Applied Catalysis A: General最新文献_第4页

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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引用次数: 0

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

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

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

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