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Adsorption behavior of low-concentration nitrous oxide on natural mordenite zeolite
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-02-17 DOI: 10.1016/j.micromeso.2025.113550
Saeko Yamaguchi , Peidong Hu , Hanlong Ya , Peipei Xiao , Ayako Nakata , Tsuyoshi Miyazaki , Yoshitada Morikawa , Junko N. Kondo , Kotaro Tange , Kenichi Tonokura , Masanori Takemoto , Yasuo Yonezawa , Toshiyuki Yokoi , Kenta Iyoki , Tatsuya Okubo , Toru Wakihara
Nitrous oxide (N2O), the third most important greenhouse gas, is discharged from various anthropogenic sources and causes severe environmental problems. Herein, the natural mordenite zeolite is demonstrated to be an effective adsorbent to capture low-concentration N2O (below 30 ppm). An adsorption capacity of 0.076 mmol g−1 can be achieved at −7 °C with 1 ppm N2O in the dynamic adsorption test, 6.3 times as high as that at 25 °C. The density functional theory calculations reveal that the Ca-exchanged MOR-type zeolite has stronger interactions with N2O compared with the Na-exchanged one. However, as evidenced by the isosteric adsorption enthalpy analysis and the Fourier transform infrared spectroscopy, the natural mordenite zeolite with both Na+ and Ca2+, as well as the synthesized analogue, demonstrates stronger and distinctive interactions with trace N2O in comparison to the MOR-type zeolites with single kind of extra-framework cation. These results provide experimental and theoretical foundations for the establishment of efficient N2O removal system using well designed zeolite-based adsorbents under proper operating conditions.
{"title":"Adsorption behavior of low-concentration nitrous oxide on natural mordenite zeolite","authors":"Saeko Yamaguchi ,&nbsp;Peidong Hu ,&nbsp;Hanlong Ya ,&nbsp;Peipei Xiao ,&nbsp;Ayako Nakata ,&nbsp;Tsuyoshi Miyazaki ,&nbsp;Yoshitada Morikawa ,&nbsp;Junko N. Kondo ,&nbsp;Kotaro Tange ,&nbsp;Kenichi Tonokura ,&nbsp;Masanori Takemoto ,&nbsp;Yasuo Yonezawa ,&nbsp;Toshiyuki Yokoi ,&nbsp;Kenta Iyoki ,&nbsp;Tatsuya Okubo ,&nbsp;Toru Wakihara","doi":"10.1016/j.micromeso.2025.113550","DOIUrl":"10.1016/j.micromeso.2025.113550","url":null,"abstract":"<div><div>Nitrous oxide (N<sub>2</sub>O), the third most important greenhouse gas, is discharged from various anthropogenic sources and causes severe environmental problems. Herein, the natural mordenite zeolite is demonstrated to be an effective adsorbent to capture low-concentration N<sub>2</sub>O (below 30 ppm). An adsorption capacity of 0.076 mmol g<sup>−1</sup> can be achieved at −7 °C with 1 ppm N<sub>2</sub>O in the dynamic adsorption test, 6.3 times as high as that at 25 °C. The density functional theory calculations reveal that the Ca-exchanged MOR-type zeolite has stronger interactions with N<sub>2</sub>O compared with the Na-exchanged one. However, as evidenced by the isosteric adsorption enthalpy analysis and the Fourier transform infrared spectroscopy, the natural mordenite zeolite with both Na<sup>+</sup> and Ca<sup>2+</sup>, as well as the synthesized analogue, demonstrates stronger and distinctive interactions with trace N<sub>2</sub>O in comparison to the MOR-type zeolites with single kind of extra-framework cation. These results provide experimental and theoretical foundations for the establishment of efficient N<sub>2</sub>O removal system using well designed zeolite-based adsorbents under proper operating conditions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"388 ","pages":"Article 113550"},"PeriodicalIF":4.8,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143445734","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}
引用次数: 0
One-step synthesis of aluminum dross-derived MIL-53(Al) as an aniline adsorbent
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-02-15 DOI: 10.1016/j.micromeso.2025.113549
Ryota Yamane , Yuki Masuda , Satoshi Kobayashi , Hiroki Konno
Aluminum dross, an industrial waste product generated during the smelting and recycling of aluminum, is used in various industries; however, its application is limited. Metal–organic frameworks (MOFs), next-generation porous materials comprising metals and organic likers, offer tunable properties, including pore structure (shape and size), hydrophobicity, hydrophilicity, and stability, making them versatile for various applications. This study successfully achieved the one-step synthesis of MIL-53(Al), an MOF, using aluminum dross as a starting material for the first time. The dross-derived MIL-53(Al) exhibited high crystallinity, similar to that of conventional MIL-53(Al). It was further evaluated as an adsorbent for aniline, a compound widely used in chemical and pharmaceutical industries but harmful to human health and ecosystems. Liquid-phase adsorption experiments demonstrated that dross-derived MIL-53(Al) achieved an adsorption capacity similar to that of conventional MIL-53(Al), primarily owing to π‒π and hydrogen bonding interactions with aniline. The adsorption isotherm of dross-derived MIL-53(Al) conformed to the Langmuir model, indicating that the primary adsorption sites for aniline were its micropores. Furthermore, this MIL-53(Al) retained its adsorption capacity after up to four regeneration cycles using calcination. Thus, this study successfully synthesized MIL-53(Al) using aluminum dross as a precursor and demonstrated its potential effectiveness as a water purification agent.
{"title":"One-step synthesis of aluminum dross-derived MIL-53(Al) as an aniline adsorbent","authors":"Ryota Yamane ,&nbsp;Yuki Masuda ,&nbsp;Satoshi Kobayashi ,&nbsp;Hiroki Konno","doi":"10.1016/j.micromeso.2025.113549","DOIUrl":"10.1016/j.micromeso.2025.113549","url":null,"abstract":"<div><div>Aluminum dross, an industrial waste product generated during the smelting and recycling of aluminum, is used in various industries; however, its application is limited. Metal–organic frameworks (MOFs), next-generation porous materials comprising metals and organic likers, offer tunable properties, including pore structure (shape and size), hydrophobicity, hydrophilicity, and stability, making them versatile for various applications. This study successfully achieved the one-step synthesis of MIL-53(Al), an MOF, using aluminum dross as a starting material for the first time. The dross-derived MIL-53(Al) exhibited high crystallinity, similar to that of conventional MIL-53(Al). It was further evaluated as an adsorbent for aniline, a compound widely used in chemical and pharmaceutical industries but harmful to human health and ecosystems. Liquid-phase adsorption experiments demonstrated that dross-derived MIL-53(Al) achieved an adsorption capacity similar to that of conventional MIL-53(Al), primarily owing to π‒π and hydrogen bonding interactions with aniline. The adsorption isotherm of dross-derived MIL-53(Al) conformed to the Langmuir model, indicating that the primary adsorption sites for aniline were its micropores. Furthermore, this MIL-53(Al) retained its adsorption capacity after up to four regeneration cycles using calcination. Thus, this study successfully synthesized MIL-53(Al) using aluminum dross as a precursor and demonstrated its potential effectiveness as a water purification agent.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"388 ","pages":"Article 113549"},"PeriodicalIF":4.8,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143422317","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}
引用次数: 0
Effect of surfactant-induced porosity and acidity modification of MOF-808 catalyst on the glycerol acetylation reaction
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-02-12 DOI: 10.1016/j.micromeso.2025.113539
César A. Bravo-Sanabria , Leidy C. Solano-Delgado , Daniela Rosas-Ardila , Carolina Ardila-Suárez , Víctor G. Baldovino-Medrano , Gustavo E. Ramírez-Caballero
A promising approach for the catalytic acetylation of glycerol to produce high value-added chemicals such as diacetins (DAGs) and triacetin (TAG) is the use of acidic Metal-Organic Frameworks (MOFs). Particularly, MOF-808 has shown potential as catalyst for this reaction due to its tunable porosity and the ability to incorporate acid sites. Herein, we focused on modifying the porosity and acidity of MOF-808 to improve its catalytic performance in the acetylation of glycerol. Porosity changes were induced during the synthesis of MOF-808 by promoting the formation of larger pores using three different surfactants: cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and pluronic P123 (PLU), in combination with propionic acid as a modulator. Results showed that the proposed modifications add either mesoporosity; pores with widths larger than 2.0 nm, or macroporosity, i.e., pores with widths larger than 50.0 nm, when it is used surfactants, to the purely microporous MOF-808. On the other hand, the acidity of porosity enhanced MOF-808 was modified by a post-synthetic acid treatment with sulfuric acid. This treatment led to the incorporation of well dispersed sulfate groups into the MOF structure which did not experienced a strong loss of porosity. Catalytic experiments demonstrated that the sulfated MOF samples exhibited higher glycerol conversion if compared to the other samples, while the non-sulfated MOF modified with pluronic P123 showed the highest selectivity towards triacetin. This suggests that the improved accessibility provided by mesopores facilitates the sequential acetylation steps, particularly favoring the formation of triacetin as the final product.
{"title":"Effect of surfactant-induced porosity and acidity modification of MOF-808 catalyst on the glycerol acetylation reaction","authors":"César A. Bravo-Sanabria ,&nbsp;Leidy C. Solano-Delgado ,&nbsp;Daniela Rosas-Ardila ,&nbsp;Carolina Ardila-Suárez ,&nbsp;Víctor G. Baldovino-Medrano ,&nbsp;Gustavo E. Ramírez-Caballero","doi":"10.1016/j.micromeso.2025.113539","DOIUrl":"10.1016/j.micromeso.2025.113539","url":null,"abstract":"<div><div>A promising approach for the catalytic acetylation of glycerol to produce high value-added chemicals such as diacetins (DAGs) and triacetin (TAG) is the use of acidic Metal-Organic Frameworks (MOFs). Particularly, MOF-808 has shown potential as catalyst for this reaction due to its tunable porosity and the ability to incorporate acid sites. Herein, we focused on modifying the porosity and acidity of MOF-808 to improve its catalytic performance in the acetylation of glycerol. Porosity changes were induced during the synthesis of MOF-808 by promoting the formation of larger pores using three different surfactants: cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and pluronic P123 (PLU), in combination with propionic acid as a modulator. Results showed that the proposed modifications add either mesoporosity; pores with widths larger than 2.0 nm, or macroporosity, i.e., pores with widths larger than 50.0 nm, when it is used surfactants, to the purely microporous MOF-808. On the other hand, the acidity of porosity enhanced MOF-808 was modified by a post-synthetic acid treatment with sulfuric acid. This treatment led to the incorporation of well dispersed sulfate groups into the MOF structure which did not experienced a strong loss of porosity. Catalytic experiments demonstrated that the sulfated MOF samples exhibited higher glycerol conversion if compared to the other samples, while the non-sulfated MOF modified with pluronic P123 showed the highest selectivity towards triacetin. This suggests that the improved accessibility provided by mesopores facilitates the sequential acetylation steps, particularly favoring the formation of triacetin as the final product.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"388 ","pages":"Article 113539"},"PeriodicalIF":4.8,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143422234","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}
引用次数: 0
Synthesis of spherical mesoporous silica beads with tunable size, stiffness and porosity
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-02-06 DOI: 10.1016/j.micromeso.2025.113534
M. Milani , K. Ahmad , E. Cavalletti , C. Ligoure , L. Cipelletti , M. Kongkaew , P. Trens , L. Ramos
We present an innovative template-free water-based sol–gel method to produce uniform mesoporous silica beads of millimeter size, which have tunable size, stiffness and porosity, and could be used for adsorption applications. Our protocol exploits an in-situ enzymatic reaction to produce spherical beads of hydrogel from a charge-stabilized suspension of silica nanoparticles confined in a millimetric drop suspended in a non-miscible oil. Once the gelation step is complete, the spherical bead of gel is cleaned from oil and deposited onto a hydrophobic surface and let dry. Separating the gelation to the drying steps ensures a spatially uniform gel and allows us to perform a solvent exchange before drying. For all beads, we observe a crack-free drying process leading to the formation of stiff quasi-spherical beads with diameter in the range 1 to 5 mm and Young modulus in the range (0.12)GPa and narrow pore size distribution, centered around 10 to 25nm depending on the experimental conditions. Finally, to demonstrate the potentiality of these materials, we graft on the bead surface aminosilane molecules, and quantify their CO2 adsorption efficiency. Overall, the production method we have developed is simple, readily adaptable, and offers promising materials for adsorption, storage, catalysis and chromatography.
{"title":"Synthesis of spherical mesoporous silica beads with tunable size, stiffness and porosity","authors":"M. Milani ,&nbsp;K. Ahmad ,&nbsp;E. Cavalletti ,&nbsp;C. Ligoure ,&nbsp;L. Cipelletti ,&nbsp;M. Kongkaew ,&nbsp;P. Trens ,&nbsp;L. Ramos","doi":"10.1016/j.micromeso.2025.113534","DOIUrl":"10.1016/j.micromeso.2025.113534","url":null,"abstract":"<div><div>We present an innovative template-free water-based sol–gel method to produce uniform mesoporous silica beads of millimeter size, which have tunable size, stiffness and porosity, and could be used for adsorption applications. Our protocol exploits an in-situ enzymatic reaction to produce spherical beads of hydrogel from a charge-stabilized suspension of silica nanoparticles confined in a millimetric drop suspended in a non-miscible oil. Once the gelation step is complete, the spherical bead of gel is cleaned from oil and deposited onto a hydrophobic surface and let dry. Separating the gelation to the drying steps ensures a spatially uniform gel and allows us to perform a solvent exchange before drying. For all beads, we observe a crack-free drying process leading to the formation of stiff quasi-spherical beads with diameter in the range 1 to 5 mm and Young modulus in the range <span><math><mrow><mrow><mo>(</mo><mn>0</mn><mo>.</mo><mn>1</mn><mo>−</mo><mn>2</mn><mo>)</mo></mrow><mspace></mspace><mi>GPa</mi></mrow></math></span> and narrow pore size distribution, centered around 10 to <span><math><mrow><mn>25</mn><mspace></mspace><mi>nm</mi></mrow></math></span> depending on the experimental conditions. Finally, to demonstrate the potentiality of these materials, we graft on the bead surface aminosilane molecules, and quantify their CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> adsorption efficiency. Overall, the production method we have developed is simple, readily adaptable, and offers promising materials for adsorption, storage, catalysis and chromatography.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"387 ","pages":"Article 113534"},"PeriodicalIF":4.8,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143372305","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Influence of the amount of sulfur supported on sustainable ordered mesoporous carbons from tannin for high-performance electrodes in lithium‒sulfur batteries
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-02-01 DOI: 10.1016/j.micromeso.2025.113530
Rubens Lucas de Freitas Filho , Keiliane Silva Santos , Rayane Cristian Ferreira Silva , Lucas Coelho de Oliveira , Igor Bolonezi Gomes , Fernanda Gabrielle Gandra , Luan Teixeira Cardoso , Danielle Diniz Justino , Paula Sevenini Pinto , Ana Paula de Carvalho Teixeira , João Paulo Campos Trigueiro , Paulo Fernando Ribeiro Ortega , Rodrigo Lassarote Lavall , Glaura Goulart Silva
Technological options for batteries are currently in great demand, and among them, lithium-sulfur batteries (Li-S) are promising. The low electrical conductivity of sulfur, the large volume variation, and the formation of soluble lithium polysulfides are the main challenges facing Li-S. This work proposes addressing these challenges by using sustainable ordered mesoporous carbon as a support for the sulfur in the cathode. The study showed how different contents of incorporated sulfur impact the electrochemical properties. Mesoporous carbons were obtained from tannins with a distribution of micro- and mesopores, and after the introduction of sulfur, the micropores were occupied. The sulfur contents in the MCS0.7, MCS1, and MCS2 composites obtained from the TG curves were 29 wt%, 39 wt%, and 61 wt%, respectively. XPS results indicated that the presence of S8 atoms infiltrated into the mesopores, and in smaller quantities, S2-4 atoms infiltrated into the interior of the micropores due to spatial constraints. The specific capacity at 0.1C was 1033 mA h gS−1 for MCS0.7, 830 mA h gS−1 for MCS1, and 666 mA h gS−1 for MCS2. The capacity values are greater for composites with lower sulfur contents, which favors charge transfer. This behavior can be explained by considering that a greater fraction of the elemental sulfur is in direct contact with the surface of the carbon matrix in these cases, as observed by the characterization of the materials. Furthermore, the MCSs showed an excellent rate capability due to their mesoporous structure. MCS1 was chosen for the cyclic stability tests, and a coulombic efficiency close to 99 % was observed during the test. The performance of these materials is among the best for Li-S batteries based on biomass-derived carbon. The results highlight the great potential of sustainable mesoporous carbon materials from biomass as efficient and environmentally friendly components for high-performance lithium‒sulfur batteries.
{"title":"Influence of the amount of sulfur supported on sustainable ordered mesoporous carbons from tannin for high-performance electrodes in lithium‒sulfur batteries","authors":"Rubens Lucas de Freitas Filho ,&nbsp;Keiliane Silva Santos ,&nbsp;Rayane Cristian Ferreira Silva ,&nbsp;Lucas Coelho de Oliveira ,&nbsp;Igor Bolonezi Gomes ,&nbsp;Fernanda Gabrielle Gandra ,&nbsp;Luan Teixeira Cardoso ,&nbsp;Danielle Diniz Justino ,&nbsp;Paula Sevenini Pinto ,&nbsp;Ana Paula de Carvalho Teixeira ,&nbsp;João Paulo Campos Trigueiro ,&nbsp;Paulo Fernando Ribeiro Ortega ,&nbsp;Rodrigo Lassarote Lavall ,&nbsp;Glaura Goulart Silva","doi":"10.1016/j.micromeso.2025.113530","DOIUrl":"10.1016/j.micromeso.2025.113530","url":null,"abstract":"<div><div>Technological options for batteries are currently in great demand, and among them, lithium-sulfur batteries (Li-S) are promising. The low electrical conductivity of sulfur, the large volume variation, and the formation of soluble lithium polysulfides are the main challenges facing Li-S. This work proposes addressing these challenges by using sustainable ordered mesoporous carbon as a support for the sulfur in the cathode. The study showed how different contents of incorporated sulfur impact the electrochemical properties. Mesoporous carbons were obtained from tannins with a distribution of micro- and mesopores, and after the introduction of sulfur, the micropores were occupied. The sulfur contents in the MCS0.7, MCS1, and MCS2 composites obtained from the TG curves were 29 wt%, 39 wt%, and 61 wt%, respectively. XPS results indicated that the presence of S<sub>8</sub> atoms infiltrated into the mesopores, and in smaller quantities, S<sub>2</sub><sub><sub>-</sub></sub><sub>4</sub> atoms infiltrated into the interior of the micropores due to spatial constraints. The specific capacity at 0.1C was 1033 mA h g<sub>S</sub><sup>−1</sup> for MCS0.7, 830 mA h g<sub>S</sub><sup>−1</sup> for MCS1, and 666 mA h g<sub>S</sub><sup>−1</sup> for MCS2. The capacity values are greater for composites with lower sulfur contents, which favors charge transfer. This behavior can be explained by considering that a greater fraction of the elemental sulfur is in direct contact with the surface of the carbon matrix in these cases, as observed by the characterization of the materials. Furthermore, the MCSs showed an excellent rate capability due to their mesoporous structure. MCS1 was chosen for the cyclic stability tests, and a coulombic efficiency close to 99 % was observed during the test. The performance of these materials is among the best for Li-S batteries based on biomass-derived carbon. The results highlight the great potential of sustainable mesoporous carbon materials from biomass as efficient and environmentally friendly components for high-performance lithium‒sulfur batteries.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"387 ","pages":"Article 113530"},"PeriodicalIF":4.8,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143163913","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}
引用次数: 0
Enhanced ion pairing of calcium, zinc, and lanthanum with acetate in silica nanopores
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-01-31 DOI: 10.1016/j.micromeso.2025.113538
Bidemi T. Fashina , Anthony P. Baldo , Heath Watts , Kevin Leung , James D. Kubicki , Anastasia G. Ilgen
The well-established intrinsic properties and reactivity of molecules in aqueous environments are influenced when confined in pores, cages, channels, or slits. Nanoconfined chemical systems are common in the environment, such as in soils and sedimentary rocks. In this study, the impact of nanoscale confinement on the ion pairing involving Ca2+, Zn2+, and La3+ with CH3COO anions was investigated. The concentrations of free (uncomplexed) CH3COO and the Mn+–CH3COO species (acetate complexed with a cation, M = Ca2+, Zn2+, or La3+) were quantified using Raman spectroscopy performed on bulk aqueous solutions and on the same solutions confined within 4 nm amorphous silica nanopores. The calculated equilibrium constants increased by 0.09, 1.70, and 2.5 units for Ca2+–, Zn2+–, and La3+–CH3COO, respectively, when compared to analogous constants measured for bulk solutions. These shifts in the equilibrium constants correspond to the free energy of formation of contact ion pairs in confinement becoming more favorable by 0.11, 0.77, and 0.40 kJ⸳mol−1 compared to bulk solution phase. In support of the experimental findings, molecular dynamics and density functional theory calculations predict the stabilization of contact ion pairs in confined systems compared to bulk aqueous environment. The observed increase in the equilibrium constants of contact ion pairing is attributed to the lower desolvation cost in the silica nanopore compared to unconfined aqueous solution.
{"title":"Enhanced ion pairing of calcium, zinc, and lanthanum with acetate in silica nanopores","authors":"Bidemi T. Fashina ,&nbsp;Anthony P. Baldo ,&nbsp;Heath Watts ,&nbsp;Kevin Leung ,&nbsp;James D. Kubicki ,&nbsp;Anastasia G. Ilgen","doi":"10.1016/j.micromeso.2025.113538","DOIUrl":"10.1016/j.micromeso.2025.113538","url":null,"abstract":"<div><div>The well-established intrinsic properties and reactivity of molecules in aqueous environments are influenced when confined in pores, cages, channels, or slits. Nanoconfined chemical systems are common in the environment, such as in soils and sedimentary rocks. In this study, the impact of nanoscale confinement on the ion pairing involving Ca<sup>2+</sup>, Zn<sup>2+</sup>, and La<sup>3+</sup> with CH<sub>3</sub>COO<sup>−</sup> anions was investigated. The concentrations of free (uncomplexed) CH<sub>3</sub>COO<sup>−</sup> and the M<sup>n+</sup>–CH<sub>3</sub>COO<sup>−</sup> species (acetate complexed with a cation, M = Ca<sup>2+</sup>, Zn<sup>2+</sup>, or La<sup>3+</sup>) were quantified using Raman spectroscopy performed on bulk aqueous solutions and on the same solutions confined within 4 nm amorphous silica nanopores. The calculated equilibrium constants increased by 0.09, 1.70, and 2.5 units for Ca<sup>2+</sup>–, Zn<sup>2+</sup>–, and La<sup>3+</sup>–CH<sub>3</sub>COO<sup>−</sup>, respectively, when compared to analogous constants measured for bulk solutions. These shifts in the equilibrium constants correspond to the free energy of formation of contact ion pairs in confinement becoming more favorable by 0.11, 0.77, and 0.40 kJ⸳mol<sup>−1</sup> compared to bulk solution phase. In support of the experimental findings, molecular dynamics and density functional theory calculations predict the stabilization of contact ion pairs in confined systems compared to bulk aqueous environment. The observed increase in the equilibrium constants of contact ion pairing is attributed to the lower desolvation cost in the silica nanopore compared to unconfined aqueous solution.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"387 ","pages":"Article 113538"},"PeriodicalIF":4.8,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143163917","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}
引用次数: 0
ZSM-5/PEG/DOX nanocarrier for pH-responsive doxorubicin release: Kinetic, isothermal, and cytotoxic studies
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-01-31 DOI: 10.1016/j.micromeso.2025.113531
Mahin Broukanlou , Seyed Ali Hosseini , Yaghub Pazhang
The application of ZSM-5/PEG nanoparticles as a drug carrier for the adsorption and release of doxorubicinas an anti-cancer drug was investigated. ZSM-5 zeolite was pegylated at different ratios, and ZSM-5/PEG with a mass ratio of (10:4) exhibited the best drug loading and loading efficiency of 83 % (14 mg/g). The carrier showed pH-responsive behaviour, releasing 65 % of the drug at pH 5.6 and 21 % at pH 7.4. The differential scanning calorimetry (DSC) approved the thermal stability of ZSM-5/PEG carrier under body conditions. The absorption models revealed that drug absorption onto ZSM-5/PEG followed the Freundlich model (R2 = 0.93), indicating multilayered absorption of DOX on ZSM-5/PEG nanoparticles. Moreover, the results of kinetic studies confirmed that among the different kinetic models, the Korsmeyer-Peppas model effectively described the release behaviour from the carrier. The values of n and K for the Korsmeyer-Peppas model resulted in 0.22 and 0.36, respectively, indicating that doxorubicin release from ZSM-5/PEG nanocarrier had a slow releasing rate and followed Fick's law. MTT assay showed that loading the DOX on the ZSM-5/PEG nanoparticles increased their cytotoxic effects on the HCT-116 cell line by almost 10 times with the lowest IC50 values(38.1, 10.4, and 2.33 μg/ml for 24 h, 48 h, and 72 h after treatment, respectively). The study found that ZSM-5/PEG/DOX has the potential to treat cancer as a pH-sensitive and slow-releasing drug.
{"title":"ZSM-5/PEG/DOX nanocarrier for pH-responsive doxorubicin release: Kinetic, isothermal, and cytotoxic studies","authors":"Mahin Broukanlou ,&nbsp;Seyed Ali Hosseini ,&nbsp;Yaghub Pazhang","doi":"10.1016/j.micromeso.2025.113531","DOIUrl":"10.1016/j.micromeso.2025.113531","url":null,"abstract":"<div><div>The application of ZSM-5/PEG nanoparticles as a drug carrier for the adsorption and release of doxorubicinas an anti-cancer drug was investigated. ZSM-5 zeolite was pegylated at different ratios, and ZSM-5/PEG with a mass ratio of (10:4) exhibited the best drug loading and loading efficiency of 83 % (14 mg/g). The carrier showed pH-responsive behaviour, releasing 65 % of the drug at pH 5.6 and 21 % at pH 7.4. The differential scanning calorimetry (DSC) approved the thermal stability of ZSM-5/PEG carrier under body conditions. The absorption models revealed that drug absorption onto ZSM-5/PEG followed the Freundlich model (<span><math><mrow><msup><mi>R</mi><mn>2</mn></msup></mrow></math></span> = 0.93), indicating multilayered absorption of DOX on ZSM-5/PEG nanoparticles. Moreover, the results of kinetic studies confirmed that among the different kinetic models, the Korsmeyer-Peppas model effectively described the release behaviour from the carrier. The values of n and K for the Korsmeyer-Peppas model resulted in 0.22 and 0.36, respectively, indicating that doxorubicin release from ZSM-5/PEG nanocarrier had a slow releasing rate and followed Fick's law. MTT assay showed that loading the DOX on the ZSM-5/PEG nanoparticles increased their cytotoxic effects on the HCT-116 cell line by almost 10 times with the lowest IC<sub>50</sub> values(38.1, 10.4, and 2.33 μg/ml for 24 h, 48 h, and 72 h after treatment, respectively). The study found that ZSM-5/PEG/DOX has the potential to treat cancer as a pH-sensitive and slow-releasing drug.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"387 ","pages":"Article 113531"},"PeriodicalIF":4.8,"publicationDate":"2025-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143163920","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}
引用次数: 0
Amino-functionalized yolk-shell magnetic silica nanoparticles for the selective removal of heavy metal ions
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-01-30 DOI: 10.1016/j.micromeso.2025.113535
Haiyu Li , Yuqian Jia , Yuan Chen , Qingyang Ye , Lichen Xian , Jieshu Qian
Heavy metals in natural waters exist in both anionic and cationic forms, posing significant risks to ecological safety and human health. However, the selective and efficient removal of these ions remains a considerable challenge. In this study, we synthesized amino-functionalized yolk-shell magnetic silica nanocomposites and evaluated their adsorption performance for heavy metal anions and cations. The nanocomposites exhibited high adsorption capacities of 210 mg/g for Pb(II) and 57.8 mg/g for Cu(II) cations, while the protonated nanocomposites achieved an adsorption capacity of 52.6 mg/g for As(V) anions. Notably, the nanocomposites maintained strong specific adsorption capabilities for heavy metal ions even in the presence of competing ions, along with excellent reusability and operational convenience. This work presents a methodically designed strategy for functionalizing magnetic solid nano-adsorbents for the selective removal of heavy metal ions from water, offering new insights into the potential applications of yolk-shell nanoparticles.
{"title":"Amino-functionalized yolk-shell magnetic silica nanoparticles for the selective removal of heavy metal ions","authors":"Haiyu Li ,&nbsp;Yuqian Jia ,&nbsp;Yuan Chen ,&nbsp;Qingyang Ye ,&nbsp;Lichen Xian ,&nbsp;Jieshu Qian","doi":"10.1016/j.micromeso.2025.113535","DOIUrl":"10.1016/j.micromeso.2025.113535","url":null,"abstract":"<div><div>Heavy metals in natural waters exist in both anionic and cationic forms, posing significant risks to ecological safety and human health. However, the selective and efficient removal of these ions remains a considerable challenge. In this study, we synthesized amino-functionalized yolk-shell magnetic silica nanocomposites and evaluated their adsorption performance for heavy metal anions and cations. The nanocomposites exhibited high adsorption capacities of 210 mg/g for Pb(II) and 57.8 mg/g for Cu(II) cations, while the protonated nanocomposites achieved an adsorption capacity of 52.6 mg/g for As(V) anions. Notably, the nanocomposites maintained strong specific adsorption capabilities for heavy metal ions even in the presence of competing ions, along with excellent reusability and operational convenience. This work presents a methodically designed strategy for functionalizing magnetic solid nano-adsorbents for the selective removal of heavy metal ions from water, offering new insights into the potential applications of yolk-shell nanoparticles.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"387 ","pages":"Article 113535"},"PeriodicalIF":4.8,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143163916","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}
引用次数: 0
The hierarchical porous material HP-UiO-NH2-X was prepared by an environmentally friendly method using water as a modulator and used for adsorption of ofloxacin
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-01-30 DOI: 10.1016/j.micromeso.2025.113532
Qingxin Lu, Jiaxin Zheng, Yaoyao Zhang, Wenjuan Lu
Hierarchical Porous Metal-Organic Frameworks (HP-MOFs) are widely recognized for their broad applications in adsorption, owing to their structural tunability and diverse pore types. However, existing synthesis methods often face challenges, including prolonged synthesis times, high energy consumption, and complex procedures. In this study, we utilized water, an environmentally friendly modulator, to successfully synthesize hierarchical porous UiO-series materials via a one-step solvothermal method. HP-UiO-66-NH2-X with varied pore structures was synthesized by adjusting the H2O/Zr4+ ratio in the precursor. The adsorption performance of the resulting materials for ofloxacin (OFL) was subsequently evaluated. Characterization results demonstrated that this approach effectively modulated the coordination between organic ligands and metal centers, leading to ligand defects and the precise tuning of the UiO-66-NH2 framework's pore structure. When the H2O/Zr4+ ratio was 22.2 (M/M), the synthesized HP-UiO-66-NH2-2 material exhibited optimal adsorption performance (233.1 mg/g) and excellent selectivity. The adsorption process involved multiple interactions, including electrostatic interactions, pore filling, metal coordination, hydrogen bonding, and π-π interactions. In adsorption-desorption cycling tests, HP-UiO-66-NH2-2 maintained over 90 % removal efficiency after 10 cycles, demonstrating its excellent reusability and stability. Therefore, this study proposes an environmentally friendly and simplified synthesis strategy, successfully producing HP-UiO-66-NH2-X materials with remarkable performance in removing OFL. This approach offers a novel perspective for improving the performance and applicability of environmentally friendly materials.
{"title":"The hierarchical porous material HP-UiO-NH2-X was prepared by an environmentally friendly method using water as a modulator and used for adsorption of ofloxacin","authors":"Qingxin Lu,&nbsp;Jiaxin Zheng,&nbsp;Yaoyao Zhang,&nbsp;Wenjuan Lu","doi":"10.1016/j.micromeso.2025.113532","DOIUrl":"10.1016/j.micromeso.2025.113532","url":null,"abstract":"<div><div>Hierarchical Porous Metal-Organic Frameworks (HP-MOFs) are widely recognized for their broad applications in adsorption, owing to their structural tunability and diverse pore types. However, existing synthesis methods often face challenges, including prolonged synthesis times, high energy consumption, and complex procedures. In this study, we utilized water, an environmentally friendly modulator, to successfully synthesize hierarchical porous UiO-series materials via a one-step solvothermal method. HP-UiO-66-NH<sub>2</sub>-X with varied pore structures was synthesized by adjusting the H<sub>2</sub>O/Zr<sup>4+</sup> ratio in the precursor. The adsorption performance of the resulting materials for ofloxacin (OFL) was subsequently evaluated. Characterization results demonstrated that this approach effectively modulated the coordination between organic ligands and metal centers, leading to ligand defects and the precise tuning of the UiO-66-NH<sub>2</sub> framework's pore structure. When the H<sub>2</sub>O/Zr<sup>4+</sup> ratio was 22.2 (M/M), the synthesized HP-UiO-66-NH<sub>2</sub>-2 material exhibited optimal adsorption performance (233.1 mg/g) and excellent selectivity. The adsorption process involved multiple interactions, including electrostatic interactions, pore filling, metal coordination, hydrogen bonding, and π-π interactions. In adsorption-desorption cycling tests, HP-UiO-66-NH<sub>2</sub>-2 maintained over 90 % removal efficiency after 10 cycles, demonstrating its excellent reusability and stability. Therefore, this study proposes an environmentally friendly and simplified synthesis strategy, successfully producing HP-UiO-66-NH<sub>2</sub>-X materials with remarkable performance in removing OFL. This approach offers a novel perspective for improving the performance and applicability of environmentally friendly materials.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"388 ","pages":"Article 113532"},"PeriodicalIF":4.8,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143378206","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}
引用次数: 0
Development of mesoporous biocatalysts synthesized from a biomass surfactant for flavorings production
IF 4.8 3区 材料科学 Q1 CHEMISTRY, APPLIED Pub Date : 2025-01-30 DOI: 10.1016/j.micromeso.2025.113536
Germán Carrillo, Eliana G. Vaschetto, Gabriel O. Ferrero, Griselda A. Eimer
Obtaining flavorings industrially requires extreme conditions such as high temperatures and pressures, operation of toxic solvents, and use of acids as catalysts. Given these limitations, more eco-friendly alternatives like enzymatic catalysts are being investigated. However, the enzymes stability in organic reagents and reuse are the main drawbacks; therefore, the use of immobilization techniques on novel inorganic supports would allow combining the enzymatic selectivity and the properties of these matrices to increase their catalytic performance. In the present work, the transesterification reaction of vinyl acetate with isoamyl alcohol to produce isoamyl acetate was conducted at 40 °C and atmospheric pressure using a mesoporous biocatalyst synthesized from a biomass-derived molding agent. The synthesized materials were characterized by N2 adsorption and desorption isotherm, Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM) and Infrared Spectroscopy (FT-IR). For the biocatalyst synthesis, the enzyme-support contact times and the enzyme loading were evaluated. The best catalytic performance was obtained with a material prepared with 96 h of immobilization and with a theoretical loading of 400 mglipase/gsupport. High vinyl acetate conversion (86 %) and isoamyl acetate yields (62 %) were achieved at 40 °C after 20 h of reaction. The results suggest that the lipases immobilization on renewable mesoporous silica offers a promising alternative route for the sustainable fragrances production under mild operating conditions.
{"title":"Development of mesoporous biocatalysts synthesized from a biomass surfactant for flavorings production","authors":"Germán Carrillo,&nbsp;Eliana G. Vaschetto,&nbsp;Gabriel O. Ferrero,&nbsp;Griselda A. Eimer","doi":"10.1016/j.micromeso.2025.113536","DOIUrl":"10.1016/j.micromeso.2025.113536","url":null,"abstract":"<div><div>Obtaining flavorings industrially requires extreme conditions such as high temperatures and pressures, operation of toxic solvents, and use of acids as catalysts. Given these limitations, more eco-friendly alternatives like enzymatic catalysts are being investigated. However, the enzymes stability in organic reagents and reuse are the main drawbacks; therefore, the use of immobilization techniques on novel inorganic supports would allow combining the enzymatic selectivity and the properties of these matrices to increase their catalytic performance. In the present work, the transesterification reaction of vinyl acetate with isoamyl alcohol to produce isoamyl acetate was conducted at 40 °C and atmospheric pressure using a mesoporous biocatalyst synthesized from a biomass-derived molding agent. The synthesized materials were characterized by N<sub>2</sub> adsorption and desorption isotherm, Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM) and Infrared Spectroscopy (FT-IR). For the biocatalyst synthesis, the enzyme-support contact times and the enzyme loading were evaluated. The best catalytic performance was obtained with a material prepared with 96 h of immobilization and with a theoretical loading of 400 mg<sub>lipase</sub>/gsupport. High vinyl acetate conversion (86 %) and isoamyl acetate yields (62 %) were achieved at 40 °C after 20 h of reaction. The results suggest that the lipases immobilization on renewable mesoporous silica offers a promising alternative route for the sustainable fragrances production under mild operating conditions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"387 ","pages":"Article 113536"},"PeriodicalIF":4.8,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143162775","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}
引用次数: 0
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Microporous and Mesoporous Materials
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