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Effect of introduced mesopore in TON zeolite on isomerization of oleic acid TON分子筛中引入介孔对油酸异构化的影响

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-19 DOI: 10.1016/j.cattod.2025.115570

Xinyu Wei, Toshiya Tsunakawa, Shaohua She, Mingming Peng, Kenji Kamiya, Eika W. Qian

TON-type zeolite ZSM-22 with meso-microporous was developed by enhancing reactant diffusion and suppressing deactivation through mesoporous structuring, with the aim of investigating the isomerization of oleic acid. A series of meso-microporous ZSM-22 zeolite were synthesized via a desilication–recrystallization method. By adjusting the NaOH solution concentration (x = 0.4–1.0 M), the mesopore size was controlled, and CTAB facilitated the recrystallization of the dissolved silica, which then deposited on the catalyst surface, deactivating the surface acid sites. All samples were thoroughly characterized and evaluated in a continuous flow reactor for their isomerization performance. The catalyst prepared with 0.6 M NaOH (0.6M-Z22) exhibited the highest yield of branched unsaturated fatty acids, reaching 67.1 %, with a significantly suppressed dimer acid yield of only 14.9 % at 260 °C under WHSV = 6h⁻¹ . These results demonstrate that meso-microporous catalysts synthesized under optimal desilication conditions can enhance reactant diffusion within the zeolite channels and improve the yield of desired isomerized products. Also, undergoing moderate desilication, the catalyst's L/B acid sites ratio decreased, resulting in enhanced isomerization capability. Moreover, CTAB facilitated the recrystallization of the dissolved silica, which then deposited on the catalyst surface, deactivating the surface acid sites and suppressing the formation of side reactions. Finally, DTG analysis was performed to evaluate the coke formation on the spent catalysts. A 96-hour long-term durability test was also conducted. After 96 h of continuous operation, the conversion of oleic acid remained above 80 %, and the yield of branched unsaturated fatty acids was maintained at over 50 %.

通过介孔结构增强反应物扩散，抑制失活，制备了具有中微孔结构的ton型分子筛ZSM-22，目的是研究油酸的异构化。采用脱硅-重结晶法制备了一系列中微孔ZSM-22分子筛。通过调节NaOH溶液浓度（x = 0.4-1.0 M），控制介孔大小，CTAB促进溶解二氧化硅的再结晶，然后沉积在催化剂表面，使表面酸位失活。所有样品都在连续流动反应器中进行了彻底的表征和评估，以确定其异构化性能。以0.6 M NaOH （0.6M- z22）为催化剂制备的支链不饱和脂肪酸的产率最高，达到67.1 %，在WHSV = 6h⁻¹ 条件下，260 ℃时二聚体酸的产率仅为14.9 %。这些结果表明，在最佳脱硅条件下合成的中微孔催化剂可以增强反应物在沸石通道内的扩散，提高期望异构产物的产率。适度脱硅后，催化剂的L/B酸位比降低，异构化能力增强。此外，CTAB促进溶解二氧化硅的再结晶，然后沉积在催化剂表面，使表面酸位失活，抑制副反应的形成。最后，通过DTG分析对废催化剂的焦炭形成进行了评价。还进行了96小时的长期耐久性试验。连续运行96 h后，油酸转化率保持在80 %以上，支链不饱和脂肪酸收率保持在50 %以上。

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引用次数: 0

CO2 methanation over BEA zeolite catalysts: Effect of MgO and in-situ Ni incorporation BEA沸石催化剂上CO2甲烷化：MgO和原位Ni掺入的影响

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-19 DOI: 10.1016/j.cattod.2025.115572

Galal A. Nasser , Akolade I. Bakare , Mohmmed A. Sanhoob , Jan Kopyscinski

Carbon dioxide methanation is a promising carbon management technology that reduces CO₂ concentrations and facilitates the long-term storage of excess renewable energy, thereby closing the carbon cycle. This study investigates the catalytic performance of BEA zeolite-based catalysts in the methanation of CO₂, focusing on the role of MgO as a promoter and investigating the incorporation of Ni by in-situ method. The catalysts were synthesized via two methods: post-modification with Ni and MgO loading, and in-situ incorporation of Ni within the zeolite framework. Characterization techniques, including X-ray diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM), H₂-TPR, and CO₂-TPD, were used to evaluate the physical and chemical properties of the catalysts. The results demonstrated that MgO promoted the catalytic activity of BEA zeolites, enhancing CO₂ conversion and methane selectivity at lower reaction temperatures. The in-situ incorporation of Ni showed negligible activity at temperatures below 350 °C but outperformed post-modified catalysts at higher temperatures, particularly above 400 °C. These findings suggest that while post-modified catalysts are more effective at lower temperatures, in-situ Ni incorporation offers superior catalytic performance at elevated temperatures, making it a promising approach for high-temperature methanation reactions. This work contributes to the development of efficient catalysts for CO₂ methanation, supporting carbon capture and utilization efforts.

二氧化碳甲烷化是一种很有前途的碳管理技术，它可以降低二氧化碳浓度，促进多余的可再生能源的长期储存，从而关闭碳循环。本研究考察了BEA沸石基催化剂在CO2甲烷化反应中的催化性能，重点研究了MgO作为促进剂的作用，并通过原位法研究了Ni的掺入。通过Ni和MgO的后改性和Ni在沸石骨架内的原位掺入两种方法合成了催化剂。采用x射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、H2-TPR、CO2-TPD等表征技术对催化剂的理化性质进行了表征。结果表明，MgO提高了BEA分子筛的催化活性，在较低的反应温度下提高了CO2转化率和甲烷选择性。原位掺入Ni的催化剂在350 °C以下的温度下表现出可以忽略不计的活性，但在较高温度下，特别是在400 °C以上的温度下，表现优于后改性催化剂。这些发现表明，虽然后改性催化剂在低温下更有效，但原位Ni掺入在高温下具有更好的催化性能，使其成为高温甲烷化反应的一种很有前途的方法。这项工作有助于开发高效的二氧化碳甲烷化催化剂，支持碳捕获和利用工作。

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引用次数: 0

Precipitated iron-based catalysts with SiO2/ZnO dual structural promoters for enhanced activity and linear α-olefin selectivity in Fischer-Tropsch synthesis 具有SiO2/ZnO双结构促进剂的沉淀铁基催化剂在费托合成中增强活性和α-烯烃的线性选择性

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-19 DOI: 10.1016/j.cattod.2025.115566

Gyoung Woo Lee , Kwang Young Kim , Geun Bae Rhim , Young Eun Kim , Yeon Hee Ro , Hyeon Song Lee , Min Hye Youn , Kwan-Young Lee , Dong Hyun Chun

Fischer-Tropsch synthesis (FTS) was carried out over industrially important precipitated Fe/Cu/K-based catalysts with three different types of structural promoters: ZnO, SiO₂, and their combination (SiO₂/ZnO). The dual structural promotion of SiO₂ and ZnO was effective in enhancing the physicochemical properties of the catalysts. The SiO₂/ZnO-incorporated catalysts, Fe/Cu/K/SiO₂/ZnO, not only exhibited improved physical properties (i.e., smaller crystallites and higher surface area) than the ZnO-incorporated catalysts, Fe/Cu/K/ZnO, but also enhanced reducibility and CO-dissociation ability compared to the SiO₂-incorporated catalysts, Fe/Cu/K/SiO₂. The improved physicochemical properties of Fe/Cu/K/SiO₂/ZnO resulted in catalytic performance superior to that of Fe/Cu/K/ZnO and Fe/Cu/K/SiO₂. Whereas Fe/Cu/K/ZnO suffered from severe deactivation, Fe/Cu/K/SiO₂/ZnO displayed relatively high and stable CO conversion. Furthermore, both the CO conversion and the linear α-olefin (LAO) selectivity of Fe/Cu/K/SiO₂/ZnO (87.1 % and 59.6 wt%) were higher than those of Fe/Cu/K/SiO₂ (75.4 % and 56.7 wt%). Considering that a trade-off relationship exists between CO conversion and LAO selectivity, this strongly demonstrates an appreciable feature of dual structural promotion in the precipitated iron-based catalysts for FTS.

采用三种不同类型的结构促进剂：ZnO、SiO2及其组合（SiO2/ZnO），在工业上重要的沉淀Fe/Cu基催化剂上进行了费托合成（FTS）。SiO2和ZnO的双重结构促进可以有效地提高催化剂的理化性能。SiO2/ZnO掺杂催化剂Fe/Cu/K/SiO2/ZnO不仅比ZnO掺杂催化剂Fe/Cu/K/ZnO具有更小的晶粒和更高的比表面积，而且比SiO2掺杂催化剂Fe/Cu/K/SiO2具有更强的还原性和co -解离能力。Fe/Cu/K/SiO2/ZnO的理化性质得到改善，催化性能优于Fe/Cu/K/ZnO和Fe/Cu/K/SiO2。Fe/Cu/K/ZnO失活严重，而Fe/Cu/K/SiO2/ZnO CO转化率较高且稳定。此外，Fe/Cu/K/SiO2/ZnO的CO转化率和α-烯烃（LAO）线性选择性（87.1 %和59.6 wt%）均高于Fe/Cu/K/SiO2（75.4 %和56.7 wt%）。考虑到CO转化率和LAO选择性之间存在权衡关系，这强烈表明沉淀铁基催化剂具有双重结构促进的显著特征。

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引用次数: 0

Operando IR of catalytic reactions under microwaves at 5.8 GHz 5.8 GHz微波下催化反应的Operando IR

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-18 DOI: 10.1016/j.cattod.2025.115571

Frédéric Thibault-Starzyk , Ana Neto , Sébastien Thomas , Carlos Henriques , Gary Bond

A new spectroscopic cell was designed for operando IR observation of heterogeneous catalysis under microwave irradiation. Oxidation of CO on Pt-H-BEA zeolite was performed under conventional and microwave heating at the same space velocity to assess the efficiency of microwave heating, which was confirmed by an infrared in-situ temperature scale. A temperature of 230–240°C was obtained after 2 min microwave irradiation. Infrared monitoring evidences a moderate sintering of the platinum particles after microwave irradiation, probably due to hotspots on the metal. Infrared observation indicates a strong perturbation of electron density in the Pt particles by microwave during catalysis.

设计了一种新的微波辐照多相催化操作红外光谱观察池。在相同的空速下，采用常规加热和微波加热对Pt-H-BEA沸石上的CO进行氧化，以评价微波加热的效率，并通过红外原位温标对其进行了验证。微波辐照2 min后温度为230-240℃。红外监测表明，微波辐照后铂颗粒有中度烧结，可能是由于金属上有热点。红外观测表明，在催化过程中，微波对铂粒子中的电子密度有很强的扰动。

引用次数: 0

The effect of mechanochemical mixing conditions on V2O5/WO3-TiO2 and zeolite Y hybrid catalyst for selective catalytic reduction of NOx with NH3 机械化学混合条件对V2O5/WO3-TiO2与沸石Y杂化催化剂选择性NH3催化还原NOx的影响

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-17 DOI: 10.1016/j.cattod.2025.115568

Hyun Sub Kim , Se Won Jeon , Hongbeom Park , Inhak Song , Do Heui Kim

V₂O₅/WO₃-TiO₂ (VWTi) catalysts are widely utilized in selective catalytic reduction with NH₃ (NH₃-SCR) for stationary sources. However, their susceptibility to ammonium bisulfate (ABS) formation due to the presence of SO₂ and H₂O in flue gases poses a significant challenge. Improving the removal of ABS formed on VWTi catalysts can enhance their SO₂ resistance, and zeolites with strong acid sites are promising materials for trapping ABS. To optimize the interaction between VWTi catalysts and zeolites, two sample preparation methods were evaluated in this work: hand-mixing and ball milling. This study investigates the catalytic activity and SO₂ resistance of these samples to evaluate the effectiveness of the mixing techniques. The sample mixed using a mixer mill (20 Hz, 10 min) exhibited superior NO_x conversion and SO₂ resistance compared to the hand-mixed VWTi and zeolite Y sample. This improvement in catalytic performance was attributed to the preservation of the TiO₂ particle during the ball milling process, coupled with partial fragmentation of the zeolite that facilitated intimate contact between mixed particles. In contrast, extending this approach to a MnO_x + zeolite Y hybrid system revealed no synergistic effect, as the MnO_x active material suffered structural damage during the ball milling process. These findings underscore the importance of ensuring that the active material maintains its structural integrity while allowing the ABS-trapping material to undergo controlled fragmentation. Such balance is crucial for maximizing the intimate contact between components and achieving optimal catalytic performance.

V2O5/WO3-TiO2 （VWTi）催化剂广泛应用于固定源的NH3选择性催化还原（NH3- scr）。然而，由于烟气中存在SO2和H2O，它们对硫酸铵（ABS）形成的易感性构成了重大挑战。提高VWTi催化剂对ABS的脱除能力可以提高其抗SO2能力，而具有强酸位的沸石是很有希望捕获ABS的材料。为了优化VWTi催化剂与沸石的相互作用，本研究评估了两种样品制备方法：手工混合和球磨。本研究考察了这些样品的催化活性和抗SO2能力，以评价混合技术的有效性。与手工混合的VWTi和沸石Y样品相比，使用混合磨（20 Hz, 10 min）混合的样品表现出更好的NOx转化和SO2抗性。这种催化性能的提高归因于在球磨过程中TiO2颗粒的保存，以及沸石的部分破碎，促进了混合颗粒之间的密切接触。相比之下，将这种方法扩展到MnOx + 沸石Y杂化体系中，发现没有协同效应，因为MnOx活性材料在球磨过程中受到了结构破坏。这些发现强调了确保活性材料保持其结构完整性的重要性，同时允许abs捕获材料经历受控的破碎。这种平衡对于最大限度地提高组分之间的密切接触和实现最佳催化性能至关重要。

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引用次数: 0

Description of the Co9S8-MoS2 interface: Insights for explaining the cobalt promoting effect in hydrodesulfurization sulfide catalysts Co9S8-MoS2界面的描述：解释加氢脱硫硫化物催化剂中钴促进作用的见解

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-17 DOI: 10.1016/j.cattod.2025.115565

Oscar A. López-Galán , D. Zahir Salazar-Sánchez , Brenda Torres , Gilles Berhault , Manuel Ramos

Hydrodesulfurization (HDS) catalysts are still a crucial part of the refining industrial strategy to achieve clean petroleum cuts, respecting regulations in terms of sulfur amount. Even if the promoting effect of cobalt or nickel over MoS₂-based catalysts has been extensively studied for decades providing satisfactory description of the promotion, electronic by nature, through the formation of the so-called CoMoS phase, discrepancy still persist when comparing the CoMoS model with the previous description of the synergy for unsupported Co/MoS₂ systems through the so-called synergy by contact model. This review summarizes the advancements made, both experimentally and through DFT calculations, to address this discrepancy, considering the description of Co₉S₈/MoS₂ interfacial models. Different aspects will be described, including transmission electron microscopy characterization of the interface, the DFT construction of the interfacial model, and its consequences in terms of electronic structure, transition state (TS) energies for the dibenzothiophene HDS reaction, as well as the spin dependence of TS energies for various MoS₂ edge sites. Finally, potential new advancements coming from the description of Co₉S₈/MoS₂ interfacial models will be presented. This review accomplishes the pressing need for a wide-ranging and swift introduction to HDS using Co-promoted MoS₂ to guide the development of next-generation catalysts for fuel production.

加氢脱硫（HDS）催化剂仍然是炼油工业战略的重要组成部分，以实现清洁石油削减，尊重规定的硫量。即使钴或镍对MoS2基催化剂的促进作用已经被广泛研究了几十年，提供了令人满意的描述，本质上是电子的，通过所谓的CoMoS相的形成，CoMoS模型与之前通过所谓的接触协同模型对无负载Co/MoS2体系的协同作用的描述仍然存在差异。本文结合Co9S8/MoS2界面模型的描述，总结了实验和DFT计算方面的进展，以解决这一差异。将描述不同的方面，包括界面的透射电子显微镜表征，界面模型的DFT构建，以及它在电子结构方面的影响，二苯并噻吩HDS反应的过渡态（TS）能量，以及各种MoS2边缘位置的TS能量的自旋依赖性。最后，将介绍Co9S8/MoS2界面模型描述的潜在新进展。这一综述完成了广泛和快速地引入使用共促进MoS2的HDS的迫切需要，以指导下一代燃料生产催化剂的开发。

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引用次数: 0

Amine-incorporated bridged polysilsesquioxane as a catalyst support for aqueous phase phenol hydrogenation 氨基桥接聚硅氧烷作为水相苯酚加氢的催化剂载体

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-17 DOI: 10.1016/j.cattod.2025.115567

Snehal S. Patil , James Nana Gyamfi , Luke Gillespie , Yehia Khalifa , Seval Gunduz , Paul L. Edmiston , Umit S. Ozkan

Cyclohexanone is an important chemical used predominantly as an intermediate in nylon manufacturing. Phenol hydrogenation, a key route for producing cyclohexanone, results in a mixture of cyclohexanone and cyclohexanol. In this work, we have attempted to enhance the selectivity of phenol hydrogenation to cyclohexanone by doping amine functionalities in aryl-bridged polysilsesquioxane (ABPS), an organosilica support for palladium catalyst. Amine sites were successfully incorporated without compromising the textural properties and the structure of the organosilica via co-condensation of bis(trimethoxysilylethyl)benzene and bis(trimethoxysilylpropyl)amine, bridged organosilane precursors. Phenol hydrogenation activity experiments were conducted in an autoclave batch reactor at 200 °C and 50 bar. Amine-doping led to a significant increase in the cyclohexanone selectivity. CO₂ TPD, phenol TPD, and aqueous phase adsorption experiments revealed that the enhanced strength of phenol adsorption in non-planar mode and preferential adsorption of phenol over cyclohexanone on basic amine-doped catalysts were responsible for the increase in cyclohexanone selectivity.

环己酮是一种重要的化学品，主要用作尼龙制造的中间体。苯酚加氢是生产环己酮的关键途径，可制得环己酮和环己醇的混合物。在这项工作中，我们试图通过在芳基桥接的聚硅氧烷（ABPS）中掺杂胺官能团来提高苯酚加氢到环己酮的选择性，ABPS是钯催化剂的有机二氧化硅载体。通过双（三甲氧基乙基）苯和双（三甲氧基丙基）胺的共缩合，成功地结合了胺位，而不影响有机硅的结构和结构。在200 °C和50 bar的高压间歇釜反应器中进行了苯酚加氢活性实验。胺掺杂导致环己酮选择性显著提高。CO2 TPD、苯酚TPD和水相吸附实验表明，在碱胺掺杂的催化剂上，苯酚在非平面模式下的吸附强度增强和苯酚对环己酮的优先吸附是环己酮选择性提高的原因。

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引用次数: 0

Effect of membrane properties on CO2 methanation reaction by using distributor type membrane reactor 分布式膜反应器中膜性能对CO2甲烷化反应的影响

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-17 DOI: 10.1016/j.cattod.2025.115569

Yuka Shimizu , Hiroto Tsuyuki , Marcin Moździerz , Grzegorz Brus , Shinichi Ookawara , Keita Yabe , Aleksandra Roszko , Elzbieta Fornalik-Wajs , Mikihiro Nomura

CO₂ methanation by using distributor type membrane reactor was investigated to control the reaction rate by distributed reactant feeding through membrane. Accurate evaluation of the thermal conductivity of the porous Al₂O₃ membrane, considering its fine physical and chemical structures, was achieved by measurements using Laser Flash Analysis. In the solid part of the 1TC sample, the thermal conductivity was found to be 36.4 % lower than that of non-porous alumina. A catalytic membrane with a silica separation layer, having an H₂ permeance of 1.4 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ and an H₂/CO₂ selectivity of 35.9, was used in the distributor type membrane reactor test, and a CO₂ conversion of 92.3 % was obtained at 350 ℃. Based on these results, simulation was performed using Ansys Fluent to investigate the influence of membrane thermal conductivity and permselectivity. The CO₂ permeance of the membrane was set equal to 3.91 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹ for all conditions. It was shown that the CO₂ permselective membrane (H₂/CO₂ selectivity = 35.9) produced about 1.4 times CH₄ than the H₂ permselective membrane (H₂/CO₂ selectivity = 0.10), and that higher thermal conductivity of the membrane suppressed the temperature rise in the reactor.

采用分布式膜反应器对CO2甲烷化反应进行了研究，通过膜给料来控制反应速率。考虑到多孔氧化铝膜的良好物理和化学结构，通过激光闪光分析实现了对多孔氧化铝膜导热系数的准确评价。在1TC样品的固体部分，热导率比无孔氧化铝低36.4% %。采用具有二氧化硅分离层的催化膜进行分布式膜反应器试验，其H₂透过率为1.4 × 10⁻26 mol m−2 s−1 Pa−1，H₂/CO₂选择性为35.9，在350℃下的CO2转化率为92.3 %。在此基础上，利用Ansys Fluent软件进行了模拟，研究了膜导热系数和透性的影响。在所有条件下，膜的CO2透过率设为3.91 × 10−8 mol m−2 s−1 Pa−1。结果表明，CO2膜（H2/CO2选择性= 35.9）比H2膜（H2/CO2选择性= 0.10）产生的CH4约为1.4倍，且膜的高热导率抑制了反应器内的升温。

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引用次数: 0

Exploration of active copper species in copper containing MWW-type zeolitic catalysts for CO oxidation 含铜mww型沸石CO氧化催化剂中活性铜种类的探索

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-15 DOI: 10.1016/j.cattod.2025.115564

Yunhye Cho , Hyeonwoo Shin , Sang Woo Byun , Trinh Thuan Khiet Nguyen , Sungjoon Kweon , Sung Bong Kang , Min Bum Park

A series of copper-containing MWW-type zeolitic catalysts (Cu-DML-x) were synthesized at various hydrothermal temperatures (x = 80–200 °C), and the catalytic activity in CO oxidation was investigated depending on the copper species. The chemical states of copper on Cu-DML-x catalysts were identified as a framework and extraframework Cu in MWW structure and copper oxides on the external surface depending on the temperature, and these Cu species coexisted with one another. While the MWW structural property was lost with increasing the synthesis temperature, the copper oxide species were additionally formed at higher temperatures. Cu-DML-100 and -120, mainly containing extraframework Cu, demonstrated superior CO oxidation activity compared to Cu-DML-80 with dominant framework Cu. Cu-DML-160, -180, and -200 catalysts, in which extraframework Cu and copper oxides were dominantly present as dual sites, showed the lowest activation energies. This indicates the critical role of extraframework Cu and copper oxides in promoting CO oxidation over zeolites.

在不同的水热温度（ = 80 ~ 200℃）下合成了一系列含铜mww型沸石催化剂Cu-DML-x，并考察了不同铜种类对CO氧化的催化活性。铜在Cu- dml -x催化剂上的化学状态随温度的变化分别为MWW结构中的框架态和框架外态Cu以及外表面的铜氧化物，并且这些Cu种相互共存。随着合成温度的升高，MWW的结构性质逐渐丧失，而在较高的合成温度下，氧化铜的种类会增加。Cu- dml -100和-120与Cu- dml -80相比，主要含有框架外Cu，表现出更强的CO氧化活性。Cu- dml -160、-180和-200催化剂的活化能最低，其中框架外Cu和铜氧化物以双位为主。这表明框架外铜和铜氧化物在促进CO在沸石上氧化中的关键作用。

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引用次数: 0

m-xylene isomerization over IWW zeolite with a three-modal pore structure: The effect of crystal morphology 具有三模态孔结构的IWW沸石间二甲苯异构化：晶体形态的影响

IF 5.3 2区化学 Q1 CHEMISTRY, APPLIED

Catalysis Today

Pub Date : 2025-09-10 DOI: 10.1016/j.cattod.2025.115563

Emad Shamma, Alica Seidlová, Subhajyoti Samanta, Michal Mazur, Maksym Opanasenko, Mariya Shamzhy

Xylene isomerization is a key zeolite-catalyzed petrochemical process for the production of p-xylene, a highly demanded intermediate in the polymer industry. While MFI-type zeolites are widely used in industry as shape-selective catalysts, xylene isomerization also serves as a benchmark reaction for evaluating the shape-selectivity of new zeolite catalysts in relation to their porosity. In this study, IWW zeolite with a three-modal pore network of isolated 8- and 12-ring pores intersected by 10-ring channels was investigated for m-xylene isomerization, with a focus on how both the multidimensional pore system and crystal morphology affect catalytic performance. IWW zeolites were synthesized as germanosilicates with platelet-like and needle-like crystals, functionalized by post-synthetic Ge-to-Al substitution, and tested in gas-phase m-xylene isomerization in comparison with reference zeolite catalysts containing unimodal 8-, 10-, or 12-ring channels. Compared to MFI with a similar concentration of acid sites, Al-IWW catalysts exhibited higher m-xylene conversion across a wide range of WHSV values (4.4 – 40 h⁻¹), regardless of crystal morphology. Needle-like Al-IWW crystals achieved para-selectivity comparable to that of MFI, while platelet-like Al-IWW outperformed MFI in p-xylene yield at short contact times (WHSV = 40 h⁻¹). STEM analysis confirmed that the 10-ring channels are aligned along the length of the needle-like crystals, promoting shape-selective p-xylene formation. In contrast, the 12-ring channels running along the extended dimension of the platelet-like crystals facilitate the diffusion of reactant and product molecules to and from the active sites. All in all, the integration of multi-sized pores and tunable crystal morphology in IWW zeolites may offer a promising strategy for balancing selectivity and activity in p-xylene synthesis.

二甲苯异构化是沸石催化石化生产对二甲苯的关键工艺，对二甲苯是聚合物工业中需求量很大的中间体。虽然mfi型沸石作为形状选择性催化剂在工业上广泛使用，但二甲苯异构化也可以作为评价新型沸石催化剂的形状选择性与其孔隙率的基准反应。在这项研究中，研究了IWW沸石的三模态孔隙网络，该网络由10环通道相交的8环和12环孤立孔隙组成，重点研究了多维孔隙系统和晶体形态对间二甲苯异构化的影响。IWW沸石被合成为具有片状和针状晶体的锗硅酸盐，通过合成后的Ge-to-Al取代进行功能化，并与含有单峰8-，10-或12环通道的参考沸石催化剂进行气相间二甲苯异构化测试。与具有相似酸位浓度的MFI相比，Al-IWW催化剂在较宽的WHSV值范围内（4.4 - 40 h−1）表现出更高的间二甲苯转化率，而不考虑晶体形态。针状Al-IWW晶体的准选择性与MFI相当，而血小板状Al-IWW在短接触时间内的对二甲苯产率优于MFI （WHSV = 40 h−1）。STEM分析证实，10环通道沿着针状晶体的长度排列，促进了对二甲苯的形状选择性形成。相比之下，沿着血小板样晶体扩展尺寸的12环通道促进了反应物和产物分子在活性位点之间的扩散。综上所述，IWW分子筛中多尺寸孔隙和可调晶体形态的整合可能为平衡对二甲苯合成的选择性和活性提供了一种有前途的策略。

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引用次数: 0