Microporous and Mesoporous Materials最新文献_第10页

Tailoring of mesostructured alumina properties by the one pot incorporation of fluorine 通过一锅加入氟来调整介结构氧化铝的性能

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-11-07 DOI: 10.1016/j.micromeso.2025.113937

Jean-Luc Blin , Sylvette Brunet , Laure Michelin , Séverinne Rigolet , Jean Dominique Comparot , Bénédicte Lebeau

In this study, to modulate the properties of mesostructured alumina synthetized by combining the sol-gel process and the surfactant templating mechanism, the introduction of fluorine has been carried out through a one step process using ammonium fluoride as fluorinating agent.

Small angle x-ray scattering, X-ray diffraction, ¹⁹F, ²⁷Al NMR and manometry nitrogen adsorption-desorption analyses show that even after heating at 500 °C, amorphous mesostructured aluminum (hydr)oxyfluoride with an intrinsic mesoporosity are obtained for NH₄F concentration in water lower than 112.5 g L⁻¹.

With the increase in the fluorine content, the mesostructuration is lost. For materials recovered after removal of the porogen agent (Pluronic P123) by Soxhlet extraction, aluminum (hydr)oxyfluoride hydrate Al₂(OH)_2.76F_3.24(H₂O) and ammonium fluoroaluminates, are detected by XRD. When the extracted materials are calcined at 500 °C, ammonium fluoroaluminates are decomposed into AlF₃ and AlF_1.96(OH)_1.04 is also detected. Because of the presence of the crystalline phases, the intrinsic porosity vanishes and the mesoporosity is mainly inter-aggregates.

Adsorption of pyridine followed by infrared spectroscopy reveals that whatever the fluorine content, no Brønsted acid site is present. The concentration of the Lewis acid sites first increases to reach a maximum value around 0.8 μmol m⁻² for a NH₄F concentration in water of 112.5 g L⁻¹, then it reaches a plateau.

本研究以氟化铵为氟化剂，通过一步法引入氟，对溶胶-凝胶法制备的介结构氧化铝的性能进行调控。小角x射线散射、x射线衍射、19F、27Al核磁共振和测压法氮吸附-解吸分析表明，当水中NH4F浓度低于112.5 g L−1时，即使在500℃加热后，也能得到具有本征介孔的无定形介孔结构氟化铝（氢氧）。随着氟含量的增加，介观结构丧失。对索氏萃取法去除多孔剂（Pluronic P123）后回收的材料，用x射线衍射仪（XRD）检测了氢化氟氧铝Al2(OH)2.76F3.24（H2O）和氟铝酸铵。提取的物料在500℃下煅烧，氟铝酸铵分解为AlF3，同时检测到AlF1.96(OH)1.04。由于结晶相的存在，本征孔隙消失，介孔主要为团聚体间孔隙。对吡啶的吸附和红外光谱分析表明，无论氟含量如何，都没有Brønsted酸位存在。当NH4F浓度为112.5 g L−1时，Lewis酸位点的浓度先升高，在0.8 μmol m−2左右达到最大值，然后趋于平稳。

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引用次数: 0

Ni-NaY zeolite-modified polyethersulfone membranes for sustainable water treatment: Enhanced flux, contaminant rejection, and life cycle assessment 用于可持续水处理的Ni-NaY沸石改性聚醚砜膜：增强通量，污染物排斥和生命周期评估

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-11-21 DOI: 10.1016/j.micromeso.2025.113958

Sayedali Mirkhalafi , Bayramali Mohammadnezhad , Milad Mousazadehgavan , Ali Altaee , Mohammadali Kiehbadroudinezhad , Homa Hosseinzadeh-Bandbafha , Khalid Hashim , Mohsen Mohammadi

The development of advanced mixed-matrix membranes incorporating microporous and mesoporous fillers offers a promising route to improve water purification performance and sustainability. In this study, polyethersulfone (PES) membranes were modified with Ni-exchanged NaY zeolite (0.3–40 wt%) and systematically evaluated for flux, contaminant rejection, and environmental impact. Structural characterization using FTIR, XRD, SEM, EDX, and TGA confirmed the successful integration of zeolite particles within the polymer matrix, leading to enhanced porosity and thermal stability. Among the series, the PES-Z₁ membrane (1 wt% Ni-NaY) exhibited the most balanced performance, achieving pure water fluxes of 64.6–82.3 L/m².h at 1–5 bar and flux recovery of 93.9 %. It demonstrated moderate salt rejection (47–52 %) but high removal efficiencies for pharmaceuticals (up to 97 %) and heavy metals (Pb, Cd, As >89 %) via combined size-exclusion and electrostatic interactions. Life cycle assessment (ReCiPe 2016) revealed that PES-Z₁ achieved significant reductions in global warming potential (39 %) and resource depletion compared with unmodified PES, while excessive loading (≥20 wt%) increased environmental burden due to zeolite agglomeration and reduced functional performance. These findings highlight the role of microporous Ni-NaY zeolite in optimizing transport pathways and active sites, providing both enhanced separation performance and sustainability benefits. The study demonstrates that judicious incorporation of zeolite into polymeric membranes can deliver high-efficiency, low-impact solutions for the removal of pharmaceuticals and heavy metals from wastewater, with potential scalability for sustainable water treatment applications.

采用微孔和介孔填料的先进混合基质膜的开发为提高水的净化性能和可持续性提供了一条有前途的途径。在这项研究中，聚醚砜（PES）膜用镍交换的NaY沸石（0.3-40 wt%）进行改性，并系统地评估通量、污染物截留和环境影响。利用FTIR、XRD、SEM、EDX和TGA进行的结构表征证实了沸石颗粒在聚合物基体中的成功整合，从而提高了孔隙度和热稳定性。其中，PES-Z1膜（1 wt% Ni-NaY）表现出最平衡的性能，在1 - 5 bar下纯水通量为64.6-82.3 L/m2.h，通量回收率为93.9%。它表现出中等的盐去除率（47 - 52%），但对药物（高达97%）和重金属（Pb, Cd, As > 89%）的去除效率，通过结合尺寸排斥和静电相互作用。生命周期评估（ReCiPe 2016）显示，与未改性PES相比，PES- z1显著降低了全球变暖潜势（39%）和资源消耗，但过度负载（≥20 wt%）增加了沸石团聚造成的环境负担，降低了功能性能。这些发现强调了微孔Ni-NaY沸石在优化运输途径和活性位点方面的作用，提供了增强的分离性能和可持续性效益。该研究表明，在聚合物膜中合理地掺入沸石可以提供高效、低影响的解决方案，用于去除废水中的药物和重金属，并具有可持续水处理应用的潜在可扩展性。

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引用次数: 0

Challenging the deactivation resistance of Co/Cu-dendritic ZSM-5 zeolites in methane pyrolysis for clean hydrogen 挑战Co/ cu枝晶ZSM-5沸石在甲烷热解制氢过程中的失活抗性

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-11-13 DOI: 10.1016/j.micromeso.2025.113939

Bruna P. Nicola , Elena A. Giner , María Romay , María del Mar Alonso-Doncel , Katia Bernardo-Gusmão , Gema Gómez-Pozuelo , Patricia Pizarro , David P. Serrano

ZSM-5 zeolites with dendritic nanoarchitecture has been recently developed, showing outstanding accessibility due to its singular multilevel porosity, high connectivity and preferential location of the acid sites on the external surface. The present work provides insights on how these features impact also positively on their resistance against deactivation by coke deposition. To that end, a variety of dendritic ZSM-5 samples, incorporating Co and Cu species, have been tested as catalysts in methane pyrolysis, being compared with several reference samples. This process is an interesting route for the production of clean (CO_x-free) hydrogen but also a strongly demanding reaction due to the huge amounts of carbon being formed and deposited over the catalyst. Using a thermobalance at different temperatures, the Co/Cu-containing dendritic zeolites exhibited very short induction times, fast kinetics, and high hydrogen selectivity, due to the good dispersion achieved of the metallic species, as demonstrated by XPS measurements. In addition, the dendritic nanoarchitecture promotes the outward growth of large carbon deposits, thus attenuating deactivation. Consequently, the dendritic catalysts retained significant activity even after carbon/catalyst ratios as high as 5.7 w/w for the Co-Al-MFI (d) sample. Moreover, in fixed-bed tests, they showed strong stability and maintained a rather constant methane conversion and high selectivity for hydrogen over time on stream.

ZSM-5分子筛具有树枝状纳米结构，由于其独特的多层孔隙度、高连通性和酸位在外表面的优先位置而具有优异的可达性。目前的工作提供了关于这些特征如何积极影响其抗焦炭沉积失活的见解。为此，我们测试了多种含有Co和Cu的树枝状ZSM-5样品作为甲烷热解催化剂，并与几种参考样品进行了比较。这个过程是生产清洁（无氧化酶）氢的有趣途径，但由于在催化剂上形成和沉积了大量的碳，这也是一个要求很高的反应。XPS测量结果表明，在不同温度下使用热天平，Co/ cu树枝状沸石表现出非常短的诱导时间、快速的动力学和高的氢选择性，这是由于金属物种的良好分散。此外，树枝状纳米结构促进了大碳沉积物的向外生长，从而减弱了失活。因此，即使在Co-Al-MFI (d)样品的碳/催化剂比高达5.7 w/w时，树突催化剂仍保持显著的活性。此外，在固定床试验中，它们表现出很强的稳定性，并在生产过程中保持相当稳定的甲烷转化和对氢气的高选择性。

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引用次数: 0

Revealing the promoting effect of ZnO on Cu clusters-embedded in self-pillared pentasil zeolites for CO2 hydrogenation to methanol 揭示了ZnO对自柱五柱沸石中Cu团簇对CO2加氢制甲醇的促进作用

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-11-25 DOI: 10.1016/j.micromeso.2025.113953

Guangying Fu , Ruiqin Ding , Qiangsheng Guo , Xiaolong Liu , Han Peng , Peng Lu , Dongsen Mao , Valentin Valtchev

Despite extensive studies on Cu-ZnO catalysts for CO₂ hydrogenation, the atomic-level understanding of Cu-ZnO interfacial synergy remains elusive due to challenges in controlling the size and spatial distribution of Cu clusters. Well-dispersed Cu clusters with an average diameter of 1.8–3.6 nm, successfully anchored in the mesopores of the self-pillared pentasil zeolite (SPP) with a narrow size distribution, were prepared using the traditional impregnation method. The abundant surface-OH groups in SPP zeolite not only facilitated the high dispersion of Cu clusters but also effectively suppressed undesirable agglomeration of the Cu clusters under reaction conditions. The highest turnover frequency (TOF) of CO₂ conversion (1.64 h⁻¹) and space-time yield (STY) of methanol (12.7 mg_MeOH × h⁻¹g_cata⁻¹) was achieved on Cu_9.4-SPP. The incorporation of ZnO significantly enhanced methanol selectivity and CO₂ conversion of CuZn-SPP. The methanol STY over it reached 45.3 mg_Methanol × h⁻¹×g_cata⁻¹, which is 3.6 times that of Cu_9.4-SPP. Quasi-in situ XPS and in situ FTIR results reveal the strong synergistic effect between partial oxidation of the Cu clusters and an interfacial ZnO, enhancing the stability of adsorbed bidentate HCOO∗ species. The set of experimental results revealed that the bidentate formate formation and consumption rates were accelerated by the addition of ZnO in the formate mechanism, which could be used for further optimization of CO₂ hydrogenation catalysts.

尽管对Cu- zno催化剂的CO2加氢作用进行了广泛的研究，但由于在控制Cu簇的大小和空间分布方面存在挑战，对Cu- zno界面协同作用的原子水平理解仍然难以实现。采用传统浸渍法制备了分散良好、平均直径为1.8 ~ 3.6 nm的Cu团簇，并成功地锚定在粒径分布较窄的自柱五柱分子筛（SPP）的介孔中。SPP沸石中丰富的表面oh基团不仅有利于Cu团簇的高度分散，而且有效抑制了反应条件下Cu团簇的不良团聚。在Cu9.4-SPP上，CO2转化的最高周转率（TOF）为1.64 h−1，甲醇的空时产率（STY）为12.7 mgMeOH × h−1gcata−1。ZnO的加入显著提高了CuZn-SPP的甲醇选择性和CO2转化率。甲醇STY达到45.3 mgMethanol × h−1×gcata−1，是Cu9.4-SPP的3.6倍。准原位XPS和原位FTIR结果表明，Cu簇的部分氧化与界面ZnO之间存在很强的协同效应，增强了吸附双齿HCOO *的稳定性。实验结果表明，在甲酸形成机理中，ZnO的加入加速了双齿甲酸的形成和消耗速率，为进一步优化CO2加氢催化剂提供了理论依据。

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引用次数: 0

Rapid solid-state 29Si NMR chemical shift refinements of pure silica zeolite frameworks with an improved structure-to-shift correlation 纯二氧化硅分子筛框架的快速固体29Si核磁共振化学位移细化与改进的结构-位移相关性

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-10-28 DOI: 10.1016/j.micromeso.2025.113914

Darren H. Brouwer

The chemical shifts measured in solid-state ²⁹Si NMR spectroscopy of pure silica zeolites are highly sensitive to the local geometry surrounding the corresponding silicon atoms and therefore hold promise for playing an important role in the structure determination of zeolite frameworks. Through an analysis of the large set of experimental ²⁹Si NMR spectra of pure silica zeolites available in the Database of Zeolite Structures, including the recently added extra-large pore zeolite ZEO-5 which has several uniquely strained silicon geometries, a new structure-to-shift correlation equation was developed that allows for rapid and accurate calculations of isotropic ²⁹Si chemical shifts from Si-O distances and Si-O-Si bond angles. This structure-to-shift relationship is supported by a comprehensive set of quantum chemical calculations of ²⁹Si chemical shieldings performed on 200 different zeolite frameworks. With this ability to rapidly and accurately calculate ²⁹Si chemical shifts, it was possible to carry out rapid structure refinements of zeolite frameworks in which small adjustments to the silicon and oxygen atomic coordinates were made until the differences between calculated and experimental chemical shifts were minimized. Chemical shift structure refinements for 51 zeolite frameworks were carried out and presented here. Based on the set of zeolites for which single-crystal X-ray diffraction structures are available, it is estimated that this chemical shift refinement strategy yields structures with silicon and oxygen atomic coordinates that differ by an average of only about 0.06 Å compared to the single crystal structures.

纯硅分子筛的固体29Si核磁共振光谱测量的化学位移对相应硅原子周围的局部几何结构高度敏感，因此有望在分子筛框架的结构确定中发挥重要作用。通过对沸石结构数据库（Database of Zeolite Structures）中大量纯硅沸石29Si NMR实验谱的分析，包括最近添加的具有几种独特应变硅几何形状的超大孔沸石ZEO-5，建立了一个新的结构位移相关方程，可以快速准确地计算Si-O距离和Si-O- si键角的各向异性29Si化学位移。在200种不同的沸石框架上进行的29Si化学屏蔽的一套全面的量子化学计算支持了这种结构-位移关系。有了这种快速准确地计算29Si化学位移的能力，就可以对沸石框架进行快速的结构改进，对硅和氧原子坐标进行微小的调整，直到计算和实验化学位移之间的差异最小化。本文对51种分子筛骨架进行了化学位移结构的改进。基于单晶x射线衍射结构的沸石，估计这种化学位移精炼策略产生的结构与单晶结构相比，硅和氧原子坐标的平均差异仅为0.06 Å。

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引用次数: 0

Advances in FAU zeolite membranes for separation and catalytic reactor applications: A comprehensive review FAU沸石膜在分离和催化反应器中的应用进展综述

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-11-19 DOI: 10.1016/j.micromeso.2025.113956

Alvin Rahmad Widyanto , Mikihiro Nomura

FAU zeolite membranes have received much attention due to their regular pore structure, good thermal resistance, and tunable surface characteristics, making them very attractive for molecular separation and catalytic reactor applications. This review presents a critical overview of recent advances in the preparation of FAU membranes with a focus on synthesis routes including secondary growth and novel approaches to control membrane crystallinity, as well as preferred orientation and defect minimization. Particular attention is devoted to explaining the correlations between the synthesis conditions and the membrane performance, under different working conditions. In addition, recent advances in the integration of FAU membranes into catalytic reactor systems are discussed, and the major challenges and opportunities for scale-up and industrial application are also discussed.

FAU沸石膜由于其规则的孔隙结构、良好的耐热性和可调的表面特性而受到广泛关注，使其在分子分离和催化反应器应用中具有很大的吸引力。本文综述了FAU膜制备的最新进展，重点介绍了合成途径，包括二次生长和控制膜结晶度的新方法，以及首选取向和缺陷最小化。特别注意解释在不同的工作条件下合成条件和膜性能之间的关系。此外，还讨论了FAU膜与催化反应器系统集成的最新进展，并讨论了扩大规模和工业应用的主要挑战和机遇。

引用次数: 0

Protein distribution in SBA-15: Insights from thermal decomposition and advanced imaging 蛋白质分布在SBA-15：从热分解和先进成像的见解

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-11-13 DOI: 10.1016/j.micromeso.2025.113938

Kristoffer Vorm , Chrysoula Stathaki , Pedro L. Oseliero Filho , Hery Mitsutake , Tereza S. Martins , Nikolay Kardjilov , Luis C. Cides-da-Silva , Márcia C.A. Fantini , François B. Lauze , Heloisa N. Bordallo

Ordered Mesoporous Silica (OMS) materials, particularly SBA-15, are widely used in drug delivery due to their structural stability and high porosity. However, the role of macroporosity (pores >50 nm) in influencing protein adsorption and spatial distribution remains poorly understood. In this study, three SBA-15 variants were produced by changing the synthesis temperature and stirring speed, and combined evolved gas analysis (EGA), Raman imaging, and X-ray micro-computed tomography (micro-CT) were used to investigate the adsorption and distribution of lysozyme, a model protein, in the samples. While thermal analysis showed comparable overall protein uptake across all variants, Raman imaging and micro-CT demonstrated that SBA-15 with the larger macropore distribution exhibited a less uniform lysozyme distribution. These observations suggest that macroporosity affects protein localization within SBA-15, which is critical for optimizing antigen delivery and release. Our results advance understanding of how OMS morphology impacts biomolecule encapsulation, offering insights valuable for the design of advanced drug delivery systems and oral vaccines.

有序介孔二氧化硅（OMS）材料，特别是SBA-15，由于其结构稳定性和高孔隙率而广泛应用于药物输送。然而，大孔隙（孔隙>；50 nm）在影响蛋白质吸附和空间分布中的作用仍然知之甚少。本研究通过改变合成温度和搅拌速度制备了3种SBA-15变异体，并结合演化气体分析（EGA）、拉曼成像（Raman imaging）和x射线微计算机断层扫描（micro-CT）研究了模型蛋白溶菌酶在样品中的吸附和分布。虽然热分析显示所有变异的总体蛋白质摄取相当，但拉曼成像和显微ct显示，具有较大大孔分布的SBA-15溶菌酶分布不均匀。这些观察结果表明，大孔隙度影响SBA-15内蛋白质的定位，这对于优化抗原的递送和释放至关重要。我们的研究结果促进了对OMS形态如何影响生物分子包封的理解，为设计先进的药物输送系统和口服疫苗提供了有价值的见解。

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引用次数: 0

Machine learning assisted high-throughput computational investigation of SF6/N2 separation in pure silica zeolite structures 机器学习辅助高通量计算研究SF6/N2在纯硅沸石结构中的分离

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-11-01 DOI: 10.1016/j.micromeso.2025.113920

Hui-Dong Zhang , Xiao-Dong Li , Yan-Yu Xie , Xiu-Ying Liu , Jing-Xin Yu , Jun-Fei Wang

This study employs high-throughput computational screening to systematically assess 247 structures of pure silica zeolite structures, aiming to identify materials with superior efficacy for the selective adsorption of the greenhouse gas sulfur hexafluoride (SF₆) from SF₆/N₂ mixtures. Utilizing Grand Canonical Monte Carlo (GCMC) simulations, we investigated the SF₆/N₂ adsorption behavior of these zeolite structures under three distinct operational modes: vacuum swing adsorption (VSA), pressure swing adsorption (PSA), and temperature swing adsorption (TSA). Two assessment metrics, namely the adsorbent performance score (APS) and the regenerability (R%), are introduced to evaluate the separation efficiency of zeolite structures and to underscore the critical importance of material regenerability in practical applications. The results demonstrate significant correlations between the key structural parameters of zeolites, including largest cavity diameter (LCD), accessible surface area (ASA), pore occupied accessible volume (POAV) and porosity, and the adsorption capacity, adsorption heat and selectivity for SF₆. The screening results identified several zeolite structures, including UOV, IWW, SAO, and BPH, that exhibited exceptional performance in VSA, PSA, and TSA processes, characterized by their high adsorption capacity and selectivity. Furthermore, the random forest model was developed to evaluate the importance of the structural features in determining the SF₆/N₂ separation performance. A multiple linear regression model was also established to quantify the correlation between the SF₆ adsorption capacity and structural parameters. We anticipate that this study can provide some theoretical insights to guide the experimental development of zeolite structures for SF₆ separation.

本研究采用高通量计算筛选方法，对247种纯硅沸石结构进行了系统评价，旨在从SF6/N2混合物中筛选出选择性吸附温室气体六氟化硫（SF6）的高效材料。利用大规范蒙特卡罗（GCMC）模拟，研究了这些沸石结构在真空变压吸附（VSA）、变压吸附（PSA）和变温吸附（TSA）三种不同工作模式下对SF6/N2的吸附行为。介绍了吸附剂性能评分（APS）和可再生性（R%）这两个评价指标来评价沸石结构的分离效率，并强调了材料可再生性在实际应用中的重要性。结果表明，沸石的主要结构参数（最大空腔直径（LCD）、可达表面积（ASA）、孔占可达体积（POAV）和孔隙率）与SF6的吸附量、吸附热和选择性之间存在显著的相关性。筛选结果确定了几种沸石结构，包括UOV、IWW、SAO和BPH，它们在VSA、PSA和TSA过程中表现出优异的性能，具有高吸附容量和选择性。此外，建立了随机森林模型来评估结构特征在决定SF6/N2分离性能中的重要性。建立了多元线性回归模型，量化了SF6吸附量与结构参数之间的相关性。我们期望本研究可以为指导SF6分离沸石结构的实验发展提供一些理论见解。

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引用次数: 0

Accessing dynamic disorder in AlPO4-5 with single crystal diffuse scattering and ab initio molecular dynamics simulations 单晶扩散散射和从头算分子动力学模拟研究AlPO4-5的动态无序性

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-10-29 DOI: 10.1016/j.micromeso.2025.113912

Michael Fischer , Daniel A. Chaney , Osasere Austine Uwumwonse , Erik Neumann , Iris Spieß , Christin Wiggers , Ella M. Schmidt

The aluminium phosphate framework materials, such as AlPO

_{4}

-5, exhibit an inherent structural flexibility due to the connectivity of their rigid tetrahedral building blocks. This structural flexibility is critical to their ability to accommodate a wide range of organic guest molecules and/or heteroatoms, where subtle distortions of the framework do not compromise the overall framework integrity. Here, we use a combination of single-crystal diffuse scattering and ab initio molecular dynamics simulations to understand the framework dynamics in AlPO

_{4}

-5. AlPO

_{4}

-5 adopts the AFI topology, where the average structure is typically described as a framework in which one of the Al-O-P bond angles approaches 180°. This configuration is considered both energetically unfavorable and unrealistic, creating a form of bond frustration that is alleviated by collective distortions that keep the Al- and P-tetrahedra rigid. Through a combination of synchrotron based diffuse X-ray scattering and ab initio molecular dynamic simulations we demonstrate that in the AlPO

_{4}

-5 framework these distortions are likely dynamic and the real structure dynamically transforms between different distorted states, which can be approximated by a three-fold superstructure along the

c

-axis.

磷酸铝框架材料，如AlPO4-5，由于其刚性四面体构建块的连通性，表现出固有的结构灵活性。这种结构的灵活性对于它们适应广泛的有机客体分子和/或杂原子的能力至关重要，在这种情况下，框架的细微扭曲不会损害整体框架的完整性。本文采用单晶扩散散射和从头算分子动力学模拟相结合的方法来了解AlPO4-5的框架动力学。AlPO4-5采用AFI拓扑结构，其平均结构通常被描述为一个Al-O-P键角接近180°的框架。这种构型被认为在能量上是不利的，也是不现实的，它造成了一种键挫折，这种挫折可以通过保持Al-和p -四面体刚性的集体扭曲来缓解。通过同步加速器x射线散射和从头算分子动力学模拟的结合，我们证明了在AlPO4-5框架中，这些扭曲可能是动态的，真实结构在不同的扭曲状态之间动态转换，可以用沿c轴的三重上层结构来近似。

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引用次数: 0

Optimized synthesis of mesoporous niobium pentoxide: influence of structure-directing agents, crystallization time, and calcination temperature 介孔五氧化二铌的优化合成：结构导向剂、结晶时间和煅烧温度的影响

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2026-02-01 Epub Date: 2025-11-06 DOI: 10.1016/j.micromeso.2025.113936

Hídila Souza Teixeira da Silva, Diogo Pimentel de Sa da Silva, Ricardo Reis Soares

This study systematically investigates the influence of structure-directing agents (urea, PVP, and F127), crystallization time (24, 36, and 48 h), and calcination temperature (400, 500, and 600 °C) on the structural, textural, and acidic properties of mesoporous niobium pentoxide (meso-Nb₂O₅). The synthesized materials were characterized by X-ray diffraction (XRD), Raman spectroscopy, nitrogen adsorption–desorption, thermogravimetric analysis (TG/DTG), scanning electron microscopy (SEM), and zeta potential measurements. Urea was identified as the most effective structure-directing agent, yielding a well-developed meso-Nb₂O₅ with a high surface area (195 m² g⁻¹) and enhanced total acidity (58 μmol g⁻¹). The crystallization time significantly affected the structural organization, with 36 h favoring the formation of the pseudo-hexagonal TT-Nb₂O₅ phase and improved textural properties. The calcination temperature played a key role in phase transitions, with 500 °C being the optimal condition to balance crystallinity and mesoporosity. Catalytic performance was evaluated in Fischer–Tropsch synthesis (FTS). The Co catalyst supported on meso-Nb₂O₅ (10Co/Meso-Nb₂O₅) exhibited higher CO conversion (23 %) than its conventional Nb₂O₅ counterpart (10Co/Conv-Nb₂O₅), which reached 12 %, as well as greater selectivity toward medium-chain hydrocarbons (C₅–C₁₂, 44.1 % vs. 28.1 %) and lower methane formation (10.4 % vs. 17.1 %). These results demonstrate that the mesoporous Nb₂O₅ structure enhances cobalt dispersion and metal–support interactions. Overall, tuning the synthesis parameters effectively tailors Nb₂O₅ properties for advanced applications in heterogeneous catalysis.

本研究系统地研究了结构导向剂（尿素、PVP和F127）、结晶时间（24、36和48 h）和煅烧温度（400、500和600℃）对介孔五氧化二铌（meso-Nb2O5）结构、结构和酸性的影响。通过x射线衍射（XRD）、拉曼光谱（Raman）、氮吸附-脱附、热重分析（TG/DTG）、扫描电镜（SEM）和zeta电位测量对合成材料进行了表征。尿素被认为是最有效的结构导向剂，生成了发育良好的介观nb2o5，具有高表面积（195 m2 g−1）和增强的总酸度（58 μmol g−1）。晶化时间对结构组织有显著影响，36 h有利于TT-Nb2O5伪六方相的形成和织构性能的改善。煅烧温度对相变起关键作用，500℃是平衡结晶度和介孔率的最佳条件。评价了费托合成（FTS）的催化性能。介观Nb2O5负载Co催化剂（10Co/介观Nb2O5）的Co转化率（23%）高于传统Nb2O5催化剂（10Co/ convo -Nb2O5），达到12%，对中链烃（C5-C12, 44.1%比28.1%）的选择性更高，甲烷生成率（10.4%比17.1%）更低。这些结果表明介孔Nb2O5结构增强了钴的分散和金属-载体相互作用。总的来说，调整合成参数可以有效地调整Nb2O5的性能，使其在多相催化中得到更广泛的应用。

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