIR) photothermal conversion and on-demand drug release upon local NIR irradiation. The surface is finally modified with hyaluronic acid (HA) for active targeting. The HA-CD44-mediated active targeting and enhanced permeability and retention (EPR) passive targeting increase drug accumulation at the tumor site. Localized drug release within the tumor minimizes systemic toxicity and enhances the bioavailability of the chemotherapeutic drug. Importantly, the synergistic effect of PTT and chemotherapy in tumor cell inhibition has been validated by the combination index (CI), providing theoretical evidence for optimizing clinical combination treatment strategies for breast cancer.
{"title":"Harnessing multimodality with mesoporous Silica@Polydopamine@Hyaluronic acid nano-vehicle for synergistic chemo-photothermal breast cancer therapy","authors":"Huazhang Zeng , Ying Huang , Jiapan Huang , Jiajun Liu , Guangfu Yin , Zhongbing Huang , Xiaoming Liao , Ximing Pu , Shunze Cao , Boxuan Li , Juan Wang","doi":"10.1016/j.micromeso.2026.114052","DOIUrl":"10.1016/j.micromeso.2026.114052","url":null,"abstract":"<div><div>Breast cancer is the primary threat to the health of women worldwide. Traditional treatment methods are limited by their toxic side effects and insufficient efficacy against metastatic tumors, and thus, there is an urgent need for breakthroughs. In this study, we designed a multifunctional nanotherapeutic platform that integrates targeted drug delivery with synergistic chemo-photothermal therapy, providing an effective paradigm for the combination of chemotherapy and photothermal therapy (PTT) for breast cancer. The nanosystem has a mesoporous silica nanoparticle (MSN) core loaded with the chemotherapeutic drug doxorubicin hydrochloride (Dox), which is encapsulated by a polydopamine (PDA) shell that enables near-infrared (NIR) photothermal conversion and on-demand drug release upon local NIR irradiation. The surface is finally modified with hyaluronic acid (HA) for active targeting. The HA-CD44-mediated active targeting and enhanced permeability and retention (EPR) passive targeting increase drug accumulation at the tumor site. Localized drug release within the tumor minimizes systemic toxicity and enhances the bioavailability of the chemotherapeutic drug. Importantly, the synergistic effect of PTT and chemotherapy in tumor cell inhibition has been validated by the combination index (CI), providing theoretical evidence for optimizing clinical combination treatment strategies for breast cancer.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114052"},"PeriodicalIF":4.7,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146185192","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}
Commercial HY zeolites have been recrystallized in the presence of 15-crown-5 molecules, using mixtures of NaOH and tetraalkylammonium hydroxides (TAAOH) with alkyl chains from C2 to C4 as alkaline reagents. At constant pH value, the gradual replacement of NaOH by TAAOH in the gel did not modify the composition of the framework but led to a progressive decrease of the crown ether content in the zeolite in favor of ammonium cations. In the particular case of propyl chains, the zeolite could completely recrystallize in the absence of Na+ cations, giving a [TPA+]-Y zeolite with SiO2/Al2O3 = 19.5, in which all negative charges of Al tetrahedra are compensated by TPA+ cations. It constitutes the first example of Y zeolite crystallized in the presence of organic molecules and in the absence of Na+ cations. Attempts to obtain similar materials with tetraethylammonium or tetrabutylammonium cations were unsuccessful, likely due to a mismatch between framework and organic charges. The [TPA+]-Y zeolite features octahedral crystals similar in size and shape to those of the initial HY with a slight increase of the mesoporous volume. Recrystallization was limited to HY zeolites with SiO2/Al2O3 ratios between ca. 30 and 60, solids obtained from precursors with SiO2/Al2O3 > 60 being systematically contaminated by MFI phase.
{"title":"Organic-directed crystallization of Na-free Y zeolite with controlled framework composition","authors":"Thibaud Aumond , Corentin Chatelard , Mathias Dodin , Raquel Martinez-Franco , Alain Tuel","doi":"10.1016/j.micromeso.2026.114045","DOIUrl":"10.1016/j.micromeso.2026.114045","url":null,"abstract":"<div><div>Commercial HY zeolites have been recrystallized in the presence of 15-crown-5 molecules, using mixtures of NaOH and tetraalkylammonium hydroxides (TAAOH) with alkyl chains from C<sub>2</sub> to C<sub>4</sub> as alkaline reagents. At constant pH value, the gradual replacement of NaOH by TAAOH in the gel did not modify the composition of the framework but led to a progressive decrease of the crown ether content in the zeolite in favor of ammonium cations. In the particular case of propyl chains, the zeolite could completely recrystallize in the absence of Na<sup>+</sup> cations, giving a [TPA<sup>+</sup>]-Y zeolite with SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> = 19.5, in which all negative charges of Al tetrahedra are compensated by TPA<sup>+</sup> cations. It constitutes the first example of Y zeolite crystallized in the presence of organic molecules and in the absence of Na<sup>+</sup> cations. Attempts to obtain similar materials with tetraethylammonium or tetrabutylammonium cations were unsuccessful, likely due to a mismatch between framework and organic charges. The [TPA<sup>+</sup>]-Y zeolite features octahedral crystals similar in size and shape to those of the initial HY with a slight increase of the mesoporous volume. Recrystallization was limited to HY zeolites with SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratios between ca. 30 and 60, solids obtained from precursors with SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> > 60 being systematically contaminated by <strong>MFI</strong> phase.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114045"},"PeriodicalIF":4.7,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975623","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 : 2026-03-15Epub Date: 2026-01-13DOI: 10.1016/j.micromeso.2026.114035
Haonan Shi, Luping Mao, He Wang, Yuyan Li, Junduo Sun, Shijian Zhou, Yan Kong
The selective hydroxylation of toluene to cresols remains a major challenge due to slow kinetics and competing over-oxidation pathways. Herein, we report a Cu/V-ZSM-5 catalyst with synergistic dual-site redox catalysis that achieves unprecedented reaction rates alongside high selectivity. Through in situ V incorporation and Cu impregnation, the catalyst features modulated pore structure and well-dispersed Cu+/Cu2+pecies stabilized by a reversible V4+/V5+ redox cycle. Critically, this unique configuration enables rapid H2O2 activation into hydroxyl radicals, the Cu+ species form Cu-OH new medium-to-strong acid sites, which drive regioselective electrophilic aromatic substitution and reduce the activation energy of the reaction, leading to 73.2 % cresol selectivity and 35.8 % yield within only 20 min—significantly outperforming conventional catalysts in both speed and efficiency. The system also exhibits low activation energy (39.9 kJ mol−1), excellent recyclability, and industrial potential. This work provides a new design principle for constructing high-performance redox catalysts that combine accelerated kinetics with precise selectivity in aromatic C-H functionalization.
{"title":"Synergistic dual-site redox catalysis in Cu/V-ZSM-5 enables rapid and selective toluene-to-cresol conversion","authors":"Haonan Shi, Luping Mao, He Wang, Yuyan Li, Junduo Sun, Shijian Zhou, Yan Kong","doi":"10.1016/j.micromeso.2026.114035","DOIUrl":"10.1016/j.micromeso.2026.114035","url":null,"abstract":"<div><div>The selective hydroxylation of toluene to cresols remains a major challenge due to slow kinetics and competing over-oxidation pathways. Herein, we report a Cu/V-ZSM-5 catalyst with synergistic dual-site redox catalysis that achieves unprecedented reaction rates alongside high selectivity. Through in situ V incorporation and Cu impregnation, the catalyst features modulated pore structure and well-dispersed Cu<sup>+</sup>/Cu<sup>2+</sup>pecies stabilized by a reversible V<sup>4+</sup>/V<sup>5+</sup> redox cycle. Critically, this unique configuration enables rapid H<sub>2</sub>O<sub>2</sub> activation into hydroxyl radicals, the Cu<sup>+</sup> species form Cu-OH new medium-to-strong acid sites, which drive regioselective electrophilic aromatic substitution and reduce the activation energy of the reaction, leading to 73.2 % cresol selectivity and 35.8 % yield within only 20 min—significantly outperforming conventional catalysts in both speed and efficiency. The system also exhibits low activation energy (39.9 kJ mol<sup>−1</sup>), excellent recyclability, and industrial potential. This work provides a new design principle for constructing high-performance redox catalysts that combine accelerated kinetics with precise selectivity in aromatic C-H functionalization.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114035"},"PeriodicalIF":4.7,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975624","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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