Microporous and Mesoporous Materials最新文献

{"title":"Phenol hydroxylation to produce dihydroxybenzenes over iron-containing UZM-35 catalysts prepared via different methods","authors":"Xinhong Zhao ,&nbsp;Jiulong Chen ,&nbsp;Mengqi Ding ,&nbsp;Hongwei Li ,&nbsp;Xuefeng Long ,&nbsp;Dong Ji ,&nbsp;Guixian Li","doi":"10.1016/j.micromeso.2025.113774","DOIUrl":"10.1016/j.micromeso.2025.113774","url":null,"abstract":"<div><div>The chemical state of iron active centers directly influences the inherent catalytic capability of iron-based zeolites. Hence, it is very important to build highly active iron species with a single coordination state through different synthetic schemes from the perspectives of both the theoretical research and practical application. Nevertheless, the identification of dominant active sites in iron-based zeolite-catalyzed phenol hydroxylation remains ambiguous, primarily due to the heterogeneous nature of iron speciation within the zeolitic framework. In this study, iron-based UZM-35 zeolite catalysts with different coordination states were obtained by three different preparation methods using UZM-35 zeolite as the supports. A comprehensive characterization of the catalysts' structure and properties was performed using SEM, XRD, FT-IR, Raman, N₂ physisorption, H₂-TPR, UV–Vis and NH₃-TPD. The findings indicate that Fe-UZM-35 zeolite prepared via the direct synthesis method predominantly contains isolated tetrahedrally coordinated framework Fe³⁺ ion species, whereas Fe/UZM-35 zeolites produced via impregnation and solid-state ion exchange methods primarily consist of octahedrally coordinated isolated extra-framework Fe³⁺ ion species. The data from the catalytic reaction showed that Fe/UZM-35 zeolite catalysts prepared by two post-treatment methods had good activity for phenol hydroxylation, while the dihydroxybenzene selectivity of solid-state ion exchange method was slightly higher than that of impregnation method. As the iron content rose, the selectivity for dihydroxybenzene increased progressively. The sample of G-6wt%Fe/UZM-35 reached a phenol conversion of 53.65 % and a dihydroxybenzene selectivity of 89.93 % (S_CAT = 46.95 %, S_HQ = 42.99 %). Moreover, it was observed that light irradiation affected the dynamics of phenol hydroxylation reaction, resulting in diminished selectivity toward dihydroxybenzene while concomitantly enhancing tar formation. According to the findings from structural analysis and assessment of catalytic performance, we proposed that the octahedral coordinated isolated extra-framework Fe³⁺ ion species have higher hydroxylation activity and dihydroxybenzene selectivity in the phenol hydroxylation reaction catalyzed by iron-based zeolites.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113774"},"PeriodicalIF":4.8,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144687117","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}

{"title":"Tuning the PCP-SAFT equation of state to estimate adsorption-desorption hysteresis of pure fluids and mixtures confined in ordered mesoporous silica","authors":"Aliakbar Roosta,&nbsp;Nima Rezaei","doi":"10.1016/j.micromeso.2025.113772","DOIUrl":"10.1016/j.micromeso.2025.113772","url":null,"abstract":"<div><div>This study presents a comprehensive model for predicting the capillary condensation-evaporation hysteresis of pure components and mixtures in nanoporous materials, by tuning the dispersion energy parameter of the perturbed-chain polar statistical associating fluid theory (PCP-SAFT) equation of state. The model is based on an extensive hysteresis dataset comprising 304 data points for 24 different components, including nonpolar, polar, and associating components. The dispersion energy parameters for both adsorption and desorption processes are determined, and new correlations are proposed to improve the accuracy of the capillary condensation and evaporation pressure predictions. The results indicate that the current model provides superior prediction accuracy, with average absolute relative deviation (AARD) values of 10.89 % for the capillary condensation pressure and 10.95 % for evaporation pressure in pure components. The study also examines the effects of pore size, temperature, and fluid interactions on the capillary condensation-evaporation hysteresis. The model demonstrates good agreement with experimental data for both pure components and mixtures, under varying temperatures and pore sizes. The findings highlight the critical role of pore size and temperature in determining the extent of hysteresis. Stronger hysteresis is observed at specific pore diameters, particularly around a ratio of the sorbent mean pore radius to the PCP-SAFT segment size (<em>r</em>_p/σ) of 15–17, and at lower temperatures. The study concludes that the model provides a reliable framework for predicting the capillary condensation-evaporation behavior in nanoporous materials, with potential applications in various fields such as gas storage, separation processes, and environmental applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113772"},"PeriodicalIF":4.8,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144687118","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}

{"title":"Nanoscale structure of ordered mesoporous carbon formed by nanocasting within a hard template: MD simulation with ML potentials","authors":"Da-Jiang Liu ,&nbsp;James W. Evans","doi":"10.1016/j.micromeso.2025.113741","DOIUrl":"10.1016/j.micromeso.2025.113741","url":null,"abstract":"<div><div>Molecular Dynamics simulations with machine learned (ML) potentials are utilized to develop models for the structure of ordered mesoporous carbons (OMC) formed by nanocasting in hard templates with linear cylindrical pores, e.g., SBA-15. Potentials are initially trained on PBE DFT, but subsequently enhanced by transfer-learning to suitably incorporate vdW energetics. Rather than analyze the larger-scale mesoporous structure, we focus on the disordered partially graphitized structure of a carbon nanorod formed within a single pore of the template. In benchmark simulations, carbon is confined to a cylindrical pore by surrounding inert immobile atoms, and in more realistic simulations by utilizing an atomistic model for amorphous mesoporous silica. We assess the dependence of OMC structure on the description of the hard template, and on the selection of the carbon precursor. Depending on the template materials and synthesis conditions, structures ranging from multi-wall carbon nanotubes or nanoscrolls to more disordered and complex structures involving carbon nanoribbon and nanodisc motifs, are found in simulations with the more realistic templates. At lower temperatures, where dehydrogenation processes occur at a similar or slower time scale than the growth of the carbon material, the choice of carbon feedstocks also affects the structures of the synthesized OMC.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113741"},"PeriodicalIF":4.8,"publicationDate":"2025-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144680098","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}

{"title":"Dynamic switch of CTAB as the sole template for the synthesis hierarchically porous ZSM-5 through a straightforward conventional static hydrothermal method","authors":"Jingce Bi ,&nbsp;Qingfeng Zhan ,&nbsp;Yujing Chen ,&nbsp;Zhiqiang Liang ,&nbsp;Ningning Liu ,&nbsp;Xia Zhang ,&nbsp;Zhuopeng Wang ,&nbsp;Yide Han","doi":"10.1016/j.micromeso.2025.113768","DOIUrl":"10.1016/j.micromeso.2025.113768","url":null,"abstract":"<div><div>At present, the construction of hierarchically porous ZSM-5 molecular sieves using only cetyltrimethylammonium bromide (CTAB) as the template represents a major challenge in the field of molecular sieve synthesis. In this work, hierarchically porous ZSM-5 zeolite was synthesized via a straightforward conventional static hydrothermal method, employing CTAB as the sole template agent derived from CTAB-encapsulated silica sphere precursors. By controlling the dissolution rate of silica spheres, the release rate of CTAB is regulated, enabling the synthesis of pure-phase hierarchical porous ZSM-5 zeolite. The influences of alkalinity, aging time, Si/Al ratio, CTAB content and addition method, and crystallization time on the construction of hierarchically porous ZSM-5 molecular sieves were examined. The experimental results indicate that the crystallization process in this system proceeds in the order: MFI → MFI + kenyaite → MFI + quartz. Additionally, by managing the crystallization process, we systematically examined the formation process of impurities and established the optimal conditions for synthesizing pure-phase hierarchically porous ZSM-5 molecular sieves in this system. Moreover, the as-prepared hierarchically porous ZSM-5 molecular sieves demonstrated enhanced selectivity towards light olefins in the MTP reaction.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113768"},"PeriodicalIF":4.8,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144653990","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}

{"title":"Accelerated synthesis of ferrierite nanoneedles via the ETL seed-assisted approach for catalytic ethanol dehydration","authors":"Narasiri Maineawklang,&nbsp;Warot Prasanseang,&nbsp;Krissanapat Yomthong,&nbsp;Ploychanok Iadrat,&nbsp;Chularat Wattanakit","doi":"10.1016/j.micromeso.2025.113769","DOIUrl":"10.1016/j.micromeso.2025.113769","url":null,"abstract":"<div><div>The rational design of zeolite nanostructures at the molecular level significantly impacts their properties and catalytic performances in various reactions, especially alcohols-to-hydrocarbons. However, most synthesis methods involve complex and time-consuming processes. To address these challenges, developing a new synthesis method to obtain hierarchical zeolites <em>via</em> an integrated one-step and rapid synthesis approach could be a promising research contribution. Herein, we report that the crystallization of hierarchical FER zeolite can be effectively accelerated <em>via</em> the ETL zeolite seed-assisted approach, resulting in a decrease of synthesis time. This behavior can be explained by the fact that both FER and ETL zeolites contain similar main building units, namely <em>mor</em>, which can assist the formation of FER when using ETL as seeds. As a result, the FER framework can be directly constructed from the building units of the ETL seed. In addition, the nanorod-like structure of ETL seeds can affect the target FER morphology, eventually forming hierarchical nanoneedle features. The catalytic activities of the synthesized hierarchical FER with a nanoneedle shape were also systematically investigated in ethanol dehydration, demonstrating the advantages of the designed materials compared to the conventional one.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113769"},"PeriodicalIF":4.8,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144662400","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}

{"title":"Oxygen-promoted plasma-catalytic dry methane reforming over mesoporous catalysts for oxygenate production","authors":"Oleg V. Golubev,&nbsp;Pavel S. Il'chuk,&nbsp;Anton L. Maximov","doi":"10.1016/j.micromeso.2025.113767","DOIUrl":"10.1016/j.micromeso.2025.113767","url":null,"abstract":"<div><div>Plasma-catalytic dry methane reforming is an advanced approach for converting methane and carbon dioxide into syngas, hydrocarbons and liquid oxygenates, offering a sustainable pathway for greenhouse gas utilization. Plasma is used to trigger chemical reactions at relatively low temperatures, making it more energy-efficient and environmentally friendly compared to traditional high-temperature methods. In present work, a plasma-driven process of dry methane reforming was performed in dielectric barrier discharge reactor filled with mesoporous catalysts. The catalysts based on mesoporous materials MCM-41, SBA-15 and MCF were synthesized and characterized by the various physico-chemical methods. These catalysts were selected for their high surface area and tailored pore structure, which may assist in enhancing plasma-catalyst interactions, improving conversion efficiency, and promoting selectivity toward desired products. It was shown that Ni-based catalysts mainly promoted syngas and C₂H₆ formation, whereas Cu-based catalysts favored in liquid oxygenate yield enhancement. Cu-containing catalyst based on mesoporous MCF material has shown better CO₂ conversion due to open wide mesopores. The oxygen addition to the CH₄/CO₂ mixture was studied. It was revealed that both gaseous products and oxygenate yields were enhanced in presence of O₂. Methanol yield was increased due to parallel reactions of dry methane reforming and partial methane oxidation.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113767"},"PeriodicalIF":4.8,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144662399","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}

{"title":"Hydrogen gas adsorption capacity of halloysite nanotubes loaded with metal-organic frameworks","authors":"Hyeyeon Cho ,&nbsp;Minjeong Kang ,&nbsp;Jungju Ryu ,&nbsp;Jaeyong Kim ,&nbsp;Daewon Sohn","doi":"10.1016/j.micromeso.2025.113764","DOIUrl":"10.1016/j.micromeso.2025.113764","url":null,"abstract":"<div><div>Halloysite is a natural, eco-friendly, material abundant that has different charges inside and outside of its structural tubular nanoparticles. The adsorption performance of the material was improved by modifying halloysite nanotubes (HNTs) to prepare a nanocomposite. Metal-organic frameworks (MOF: HKUST-1) as gas adsorbents were loaded inside the halloysite to produce the composite. An etching process using sulfuric acid was performed to increase the loading efficiency by expanding the inner space of the halloysite to effectively load precursor solution; the resulting material was known as etched HNTs (EHNTs). Structural analysis was performed with X-ray diffraction (XRD), and morphological analysis was conducted using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). In addition, the hydrogen and nitrogen adsorption capacities were measured using Brunauer-Emmett-Teller (BET) equipment. The results confirmed improved adsorption capacity of both N₂ and H₂ by HKUST-1@EHNT(5M) compared to that of HKUST-1@EHNT(1M). Etching at high concentrations allowed a larger inner space and load amount of HKUST-1. This study presented the possibility of synthesizing various hybrid materials using nanotubes, and we expect that the halloysite nanocomposite synthesis process can be used in gas adsorption applications.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113764"},"PeriodicalIF":4.8,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144654095","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}

{"title":"Highly porous and chemically stable covalent organic frameworks with designable vertex skeletons for enhanced gas capture","authors":"Wanyi Zhao ,&nbsp;Ning Chen ,&nbsp;Yunxi Huang ,&nbsp;Ce Xing ,&nbsp;Xiaolong Luo ,&nbsp;Yongfeng Zhi ,&nbsp;He Li ,&nbsp;Yuwei Zhang","doi":"10.1016/j.micromeso.2025.113766","DOIUrl":"10.1016/j.micromeso.2025.113766","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) represent a class of porous crystalline materials distinguished by their exceptionally high surface areas and well-defined ordered structures. Constructed from organic molecules interconnected through covalent bonds, COFs possess precisely tunable pore sizes, shapes, and functional groups, making them highly versatile candidates for gas capture applications. In this study, two vertex units were designed and incorporated into imine-based COF frameworks to construct highly conjugated structures, achieving exceptional porosity with a BET surface area of up to 1810 m²/g. Moreover, the synthesized COFs demonstrate remarkable chemical stability under extreme acidic and basic conditions. Notably, the resulting TB-COFs exhibit exceptional propane uptake of 197.2 cm³/g and iodine adsorption capacity of 5.6 g/g, positioning them among the top-performing COFs reported to date. These outstanding adsorption performances are attributed primarily to the large accessible surface area and strong affinity between the COF frameworks and iodine molecules.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113766"},"PeriodicalIF":4.8,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144653992","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}

{"title":"The art of adsorption in Moisture: Improving operational conditions for selective formaldehyde adsorption in ZSM-5 zeolite","authors":"Huimin Zheng ,&nbsp;Jingyu Zhang ,&nbsp;Yinan Liu ,&nbsp;Shenfei Bai ,&nbsp;Jing Ji ,&nbsp;Shilin Tian ,&nbsp;Zheyuan Tang","doi":"10.1016/j.micromeso.2025.113765","DOIUrl":"10.1016/j.micromeso.2025.113765","url":null,"abstract":"<div><div>Formaldehyde, a pervasive and hazardous indoor pollutant, demands efficient adsorption-based removal. Molecular simulations of ZSM-5 zeolite, a multifunctional substrate for photocatalytic and adsorbent applications, provide critical insights into its capture mechanisms. Here, Monte Carlo simulations are employed to investigate the competitive adsorption of formaldehyde and water in all-silica ZSM-5 zeolites under varying temperatures and molecular loadings. At low loading, water preferentially occupies the straight channels, while increasing loading shifts dominance to formaldehyde in these regions, with water migrating toward zigzag pores. Elevated temperatures weaken hydrogen bonding among water molecules, promoting more stable formaldehyde adsorption. A transition is observed around 128 molecules/supercell, indicating the formation of HCHO-H₂O cooperative clusters. Surface modification can further enhance formaldehyde selectivity. These findings highlight the critical roles of geometric confinement and intermolecular interactions in co-adsorption, providing a theoretical basis for optimizing ZSM-5-based indoor formaldehyde removal systems.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113765"},"PeriodicalIF":4.8,"publicationDate":"2025-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144680097","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}

{"title":"Investigating cooperative interactions for the nitroaldol reaction and condensation: Clarifying the impact of microporosity and pore size on catalytic activity of mesoporous aminosilica materials","authors":"Paul Neff,&nbsp;Jee-Yee Chen,&nbsp;Ryan Burrows,&nbsp;Nicholas A. Brunelli","doi":"10.1016/j.micromeso.2025.113762","DOIUrl":"10.1016/j.micromeso.2025.113762","url":null,"abstract":"<div><div>Mesoporous aminosilica materials are active and selective heterogeneous catalysts for the nitroaldol reaction and have many physical and structural characteristics that can be tuned to desired effects. Previous work investigated the impact of tuning pore diameter on catalytic activity in the nitroaldol reaction and observed the highest activity with an MCM-41 support containing pores with an average diameter of 4.5 nm. Our understanding now suggests that these results may have been influenced by differences in microporosity between materials, undermining a comparison between non-microporous MCM-41 and SBA-15 that is known to have micropores. In this work, we introduce a line of SBA-15 supports with negligible microporosity and varied pore diameter. Compared to typical syntheses of SBA-15, these materials show increased catalytic activity as a result of decreased microporosity. Interestingly, a material with a pore diameter of 7.1 nm yields the highest activity among SBA-15-type materials with reduced micropore volume. This is similar to the catalytic activity recorded with an MCM-41 material, suggesting that perceived effects of pore diameter are less important than effects of microporosity. Since SBA-15 is more hydrothermally stable than MCM-41, the ability to use it as a suitable alternative for the nitroaldol reaction when microporosity is reduced is encouraging for future development.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"397 ","pages":"Article 113762"},"PeriodicalIF":4.8,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144653991","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}