Pub Date : 2026-04-01Epub Date: 2026-02-06DOI: 10.1016/j.micromeso.2026.114056
Marina G. Shelyapina , Denis A. Pankratov , Anton S. Masur , Rosario I. Yocupicio-Gaxiola , Vitalii Petranovskii
This paper details the actual composition and some properties of bimetallic Cu-Fe systems deposited on mordenite using sources of iron ions in both oxidation states – Fe2+ or Fe3+. By methods of Nuclear Magnetic Resonance, UV-Vis, and Mössbauer spectroscopy, details of the reciprocal influence of Cu and Fe ions on the formation of metallic centers/species are revealed, depending on the degree of oxidation of iron ions during simultaneous deposition of a mixture of Cu-Fe ions on mordenite under microwave irradiation. Fundamental differences in the behavior of Fe2+ and Fe3+ ions are shown. According to the simplest model, ion exchange in zeolites occurs because the role of cations is solely to neutralize the negative charge of the zeolite crystal framework associated with the presence of trivalent Al instead of tetravalent silicon in the tetrahedral environment. The relative decoupling of the cationic group from the zeolite crystal framework allows for its relatively independent modification, creating effective catalytic centers. However, with all the apparent simplicity of this process, a closer examination of the materials obtained through ion exchange process, in many cases allows one to notice certain effects associated with the peculiarities of the chemical properties of each of the elements, their potential interaction with the matrix, and the formation of admixed phases and nanoparticles based on the same elements supported on the zeolite.
{"title":"Bimetallic Cu-Fe(II) and Cu-Fe(III) systems supported on mordenite: A spectroscopic insight","authors":"Marina G. Shelyapina , Denis A. Pankratov , Anton S. Masur , Rosario I. Yocupicio-Gaxiola , Vitalii Petranovskii","doi":"10.1016/j.micromeso.2026.114056","DOIUrl":"10.1016/j.micromeso.2026.114056","url":null,"abstract":"<div><div>This paper details the actual composition and some properties of bimetallic Cu-Fe systems deposited on mordenite using sources of iron ions in both oxidation states – Fe<sup>2+</sup> or Fe<sup>3+</sup>. By methods of Nuclear Magnetic Resonance, UV-Vis, and Mössbauer spectroscopy, details of the reciprocal influence of Cu and Fe ions on the formation of metallic centers/species are revealed, depending on the degree of oxidation of iron ions during simultaneous deposition of a mixture of Cu-Fe ions on mordenite under microwave irradiation. Fundamental differences in the behavior of Fe<sup>2+</sup> and Fe<sup>3+</sup> ions are shown. According to the simplest model, ion exchange in zeolites occurs because the role of cations is solely to neutralize the negative charge of the zeolite crystal framework associated with the presence of trivalent Al instead of tetravalent silicon in the tetrahedral environment. The relative decoupling of the cationic group from the zeolite crystal framework allows for its relatively independent modification, creating effective catalytic centers. However, with all the apparent simplicity of this process, a closer examination of the materials obtained through ion exchange process, in many cases allows one to notice certain effects associated with the peculiarities of the chemical properties of each of the elements, their potential interaction with the matrix, and the formation of admixed phases and nanoparticles based on the same elements supported on the zeolite.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114056"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186158","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: 2026-02-10DOI: 10.1016/j.micromeso.2026.114082
Han Gao , Songlin Zuo
Using graphitic crystallite nanomaterials(GCNs)as a reinforcement phase, resorcinol-formaldehyde (RF) precursors were induced to form composite gels through a hydrothermal reaction, and then were carbonized to prepare biomimetic sponge-like mesoporous carbon. Biomimetic sponge-like mesoporous carbon with adjustable pore size was prepared by adjusting the content of GCNs and the volume ratio of alcohol to water. Nitrogen-doped biomimetic sponge-like mesoporous carbon with a specific surface area of 1152 m2/g and mesoporous size of 3∼4 nm was prepared by high temperature NH3 heat treatment. Electrocatalytic oxygen reduction tests showed that the initial potential of electrocatalytic oxygen reduction was −0.02 V, and the limiting current is 5.1 mA/cm2 (at −1.0 V), both of which achieve the performance of commercial 20 wt% Pt/C catalysts. After 2000 cycles, the electrocatalytic oxygen reduction performance of biomimetic mesoporous carbon maintained about 98% of the catalytic capacity, indicating a very high electrocatalytic cycling stability. GCNs promote cross-linking to construct biomimetic mesoporous networks, which not only accelerate mass transfer and expose active sites, but also improve skeleton stability and inhibit cyclic collapse.
{"title":"Biomimetic sponge-like mesoporous carbon from resorcinol-formaldehyde via GCNs-facilitated gelation for ORR","authors":"Han Gao , Songlin Zuo","doi":"10.1016/j.micromeso.2026.114082","DOIUrl":"10.1016/j.micromeso.2026.114082","url":null,"abstract":"<div><div>Using graphitic crystallite nanomaterials(GCNs)as a reinforcement phase, resorcinol-formaldehyde (RF) precursors were induced to form composite gels through a hydrothermal reaction, and then were carbonized to prepare biomimetic sponge-like mesoporous carbon. Biomimetic sponge-like mesoporous carbon with adjustable pore size was prepared by adjusting the content of GCNs and the volume ratio of alcohol to water. Nitrogen-doped biomimetic sponge-like mesoporous carbon with a specific surface area of 1152 m<sup>2</sup>/g and mesoporous size of 3∼4 nm was prepared by high temperature NH<sub>3</sub> heat treatment. Electrocatalytic oxygen reduction tests showed that the initial potential of electrocatalytic oxygen reduction was −0.02 V, and the limiting current is 5.1 mA/cm<sup>2</sup> (at −1.0 V), both of which achieve the performance of commercial 20 wt% Pt/C catalysts. After 2000 cycles, the electrocatalytic oxygen reduction performance of biomimetic mesoporous carbon maintained about 98% of the catalytic capacity, indicating a very high electrocatalytic cycling stability. GCNs promote cross-linking to construct biomimetic mesoporous networks, which not only accelerate mass transfer and expose active sites, but also improve skeleton stability and inhibit cyclic collapse.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114082"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186195","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.2026.114057
ShuHuan Chen , Panweiyi Wang , Teshale Ayano Begeno , Afaq Nazir , ZhenXia Du , Shuping Qu
Luminescent metal-organic frameworks (LMOFs) have emerged as promising materials for optical sensing, owing to their tunable luminescent properties. However, most existing LMOF-based sensors rely on single-wavelength fluorescence intensity changes, which suffer from poor resistance to environmental fluctuations due to the absence of auxiliary reference signals, limiting their accuracy, especially for trace ammonia(NH3) below the human olfactory threshold, which evades sensory perception yet poses long-term risks. To address this limitation, UIO-67-x where x denotes the molar ratio of terephthalic acid (H2BDC) to biphenyl-4,4′-dicarboxylic acid (H2BPDC) was designed. By optimizing the ligand ratio, UIO-67-0.2 was synthesized with well-defined crystallinity, large specific surface area and high fluorescence emission peak intensity. Its regular structure enables efficient encapsulation of rhodamine B (RhB) forming the dual-emission [email protected] platform. This platform has two adjustable emission peaks, both of which respond sensitively and synchronously to ammonia, thereby strengthening signal reliability and anti-interference capability through dual-channel synergistic verification. Notably [email protected] achieves an ultra-low NH3 limit of detection (LOD) of 0.2 ppm, far below the olfactory threshold, and maintains remarkable stability after 5 cycles with stable reusability. Combining experiments and Density functional theory (DFT) calculations the quenching mechanism is clarified as the synergistic effect of static quenching and charge transfer. A [email protected] drop-cast film exhibits naked-eye distinguishable color change at 2.5 ppm NH3 under 365 nm Ultraviolet(UV) light. It remains unchanged with other volatile organic compounds (VOCs) and shows concentration-dependent color gradation for semi-quantitative assessment. Furthermore, Digital conversion of fluorescence color signals via ΔE analysis enabled truly quantitative ammonia detection with a linear calibration curve (R2 = 0.968), eliminating the subjectivity of naked-eye judgment. This work develops a dual-mode LMOF for sub-olfactory-threshold NH3 detection and informs anti-interference dual-emission platform design enabling on-site low-cost monitoring.
{"title":"Dual-emission [email protected]: A platform for ultra-low LOD ammonia detection and on-site visual recognition","authors":"ShuHuan Chen , Panweiyi Wang , Teshale Ayano Begeno , Afaq Nazir , ZhenXia Du , Shuping Qu","doi":"10.1016/j.micromeso.2026.114057","DOIUrl":"10.1016/j.micromeso.2026.114057","url":null,"abstract":"<div><div>Luminescent metal-organic frameworks (LMOFs) have emerged as promising materials for optical sensing, owing to their tunable luminescent properties. However, most existing LMOF-based sensors rely on single-wavelength fluorescence intensity changes, which suffer from poor resistance to environmental fluctuations due to the absence of auxiliary reference signals, limiting their accuracy, especially for trace ammonia(NH<sub>3</sub>) below the human olfactory threshold, which evades sensory perception yet poses long-term risks. To address this limitation, UIO-67-x where x denotes the molar ratio of terephthalic acid (H<sub>2</sub>BDC) to biphenyl-4,4′-dicarboxylic acid (H<sub>2</sub>BPDC) was designed. By optimizing the ligand ratio, UIO-67-0.2 was synthesized with well-defined crystallinity, large specific surface area and high fluorescence emission peak intensity. Its regular structure enables efficient encapsulation of rhodamine B (RhB) forming the dual-emission [email protected] platform. This platform has two adjustable emission peaks, both of which respond sensitively and synchronously to ammonia, thereby strengthening signal reliability and anti-interference capability through dual-channel synergistic verification. Notably [email protected] achieves an ultra-low NH<sub>3</sub> limit of detection (LOD) of 0.2 ppm, far below the olfactory threshold, and maintains remarkable stability after 5 cycles with stable reusability. Combining experiments and Density functional theory (DFT) calculations the quenching mechanism is clarified as the synergistic effect of static quenching and charge transfer. A [email protected] drop-cast film exhibits naked-eye distinguishable color change at 2.5 ppm NH<sub>3</sub> under 365 nm Ultraviolet(UV) light. It remains unchanged with other volatile organic compounds (VOCs) and shows concentration-dependent color gradation for semi-quantitative assessment. Furthermore, Digital conversion of fluorescence color signals via <em>ΔE</em> analysis enabled truly quantitative ammonia detection with a linear calibration curve (<em>R</em><sup><em>2</em></sup> = 0.968), eliminating the subjectivity of naked-eye judgment. This work develops a dual-mode LMOF for sub-olfactory-threshold NH<sub>3</sub> detection and informs anti-interference dual-emission platform design enabling on-site low-cost monitoring.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114057"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186156","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.2026.114076
Young Gul Hur , Deng-Yang Jan , Rajamani Gounder , James W. Harris
Inclusion of boron in growth mixtures for aluminosilicate Beta zeolites has been used previously as a strategy to vary zeolite crystallite sizes, yet prior reports describe limited compositional regimes of silicon-to-aluminum and silicon-to-boron molar ratios in which the Beta topology will crystallize. This study demonstrates that manipulation of growth mixture compositions can enable crystallization of Beta zeolites across a broader range of silicon-to-aluminum and silicon-to-boron molar ratios in boron-and aluminum-containing Beta zeolites (B-Al-Beta) than previously reported. B-Al-Beta samples are characterized by X-ray diffraction, solid-state 11B magic angle spinning nuclear magnetic resonance (MAS NMR), nitrogen physisorption, elemental analysis, scanning electron microscopy, and ammonia temperature programmed desorption (TPD). Silicon-to-aluminum molar ratios in the crystallized B-Al-Beta solids were directly proportional to those present in growth mixtures, reflecting more equal extents of Si and Al incorporation than is typical when aluminosilicate Beta is synthesized in hydroxide media. Beta crystallite sizes were found to increase with increasing B content at constant Si/Al ratio. Ammonia TPD protocols developed previously to selectively quantify protons at Al-O-Si linkages, but not at B-O-Si linkages, in B-Al-MFI zeolites were demonstrated here to also do so for B-Al-Beta zeolites. These synthesis and characterization protocols enable synthesis of Beta zeolites with constant silicon-to-aluminum ratios but varied crystallite sizes, achieved via variation in the silicon-to-boron molar ratio, and selective quantification of the Brønsted acid sites associated with Al centers in the framework.
在铝硅酸盐β沸石的生长混合物中加入硼曾被用作改变沸石晶体尺寸的策略，但之前的报告描述了硅与铝和硅与硼的摩尔比的有限组成体系，其中β拓扑结构将结晶。该研究表明，与之前报道的相比，控制生长混合物的组成可以使β沸石在更大范围内的硅与铝和硅与硼的摩尔比中结晶。采用x射线衍射、固态11B魔角自旋核磁共振（MAS NMR）、氮物理吸附、元素分析、扫描电镜和氨温度程序脱附（TPD）对b - al - β样品进行了表征。在结晶的b -Al- β固体中，硅与铝的摩尔比与生长混合物中存在的摩尔比成正比，反映出比在氢氧化物介质中合成铝硅酸盐β时更均匀的硅和铝掺入程度。在一定Si/Al比下，随着B含量的增加，β晶粒尺寸增大。之前开发的氨TPD方案可以选择性地量化B-Al-MFI沸石中Al-O-Si键上的质子，但不能量化B-O-Si键上的质子，这里证明了b - al - β沸石也可以这样做。这些合成和表征方案可以通过改变硅与硼的摩尔比，以及对框架中与Al中心相关的Brønsted酸位的选择性量化来合成具有恒定硅铝比但不同晶粒尺寸的β沸石。
{"title":"Expanding the phase space for crystallization of boron and aluminum containing Beta zeolites","authors":"Young Gul Hur , Deng-Yang Jan , Rajamani Gounder , James W. Harris","doi":"10.1016/j.micromeso.2026.114076","DOIUrl":"10.1016/j.micromeso.2026.114076","url":null,"abstract":"<div><div>Inclusion of boron in growth mixtures for aluminosilicate Beta zeolites has been used previously as a strategy to vary zeolite crystallite sizes, yet prior reports describe limited compositional regimes of silicon-to-aluminum and silicon-to-boron molar ratios in which the Beta topology will crystallize. This study demonstrates that manipulation of growth mixture compositions can enable crystallization of Beta zeolites across a broader range of silicon-to-aluminum and silicon-to-boron molar ratios in boron-and aluminum-containing Beta zeolites (B-Al-Beta) than previously reported. B-Al-Beta samples are characterized by X-ray diffraction, solid-state <sup>11</sup>B magic angle spinning nuclear magnetic resonance (MAS NMR), nitrogen physisorption, elemental analysis, scanning electron microscopy, and ammonia temperature programmed desorption (TPD). Silicon-to-aluminum molar ratios in the crystallized B-Al-Beta solids were directly proportional to those present in growth mixtures, reflecting more equal extents of Si and Al incorporation than is typical when aluminosilicate Beta is synthesized in hydroxide media. Beta crystallite sizes were found to increase with increasing B content at constant Si/Al ratio. Ammonia TPD protocols developed previously to selectively quantify protons at Al-O-Si linkages, but not at B-O-Si linkages, in B-Al-MFI zeolites were demonstrated here to also do so for B-Al-Beta zeolites. These synthesis and characterization protocols enable synthesis of Beta zeolites with constant silicon-to-aluminum ratios but varied crystallite sizes, achieved via variation in the silicon-to-boron molar ratio, and selective quantification of the Brønsted acid sites associated with Al centers in the framework.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114076"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186162","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.2026.114077
Volkan Şahin
Hierarchical zeolites confine nanoscale metal species that hold great appeal for multifunctional catalysis, although controlled synthesis still remains a challenge. In this paper, hierarchical Beta (hBEA) zeolite confining subnanometric metal species was synthesized with the strategy of cooperative ethylenediamine (en) ligand protection and seed-assisted crystallization in the presence of the unique tetraquaternary ammonium structure-directing agent (SDA). Such a cooperative synthesis environment allowed SDA to direct mesostructure formation while bulk BEA seed maintained framework topology, leading to an interconnected micro-mesoporous architecture with improved textural properties. The en-ligand protection effectively suppressed metal hydroxide precipitation under strongly basic hydrothermal conditions, allowing for the confinement of Pd, Co, Ni, and Cu metal centers within the framework. Characterization by XRD, XPS, and HAADF-STEM confirmed the uniform dispersion of isolated and ultra-small metal nanosites without metallic nanoparticle formation. Building on this design, dimetallic Pd-Co, Pd-Ni, and Pd-Cu@hBEA catalysts were prepared using preformed metal-containing seeds as both structural templates and secondary metal sources, achieving homogeneous co-distribution of both metals. This study demonstrates a versatile and generalizable route for constructing multimetallic hierarchical zeolites capable of stabilizing multiple active centers, offering a robust platform for designing selective and sustainable catalysts for tandem reactions.
{"title":"Engineering hierarchical beta zeolites with isolated metal centers for adjustable catalytic functionality","authors":"Volkan Şahin","doi":"10.1016/j.micromeso.2026.114077","DOIUrl":"10.1016/j.micromeso.2026.114077","url":null,"abstract":"<div><div>Hierarchical zeolites confine nanoscale metal species that hold great appeal for multifunctional catalysis, although controlled synthesis still remains a challenge. In this paper, hierarchical Beta (hBEA) zeolite confining subnanometric metal species was synthesized with the strategy of cooperative ethylenediamine (en) ligand protection and seed-assisted crystallization in the presence of the unique tetraquaternary ammonium structure-directing agent (SDA). Such a cooperative synthesis environment allowed SDA to direct mesostructure formation while bulk BEA seed maintained framework topology, leading to an interconnected micro-mesoporous architecture with improved textural properties. The en-ligand protection effectively suppressed metal hydroxide precipitation under strongly basic hydrothermal conditions, allowing for the confinement of Pd, Co, Ni, and Cu metal centers within the framework. Characterization by XRD, XPS, and HAADF-STEM confirmed the uniform dispersion of isolated and ultra-small metal nanosites without metallic nanoparticle formation. Building on this design, dimetallic Pd-Co, Pd-Ni, and Pd-Cu@hBEA catalysts were prepared using preformed metal-containing seeds as both structural templates and secondary metal sources, achieving homogeneous co-distribution of both metals. This study demonstrates a versatile and generalizable route for constructing multimetallic hierarchical zeolites capable of stabilizing multiple active centers, offering a robust platform for designing selective and sustainable catalysts for tandem reactions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114077"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186160","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: 2026-02-02DOI: 10.1016/j.micromeso.2026.114066
Yujing Zhou , Yizhe Yang , Yinqi Sun , Zihao Wang , Hengbo Ding , Kai Liu , Weiguo Zhang , Songke Feng
To overcome the low nitrogen use efficiency (<40%) of conventional urea, this study utilizes the metal–organic framework MIL-100(Fe)—characterized by ultrahigh surface area and tunable mesoporosity—as a promising carrier for nano slow-release fertilizers with enhanced nutrient stability. Fourier transform infrared spectroscopy, thermogravimetric analysis, and Brunauer–Emmett–Teller measurements confirmed that urea was uniformly accommodated within the MOF channels in an amorphous, physically adsorbed state without chemical bonding. High-performance liquid chromatography revealed that loading capacity was primarily determined by the urea-to-MOF mass ratio, whereas loading temperature and duration had negligible effects, enabling precise synthesis control. Orthogonal optimization identified the optimal parameters (mass ratio 1:1, 110 °C, 7 h), yielding a urea loading of 59.2% and encapsulation efficiency of 51.8%. Release experiments demonstrated a 22.5-fold extension in release duration compared to pure urea, with 87.6% cumulative release over 180 h governed by Fickian diffusion. Furthermore, physical characterization and bench-scale metering tests verified the granules' mechanical adaptability, achieving stable, continuous discharge comparable to urea. This work validates MIL-100(Fe)@UREA as a high-capacity, mechanically viable platform for sustainable and precision nutrient delivery. These results not only highlight the potential of MIL-100(Fe) in advanced slow-release fertilizer systems but also provide valuable insights for designing efficient and environmentally sustainable nutrient delivery platforms.
{"title":"A study on a novel MIL-100(Fe)@UREA Nano-Fertilizer with high loading capacity and superior sustained-release performance","authors":"Yujing Zhou , Yizhe Yang , Yinqi Sun , Zihao Wang , Hengbo Ding , Kai Liu , Weiguo Zhang , Songke Feng","doi":"10.1016/j.micromeso.2026.114066","DOIUrl":"10.1016/j.micromeso.2026.114066","url":null,"abstract":"<div><div>To overcome the low nitrogen use efficiency (<40%) of conventional urea, this study utilizes the metal–organic framework MIL-100(Fe)—characterized by ultrahigh surface area and tunable mesoporosity—as a promising carrier for nano slow-release fertilizers with enhanced nutrient stability. Fourier transform infrared spectroscopy, thermogravimetric analysis, and Brunauer–Emmett–Teller measurements confirmed that urea was uniformly accommodated within the MOF channels in an amorphous, physically adsorbed state without chemical bonding. High-performance liquid chromatography revealed that loading capacity was primarily determined by the urea-to-MOF mass ratio, whereas loading temperature and duration had negligible effects, enabling precise synthesis control. Orthogonal optimization identified the optimal parameters (mass ratio 1:1, 110 °C, 7 h), yielding a urea loading of 59.2% and encapsulation efficiency of 51.8%. Release experiments demonstrated a 22.5-fold extension in release duration compared to pure urea, with 87.6% cumulative release over 180 h governed by Fickian diffusion. Furthermore, physical characterization and bench-scale metering tests verified the granules' mechanical adaptability, achieving stable, continuous discharge comparable to urea. This work validates MIL-100(Fe)@UREA as a high-capacity, mechanically viable platform for sustainable and precision nutrient delivery. These results not only highlight the potential of MIL-100(Fe) in advanced slow-release fertilizer systems but also provide valuable insights for designing efficient and environmentally sustainable nutrient delivery platforms.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114066"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186161","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.2026.114059
Robert E. Mustakimov, Nina V. Arzyaeva, Gleb V. Nikolaevich, Matvei D. Sukmanov, Anna V. Vutolkina, Argam V. Akopyan
Developing low-energy and waste-minimizing desulfurization technologies is essential for cleaner fuel production. Here, we report superhydrophobic molybdenum catalysts based on SBA-15, prepared by grafting octyltriethoxysilane (up to 20 mass %) while preserving the mesoporous framework. The hydrophobic surface significantly improves interfacial mass transfer and suppresses catalyst deactivation by excess aqueous H2O2 adsorption, enabling oxidative desulfurization (ODS) at room temperature without any organic co-solvents. Characterization (elemental analysis, TGA, N2 physisorption, FTIR, SEM/TEM, contact-angle measurements) confirms successful modification and enhanced stability.
The catalyst 20oct/Mo/SBA under optimized solvent-free conditions allows to achieve 99 % conversion for a high-sulfur model fuel (8000 ppmS) at 2 mass % dosage, representing the first demonstration of complete ODS of such sulfur-rich feed at ambient temperature. The catalyst also showed sufficient activity to oxidize straight-run diesel under mild, co-solvent-free conditions. These results establish hydrophobic Mo/SBA-15 catalysts as an energy-efficient and environmentally benign platform for deep oxidative desulfurization.
{"title":"Solvent-free room-temperature oxidative desulfurization enabled by superhydrophobic Mo/SBA-15 catalysts","authors":"Robert E. Mustakimov, Nina V. Arzyaeva, Gleb V. Nikolaevich, Matvei D. Sukmanov, Anna V. Vutolkina, Argam V. Akopyan","doi":"10.1016/j.micromeso.2026.114059","DOIUrl":"10.1016/j.micromeso.2026.114059","url":null,"abstract":"<div><div>Developing low-energy and waste-minimizing desulfurization technologies is essential for cleaner fuel production. Here, we report superhydrophobic molybdenum catalysts based on SBA-15, prepared by grafting octyltriethoxysilane (up to 20 mass %) while preserving the mesoporous framework. The hydrophobic surface significantly improves interfacial mass transfer and suppresses catalyst deactivation by excess aqueous H<sub>2</sub>O<sub>2</sub> adsorption, enabling oxidative desulfurization (ODS) at room temperature without any organic co-solvents. Characterization (elemental analysis, TGA, N<sub>2</sub> physisorption, FTIR, SEM/TEM, contact-angle measurements) confirms successful modification and enhanced stability.</div><div>The catalyst 20oct/Mo/SBA under optimized solvent-free conditions allows to achieve 99 % conversion for a high-sulfur model fuel (8000 ppmS) at 2 mass % dosage, representing the first demonstration of complete ODS of such sulfur-rich feed at ambient temperature. The catalyst also showed sufficient activity to oxidize straight-run diesel under mild, co-solvent-free conditions. These results establish hydrophobic Mo/SBA-15 catalysts as an energy-efficient and environmentally benign platform for deep oxidative desulfurization.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114059"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186164","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: 2026-02-03DOI: 10.1016/j.micromeso.2026.114065
Yutong Zou , Junbiao Wu , Meng Li , Gege Li , Yide Han , Yan Xu , Zhuopeng Wang
During the study of hydrothermal synthesis of nickel-encapsulated zeolite catalyst using the ligand-protection method, uniform nanofibers (∼10 nm diameter, hundreds of nanometers long) were unexpectedly observed on the surface of zeolite crystals. These nanofibers were subsequently synthesized independently outside the zeolite synthesis system and were identified as nickel-kerolite, a kind of talc-like nickel phyllosilicate. An optimal synthesis approach of the nickel phyllosilicate fibers was realized via a hydrothermal method using a synthetic gel comprising a silicon source, sodium hydroxide, nickel nitrate, and ethylenediamine (EDA). It is found that the formation of the unique fibrous morphology of nickel phyllosilicate requires a sufficiently strong alkaline medium and the presence of EDA. Ethylenediamine was proven to be essential for achieving the nano-fibrous morphology, probably due to the anisotropic growth inhibition from both EDA and its nickel complex (Ni-EDA), which restrict crystal development predominantly along one direction.
{"title":"Unexpected ultra-fine nickel phyllosilicate nanofibers formed on the surface of Ni-encapsulated zeolite catalyst: Phase identification and independent synthesis","authors":"Yutong Zou , Junbiao Wu , Meng Li , Gege Li , Yide Han , Yan Xu , Zhuopeng Wang","doi":"10.1016/j.micromeso.2026.114065","DOIUrl":"10.1016/j.micromeso.2026.114065","url":null,"abstract":"<div><div>During the study of hydrothermal synthesis of nickel-encapsulated zeolite catalyst using the ligand-protection method, uniform nanofibers (∼10 nm diameter, hundreds of nanometers long) were unexpectedly observed on the surface of zeolite crystals. These nanofibers were subsequently synthesized independently outside the zeolite synthesis system and were identified as nickel-kerolite, a kind of talc-like nickel phyllosilicate. An optimal synthesis approach of the nickel phyllosilicate fibers was realized via a hydrothermal method using a synthetic gel comprising a silicon source, sodium hydroxide, nickel nitrate, and ethylenediamine (EDA). It is found that the formation of the unique fibrous morphology of nickel phyllosilicate requires a sufficiently strong alkaline medium and the presence of EDA. Ethylenediamine was proven to be essential for achieving the nano-fibrous morphology, probably due to the anisotropic growth inhibition from both EDA and its nickel complex (Ni-EDA), which restrict crystal development predominantly along one direction.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114065"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186166","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: 2026-02-03DOI: 10.1016/j.micromeso.2026.114063
M. Yehia , Shukri Ismael , Sherif Elbasuney , Ahmed M. EL-Khawaga , Ana Sousa-Castillo , Margarita Vázquez-González , Miguel A. Correa-Duarte
The scarcity of water has emerged as a critical concern; an economical purification method is greatly valued. This study reports on the facile synthesis of novel Ag@ZIF-8 photocatalyst via chemical reduction method. The synthesized nanocomposite exhibited a rhomboid dodecahedron structure measuring 400 nm. The crystalline structure was evaluated using X-ray diffraction (XRD). EDAX analysis was utilized to study and evaluate the chemical composition of Ag@ZIF-8. Silver doping content of 5 wt % was verified using inductivity coupled plasma -optical emission spectroscopy (ICP-OES). Furthermore, the photo-assisted degradation of Eriochrome cyanin R (ECR) under visible and UV irradiation was investigated. The high photocatalytic efficacy effectively eliminated about 96.8 % of the 5.0 mg/L ECR using 10 mg of Ag@ZIF-8 at pH 5 under Visible light irradiation. The highest photocatalytic degradation of ECR at pH 5.0 could be correlated to electrostatic attraction between positively charged Ag@ZIF-8 catalyst surface and negatively charged ECR ions. Ag@ZIF-8 show good performance stability (70%) after five cycles of photocatalytic degradation of ECR dye. Silver doping endows the material with significant antimicrobial activity. Ag@ZIF-8 nanocomposite displayed great activity against gram-positive (S. aureus), and Gram-negative (E. coli) bacteria with a zone of inhibition (ZOI) mm value of 24.0 ± 0.44 and 13 ± 0.32 mm, respectively. Ag@ZIF-8's antioxidant activity was assessed and compared to ZIF-8, showing much higher ABTS radical scavenging (97.5% vs. 56.5%). These findings suggest that Ag@ZIF-8 holds promise not only for advanced wastewater treatment but also for biological and biomedical applications.
{"title":"Facile synthesis of Ag@ZIF-8 photocatalyst with superior wastewater treatment, antibacterial, and antioxidant properties","authors":"M. Yehia , Shukri Ismael , Sherif Elbasuney , Ahmed M. EL-Khawaga , Ana Sousa-Castillo , Margarita Vázquez-González , Miguel A. Correa-Duarte","doi":"10.1016/j.micromeso.2026.114063","DOIUrl":"10.1016/j.micromeso.2026.114063","url":null,"abstract":"<div><div>The scarcity of water has emerged as a critical concern; an economical purification method is greatly valued. This study reports on the facile synthesis of novel Ag@ZIF-8 photocatalyst via chemical reduction method. The synthesized nanocomposite exhibited a rhomboid dodecahedron structure measuring 400 nm. The crystalline structure was evaluated using X-ray diffraction (XRD). EDAX analysis was utilized to study and evaluate the chemical composition of Ag@ZIF-8. Silver doping content of 5 wt % was verified using inductivity coupled plasma -optical emission spectroscopy (ICP-OES). Furthermore, the photo-assisted degradation of Eriochrome cyanin R (ECR) under visible and UV irradiation was investigated. The high photocatalytic efficacy effectively eliminated about 96.8 % of the 5.0 mg/L ECR using 10 mg of Ag@ZIF-8 at pH 5 under Visible light irradiation. The highest photocatalytic degradation of ECR at pH 5.0 could be correlated to electrostatic attraction between positively charged Ag@ZIF-8 catalyst surface and negatively charged ECR ions. Ag@ZIF-8 show good performance stability (70%) after five cycles of photocatalytic degradation of ECR dye. Silver doping endows the material with significant antimicrobial activity. Ag@ZIF-8 nanocomposite displayed great activity against gram-positive (<em>S. aureus</em>), and Gram-negative (<em>E. coli</em>) bacteria with a zone of inhibition (ZOI) mm value of 24.0 ± 0.44 and 13 ± 0.32 mm, respectively. Ag@ZIF-8's antioxidant activity was assessed and compared to ZIF-8, showing much higher ABTS radical scavenging (97.5% vs. 56.5%). These findings suggest that Ag@ZIF-8 holds promise not only for advanced wastewater treatment but also for biological and biomedical applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114063"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186196","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: 2026-02-06DOI: 10.1016/j.micromeso.2026.114064
Adonay R. Loiola , Ingrid A.L. Azevedo , Nathalia S. Teixeira , Marcos A. Nascimento Junior , Fernanda F.A. Macedo , Cristiane P.O.G. Vasconcellos , Manuela S.M. Oliveira , Tiago P. Braga , Sibele B.C. Pergher
The relevance of zeolites encompasses numerous industrial fields, and new approaches are continually being applied to enhance their uses. In this sense, several advantages can be attained by using zeolites in form of nanoparticles and, as an alternative to conventional synthesis routes, nanozeolites can be prepared by using ball milling combined with recrystallization. In this work, a comprehensive evaluation of different parameters of ball milling applied to the generation of zeolite NaA nanoparticles is presented, which includes milling agent/zeolite ratio, time, speed, bead diameter, solvent and recrystallization. The decrease in the zeolite particle size is readily achieved and the conditions can be optimized. A partial loss in crystalline is observed, but it is easily restored via recrystallization under mild conditions. To illustrate some remarkable features of the nanozeolite, a final sample was assessed both as a catalyst and as water softener, showing noteworthy results.
{"title":"Combining ball milling and recrystallization as a cost-effective approach to producing high-quality nanozeolite NaA: assessment of its performance in catalysis and to water softening","authors":"Adonay R. Loiola , Ingrid A.L. Azevedo , Nathalia S. Teixeira , Marcos A. Nascimento Junior , Fernanda F.A. Macedo , Cristiane P.O.G. Vasconcellos , Manuela S.M. Oliveira , Tiago P. Braga , Sibele B.C. Pergher","doi":"10.1016/j.micromeso.2026.114064","DOIUrl":"10.1016/j.micromeso.2026.114064","url":null,"abstract":"<div><div>The relevance of zeolites encompasses numerous industrial fields, and new approaches are continually being applied to enhance their uses. In this sense, several advantages can be attained by using zeolites in form of nanoparticles and, as an alternative to conventional synthesis routes, nanozeolites can be prepared by using ball milling combined with recrystallization. In this work, a comprehensive evaluation of different parameters of ball milling applied to the generation of zeolite NaA nanoparticles is presented, which includes milling agent/zeolite ratio, time, speed, bead diameter, solvent and recrystallization. The decrease in the zeolite particle size is readily achieved and the conditions can be optimized. A partial loss in crystalline is observed, but it is easily restored via recrystallization under mild conditions. To illustrate some remarkable features of the nanozeolite, a final sample was assessed both as a catalyst and as water softener, showing noteworthy results.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"405 ","pages":"Article 114064"},"PeriodicalIF":4.7,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186157","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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