Microporous and Mesoporous Materials最新文献_第9页

NiPt/SAPO-11 catalysts for hydrodeoxygenation of anisole to cyclohexane: effect of the support's Si/al molar ratio on catalytic performance NiPt/SAPO-11催化苯甲醚加氢脱氧制环己烷：载体硅铝摩尔比对催化性能的影响

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-12-10 DOI: 10.1016/j.micromeso.2025.113992

Alejandro Suárez-Méndez , Fernanda Castelán-González , Rubén Mendoza-Cruz , Lázaro Huerta , Jonas S. Albuquerque , Gustavo A. Fuentes , Tatiana E. Klimova

NiPt catalysts supported on SAPO-11 zeolite were synthesized with the aim to inquire into the influence of the support's Si/Al molar ratio (0.075–0.60) on the activity and selectivity of the catalysts in the hydrodeoxygenation of anisole. An increase in Si content led to a reduction in the crystallinity of SAPO-11, attributed to the higher number of SiO₂ islands (extra-framework silica species). Acidity of supports and catalysts passed through the maximum at a Si/Al molar ratio of 0.15 and then decreased with further increase in Si/Al ratio. All the NiPt/SAPO-11 catalysts demonstrated high activity in the hydrodeoxygenation of anisole in a batch reactor at 250 °C and 6.8 MPa of H₂ pressure, achieving conversions of 96–98 % at 6 h reaction time. The best activity results were obtained with the NiPt/SAPO-11 catalysts with Si/Al molar ratios in the supports between 0.30 and 0.60. Supports with lower Si/Al molar ratios (0.075 and 0.15) resulted in lower activity, which was attributed to an increase in the fraction of NiAl₂O₄ with Ni²⁺ species non-reducible upon the activation conditions used (400 °C, 4 h). Regarding selectivity to cyclohexane, catalysts with intermediate Si/Al ratios (0.15–0.45) exhibited higher selectivity (∼94–96 %) than other catalysts, attributed to their elevated acidity as measured by temperature-programmed desorption of ammonia. Finally, the experimental data were fitted to a kinetic model that considered the hydrogenation-deoxygenation pathway, correlating the kinetic constants with the metal-acid characteristics of the catalysts, namely, the amount of reduced Ni and total amount of acid sites.

合成了负载在SAPO-11分子筛上的NiPt催化剂，探讨了负载Si/Al摩尔比（0.075 ~ 0.60）对苯甲醚加氢脱氧活性和选择性的影响。Si含量的增加导致SAPO-11的结晶度降低，这是由于SiO2岛（框架外二氧化硅物种）的数量增加。载体和催化剂的酸性在Si/Al摩尔比为0.15时达到最大值，然后随着Si/Al摩尔比的进一步增加而降低。NiPt/SAPO-11催化剂在间歇反应器中，在250℃、6.8 MPa的H2压力下，对苯甲醚的加氢还原反应均表现出较高的活性，反应时间为6 h，转化率为96 ~ 98%。载体中Si/Al摩尔比为0.30 ~ 0.60的NiPt/SAPO-11催化剂活性最佳。较低Si/Al摩尔比（0.075和0.15）的载体活性较低，这是由于在使用的活化条件下（400°C, 4 h）， Ni2+不可还原的NiAl2O4的比例增加。至于对环己烷的选择性，中间Si/Al比（0.15-0.45）的催化剂比其他催化剂表现出更高的选择性（~ 94 - 96%），这是由于它们的酸度升高（通过程序升温解吸氨来测量）。最后，将实验数据拟合到考虑加氢-脱氧途径的动力学模型中，将动力学常数与催化剂的金属-酸特性，即Ni的还原量和酸位的总量相关联。

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引用次数: 0

The influence of C-F- and C-H-bonds on the adsorption of propane and perfluoropropane on FAU-type zeolites C-F-键和c - h键对fu型沸石吸附丙烷和全氟丙烷的影响

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-12-09 DOI: 10.1016/j.micromeso.2025.113988

Malte Menk , Christian Bläker , Christoph Pasel , Dieter Bathen

This study aims to investigate the influence of carbon-fluorine- and carbon-hydrogen-bonds on adsorption. Therefore, we performed comparative experiments with perfluoropropane (C₃F₈) and propane (C₃H₈) on FAU-type zeolites (NaX and CaNaX) over a temperature range of −20 to 25 °C. Breakthrough curves measured by FTIR are used to obtain both pure component and mixture isotherms. Additionally, mixture isotherms were predicted using the Ideal Adsorbed Solution Theory (IAST). While in pure component adsorption at low relative pressure on NaX the loading of C₃F₈ achieves higher values than the loading of C₃H₈ the loadings of C₃F₈ and C₃H₈ on CaNaX are similar. Obviously, propane benefits from ion exchange (from sodium to calcium) which increases propane interactions while perfluoropropane interaction are not significantly affected due to its bulkier structure. Due to its larger molecular dimensions C₃F₈ has lower saturation capacities. Electrostatic and steric effects are combined in mixed adsorption. Mixture data show that C₃H₈ displaces C₃F₈ more strongly, especially on zeolite NaX, as the degree of coverage increases and the temperature decreases. IAST predictions qualitatively reflect the experimental data but partly show significant deviations. These can be attributed to inaccuracies in fitting pure component isotherms and to non-idealities. The largest deviations between IAST predictions and experimental data occur at low relative pressure of the respective component, likely due to the lack of experimental data in particular in the low-pressure region, the limited representation of molecular size effects, interaction-specific effects and the lack of consideration for the energetic heterogeneity of the adsorption sites. The results of this study provide mechanistic insights into the role of C-F and C-H functionalities in influencing selectivity and capacity in competitive adsorption and support the development of selective separation processes for fluorinated hydrocarbons.

本研究旨在探讨碳氟键和碳氢键对吸附的影响。因此，我们在- 20至25°C的温度范围内，用全氟丙烷（C3F8）和丙烷（C3H8）在fu型沸石（NaX和CaNaX）上进行了对比实验。用FTIR测得的突破曲线得到了纯组分和混合组分的等温线。此外，利用理想吸附溶液理论（IAST）预测了混合等温线。而在NaX上低相对压力的纯组分吸附中，C3F8的上载量高于C3H8的上载量，C3F8和C3H8在CaNaX上的上载量相似。显然，丙烷受益于离子交换（从钠到钙），这增加了丙烷的相互作用，而全氟丙烷的相互作用由于其体积较大的结构而没有受到显著影响。由于C3F8分子尺寸较大，饱和容量较低。在混合吸附中，静电和空间效应相结合。混合物数据表明，随着覆盖度的增加和温度的降低，C3H8对C3F8的置换作用更强，尤其是在沸石NaX上。IAST预测定性地反映了实验数据，但部分显示出显著的偏差。这些可归因于拟合纯分量等温线的不准确性和非理想性。IAST预测与实验数据之间的最大偏差发生在各自组分相对压力较低的情况下，这可能是由于缺乏实验数据，特别是在低压区域，分子大小效应的有限代表，相互作用特异性效应以及缺乏考虑吸附位点的能量异质性。本研究的结果为C-F和C-H官能团在影响竞争性吸附的选择性和容量方面的作用提供了机制见解，并支持氟化烃选择性分离工艺的发展。

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引用次数: 0

The room-temperature and rapid synthesis of nitrogen-rich metal organic framework for effectively catalyzing the CO2 cycloaddition with epoxides 室温下快速合成富氮金属有机骨架，有效催化CO2与环氧化物的环加成反应

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-12-13 DOI: 10.1016/j.micromeso.2025.113982

Jianwen Lan , Shuang Liu , Jiayang Zhang, Yang Cheng, Xu Yang

A nitrogen-enriched Zn-based metal-organic framework Zn-MA-Htdc-RT was facilely synthesized via a room-temperature method, wherein easily removable ammonium hydroxide served as the deprotonating agent. Compared with the conventional solvothermal method and other widely adopted room-temperature synthesis strategies, this approach remarkably shortened the preparation cycle to 2 h, featuring prominent advantages of energy efficiency and environmental benignity. Endowed with amine groups (Lewis base sites) and Zn metal centers (Lewis acid sites), Zn-MA-Htdc-RT exhibited excellent catalytic performance in the cycloaddition reaction of CO₂ with epoxides. Under mild and solvent-free conditions (60 °C, 1.0 MPa CO₂, 6 h), the yield of propylene carbonate (PC) reached up to 99 % with full conversion. Notably, even at room temperature, an impressive PC yield of 87 % could be achieved by extending the reaction time to 24 h. Furthermore, Zn-MA-Htdc-RT demonstrated satisfactory reusability and broad applicability towards various epoxide substrates. Collectively, this green, rapid, and room-temperature synthetic route for the high-performance nitrogen-rich Zn-MA-Htdc-RT provides a competitive alternative for the capture and utilization of CO₂.

以易去除的氢氧化铵为脱质子剂，采用室温法制备了富氮锌基金属-有机骨架Zn-MA-Htdc-RT。与传统的溶剂热法和其他广泛采用的室温合成策略相比，该方法将制备周期显著缩短至2 h，具有显著的节能和环保优势。Zn- ma - htdc - rt具有胺基（Lewis碱位）和Zn金属中心（Lewis酸位），在CO2与环氧化物的环加成反应中表现出优异的催化性能。在温和无溶剂条件下（60℃，1.0 MPa CO2, 6 h），全转化率下碳酸丙烯酯收率可达99%。值得注意的是，即使在室温下，通过延长反应时间至24小时，PC收率也可以达到令人印象深刻的87%。此外，Zn-MA-Htdc-RT表现出令人满意的可重复使用性和对各种环氧化物衬底的广泛适用性。总的来说，这种绿色、快速、室温的高性能富氮Zn-MA-Htdc-RT合成路线为二氧化碳的捕获和利用提供了一个有竞争力的替代方案。

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引用次数: 0

Extension of Pechini synthesis of high-entropy oxides: Preparation of mesoporous high-entropy materials Pechini高熵氧化物合成的延伸：介孔高熵材料的制备

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-12-13 DOI: 10.1016/j.micromeso.2025.113996

Manjula M. Kandage, Michal Marszewski

High-entropy oxides (HEOs) are rapidly finding applications in catalysis, energy storage, and energy conversion, thanks to their unique properties, such as high compositional complexity, diversity of chemical environments in the material and on its surface, as well as a high potential for synergistic and cocktail effects. However, as HEOs are frequently synthesized using solids-state or similar high-temperature methods, they also feature rather low surface areas and pore volumes, which negatively impacts their performance in applications involving surface and interface phenomena. The present work demonstrates two extensions to the Pechini-type synthesis of high-entropy oxides that aim to afford mesoporous HEOs with well-developed pore structures. Five example HEOs, with varied compositions and structures, were used as model HEOs, including fluorite (Gd_0.2La_0.2Y_0.2Hf_0.2Zr_0.2)O_2-x, spinel (Al_1/6Co_1/6Cr_1/6Fe_1/6Mn_1/6Ni_1/6)₃O₄, perovskite (Na_0.2Bi_0.2Ba_0.2Sr_0.2Ca_0.2)TiO₃, perovskite (Na_0.2K_0.2Ca_0.2La_0.2Ce_0.2)TiO₃, and rock-salt (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O. These HEOs were tested in (i) a hard-templating Pechini synthesis with Ludox SM-AS colloidal silica as the template and (ii) a two-step Pechini synthesis with the carbon template generated in-situ, and compared with HEOs synthesized using the original Pechini-type synthesis. Both extensions successfully afforded mesoporous HEOs with well-developed pore structures, with the former method affording materials with specific surface areas up to 142 m² g^–1 and total pore volumes up to 0.19 cm³ g^–1 while the latter up to 164 m² g^–1 and 0.25 cm³ g^–1, respectively. Both strategies have similar set of limitations, including low crystallinity and limited compatibility. Thus, both methods seem to be complimentary strategies for the synthesis of mesoporous HEOs, chosen mainly based on the compatibility with the target HEO.

高熵氧化物（HEOs）由于其独特的性质，如高组成复杂性，材料及其表面化学环境的多样性，以及协同效应和鸡尾酒效应的高潜力，正迅速在催化、能量存储和能量转换方面得到应用。然而，由于heo通常使用固态或类似的高温方法合成，它们的表面积和孔隙体积也很低，这对它们在涉及表面和界面现象的应用中的性能产生了负面影响。本研究展示了pechini型高熵氧化物合成的两个扩展，旨在提供具有良好孔隙结构的介孔HEOs。以五种不同组成和结构的HEOs为模型，分别为萤石（Gd0.2La0.2Y0.2Hf0.2Zr0.2）O2-x、尖晶石（Al1/6Co1/6Cr1/6Fe1/6Mn1/6Ni1/6）3O4、钙钛矿（Na0.2Bi0.2Ba0.2Sr0.2Ca0.2）TiO3、钙钛矿（Na0.2K0.2Ca0.2La0.2Ce0.2）TiO3、岩盐（Co0.2Cu0.2Mg0.2Ni0.2Zn0.2）O。在(i)以Ludox SM-AS胶体二氧化硅为模板的硬模板法Pechini合成和（ii）以原位生成的碳模板法两步法Pechini合成中对这些HEOs进行了测试，并与原始Pechini型合成法合成的HEOs进行了比较。两种扩展方法都成功地提供了具有良好孔隙结构的介孔HEOs，前者方法提供的材料比表面积高达142 m2 g-1，总孔隙体积高达0.19 cm3 g-1，后者分别高达164 m2 g-1和0.25 cm3 g-1。这两种策略都有类似的局限性，包括低结晶度和有限的相容性。因此，这两种方法似乎是合成介孔HEO的互补策略，主要基于与目标HEO的相容性进行选择。

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引用次数: 0

Influence of mesostructural order on the gas-sensing performance of tin dioxide-mesoporous alumina composite 介孔结构顺序对二氧化锡-介孔氧化铝复合材料气敏性能的影响

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-12-01 DOI: 10.1016/j.micromeso.2025.113962

Federico Schipani , David Smirnoff , Fernando P. Cometto , Rodrigo Parra , Carla di Luca

This study investigates the synthesis and gas-sensing performance of SnO₂- mesoporous alumina, focusing on the influence of pore ordering and calcination temperature on sensing response. Two sol-gel routes based on the Evaporation-Induced Self-Assembly (EISA) strategy were employed: Method M, which produced ordered mesoporous structures, and Method C, which led to disordered porosity. Both methods yielded materials with high surface areas (∼250 m²/g) and uniform tin dispersion within an amorphous alumina matrix after heat-treatment at 400 °C. The samples were thoroughly characterized by TEM, FESEM-EDS, N₂ physisorption, XPS, and XRD, confirming the development of well-defined mesostructures. Gas-sensing tests revealed that the disordered sample (Method C) exhibited markedly higher sensitivity, up to a 230-fold increase in conductivity and faster response times (∼4 s) when exposed to CO₂, NO₂, and H₂, compared to the ordered counterpart. Furthermore, increasing the heat-treatment temperature to 900 °C induced structural collapse and phase segregation, significantly worsening sensor performance. In agreement with the insulating nature of the host matrix, electrical conductivity arises primarily via thermally activated electron hopping. These results reveal that structural disorder enhances surface reactivity and electrical conductivity. These findings underscore the potential of tin dioxide-mesoporous alumina composite as a robust and efficient material for gas detection applications.

本文研究了SnO2-介孔氧化铝的合成及其气敏性能，重点研究了孔序和煅烧温度对气敏响应的影响。采用了两种基于蒸发诱导自组装（EISA）策略的溶胶-凝胶途径：方法M产生有序介孔结构，方法C产生无序孔隙结构。在400°C热处理后，两种方法都产生了高表面积（~ 250 m2/g）和均匀的锡分散在无定形氧化铝基体中的材料。通过TEM， FESEM-EDS， N2物理吸附，XPS和XRD对样品进行了全面的表征，证实了样品具有明确的介观结构。气敏测试表明，与有序样品相比，当暴露于CO2、NO2和H2中时，无序样品（方法C）表现出明显更高的灵敏度，电导率增加高达230倍，响应时间更快（~ 4 s）。此外，将热处理温度提高到900°C会导致结构崩溃和相偏析，显著降低传感器性能。与宿主基质的绝缘性质一致，电导率主要通过热激活的电子跳变产生。这些结果表明，结构紊乱增强了表面反应性和导电性。这些发现强调了二氧化锡-介孔氧化铝复合材料作为一种强大而高效的气体检测应用材料的潜力。

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引用次数: 0

Biomass based ultralight monolithic aerogels of two-dimensional nanostructures 基于生物质的二维纳米结构超轻单片气凝胶

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-12-02 DOI: 10.1016/j.micromeso.2025.113978

Apostolos Koutsioukis , Christina Rista , Eleni Tegkelidi , Christos Priovolos , Dimitris Manolis , Konstantina Goumenou , Elli Bellou , Argyris Kolokithas Ntoukas , Konstantinos Ar Papageorgiou , Vasilios I. Georgakilas

The biomass extracted in water after ultrasonic treatment of red pepper powder contributes to the liquid exfoliation of solids such as graphite, hematite, magnetite and silicon and the formation of two-dimensional nanostructures. Afterwards, the amphiphilic biomass acting as a gelator, contributes to the formation of soft hydrogels and the corresponding ultralight monolithic aerogels based on the graphene, hematene, magnetene and silicene nanosheets resulting from the liquid exfoliation. Depending on the basic chemical element of the nanostructures, these novel aerogels exhibited extremely low densities, between 4.22 mg cm⁻³ with silicene and 14.35 mg cm⁻³ with magnetene and porosities exceeding 99.7 %. The monolithic ultralight graphene, hematene and magnetene aerogels were fully sustainable as they are derived from natural materials such as minerals hematite, magnetite and graphite, a natural product such as red pepper and water as solvent. Energy consumption for the basic aerogel formation process was also limited compared to other techniques due to the use of short-duration ultrasound.

超声波处理后的红椒粉在水中提取的生物质有助于石墨、赤铁矿、磁铁矿和硅等固体物质的液体剥落，形成二维纳米结构。然后，两亲性生物质作为凝胶剂，以液体剥离产生的石墨烯、血红素、磁烯和硅烯纳米片为基础，形成软水凝胶和相应的超轻单片气凝胶。根据纳米结构的基本化学元素，这些新型气凝胶表现出极低的密度，在含硅的4.22 mg cm - 3和含磁烯的14.35 mg cm - 3之间，孔隙率超过99.7%。单片超轻石墨烯、赤铁矿和磁烯气凝胶是完全可持续的，因为它们是从天然材料中提取的，如矿物赤铁矿、磁铁矿和石墨，一种天然产物，如红辣椒和水作为溶剂。由于使用短时间超声，与其他技术相比，基本气凝胶形成过程的能耗也很有限。

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引用次数: 0

Three-dimensional heterogeneous electro-Fenton with traditional Fe-zeolites for the efficient removal of 1,4-dioxane 三维非均相电fenton与传统铁分子筛的高效去除1,4-二氧六环

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-12-01 DOI: 10.1016/j.micromeso.2025.113973

Xiaosan Song , Po Zhao , Xuan Zhang

1,4-Dioxane (1.4-DX) as an emerging organic pollutant poses a serious threat to human health and the ecological environment. However, effective removal is still a challenge in wastewater treatment. In this study, we successfully synthesized Fe-ZSM-5 zeolite and employed it as an adsorbent/catalyst for the removal of 1,4-DX. The characterization results of SEM, XRD and N₂ adsorption-desorption exhibited a large surface and good textural properties of Fe-ZSM-5 zeolite, implying excellent adsorption performance and high catalytic efficiency for 1,4-DX. The adsorption equilibrium of 1,4-DX on Fe-ZSM-5 zeolite can be reached a maximum adsorbed amount of 43.15 mg/g within 5 min, and experimental adsorption data were fitted well with the Langmuir isotherms and pseudo-second-order kinetics. The optimum removal efficiency of 1,4-DX, i.e. 90.3 % for 180 min of treatment, was observed at pH of 3.0–5.0, anode of Ti/pt, catalyst dosage of 1 g/L, current density of 20 mA/cm², and initial target pollutant concentration of 10 mg/L. Moreover, Fe-ZSM-5 zeolite showed an exhibited excellent stability and reusability, with little change in removal efficiency over five cycles. Degradation product analysis speculated possible oxidative degradation pathways. Quenching experiments indicated that ^.OH and O₂^.^- formed by the oxidation reaction of Fe-ZSM-5 zeolite with hydrogen peroxide produced by electrochemical in-situ oxidation were the main reactive oxygen species for the oxidative degradation of 1,4-DX. This study demonstrated that the three-dimensional heterogeneous electro-Fenton with traditional Fe-zeolites may be a promising technology for organic wastewater.

1,4-二恶烷（1.4-DX）是一种新兴的有机污染物，对人类健康和生态环境构成严重威胁。然而，在废水处理中，有效去除仍是一个挑战。在本研究中，我们成功合成了Fe-ZSM-5沸石，并将其作为吸附/催化剂去除1,4- dx。SEM、XRD和N2吸附-脱附表征结果表明，Fe-ZSM-5分子筛具有较大的表面和良好的结构性能，表明其具有优异的吸附性能和对1,4- dx的催化效率。1,4- dx在Fe-ZSM-5分子筛上的吸附平衡在5 min内达到最大吸附量43.15 mg/g，实验吸附数据符合Langmuir等温线和拟二级动力学。当pH为3.0 ~ 5.0，阳极为Ti/pt，催化剂用量为1 g/L，电流密度为20 mA/cm2，初始目标污染物浓度为10 mg/L时，处理180 min， 1,4- dx的最佳去除率为90.3%。此外，Fe-ZSM-5分子筛表现出优异的稳定性和可重复使用性，在5个循环中去除效率变化不大。降解产物分析推测了可能的氧化降解途径。淬火实验表明。OH和O2。Fe-ZSM-5沸石与电化学原位氧化生成的过氧化氢氧化反应生成的-是氧化降解1,4- dx的主要活性氧。该研究表明，三维非均相电fenton与传统铁分子筛的结合是一种很有前途的有机废水处理技术。

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引用次数: 0

Chromonic-liquid-crystal-templated synthesis of powdered and monolithic silica materials: mechanism, textural properties and drug delivery 铬-液晶模板法合成粉状和单片二氧化硅材料：机理、结构性能和给药性能

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-12-01 DOI: 10.1016/j.micromeso.2025.113977

Adrià Pérez-Calm , Claudia Müller-Sánchez , Anna Maria Piña Cañaveras , Eva Berteloot , Santiago Grijalvo , Soraia P.S. Fernandes , Yury V. Kolen'ko , Oleg Lebedev , Jordi Esquena , Manuel Reina , Carlos Rodríguez-Abreu

Lyotropic chromonic liquid crystals (LCLC) enable the templating of silica fibers with aligned porous structures and tunable pore size, properties that hold significant potential for applications like controlled drug delivery. LCLC guide the synthesis of microporous and mesoporous silicas through sol-gel reactions in the presence of silicon alkoxides, such as tetraethyl orthosilicate (TEOS), typically producing fibers with long, aligned pores and specific surface areas around 200–300 m²/g. Here, we develop micro/mesoporous silica materials using a cationic chromonic perylene diimide as template, combined with a porogenic silica precursor, hexadecyl trimethoxysilane (HDTMS), to achieve increased specific surface areas and larger pore sizes compared to conventional TEOS-based chromonic-templated silicas. The resulting silica materials can be fabricated as macroscopic, centimeter-sized monoliths with tunable porosity, composed of entangled silica nanofibers forming a networked structure. These highly porous monoliths were evaluated as carriers of small drugs (ibuprofen), and demonstrated high encapsulation efficiencies, as well as sustained drug release in a simulated body fluid (SBF, pH = 7.4), achieving complete release within 24 h. In contrast, powdered silica samples of the same composition showed poorer encapsulation efficiencies and faster release rates, highlighting the advantages of monolithic structures for drug delivery. Furthermore, hydroxyapatite (HAp) was deposited onto the silica monoliths to produce robust composite scaffolds, whose degradation products did not affect HEK293 cell viability.

溶致变色液晶（LCLC）使二氧化硅纤维的模板具有排列的多孔结构和可调节的孔径，这些特性在控制药物输送等应用中具有巨大的潜力。LCLC通过溶胶-凝胶反应在硅烷氧化物（如正硅酸四乙酯（TEOS））的存在下指导微孔和介孔二氧化硅的合成，通常产生具有长而排列的孔隙和比表面积约200-300 m2/g的纤维。在这里，我们开发了微孔/介孔二氧化硅材料，使用阳离子的慢性苝酰二亚胺作为模板，结合成孔二氧化硅前驱体，十六烷基三甲氧基硅烷（HDTMS），与传统的基于正硅酸盐的慢性模板二氧化硅相比，实现了增加的比表面积和更大的孔径。由此产生的二氧化硅材料可以制成宏观的、厘米大小的单体，具有可调的孔隙率，由纠缠的二氧化硅纳米纤维组成，形成网络结构。这些高多孔的单片被评估为小药物（布洛芬）的载体，并且具有高的包封效率，并且在模拟体液（SBF, pH = 7.4）中持续释放药物，在24小时内实现完全释放。相比之下，相同成分的粉状二氧化硅样品的包封效率较低，释放速度较快，突出了单片结构用于药物递送的优势。此外，羟基磷灰石（HAp）沉积在硅胶单体上，制备了坚固的复合支架，其降解产物不影响HEK293细胞的活力。

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引用次数: 0

Influence of solvent effect on the amine-free synthesis of high-silica ZSM-5 with the investigation of mechanism 溶剂效应对无胺合成高硅ZSM-5的影响及机理研究

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-11-04 DOI: 10.1016/j.micromeso.2025.113924

Aojing Deng , Ruizhen Zhang , Jiamin Li , Yifei Pan , Danxue Zhang , Kai Zong

Amine-free synthesis of high-silica ZSM-5 (SAR ≥200) remained a significant challenge due to the instability of the silica-rich framework under alkaline conditions. In this study, a facile and efficient synthetic route for high-silica ZSM-5 (SAR = 300) was developed with the assistance of silicalite-1 seed and short-chain alcohol. Firstly, high-crystalline ZSM-5 (80 % relative crystallinity) with hexagonal prism morphology and the size of 850–1500 nm was successfully synthesized by systematically optimizing the solvent composition (EtOH/SiO₂ = 4–8, H₂O/SiO₂ = 15–25) and alkalinity (Na₂O/SiO₂ = 0.03–0.04). Then, replacing ethanol with butanol further enhanced the crystallinity (>95 %) and reduced crystal size (750–1300 nm), attributed to the fact that water-butanol mixture had a lower dielectric constant than water-ethanol mixture, which could more effectively weaken the solvent's charge-shielding capability and improve the electrostatic interaction between Na⁺ and negatively charged species, thereby promoting the nucleation and the assembly of MFI skeleton. In summary, this work provided a concise process for the synthesis of high-silica ZSM-5 with the assistance of alcohol and silicalite-1 seed, which enabled the cost-effective, eco-friendly production of high-silica ZSM-5 with high crystallinity in the amine-free system.

由于富硅骨架在碱性条件下的不稳定性，无胺合成高硅ZSM-5 （SAR≥200）仍然是一个重大挑战。本研究以硅石-1种子和短链醇为辅助原料，建立了一条简便、高效的合成高硅ZSM-5 （SAR = 300）的路线。首先，通过系统优化溶剂组成（EtOH/SiO2 = 4-8, H2O/SiO2 = 15-25）和碱度（Na2O/SiO2 = 0.03-0.04），成功合成了尺寸为850 ~ 1500 nm的六棱柱型高晶ZSM-5（相对结晶度80%）。然后，用丁醇取代乙醇进一步提高了结晶度（95%），减小了晶体尺寸（750-1300 nm），这是由于水-丁醇混合物比水-乙醇混合物具有更低的介电常数，这可以更有效地削弱溶剂的电荷屏蔽能力，提高Na+与带负电荷的物质之间的静电相互作用，从而促进MFI骨架的成核和组装。综上所述，本工作提供了一种在醇和硅酸-1种子的辅助下合成高硅ZSM-5的简明工艺，实现了在无胺体系中经济、环保地生产高结晶度的高硅ZSM-5。

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引用次数: 0

Efficient synthesis of well-defined ordered mesoporous aluminosilicates with tailorable acidity 具有适宜酸度的有序介孔硅酸盐铝的高效合成

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-15 Epub Date: 2025-12-10 DOI: 10.1016/j.micromeso.2025.113991

Selina Itzigehl , Tom Ott , Anne-Kathrin Ströhle , Hoang-Huy Nguyen , Roham Talei , Nağme Ay , Maxwell W. Terban , Michael Dyballa , Guido Schmitz , Deven P. Estes , Johanna R. Bruckner

This study systematically investigates the synthesis and structural properties of ordered mesoporous aluminosilicates (OMAS) prepared via a direct liquid crystal templating (DLCT) approach. By varying the aluminum concentration and polycondensation temperature, we assess their impact on the materials’ structural order, pore size distribution, and surface acidity. Unlike conventional preparation processes, the DLCT method allows a near-stochiometric incorporation of aluminum into OMAS, without formation of detectable aluminum deposits, in a simple one-pot synthesis. Small-angle X-ray scattering and nitrogen physisorption analyses reveal that increasing aluminum content initially enhances mesostructural order, which again deteriorates at molar silicon to aluminum ratios below 5. Additionally, even small amounts of aluminum reduce the pore size by a constant value, likely due to a salting-out effect which reduces the micelle size. Total scattering and ²⁷Al MAS NMR provide insights into the atomic structure of the OMAS. Brønsted acid site density peaks at intermediate aluminum loadings, while the number of Lewis acid sites increases steadily with the total Al content. The polycondensation temperature plays a crucial role in structure formation, with higher temperatures favoring better mesostructural order in OMAS, contrasting with trends in ordered mesoporous silica, where lower temperatures are typically more favorable. These findings provide crucial insights into the preparation of OMAS with tunable acidity and well-defined structural properties for advanced catalytic applications.

本研究系统地研究了直接液晶模板法制备的有序介孔硅酸铝（OMAS）的合成及其结构性能。通过改变铝浓度和缩聚温度，我们评估了它们对材料结构顺序、孔径分布和表面酸度的影响。与传统的制备工艺不同，DLCT方法允许在简单的一锅合成中将铝加入到OMAS中，而不会形成可检测的铝沉积物。小角度x射线散射和氮物理吸附分析表明，铝含量的增加首先增强了细观结构秩序，当硅铝摩尔比低于5时，细观结构秩序再次恶化。此外，即使是少量的铝也会使孔径减小一个恒定值，这可能是由于盐析效应减小了胶束尺寸。总散射和27Al MAS NMR提供了对OMAS原子结构的见解。Brønsted酸位密度在中等铝含量时达到峰值，而Lewis酸位数量随着总铝含量的增加而稳步增加。缩聚温度在结构形成中起着至关重要的作用，在OMAS中，较高的温度有利于更好的介孔结构秩序，而在有序的介孔二氧化硅中，较低的温度通常更有利。这些发现为制备具有可调酸度和明确结构特性的高级催化应用的OMAS提供了重要见解。

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引用次数: 0