Pub Date : 2025-10-22DOI: 10.1016/j.micromeso.2025.113898
Taeyi Nam, Shunsaku Yasumura, Masaru Ogura
In this study, we investigate the Cs+ ion-exchange behavior of eight zeolites (K-A, Na-A, Ca-A, Na-X, Na-Y, Na-mordenite, Na-ZSM-5, and Na-SSZ-13) with varying framework structures, SiO2/Al2O3 ratios, and Brønsted acidity. Experimental results demonstrate that Na-type zeolites undergo a 1:1 ion-exchange reaction with Cs+. Additionally, Na-type zeolites exhibited significantly higher Cs+ exchange capacities compared to K-type and Ca-type zeolites. Zeolites containing 8-membered rings (8 MR) and those with high SiO2/Al2O3 ratios showed enhanced Cs + ion-exchange selectivity. Brønsted acidity significantly promoted Cs+ exchange in Na-mordenite and Na-ZSM-5, but had little effect on LTA and FAU. These findings clarify the structural and chemical factors influencing Cs+ ion-exchange and provide valuable insights for designing optimized zeolites for radioactive Cs+ removal.
{"title":"Comparative study on Cs+ ion-exchange behavior in zeolites with different framework structures and compositional characteristics","authors":"Taeyi Nam, Shunsaku Yasumura, Masaru Ogura","doi":"10.1016/j.micromeso.2025.113898","DOIUrl":"10.1016/j.micromeso.2025.113898","url":null,"abstract":"<div><div>In this study, we investigate the Cs<sup>+</sup> ion-exchange behavior of eight zeolites (K-A, Na-A, Ca-A, Na-X, Na-Y, Na-mordenite, Na-ZSM-5, and Na-SSZ-13) with varying framework structures, SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratios, and Brønsted acidity. Experimental results demonstrate that Na-type zeolites undergo a 1:1 ion-exchange reaction with Cs<sup>+</sup>. Additionally, Na-type zeolites exhibited significantly higher Cs<sup>+</sup> exchange capacities compared to K-type and Ca-type zeolites. Zeolites containing 8-membered rings (8 MR) and those with high SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> ratios showed enhanced Cs <sup>+</sup> ion-exchange selectivity. Brønsted acidity significantly promoted Cs<sup>+</sup> exchange in Na-mordenite and Na-ZSM-5, but had little effect on LTA and FAU. These findings clarify the structural and chemical factors influencing Cs<sup>+</sup> ion-exchange and provide valuable insights for designing optimized zeolites for radioactive Cs<sup>+</sup> removal.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113898"},"PeriodicalIF":4.7,"publicationDate":"2025-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145359751","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-21DOI: 10.1016/j.micromeso.2025.113902
K.J.B. Alloko , L. Cantrel , J. Denis , T. Loiseau , X. Deschanels , J. Causse , A. Moissette , C. Volkringer , A. Grégoire
This study investigates the property of Metal-Organic Frameworks (MOFs) grafted with Prussian blue analogs (PBA) for the efficient removal of Cs+ ions from aqueous solutions. MIL-101(Cr)-SO3H-PBA material was synthesized using a two-step process: hydrothermal reaction between monosodium 2-sulfoterephthalic acid (BDC-SO3Na) and chromium oxide (CrO3) to produce MIL-101(Cr)-SO3H, followed by grafting with CuK2[Fe(CN)6] (PBA). Both materials were characterized using XRD, IR, N2 sorption and Raman spectroscopy. The results confirmed the conservation of MOF porosity after functionalization and the successful incorporation of PBA. Batch adsorption experiments were conducted to evaluate Cs + removal performance of the adsorbents. The study examined contact time (up to 1440 min), pH (2, 7 and 11), initial Cs+ concentration (from 9 ppb to 1800 ppm) and competing ions. The resistance of the porous solids under drastic conditions involving gamma radiation (from 0.5 MGy up to10 MGy) was also investigated.
MI-101(Cr)-SO3H-PBA exhibited a maximum Cs + adsorption capacity of 242 mg.gMOF−1, compared to 161 mg.gMOF−1 for pristine MIL-101(Cr)-SO3H and showed high selectivity toward Cs+ in the presence of competing ions (Na+, K+, Mg2+, Ca2+, Sr2+). MI-101(Cr)-SO3H-PBA also demonstrates remarkable stability under radiation and alkaline conditions, maintaining 95 % efficiency, whereas the performance of pristine MIL-101(Cr)-SO3H material decreased significantly (7.5-fold decrease).
{"title":"Prussian blue functionalized MIL-101(Cr)-SO3H for Cs+ ion capture for the management of contaminated water","authors":"K.J.B. Alloko , L. Cantrel , J. Denis , T. Loiseau , X. Deschanels , J. Causse , A. Moissette , C. Volkringer , A. Grégoire","doi":"10.1016/j.micromeso.2025.113902","DOIUrl":"10.1016/j.micromeso.2025.113902","url":null,"abstract":"<div><div>This study investigates the property of Metal-Organic Frameworks (MOFs) grafted with Prussian blue analogs (PBA) for the efficient removal of Cs<sup>+</sup> ions from aqueous solutions. MIL-101(Cr)-SO<sub>3</sub>H-PBA material was synthesized using a two-step process: hydrothermal reaction between monosodium 2-sulfoterephthalic acid (BDC-SO<sub>3</sub>Na) and chromium oxide (CrO<sub>3</sub>) to produce MIL-101(Cr)-SO<sub>3</sub>H, followed by grafting with CuK<sub>2</sub>[Fe(CN)<sub>6</sub>] (PBA). Both materials were characterized using XRD, IR, N<sub>2</sub> sorption and Raman spectroscopy. The results confirmed the conservation of MOF porosity after functionalization and the successful incorporation of PBA. Batch adsorption experiments were conducted to evaluate Cs <sup>+</sup> removal performance of the adsorbents. The study examined contact time (up to 1440 min), pH (2, 7 and 11), initial Cs<sup>+</sup> concentration (from 9 ppb to 1800 ppm) and competing ions. The resistance of the porous solids under drastic conditions involving gamma radiation (from 0.5 MGy up to10 MGy) was also investigated.</div><div>MI-101(Cr)-SO<sub>3</sub>H-PBA exhibited a maximum Cs <sup>+</sup> adsorption capacity of 242 mg.g<sub>MOF</sub><sup>−1</sup>, compared to 161 mg.g<sub>MOF</sub><sup>−1</sup> for pristine MIL-101(Cr)-SO<sub>3</sub>H and showed high selectivity toward Cs<sup>+</sup> in the presence of competing ions (Na<sup>+</sup>, K<sup>+</sup>, Mg<sup>2+</sup>, Ca<sup>2+</sup>, Sr<sup>2+</sup>). MI-101(Cr)-SO<sub>3</sub>H-PBA also demonstrates remarkable stability under radiation and alkaline conditions, maintaining 95 % efficiency, whereas the performance of pristine MIL-101(Cr)-SO<sub>3</sub>H material decreased significantly (7.5-fold decrease).</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113902"},"PeriodicalIF":4.7,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-21DOI: 10.1016/j.micromeso.2025.113899
Jaeyul Kim , Sunkyu Kim , Seungwan Seo , Raul F. Lobo , Jeffrey D. Rimer
Gallium nitride (GaN) has gained attention owing to its discovery as a thermal catalyst for non-oxidative aromatization of alkanes. Here, we discuss a new in situ method for generating extra-framework GaN encapsulated within the small pores of a Ga-chabazite (or Ga-CHA) zeolite. This is accomplished by the concerted demetallation of framework Ga in the presence of a nitrogen source (e.g., NH3 gas) at high temperature. This method involves nitridation through the decomposition of ammonia with concomitant extraction of framework gallium, forming GaN clusters within the cha cages. This approach avoids post-synthesis impregnation with GaN particles, which is challenging due to steric effects imposed by small-pore zeolites. GaN formation was validated by: (1) a visible shift in the color of extracted powders from white (H-Ga-CHA) to yellow ([GaN]-Ga-CHA), intensifying with increases in Ga content; (2) powder X-ray diffraction (PXRD), which confirmed peak shifts of framework Ga to those of GaN after treatment with ammonia; and (3) X-ray photoelectron spectroscopy (XPS). A series of [GaN]-Ga-CHA catalysts were prepared with different Ga content and were assessed in the ethane dehydrogenation (EDH) reaction. The parent sample, H-Ga-CHA, containing predominantly framework Ga, exhibits low activity. Conversely, the in situ generation of [Ga]-Ga-CHA containing extra-framework GaN exhibits higher initial rates of ethylene formation. Collectively, this study is a proof of principle for the method of scavenging metals in zeolites frameworks to generate multifunctional catalysts in situ, thereby circumventing the difficulties associated with encapsulating large active sites in small pores of zeolite catalysts.
{"title":"Formation of GaN in chabazite by scavenging framework gallium","authors":"Jaeyul Kim , Sunkyu Kim , Seungwan Seo , Raul F. Lobo , Jeffrey D. Rimer","doi":"10.1016/j.micromeso.2025.113899","DOIUrl":"10.1016/j.micromeso.2025.113899","url":null,"abstract":"<div><div>Gallium nitride (GaN) has gained attention owing to its discovery as a thermal catalyst for non-oxidative aromatization of alkanes. Here, we discuss a new <em>in situ</em> method for generating extra-framework GaN encapsulated within the small pores of a Ga-chabazite (or Ga-CHA) zeolite. This is accomplished by the concerted demetallation of framework Ga in the presence of a nitrogen source (e.g., NH<sub>3</sub> gas) at high temperature. This method involves nitridation through the decomposition of ammonia with concomitant extraction of framework gallium, forming GaN clusters within the <em>cha</em> cages. This approach avoids post-synthesis impregnation with GaN particles, which is challenging due to steric effects imposed by small-pore zeolites. GaN formation was validated by: (1) a visible shift in the color of extracted powders from white (H-Ga-CHA) to yellow ([GaN]-Ga-CHA), intensifying with increases in Ga content; (2) powder X-ray diffraction (PXRD), which confirmed peak shifts of framework Ga to those of GaN after treatment with ammonia; and (3) X-ray photoelectron spectroscopy (XPS). A series of [GaN]-Ga-CHA catalysts were prepared with different Ga content and were assessed in the ethane dehydrogenation (EDH) reaction. The parent sample, H-Ga-CHA, containing predominantly framework Ga, exhibits low activity. Conversely, the <em>in situ</em> generation of [Ga]-Ga-CHA containing extra-framework GaN exhibits higher initial rates of ethylene formation. Collectively, this study is a proof of principle for the method of scavenging metals in zeolites frameworks to generate multifunctional catalysts <em>in situ</em>, thereby circumventing the difficulties associated with encapsulating large active sites in small pores of zeolite catalysts.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113899"},"PeriodicalIF":4.7,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145425234","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-19DOI: 10.1016/j.micromeso.2025.113900
Peng Cheng , Guanzuo Liu , Li Ma , Binhao Yang , Xin You , Shuo Qi , Hongdan Zhang
In this work, we prepared hollow HZSM-5 encapsulating Pt nanoparticles catalysts uniformly covered with highly dispersed La2O3, which were applied to the catalytic cracking of iso-butane. The hollow structures reduced the possibility of secondary cracking of propylene products and improved the stability of the catalysts. More importantly, the synergistic effect of Pt nanoparticles and La2O3 further increased the selectivity of propylene in the products. The as-synthesized catalysts in terms of crystallinity, morphology, porosity, acid strength and distribution, and metal state were investigated in detail by a series of physicochemical characterizations. Pt nanoparticles promoted the synergistic dehydrogenation and cracking effect for iso-butane by activating C-C bonds and C-H bonds. The addition of La significantly affected the amounts of acid sites and acid type of catalysts, thereby increasing the propylene to ethylene (P/E) ratio of products in the catalytic cracking of iso-butane. The P/E ratio over Pt@Hol-HZSM-5-9 %La was 1.64, which was 2.34 times and 1.62 times over Pt@Hol-HZSM-5 and Hol-HZSM-5, respectively. Moreover, the hollow structures shortened the diffusion path of products and intermediates, and reduced the probability of hydrogen transfer reactions, which increased the selectivity of propylene and reduced the coke generation.
{"title":"La2O3 and Pt modified hollow ZSM-5 improving catalytic performance for iso-butane cracking","authors":"Peng Cheng , Guanzuo Liu , Li Ma , Binhao Yang , Xin You , Shuo Qi , Hongdan Zhang","doi":"10.1016/j.micromeso.2025.113900","DOIUrl":"10.1016/j.micromeso.2025.113900","url":null,"abstract":"<div><div>In this work, we prepared hollow HZSM-5 encapsulating Pt nanoparticles catalysts uniformly covered with highly dispersed La<sub>2</sub>O<sub>3</sub>, which were applied to the catalytic cracking of iso-butane. The hollow structures reduced the possibility of secondary cracking of propylene products and improved the stability of the catalysts. More importantly, the synergistic effect of Pt nanoparticles and La<sub>2</sub>O<sub>3</sub> further increased the selectivity of propylene in the products. The as-synthesized catalysts in terms of crystallinity, morphology, porosity, acid strength and distribution, and metal state were investigated in detail by a series of physicochemical characterizations. Pt nanoparticles promoted the synergistic dehydrogenation and cracking effect for iso-butane by activating C-C bonds and C-H bonds. The addition of La significantly affected the amounts of acid sites and acid type of catalysts, thereby increasing the propylene to ethylene (P/E) ratio of products in the catalytic cracking of iso-butane. The P/E ratio over Pt@Hol-HZSM-5-9 %La was 1.64, which was 2.34 times and 1.62 times over Pt@Hol-HZSM-5 and Hol-HZSM-5, respectively. Moreover, the hollow structures shortened the diffusion path of products and intermediates, and reduced the probability of hydrogen transfer reactions, which increased the selectivity of propylene and reduced the coke generation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113900"},"PeriodicalIF":4.7,"publicationDate":"2025-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145334223","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}
Zeolites, a cornerstone of the diverse porous framework materials and heterogeneous catalysis, continues to provide solutions for challenging organic transformations. Despite the tremendous advancements, still there remains room for extending the catalytic applications of zeolitic materials. Here we show the catalytic efficacy of silver exchanged zeolite-13X without the requirement of external base for the chemical fixation of carbon dioxide with propargylic alcohol derivatives (up to 99 %) at room temperature and atmospheric pressure conditions. Extensive characterization including Auger parameter discloses the presence of silver oxide in the zeolite environment. The experimental and NMR studies clearly depicts the synergistic role of catalyst and additive towards the formation of α-alkylidene cyclic carbonate. The choice of zeolite and solvent plays a crucial role in the catalytic chemical fixation of CO2 with propargylic alcohol derivatives.
{"title":"Silver species in the zeolite zone: Implications on catalytic fixation of CO2 with propargylic alcohol derivatives and mechanistic investigations","authors":"Manas Barik , Brijesh Patel , Shilpa Dabas , Parul Rathour , T.G. Ajithkumar , Palani S. Subramanian , Saravanan Subramanian","doi":"10.1016/j.micromeso.2025.113897","DOIUrl":"10.1016/j.micromeso.2025.113897","url":null,"abstract":"<div><div>Zeolites, a cornerstone of the diverse porous framework materials and heterogeneous catalysis, continues to provide solutions for challenging organic transformations. Despite the tremendous advancements, still there remains room for extending the catalytic applications of zeolitic materials. Here we show the catalytic efficacy of silver exchanged zeolite-13X without the requirement of external base for the chemical fixation of carbon dioxide with propargylic alcohol derivatives (up to 99 %) at room temperature and atmospheric pressure conditions. Extensive characterization including Auger parameter discloses the presence of silver oxide in the zeolite environment. The experimental and NMR studies clearly depicts the synergistic role of catalyst and additive towards the formation of α-alkylidene cyclic carbonate. The choice of zeolite and solvent plays a crucial role in the catalytic chemical fixation of CO<sub>2</sub> with propargylic alcohol derivatives.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113897"},"PeriodicalIF":4.7,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145359749","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-10DOI: 10.1016/j.micromeso.2025.113896
Anna Olejnik , Aleksander Ejsmont , Suhas , Monika Chaudhary , Anna Olejnik , Inderjeet Tyagi , Joanna Goscianska
Controlled drug delivery systems are increasingly investigated to optimize therapeutic efficacy and reduce the dosing frequency of antihypertensive agents such as losartan potassium. Ordered mesoporous carbons (OMCs), featuring uniform pore architecture, high loading capacity, and tunable surface chemistry, offer a versatile platform for the incorporation of drugs, while maintaining structural stability under physiological conditions. In this study, OMCs templated from KIT-6 were synthesized and functionalized with either urea or cetyltrimethylammonium bromide to enhance drug–carrier interactions. The functionalization route was modulated using different solvents to alter surface chemistry and partially preserve porosity. Structural and chemical characterization confirmed that solvent polarity influenced both the extent and location of modification: alcohols promoted internal grafting, whereas aqueous systems favored surface-level alteration. Functionalization significantly affected the pH responsiveness of the materials, shifting the zeta potential from consistently negative (pristine carbon) to a tunable range: slightly positive in acidic media, near-neutral at pH 7.2, and highly negative at basic pH. The highest adsorption capacity (280 mg/g) towards losartan potassium was achieved for carbon modified with urea in ethanol. At the same time, the greatest drug release (98.3 %) under near-neutral conditions occurred for the sample treated with surfactant in isopropanol. The thermodynamic analysis confirmed spontaneous physisorption across all materials, and release studies demonstrated clear pH-dependent desorption behavior. Cytotoxicity assays on Caco-2 and HIEC-2 cell lines further verified that the functionalized OMCs are non-toxic under biologically relevant conditions, underscoring their safety for oral administration. These findings support the use of surface-engineered mesoporous carbons as responsive drug carriers.
{"title":"High-capacity adsorption and pH-responsive release of an antihypertensive drug via urea- and cetyltrimethylammonium bromide-functionalized mesoporous carbons","authors":"Anna Olejnik , Aleksander Ejsmont , Suhas , Monika Chaudhary , Anna Olejnik , Inderjeet Tyagi , Joanna Goscianska","doi":"10.1016/j.micromeso.2025.113896","DOIUrl":"10.1016/j.micromeso.2025.113896","url":null,"abstract":"<div><div>Controlled drug delivery systems are increasingly investigated to optimize therapeutic efficacy and reduce the dosing frequency of antihypertensive agents such as losartan potassium. Ordered mesoporous carbons (OMCs), featuring uniform pore architecture, high loading capacity, and tunable surface chemistry, offer a versatile platform for the incorporation of drugs, while maintaining structural stability under physiological conditions. In this study, OMCs templated from KIT-6 were synthesized and functionalized with either urea or cetyltrimethylammonium bromide to enhance drug–carrier interactions. The functionalization route was modulated using different solvents to alter surface chemistry and partially preserve porosity. Structural and chemical characterization confirmed that solvent polarity influenced both the extent and location of modification: alcohols promoted internal grafting, whereas aqueous systems favored surface-level alteration. Functionalization significantly affected the pH responsiveness of the materials, shifting the zeta potential from consistently negative (pristine carbon) to a tunable range: slightly positive in acidic media, near-neutral at pH 7.2, and highly negative at basic pH. The highest adsorption capacity (280 mg/g) towards losartan potassium was achieved for carbon modified with urea in ethanol. At the same time, the greatest drug release (98.3 %) under near-neutral conditions occurred for the sample treated with surfactant in isopropanol. The thermodynamic analysis confirmed spontaneous physisorption across all materials, and release studies demonstrated clear pH-dependent desorption behavior. Cytotoxicity assays on Caco-2 and HIEC-2 cell lines further verified that the functionalized OMCs are non-toxic under biologically relevant conditions, underscoring their safety for oral administration. These findings support the use of surface-engineered mesoporous carbons as responsive drug carriers.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113896"},"PeriodicalIF":4.7,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145334220","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-10DOI: 10.1016/j.micromeso.2025.113894
Megha Mohan , Anu M. Kantola , Sanna Komulainen , Juha Vaara , Ulla Gro Nielsen , Ville-Veikko Telkki
Layered double hydroxides (LDHs) are promising materials for ion exchange, catalytic and electrochemical applications. Typically, the materials are composed of agglomerates of LDH platelets with complex mesoporous and macroporous networks within and between the particles. These networks control the diffusion of substrates and thereby influence the kinetics of, e.g., anion exchange and catalytic properties. Here, we use 129Xe NMR spectroscopy, field-emission scanning electron microscopy and N2 sorption to study porous structures and gas transport in Mg2-xNixAl layered double hydroxides. N2 adsorption analysis shows that mesopore and macropore surface area and pore volume increase with increasing Ni content (x). 129Xe NMR spectra indicate that the mean pore diameter decreases from 28 ± 5 to 16 ± 2 nm and the effective heat of adsorption increases from 8.7 ± 0.4 to 9.4 ± 0.2 kJ/mol, when x increases from 2/3 to 5/3.129Xe exchange NMR spectroscopy reveals that the exchange rate of Xe between mesopore and macropore sites for the x = 0 sample is high, about 4700 s−1. The 129Xe T1 relaxation time appears to be a very sensitive probe for paramagnetic Ni, whereas the T2 relaxation time predominantly reflects exchange dynamics. Overall, the 129Xe NMR analysis, complemented with other methods, provides detailed information about the properties of LDHs on length scale from atomic to bulk thereby improving our understanding of LDH properties and performance.
{"title":"129Xe NMR spectroscopy of paramagnetic Mg2-xNixAl layered double hydroxides","authors":"Megha Mohan , Anu M. Kantola , Sanna Komulainen , Juha Vaara , Ulla Gro Nielsen , Ville-Veikko Telkki","doi":"10.1016/j.micromeso.2025.113894","DOIUrl":"10.1016/j.micromeso.2025.113894","url":null,"abstract":"<div><div>Layered double hydroxides (LDHs) are promising materials for ion exchange, catalytic and electrochemical applications. Typically, the materials are composed of agglomerates of LDH platelets with complex mesoporous and macroporous networks within and between the particles. These networks control the diffusion of substrates and thereby influence the kinetics of, <em>e.g.</em>, anion exchange and catalytic properties. Here, we use <sup>129</sup>Xe NMR spectroscopy, field-emission scanning electron microscopy and N<sub>2</sub> sorption to study porous structures and gas transport in Mg<sub>2-<em>x</em></sub>Ni<sub><em>x</em></sub>Al layered double hydroxides. N<sub>2</sub> adsorption analysis shows that mesopore and macropore surface area and pore volume increase with increasing Ni content (<em>x</em>). <sup>129</sup>Xe NMR spectra indicate that the mean pore diameter decreases from 28 ± 5 to 16 ± 2 nm and the effective heat of adsorption increases from 8.7 ± 0.4 to 9.4 ± 0.2 kJ/mol, when <em>x</em> increases from 2/3 to 5/3.<sup>129</sup>Xe exchange NMR spectroscopy reveals that the exchange rate of Xe between mesopore and macropore sites for the <em>x</em> = 0 sample is high, about 4700 s<sup>−1</sup>. The <sup>129</sup>Xe <em>T</em><sub>1</sub> relaxation time appears to be a very sensitive probe for paramagnetic Ni, whereas the <em>T</em><sub>2</sub> relaxation time predominantly reflects exchange dynamics. Overall, the <sup>129</sup>Xe NMR analysis, complemented with other methods, provides detailed information about the properties of LDHs on length scale from atomic to bulk thereby improving our understanding of LDH properties and performance.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113894"},"PeriodicalIF":4.7,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145334250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-10DOI: 10.1016/j.micromeso.2025.113891
Nirupama Parida , Paresh Kumar Mohanty , Sharada Shrinivas Pati , Sushanta K. Badamali
Mesoporous materials with open frameworks, tunable pore sizes, high surface areas, and excellent thermal stability are well-suited for applications as heterogeneous catalysts. In this study, the insertion of Ti (IV) into the mesoporous frameworks of SBA-1 and MCM-48 and assessment of their efficacy for the selective oxidation of veratryl alcohol, under mild reaction conditions, is reported. XRD analysis of TiSBA-1 and TiMCM-48 confirmed the formation of cubic, 3-D mesoporous structures. HRTEM revealed a uniform and ordered pore structure having ∼21 and 35 Å diameters for TiSBA-1 and TiMCM-48, respectively. FESEM demonstrated the regular-shaped spherical morphology for TiSBA-1 and TiMCM-48, having dimensions of ∼0.71 and 0.36 μm, respectively. Nitrogen adsorption-desorption analysis revealed a BET surface area of 1250 m2 g−1 for TiSBA-1 and 217 m2 g−1 for TiMCM-48, with pore diameters of ∼21 and 35 Å, respectively. The mesoporous nature of TiSBA-1 and TiMCM-48 was further supported by TGA studies. DRUV-VIS analyses revealed the occurrence of ligand-to-metal charge transfer bands [O→Ti (IV)] at 220 nm, suggesting Ti–O–Si linkages within a tetrahedral silicate framework. FTIR studies supported the existence of Ti–O–Si bonds in TiSBA-1 and TiMCM-48. The presence of the TiO2 nanophase in TiMCM-48 was evidenced by Raman studies. Catalytic reactions conducted with TiMCM-48 along with TBHP yielded greater than 70 % of substrate conversion and 99 % selectivity towards veratraldehyde. On the contrary, TiSBA-1 resulted in very high veratryl alcohol conversion; however, both veratraldehyde and veratric acid were produced.
介孔材料具有开放的框架、可调节的孔径、高表面积和优异的热稳定性，非常适合作为多相催化剂的应用。在本研究中，将Ti （IV）插入到SBA-1和MCM-48的介孔框架中，并评估了它们在温和反应条件下选择性氧化戊四醇的效果。对TiSBA-1和TiMCM-48的XRD分析证实了三维立体介孔结构的形成。HRTEM显示，TiSBA-1和TiMCM-48的孔隙结构均匀有序，直径分别为~ 21和35 Å。FESEM显示了TiSBA-1和TiMCM-48的规则球形形貌，尺寸分别为~ 0.71和0.36 μm。氮吸附-解吸分析显示，TiSBA-1的BET表面积为1250 m2 g -1， TiMCM-48的BET表面积为217 m2 g -1，孔径分别为~ 21和35 Å。TGA研究进一步证实了TiSBA-1和TiMCM-48的介孔性质。DRUV-VIS分析显示，在220 nm处存在配体到金属的电荷转移带[O→Ti (IV)]，表明在四面体硅酸盐框架内存在Ti - O - si键。FTIR研究支持TiSBA-1和TiMCM-48中存在Ti-O-Si键。Raman实验证实了TiMCM-48中存在TiO2纳米相。用TiMCM-48和thbhp进行的催化反应产生了大于70%的底物转化率和99%的对戊醛的选择性。相反，TiSBA-1导致非常高的戊戊醇转化率；然而，戊二醛和戊二酸都产生了。
{"title":"Selective oxidation of lignin model non-phenolic monomer-veratryl alcohol over titanium containing mesoporous SBA-1 and MCM-48 catalysts","authors":"Nirupama Parida , Paresh Kumar Mohanty , Sharada Shrinivas Pati , Sushanta K. Badamali","doi":"10.1016/j.micromeso.2025.113891","DOIUrl":"10.1016/j.micromeso.2025.113891","url":null,"abstract":"<div><div>Mesoporous materials with open frameworks, tunable pore sizes, high surface areas, and excellent thermal stability are well-suited for applications as heterogeneous catalysts. In this study, the insertion of Ti (IV) into the mesoporous frameworks of SBA-1 and MCM-48 and assessment of their efficacy for the selective oxidation of veratryl alcohol, under mild reaction conditions, is reported. XRD analysis of TiSBA-1 and TiMCM-48 confirmed the formation of cubic, 3-D mesoporous structures. HRTEM revealed a uniform and ordered pore structure having ∼21 and 35 Å diameters for TiSBA-1 and TiMCM-48, respectively. FESEM demonstrated the regular-shaped spherical morphology for TiSBA-1 and TiMCM-48, having dimensions of ∼0.71 and 0.36 μm, respectively. Nitrogen adsorption-desorption analysis revealed a BET surface area of 1250 m<sup>2</sup> g<sup>−1</sup> for TiSBA-1 and 217 m<sup>2</sup> g<sup>−1</sup> for TiMCM-48, with pore diameters of ∼21 and 35 Å, respectively. The mesoporous nature of TiSBA-1 and TiMCM-48 was further supported by TGA studies. DRUV-VIS analyses revealed the occurrence of ligand-to-metal charge transfer bands [O→Ti (IV)] at 220 nm, suggesting Ti–O–Si linkages within a tetrahedral silicate framework. FTIR studies supported the existence of Ti–O–Si bonds in TiSBA-1 and TiMCM-48. The presence of the TiO<sub>2</sub> nanophase in TiMCM-48 was evidenced by Raman studies. Catalytic reactions conducted with TiMCM-48 along with TBHP yielded greater than 70 % of substrate conversion and 99 % selectivity towards veratraldehyde. On the contrary, TiSBA-1 resulted in very high veratryl alcohol conversion; however, both veratraldehyde and veratric acid were produced.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113891"},"PeriodicalIF":4.7,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145334222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-09DOI: 10.1016/j.micromeso.2025.113893
Jingjing Li, Lu Tong, Miaomiao He, Shunze Cao, Juan Wang, Xiaoming Liao, Zhongbing Huang, Guangfu Yin
The integration of photothermal therapy and ultrasound imaging achieves superior curative effect via tumor location and treatment navigation, but its availability is greatly reduced due to premature leakage and unintended vaporization of the used liquid ultrasound contrast agent (UCA) before enriching into tumor stroma. In this study, a novel Prussian Blue (PB) nano-system wrapped in mesoporous silica (mSiO2) and loaded with liquid perfluorohexane (PFH) was proposed as both the photothermal agent (PTA) and the UCA to achieve enhanced ultrasound imaging and precise tumor photothermal therapy. Primarily, the volatile PFH confined within the mesoporous channels of mSiO2 was effectively stabilized by mesoporous framework through confinement effect, interface binding effect, and Kelvin effect, minimizing leakage and vaporization during in vivo transport while enhancing its enrichment in tumor through enhanced permeability and retention (EPR) effect. Moreover, the synthesized PB@mSiO2-PFH exhibited excellent photothermal conversion under near-infrared (NIR) irradiation, inducing hyperthermic tumor cell death. Furthermore, the PFH loaded in mSiO2 underwent a liquid-to-gas phase transition under the triggering of ultrasound and/or local hyperthermia at the tumor site, enhancing the clarity and contrast of the ultrasound images of tumor due to the significant acoustic impedance difference between the generated microbubbles and surrounding tissues. This enhanced ultrasound imaging could real-timely locate tumor areas and accurately guide the NIR irradiation, thereby significantly improving the treatment accuracy and safety.
{"title":"Mesoporous silica-wrapped prussian blue for integration of tumor photothermal therapy and ultrasound imaging enhancement","authors":"Jingjing Li, Lu Tong, Miaomiao He, Shunze Cao, Juan Wang, Xiaoming Liao, Zhongbing Huang, Guangfu Yin","doi":"10.1016/j.micromeso.2025.113893","DOIUrl":"10.1016/j.micromeso.2025.113893","url":null,"abstract":"<div><div>The integration of photothermal therapy and ultrasound imaging achieves superior curative effect via tumor location and treatment navigation, but its availability is greatly reduced due to premature leakage and unintended vaporization of the used liquid ultrasound contrast agent (UCA) before enriching into tumor stroma. In this study, a novel Prussian Blue (PB) nano-system wrapped in mesoporous silica (<em>m</em>SiO<sub>2</sub>) and loaded with liquid perfluorohexane (PFH) was proposed as both the photothermal agent (PTA) and the UCA to achieve enhanced ultrasound imaging and precise tumor photothermal therapy. Primarily, the volatile PFH confined within the mesoporous channels of <em>m</em>SiO<sub>2</sub> was effectively stabilized by mesoporous framework through confinement effect, interface binding effect, and Kelvin effect, minimizing leakage and vaporization during <em>in vivo</em> transport while enhancing its enrichment in tumor through enhanced permeability and retention (EPR) effect. Moreover, the synthesized PB@<em>m</em>SiO<sub>2</sub>-PFH exhibited excellent photothermal conversion under near-infrared (NIR) irradiation, inducing hyperthermic tumor cell death. Furthermore, the PFH loaded in <em>m</em>SiO<sub>2</sub> underwent a liquid-to-gas phase transition under the triggering of ultrasound and/or local hyperthermia at the tumor site, enhancing the clarity and contrast of the ultrasound images of tumor due to the significant acoustic impedance difference between the generated microbubbles and surrounding tissues. This enhanced ultrasound imaging could real-timely locate tumor areas and accurately guide the NIR irradiation, thereby significantly improving the treatment accuracy and safety.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113893"},"PeriodicalIF":4.7,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145334221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-08DOI: 10.1016/j.micromeso.2025.113895
Hong-Ying Xia , Jie Li , Ying-Tong Ye , Ai-Zheng Chen , Shi-Bin Wang , Ranjith Kumar Kankala
Engineering inorganic nanoarchitectonics has garnered enormous interest in improving their morphological, physicochemical, and performance attributes. Despite the success in doping various metals (transition and non-transition species), the selection of appropriate metals and their interactions within the inorganic siliceous pool, as well as the required processing parameters, leading to morphologically altered frameworks, remains unexplored. In this study, we demonstrate the fabrication of innovative mesoporous silica nanoarchitectures (MSNs) by doping various metal species and their combinations at varied ratios in the siliceous pool. While considering the different elements with antibacterial efficacy and suitability for incorporation into the siliceous pool, appropriate metals (Ca, Zn, and Y) were optimally selected, resulting in a morphologically altered structure and ultimately exhibiting a comma/cashew/vibrio-shaped CaZnY-doped MSNs. Further, these cashew-shaped CaZnY-MSNs were successfully characterized using various techniques. These doped elements lead to the formation of large pore sizes in MSNs, providing effective contact sites. The designed CaZnY-MSNs showed excellent antibacterial properties against methicillin-resistant Staphylococcus aureus (MRSA). Among them, the released Zn2+ and Y3+ ions could effectively bind to bacterial intracellular proteins, affecting the bacterial cell membrane function and leading to deformation of the bacterial cell membranes, with a tendency for bacterial cytoplasm leakage. In summary, we believe that these cashew-shaped, three-metal-doped MSNs as drug-like therapeutics will provide a novel approach for effective antibacterial treatment in pharmaceutics.
{"title":"Rerouting the siliceous framework with different metals to Vibrio/cashew-shaped mesoporous silica nanoparticles as drug-like architectures with antibacterial properties","authors":"Hong-Ying Xia , Jie Li , Ying-Tong Ye , Ai-Zheng Chen , Shi-Bin Wang , Ranjith Kumar Kankala","doi":"10.1016/j.micromeso.2025.113895","DOIUrl":"10.1016/j.micromeso.2025.113895","url":null,"abstract":"<div><div>Engineering inorganic nanoarchitectonics has garnered enormous interest in improving their morphological, physicochemical, and performance attributes. Despite the success in doping various metals (transition and non-transition species), the selection of appropriate metals and their interactions within the inorganic siliceous pool, as well as the required processing parameters, leading to morphologically altered frameworks, remains unexplored. In this study, we demonstrate the fabrication of innovative mesoporous silica nanoarchitectures (MSNs) by doping various metal species and their combinations at varied ratios in the siliceous pool. While considering the different elements with antibacterial efficacy and suitability for incorporation into the siliceous pool, appropriate metals (Ca, Zn, and Y) were optimally selected, resulting in a morphologically altered structure and ultimately exhibiting a comma/cashew/vibrio-shaped CaZnY-doped MSNs. Further, these cashew-shaped CaZnY-MSNs were successfully characterized using various techniques. These doped elements lead to the formation of large pore sizes in MSNs, providing effective contact sites. The designed CaZnY-MSNs showed excellent antibacterial properties against methicillin-resistant <em>Staphylococcus aureus</em> (<em>MRSA</em>). Among them, the released Zn<sup>2+</sup> and Y<sup>3+</sup> ions could effectively bind to bacterial intracellular proteins, affecting the bacterial cell membrane function and leading to deformation of the bacterial cell membranes, with a tendency for bacterial cytoplasm leakage. In summary, we believe that these cashew-shaped, three-metal-doped MSNs as drug-like therapeutics will provide a novel approach for effective antibacterial treatment in pharmaceutics.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"400 ","pages":"Article 113895"},"PeriodicalIF":4.7,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145334224","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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