Pub Date : 2026-01-13DOI: 10.1016/j.micromeso.2026.114043
Daniel Roberto Sáenz García , Gemma Turnes Palomino , Luz O. Leal , Carlos Palomino Cabello
A series of porous carbons were prepared from the metal–organic framework ZIF-8 by tuning the calcination temperature and applying post-synthetic chemical treatments aimed at controlling porosity, surface chemistry and hydrophobicity. The resulting materials were thoroughly characterized by XRD, nitrogen adsorption–desorption, electron microscopy, XPS, Boehm titration and contact angle measurements. Their adsorption performance was evaluated using ibuprofen as a model pharmaceutical pollutant. Among the prepared materials, the carbon obtained by direct calcination at 1000 °C (C1000ZIF-8) exhibited the highest surface area (951 m2 g−1), the lowest heteroatom content and the most hydrophobic surface (contact angle 127°), leading to superior adsorption behaviour. Ibuprofen adsorption followed the Langmuir model with a maximum capacity of 62.6 mg g−1 and showed fast kinetics, with more than 50 % removal within the first 15 min and an excellent fit to the pseudo-second-order model (R2 = 0.998). The material retained over 93 % of its initial adsorption capacity after ten adsorption–desorption cycles, demonstrating high stability and reusability. Finally, C1000ZIF-8 achieved removal efficiencies above 88 % for several pharmaceuticals in real water matrices, including seawater, tap water and groundwater, highlighting the key role of hydrophobic interactions and pore filling and confirming the strong potential of this material for practical water remediation applications.
{"title":"Tailoring ZIF-8-derived carbons through surface modifications for enhanced pharmaceutical removal","authors":"Daniel Roberto Sáenz García , Gemma Turnes Palomino , Luz O. Leal , Carlos Palomino Cabello","doi":"10.1016/j.micromeso.2026.114043","DOIUrl":"10.1016/j.micromeso.2026.114043","url":null,"abstract":"<div><div>A series of porous carbons were prepared from the metal–organic framework ZIF-8 by tuning the calcination temperature and applying post-synthetic chemical treatments aimed at controlling porosity, surface chemistry and hydrophobicity. The resulting materials were thoroughly characterized by XRD, nitrogen adsorption–desorption, electron microscopy, XPS, Boehm titration and contact angle measurements. Their adsorption performance was evaluated using ibuprofen as a model pharmaceutical pollutant. Among the prepared materials, the carbon obtained by direct calcination at 1000 °C (C1000ZIF-8) exhibited the highest surface area (951 m<sup>2</sup> g<sup>−1</sup>), the lowest heteroatom content and the most hydrophobic surface (contact angle 127°), leading to superior adsorption behaviour. Ibuprofen adsorption followed the Langmuir model with a maximum capacity of 62.6 mg g<sup>−1</sup> and showed fast kinetics, with more than 50 % removal within the first 15 min and an excellent fit to the pseudo-second-order model (R<sup>2</sup> = 0.998). The material retained over 93 % of its initial adsorption capacity after ten adsorption–desorption cycles, demonstrating high stability and reusability. Finally, C1000ZIF-8 achieved removal efficiencies above 88 % for several pharmaceuticals in real water matrices, including seawater, tap water and groundwater, highlighting the key role of hydrophobic interactions and pore filling and confirming the strong potential of this material for practical water remediation applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114043"},"PeriodicalIF":4.7,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975621","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 : 2026-01-11DOI: 10.1016/j.micromeso.2026.114034
Kasmen Dogo , Isaac Alhamdu Baba , Habila Samson Paul , Manase Auta , Ambali Saka Abdulkareem , Uduak George Akpan , Moses Aderemi Olutoye , Chidi Evans Egwim , Sunday Albert Lawal , Elizabeth Jumoke Eterigho , Kehinde Shola Obayomi
Rapid industrialization has increased the discharge of heavy-metal-laden petroleum wastewater into water bodies, posing severe health and ecological risks due to the persistence, bioaccumulation, and toxicity of these contaminants. However, the simultaneous removal of these persistent inorganic pollutants from water bodies remains a major challenge. To mitigate this issue, we designed multi-walled carbon nanotubes (MWCNTs) impregnated with magnetite at different mixing ratios (magnetite/MWCNTs@1:1, magnetite/MWCNTs@2:1, and magnetite/MWCNTs@1:2) via a two-step process involving chemical vapor deposition (CVD) followed by wet impregnation to remove Cr(VI), Cd(II), Pb(II), and Ni(II) from petroleum-contaminated wastewater. The uniform dispersion of magnetite on the MWCNTs matrix, along with the resulting synergistic effects, was confirmed through physicochemical characterization. The impregnation of magnetite improved the surface potential of the MWCNTs, offering magnetic separability, synergistic adsorption effects, and metal-binding sites with increased BET surface area. In a batch adsorption system, the influence of contact time, adsorbent dosage, and temperature revealed that the adsorption performance followed the order 1:2 > 1:1 > 2:1, with the magnetite/MWCNTs@1:2 nanocomposite exhibiting optimum removal efficiencies of 100 % for Ni(II), 100 % for Cd(II), 89.97 % for Pb(II), and 83.86 % for Cr(VI). The adsorption kinetics and isotherm fitting confirmed that the adsorption process was more consistent with pseudo-second-order kinetic and Langmuir isotherm models, suggesting the dominance of chemical adsorption on homogenous surfaces. The magnetite/MWCNTs@1:2 nanocomposite exhibited maximum capacities of 585.3 mg/g for Cr(VI), 658.1 mg/g for Cd(II), 551.1 mg/g for Pb(II), and 468.6 mg/g for Ni(II). Thermodynamic examination revealed that the adsorption reactions were spontaneous, feasible, and proceeded endothermically. The cyclic experiment demonstrated that magnetite/MWCNTs with different mixing ratios still maintained >75 % removal efficiencies after seven cycles, confirming their potential in practical applications. Remarkably, the iron leaching from magnetite/MWCNTs@1:2 is only 0.06 mg/L, which is significantly below the WHO/EPA guideline limit for drinking water of 0.3 mg/L. Overall, this study demonstrates for the first time how the magnetite/MWCNTs mixing ratio governs the surface and structural properties of the nanocomposites, enabling effective heavy metal ions adsorption and recovery from petroleum-contaminated wastewater.
{"title":"Effect of mixing ratio on magnetite-incorporated MWCNTs for enhanced heavy metal ions adsorption from petroleum-contaminated wastewater","authors":"Kasmen Dogo , Isaac Alhamdu Baba , Habila Samson Paul , Manase Auta , Ambali Saka Abdulkareem , Uduak George Akpan , Moses Aderemi Olutoye , Chidi Evans Egwim , Sunday Albert Lawal , Elizabeth Jumoke Eterigho , Kehinde Shola Obayomi","doi":"10.1016/j.micromeso.2026.114034","DOIUrl":"10.1016/j.micromeso.2026.114034","url":null,"abstract":"<div><div>Rapid industrialization has increased the discharge of heavy-metal-laden petroleum wastewater into water bodies, posing severe health and ecological risks due to the persistence, bioaccumulation, and toxicity of these contaminants. However, the simultaneous removal of these persistent inorganic pollutants from water bodies remains a major challenge. To mitigate this issue, we designed multi-walled carbon nanotubes (MWCNTs) impregnated with magnetite at different mixing ratios (magnetite/MWCNTs@1:1, magnetite/MWCNTs@2:1, and magnetite/MWCNTs@1:2) via a two-step process involving chemical vapor deposition (CVD) followed by wet impregnation to remove Cr(VI), Cd(II), Pb(II), and Ni(II) from petroleum-contaminated wastewater. The uniform dispersion of magnetite on the MWCNTs matrix, along with the resulting synergistic effects, was confirmed through physicochemical characterization. The impregnation of magnetite improved the surface potential of the MWCNTs, offering magnetic separability, synergistic adsorption effects, and metal-binding sites with increased BET surface area. In a batch adsorption system, the influence of contact time, adsorbent dosage, and temperature revealed that the adsorption performance followed the order 1:2 > 1:1 > 2:1<strong>,</strong> with the magnetite/MWCNTs@1:2 nanocomposite exhibiting optimum removal efficiencies of 100 % for Ni(II)<strong>,</strong> 100 % for Cd(II)<strong>,</strong> 89.97 % for Pb(II)<strong>,</strong> and 83.86 % for Cr(VI)<strong>.</strong> The adsorption kinetics and isotherm fitting confirmed that the adsorption process was more consistent with pseudo-second-order kinetic and Langmuir isotherm models, suggesting the dominance of chemical adsorption on homogenous surfaces. The magnetite/MWCNTs@1:2 nanocomposite exhibited maximum capacities of 585.3 mg/g for Cr(VI), 658.1 mg/g for Cd(II), 551.1 mg/g for Pb(II), and 468.6 mg/g for Ni(II). Thermodynamic examination revealed that the adsorption reactions were spontaneous, feasible, and proceeded endothermically. The cyclic experiment demonstrated that magnetite/MWCNTs with different mixing ratios still maintained >75 % removal efficiencies after seven cycles, confirming their potential in practical applications. Remarkably, the iron leaching from magnetite/MWCNTs@1:2 is only 0.06 mg/L, which is significantly below the WHO/EPA guideline limit for drinking water of 0.3 mg/L. Overall, this study demonstrates for the first time how the magnetite/MWCNTs mixing ratio governs the surface and structural properties of the nanocomposites, enabling effective heavy metal ions adsorption and recovery from petroleum-contaminated wastewater.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114034"},"PeriodicalIF":4.7,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975626","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}
Clinoptilolite is a natural microporous aluminosilicate whose structure underly unique physicochemical properties. These properties support its growing use in medical and pharmaceutical applications. Clinoptilolite has a high surface area and a high ion exchange capacity exploited in many medical applications. Recently, its selective adsorption properties have prompted researchers to study its potential for controlled or targeted drug delivery. In this particular field of application its unmodified, naturally occurring form showed limitations due to its hydrophilicity and small pore size. This is why the natural clinoptilolite mainly shows transient uptake of small or polar drug molecules and is not appropriate for delivery of larger or nonpolar pharmaceutical compounds. The presented review provides a summarized overview of the clinoptilolite physical-chemical properties relevant for its potential drug delivery properties and examines various strategies used to modify the clinoptilolite surface with different organic and inorganic agents. One large portion of studies have provided data on usage of surfactants, chitosan, amine-containing polymers, and green-synthesized nanoparticles for improvement of the clinoptilolite adsorption capacity. Therapeutic functionality of clinoptilolite has been achieved by these surface modifications, i.e. chitosan modified clinoptilolite enabled targeted delivery and wound healing applications. Nanoparticles usage for surface modification, i.e. CaO and MgO were also successfully tested for sustained 5-fluorouracil release in colon cancer therapy. Moreover, the clinoptilolite surface has been successfully functionalized with antioxidant and enzymatic agents. In summary, modifications of the clinoptilolite surface are a growing area of research for obtaining versatile platforms for controlled drug delivery and advanced therapeutic systems. Some of the fields that might benefit the most are oncology and wound care.
{"title":"Natural clinoptilolite and its functionalization: From limited adsorption to tailored performance for pharmaceutical use","authors":"Gioconda Millotti , Rumenka Markoska , Krešimir Pavelić , Sandra Kraljević Pavelić","doi":"10.1016/j.micromeso.2026.114028","DOIUrl":"10.1016/j.micromeso.2026.114028","url":null,"abstract":"<div><div>Clinoptilolite is a natural microporous aluminosilicate whose structure underly unique physicochemical properties. These properties support its growing use in medical and pharmaceutical applications. Clinoptilolite has a high surface area and a high ion exchange capacity exploited in many medical applications. Recently, its selective adsorption properties have prompted researchers to study its potential for controlled or targeted drug delivery. In this particular field of application its unmodified, naturally occurring form showed limitations due to its hydrophilicity and small pore size. This is why the natural clinoptilolite mainly shows transient uptake of small or polar drug molecules and is not appropriate for delivery of larger or nonpolar pharmaceutical compounds. The presented review provides a summarized overview of the clinoptilolite physical-chemical properties relevant for its potential drug delivery properties and examines various strategies used to modify the clinoptilolite surface with different organic and inorganic agents. One large portion of studies have provided data on usage of surfactants, chitosan, amine-containing polymers, and green-synthesized nanoparticles for improvement of the clinoptilolite adsorption capacity. Therapeutic functionality of clinoptilolite has been achieved by these surface modifications, i.e. chitosan modified clinoptilolite enabled targeted delivery and wound healing applications. Nanoparticles usage for surface modification, i.e. CaO and MgO were also successfully tested for sustained 5-fluorouracil release in colon cancer therapy. Moreover, the clinoptilolite surface has been successfully functionalized with antioxidant and enzymatic agents. In summary, modifications of the clinoptilolite surface are a growing area of research for obtaining versatile platforms for controlled drug delivery and advanced therapeutic systems. Some of the fields that might benefit the most are oncology and wound care.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114028"},"PeriodicalIF":4.7,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975625","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 : 2026-01-08DOI: 10.1016/j.micromeso.2026.114033
Joaquín Martínez-Ortigosa , J. Alejandro Vidal-Moya , Reisel Millán , Vincent Sarou-Kanian , Fernando Rey , Teresa Blasco
Host-guest interactions in pure silica MFI zeolites synthesized in fluoride media using a range of organic structure-directing agents (OSDAs) (TEA, TPA, TPMA, TBA and TBMA) were investigated with emphasis on the influence of OSDA symmetry. Solid-state NMR techniques, notably bidimensional 1H–19F heteronuclear correlation (1H–19F HMQC) and the Rotational Echo Double Resonance (REDOR) were employed. Fluoride bonds silicon at the Si9 site and, depending on the OSDA, also to the Si12 giving rise to characteristic 19F NMR signals at −65 ppm and −80 ppm, respectively. Bulky OSDAs reduces fluoride incorporation and promotes bonding at Si12 site along with the formation of siloxy-silanol defects. Triple Quantum-Single Quamtum (TQ-SQ) 1H NMR spectra confirm the involvement of three neighboring silanol groups in the siloxy-silanol defects. 1H–13C HMQC spectra revealed that these defects are located near the terminal methyl groups of the longer OSDA chains and are distributed along both straight and sinusoidal channels of the MFI structure. REDOR experiments demonstrated that in MFI zeolites synthesized with asymmetric trialkyl methyl ammonium OSDAs, fluoride at the Si9 site is closer to the N–CH3 group, as confirmed by theoretical calculations. These findings highlight the critical role of OSDA structure in directing charge distribution and defect formation during zeolite crystallization. The study showcases the power of advanced solid-state NMR methods for probing framework–OSDA interactions, which are essential for tailoring zeolite properties for different applications.
{"title":"Framework–OSDA interactions and charge compensation in pure silica MFI zeolites revealed by solid-state NMR","authors":"Joaquín Martínez-Ortigosa , J. Alejandro Vidal-Moya , Reisel Millán , Vincent Sarou-Kanian , Fernando Rey , Teresa Blasco","doi":"10.1016/j.micromeso.2026.114033","DOIUrl":"10.1016/j.micromeso.2026.114033","url":null,"abstract":"<div><div>Host-guest interactions in pure silica MFI zeolites synthesized in fluoride media using a range of organic structure-directing agents (OSDAs) (TEA, TPA, TPMA, TBA and TBMA) were investigated with emphasis on the influence of OSDA symmetry. Solid-state NMR techniques, notably bidimensional <sup>1</sup>H–<sup>19</sup>F heteronuclear correlation (<sup>1</sup>H–<sup>19</sup>F HMQC) and the Rotational Echo Double Resonance <strong>(</strong>REDOR) were employed. Fluoride bonds silicon at the Si9 site and, depending on the OSDA, also to the Si12 giving rise to characteristic <sup>19</sup>F NMR signals at −65 ppm and −80 ppm, respectively. Bulky OSDAs reduces fluoride incorporation and promotes bonding at Si12 site along with the formation of siloxy-silanol defects. Triple Quantum-Single Quamtum (TQ-SQ) <sup>1</sup>H NMR spectra confirm the involvement of three neighboring silanol groups in the siloxy-silanol defects. <sup>1</sup>H–<sup>13</sup>C HMQC spectra revealed that these defects are located near the terminal methyl groups of the longer OSDA chains and are distributed along both straight and sinusoidal channels of the MFI structure. REDOR experiments demonstrated that in MFI zeolites synthesized with asymmetric trialkyl methyl ammonium OSDAs, fluoride at the Si9 site is closer to the N–CH<sub>3</sub> group, as confirmed by theoretical calculations. These findings highlight the critical role of OSDA structure in directing charge distribution and defect formation during zeolite crystallization. The study showcases the power of advanced solid-state NMR methods for probing framework–OSDA interactions, which are essential for tailoring zeolite properties for different applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114033"},"PeriodicalIF":4.7,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145950096","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, Cu-based hydrotalcite-zeolite (CuHT-ZSM-5) composites were synthesized and characterized to explore their potential as catalyst precursors. The hydrotalcite phase was successfully formed on ZSM-5 zeolite supports with different Si/Al ratios under standard co-precipitation conditions (pH = 10, T = 65 °C). Structural analysis confirmed that the zeolite framework remained intact during synthesis, with only minor acidity modifications observed for Al-containing ZSM-5. The hydrotalcite layers were composed of copper, magnesium and aluminium cations, while the carbonate anions were used as interlayer anions.
Thermal decomposition of the CuHT phase resulted in in-situ generation of highly dispersed mixed metal oxides (MMOs). Textural characterization revealed that optimal calcination temperatures (500–600 °C) allow to obtain materials with high specific surface areas, while excessive heating (≥800 °C) led to partial collapse of the porous structure and formation of new MgSiO3 phases.
The study demonstrates that CuHT-ZSM-5 composites are structurally stable, thermally resistant, and exhibit tuneable acidity – key properties for catalytic applications. These findings open new possibilities for optimizing MMO-zeolite catalysts, particularly for NH3-SCO reactions.
本研究合成了cu基水滑石-沸石（CuHT-ZSM-5）复合材料，并对其进行了表征，以探索其作为催化剂前驱体的潜力。在标准共沉淀条件下（pH = 10, T = 65℃），在不同Si/Al比的ZSM-5沸石载体上成功形成水滑石相。结构分析证实，分子筛框架在合成过程中保持完整，仅观察到含al的ZSM-5有轻微的酸性修饰。水滑石层由铜、镁、铝阳离子组成，碳酸盐阴离子作为层间阴离子。CuHT相的热分解导致原位生成高度分散的混合金属氧化物（MMOs）。结构表征表明，最佳的煅烧温度（500-600℃）可以获得高比表面积的材料，而过度加热（≥800℃）会导致多孔结构的部分坍塌并形成新的MgSiO3相。研究表明，CuHT-ZSM-5复合材料结构稳定，耐热，并具有可调的酸度-催化应用的关键性能。这些发现为优化mmo -沸石催化剂，特别是NH3-SCO反应开辟了新的可能性。
{"title":"Hydrotalcite-zeolite composites as precursors for catalysis: Synthesis, transformation and structural stability","authors":"Sylwia Górecka , Kateřina Pacultová , Kateřina Karásková , Kamil Górecki , Kateřina Kupková , Eva Kinnertová , Antonio Eduardo Palomares Gimeno , Lucie Obalová","doi":"10.1016/j.micromeso.2026.114031","DOIUrl":"10.1016/j.micromeso.2026.114031","url":null,"abstract":"<div><div>In this study, Cu-based hydrotalcite-zeolite (CuHT-ZSM-5) composites were synthesized and characterized to explore their potential as catalyst precursors. The hydrotalcite phase was successfully formed on ZSM-5 zeolite supports with different Si/Al ratios under standard co-precipitation conditions (pH = 10, T = 65 °C). Structural analysis confirmed that the zeolite framework remained intact during synthesis, with only minor acidity modifications observed for Al-containing ZSM-5. The hydrotalcite layers were composed of copper, magnesium and aluminium cations, while the carbonate anions were used as interlayer anions.</div><div>Thermal decomposition of the CuHT phase resulted in in-situ generation of highly dispersed mixed metal oxides (MMOs). Textural characterization revealed that optimal calcination temperatures (500–600 °C) allow to obtain materials with high specific surface areas, while excessive heating (≥800 °C) led to partial collapse of the porous structure and formation of new MgSiO<sub>3</sub> phases.</div><div>The study demonstrates that CuHT-ZSM-5 composites are structurally stable, thermally resistant, and exhibit tuneable acidity – key properties for catalytic applications. These findings open new possibilities for optimizing MMO-zeolite catalysts, particularly for NH<sub>3</sub>-SCO reactions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114031"},"PeriodicalIF":4.7,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-08DOI: 10.1016/j.micromeso.2026.114029
Roy M. Sullivan , Emmanuel N. Skountzos , Chris M. Brady , Ashwin Ravichandran , William H. Huddleston , Daniel L. Vigil , John W. Lawson , Lyndsey McMillon-Brown
A multi-scale analysis approach is presented for simulating CO2 capture in a packed bed of zeolite 13X beads. The multi-scale modeling scheme consists of a macro-scale model for simulating the flow of a gas mixture containing CO2 through a particle bed with the local adsorption of CO2 into the zeolite particles and a series of molecular simulations performed to inform the macro-scale model regarding the storage capacity and adsorption rate behavior. Two complementary molecular simulation techniques were employed: Grand Canonical Monte Carlo (GCMC) for calculating the equilibrium adsorption isotherms, and Molecular Dynamics (MD) to predict the diffusivity of CO2 in a representative zeolite 13X microstructure. The resulting porous media and adsorption model is a nonequilibrium approach as it allows for both equilibrium and nonequilibrium adsorption states. The porous media and adsorption model is applied to simulate the breakthrough experiments reported in the literature, in order to validate the multi-scale solution approach. The model is also utilized to perform a sensitivity analysis to quantify the effects of four adsorption parameters on the adsorption efficiency and to demonstrate the potential benefits of this nonequilibrium approach over more simplified methods that have been used for systems-level design studies. The capabilities of the integrated approach to predict adsorption capacity, rate, and systems level performance metrics were sought for exploration of novel adsorber compositions to enable discovery of new materials for enhanced performance in direct air capture systems.
{"title":"A multi-scale analysis of CO2 adsorption in zeolite 13X","authors":"Roy M. Sullivan , Emmanuel N. Skountzos , Chris M. Brady , Ashwin Ravichandran , William H. Huddleston , Daniel L. Vigil , John W. Lawson , Lyndsey McMillon-Brown","doi":"10.1016/j.micromeso.2026.114029","DOIUrl":"10.1016/j.micromeso.2026.114029","url":null,"abstract":"<div><div>A multi-scale analysis approach is presented for simulating CO<sub>2</sub> capture in a packed bed of zeolite 13X beads. The multi-scale modeling scheme consists of a macro-scale model for simulating the flow of a gas mixture containing CO<sub>2</sub> through a particle bed with the local adsorption of CO<sub>2</sub> into the zeolite particles and a series of molecular simulations performed to inform the macro-scale model regarding the storage capacity and adsorption rate behavior. Two complementary molecular simulation techniques were employed: Grand Canonical Monte Carlo (GCMC) for calculating the equilibrium adsorption isotherms, and Molecular Dynamics (MD) to predict the diffusivity of CO<sub>2</sub> in a representative zeolite 13X microstructure. The resulting porous media and adsorption model is a nonequilibrium approach as it allows for both equilibrium and nonequilibrium adsorption states. The porous media and adsorption model is applied to simulate the breakthrough experiments reported in the literature, in order to validate the multi-scale solution approach. The model is also utilized to perform a sensitivity analysis to quantify the effects of four adsorption parameters on the adsorption efficiency and to demonstrate the potential benefits of this nonequilibrium approach over more simplified methods that have been used for systems-level design studies. The capabilities of the integrated approach to predict adsorption capacity, rate, and systems level performance metrics were sought for exploration of novel adsorber compositions to enable discovery of new materials for enhanced performance in direct air capture systems.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114029"},"PeriodicalIF":4.7,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975622","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 : 2026-01-07DOI: 10.1016/j.micromeso.2026.114032
Nelcari-Trinidad Ramírez-Marquez , Ion Such Basáñez , Noemí Linares , Carlos Alexander Trujillo
Reliable quantification of zeolite acidity by ammonia temperature-programmed desorption (NH3-TPD) is often hindered by the presence of water, particularly in ammonium-exchanged zeolites where water desorption and ammonium decomposition occur concurrently. In such systems, differential detectors such as thermal conductivity (TCD) and mass spectrometry (MS) exhibit significant interference: premature signal onset, peak broadening, and shifts to lower temperatures, ultimately leading to an overestimation of acidity. In this work, we evaluate the performance of TCD, MS, and an ionic conductivity detector (ICD) for NH3-TPD measurements of ammonium- and protonic-Y zeolites (CBV300, CBV720, CBV780). The ICD provides a selective, water-insensitive response, detecting only ammonia that is dissolved and ionized as NH4+ in boric acid solution. As a result, the ICD successfully quantifies acidity in non-activated ammonium zeolites, where TCD and MS responses are affected by water. For activated zeolites saturated with ammonia, all detectors produce comparable desorption profiles; however, MS exhibits the lowest noise-to-signal ratio, followed by ICD, while TCD shows the poorest stability. These results demonstrate that the ICD is a robust, cost-effective, and water-insensitive detector that significantly extends the applicability of NH3-TPD to zeolites previously considered incompatible with the technique.
{"title":"Ionic conductivity detection as a water-insensitive alternative for NH3-TPD acidity measurements in zeolites","authors":"Nelcari-Trinidad Ramírez-Marquez , Ion Such Basáñez , Noemí Linares , Carlos Alexander Trujillo","doi":"10.1016/j.micromeso.2026.114032","DOIUrl":"10.1016/j.micromeso.2026.114032","url":null,"abstract":"<div><div>Reliable quantification of zeolite acidity by ammonia temperature-programmed desorption (NH<sub>3</sub>-TPD) is often hindered by the presence of water, particularly in ammonium-exchanged zeolites where water desorption and ammonium decomposition occur concurrently. In such systems, differential detectors such as thermal conductivity (TCD) and mass spectrometry (MS) exhibit significant interference: premature signal onset, peak broadening, and shifts to lower temperatures, ultimately leading to an overestimation of acidity. In this work, we evaluate the performance of TCD, MS, and an ionic conductivity detector (ICD) for NH<sub>3</sub>-TPD measurements of ammonium- and protonic-Y zeolites (CBV300, CBV720, CBV780). The ICD provides a selective, water-insensitive response, detecting only ammonia that is dissolved and ionized as NH<sub>4</sub><sup>+</sup> in boric acid solution. As a result, the ICD successfully quantifies acidity in non-activated ammonium zeolites, where TCD and MS responses are affected by water. For activated zeolites saturated with ammonia, all detectors produce comparable desorption profiles; however, MS exhibits the lowest noise-to-signal ratio, followed by ICD, while TCD shows the poorest stability. These results demonstrate that the ICD is a robust, cost-effective, and water-insensitive detector that significantly extends the applicability of NH<sub>3</sub>-TPD to zeolites previously considered incompatible with the technique.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"404 ","pages":"Article 114032"},"PeriodicalIF":4.7,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035761","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 : 2026-01-03DOI: 10.1016/j.micromeso.2025.114025
Tuyen Anh Luu , Andrzej Olejniczak , Nguyen Vu Minh Trung , Huan V. Doan , Hue Thi Pham , Hue Thi Ngoc Nguyen , Jerzy P. Lukaszewicz , Nguyen La Ly , Samir F. Samadov , Marcin Turek , Tran V. Phuc , Hoang Anh Tuan Kiet , Nguyen Anh Tuan , Semyon V. Mitrofanov , Ngo Dang Trung , Nguyen Quang Hung , Tiep Nguyen Van
Hydrothermal synthesis is a well-established and scalable route for producing well-ordered zeolites that underpin industrial catalysis, separation, and adsorption. However, the concurrent chemical condensation and structural reorganization occurring at elevated temperatures make it difficult to elucidate how framework order and connectivity emerge from amorphous precursors, hindering the rational design of zeolites with tailored structural and catalytic properties. Here, we employ a time-resolved, multimodal approach to track the crystallization of Silicalite-1 (MFI) at 180 °C over shortened synthesis durations (1–5 h). The results reveal a sequential evolution from short-range ordering to partially organized pre-channels and pre-intersections that gradually link into a continuous microporous framework. Unexpectedly, transient mesopores act as temporary reservoirs for bound water, silanol groups, and template species, mediating condensation and defect healing that drive the assembly of pre-channels and their consolidation into stable intersections. This cooperative interplay between mesopores and framework growth clarifies how hierarchical order develops in the early stages of crystallization. Upon calcination, extended treatment removes residual species, opens pore network, and enhances accessibility, consolidating the matured MFI lattice. The resulting holistic, time-resolved mechanism offers mechanistic insight into framework evolution and provides a foundation for designing more time- and energy-efficient hydrothermal synthesis routes of zeolites.
{"title":"Early-stage silanol condensation, defect healing and temporary reservoirs drive the development of the framework and porous system in silicalite-1 synthesized at 180 0C","authors":"Tuyen Anh Luu , Andrzej Olejniczak , Nguyen Vu Minh Trung , Huan V. Doan , Hue Thi Pham , Hue Thi Ngoc Nguyen , Jerzy P. Lukaszewicz , Nguyen La Ly , Samir F. Samadov , Marcin Turek , Tran V. Phuc , Hoang Anh Tuan Kiet , Nguyen Anh Tuan , Semyon V. Mitrofanov , Ngo Dang Trung , Nguyen Quang Hung , Tiep Nguyen Van","doi":"10.1016/j.micromeso.2025.114025","DOIUrl":"10.1016/j.micromeso.2025.114025","url":null,"abstract":"<div><div>Hydrothermal synthesis is a well-established and scalable route for producing well-ordered zeolites that underpin industrial catalysis, separation, and adsorption. However, the concurrent chemical condensation and structural reorganization occurring at elevated temperatures make it difficult to elucidate how framework order and connectivity emerge from amorphous precursors, hindering the rational design of zeolites with tailored structural and catalytic properties. Here, we employ a time-resolved, multimodal approach to track the crystallization of Silicalite-1 (MFI) at 180 °C over shortened synthesis durations (1–5 h). The results reveal a sequential evolution from short-range ordering to partially organized pre-channels and pre-intersections that gradually link into a continuous microporous framework. Unexpectedly, transient mesopores act as temporary reservoirs for bound water, silanol groups, and template species, mediating condensation and defect healing that drive the assembly of pre-channels and their consolidation into stable intersections. This cooperative interplay between mesopores and framework growth clarifies how hierarchical order develops in the early stages of crystallization. Upon calcination, extended treatment removes residual species, opens pore network, and enhances accessibility, consolidating the matured MFI lattice. The resulting holistic, time-resolved mechanism offers mechanistic insight into framework evolution and provides a foundation for designing more time- and energy-efficient hydrothermal synthesis routes of zeolites.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114025"},"PeriodicalIF":4.7,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921900","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 : 2026-01-03DOI: 10.1016/j.micromeso.2026.114030
Baomin Wang, Haoxiang Yang, Chengcheng Fan, Fei Liu, Wenxin Lu
Alkali-activated materials show excellent capture capacity on heavy metals, but the mechanisms to immobilize heavy metals remain inadequately explored. This work investigated the main hydration product C-A-S-H gels for encapsulation of heavy metals such as Pb(II), Zn(II) and Cd(II). Furthermore, the adsorption behavior and mechanisms of Pb(II) in pore solutions by C-A-S-H were examined. These findings reveal that aluminum is incorporated into the silicon chains of C-S-H in the form of aluminum-oxygen tetrahedra, thereby generating C-A-S-H. The bonding ratio, which depends on the Ca/Si ratio, reaches its peak value of 0.139 when the Ca/Si ratio is 0.9. In highly alkaline environments, amphoteric Pb(II) and Zn(II) form hydroxyl coordination polyhedra, enhancing silicon chain polymerization, whereas Cd(II) is immobilized via ion exchange with Ca(II), resulting in solid solutions. For C-A-S-H with a Ca/Si ratio of 0.6, Pb(II) adsorption occurs predominantly through physical interactions. However, as the Ca/Si molar ratio increases, the effect chemisorption and ion exchange become more significant along with the formation of Pb8Ca(Si2O7)3. C-A-S-H gel with a Ca/Si ratio of 0.9 has the highest Pb(II) adsorption capacity, reaching 92.55 mg/g.
{"title":"Adsorption behavior and immobilization mechanism of typical heavy metals in synthetic C-A-S-H gels","authors":"Baomin Wang, Haoxiang Yang, Chengcheng Fan, Fei Liu, Wenxin Lu","doi":"10.1016/j.micromeso.2026.114030","DOIUrl":"10.1016/j.micromeso.2026.114030","url":null,"abstract":"<div><div>Alkali-activated materials show excellent capture capacity on heavy metals, but the mechanisms to immobilize heavy metals remain inadequately explored. This work investigated the main hydration product C-A-S-H gels for encapsulation of heavy metals such as Pb(II), Zn(II) and Cd(II). Furthermore, the adsorption behavior and mechanisms of Pb(II) in pore solutions by C-A-S-H were examined. These findings reveal that aluminum is incorporated into the silicon chains of C-S-H in the form of aluminum-oxygen tetrahedra, thereby generating C-A-S-H. The bonding ratio, which depends on the Ca/Si ratio, reaches its peak value of 0.139 when the Ca/Si ratio is 0.9. In highly alkaline environments, amphoteric Pb(II) and Zn(II) form hydroxyl coordination polyhedra, enhancing silicon chain polymerization, whereas Cd(II) is immobilized via ion exchange with Ca(II), resulting in solid solutions. For C-A-S-H with a Ca/Si ratio of 0.6, Pb(II) adsorption occurs predominantly through physical interactions. However, as the Ca/Si molar ratio increases, the effect chemisorption and ion exchange become more significant along with the formation of Pb<sub>8</sub>Ca(Si<sub>2</sub>O<sub>7</sub>)<sub>3</sub>. C-A-S-H gel with a Ca/Si ratio of 0.9 has the highest Pb(II) adsorption capacity, reaching 92.55 mg/g.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114030"},"PeriodicalIF":4.7,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921897","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 : 2026-01-02DOI: 10.1016/j.micromeso.2026.114027
Yangyu Liu , Ke Ren , Jiuyue Wang , Arman Peyravi , Zaher Hashisho , Yuping Tong , Xiao Wang , Xi Chen , Jinggan Shao , Jinyong Wu , Ruqin Gao
In this study, CoFe2O4 nanoparticles were anchored onto natural Opoka-derived MCM-41 (denoted as CFMCM) using a facile citrate combustion method, resulting in a composite with excellent performance and stability. Systematic characterization and peroxymonosulfate (PMS) activation experiments were conducted to evaluate tetracycline (TC) degradation performance. Compared to bare CoFe2O4, CFMCM exhibited greatly enhanced specific surface area and pore volume. The MCM-41 support facilitated multidirectional crystallization of CoFe2O4 nanoparticles, resulting in reduced grain size and lower crystallinity, thereby providing abundant active sites for PMS activation. The CFMCM composite demonstrated superior PMS activation capability with a degradation rate constant that was 3.3 times higher than bare CoFe2O4. The uniform anchoring of highly dispersed CoFe2O4 nanoparticles on MCM-41 effectively prevented metal leaching, ensuring excellent reusability. Radical quenching tests and electron paramagnetic resonance (EPR) analysis revealed that reactive oxygen species (•OH, SO4•-, and 1O2) participated in the degradation process, with SO4•- and 1O2 being the dominant species. These reactive species were generated through the redox cycling between Co2+/Co3+ and Fe2+/Fe3+ pairs. Furthermore, possible TC degradation pathways were proposed based on intermediates identification. This work provides new insights into developing high-efficiency PMS-activating catalysts derived from natural minerals for wastewater treatment.
{"title":"CoFe2O4 nanoparticles supported on MCM-41 as highly efficient peroxymonosulfate catalyst for tetracycline degradation","authors":"Yangyu Liu , Ke Ren , Jiuyue Wang , Arman Peyravi , Zaher Hashisho , Yuping Tong , Xiao Wang , Xi Chen , Jinggan Shao , Jinyong Wu , Ruqin Gao","doi":"10.1016/j.micromeso.2026.114027","DOIUrl":"10.1016/j.micromeso.2026.114027","url":null,"abstract":"<div><div>In this study, CoFe<sub>2</sub>O<sub>4</sub> nanoparticles were anchored onto natural Opoka-derived MCM-41 (denoted as CFMCM) using a facile citrate combustion method, resulting in a composite with excellent performance and stability. Systematic characterization and peroxymonosulfate (PMS) activation experiments were conducted to evaluate tetracycline (TC) degradation performance. Compared to bare CoFe<sub>2</sub>O<sub>4</sub>, CFMCM exhibited greatly enhanced specific surface area and pore volume. The MCM-41 support facilitated multidirectional crystallization of CoFe<sub>2</sub>O<sub>4</sub> nanoparticles, resulting in reduced grain size and lower crystallinity, thereby providing abundant active sites for PMS activation. The CFMCM composite demonstrated superior PMS activation capability with a degradation rate constant that was 3.3 times higher than bare CoFe<sub>2</sub>O<sub>4</sub>. The uniform anchoring of highly dispersed CoFe<sub>2</sub>O<sub>4</sub> nanoparticles on MCM-41 effectively prevented metal leaching, ensuring excellent reusability. Radical quenching tests and electron paramagnetic resonance (EPR) analysis revealed that reactive oxygen species (•OH, SO<sub>4</sub>•<sup>-</sup>, and <sup>1</sup>O<sub>2</sub>) participated in the degradation process, with SO<sub>4</sub>•<sup>-</sup> and <sup>1</sup>O<sub>2</sub> being the dominant species. These reactive species were generated through the redox cycling between Co<sup>2+</sup>/Co<sup>3+</sup> and Fe<sup>2+</sup>/Fe<sup>3+</sup> pairs. Furthermore, possible TC degradation pathways were proposed based on intermediates identification. This work provides new insights into developing high-efficiency PMS-activating catalysts derived from natural minerals for wastewater treatment.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"403 ","pages":"Article 114027"},"PeriodicalIF":4.7,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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