Microporous and Mesoporous Materials最新文献_第4页

FTIR traced modification of defect-engineered UiO-66 for enhanced accessibility of zirconium sites 傅立叶变换红外光谱（FTIR）追踪缺陷工程 UiO-66 的改性，提高锆位点的可及性

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-15 DOI: 10.1016/j.micromeso.2024.113372

Vera V. Butova , Videlina R. Zdravkova , Olga A. Burachevskaia , Ivan E. Gorban , Mikhail A. Soldatov , Konstantin I. Hadjiivanov

This research focuses on identifying the accessibility of active sites within the defect-engineered UiO-66 framework. The task is particularly challenging due to reversible changes in the framework during dehydroxylation: the loss of μ₃-OH groups with simultaneous reduction of the Zr coordination number and the possible creation of Zr⁴⁺ Lewis acid sites in defect MOFs. We used in-situ FTIR and XANES analyses, as well as interaction with probe molecules, to monitor the changes in Zr coordination and the host-guest interaction. The defects were introduced using benzoic acid as a modulator, which coordinated to Zr⁴⁺ in defective pores. Our results showed that the UiO-66 sample synthesized with benzoic acid contained defects, but these were concealed under benzoate residues and thus inaccessible. Standard washing and heating did not remove benzoate anions. Dehydroxylation of the sample leads to the development of “hidden” Lewis acidity: some Zr⁴⁺ sites were not able to form complexes with the weak base CO, but they interact with the stronger bases acetonitrile. Additionally, in-situ XANES analysis revealed that the effect of acetonitrile adsorption is similar to that of water rehydration. Treatment of the sample with HCl and DMF led to the replacement of benzoates with formate ions, exposing the bare Zr⁴⁺ sites within the defective pores. These cationic sites acted as true Lewis acids and were able to coordinate both CO and acetonitrile. Our findings emphasize that the active sites in UiO-66 highly depend on synthesis conditions and post-synthetic treatments. Comprehensive site-specific methods are crucial for accurately predicting and identifying these active sites.

这项研究的重点是确定缺陷工程 UiO-66 框架内活性位点的可达性。由于框架在脱羟基过程中发生了可逆变化：μ3-OH 基团消失，同时 Zr 配位数减少，并可能在缺陷 MOF 中产生 Zr4+ 路易斯酸位点，因此这项任务尤其具有挑战性。我们利用原位傅立叶变换红外光谱（FTIR）和 XANES 分析以及与探针分子的相互作用来监测 Zr 配位的变化以及主客体之间的相互作用。缺陷是用苯甲酸作为调制剂引入的，苯甲酸在缺陷孔中与 Zr4+ 配位。我们的结果表明，用苯甲酸合成的 UiO-66 样品含有缺陷，但这些缺陷被掩盖在苯甲酸残留物之下，因此无法进入。标准洗涤和加热并不能去除苯甲酸阴离子。对样品进行脱羟基处理会产生 "隐藏的 "路易斯酸：一些 Zr4+ 位点无法与弱碱 CO 形成络合物，但却能与强碱乙腈相互作用。此外，原位 XANES 分析表明，乙腈吸附的效果与水的再水化效果类似。用盐酸和 DMF 处理样品会导致甲酸根离子取代苯甲酸根离子，从而暴露出缺陷孔隙中的 Zr4+ 裸露位点。这些阳离子位点充当了真正的路易斯酸，能够配位一氧化碳和乙腈。我们的研究结果表明，UiO-66 中的活性位点在很大程度上取决于合成条件和合成后的处理。针对特定位点的综合方法对于准确预测和识别这些活性位点至关重要。

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引用次数: 0

Application of aluminosilicate residue-based zeolite from lithium extraction in water treatment 在水处理中应用提取锂的铝硅酸盐残渣基沸石

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-13 DOI: 10.1016/j.micromeso.2024.113370

Fatima Ibsaine , Justine Dionne , Lan Huong Tran , Lucie Coudert , Louis-César Pasquier , Jean-François Blais

In a previous study, the Na-P1 type zeolites were synthesized from aluminosilicate residues using an efficient and cost-effective process, exhibiting an excellent adsorption capacity for Ca²⁺ in comparison to commercial zeolites 13X and A. Building upon this, the current study evaluates their performance for the adsorption of various elements, including Ca²⁺, Mg²⁺, and NH₄⁺. The objective was to evaluate the performance of the Na-P1 type zeolites for the adsorption of various elements, including Ca²⁺, Mg²⁺, and rare earth elements, with a particular emphasis on the adsorption kinetics and water hardness removal in comparison to commercial zeolite A. The results demonstrated that the Na-P1 zeolite exhibited a satisfactory sorption capacity for Ca²⁺ and NH₄⁺ ions (66 mg/g), while displaying a relatively lower effectiveness for the sorption of Mg²⁺ ions (5.6 mg/g). The Langmuir model is particularly well suited to the sorption of Ca²⁺, while the Freundlich model is more appropriate for Mg²⁺. Both models demonstrated satisfactory representation of NH₄ ⁺ sorption. Moreover, the pseudo-second-order kinetic model provides an excellent description of the Ca²⁺ and Mg²⁺ sorption processes, while both models effectively describe the NH₄⁺ adsorption kinetics. Additionally, Na-P1 zeolite was observed to effectively reduce water hardness from 322 to 63 mg CaCO₃/L at temperatures of 10, 20, and 38 °C, and to 18 mg/L at 58 °C. These findings suggest that Na-P1 zeolite has promising potential for applications as a water softening agent. Regarding metals and rare earths, the Na-P1 zeolite demonstrated noteworthy sorption efficiencies for Cd²⁺ (138 mg/g), Ce³⁺ (209 mg/g), Cr³⁺ (56.2 mg/g), and Cu²⁺ (60.5 mg/g). However, it demonstrated lower sorption efficiencies for Co²⁺, Mn²⁺, Ni²⁺ and Dy³⁺ (below 16 mg/g). The findings illustrate that Na-P1 zeolites are effective for the adsorption of diverse elements, offering a promising avenue for the sustainable transformation of industrial waste into valuable materials for environmental applications.

在之前的一项研究中，利用高效、经济的工艺从硅酸铝残渣中合成了 Na-P1 型沸石，与商用沸石 13X 和 A 相比，Na-P1 型沸石对 Ca2+ 具有出色的吸附能力。在此基础上，本研究评估了它们对 Ca2+、Mg2+ 和 NH4+ 等各种元素的吸附性能。结果表明，Na-P1 型沸石对 Ca2+ 和 NH4+ 离子（66 毫克/克）的吸附能力令人满意，而对 Mg2+ 离子（5.6 毫克/克）的吸附效果相对较低。Langmuir 模型特别适合 Ca2+ 的吸附，而 Freundlich 模型则更适合 Mg2+。这两种模型都能令人满意地反映 NH⁺ 的吸附情况。此外，伪二阶动力学模型很好地描述了 Ca2⁺和 Mg2⁺的吸附过程，而两种模型都有效地描述了 NH₄⁺ 的吸附动力学。此外，在温度为 10、20 和 38 °C 时，Na-P1 沸石可有效地将水硬度从 322 毫克 CaCO₃/L 降至 63 毫克 CaCO₃/L，在 58 °C 时降至 18 毫克/L。这些研究结果表明，Na-P1 沸石具有作为水软化剂的应用潜力。在金属和稀土方面，Na-P1 沸石对 Cd2+（138 毫克/克）、Ce3+（209 毫克/克）、Cr3+（56.2 毫克/克）和 Cu2+（60.5 毫克/克）具有显著的吸附效率。不过，它对 Co2+、Mn2+、Ni2+ 和 Dy3+（低于 16 毫克/克）的吸附效率较低。研究结果表明，Na-P1 沸石能有效吸附多种元素，为可持续地将工业废物转化为有价值的环境应用材料提供了一条前景广阔的途径。

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引用次数: 0

Non-hydrolytic sol-gel synthesis of amine-functionalized silica: Template- and catalyst-free preparation of mesoporous catalysts for CO2 valorization 胺功能化二氧化硅的非水解溶胶-凝胶合成：无模板和催化剂制备用于二氧化碳价值化的介孔催化剂

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-12 DOI: 10.1016/j.micromeso.2024.113371

Thai Q. Bui , Tomas Pokorny , Petr Machac , Zdenek Moravec , Eva Domincova Bergerova , Ales Styskalik

Carbon dioxide utilization presents an important and topical research topic. However, the performance of catalysts needed for CO₂ transformations does not achieve the necessary levels for their widespread application. To this end, we decided to study non-aqueous condensations providing amine-functionalized silica catalysts, possibly active in CO₂-epoxide cycloaddition reaction. While non-hydrolytic sol-gel method is well-known for its efficiency in providing highly porous Lewis and Brønsted acid metallosilicates, here we show for the first time its application for the preparation of silica-based catalysts containing basic groups. First, the reaction conditions were screened to reproducibly obtain porous materials with preserved amine moieties. These were identified as follows: silicon tetraacetate and bridging tertiary amine silanes as precursors, toluene as a solvent, and temperature between 160 and 180 °C. In such a way, materials with up to 776 m² g⁻¹ and 1.58 cm³ g⁻¹ were obtained in one-step process, without any template, after conventional drying step. Next, the amine-functionalized materials were tested in CO₂-epoxide coupling providing cyclic organic carbonates with high selectivity (>99 %) and moderate activity (up to 86 % epichlorohydrin conversion after 1 h at 120 °C and 10 bar CO₂). The characterization of spent catalysts revealed a presence of cyclic organic carbonates at the catalyst surface as well as conversion of tertiary amine groups to quaternary ammonium moieties.

二氧化碳的利用是一个重要而热门的研究课题。然而，二氧化碳转化所需的催化剂性能并未达到广泛应用所需的水平。为此，我们决定研究非水缩合提供胺功能化二氧化硅催化剂的方法，这种催化剂可能在二氧化碳环氧化物环加成反应中具有活性。非水解溶胶-凝胶法因其在提供高多孔性路易斯酸和布伦斯特酸金属硅酸盐方面的高效性而闻名，而在这里，我们首次展示了该方法在制备含有碱性基团的硅基催化剂方面的应用。首先，我们对反应条件进行了筛选，以重复获得保留胺分子的多孔材料。这些条件确定如下：以四乙酸硅酯和桥接叔胺硅烷为前驱体，以甲苯为溶剂，温度在 160 至 180 °C 之间。这样，在传统的干燥步骤之后，无需任何模板，一步法就能获得最大 776 平方米 g-1 和 1.58 立方厘米 g-1 的材料。接下来，对胺功能化材料进行了 CO2- 环氧化物偶联测试，结果表明，这些材料可提供环状有机碳酸盐，具有高选择性（99%）和中等活性（在 120 °C 和 10 bar CO2 下反应 1 小时后，环氧氯丙烷的转化率高达 86%）。对废催化剂的表征显示，催化剂表面存在环状有机碳酸盐，并且叔胺基团转化为季铵基团。

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引用次数: 0

Study of metal sequenced spray impregnation method towards Co-Mo/γ-Al2O3 catalytic performance in hydrotreating of used coconut oil to liquid biohydrocarbon 将废椰子油加氢处理为液态生物烃的金属序贯喷雾浸渍法对 Co-Mo/γ-Al2O3 催化性能的研究

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-12 DOI: 10.1016/j.micromeso.2024.113357

Meissha Ayu Ardini , Triyono , Takayoshi Hara , Nobuyuki Ichikuni , Wega Trisunaryanti

A series of bifunctional catalyst CoMo on γ-Al₂O₃ have been successfully prepared using the spray impregnation (dry impregnation), with the variation in the metal sequence (Co-Mo and Mo-Co) and metal impregnation time gap (1-h, 24-h, and simultaneous). XRF indicated that the developed method causes a minimal amount of metal loss during the impregnation process. XRD shows that 24-h treatment reduces crystallinity compared to the 1-h and simultaneous catalysts. Co and Mo existed as CoAl₂O₄, CoO, and MoO₃ as reported by XANES and XPS. The preparation technique signified the catalyst's acidity and surface area. The Co-Mo/γ-Al₂O₃ 24H has a high surface area (118.32 m² g⁻¹), with a pore volume of 0.22 cm³ g⁻¹, and a pore diameter of 7.48 nm. It has a high proportion of weak acid sites (41.32 %) which is crucial to perform HDO reactions. Co-Mo/γ-Al₂O₃ 24H showed high catalytic activity (40.32 wt% liquid product) and selectivity (85.61 % of biogasoline and 9.75 % of diesel fractions) from the hydrotreatment. Kimi@UGM2010.

利用喷雾浸渍法（干法浸渍）成功制备了一系列γ-Al2O3 上的双功能催化剂 CoMo，金属序列（Co-Mo 和 Mo-Co）和金属浸渍时间间隙（1 小时、24 小时和同时）各不相同。XRF 显示，所开发的方法在浸渍过程中造成的金属损失极少。XRD 显示，与 1 小时和同时处理催化剂相比，24 小时处理降低了结晶度。根据 XANES 和 XPS 的报告，钴和钼以 CoAl2O4、CoO 和 MoO3 的形式存在。制备技术决定了催化剂的酸度和表面积。Co-Mo/γ-Al2O3 24H 具有较高的比表面积（118.32 m2 g-1），孔体积为 0.22 cm3 g-1，孔直径为 7.48 nm。它具有较高比例的弱酸位点（41.32 %），这对进行 HDO 反应至关重要。Co-Mo/γ-Al2O3 24H 在加氢处理中表现出很高的催化活性（40.32 wt% 的液体产物）和选择性（85.61 % 的生物汽油和 9.75 % 的柴油馏分）。Kimi@UGM2010。

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引用次数: 0

Direct synthesis of low-silica ZSM-48 zeolite via seed-assisted hydrothermal synthesis with 1,6-hexanediamine as template 以 1,6-hexanediamine 为模板，通过种子辅助水热合成法直接合成低硅 ZSM-48 沸石

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-12 DOI: 10.1016/j.micromeso.2024.113369

Shiao Gao , Ahui Ma , Zhennan Yang, Sida Ge, Zhuwen Zhang, Zhijie Wu

ZSM-48 zeolite is characteristic of 10-member ring (10-MR) one-dimensional tubular channel structure and finds extensive applications in catalytic hydroisomerization reactions. Here we developed an efficient synthetic strategy for low-silica ZSM-48 zeolite with a SiO₂/Al₂O₃ ratio at 30–176 via a seed-assisted hydrothermal synthesis method, overcoming the limit that 1,6-hexanediamine (HDA) template can only be used to synthesize high-silica (i.e., SiO₂/Al₂O₃ ratio >200) zeolites. A two-step crystallization procedure coupled with zeolite seed-assisted synthesis strategy was enrolled to realize well crystallized ZSM-48 zeolites, in which the zeolite nuclei are sufficiently produced at the nucleation temperature at 100 °C for 24 h with the aid of zeolite seeds, and the zeolite growth is proceeded at the crystallization temperature at 160 °C for 48 h. The morphology and particle size of low-silica ZSM-48 zeolite have been manipulated by adjusting the synthetic parameters, such as the alkalinity and silicon source of aluminosilicate gel for zeolite, the crystallization manner (static or dynamic crystallization), as well as the presence of additive (i.e., sodium chloride). The as-synthesized ZSM-48 zeolite possesses a high acid content of 0.194 mmol/g, highlighting its potential as an excellent acidic support for hydroisomerization catalysts. The cost-effective and environmentally friendly synthesis strategy, which is anticipated to expand the application of alkylamine organic templates in the synthesis of low-silica ZSM-48 zeolite.

ZSM-48 沸石具有 10 元环（10-MR）一维管状通道结构，在催化加氢异构化反应中应用广泛。在这里，我们通过种子辅助水热合成法开发出了一种 SiO2/Al2O3 比为 30-176 的低硅 ZSM-48 沸石的高效合成策略，突破了 1,6-hexanediamine (HDA) 模板只能用于合成高硅（即 SiO2/Al2O3 比为 >200）沸石的限制。在沸石种子的帮助下，沸石核在 100 ℃ 的成核温度下充分生成 24 小时，沸石在 160 ℃ 的结晶温度下生长 48 小时。低硅 ZSM-48 沸石的形态和粒度可通过调整合成参数来控制，如沸石用铝硅酸盐凝胶的碱度和硅源、结晶方式（静态结晶或动态结晶）以及添加剂（如氯化钠）的存在、氯化钠）。合成的 ZSM-48 沸石具有 0.194 mmol/g 的高酸含量，突显了其作为加氢异构化催化剂的优良酸性载体的潜力。该合成策略成本低、环境友好，有望拓展烷基胺有机模板在低硅 ZSM-48 沸石合成中的应用。

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引用次数: 0

Controllable assembly of NiMo nano-wool shell on zeolite Y and its advanced behavior of hydrodesulfurization toward dibenzothiophene 沸石 Y 上镍钼纳米羊毛壳的可控组装及其对二苯并噻吩的先进加氢脱硫行为

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-11 DOI: 10.1016/j.micromeso.2024.113368

Xiaoqian Li , Shenyong Ren , Lu Liu, Chi Yang

A core-shell structured USY-xTT@NiMo catalyst was prepared through thermal treatment method and evaluated for the catalytic hydrodesulfurization (HDS) performance toward dibenzothiophene (DBT). The shell assembled from NiMoS nano-wool provided abundant active site. This nano-wool morphology and core-shell structure resulted in the catalyst with enhanced specific surface area, pore volume, lower interaction between the support and active metals, and facilitated metal dispersion. In addition, the nano-wool morphology and core-shell structure also promoted the degree of sulfurization and provided more sulfur vacancies, which enhanced the HDS performance of the corresponding catalysts. An efficient USY-16TT@NiMo catalyst with shorter slab lengths (average 2.50 nm), higher average stacking number (3.37 layers), and more edge active sites was assembled, which showed superior k_HDS value of DBT up to 8.29 × 10⁻⁴ mol g⁻¹ h⁻¹ and high direct desulfurization selectivity to be 88 %.

通过热处理方法制备了一种核壳结构 USY-xTT@NiMo催化剂，并评估了其对二苯并噻吩（DBT）的催化加氢脱硫（HDS）性能。由 NiMoS 纳米棉组装而成的外壳提供了丰富的活性位点。这种纳米羊毛形态和核壳结构使催化剂具有更高的比表面积和孔隙率，降低了载体与活性金属之间的相互作用，并促进了金属的分散。此外，纳米絮状形态和核壳结构还提高了硫化程度，提供了更多的硫空位，从而增强了相应催化剂的加氢脱硫性能。组装出的高效 USY-16TT@NiMo 催化剂具有更短的板坯长度（平均 2.50 nm）、更高的平均堆积数（3.37 层）和更多的边缘活性位点，DBT 的 kHDS 值高达 8.29 × 10-4 mol g-1 h-1，直接脱硫选择性高达 88%。

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引用次数: 0

Catalytic upgrading of lignite pyrolysis volatiles to light aromatics under methanol atmosphere over Zr and/or Fe modified hollow ZSM-5 zeolites 在甲醇气氛下，在 Zr 和/或 Fe 改性空心 ZSM-5 沸石上催化褐煤热解挥发物升级为轻芳烃

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-11 DOI: 10.1016/j.micromeso.2024.113362

Yue-lun Wang , Han-bing Gao , Wei-hua Zhao , Xu Yan , Jing Liang , Yun-Peng Zhao , Jing-pei Cao , Lin-jun Zhu

Fe and Zr modified hollow ZSM-5 zeolites were prepared and their applications in upgrading of lignite pyrolysis volatiles coupling with methanol to light aromatics were investigated. The results demonstrated that hollow zeolites with larger voids and shorter diffusion length favored the production of light aromatics. Adding Fe and Zr into ZSM-5 zeolites further enhanced BTX yields due to the synergism between metals and acid sites for promoting hydrodeoxygenation reactions. Meanwhile, Zr-Fe/HZ-5 catalyst with increasing Lewis acid sites facilitated methylation leading to high selectivity of xylene under methanol atmosphere. Moreover, diffusion behaviors of xylene were quantified. Higher self-diffusion coefficient of molecules in hollow zeolites led to the formation of less coke, while the incorporation of Fe and Zr promoted the formation of catalytic coke due to the increase of alkylation resulting in partial conversion of BTX into PAHs on external surfaces although the total coke yields were further decreased.

制备了铁和锆改性的空心 ZSM-5 沸石，并研究了它们在将褐煤热解挥发物与甲醇偶联升级为轻芳烃中的应用。结果表明，空隙较大、扩散长度较短的空心沸石有利于轻芳烃的生产。在 ZSM-5 沸石中添加 Fe 和 Zr 可进一步提高 BTX 产量，这是因为金属与酸性位点之间的协同作用可促进加氢脱氧反应。同时，增加路易斯酸位点的 Zr-Fe/HZ-5 催化剂可促进甲基化，从而在甲醇气氛下提高二甲苯的选择性。此外，还对二甲苯的扩散行为进行了量化。分子在空心沸石中的自扩散系数越高，形成的焦炭就越少，而铁和锆的加入则促进了催化焦炭的形成，这是因为烷基化作用的增加导致 BTX 部分转化为外表面的多环芳烃，尽管总焦炭产率进一步降低。

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引用次数: 0

Efficient low-temperature CO removal from high-humidity sintering flue gas by combination Cu and OMS-2 利用 Cu 和 OMS-2 组合高效去除高湿度烧结烟气中的低温 CO

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-11 DOI: 10.1016/j.micromeso.2024.113358

Jinxin Yu, Xin Min, Xueqian Wu, Tianhong Mei, Ke Chen, Zhen Li, Songjian Zhao

The non-precious metal manganese-based catalysts currently show insufficient CO catalytic oxidation performance in actual sintering flue gas conditions, with increased water vapor levels causing catalyst deactivation. This study utilized a high-performance manganese dioxide octahedral molecular sieve (OMS-2). The effect of metal doping on the catalytic CO oxidation performance was investigated in preparing OMS-2 using the co-precipitation method. The experiments showed that Cu doping increased CO conversion efficiency more than other metals (Co, Ag, Zn, and Fe), with optimal performance achieved at a 1.91 wt% doping level. Besides, Cu doping significantly enhanced water resistance of the catalyst, enabling effective CO removal in high-humidity conditions. The study observed that Cu ions infiltrated the catalyst framework by substituting some of the Mn ions, creating additional active sites in the form of oxygen vacancies and improving surface oxygen mobility, thereby enhancing the performance of CO catalytic oxidation. Furthermore, Cu doping demonstrated selective absorption of water vapor, with Cu_xO in the catalyst, effectively adsorbing water vapor and protecting the initial active sites, thereby mitigating water vapor-induced poisoning. Even in 15 vol% H₂O at 150 °C, 1.91%Cu-OMS-2 maintained total catalytic activity. Therefore, the co-precipitation method-prepared 1.91%Cu-OMS-2 catalyst holds excellent potential for CO removal in sintering flue gas and shows promise for practical applications.

目前，非贵金属锰基催化剂在实际烧结烟气条件下的一氧化碳催化氧化性能不足，水蒸气含量增加会导致催化剂失活。本研究采用了高性能八面体分子筛二氧化锰（OMS-2）。在使用共沉淀法制备 OMS-2 的过程中，研究了金属掺杂对催化 CO 氧化性能的影响。实验结果表明，与其他金属（Co、Ag、Zn 和 Fe）相比，掺杂 Cu 更能提高 CO 的转化效率，在 1.91 wt% 的掺杂水平下达到最佳性能。此外，掺杂铜还能显著提高催化剂的耐水性，从而在高湿度条件下有效去除一氧化碳。研究观察到，Cu 离子通过取代部分 Mn 离子渗入催化剂框架，以氧空位的形式产生了额外的活性位点，并改善了表面氧的流动性，从而提高了 CO 催化氧化的性能。此外，催化剂中的 CuxO 可选择性地吸收水蒸气，有效地吸附了水蒸气并保护了初始活性位点，从而减轻了水蒸气引起的中毒。即使在 150 °C、15 vol% H2O 的条件下，1.91%Cu-OMS-2 也能保持完全的催化活性。因此，共沉淀法制备的 1.91%Cu-OMS-2 催化剂在烧结烟气中脱除 CO 方面具有很好的潜力，有望得到实际应用。

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引用次数: 0

Facile synthesis of SSZ-16 nanoaggregates with excellent performance in NH3-SCR reaction 简便合成在 NH3-SCR 反应中性能优异的 SSZ-16 纳米沉积物

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-10 DOI: 10.1016/j.micromeso.2024.113367

Shichao Han , Huan Zhou , Ye Ma , Jiusheng Li , Xiangju Meng , Wenpo Shan

d6r units were proved to be crucial for the synthesis of SSZ-16 zeolite with AFX topology, and FAU zeolite owning plenty of d6r units was chosen as the essential raw material for constructing AFX frameworks. In this work, SSZ-16 zeolite was directly synthesized using colloidal silica and sodium aluminate as the raw materials in short crystallization time of 5 h. The corresponding crystallization process were carefully investigated by various characterizations, demonstrating that the key to this success was the formation of d6r units built up by a large amount of s4r units which were formed with the assistance of the appropriate organic structure directing agent (OSDA) and seeds in the synthetic media. Interestingly, the products of C-SSZ-16 zeolites presented spherical shapes consisted of relatively small particles with size range from 30 to 50 nm. Moreover, after ion-exchanged with Cu ions, the Cu-C-SSZ-16 products showed excellent performance in the selective catalytic reduction of NO_x with NH₃ (NH₃-SCR) and better hydrothermal stability than conventional Cu-SSZ-16-con samples due to slightly higher Si/Al ratio of the Cu-C-SSZ-16. Therefore, remarkable catalytic performance and the use of low-cost raw materials as well as short period of synthesis time make AFX zeolites as potential applicants in NH₃-SCR field, from an industrial viewpoint.

d6r单元被证明是合成具有AFX拓扑结构的SSZ-16沸石的关键，而拥有大量d6r单元的FAU沸石被选为构建AFX框架的重要原料。本研究以胶体二氧化硅和铝酸钠为原料，在短短5小时的结晶时间内直接合成了SSZ-16沸石。通过对相应结晶过程的各种表征进行仔细研究，结果表明成功的关键在于合成介质中大量的s4r单元在适当的有机结构引导剂（OSDA）和种子的帮助下形成了d6r单元。有趣的是，C-SSZ-16 沸石的产物呈球形，由相对较小的颗粒组成，粒径范围为 30 至 50 纳米。此外，与传统的 Cu-SSZ-16-con 样品相比，Cu-C-SSZ-16 产物在与 Cu 离子进行离子交换后，在氮氧化物与 NH3 的选择性催化还原（NH3-SCR）中表现出优异的性能和更好的水热稳定性，这是因为 Cu-C-SSZ-16 的 Si/Al 比率略高。因此，从工业角度来看，AFX 沸石催化性能优异、原料成本低、合成时间短，是 NH3-SCR 领域的潜在应用领域。

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引用次数: 0

MOF derived porous Fe-Cu@carbon catalyst for the degradation of bisphenol A through a persulfate-based advanced oxidation process 通过基于过硫酸盐的高级氧化工艺降解双酚 A 的 MOF 衍生多孔铁-铜@碳催化剂

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials

Pub Date : 2024-10-10 DOI: 10.1016/j.micromeso.2024.113366

Andrea Están García, Neus Crespí Sánchez, Gemma Turnes Palomino, Carlos Palomino Cabello

A calcination strategy based on the use of mixed MOF HKUST-1/MIL-100 as precursor was used for the obtention of a porous carbon composite (C-HKUST-1/MIL-100) containing iron-copper bimetallic particles within it. The prepared carbon was characterized by XRD, SEM, EDS spectroscopy and N₂ adsorption-desorption, confirming the obtention of a micro-mesoporous carbon with Fe-Cu particles homogenously distributed within the structure. For comparison, Cu and Fe-carbons (C-HKUST-1 and C-MIL-100, respectively) were also prepared from the corresponding HKUST-1 and MIL-100 MOFs, respectively. The catalytic performance of the developed carbons as heterogeneous catalysts for persulfate-based advanced oxidation degradation of bisphenol A was evaluated. The Fe-Cu@carbon showed the best catalytic performance, leading to a total BPA degradation after just 10 min of reaction, which was closely related to the synergistic effect of iron and copper. The effect of some key parameters including initial pH value, PS concentration and catalyst dosage was investigated using the Fe-Cu@carbon. In addition, the developed carbon showed good reusability, with no apparent loss in BPA degradation, after five cycles and the ability to treat real water samples, with the advantage that the recovery process after degradation is facilitated thanks to its magnetic properties.

以混合 MOF HKUST-1/MIL-100 为前驱体，采用煅烧策略制备了含有铁铜双金属颗粒的多孔复合碳（C-HKUST-1/MIL-100）。通过 XRD、SEM、EDS 光谱和 N2 吸附-解吸对制备的碳进行了表征，证实获得了一种微多孔碳，其结构中均匀分布着铁-铜颗粒。为了进行比较，还分别从相应的 HKUST-1 和 MIL-100 MOFs 中制备了铜碳和铁碳（C-HKUST-1 和 C-MIL-100）。评估了所制备的碳作为异相催化剂对基于过硫酸盐的双酚 A 高级氧化降解的催化性能。铁-铜@碳显示出最佳的催化性能，仅在反应 10 分钟后就能完全降解双酚 A，这与铁和铜的协同作用密切相关。利用铁-铜@碳研究了一些关键参数的影响，包括初始 pH 值、PS 浓度和催化剂用量。此外，所开发的碳具有良好的重复使用性，经过五个循环后，双酚 A 降解效果没有明显下降，并且能够处理实际水样，其优点是由于其磁性，降解后的回收过程变得更加容易。

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