Applied Catalysis A: General最新文献_第9页

Kinetic modeling of the combined HCHO/SCR reaction on V2O5/WO3/TiO2 catalyst in lean exhaust gas of stationary gas engines 固定式燃气发动机稀废气中V2O5/WO3/TiO2催化剂上HCHO/SCR联合反应动力学建模

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-17 DOI: 10.1016/j.apcata.2025.120709

Christoph Hahn, Sven Kureti

For the simultaneous removal of NO_x and HCHO from lean exhaust gas of stationary gas engines, V₂O₅/WO₃/TiO₂ (VWT) catalysts are used. The VWT catalysts oxidize HCHO and convert NO_x according to the selective catalytic reduction (SCR). However, the combined HCHO/SCR conversion leads to the production of HCN, which can subsequently decompose along the VWT catalyst.

In this context, a global kinetic model of the combined HCHO/SCR conversion was developed using a VWT monolith with a V₂O₅ load of 2 %. The model was based on a systematic series of kinetic studies performed in a gradient free loop reactor as well as a plug flow reactor The kinetic model represented a network of 8 reactions consisting of the NH₃ adsorption and desorption, SCR reaction, NH₃ oxidation, HCHO oxidation, HCN formation as well as hydrolysis and oxidation of HCN. The kinetics of the respective reactions was described by Arrhenius-based rate expressions including 19 kinetic parameters. The kinetic parameters were primarily obtained from numerical fitting calculations. The model and the implemented kinetic parameters were finally validated by predicting kinetic experiments.

Moreover, the model was used to simulate the fractions of NO_x, NH₃, HCHO and HCN along the VWT monolith. Using these axial profiles operation temperatures and design of the monolith were evaluated to limit the emissions of a stationary lean-burn gas engine.

为了同时从固定式燃气发动机的稀薄废气中去除NOx和HCHO，使用V₂O₅/WO₃/TiO₂（VWT）催化剂。VWT催化剂通过选择性催化还原（selective catalytic reduction， SCR）作用氧化HCHO并转化NOx。然而，HCHO/SCR联合转化会产生HCN， HCN随后会沿着VWT催化剂分解。在这种情况下，使用VWT单体，V2O5负载为2 %，建立了HCHO/SCR联合转化的全局动力学模型。该模型基于在梯度自由循环反应器和塞流反应器中进行的一系列系统动力学研究，动力学模型代表了8个反应网络，包括NH3吸附和解吸，SCR反应，NH3氧化，HCHO氧化，HCN形成以及HCN的水解和氧化。各反应的动力学用包含19个动力学参数的Arrhenius-based速率表达式来描述。动力学参数主要通过数值拟合计算得到。最后通过预测动力学实验对模型和实现的动力学参数进行了验证。此外，利用该模型模拟了NOx、NH3、HCHO和HCN沿VWT整体的组分。使用这些轴向剖面，评估了运行温度和整体设计，以限制固定稀燃燃气发动机的排放。

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引用次数: 0

Influence of pretreatment conditions and support type on CO oxidation activity of Au–Ni catalysts: Insights from operando DRIFTS 预处理条件和载体类型对Au-Ni催化剂CO氧化活性的影响：来自operando DRIFTS的见解

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-17 DOI: 10.1016/j.apcata.2025.120711

Alexis Hellmer , Rubén Mendoza-Cruz , Benjamín Portales-Martínez , Rodolfo Zanella

In this report, operando DRIFTS–MS analyses were applied to determine the influence of thermal pretreatment on the oxidation states and catalytic performance of Au–Ni catalysts supported on TiO₂ or γ-Al₂O₃ during the catalytic CO oxidation reaction over a temperature range of –100 °C to 200 °C, monitoring the real-time evolution of surface-adsorbed intermediates. Operando DRIFTS–MS, XPS, TPR, and STEM–HAADF revealed that support material critically influences catalyst behavior: TiO₂-supported catalysts exhibit enhanced CO conversion compared to those on Al₂O₃. Notably, pre-reduced catalysts on TiO₂ showed an important synergistic effect, primarily through the formation of reactive Au^δ- species resulting from the partial reduction of Au⁰ sites. In contrast, pre-oxidized catalysts maintained a higher fraction of oxidized Au species, correlating with moderate activity. Operando DRIFTS–MS data showed that the incorporation of Ni into the bimetallic nanoparticles prevents the formation of adsorbed bicarbonate species or promotes their conversion into more reactive carbonate and carboxylate species, coinciding with the formation of Au^δ- sites and leading to increased CO₂ production. Al₂O₃-supported catalysts exhibit persistent spectator intermediates, such as formate species, which likely block active sites and slow CO₂ production. These insights underscore the significant roles of metal–support interactions, thermal pretreatment conditions, and bimetallic synergistic effects in catalyst design, providing a rational basis for developing more effective Au–Ni catalysts for low-temperature CO oxidation.

本文采用operando drift - ms分析方法，在-100℃至200℃的温度范围内，测定了热预处理对负载在TiO2或γ-Al2O3上的Au-Ni催化剂在催化CO氧化反应中的氧化态和催化性能的影响，并实时监测了表面吸附中间体的演变。Operando drift - ms、XPS、TPR和STEM-HAADF表明，载体材料对催化剂的行为有重要影响：与Al2O3载体相比，tio2载体催化剂表现出更高的CO转化率。值得注意的是，预还原催化剂在TiO2上表现出重要的协同作用，主要是通过部分还原Au0位点形成活性Auδ-来实现的。相比之下，预氧化催化剂保持了较高比例的氧化金，与中等活性相关。Operando漂移- ms数据表明，在双金属纳米颗粒中掺入Ni可以阻止被吸附的碳酸氢盐的形成或促进其转化为活性更强的碳酸盐和羧酸盐，与Auδ-位点的形成相一致，导致二氧化碳产量增加。al2o3负载的催化剂表现出持久的旁观者中间体，如甲酸盐，可能会阻塞活性位点，减缓二氧化碳的产生。这些发现强调了金属-载体相互作用、热预处理条件和双金属协同效应在催化剂设计中的重要作用，为开发更有效的Au-Ni低温CO氧化催化剂提供了合理的基础。

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引用次数: 0

Experimental and DFT studies on the preparation of boron-doped Pd/Al2O3 foam ceramic-based catalysts for mirabelon intermediates 制备掺硼Pd/Al2O3泡沫陶瓷基mirabelon中间体催化剂的实验和DFT研究

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-15 DOI: 10.1016/j.apcata.2025.120704

Fangxu Shi , Fuxin Liang , Yulin Wei , Junyan Wu , Sai Huang , Honglei Wang , Zhi Wang , Guopu Shi

The hydrogenation-catalyzed synthesis of mirabellone, a drug for the treatment of overactive bladder (OAB), faces the challenge of catalytic efficiency and selectivity regulation of its core intermediate. In this study, we propose an innovative strategy for constructing a Pd/B-Al₂O₃ composite catalytic system on a foam ceramic substrate using the impregnation method, and systematically investigate the modulation mechanism of different boron doping ratios on the catalyst's performance. Experimental and density functional theory studies demonstrate that the incorporation of boron synergistically enhances surface adsorption of reaction intermediates, facilitates the efficient reduction of PdO, and precisely modulates the distribution of acidic sites, thereby establishing a catalytic environment more favorable for the selective reduction of nitro groups. This catalyst, characterized by its unique three-dimensional pore structure and the interface synergistic effect resulting from boron modification, enables a uniform distribution of catalytically active centers and enhances the efficiency of reaction mass transfer. Through the optimization of process parameters, the yield of the target product was significantly improved, providing an innovative technological path for the preparation of the key intermediate of mirabilon.

治疗膀胱过动症（OAB）药物mirabellone的氢化催化合成面临催化效率和核心中间体选择性调控的挑战。在本研究中，我们提出了一种创新的策略，利用浸渍法在泡沫陶瓷衬底上构建Pd/B-Al2O3复合催化体系，并系统地研究了不同硼掺杂比例对催化剂性能的调节机理。实验和密度泛函数理论研究表明，硼的加入协同增强了反应中间体的表面吸附，促进了PdO的高效还原，并精确调节了酸性位点的分布，从而建立了更有利于硝基选择性还原的催化环境。该催化剂具有独特的三维孔隙结构和硼改性产生的界面协同效应，使催化活性中心分布均匀，提高了反应传质效率。通过工艺参数的优化，目标产物的收率显著提高，为mirabilon关键中间体的制备提供了一条创新的技术路径。

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引用次数: 0

{FeMo6}@Ru(N^N)3-covalent organic frameworks for enhanced aldehyde photooxidation {FeMo6}@Ru(N^N)3-共价有机骨架增强醛光氧化

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-15 DOI: 10.1016/j.apcata.2025.120706

Bi-Ying Wang , Zhan-Xin Zhang , Tao Zhang , Ai-Juan Li , Jing Li , Sheng-Li Huang

An efficient green oxidative synthesis was achieved through the development of a bi-functional {FeMo₆}⊂[Ru(N^N)₃@Q-COF] photocatalyst. This catalyst integrates a Ru(N^N)₃ photosensitizer, a stable quinoline-based covalent organic framework (COF), and Anderson polyoxometalates (POMs) via coordination and electrostatic interactions. The combination enhances light absorption, charge transfer, Lewis acid activity, and substrate enrichment within a confined nano-channel environment. Compared to individual catalytic systems, this integrated catalyst demonstrates superior efficiency and selectivity in the photocatalytic oxidation of aldehydes to carboxylic acids. Moreover, it shows excellent recyclability, making it a promising platform for sustainable and efficient catalytic processes.

通过开发双功能{FeMo6}∧[Ru(N^N)3@Q-COF]光催化剂，实现了高效的绿色氧化合成。该催化剂通过配位和静电相互作用将Ru(N^N)3光敏剂、稳定的喹啉共价有机骨架（COF）和Anderson多金属氧酸盐（pom）集成在一起。这种组合增强了光吸收、电荷转移、路易斯酸活性和在受限纳米通道环境中的底物富集。与单独的催化系统相比，这种集成催化剂在光催化氧化醛制羧酸方面表现出优越的效率和选择性。此外，它具有良好的可回收性，使其成为可持续和高效催化过程的有前途的平台。

引用次数: 0

Co/SiO₂ eggshell catalysts: An efficient and controllable synthesis method Co/ sio2蛋壳催化剂：一种高效可控的合成方法

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-15 DOI: 10.1016/j.apcata.2025.120707

Fernanda S. Pimenta, Alexis Godet, Babu Joseph, John N. Kuhn

Eggshell catalysts are characterized by the deposition of the active phase near the outer layer of the pellet, offering advantages for diffusion-limited reactions. In this work, a scalable and reproducible method for synthesizing Co/SiO₂ eggshell catalysts using 2 mm spherical silica pellets is presented. Unlike reported procedures, this method does not require multiple impregnations, the use of a nitrogen glovebox, drying of pellets soaked in non-polar solvent, and the use of viscosifying agents. The influence of contact time in the precursor solution on shell thickness and Co loading was investigated. Shell thicknesses between 0.21 and 0.37 mm were achieved, with standard deviations of 0.02 – 0.06 mm. A cobalt loading of 19.6 wt% (XRF) was obtained in one impregnation step, with average crystallite sizes of 13–16 nm (Scherrer analysis). Fischer–Tropsch Synthesis (230 ℃ and 10 bar) confirmed that shell thickness impacts product selectivity. The catalyst with 0.37 mm shell thickness resulted in higher C₅⁺ selectivity and lower CO₂ and CH₄ formation than catalysts with thinner shells and one with a uniform distribution, which highlights the importance of precision in tuning the shell thickness during synthesis. The catalysis trends with shell thickness are attributed to residence time in the pores and Co particles encountered during the diffusion path, which promotes olefin re-adsorption and chain growth to middle distillates (

C_{10}

-

C_{20})

hydrocarbons while deterring saturation of light hydrocarbons. Overall, the proposed method enables high Co loading with one impregnation and controlled shell thickness with improved reproducibility and scalability.

蛋壳催化剂的特点是活性相沉积在颗粒的外层附近，为限制扩散的反应提供了优势。在这项工作中，提出了一种可扩展和可重复的方法，用于合成Co/ sio2蛋壳催化剂使用2 毫米球形硅球。与报道的方法不同，该方法不需要多次浸渍，使用氮气手套箱，干燥浸泡在非极性溶剂中的颗粒，以及使用增粘剂。研究了前驱体溶液中接触时间对壳体厚度和Co载荷的影响。壳体厚度在0.21 ~ 0.37 mm之间，标准偏差为0.02 ~ 0.06 mm。在一个浸渍步骤中获得了19.6 wt% （XRF）的钴负载，平均晶粒尺寸为13-16 nm （Scherrer分析）。费托合成（230℃，10 bar）证实了壳层厚度影响产物的选择性。壳层厚度为0.37 mm的催化剂比壳层较薄和分布均匀的催化剂具有更高的C₅⁺选择性，更低的CO₂和CH₄生成，这突出了在合成过程中调整壳层厚度精度的重要性。随着壳层厚度的增加，烯烃在孔隙中的停留时间和扩散过程中遇到的Co颗粒会促进烯烃的再吸附和链式生长，形成中间馏分（C10 - C20）烃，同时阻碍轻烃的饱和。总的来说，该方法可以在一次浸渍的情况下实现高Co负载，并控制外壳厚度，提高了可重复性和可扩展性。

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引用次数: 0

Mesoporous alumina-carbon supported copper nanocatalyst for ethanol dehydrogenation: Balancing acidic and metallic properties for optimal performance 用于乙醇脱氢的介孔铝碳负载铜纳米催化剂：平衡酸性和金属性质以获得最佳性能

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-15 DOI: 10.1016/j.apcata.2025.120705

Yan Hao , Linlin Du , Yang Zhou , Zheng Gao , Yang Zhang , Qinghu Tang

The mesoporous alumina-carbon with the advantages of mesoporous structure and acid-base properties was selected as support, and the copper nanoparticles were prepared by a facile impregnation and subsequent pyrolysis procedure. Well distributed copper nanoparticles were obtained with a mean size of 3 nm due to the mesopore structure and strong metal-support interaction. At an operating temperature of 250 °C, the Cu/Al₂O₃-C catalyst was able to achieve up to 98 % ethanol conversion and an ideal > 99 % selectivity of acetaldehyde, owing to a high Cu active surface, a large (Cu⁰+Cu⁺)/Cu_total ratio, and suitable weak and moderate-strong acid active sites, which were conducive to the ethanol dehydrogenation reaction. By controlling the content of alumina in the support to regulate the acidic properties, the catalyst possessing an optimal weak and moderate-strong acid/total acid ratio of 0.86 was the most favorable for ethanol dehydrogenation. This catalyst also presented good reusability and regeneration ability, providing a good choice for ethanol dehydrogenation.

选择具有介孔结构和酸碱性能优点的介孔铝碳作为载体，采用快速浸渍和后续热解法制备纳米铜。由于介孔结构和强的金属-载体相互作用，获得了均匀分布的铜纳米颗粒，平均尺寸为3 nm。在250 ℃的操作温度下，Cu/Al2O3-C催化剂具有较高的Cu活性表面、较大的(Cu0+Cu+)/Cutotal比和适宜的弱、中强酸活性位点，有利于乙醇脱氢反应，可实现98% %的乙醇转化率和 99% %的乙醛选择性。通过控制载体中氧化铝的含量来调节催化剂的酸性，弱、中强酸/总酸比为0.86的催化剂最有利于乙醇脱氢。该催化剂具有良好的可重复使用性和再生能力，为乙醇脱氢提供了良好的选择。

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引用次数: 0

Efficient and green synthesis of dimethyl succinate via palladium-catalyzed acetylene dicarbonylation assisted by methanedisulfonic acid under ambient conditions 环境条件下甲二磺酸辅助钯催化乙炔二羰基化高效绿色合成琥珀酸二甲酯

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-15 DOI: 10.1016/j.apcata.2025.120698

Yunpeng Qiu , Yi Zeng , Teng Sun , Qingyin Wang , Gongying Wang , Honglin Chen , Weixin Qian

With the implementation of global single-use plastic restrictions, the demand for biodegradable plastics has increased substantially. As a key raw material for synthesizing polybutylene succinate (PBS) through transesterification polymerization, dimethyl succinate (DMS) has demonstrated growing market demand. Efficient and green synthesis technologies for DMS production is now a critical priority. In this study, methanedisulfonic acid (MDSA) was introduced into the acetylene dicarbonylation reaction for the first time. The results demonstrated that the addition of MDSA can achieve a relatively high yield under ambient conditions. PdBr₂, MDSA, and PdBr₂-MDSA have been characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and Single-Crystal X-ray diffraction (SC-XRD) confirmed the coordination between Pd(II) and MDSA. The electrons transferred from the -SO₃H group to Pd(Ⅱ) enhanced the catalytic activity. Density functional theory (DFT) calculations revealed that the negative inductive effect of -SO₃H groups at both ends of the MDSA molecule induced a positive charge on the connected -CH₂- moiety. The effects of parameters including catalyst dosage, proportion of promoters, reaction temperature and reaction time on the combined yield of DMS, dimethyl fumarate (DMF) and dimethyl maleate (DMM) have been systematically investigated. Under the optimal conditions, the combined yield achieved up to 87.82 %. This study demonstrates a green and energy-efficient route for DMS synthesis with reduced carbon emissions, offering a promising strategy for industrial applications.

随着全球一次性塑料限制的实施，对生物降解塑料的需求大幅增加。丁二酸二甲酯（DMS）作为酯交换聚合法制备聚丁二酸丁二酯（PBS）的关键原料，市场需求日益增长。高效和绿色合成技术的DMS生产现在是一个关键的优先事项。本研究首次将甲基二磺酸（MDSA）引入乙炔二羰基化反应中。结果表明，在环境条件下，加入MDSA可以获得较高的收率。通过傅里叶变换红外光谱（FT-IR）、x射线光电子能谱（XPS）和单晶x射线衍射（SC-XRD）对PdBr2、MDSA和PdBr2-MDSA进行了表征，证实了Pd（II）与MDSA之间的配位。电子从-SO3H基团转移到Pd（Ⅱ）上，提高了催化活性。密度泛函理论（DFT）计算表明，MDSA分子两端- so3h基团的负诱导作用在连接的- ch2 -上诱导了一个正电荷。系统研究了催化剂用量、促进剂比例、反应温度和反应时间等参数对DMS、富马酸二甲酯（DMF）和马来酸二甲酯（DMM）联合产率的影响。在最优条件下，复合收率可达87.82 %。本研究展示了一种绿色节能的DMS合成途径，减少了碳排放，为工业应用提供了一个有前途的策略。

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引用次数: 0

Quinoline-linked covalent organic frameworks for efficient photocatalytic reduction of aqueous chromium(Ⅵ) 喹啉连接的共价有机框架高效光催化还原水性铬（Ⅵ）

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-13 DOI: 10.1016/j.apcata.2025.120702

Mingyue Chen , Shibing Wu , Run Wang , Xiaojie Wu , Jiang Liu , Yang Li , Ligong Chen , Xilong Yan , Bowei Wang

The photocatalytic reduction of highly toxic Cr(Ⅵ) to harmless Cr(Ⅲ) represents a promising remediation strategy, characterized by mild reaction conditions, low energy consumption, and absence of secondary pollution. However, conventional photocatalysts suffer from narrow visible-light absorption zone and rapid electron-hole recombination. Recently, there have been reports suggesting that covalent organic frameworks (COFs) might be a good solution to this problem. Herein, two benzothiazole (BT)-functionalized quinoline-linked COFs (BT-TAPT-COF-Q and BT-TAPB-COF-Q) were constructed via the four-step tandem reaction of 2,1,3-benzothiadiazole-4,7-dicarbaldehyde (BT) respectively with 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) using one-pot synthesis. XRD results indicated that the rigid planar structure of quinoline significantly enhanced the crystallinity and stability of the frameworks. Notably, the incorporation of electron-deficient BT unit made BT-TAPB-COF-Q to be donor-acceptor (D-A) COF, thereby endowing it with even more superior optoelectronic properties. The experimental and theoretical calculation results collectively indicated that BT-TAPB-COF-Q exhibits excellent photogenerated carrier separation and transport efficiency. Consequently, under visible-light irradiation, without the need for sacrificial agents or pH adjustment, BT-TAPB-COF-Q achieved 99 % Cr(Ⅵ) reduction within 2 h, and maintained its catalytic activity after 7 cycles. This study presented the rational design of novel COFs that integrated high catalytic activity, exceptional stability, and superior recyclability, demonstrating highly efficient aqueous Cr(Ⅵ) reduction under ambient conditions.

光催化还原高毒性Cr（Ⅵ）为无害Cr（Ⅲ）是一种很有前途的修复策略，具有反应条件温和、能耗低、无二次污染等特点。然而，传统的光催化剂存在可见光吸收区窄、电子空穴复合快的缺点。最近有报道指出，共价有机框架（COFs）可能是解决这一问题的一个很好的方法。本文以2,1,3-苯并噻唑-4,7-二乙醛（BT）和2,4,6-三（4-氨基苯基）-1,3,5-三嗪（TAPT）为原料，采用一锅法，通过四步串联反应，构建了两个苯并噻唑（BT）功能化喹啉连接的COFs （BT- tpt - cof - q和BT- ttap - cof - q）。XRD结果表明，喹啉的刚性平面结构显著提高了骨架的结晶度和稳定性。值得注意的是，缺电子BT单元的加入使BT- tapb -COF- q成为供体-受体（D-A） COF，从而使其具有更优越的光电性能。实验和理论计算结果共同表明，BT-TAPB-COF-Q具有良好的光生载流子分离和输运效率。因此，在可见光照射下，不需要牺牲剂或pH调节，BT-TAPB-COF-Q在2 h内达到99% % Cr（Ⅵ）的还原，并在7个循环后保持其催化活性。本研究提出了新型COFs的合理设计，该COFs集高催化活性，卓越的稳定性和卓越的可回收性于一体，在环境条件下表现出高效的水相Cr（Ⅵ）还原。

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引用次数: 0

Boosting the high-stable production of light olefins via coupling n-hexane and ethanol cracking over Zr-doped HZSM-5 at high temperature 正己烷与乙醇在zr掺杂HZSM-5上的高温偶联裂解促进了轻质烯烃的高稳定生产

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-13 DOI: 10.1016/j.apcata.2025.120703

Qilun Huang , Xu Hou , Siqi Liu , Jiayu Wang , Jing Huang , Li Yin , Enxian Yuan

Catalytic cracking process is an important technology for the efficient utilization of hydrocarbon resources, and the development of novel HZSM-5 catalysts is promising to improve light olefins production. Herein, the effects of ethanol additive and Zr-doped HZSM-5 on n-hexane catalytic cracking were explored and optimized to achieve the high-stable production of light olefins. It was found that n-hexane catalytic cracking over HZSM-5 zeolites at 600 °C exhibited a sharp catalyst deactivation, and the yield of light olefins higher than 20 % was only maintained for 1 h on stream. While, adding ethanol (10 %) into n-hexane and incorporating Zr-doping (1 %) into HZSM-5 significantly improved the catalytic stability at 600 °C, and the yield of light olefins was maintained at a high-stable level of 43.6 %-52.4 % for at least 6 h on stream. Based on the detailed analysis of product distribution, catalyst characterizations and mechanism indexes, it was deduced that adding ethanol and introducing Zr-doping were effective to promote the monomolecular cracking and inhibit the oligomerization and aromatization, which improved alkenes selectivity and light olefins production; meanwhile, the presence of ethanol enhanced the removal of coke deposit, and the presence of ZrO₂ protected HZSM-5 structure, which alleviated the deactivation of HZSM-5 catalysts and achieved a high-stable production of light olefins at 600 °C. This work may provide a theoretical basis for the design and preparation of efficient HZSM-5 catalysts to boost light olefins production via coupling hydrocarbon and alcohol cracking.

催化裂化工艺是油气资源高效利用的重要技术，新型HZSM-5催化剂的开发有望提高轻质烯烃的产量。研究了乙醇添加剂和zr掺杂HZSM-5对正己烷催化裂化的影响，以实现轻质烯烃的高稳定生产。结果表明，HZSM-5分子筛在600℃下的正己烷催化裂化反应出现了明显的失活现象，在1 h的反应时间内能保持20% 以上的轻烯烃产率。而在正己烷中加入乙醇（10 %）和在HZSM-5中掺入zr（1 %）显著提高了600℃下的催化稳定性，轻烯烃的产率保持在43.6 %-52.4 %的高稳定水平至少6 h。通过对产物分布、催化剂表征和机理指标的详细分析，得出添加乙醇和引入zr掺杂能有效促进单分子裂解，抑制低聚和芳构化反应，提高烯烃选择性和轻烯烃产量；同时，乙醇的存在促进了焦炭沉积的去除，ZrO2的存在保护了HZSM-5的结构，减轻了HZSM-5催化剂的失活，在600℃下实现了轻质烯烃的高稳定生产。本研究为设计和制备高效的HZSM-5催化剂提供了理论依据，以促进烃醇耦合裂化生产轻烯烃。

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引用次数: 0

Selective oxidation of aryl alcohols to aldehydes/ketones on Pd/Co3O4-bimetallic catalysts Pd/ co3o4双金属催化剂上芳醇选择性氧化制醛/酮的研究

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-12 DOI: 10.1016/j.apcata.2025.120699

Shuai Yang , Changyan Guo , Yanan Niu , Wenchao Tang , Ziren Chen , Yu Xia , Shaofeng Wu , Bin Wang , Yubin Wang , Ablimit Abdukader , Jide Wang , Chenjiang Liu , Yonghong Zhang

The selective oxidation of aryl alcohols to carbonyl compounds is pivotal in organic synthesis, yet suppressing overoxidation and avoiding harmful oxidants remain key challenges. Herein, we report a heterogeneous Pd/Co₃O₄ nanocatalyst for oxidant-free dehydrogenative oxidation of aryl alcohols in water. Structural characterizations confirm uniformly dispersed 10–20 nm nanoparticles with intimate Pd⁰-Co₃O₄ interfacial contact. The catalyst achieves 99 % yield and selectivity for benzyl alcohol-to-benzaldehyde conversion, with a TOF of 629 h⁻¹ , outperforming commercial Pd/C and PdCl₂. It exhibits broad substrate tolerance (47–99 % yields for substituted benzyl alcohols, phenylethanol, etc.) and stable activity over five cycles (91 % yield retention) with negligible Pd leaching (0.02 %). A non-radical mechanism is supported, involving interfacial synergy for O—H cleavage (Co₃O₄) and α-C—H activation/hydride transfer (Pd⁰). Gram-scale synthesis (60 % yield) validates practicality, presenting a sustainable catalytic system aligned with green chemistry.

芳基醇选择性氧化为羰基化合物是有机合成的关键，但抑制过度氧化和避免有害氧化剂仍然是关键的挑战。本文报道了一种非均相Pd/Co₃O₄纳米催化剂，用于芳基醇在水中的无氧化剂脱氢氧化。结构表征证实了均匀分散的10-20 nm纳米颗粒具有亲密的Pd⁰-Co₃O₄界面接触。该催化剂的苯甲醇转化为苯甲醛的收率和选择性为99% %，TOF为629 h⁻¹ ，优于商品Pd/C和PdCl₂。它具有广泛的底物耐受性（对取代苯甲醇、苯乙醇等的收率为47-99 %），并且在5个循环中具有稳定的活性（91 %的收率保留），Pd浸出可以忽略不计（0.02 %）。支持非自由基机制，涉及O - h裂解（Co₃O₄）和α-C-H活化/氢化物转移（Pd⁰）的界面协同作用。克级合成（60% %收率）验证了实用性，呈现了与绿色化学一致的可持续催化系统。

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