Microporous and Mesoporous Materials最新文献_第10页

Revealing the structural complexity of ETS-10 using 4D-STEM & electron ptychography 利用4D-STEM和电子型图技术揭示ETS-10的结构复杂性

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-10-29 DOI: 10.1016/j.micromeso.2025.113913

Daiyuan Li , Sara Kayani , Zhuoya Dong , Qing Zhang , Santiago Cobreces , Daniel Pizarro , Alvaro Mayoral

Atomic-level structural elucidation of zeolites remains challenging, particularly due to their sensitivity to the electron beam, as in the case of ETS-10, which features a unique 12-membered ring titanosilicate framework with linear Ti–O–Ti chains. In this study, we demonstrate the use of four-dimensional scanning transmission electron microscopy (4D-STEM) combined with electron ptychography to image Eu-exchanged ETS-10 (Eu-ETS-10) at sub-angstrom resolution. A homemade ptychographic reconstruction algorithm based on the extended ptychographical iterative engine (ePIE) was developed, enabling recovery of high-fidelity phase contrast images. The reconstructed images reveal not only all T-sites, including Si and Ti atoms, but also light elements such as oxygen and extraframework Eu³⁺ cations. Surface terminations and stacking faults were clearly resolved, allowing identification of the ABA and ABC polymorphs and their local transformations along the three dimensions through multislice reconstruction. These results validate ptychography as a powerful technique for atomic-scale analysis of fragile zeolitic materials offering unique insights into the structural complexity of ETS-10.

沸石的原子级结构解析仍然具有挑战性，特别是由于它们对电子束的敏感性，例如ETS-10，它具有独特的12元环形钛酸盐框架和线性Ti-O-Ti链。在这项研究中，我们展示了使用四维扫描透射电子显微镜（4D-STEM）结合电子平面摄影在亚埃分辨率下对eu -交换ETS-10 （Eu-ETS-10）进行成像。提出了一种基于扩展型阵图迭代引擎（ePIE）的自制阵图重建算法，实现了高保真相衬图像的恢复。重建的图像不仅显示了所有的t位，包括Si和Ti原子，还显示了轻元素，如氧和框架外的Eu3+阳离子。清晰地解决了表面终止和堆积错误，从而可以通过多层重建识别ABA和ABC多态及其沿三维方向的局部转换。这些结果验证了触电成像是一种强大的技术，可以在原子尺度上分析脆弱的沸石材料，为ETS-10的结构复杂性提供独特的见解。

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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 : 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

Synthesis of flexible triazine core covalent organic framework for the adsorption and removal of charged dyes 柔性三嗪核共价有机骨架的合成及其对带电染料的吸附和去除

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-10-28 DOI: 10.1016/j.micromeso.2025.113916

Premchand Panda , Arjun Warrier , Tamas Panda

Water contamination by synthetic chemicals, pharmaceuticals, fertilizers, and organic dyes has emerged as a critical environmental issue due to its detrimental impact on ecosystems and human health. In particular, the efficient removal of organic dyes from wastewater requires the development of advanced porous adsorbents with high capacity and stability. Herein, we report moderate temperature (65 °C) synthesis of imine-linked covalent organic framework (COF), termed TPT-TAPT-COF, via a Schiff base condensation between 2,4,6-tris-(4-formyl phenoxy)-1,3,5-triazine (TPT-CHO) and 2,4,6-tris-(4-amino phenyl)-1,3,5-triazine (TAPT) under solvothermal conditions. PXRD, FTIR, XPS and BET surface area measurements confirmed its high crystallinity, porosity, chemical and thermal stability. TPT-TAPT-COF was employed as an efficient adsorbent for both cationic and anionic dyes, including crystal violet (CV), malachite green (MG), methyl orange (MO), and congo red (CR). Under ambident temperature and neutral pH (pH = 7) rapid adsorption kinetics were observed, with equilibrium reached within 10 min. The maximum adsorption capacities were determined to be 290 mg g⁻¹ (CV), 268 mg g⁻¹ (MG), 238 mg g⁻¹ (MO), and 233 mg g⁻¹ (CR), (CV > MG > MO > CR) highlighting the material's broad-spectrum dye removal capability. These findings underscore the potential of TPT-TAPT-COF as a promising platform for wastewater treatment and contribute to the rational design of high-performance COF-based adsorbents.

由于对生态系统和人类健康的有害影响，合成化学品、药品、肥料和有机染料对水的污染已成为一个重要的环境问题。特别是，高效去除废水中的有机染料需要开发具有高容量和稳定性的高级多孔吸附剂。在此，我们报道了在溶剂热条件下，通过2,4,6-三-（4-甲氧基苯氧基）-1,3,5-三嗪（TPT-CHO）和2,4,6-三-（4-氨基苯基）-1,3,5-三嗪（tpt）之间的席夫碱缩合，在65℃的温度下合成亚胺连接的共价有机框架（COF），称为tpt - tpt -COF。PXRD， FTIR， XPS和BET表面积测量证实了其高结晶度，孔隙度，化学和热稳定性。采用tpt - tpt - cof作为阳离子和阴离子染料的高效吸附剂，包括结晶紫（CV）、孔雀石绿（MG）、甲基橙（MO）和刚果红（CR）。在常温和中性pH （pH = 7）条件下观察到快速吸附动力学，吸附在10 min内达到平衡。最大吸附量分别为290 mg g−1 （CV）、268 mg g−1 （mg）、238 mg g−1 （MO）和233 mg g−1 (CR), （CV > mg > MO >； CR）表明该材料具有广谱脱色能力。这些发现强调了tpt - tpt - cof作为一个有前途的废水处理平台的潜力，并有助于合理设计高性能的cof基吸附剂。

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引用次数: 0

Dual-modified tobermorite with carbon and magnesium oxide for adsorbing methyl orange and methylene blue 碳氧化镁双改性托伯莫来石吸附甲基橙和亚甲基蓝

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-10-28 DOI: 10.1016/j.micromeso.2025.113911

Guoyi Cao , Jian Zhou , Jiayu Shi , Jiarui Lv , Changjin Ou , Jian Shi , Juan Qin

In this study, a novel adsorbent, tobermorite/carbon/MgO (TCM), was successfully synthesized by dual-functionalizing tobermorite with carbon and MgO nanoparticles. This modification strategy aimed to synergistically combine the structural advantages of tobermorite with the high reactivity of MgO and the porosity of carbon. Compared to the unmodified tobermorite, the resulting TCM composite exhibited a remarkable 8-fold increase in specific surface area (from 47.56 m²/g to 386.52 m²/g) and dramatically enhanced removal efficiencies for Methyl Orange (MO) and Methylene Blue (MB), elevating them from 7.14 % to 82.54 % and from 43.66 % to ∼100 %, respectively. The adsorption kinetics revealed a distinct difference, with MO reaching equilibrium within 1 h, significantly faster than MB (48 h). The maximum experimental adsorption capacities for MO and MB were 792.33 mg/g and 641.40 mg/g, respectively. Furthermore, TCM demonstrated robust performance across a wide pH range, in actual water matrices, and over multiple regeneration cycles. While the adsorption kinetics for both dyes followed the pseudo-second-order model, the equilibrium data were best fitted by the Langmuir isotherm for MO and the Freundlich isotherm for MB. Comprehensive characterization confirmed that the underlying mechanisms involved electrostatic attraction, hydrogen bonding, surface complexation, and pore filling. These findings not only establish TCM as a versatile and high-performance adsorbent for anionic and cationic dye remediation but also provide fundamental insights for the subsequent resource utilization of waste autoclaved aerated concrete (AAC), a tobermorite-rich construction waste.

在本研究中，通过碳和MgO纳米粒子对托贝莫来石进行双功能化，成功合成了一种新型吸附剂托贝莫来石/碳/MgO （TCM）。这种改性策略旨在将托贝莫来石的结构优势与MgO的高反应性和碳的孔隙性协同结合。与未改性的托伯莫来石相比，所得到的TCM复合材料的比表面积显著增加了8倍（从47.56 m2/g增加到386.52 m2/g），对甲基橙（MO）和亚甲基蓝（MB）的去除率分别从7.14%提高到82.54%和43.66%提高到100%。吸附动力学差异明显，MO在1 h内达到平衡，明显快于MB （48 h）。对MO和MB的最大吸附量分别为792.33 mg/g和641.40 mg/g。此外，TCM在广泛的pH范围内，在实际的水基质中，以及在多个再生循环中表现出稳健的性能。虽然两种染料的吸附动力学都遵循准二阶模型，但平衡数据最适合MO的Langmuir等温线和MB的Freundlich等温线。综合表征证实了潜在的机制包括静电吸引、氢键、表面络合和孔隙填充。这些发现不仅确立了中药作为阴离子和阳离子染料修复的多功能和高性能吸附剂的地位，而且为后续对富含托贝沸石的建筑垃圾——高压灭菌加气混凝土（AAC）的资源化利用提供了基础见解。

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引用次数: 0

Microfluidic and microwave approaches for the rapid synthesis of Cu-CPO-27 metal-organic framework 微流控和微波方法快速合成Cu-CPO-27金属有机骨架

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-10-27 DOI: 10.1016/j.micromeso.2025.113901

M.E.A. Eid , A.D. Zagrebaev , A.Y. Pnevskaya , I.O. Nechitailova , V.V. Butova , M.V. Manushko , K.K. Volik , A.A. Guda , A.V. Soldatov

Metal-organic frameworks (MOFs) are promising substances for catalytic transformations, selective gas adsorption, and drug delivery. However, their synthesis and application are complicated by issues of production, storage, and scaling. The optimization of synthesis using microwave and microfluidic technologies can significantly reduce the time and facilitate further study and application of these materials. The goal of our work is to revise the approaches for Cu-CPO-27 synthesis, including hydrothermal, microwave, and microfluidic ones, and their effect on structural properties and porosity. Our research included a thorough optimization of the classical hydrothermal method aimed at reducing the synthesis time and increasing yields. Additionally, we explored the possibility of using microwave and microfluidic technologies to accelerate the Cu-CPO-27 synthesis process. The optimized methodology allows to reduce autoclaving time below 8 h. The use of microwave stimuli enables the production of structured, rod-like crystals at lower temperatures and time below 2 h, while MOF crystals form in a record short time, just 1.5 min, in microfluidic conditions.

金属有机骨架（mof）在催化转化、选择性气体吸附和药物传递等方面具有广阔的应用前景。然而，它们的合成和应用由于生产、存储和扩展问题而变得复杂。利用微波和微流控技术对合成工艺进行优化，可以大大缩短合成时间，促进材料的进一步研究和应用。我们的工作目标是修正Cu-CPO-27的合成方法，包括水热法、微波法和微流控法，以及它们对结构性质和孔隙率的影响。我们的研究包括对经典的水热法进行彻底的优化，以减少合成时间和提高收率。此外，我们还探索了利用微波和微流控技术加速Cu-CPO-27合成过程的可能性。优化后的方法可以将高压灭菌时间减少到8小时以下。使用微波刺激可以在较低的温度和低于2小时的时间内生产结构化的棒状晶体，而在微流体条件下，MOF晶体在创纪录的短时间内形成，仅为1.5分钟。

{"title":"Microfluidic and microwave approaches for the rapid synthesis of Cu-CPO-27 metal-organic framework","authors":"M.E.A. Eid , A.D. Zagrebaev , A.Y. Pnevskaya , I.O. Nechitailova , V.V. Butova , M.V. Manushko , K.K. Volik , A.A. Guda , A.V. Soldatov","doi":"10.1016/j.micromeso.2025.113901","DOIUrl":"10.1016/j.micromeso.2025.113901","url":null,"abstract":"<div><div>Metal-organic frameworks (MOFs) are promising substances for catalytic transformations, selective gas adsorption, and drug delivery. However, their synthesis and application are complicated by issues of production, storage, and scaling. The optimization of synthesis using microwave and microfluidic technologies can significantly reduce the time and facilitate further study and application of these materials. The goal of our work is to revise the approaches for Cu-CPO-27 synthesis, including hydrothermal, microwave, and microfluidic ones, and their effect on structural properties and porosity. Our research included a thorough optimization of the classical hydrothermal method aimed at reducing the synthesis time and increasing yields. Additionally, we explored the possibility of using microwave and microfluidic technologies to accelerate the Cu-CPO-27 synthesis process. The optimized methodology allows to reduce autoclaving time below 8 h. The use of microwave stimuli enables the production of structured, rod-like crystals at lower temperatures and time below 2 h, while MOF crystals form in a record short time, just 1.5 min, in microfluidic conditions.</div></div>","PeriodicalId":392,"journal":{"name":"Microporous and Mesoporous Materials","volume":"401 ","pages":"Article 113901"},"PeriodicalIF":4.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145428736","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}

引用次数: 0

Submicron-sized SAPO-11 molecular sieve synthesized by induction of micron-sized heterologous seeds shows superiority in hydroisomerization of n-hexane 采用微米级异源种子诱导合成的亚微米级SAPO-11分子筛在正己烷的加氢异构化方面具有优势

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-10-25 DOI: 10.1016/j.micromeso.2025.113908

Jintang Xue, Jianing Ge, Huili Liu, Yiran Wang, Hong Wang, Chenchong Zhu, Chuangye Wang

In this work, submicron-sized SAPO-11 molecular sieves were successfully synthesized by introducing micron-sized heterologous SAPO-5 seed into the synthesis system. Phosphorylated polyvinyl alcohol (PPVA) was additionally introduced into the synthesis as a mesoporous templating agent to achieve small-sized hierarchical SAPO-11. Comprehensive characterizations revealed that the addition of heterologous seeds reduced the average particle size of SAPO-11 from 7.52 μm to a minimum of 0.38 μm. Compared to conventional SAPO-11, the samples synthesized via the heterologous seed method exhibited higher relative crystallinity, increased BET specific surface area and significantly enhanced mesopore volume. The formation mechanism of the submicron-sized SAPO-11 molecular sieve was elucidated by investigating the crystallization process of the submicron-sized SAPO-11 and its conventional counterpart without heterologous seed assistance. Catalytic performance tests demonstrated that the submicron-sized SAPO-11 has superior performance in the hydroisomerization of n-hexane. The micron-sized heterologous seed-assisted synthesis method reported herein offers advantages of simple procedure and low cost to synthesize submicron-sized SAPO-11. It enables the submicron-sized SAPO-11 molecular sieves with enhanced catalytic performance, while also provides a novel strategy for synthesizing other submicron-sized silicoaluminophosphate molecular sieves.

本研究通过在合成体系中引入微米级的异源SAPO-5种子，成功合成了亚微米级的SAPO-11分子筛。将磷酸聚乙烯醇（PPVA）作为介孔模板剂引入合成，得到了小尺寸的分级SAPO-11。综合表征表明，异种种子的加入使SAPO-11的平均粒径从7.52 μm减小到最小0.38 μm。与常规SAPO-11相比，异源种子法合成的样品具有更高的相对结晶度，BET比表面积增加，介孔体积显著增加。通过研究亚微米级SAPO-11分子筛的结晶过程，阐明了亚微米级SAPO-11分子筛的形成机理。催化性能测试表明，亚微米尺寸的SAPO-11在正己烷的加氢异构化反应中具有优异的性能。本文报道的微米级异源种子辅助合成方法具有合成亚微米级SAPO-11的过程简单、成本低等优点。它使亚微米尺寸的SAPO-11分子筛具有更强的催化性能，同时也为合成其他亚微米尺寸的硅铝磷酸酯分子筛提供了一种新的策略。

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引用次数: 0

Effect of extra-framework Ga2O3 species in Ga/ZSM-5 catalysts on methanol-to-aromatics reaction Ga/ZSM-5催化剂中框架外Ga2O3对甲醇-芳烃反应的影响

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-10-25 DOI: 10.1016/j.micromeso.2025.113907

Rui Geng, Xianjun Niu, Yajie Liu

HZSM-5 zeolite is extensively used in methanol-to-aromatics (MTA) reactions; however, its low aromatics selectivity limits its performance due to weak intrinsic aromatization ability. In this study, a series of bifunctional x-Ga₂O₃/HZSM-5 were synthesized by mechanically mixing different Ga₂O₃ isomers with HZSM-5 to systematically investigate the influence of the crystal structure on methanol aromatization. Among them, β-Ga₂O₃/HZSM-5 catalyst exhibited the highest aromatic selectivity, reaching 40 mol%. Structural characterization by XRD, N₂ adsorption, XPS, H₂-TPR, XANES, and EXAFS analyses revealed that the dispersion and reducibility of extra-framework Ga³⁺ species varied with the Ga₂O₃ structure. In particular, the monoclinic β-Ga₂O₃ exhibited a pronounced interaction with Brønsted acid sites of HZSM-5, promoting the formation of highly active and stable four-coordinated [Ga₂O₂]²⁺ dimers. These species functioned as efficient dehydrogenation and cyclization centers, thereby markedly promoting aromatics production.

HZSM-5沸石广泛用于甲醇制芳烃反应；但其固有芳构化能力较弱，芳烃选择性较低，限制了其性能。本研究通过机械混合不同的Ga2O3异构体与HZSM-5，合成了一系列双官能团x-Ga2O3/HZSM-5，系统研究了晶体结构对甲醇芳构化的影响。其中，β-Ga2O3/HZSM-5催化剂的芳香选择性最高，达到40 mol%。通过XRD、N2吸附、XPS、H2-TPR、XANES和EXAFS等分析表明，框架外Ga3+的分散性和还原性随Ga2O3结构的变化而变化。特别是，单斜晶β-Ga2O3与HZSM-5的Brønsted酸位表现出明显的相互作用，促进了高活性和稳定的四配位[Ga2O2]2+二聚体的形成。这些物种作为有效的脱氢和环化中心，从而显著促进芳烃的生产。

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引用次数: 0

Accelerated, impurity-free crystallization of aluminum-rich beta zeolite with aluminophosphate as the aluminum carrier 以磷酸铝为铝载体的富铝沸石的加速、无杂质结晶

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-10-25 DOI: 10.1016/j.micromeso.2025.113903

Zhiping Wang , Rui Zhu , Jiejie Ling , Han Jiang , Lei Liu , Yan Gao , Hailang Liu , Le Xu

Zeolite Beta, discovered in 1967, features a unique three-dimensional (3D) 12-ring channel system and a highly tunable Si/Al ratio (SAR), granting exceptional stability and acidity crucial for catalysis. While conventional hydrothermal synthesis normally yields zeolite Beta with the SAR range of 10–30 using tetraethylammonium hydroxide (TEAOH) as the organic structure-directing agent (OSDA), the discovery of Al-rich natural mineral (Tschernichite) with the ∗BEA topology (SAR∼3.3) spurred efforts to synthesize low-SAR Beta zeolite for enhanced acid site density, hydrophilicity and ion-exchange capacity, enabling applications like dehydration, separation and shape-selective catalysis. However, achieving low SARs for the hydrothermal crystallization of zeolite Beta is still challenging, requiring excess Na⁺ which promotes impurity phases (e.g., GIS, ANA, MOR), prolongs crystallization period and reduces yield. Inspired by our recent work on the kinetic-control synthesis of high-silica NaY zeolite using aluminophosphate as the aluminum carrier, this study presents an accelerated, impurity-free synthetic route to achieve Al-rich zeolite Beta. Using the pre-synthesized aluminophosphate (e.g., AlPO-5) as a partial Al source favors the formation of a silica-rich Beta zeolite nucleus, thus effectively suppresses impurities (eliminating GIS phase in Na⁺-containing system) and amorphous phase (in Na⁺-free system), ultimately accelerating crystallization process. Based on this synthetic control, this study successfully synthesized the phase-pure Beta zeolite at SAR of 7.55 (Na⁺-free) and 6.58 (Na⁺-containing), while this strategy was extended to the Beta zeolite synthesis with other aluminophosphate, including SSZ-51 (SFO) and AlPO-18 (AEI).

Beta沸石于1967年被发现，具有独特的三维（3D） 12环通道系统和高度可调的Si/Al比（SAR），具有卓越的稳定性和对催化至关重要的酸度。传统的水热合成通常使用四乙基氢氧化铵（TEAOH）作为有机结构导向剂（OSDA）产生SAR范围为10-30的β沸石，而具有* BEA拓扑（SAR ~ 3.3）的富铝天然矿物（Tschernichite）的发现刺激了合成低SAR β沸石的努力，以增强酸位密度，亲水性和离子交换能力，使脱水，分离和形状选择催化等应用成为可能。然而，实现β沸石水热结晶的低sar仍然具有挑战性，需要过量的Na+，这会促进杂质相（例如GIS， ANA， MOR），延长结晶周期并降低收率。受我们最近以磷酸铝为铝载体的动力学控制合成高硅NaY沸石的启发，本研究提出了一种加速、无杂质合成富铝沸石β的方法。使用预合成的磷酸铝（如AlPO-5）作为部分Al源有利于富硅β沸石核的形成，从而有效抑制杂质（在含Na+体系中消除GIS相）和非晶相（在无Na+体系中），最终加速结晶过程。在此合成对照的基础上，本研究成功合成了相纯的β沸石，合成SAR分别为7.55（无Na+）和6.58（含Na+），并将此策略推广到与其他磷酸铝（包括SSZ-51 （SFO）和AlPO-18 (AEI)）合成β沸石。

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引用次数: 0

Lanthanide adsorption kinetics in silica nanopores 镧系元素在二氧化硅纳米孔中的吸附动力学

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-10-24 DOI: 10.1016/j.micromeso.2025.113906

Bidemi T. Fashina, Anastasia G. Ilgen

The understanding of reactions in nanoscale confinement is important for predicting fate and transport of ions and the development of environmental remediation and resource recovery technologies. Here, we investigated the effect of nanoconfinement on the adsorption kinetics of lutetium (Lu³⁺), europium (Eu³⁺), and neodymium (Nd³⁺) on two cylindrical mesoporous silicas with pore diameters of 4 nm and 7 nm, and one non-porous silica. The three lanthanides differ in their solvated radius, solvation energy, and water exchange rate constants, which enables inquiry into the role of solvation properties on the adsorption kinetics of the three lanthanides. The measured values of the adsorption rate constants (k) and the equilibrium surface coverages (q_e) indicate that the uptake of the three lanthanides is faster, and coverage is higher on non-porous silica compared to the porous silicas. We assign this trend to the energy barrier associated with permeation of ions into nanoscale pores and the larger ratio of outer-sphere to inner-sphere complexes that form on the non-porous silica. The k was higher on the 7 nm porous compared 4 nm porous silica suggesting that the energy barrier for ion permeation into smaller pores is higher (less favorable). The q_e increased with decreasing pore diameter, which we attribute to the lower desolvation cost in smaller pores thus facilitating more inner-sphere complexation. The solvation energy and solvated radius were the most important solvation properties dictating the adsorption kinetics of the three lanthanides. The reported water exchange rate for the first solvation shell for the three lanthanides did not correlate with the observed adsorption rate constants.

了解纳米尺度约束下的反应对于预测离子的命运和迁移以及环境修复和资源回收技术的发展具有重要意义。本文研究了纳米约束对镥（Lu3+）、铕（Eu3+）和钕（Nd3+）在两种直径分别为4 nm和7 nm的圆柱形介孔二氧化硅和一种无孔二氧化硅上吸附动力学的影响。这三种镧系元素在溶剂化半径、溶剂化能和水交换速率常数上存在差异，从而可以探讨溶剂化性质对三种镧系元素吸附动力学的影响。吸附速率常数(k)和平衡表面覆盖率（qe）的测量值表明，三种镧系元素在非多孔二氧化硅上的吸附速度更快，与多孔二氧化硅相比，非多孔二氧化硅上的覆盖率更高。我们将这种趋势归因于离子渗透到纳米级孔中的能量势垒，以及在非多孔二氧化硅上形成的外球与内球络合物的较大比例。7 nm孔的k比4 nm孔的高，表明离子渗透到较小孔的能垒更高（不太有利）。qe随孔径的减小而增大，这是由于孔径越小，溶解度越低，有利于球内络合。溶剂化能和溶剂化半径是决定三种镧系元素吸附动力学的最重要的溶剂化性质。报道的三种镧系元素的第一溶剂化壳的水交换速率与观察到的吸附速率常数不相关。

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引用次数: 0

CO2 adsorption by zeolites: State-of-Art, techniques and emerging trends 沸石吸附二氧化碳：最新技术、技术和新趋势

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-10-23 DOI: 10.1016/j.micromeso.2025.113904

Eduardo Antonio Pinto Dias , Débora Guimarães da Silva , Marcelo da Costa Amaral , Leonardo dos Santos Pereira , Darley Carrijo de Melo , Wander Luiz Vasconcelos

Over the past few years, efforts have been made to find solutions to combat climate change by capturing CO₂ from industrial processes and from the atmosphere. Zeolites, a class of microporous materials with crystalline structures that display properties for adsorption, separation, and capture of gases, have been praised for effectively capturing and removing CO₂. In this review, the properties of zeolites as CO₂ adsorbents are discussed, presenting and addressing their potential and drawbacks. For this purpose, an overview of the types of zeolites (structures, classification and industrial applications) is presented. Then, the adsorption mechanisms, the relationship between the physicochemical properties of zeolites and their performance as CO₂ adsorbents are systematically discussed. Based on the trends and properties identified, the state of the art on the synthesis, modification and shaping of zeolites, a fundamental step for their application as industrial adsorbents, is discussed. The application in gas processing is examined, focusing on natural gas processing. Finally, the challenges and the outlook for CO₂ adsorption are highlighted. Recent advancements in zeolite development and application have demonstrated remarkable improvements in CO₂ adsorption efficiency and versatility, reaffirming their importance in the transition to a low-carbon economy. However, the industrial application of zeolite in CO₂ adsorption still presents significant challenges, such as enhancing adsorption and desorption capacity under real conditions, reducing the costs and impacts of synthesis and ensuring that the processes are environmentally viable.

在过去的几年里，人们一直在努力寻找通过从工业过程和大气中捕获二氧化碳来应对气候变化的解决方案。沸石是一类具有晶体结构的微孔材料，具有吸附、分离和捕获气体的特性，因有效捕获和去除二氧化碳而受到称赞。本文综述了沸石作为CO2吸附剂的性能，并指出了它们的潜力和不足。为此，概述了沸石的类型（结构、分类和工业应用）。然后，系统地讨论了沸石的吸附机理、其物理化学性质与CO2吸附剂性能的关系。在此基础上，讨论了沸石的合成、改性和成型的研究现状，这是沸石作为工业吸附剂应用的基础步骤。重点介绍了其在天然气加工中的应用。最后，对CO2吸附技术面临的挑战和前景进行了展望。最近沸石的开发和应用取得了显著的进步，在二氧化碳吸附效率和多功能性方面取得了显著的进步，重申了它们在向低碳经济转型中的重要性。然而，沸石在二氧化碳吸附中的工业应用仍然面临着重大挑战，例如提高实际条件下的吸附和解吸能力，降低合成成本和影响，并确保工艺的环境可行性。

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