Applied Catalysis A: General最新文献_第8页

Methane pyrolysis on fused Fe-Al2O3 catalysts: Characterization of catalyst structure, performance and carbon formation 熔融Fe-Al2O3催化剂催化甲烷热解：催化剂结构、性能及碳生成表征

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-25 DOI: 10.1016/j.apcata.2025.120719

Chiara Negri , Veronica Piazza , Marco Orsenigo, Matteo Maestri, Gianpiero Groppi, Lidia Castoldi, Alessandra Beretta

In this work, an investigation of methane pyrolysis over Fe/Al-based catalysts has been carried out to optimize the formulation, that is to obtain structural features suitable to high C/Fe ratios before the catalyst is fully deactivated. At this scope, Fe-Al₂O₃ catalysts at different Fe-Al ratios were prepared by the fusion-decomposition method and reduction in H₂; fresh and reduced samples were extensively characterized by N₂ adsorption/desorption, electron microscopies, X-Ray Diffraction and Raman spectroscopy. As a general feature, the reduced catalyst structures are characterized by mesoporous Fe aggregates dispersed in microporous alumina, with presence of FeAl₂O₄ at the interface; however, several textural parameters (including specific surface area, pore size distribution, Fe crystallite size, FeAl₂O₄ abundance) change importantly with increasing Fe/Al ratio. Close to the equimolar Fe-Al ratio, such textural properties appear optimal to guarantee high Fe dispersion and accessibility. All the formulations were first screened in methane pyrolysis in a thermobalance; a selected subset of formulations was then tested in a packed bed reactor. The study reveals that formulations with Fe-Al molar ratios from 50–50 to 75–25 are all characterized by high initial activity and lower deactivation rate, thus achieving the maximum C-accumulation capacity. Among them, the equimolar formulation achieved the highest C/Fe ratio, reaching 2.5 g_C/g_Fe after 1 h testing with 40 % CH₄ at 800°C. The spent catalysts were characterized by electron microscopies, X-Ray Diffraction and Raman spectroscopy to better comprehend the effects of extent of reaction and Fe-Al ratio on the characteristics of the solid. In all the samples, after reaction, the Fe₃C was the main iron-containing phase and a progressive decrease of the residual Fe phase was observed at increasing C-accumulation. Concerning the nature of C-structures, a large variety of them was observed depending on Fe content and crystalline size.

本研究通过对Fe/ al基催化剂上的甲烷热解进行研究，优化配方，即在催化剂完全失活之前获得适合高C/Fe比的结构特征。在此范围内，采用熔解法和H2还原法制备了不同Fe-Al比的Fe-Al2O3催化剂；通过N2吸附/解吸、电子显微镜、x射线衍射和拉曼光谱对新鲜样品和还原样品进行了广泛的表征。总体而言，还原后的催化剂结构表现为介孔Fe团聚体分散在微孔氧化铝中，界面处存在FeAl2O4；但随着铁铝比的增加，结构参数（比表面积、孔径分布、铁晶粒尺寸、FeAl2O4丰度）发生了显著变化。接近等摩尔的铁铝比，这样的织构性能似乎是最佳的，以保证高铁的分散性和可及性。所有配方首先在热平衡甲烷热解中筛选；然后在填充床反应器中对选定的配方子集进行了测试。研究表明，Fe-Al摩尔比在50-50 ~ 75-25之间的配方具有初始活性高、失活率低的特点，积累c的能力最大。其中，等摩尔配方的C/Fe比最高，在800℃条件下，以40 % CH4测试1 h，达到2.5 gC/gFe。利用电子显微镜、x射线衍射和拉曼光谱对废催化剂进行了表征，以更好地了解反应程度和铁铝比对固体特性的影响。在所有样品中，反应后，Fe3C是主要的含铁相，随着c积累量的增加，残余Fe相逐渐减少。关于c结构的性质，根据铁含量和晶粒尺寸的不同，可以观察到多种不同的c结构。

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引用次数: 0

Sustainable catalytic strategies for carbon–carbon and carbon–heteroatom (C–S, C–N, C–O, C–Se) bond formation: Green pathways to advanced molecules 碳碳和碳杂原子（C-S, C-N, C-O, C-Se）键形成的可持续催化策略：通往先进分子的绿色途径

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-25 DOI: 10.1016/j.apcata.2025.120714

Aeyaz Ahmad Bhat , Noureddine Elboughdiri , Abhinav Kumar , Ankit Dilipkumar Oza , Karim Kriaa , Chemseddine Maatki , Bilel Hadrich , Anjuman Ayub , Meraj Ahmed , Atif Khurshid Wani

An imperative cornerstone of modern organic synthesis lies in the ability to actively shape molecular frameworks through selective bond formation. Carbon–carbon (C–C) bonds provide the fundamental backbone of organic molecules, whereas carbon–heteroatom linkages, particularly C–N, C–O, and C–S bonds, impart essential structural and functional diversity that underpins chemical reactivity, bioactivity, and material properties. Over the past few decades, the evolution from classical strategies such as Wurtz coupling, Grignard addition, aldol condensation, and nucleophilic substitutions towards catalytic methodologies has transformed the synthetic landscape. Transition-metal catalysis, exemplified by Suzuki, Heck, and Negishi cross-couplings, has enabled highly efficient, selective, and mild routes for C–C and carbon–heteroatom bond construction. Parallel developments in photocatalysis and organocatalysis have expanded the synthetic toolbox by offering environmentally benign and metal-free alternatives with broad substrate tolerance. These advances have not only enhanced regio- and stereocontrol but also facilitated late-stage functionalization of complex molecules, thereby streamlining the synthesis of bioactive compounds and functional materials. Increasing emphasis on sustainability has further driven the integration of green chemistry principles, including renewable feedstocks, recyclable catalysts, and energy-efficient conditions. This review highlights recent catalytic innovations in C–C, C–N, C–O, and C–S bond formation, discusses their mechanistic foundations, and underscores their implications in medicinal chemistry, materials science, and sustainable synthesis.

现代有机合成的一个重要基石在于通过选择性键形成主动塑造分子框架的能力。碳-碳（C-C）键提供了有机分子的基本骨架，而碳-杂原子键，特别是C-N、C-O和C-S键，赋予了基本的结构和功能多样性，支撑了化学反应性、生物活性和材料特性。在过去的几十年里，从经典策略如Wurtz偶联、格氏加成、醛醇缩合和亲核取代到催化方法的演变已经改变了合成领域。以Suzuki、Heck和Negishi交叉偶联为例的过渡金属催化，为碳-碳和碳杂原子键的构建提供了高效、选择性和温和的途径。光催化和有机催化的平行发展通过提供具有广泛底物耐受性的环保和无金属替代品，扩大了合成工具箱。这些进展不仅增强了区域和立体控制，而且促进了复杂分子的后期功能化，从而简化了生物活性化合物和功能材料的合成。对可持续性的日益重视进一步推动了绿色化学原则的整合，包括可再生原料、可回收催化剂和节能条件。本文综述了近年来在C-C、C-N、C-O和C-S键形成方面的催化创新，讨论了它们的机制基础，并强调了它们在药物化学、材料科学和可持续合成方面的意义。

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引用次数: 0

Production of aromatics from furfural and ethanol over zeolite catalysts: Reaction and deactivation mechanisms, effect of acidity and zeolite structures 糠醛和乙醇在沸石催化剂上生产芳烃：反应和失活机理，酸度和沸石结构的影响

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-25 DOI: 10.1016/j.apcata.2025.120718

Francesco Sandri , Jennifer Cueto , Christoph Schmidt , Anssi Peuronen , Pia Damlin , Teija Tirri , Kari Eränen , Mika Lastusaari , Narendra Kumar , David P. Serrano , Päivi Mäki-Arvela , Dmitry Yu. Murzin

The production of aromatics, specifically benzene, toluene and xylenes (BTX), from bio-derived feedstock such as ethanol and furfural can be achieved by zeolite catalysts. However, the formation of coke strongly limits this reaction leading to catalyst deactivation. In-depth understanding of the relationship between the catalyst characteristics and the mechanism of carbon deposit is needed to improve potential applicability of this novel approach for BTX production. Evaluation of the catalytic activity of β and ZSM-5 zeolites in the aromatization of ethanol and furfural, coupled with the characterization of the spent catalysts, gave important insights on the structure and features that are required to increase the aromatics formation. With these investigations it was possible to determine the location of the catalytic sites that are active in the aromatization reaction, defining at the same time the mechanism of deactivation by coke formation. These findings give important advances for the future design of efficient catalysts for the aromatics production.

用沸石催化剂可以从乙醇和糠醛等生物原料中生产芳烃，特别是苯、甲苯和二甲苯（BTX）。然而，焦炭的形成强烈地限制了这种反应，导致催化剂失活。需要深入了解催化剂特性与积碳机理之间的关系，以提高该新方法在BTX生产中的潜在适用性。对β和ZSM-5沸石在乙醇和糠醛芳构化反应中的催化活性进行了评价，并对废催化剂进行了表征，对提高芳构化反应所需的结构和特征有了重要的认识。通过这些研究，可以确定在芳构化反应中活跃的催化位点的位置，同时确定由焦炭形成的失活机制。这些发现为未来设计高效的芳烃生产催化剂提供了重要的进展。

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引用次数: 0

Single-atom catalysts with p-block metals for the electrocatalytic semi-hydrogenation of acetylene: A DFT study 电催化乙炔半加氢用p嵌段金属单原子催化剂的DFT研究

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-23 DOI: 10.1016/j.apcata.2025.120716

Xiaoqing Gong, Yi Yang, Yuanyuan Yu, Mingqiang Liu, Xiaohong Song, Kefeng Xie

In the industrial production of high value-added polyethylene, the efficient removal of trace acetylene impurities from raw ethylene is a key step to ensure the quality of the polymer. However, current mainstream industrial technology relies on the thermally catalysed selective hydrogenation of acetylene under high-temperature and high-pressure conditions. Electrocatalytic acetylene semi-hydrogenation (EASH) is an alternative, environmentally friendly strategy that can be performed under mild reaction conditions. Herein, using density functional theory calculations, the performances of nine p-block single-metals (ie, Al, Ga, Ge, Tl, Sb, Sn, Bi, In and Pb) supported on a N-doped graphene (MN₄-G) catalyst are studied to screen single-atom catalysts with high activity and selectivity for EASH. Firstly, comprehensive evaluations of binding, cohesive and formation energies confirm that MN₄-G configurations are thermodynamically stable. Secondly, Gibbs free energy analysis shows that PbN₄-G catalysts promote EASH and inhibit the side reaction of hydrogen evolution. Thirdly, the analysis and calculation results show that the adsorption energy of acetylene and ethylene can be used as characteristic descriptors to predict the EASH selectivity of the catalyst. Finally, the mechanism of its catalytic activity is explained from the electronic and orbital perspectives. Our results show that the directional coupling between P_z and C₂H₄-

π_{z}^{*}

anti-bonding orbitals is the key to regulating ethylene desorption. Moderate electronic feedback can weaken C₂H₄ adsorption and avoid excessive hydrogenation, ensuring high selectivity. This study provides a preferred systems for designing high-performance EASH catalysts as well as a theoretical basis and a design strategy for EASH catalysts for industrial applications.

在高附加值聚乙烯工业生产中，原料乙烯中微量乙炔杂质的高效脱除是保证聚合物质量的关键环节。然而，目前主流的工业技术依赖于高温高压条件下乙炔的热催化选择性加氢。电催化乙炔半加氢（ash）是一种可在温和的反应条件下进行的环境友好的替代策略。本文利用密度泛函理论计算，研究了掺杂n的石墨烯（MN4-G）催化剂上9种p嵌段单金属（Al, Ga, Ge, Tl, Sb, Sn, Bi， In和Pb）的性能，以筛选具有高活性和选择性的ash单原子催化剂。首先，结合能、内聚能和形成能的综合评价证实了MN4-G构型是热力学稳定的。其次，Gibbs自由能分析表明，PbN4-G催化剂促进了ash，抑制了析氢副反应。第三，分析计算结果表明，乙炔和乙烯的吸附能可以作为预测催化剂选择性的特征描述符。最后，从电子和轨道的角度解释了其催化活性的机理。结果表明，Pz与C2H4-π *反键轨道之间的定向耦合是调控乙烯脱附的关键。适度的电子反馈可以减弱C2H4吸附，避免过度加氢，保证高选择性。本研究为设计高性能的ash催化剂提供了优选体系，为ash催化剂的工业应用提供了理论基础和设计策略。

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引用次数: 0

Recent advances in single-atom-based photo-Fenton catalysts for the degradation of antibiotics, pesticides, and phenols 单原子光fenton催化剂在抗生素、农药和酚类降解中的研究进展

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-23 DOI: 10.1016/j.apcata.2025.120717

Sahil Rana , Pooja Dhiman , Pankaj Sharma , Mashallah Rezakazemi , Gaurav Sharma

The persistent nature, toxicity, and resistance to traditional treatment procedures of antibiotics, pesticides, and phenols have made their growing presence in water bodies a major environmental and public health challenge. The degradation of these emerging pollutants has shown great promise using advanced oxidation processes (AOPs), particularly the photo-Fenton process. This review highlights the growing levels of contaminants in water, such as antibiotics, pesticides, and phenols, along with their sources, fate, and impacts on human health and the environment. The fundamentals and mechanistic processes of the photo-Fenton approach are briefly discussed. Under visible light, single-atom catalysts (SACs) offer greater efficiency, selectivity, and recyclability in pollutant degradation due to their atomically distributed metal sites, high catalytic activity, and variable coordination environments. The most recent developments in single-atom-based photo-Fenton catalysts, their design, synthesis strategies, and applications for the degradation of antibiotics, pesticides, and phenolic pollutants in water are thoroughly discussed and summarized in this review. A critical discussion of essential issues, including catalyst performance under actual water conditions, scalability, and stability, is provided. The article concludes by outlining potential directions for the sustainable implementation and logical design of SAC-based photo-Fenton systems in environmental remediation.

抗生素、杀虫剂和酚类的持久性、毒性和对传统处理程序的耐药性使它们在水体中的存在日益增加，成为一个主要的环境和公共卫生挑战。利用先进的氧化工艺（AOPs），特别是光fenton工艺，降解这些新出现的污染物显示出巨大的前景。这篇综述强调了水中不断增长的污染物水平，如抗生素、杀虫剂和酚类，以及它们的来源、归宿和对人类健康和环境的影响。简要讨论了光-芬顿法的基本原理和机理过程。在可见光下，单原子催化剂（SACs）由于其原子分布的金属位点、高催化活性和可变的配位环境，在污染物降解方面提供了更高的效率、选择性和可回收性。综述了单原子光fenton催化剂的设计、合成策略及其在降解水中抗生素、农药和酚类污染物方面的应用。关键问题的关键讨论，包括催化剂在实际水条件下的性能，可扩展性和稳定性，提供。文章最后概述了基于sac的光fenton系统在环境修复中的可持续实施和逻辑设计的潜在方向。

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引用次数: 0

Simultaneous multianalysis of substituent effects in the catalytic degradation of organophosphates by imidazoles 咪唑催化降解有机磷中取代基效应的同时多重分析

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-22 DOI: 10.1016/j.apcata.2025.120715

Valmir B. Silva , Patrícia M. Soares, Elisa S. Orth

Understanding how substituents influence chemical reactivity is strategic when screening and predicting catalysts, especially towards the neutralization of toxic organophosphates, present in agrochemicals and chemical warfare. Herein, the substituent effects were concomitantly investigated on both nucleophilic and electrophilic centers in catalytic dephosphorylation reactions, focusing on imidazole-based nucleophiles and aryl organophosphates. Eight imidazole derivatives, bearing methyl, carboxylic acid, or hydroxyl groups, and two aryl organophosphates, were studied. High catalytic outcomes were obtained: nearly 2 min, that would take over 7 days in their absence. A simultaneous multianalysis approach (combining our data with the literature) was proposed with a novel trilinear Brønsted-type relationship correlating the reaction rate constants with the basicity of the imidazole nucleophiles and the pK_a values of both the leaving and non-leaving groups of the organophosphates. While the nucleophile and leaving group exert major influences on reactivity, the non-leaving group's contribution is lower. Particularly, imidazoles display higher sensitivity to substituent variations compared to other nucleophiles, suggesting that structural tuning of the imidazole core can greatly enhance catalytic efficiency. As a proof of concept, the model accurately predicted the catalytic performance for a given reaction, compared to the one reported experimentally (∼3 % deviation). This approach offers a valuable framework for designing efficient catalysts and guiding safe, targeted experimentation in organophosphate degradation and related applications, avoiding unnecessary experiments with highly toxic agents. Such structure-reactivity relationships can foster chemical security and safety in the scope of organophosphate degradation and detection and be broaden to other classes of reactions.

了解取代基如何影响化学反应性是筛选和预测催化剂的战略，特别是对农药和化学战中存在的有毒有机磷的中和。本文研究了取代基对催化去磷酸化反应中亲核中心和亲电中心的影响，重点研究了咪唑基亲核试剂和芳基有机磷酸盐。研究了含甲基、羧酸或羟基的八种咪唑衍生物和两种芳基有机磷酸盐。获得了高催化效果：近2 min，在没有它们的情况下需要7天以上的时间。我们提出了一种同时多重分析方法（结合我们的数据和文献），将反应速率常数与咪唑亲核试剂的碱度以及有机磷酸盐的离去基和非离去基的pKa值联系起来，建立了一种新的三线性br ønsted型关系。亲核试剂和离去基对反应性的影响较大，非离去基对反应性的影响较小。特别是，咪唑对取代基变化的敏感性高于其他亲核试剂，这表明咪唑核的结构调整可以大大提高催化效率。作为概念证明，与实验报告的模型相比，该模型准确地预测了给定反应的催化性能（~ 3 %偏差）。该方法为设计高效催化剂和指导安全、有针对性的有机磷酸盐降解实验及相关应用提供了有价值的框架，避免了不必要的高毒性试剂实验。这种结构-反应性关系可以促进有机磷酸酯降解和检测范围内的化学安全性和安全性，并可扩展到其他类型的反应。

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引用次数: 0

Synergistic three-in-one photo-synthesis of benzimidazoles and H2O2 by porous N-rich g-C3N4/g-C3N5 isotype heterojunction 富n多孔g-C3N4/g-C3N5异质结协同作用下苯并咪唑与H2O2的三合一光合作用

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-20 DOI: 10.1016/j.apcata.2025.120713

Wenjie Tian , Xiongxiong Zeng , Wencong Liu , Lei Mao , Fen Guo , Yang Gui , Lan Yuan

Constructing a dual-functional photoredox system coupling fine-chemical synthesis with hydrogen peroxide (H₂O₂) production provides an intriguing and eco-friendly protocol for advancing sustainable practical applications. Herein, we present a facile one-pot strategy for fabricating a porous N-rich g-C₃N₄/g-C₃N₅ heterojunction (denoted as pN-N₄-N₅) using mixed melamine and 3-amino-1,2,4-triazine as the precursors with NH₄Cl as a penetrant for in-situ structure engineering. The resultant metal-free pN-N₄-N₅ exhibited a remarkable performance of H₂O₂ generation rate of 2.71 mmol g⁻¹ h⁻¹ with simultaneous production of industrially important 2-phenylbenzimidazole (2-BZ) under visible light and open air, along with a yield of 97 % and selectivity of > 99 %, outperforming most of the reported carbon nitride-based reaction systems for single-functional H₂O₂ or 2-BZ synthesis. Extensive characterizations and density functional theory (DFT) studies revealed that such a heterojunction with well-matched band structure, enlarged interlayer space and enriched amino groups on the catalyst surface enables the facilitated spatially oriented charge flow, efficient mass transfer and reactants activation, thus offering an efficient and sustainable platform to furnishing the three-in-one photoredox systems to produce bidirectional valuable products.

构建一个耦合精细化学合成与过氧化氢（H2O2）生产的双功能光氧化还原系统，为推进可持续的实际应用提供了一个有趣且环保的方案。在此，我们提出了一种简单的一锅策略，以混合三聚氰胺和3-氨基-1,2,4-三嗪为前驱体，以NH4Cl为渗透剂，制备多孔富n g-C3N4/g-C3N5异质结（简称pN-N4-N5），用于原位结构工程。得到的无金属pN-N4-N5的H2O2生成速率为2.71 mmol g−1 h−1，在可见光和空气条件下可同时生成工业上重要的2-苯基苯并咪唑（2-BZ），产率为97% %，选择性为 99 %，优于大多数基于氮化碳的单功能H2O2或2-BZ合成体系。广泛的表征和密度泛函数理论（DFT）研究表明，这种异质结具有良好匹配的带结构、扩大的层间空间和丰富的催化剂表面氨基，有利于电荷的空间定向流动、高效的传质和反应物的活化，从而为三合一光氧化还原体系生产双向有价产品提供了一个高效和可持续的平台。

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引用次数: 0

Controllable synthesis of SiO₂-supported cobalt nanocatalysts for selective hydrogenation of dinitriles to primary diamines 二腈选择性加氢制伯胺用二氧化硅负载钴纳米催化剂的可控合成

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-19 DOI: 10.1016/j.apcata.2025.120712

Yiheng Cui , Kailin Han , Tingting Ge, Yanxia Zheng, Haofei Huang, Cuncun Zuo, Ming Wang

Powdered Co/SiO₂ catalysts with varying cobalt loadings were prepared via the precipitation method for the selective hydrogenation of 3,3′-(cyclohexylazanediyl)dipropanenitrile (CDP) to produce N ¹ -(3-aminopropyl)-N ¹ -cyclohexylpropane-1,3-diamine (ACD). Compared to nickel-based catalysts, the cobalt-based catalysts exhibited moderate H₂ adsorption energy, which helps to suppress the cleavage of the C-N bond and thereby effectively inhibits the dealkylation reaction of amines, reducing the formation of the by-product N ¹ -cyclohexylpropane-1,3-diamine (CD). Characterization techniques including XRD, FT-IR, SEM, BET, and H₂-TPD confirmed that the catalyst with a 60 wt% cobalt loading possesses the optimal active crystalline phase, achieving 100 % CDP conversion and an 81 % yield of ACD. Furthermore, the introduction of ammonia water serves to neutralize surface acidity and establish a moderate interaction with the Co active sites, thereby reducing the energy barrier for H₂ dissociation. This modification significantly enhances both the hydrogenation activity and selectivity of the cobalt-based powder catalyst; however, excessive ammonia led to over-hydrogenation and increased CD formation. Through systematic optimization of solvent type, reaction temperature, pressure, and time, the optimal process conditions for CDP hydrogenation were determined, and a kinetic model of the reaction was established, providing theoretical and data support for industrial application.

采用沉淀法制备了不同钴载量的Co/ sio2粉末催化剂，对3,3′-（环己基二基）二丙腈（CDP）进行选择性加氢反应，得到N ¹ -（3-氨基丙基）-N ¹ -环己基丙烷-1,3-二胺（ACD）。与镍基催化剂相比，钴基催化剂具有中等的H2吸附能，这有助于抑制C-N键的断裂，从而有效抑制胺的脱烷基反应，减少副产物N ¹ -环己基丙烷-1,3-二胺（CD）的生成。表征技术包括XRD， FT-IR， SEM， BET和H₂-TPD证实，钴负载为60 wt%的催化剂具有最佳的活性晶相，实现了100% %的CDP转化率和81% %的ACD收率。此外，氨水的引入有助于中和表面酸性，并与Co活性位点建立适度的相互作用，从而降低H₂解离的能量屏障。该改性显著提高了钴基粉末催化剂的加氢活性和选择性；然而，过量的氨导致过氢化和CD形成增加。通过对溶剂类型、反应温度、压力、时间等进行系统优化，确定了CDP加氢的最佳工艺条件，并建立了反应动力学模型，为工业应用提供了理论和数据支持。

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引用次数: 0

Carboxyl-induced surface modification of Cu-based catalysts for acetylene semi-hydrogenation 乙炔半加氢cu基催化剂的羧基表面改性研究

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-17 DOI: 10.1016/j.apcata.2025.120710

Ao Li , Zilong Zhang , Ruoting Liu , Yuxue Yue , Bolin Wang

The synergy of O-functional groups in the semi-hydrogenation of acetylene is indispensable for reasonably modulating the product distributions and improving the catalyst design. However, distinguishing the interaction between various O-functional groups and quantifying and tuning each functionality is still difficult. In this study, the developed Cu/AC-solvent catalysts promote directional carboxyl groups enrichment by systematically regulating the solvent polarity, ranging from water (H₂O) to tetrahydrofuran (THF). The optimized Cu/AC-THF catalyst demonstrates superior performance over a broad operational range (413–503 K), with a remarkable 6.49-fold improvement compared to Cu/AC-H₂O catalyst. Comprehensive characterization techniques and theoretical calculations show that Cu sites are anchored by carboxyl groups and modified into electron-deficient states through electron transfer. It improved the adsorption of the acetylene and facilitated trapping them on Cu sites, thus boosting performance. This study highlights the influence of carboxyl groups on Cu-based catalysts, providing a universal paradigm for designing Cu-based catalysts in acetylene semi-hydrogenation.

在乙炔半加氢反应中，o官能团的协同作用对于合理调节产物分布和改进催化剂设计是必不可少的。然而，区分各种o官能团之间的相互作用以及量化和调优每个功能仍然很困难。在本研究中，开发的Cu/ ac溶剂催化剂通过系统调节溶剂极性，从水（H2O）到四氢呋喃（THF），促进了羧基的定向富集。优化后的Cu/AC-THF催化剂在较宽的工作范围内（413-503 K）表现出优异的性能，与Cu/AC-H2O催化剂相比，性能提高了6.49倍。综合表征技术和理论计算表明，Cu位点被羧基锚定，并通过电子转移修饰成缺电子态。它改善了对乙炔的吸附，并有助于将其捕获在Cu位点上，从而提高了性能。该研究突出了羧基对cu基催化剂的影响，为设计乙炔半加氢cu基催化剂提供了一个通用的范例。

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引用次数: 0

Esterification of valeric acid and glycerol via various acidic zeolites 不同酸性沸石催化戊酸和甘油酯化反应

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-17 DOI: 10.1016/j.apcata.2025.120708

Rawipa Intakul , Phuoc Hoang Ho , Derek Creaser , Oleg Pajalic , Louise Olsson

Biomass-derived green esters can be produced from the esterification of valeric acid and glycerol. In this work, various zeolites (ZSM-5, Y, and BEA) were examined, specifically targeting divalerin and trivalerin esters. A direct link between pore size and esterification performance was not evident. This outcome can be attributed to the combined influence of various characteristics such as acidity, hydrophobicity and mesoporous structure. Among the zeolite types tested, HZSM-5, HY, and HBEA with SiO₂/Al₂O₃ ratios of 87, 88.6, and 45.2, respectively, showed the best performance. The Y-zeolite with a SiO₂/Al₂O₃ atomic ratio of 88.6 produced the lowest amount of by-products. This sample had a combination of low acidity (indicating high hydrophobicity), the highest mesoporous area and a relatively high mesoporous volume. These balanced properties rendered Y zeolite with active acid sites that were easily accessible, and facilitated effective pore diffusion properties for both the reactants and products during the esterification of glycerol and valeric acid. This zeolite achieved complete glycerol conversion and a 52.9 % yield of divalerin and a 25 % of trivalerin at 130 °C after 6 h, using 1 wt% catalyst, a 5:1 acid-to-glycerol mole ratio, and continuous water removal. Additionally, the reusability of the zeolite was demonstrated, as the Y zeolite could be recycled four times with only a minimal decrease in glycerol conversion. Complete regeneration of the zeolite was also achieved through re-calcination. This study demonstrates that acidic commercial zeolites are a promising option for esterification processes due to their good catalytic performance, long-term stability and easy regeneration.

由戊酸和甘油的酯化反应可生产生物质衍生的绿酯。在这项工作中，研究了各种沸石（ZSM-5， Y和BEA），专门针对二缬草素和三缬草素酯。孔径大小与酯化性能之间的直接联系并不明显。这一结果可归因于酸度、疏水性和介孔结构等多种特性的综合影响。其中，SiO2/Al2O3比分别为87、88.6和45.2的HZSM-5、HY和HBEA分子筛性能最好。SiO2/Al2O3原子比为88.6的y型分子筛副产物量最少。该样品具有低酸度（表明高疏水性），最高介孔面积和相对较高的介孔体积的组合。这些平衡的性质使得Y沸石具有易于接近的活性酸位点，并且在甘油和戊酸酯化过程中促进了反应物和产物的有效孔隙扩散特性。该分子筛使用1 wt%的催化剂，酸与甘油摩尔比为5:1，连续脱水，在130°C下，6 h后，甘油完全转化，二缬草素的收率为52.9% %，三缬草素的收率为25% %。此外，沸石的可重复使用性也得到了证明，因为Y型沸石可以循环使用四次，而甘油转化率只有很小的降低。通过再煅烧也实现了沸石的完全再生。该研究表明，酸性工业沸石具有良好的催化性能、长期稳定性和易于再生等优点，是酯化反应的理想选择。

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