Microporous and Mesoporous Materials最新文献_第8页

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 : 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

Fabrication of ZIF-loaded polymer composites with antimicrobial properties towards food packaging solutions 具有抗菌性能的zif负载高分子复合材料在食品包装中的应用

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-11-24 DOI: 10.1016/j.micromeso.2025.113961

Laura Premet , Emmanuel Oheix , Gérald Chaplais , Eliane Bou Orm , Habiba Nouali , Laure Michelin , Ludovic Josien , T. Jean Daou , Laurent Pieuchot

Microporous materials are widely explored as carriers for the controlled release of antimicrobial agents, yet their practical application requires the development of scalable and adaptable shaping processes. Metal-organic frameworks (MOFs) have the potential to exert antimicrobial effects through the release of either inorganic nodes, organic linkers, encapsulated antimicrobial agents or their combinations. In this study, the preparation and antimicrobial study of polymer-based composite films containing zeolitic imidazolate frameworks (ZIFs) on a pilot-scale are reported. Such materials are intended to be shaped for applications in food packaging. To fulfill our aim, ZIF materials have been synthesized on a large scale (>200 g scale) and fully characterized (X-Ray Diffraction, Scanning Electronic Microscopy/coupled to Energy-Dispersive X-Ray spectroscopy, thermogravimetry, low-temperature nitrogen physisorption). Structural and morphological analyses are consistent with the coexistence of two polymorphs in the large scale samples (35 wt.% ZIF-8 and 65 wt..% ZIF-dia(Zn)). Nevertheless, complementary and initial study involving pure ZIF-8 and ZIF-dia solids highlights similar antimicrobial activity for the two MOFs. Large scale samples were subsequently used for the preparation of polymer-based composite films, containing 5, 10 and 30 wt.% of ZIF-8/ZIF-dia(Zn), which were fully characterized and compared to MOF-free film. The antimicrobial disinfection studies indicate that the film with 30 wt.% MOF display significantly higher ability to inhibit Escherichia Coli growth compared to 5, 10 wt.% MOF and MOF-free formulations. Importantly, the pilot-scale process developed here is readily translatable to industrial-scale production, offering a viable route for the integration of MOF-based antimicrobial materials into commercial food packaging solutions.

微孔材料作为抗菌药物控释载体被广泛探索，但其实际应用需要开发可扩展和适应性强的成型工艺。金属-有机框架（mof）具有通过释放无机节点、有机连接体、封装抗菌剂或它们的组合来发挥抗菌作用的潜力。本文报道了含咪唑酸沸石骨架（ZIFs）聚合物基复合膜的制备及其抗菌性能的中试研究。这类材料的成型目的是用于食品包装。为了实现我们的目标，ZIF材料已经大规模合成（>； 200g规模）并进行了充分的表征（x射线衍射，扫描电子显微镜/耦合能量色散x射线光谱，热重法，低温氮物理吸附）。结构和形态分析与两种多态共存的大规模样品（35 wt.% ZIF-8和65 wt.% ZIF-8）一致。% ZIF-dia(锌))。然而，涉及纯ZIF-8和ZIF-dia固体的互补和初步研究表明，这两种mof具有相似的抗菌活性。随后，大规模样品用于制备聚合物基复合膜，其中ZIF-8/ZIF-dia（Zn）的含量分别为5%、10%和30wt .%，对其进行了充分表征，并与无mof膜进行了比较。抗菌消毒研究表明，30 wt.% MOF的膜比5、10 wt.% MOF和不含MOF的膜抑制大肠杆菌生长的能力明显更高。重要的是，这里开发的中试规模工艺很容易转化为工业规模生产，为将mof基抗菌材料整合到商业食品包装解决方案中提供了一条可行的途径。

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引用次数: 0

Activation of Prussian blue analogues: Temperature effects on structure, porosity, and open metal site accessibility 普鲁士蓝类似物的活化：温度对结构、孔隙度和开放金属位点可及性的影响

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-11-22 DOI: 10.1016/j.micromeso.2025.113959

Jelco Albertsma, Christel I. Koopman, Eise Draaijer, Willy Rook, David A. Vermaas, Monique A. van der Veen

Prussian blue analogues (PBAs) are low-cost porous materials with promising potential in gas separation, owing to their abundance of open metal sites. To access these open metal sites PBAs need to be activated through removal of water from the porous structure. However, the conditions required for effective activation and their structural consequences remain poorly understood, with existing effective methods being costly. Therefore, to gain insights in the activation process and its effects on structure, we systematically investigated the effect of activation temperature on three different ferricyanide-based PBAs (FePBA, CoPBA, and CuPBA) using a simple nitrogen flow activation procedure. We successfully synthesised these structures and optimised the activation procedure for micropore capacity and crystallinity. Infrared spectroscopy as well as CO₂ and CO adsorption measurements revealed that, even under optimised conditions, water remained within the PBAs, with only a limited number of open metal sites accessible. At higher activation temperatures, micropore capacity and crystallinity decrease. This hydrophilicity, however, also showed positives, for example in the application of PBAs as desiccants. CuPBA, specifically, boasts a water adsorption of 355 mg g⁻¹ at a relative humidity of ≤10%, competitive with zeolites and silica per weight unit, but higher per volume unit. Overall, however, while PBAs offer promise for gas adsorption owing to their high surface area and low cost, practical utilisation of their open metal sites remains challenging due to their strong affinity for water.

普鲁士蓝类似物（PBAs）是一种低成本的多孔材料，由于其丰富的开放金属位点，在气体分离中具有很好的潜力。为了进入这些开放的金属位置，PBAs需要通过从多孔结构中去除水来激活。然而，有效激活所需的条件及其结构后果仍然知之甚少，现有的有效方法成本高昂。因此，为了深入了解活化过程及其对结构的影响，我们使用简单的氮气流活化程序系统地研究了活化温度对三种不同的铁氰化物基PBAs （FePBA， CoPBA和CuPBA）的影响。我们成功地合成了这些结构，并优化了微孔容量和结晶度的激活程序。红外光谱以及CO2和CO吸附测量表明，即使在优化条件下，水仍留在PBAs中，只有有限数量的开放金属位点可进入。在较高的活化温度下，微孔容量和结晶度降低。然而，这种亲水性也显示出积极的一面，例如在PBAs作为干燥剂的应用中。具体来说，在相对湿度≤10%时，CuPBA的吸水性为355 mg g - 1，与沸石和二氧化硅在重量单位上具有竞争力，但在体积单位上更高。然而，总体而言，尽管PBAs由于其高表面积和低成本而为气体吸附提供了希望，但由于其对水的强亲和力，其开放金属位点的实际利用仍然具有挑战性。

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引用次数: 0

Transition metal docking in MOF-303 for enhanced Atmospheric Water Harvesting: A multiscale simulation approach MOF-303过渡金属对接增强大气集水：一种多尺度模拟方法

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-11-22 DOI: 10.1016/j.micromeso.2025.113943

Mehrzad Arjmandi , Mohamed Khayet , Sofia Calero

We present a multiscale computational study on water adsorption and transport in pristine and metal-functionalized MOF-303 frameworks for Atmospheric Water Harvesting (AWH). Using Grand Canonical Monte Carlo (GCMC), Kinetic Monte Carlo (KMC), and Molecular Dynamics (MD) simulations, we evaluated the thermodynamic uptake, adsorption kinetics, and mobility of water under varying humidity. Post-synthetic metalation with Cu(I) and Ag(I) increased the hydrophilicity of the framework, with Cu@MOF-303 and Ag@MOF-303 achieving a 37 % and 27 % higher uptake and faster saturation kinetics, respectively. Density Functional Theory (DFT) calculations revealed enhanced binding energies and localized polarization effects at Cu sites, supported by electrostatic potential maps and charge redistribution analyses. Radial distribution function (RDF) analyses revealed that metalation, especially with Cu, enhances water structuring near specific adsorption sites through localized polarization and extended electronic redistribution. Reduced water diffusion in Cu@MOF-303, observed via mean square displacement (MSD) profiles, confirmed stronger confinement. Additionally, temperature-dependent desorption analyses indicated that Ag@MOF-303 offers a more favorable balance between high uptake and moderate regeneration temperatures, reinforcing its practical viability under solar-driven AWH conditions. These results underscore the potential of targeted metal docking to fine-tune MOF performance for water harvesting in low-humidity and off-grid environments.

我们提出了用于大气集水（AWH）的原始和金属功能化MOF-303框架中水吸附和输运的多尺度计算研究。利用大规范蒙特卡罗（GCMC）、动力学蒙特卡罗（KMC）和分子动力学（MD）模拟，我们评估了不同湿度下水的热力学吸收、吸附动力学和迁移率。合成后与Cu(I)和Ag(I)的金属化提高了骨架的亲水性，Cu@MOF-303和Ag@MOF-303分别获得了37%和27%的高吸收率和更快的饱和动力学。密度泛函理论（DFT）计算结果显示，静电势图和电荷再分配分析支持了Cu位点结合能和局域极化效应的增强。径向分布函数（RDF）分析表明，金属化，特别是与Cu的金属化，通过局部极化和扩展的电子重分布增强了特定吸附位点附近的水结构。通过均方位移（MSD）剖面观察到，Cu@MOF-303中水扩散减少，证实了更强的约束。此外，温度相关的解吸分析表明，Ag@MOF-303在高吸收率和中等再生温度之间提供了更有利的平衡，增强了其在太阳能驱动的AWH条件下的实际可行性。这些结果强调了定向金属对接的潜力，可以微调MOF在低湿度和离网环境下的集水性能。

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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 : 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

Three-dimensional visualisation of hierarchical zeolitic materials with ptychographic X-ray computed tomography 分层沸石材料的三维可视化与平面x射线计算机断层扫描

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-11-21 DOI: 10.1016/j.micromeso.2025.113955

Gabriel B. Báfero , Luiza M. Manente , Mariana V. Rodrigues , Tiago A. Kalile , Carla C. Polo , Marlon M. Silva , Amélie Rochet , Peng Qi , Christian David , Ana Diaz , Florian Meneau

Hierarchical zeolites have become benchmark catalysts in reactions such as methanol-to-hydrocarbons and selective oxidations, owing to their enhanced diffusion, improved accessibility to acid sites, and extended lifetimes relative to their purely microporous counterparts. Among them, ZSM-5 stands out for its structural stability and tunable acidity. However, characterising the spatial distribution of porosity within individual crystals remains challenging. Conventional techniques either lack internal spatial resolution or require destructive sample preparation, limiting their ability to resolve intracrystalline heterogeneity. Here, we employ ptychography X-ray Computed Tomography (PXCT) to non-destructively visualise and quantify the internal porosity in hierarchical ZSM-5 crystals. Experiments were carried out at the Cateretê beamline of the 4th generation SIRIUS synchrotron (LNLS/CNPEM), achieving three-dimensional resolution of 40 nm. The 3D volume reveals spatially heterogeneous porous networks, including core-shell-like structures and porosity gradients introduced by post-synthetic desilication. This study highlights the potential of PXCT for the advanced characterisation of porous catalysts. Beyond enabling direct visualisation of the porosity architecture, the method provides structural insights relevant for interpreting diffusion behaviour, reactivity patterns, and deactivation mechanisms. PXCT opens new possibilities for the rational design of porous catalysts, allowing spatial correlations between synthesis, structure, and function to be experimentally resolved.

与纯微孔分子筛相比，分级沸石具有更强的扩散能力、更易于接近酸位以及更长的使用寿命，因此已成为甲醇制烃和选择性氧化等反应的基准催化剂。其中，ZSM-5因其结构稳定性和酸度可调而脱颖而出。然而，表征单个晶体内孔隙度的空间分布仍然具有挑战性。传统的技术要么缺乏内部空间分辨率，要么需要破坏性的样品制备，限制了它们解决晶内非均质性的能力。在这里，我们使用x射线计算机断层扫描（PXCT）来非破坏性地可视化和量化分层ZSM-5晶体的内部孔隙度。实验在第四代SIRIUS同步加速器（LNLS/CNPEM）的Cateretê光束线上进行，实现了40 nm的三维分辨率。三维体积揭示了空间上不均匀的多孔网络，包括核壳状结构和合成脱硅后引入的孔隙度梯度。这项研究突出了PXCT在多孔催化剂高级表征方面的潜力。除了能够直接可视化孔隙结构外，该方法还提供了与解释扩散行为、反应模式和失活机制相关的结构见解。PXCT为合理设计多孔催化剂开辟了新的可能性，使合成、结构和功能之间的空间相关性得以实验解决。

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引用次数: 0

FDU-12 silica functionalized with sulfonic groups for esterification of glycerin with stearic acid 用磺酸基官能化的FDU-12二氧化硅用于甘油与硬脂酸的酯化反应

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-11-20 DOI: 10.1016/j.micromeso.2025.113957

L. Vergara, H.P. Decolatti, G. Mendow, B.S. Sánchez

FDU-12 silica was functionalized with sulfonic groups by grafting and co-condensation methods to obtain solid acid catalysts with S/Si molar ratios of 10 and 15 %. In the grafting method, the functional groups are incorporated after the formation of the mesoporous material, whereas the co-condensation methodologies introduce the sulfonic groups during the formation of the FDU-12 structure. The resulting solids were characterized by various techniques, which revealed that catalysts obtained by grafting preserved the three-dimensional mesoporous structure of the parent silica, although with a lower degree of –SO₃H incorporation. In contrast, the co-condensation route led to higher sulfur incorporation and oxidation, despite partial loss of structural order. The catalysts were evaluated in the glycerolisis of stearic acid in a batch reactor under vacuum at 160 °C. All catalysts achieved high conversions, with the 15 % S/Si sample prepared by the co-condensation (C2) route standing out by reaching 97 % conversion within 150 min. The reuse of this catalyst was also assessed, showing stable activity over three consecutive cycles and satisfactory selectivity toward the desired products. These results highlight the potential of co-condensation synthesis to enhance catalytic performance while maintaining reasonable stability.

通过接枝和共缩合的方法，将FDU-12硅石与磺酸基进行了官能团化，得到了S/Si摩尔比分别为10%和15%的固体酸催化剂。在接枝方法中，官能团在介孔材料形成后加入，而共缩合方法在FDU-12结构形成过程中引入磺酸基。通过各种技术对所得固体进行了表征，结果表明，通过接枝得到的催化剂保留了母体二氧化硅的三维介孔结构，尽管-SO3H的掺入程度较低。相比之下，共缩聚路线导致了更高的硫掺入和氧化，尽管部分结构秩序的损失。在真空间歇式反应器中，在160℃条件下对催化剂进行了硬脂酸甘油化反应。所有催化剂都实现了高转化率，其中通过共缩合（C2）途径制备的15% S/Si样品在150分钟内达到了97%的转化率。对该催化剂的重复使用也进行了评估，在连续三个循环中表现出稳定的活性和对所需产物的满意选择性。这些结果突出了共缩合合成在保持合理稳定性的同时提高催化性能的潜力。

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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 : 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

Tuning electrophoretic deposition parameters for the fabrication of MOF-based electrochemical coatings 调整电泳沉积参数制备mof基电化学涂层

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2025-11-16 DOI: 10.1016/j.micromeso.2025.113954

Duarte Borralho , Mariana Ferreira , Telmo Nunes , Paulo N. Martinho , Sara Realista

The development of scalable, efficient methods for fabricating metal–organic framework thin films is vital for expanding their application in electrochemical sensing. In this work, we systematically explore the use of electrophoretic deposition to immobilise two zirconium-based metal-organic frameworks—UiO-66 and its amine-functionalised analogue UiO-66-NH₂—onto fluorine-doped tin oxide (FTO) substrates. A comprehensive optimisation of solvent systems, deposition time, and electric field strength revealed that short deposition times (5 min) under an electric field of 90 V cm⁻¹ in ethanol with 0.05 % acetic acid yield the most uniform, crystalline, and adherent coatings. This work presents, for the first time, the successful immobilisation of UiO-66-NH₂ using electrophoretic deposition. Structural integrity was confirmed via powder X-Ray diffraction and infrared spectroscopy, with scanning electron microscopy highlighting improved homogeneity in UiO-66-NH₂ coatings. Electrochemical characterisation in aqueous NH₄Cl with variable NH₃ concentrations showed that UiO-66-NH₂@FTO exhibited superior responsiveness compared to UiO-66@FTO and bare FTO. At an optimised potential of 1.1 V vs. Ag/AgCl, UiO-66-NH₂@FTO demonstrated a clear, linear current response to both NH₄⁺ (0.475–0.495 M, R² = 0.9520, sensitivity = 8.044 mA M⁻¹) and NH₃ (0.000–0.040 M, R² = 0.9521, sensitivity = 4.029 mA M⁻¹). This enhancement is attributed to the amine functionalities that promote proton-coupled electron transfer (PCET) and increase analyte affinity. These findings highlight electrophoretic deposition as a viable strategy for metal-organic framework film fabrication and establish UiO-66-NH₂@FTO as a promising platform for ammonia sensing.

开发可扩展的、高效的金属有机骨架薄膜制造方法对于扩大其在电化学传感中的应用至关重要。在这项工作中，我们系统地探索了使用电泳沉积将两种锆基金属有机骨架- uio -66及其胺功能化类似物uio -66- nh2固定在氟掺杂氧化锡（FTO）底物上。对溶剂体系、沉积时间和电场强度进行了综合优化，结果表明，在0.05%醋酸和90v cm−1的电场条件下，在短时间内（5分钟）沉积，可以得到最均匀、结晶和粘附性最好的涂层。这项工作首次提出了使用电泳沉积成功固定UiO-66-NH2的方法。通过粉末x射线衍射和红外光谱证实了结构的完整性，扫描电镜显示UiO-66-NH2涂层的均匀性得到改善。在不同NH3浓度的NH4Cl水溶液中的电化学表征表明，UiO-66-NH2@FTO与UiO-66@FTO和裸FTO相比，具有更好的响应性。在优化电位为1.1 V vs. Ag/AgCl时，UiO-66-NH2@FTO对NH4+ （0.475-0.495 M, R2 = 0.9520，灵敏度= 8.044 mA M - 1）和NH3 （0.000-0.040 M, R2 = 0.9521，灵敏度= 4.029 mA M - 1）均表现出清晰的线性电流响应。这种增强归因于胺的功能，促进质子耦合电子转移（PCET）和增加分析物亲和力。这些发现突出了电泳沉积作为金属有机框架薄膜制造的可行策略，并建立了UiO-66-NH2@FTO作为氨传感的有前途的平台。

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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 : 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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