Applied Catalysis A: General最新文献_第10页

Valorization of mixed plastics via catalytic hydrogenolysis over layered multifunctional Ru/Nb-MMT catalyst 层状多功能Ru/Nb-MMT催化剂催化氢解混合塑料的增值

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-12 DOI: 10.1016/j.apcata.2025.120701

Yingxiu Gao , Bo Feng , Xiaohui Liu , Yanqin Wang

Catalytic hydrogenolysis, as a relatively mature technique, has attracted considerable attention for plastic waste recycling due to its potential applications. However, existing processes are primarily limited to single-type plastics and are seldom effective for complex real-world mixtures, such as those containing polyolefins, oxygenated plastics, and chlorinated plastics. Thus, the development of multifunctional catalysts capable of efficiently converting mixed plastics remains a critical challenge. In this study, we designed a layered multifunctional solid catalyst, Ru/Nb-MMT, which was engineered by supporting NbO_x species and Ru nanoparticles on montmorillonite (MMT) to synergistically activate C-C, C-O, and C-Cl bonds. Additionally, CaO mitigates the inhibitory effect of in-situ generated water by regenerating accessible active sites and thus restores catalytic performance. Moreover, Ru/Nb-MMT exhibits excellent dechlorination capability in the co-conversion of polyethylene (PE) and polyvinyl chloride (PVC), yielding over 99 % non-solid products, demonstrating high efficiency in treating chlorinated plastic waste. The synergistic “layered mass transport–acid activation–metal hydrogenolysis” mechanism endows Ru/Nb-MMT with high activity, stability, and cost-effectiveness in the one-pot conversion of multi-component plastic mixtures (PE, PET, PPO, PC, PVC). This approach significantly simplifies the valorization of complex plastic wastes, showing great potential to improve process efficiency and economic viability, while also providing new insights for the design of catalysts in catalytic hydrogenolysis.

催化氢解技术作为一项较为成熟的技术，因其潜在的应用前景而引起了人们的广泛关注。然而，现有的工艺主要局限于单一类型的塑料，很少有效的复杂的现实世界的混合物，如那些含有聚烯烃，含氧塑料和氯化塑料。因此，开发能够有效转化混合塑料的多功能催化剂仍然是一个关键的挑战。在这项研究中，我们设计了一种层状多功能固体催化剂Ru/Nb-MMT，通过在蒙脱土（MMT）上支持NbOx物质和Ru纳米颗粒来协同激活C-C、C-O和C-Cl键。此外，CaO通过再生可达活性位点来减轻原位生成水的抑制作用，从而恢复催化性能。此外，Ru/Nb-MMT在聚乙烯（PE）和聚氯乙烯（PVC）共转化中表现出优异的脱氯能力，非固体产物收率超过99% %，显示出对氯化塑料废物的高效处理。Ru/Nb-MMT在多组分塑料混合物（PE、PET、PPO、PC、PVC）的一锅转化中具有“层状质量传递-酸活化-金属氢解”的协同机制，具有高活性、稳定性和高成本效益。该方法大大简化了复杂塑料废物的增值，显示出提高工艺效率和经济可行性的巨大潜力，同时也为催化氢解催化剂的设计提供了新的见解。

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引用次数: 0

Catalytic conversion of renewable limonene to homolimonenol over Sn-modified BETA zeolite 可再生柠檬烯在sn改性β沸石上催化转化为同戊烯醇

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-12 DOI: 10.1016/j.apcata.2025.120700

Eva Vrbková, Michaela Hlinková, Martin Zapletal, Eliška Vyskočilová

The Prins reaction is an acid-catalyzed transformation between an aldehyde and an alkene, resulting in the formation of either a C–C or C–O bond. Limonene, a naturally occurring terpene, represents a highly attractive renewable feedstock. It can be sustainably sourced from citrus essential oils obtained from citrus peels—byproducts of the juice industry—as well as from turpentine or through the pyrolysis of waste rubber materials such as used tires. Its bio-based origin and widespread availability make limonene a promising raw material for the development of greener chemical processes. In this study, the reaction of limonene with formaldehyde was used to produce homolimonenol, a valuable intermediate for the synthesis of a wide range of biologically active molecules (e.g., antibiotics, insect hormones) and fragrance compounds such as cyclomethylene citronellol. A series of Sn-modified (1–5 wt%) zeolite BETA catalysts were prepared by wet impregnation and solid-state impregnation method and characterized using various analytical techniques, including X-ray diffraction (XRD), X-ray fluorescence (XRF), and nitrogen physisorption. Their catalytic activity was evaluated in the Prins reaction of limonene and formaldehyde under batch conditions. One selected catalyst was further used to optimize reaction parameters—such as temperature (RT–100 °C), solvent, and catalyst loading—achieving high selectivity 91 % at 55 % conversion under ambient conditions. The possibility of catalyst reuse was also demonstrated, supporting the potential for sustainable process development.

普林斯反应是酸催化的醛和烯烃之间的转化，导致形成C-C或C-O键。柠檬烯是一种天然存在的萜烯，是一种极具吸引力的可再生原料。它可以从柑橘皮中提取的柑橘精油（果汁工业的副产品）以及松节油或废橡胶材料（如废旧轮胎）的热解中可持续地获取。柠檬烯的生物来源和广泛可用性使其成为发展绿色化学工艺的有前途的原料。在这项研究中，柠檬烯与甲醛的反应被用来生产同型柠檬烯醇，这是一种有价值的中间体，用于合成广泛的生物活性分子（如抗生素、昆虫激素）和芳香化合物，如环亚甲基香茅醇。采用湿浸渍法和固浸渍法制备了一系列sn修饰（1-5 wt%）的沸石β催化剂，并利用x射线衍射（XRD）、x射线荧光（XRF）和氮物理吸附等多种分析技术对其进行了表征。在间歇条件下，对其在柠檬烯与甲醛的Prins反应中的催化活性进行了评价。选择一种催化剂进一步优化反应参数，如温度（RT-100°C）、溶剂和催化剂负载，在环境条件下获得高选择性91 %，转化率55 %。还证明了催化剂重复使用的可能性，支持了可持续工艺开发的潜力。

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引用次数: 0

Electromagnetic-wave assisted rapid synthesis of MOF with coordination unsaturated metal sites for enhanced activity in Fenton-like reaction 电磁波辅助下快速合成具有配位不饱和金属位的MOF以增强类芬顿反应活性

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-10 DOI: 10.1016/j.apcata.2025.120696

Rui Jie , Yang Gao , Haiyan Qi , Jinzhi Yu , Chenyu Qi , Wanting Hui

As Lewis acidic sites, coordination unsaturated metal sites (CUMSs) on ZIF-67 surface were widely employed to accelerate PMS (Lewis base) activation in Fenton-like reaction. Nevertheless, it usually took at least several hours to produce CUMSs, resulting in a low-efficient process and limited yield. To overcome the shortcoming, herein, an alternating electromagnetic field was used to shorten preparation time by precisely generating heat-energy on magnetic Co^3+/2+ sites. Merely 2.0 min later, the CUMSs number had peaked in yolk@shell ZIF-67@Co₂SiO₄-2 nanostructure. They displayed better PMS utilization efficiency (49.7 %) and MTZ degradation efficiency (99.8 %) than reference catalysts in Fenton-like reaction. The activation energy of MTZ degradation over ZIF-67@Co₂SiO₄-2 was 31.51 kJ/mol, which was much lower than the activation energy in absence of catalysts (103.14 kJ/mol). In mechanism study, the important role of Co₂SiO₄ shell in controllable CUMSs production, the degradation contribution of various reactive species, the source the primary ¹O₂, the confinement effect inside the yolk@shell nanostructure and the enhanced Lewis acidity on CUMSs were revealed by Electron Paramagnetic Resonance analysis, radical trapping experiment and NH₃-Temperature Programmed Desorption analysis. This study provides a feasible method for the rapid removal of organic groups on the outer surface of ZIF-67 to prepare more CUMSs.

ZIF-67表面的配位不饱和金属位点（CUMSs）作为Lewis酸位点被广泛应用于类芬顿反应中加速PMS （Lewis碱）的活化。然而，通常需要至少几个小时才能生产出coms，这导致了低效率的工艺和有限的产量。为了克服这一缺点，本文利用交变电磁场在磁性Co3+/2+位点上精确产生热能，缩短了制备时间。2.0 min后，cums数量在yolk@shell ZIF-67@Co2SiO4-2纳米结构中达到峰值。在Fenton-like反应中，它们的PMS利用率（49.7 %）和MTZ降解效率（99.8 %）均优于参考催化剂。在ZIF-67@Co2SiO4-2上，MTZ降解的活化能为31.51 kJ/mol，远低于无催化剂时的活化能103.14 kJ/mol。在机理研究方面，通过电子顺磁共振分析、自由基俘获实验和nh3 -温度程序脱附分析，揭示了Co2SiO4壳层在可控合成cums中的重要作用、各种反应物质的降解贡献、原生1O2的来源、yolk@shell纳米结构内部的约束效应以及对cums Lewis酸度的增强。本研究为快速去除ZIF-67外表面的有机基团以制备更多的coms提供了一种可行的方法。

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引用次数: 0

Furazan-based donor-acceptor covalent organic polymers for directional electron transfer via electron-rich effect from lone electron pairs of multiple heteroatoms and efficient photocatalysis 基于呋喃氮杂原子的供受体共价有机聚合物，通过多杂原子的孤电子对富电子效应和高效光催化进行定向电子转移

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-10 DOI: 10.1016/j.apcata.2025.120697

Baiwei Ma , Wangxuan Chen , Wenxin Liu , Xiaoming Zhang , Pengjing Chen , Ping Li , Ning Huang , Xiaobin Lin , Mengyang Li , Mingli Jiao

The photoelectric properties of covalent organic polymers (COPs) can be precisely tuned through donor-acceptor (D–A) structural engineering. Herein, we synthesize two two-dimensional D–A COPs—QPFA-COP and PYFA-COP—via solvothermal methods, with the latter exhibiting superior photoelectric characteristics. Crucially, a strong electron-donating furazan moiety benefiting from multiple lone pairs of electrons in PYFA-COP enhances directional electron transfer from it to the acceptor unit. And the pyrene unit serves as an acceptor featuring an extended π-conjugated network at the COP node. Hence, they synergistically establish a robust electron push-pull system that significantly promotes exciton separation and transfer. As a result, PYFA-COP demonstrates exceptional photocatalytic activity in visible-light-driven selenocyanation, thiocyanation, and oxidative C–H functionalization. This work pioneers a high-efficiency furazan-based D–A COP photocatalyst by strategically leveraging the linker’s electron-rich effect from lone electron pairs of multiple heteroatoms, thereby expanding the diversity of electron-acceptor motifs in D–A COP design.

共价有机聚合物（cop）的光电性质可以通过供体-受体（D-A）结构工程进行精确调控。本文采用溶剂热法合成了两种二维D-A cop - qpfa - cop和pyfa - cop，其中pyfa - cop具有优异的光电特性。至关重要的是，PYFA-COP中受益于多个孤对电子的强给电子呋喃基团增强了从它到受体单元的定向电子转移。芘单元作为受体，在COP节点上具有扩展的π共轭网络。因此，它们协同建立了一个强大的电子推拉系统，显著促进激子的分离和转移。因此，PYFA-COP在可见光驱动的硒氰化、硫氰化和氧化C-H功能化中表现出优异的光催化活性。这项工作通过战略性地利用多杂原子的孤电子对的连接体富电子效应，开创了一种高效的呋喃嘧啶基D-A COP光催化剂，从而扩大了D-A COP设计中电子受体基序的多样性。

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引用次数: 0

Effect of axial coordination on oxygen reduction/evolution reaction of 2D Mn3(HXBHYB)@MOF 轴向配位对二维Mn3(HXBHYB)@MOF氧还原/析出反应的影响

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-10 DOI: 10.1016/j.apcata.2025.120695

Shuyan Liu , Kun Xie , Long Lin

Developing efficient and stable oxygen reduction/evolution reaction (ORR/OER) catalysts is crucial to enhance energy conversion efficiency and reduce reliance on precious metals. This study focuses on the rational design of single-atom catalysts (SACs) and the modulation of their ORR/OER catalytic performance via coordination environment engineering. Through density functional theory (DFT) calculations, we systematically investigated the effects of axial coordination on the electrocatalytic ORR/OER performance of TMN₄-group-supported catalysts. Specifically, axial-coordinated 2D Mn₃(HXBHYB)-Ls@MOF systems (where Ls denotes axial ligands: -OH/-Cl) were constructed to probe the tuning effects of axial ligands on the ORR/OER activity of -MnA₂B₂ moieties. Key findings reveal that: (i) The p_z orbitals of axial ligands interact with the d_z^₂ orbitals of Mn, modulating the magnetic moment and d-orbital distribution of Mn centers; (ii) This electronic regulation optimizes the adsorption strength of O* and OH* intermediates on Mn sites, thereby synergistically enhancing ORR/OER performance; (iii) The -OH ligand demonstrates superior ORR modulation compared to -Cl. Notably, promising catalyst configurations were identified, including OH-MnN₄ (η^ORR = 0.307 V) and Cl-MnN₂O₂ (η^OER = 0.358 V). This work elucidates the pivotal role of axial ligands in regulating electronic energy levels and spin states, paving the way for designing high-performance bifunctional electrocatalysts.

开发高效稳定的氧还原/析出反应催化剂对于提高能量转换效率和减少对贵金属的依赖至关重要。本研究的重点是合理设计单原子催化剂，并通过配位环境工程对其ORR/OER催化性能进行调节。通过密度泛函理论（DFT）计算，系统研究了轴向配位对TMN₄基负载催化剂电催化ORR/OER性能的影响。具体而言，构建了轴位二维Mn3(HXBHYB)-Ls@MOF体系（Ls表示轴向配体：-OH/-Cl），以探索轴向配体对-MnA₂B₂部分的ORR/OER活性的调节作用。主要发现表明：(1)轴向配体的pz轨道与Mn的dz₂轨道相互作用，调节了Mn中心的磁矩和d轨道分布；（ii）这种电子调控优化了O*和OH*中间体在Mn位点上的吸附强度，从而协同提高了ORR/OER性能；（iii）与-Cl相比，-OH配体表现出更好的ORR调制。值得注意的是，确定了有前景的催化剂构型，包括OH-MnN₄（ηORR = 0.307 V）和Cl-MnN₂O₂（ηOER = 0.358 V）。这项工作阐明了轴向配体在调节电子能级和自旋态中的关键作用，为设计高性能双功能电催化剂铺平了道路。

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引用次数: 0

Excellent performance of porous hollow microspheric VCrO composite oxides for chlorotoluenes ammoxidation 多孔空心微球VCrO复合氧化物在氯甲苯氨氧化中的优异性能

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-10 DOI: 10.1016/j.apcata.2025.120694

Yuan Chen , Jiale Tong , Wanjun Tang, Lang Sun, Tingcheng Li, Guangyong Xie

Porous vanadium-chromium oxide (VCrO) hollow microspheres were synthesized for the first time via glucose-assisted hydrothermal method, and the effect of glucose ratio on their morphology and catalytic performance was investigated. It was found that glucose addition induced a morphological transformation, resulting in marked enhancement in catalytic performance. Notably, compared to the glucose-free catalyst VCr-G₀, at a glucose/V₂O₅ molar ratio of 3, the catalyst VCr-G₃ formed porous hollow microspheres with a diameter of approximately 5 μm. This new structure exhibited a more than fourfold increase in specific surface area and a threefold increase in pore volume, which substantially facilitated active site exposure and the interaction between active centers and reactants. Furthermore, the addition of glucose significantly improved the catalyst's redox properties and acidity. The reduction temperature decreased by over 30 °C, while the moderate-strength acidic site density increased significantly from 0.085 mmol/g (VCr-G₀) to 0.163 mmol/g (VCr-G₃). These enhanced properties promote both ammonia chemisorption and desorption of reaction intermediates, which collectively contribute to a marked boost in catalytic performance. Comparative studies revealed that the glucose-modified catalyst demonstrated excellent activity in the ammoxidation of ortho-, meta-, and para-chlorotoluenes.

采用葡萄糖辅助水热法首次合成了多孔氧化钒铬（VCrO）空心微球，并研究了葡萄糖配比对其形貌和催化性能的影响。结果表明，葡萄糖的加入引起了其形态的转变，从而显著提高了其催化性能。值得注意的是，与无葡萄糖催化剂VCr-G0相比，在葡萄糖/V2O5摩尔比为3时，催化剂VCr-G3形成了直径约为5 μm的多孔空心微球。这种新结构的比表面积增加了4倍以上，孔隙体积增加了3倍，极大地促进了活性位点的暴露以及活性中心与反应物之间的相互作用。此外，葡萄糖的加入显著改善了催化剂的氧化还原性能和酸度。还原温度降低30 ℃以上，中强酸性位点密度由0.085 mmol/g （VCr-G0）显著提高到0.163 mmol/g （VCr-G3）。这些增强的性能促进了氨的化学吸附和反应中间体的解吸，这共同促进了催化性能的显著提高。比较研究表明，葡萄糖修饰的催化剂在邻氯甲苯、间氯甲苯和对氯甲苯的氨氧化反应中表现出优异的活性。

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引用次数: 0

Doped In2O3/ZrO2 catalysts to drive selectivity toward DME in one-pot CO2 hydrogenation 掺杂In2O3/ZrO2催化剂在一锅CO2加氢中对二甲醚的选择性驱动

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-08 DOI: 10.1016/j.apcata.2025.120682

Simona Renda, Jaime Soler, Miguel Menéndez, Javier Herguido

This study investigates single-pass dimethyl ether synthesis at mild pressure conditions using novel bifunctional catalysts based on indium-modified formulations and incorporating Ni, Cu, Pt, and Pd as active metals. Additionally, the substitution of the conventional HZSM-5 zeolite with 4A zeolite as the dehydration component was evaluated. Although 4A zeolite exhibited lower dehydration activity, it contributed to an overall improvement in DME selectivity. The incorporation of secondary metals into the In₂O₃-ZrO₂ formulation reduced catalytic activity but enhanced selectivity, ultimately increasing DME yield. The formation of by-products such as light olefins and methane was significantly dependent on the metal used: Ni, Pt, and Pd reduced olefin production, though Ni promoted excessive methane formation across the whole temperature range. Notably, the Pt-based catalyst completely suppressed by-product formation across the temperature range studied. While the In₂O₃-ZrO₂-based catalysts generally displayed lower space–time yields than the commercial reference, they achieved comparable performance at 280 °C. Due to their superior selectivity, these formulations are promising for developing even better performing catalysts, to be excellent candidates in industrial processes, where the operation with recycle loops requires a high product purity.

本研究研究了在温和的压力条件下，使用基于铟改性配方的新型双功能催化剂，并加入Ni， Cu， Pt和Pd作为活性金属，进行单道二甲醚合成。此外，还对4A沸石代替HZSM-5沸石作为脱水组分进行了评价。虽然4A分子筛脱水活性较低，但其对二甲醚的选择性总体上有所提高。在In2O3-ZrO2配方中加入二次金属降低了催化活性，但提高了选择性，最终提高了二甲醚的收率。副产物如轻烯烃和甲烷的形成很大程度上取决于所使用的金属：Ni、Pt和Pd降低了烯烃产量，尽管Ni在整个温度范围内促进了过量的甲烷生成。值得注意的是，在研究的温度范围内，pt基催化剂完全抑制了副产物的形成。虽然基于in2o3 - zro2的催化剂的时空产率通常低于商业参考，但它们在280°C下取得了相当的性能。由于其优越的选择性，这些配方有望开发出性能更好的催化剂，在工业过程中是极好的候选者，其中循环循环操作需要高产品纯度。

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引用次数: 0

Selective methanol-to-dimethyl ether conversion in a through-flow γ-Al2O3 catalytic membrane contactor: Performance and comparative analysis 通流γ-Al2O3催化膜接触器中选择性甲醇转化为二甲醚：性能和比较分析

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-08 DOI: 10.1016/j.apcata.2025.120683

Elisa Avruscio , Adele Brunetti , Enrico Catizzone , Massimo Migliori , Girolamo Giordano , Giuseppe Barbieri

Dimethyl ether (DME) is a clean and efficient alternative fuel and chemical intermediate, typically produced by methanol dehydration over solid acid catalysts. In this study, the catalytic performance of a γ-Al₂O₃ membrane operated in a through-flow configuration was evaluated for DME production. The membrane exhibited high methanol conversion and complete DME selectivity (100 %) over the 260–300 °C temperature range, showing optimal performance at 280°C and low WHSV (0.4 h⁻¹), where equilibrium conditions are approached. Comparative tests with γ-Al₂O₃ pellets demonstrated the membrane superior selectivity and enhanced stability with the time-on-stream. A 30-hour time-on-stream experiment showed a good resistance of membrane to deactivation, with catalytic activity fully restored through a thermal regeneration step. The γ-Al₂O₃ membrane was further benchmarked against literature-reported ZSM-5 and BEA zeolite membranes, showing better performance in the explored operating conditions.

二甲醚（DME）是一种清洁高效的替代燃料和化学中间体，通常由固体酸催化剂上的甲醇脱水产生。在这项研究中，研究了γ-Al2O3膜在通流配置下对二甲醚生产的催化性能。在260-300°C的温度范围内，膜表现出高的甲醇转化率和完全的二甲醚选择性（100 %），在280°C和较低的WHSV（0.4 h−1）下表现出最佳性能，接近平衡条件。与γ-Al2O3微球的对比实验表明，该膜具有较好的选择性和较强的稳定性。30小时的流上时间实验表明，膜具有良好的抗失活能力，通过热再生步骤完全恢复催化活性。γ-Al2O3膜进一步与文献报道的ZSM-5和BEA沸石膜进行了基准测试，在探索的操作条件下表现出更好的性能。

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引用次数: 0

Comparative study of multi-element modification and rhodium promotion of Co3O4-based spinel catalysts for N2O decomposition co3o4基尖晶石催化剂分解N2O的多元素改性与铑促进对比研究

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-08 DOI: 10.1016/j.apcata.2025.120681

Daniel C. Cano-Blanco , Jarne van Aubel , Silvio Bellomi , Ivo Alxneit , Karin Föttinger , Oliver Kröcher , Davide Ferri

The removal of nitrous oxide (N₂O) from industrial flue gases remains a significant environmental challenge due to the intrinsic kinetic stability of the N₂O molecule. Among available abatement technologies, the direct catalytic decomposition of N₂O into harmless N₂ and O₂ (deN₂O) represents a promising, reagent-free solution. In this study, we systematically screened a series of catalysts obtained from Co₃O₄ by addition of transition elements, magnesium and aluminum (10 wt%), and analog series with addition of rhodium (Rh; 1 wt%), from which Co-Al-Rh emerged as the most active catalyst formulation. Characterization by H₂-TPR and XPS indicated improvement in the redox performance and increasing weakening of the Co-O bond upon addition of a second element and of Rh. The addition of Rh resulted also in a significant enhancement in catalytic activity. Complementary kinetic studies revealed a shift in the rate-determining step (RDS) between N-O bond cleavage and O₂ desorption, depending on catalyst composition. These results highlight the critical role of Co-O bond weakening in facilitating oxygen mobility and promoting activity.

由于N2O分子固有的动力学稳定性，从工业烟气中去除一氧化二氮（N2O）仍然是一个重大的环境挑战。在现有的治理技术中，直接催化分解N2O为无害的N2和O2 （deN2O）是一种很有前途的无试剂解决方案。在这项研究中，我们系统地筛选了一系列由Co3O4添加过渡元素，镁和铝（10 wt%）得到的催化剂，以及添加铑（1 wt%）的模拟系列，其中Co-Al-Rh成为最活跃的催化剂配方。H2-TPR和XPS表征表明，添加第二元素和Rh后，Co-O键的氧化还原性能得到改善，Co-O键的减弱程度增加。Rh的加入也显著提高了催化活性。互补动力学研究表明，N-O键裂解和O2脱附之间的速率决定步骤（RDS）发生了变化，这取决于催化剂的组成。这些结果突出了Co-O键减弱在促进氧迁移和促进活性方面的关键作用。

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引用次数: 0

Machine learning for mechanistic insights and optimization in CO₂ cycloaddition catalysis 机器学习在CO₂环加成催化中的机理洞察和优化

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2025-11-07 DOI: 10.1016/j.apcata.2025.120679

Yasmin Abdul Wahab, Nur’ain Nadia Shapril, Suzaimi Johari, Mohd Rafie Johan

Converting CO₂ into cyclic carbonates via cycloaddition with epoxides is a key catalytic process for sustainable chemical synthesis and carbon mitigation, with 100 % atom economy. Machine learning (ML) drives catalyst design, reaction optimization, and mechanistic insights, achieving predictive accuracies up to R² = 0.99. This review (2020–2025) covers ionic liquids, metal-organic frameworks, and single-atom catalysts, achieving > 90 % yields at ambient conditions with activation energies of 10–20 kcal/mol. Despite challenges like dataset biases, the novel UniDesc-CO2 framework scales datasets to > 10,000 entries using standardized descriptors and active learning. Explainable AI (e.g., SHAP) clarifies descriptors like anion nucleophilicity, advancing sustainable CO₂ cycloaddition catalysis for scalable processes.

通过与环氧化物的环加成将CO 2转化为环状碳酸盐是可持续化学合成和碳减排的关键催化过程，具有100% %的原子经济性。机器学习（ML）驱动催化剂设计，反应优化和机理洞察，实现预测精度高达R²= 0.99。这篇综述（2020-2025）涵盖了离子液体、金属有机框架和单原子催化剂，在环境条件下达到了>； 90 %的产率，活化能为10-20 kcal/mol。尽管存在数据集偏差等挑战，但新的联合国环境规划署-二氧化碳框架使用标准化描述符和主动学习将数据集扩展到 10,000个条目。可解释的AI（例如，SHAP）澄清了阴离子亲核性等描述符，推进了可扩展过程的可持续CO₂环加成催化。

引用次数: 0