Journal of Catalysis最新文献_第6页

Photocatalytic H2 production from HCOOH over Pd/TiO2: Pd2+/Pd0 self-cycle and adsorption-induced electron transfer mechanism HCOOH在Pd/TiO2上光催化制氢：Pd2+/Pd0自循环及吸附诱导的电子转移机理

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-12 DOI: 10.1016/j.jcat.2026.116697

Hong Wang , Yan Wang , Yong Jia , Lina Guo , Gang Cheng , Zhongming Wang , Kai Yang , Wenxin Dai

Research on the photocatalytic production of H₂ from HCOOH decomposition provides scientific guidance for hydrogen energy development. In this study, a Pd-doped oxygen-deficient TiO₂ catalyst featuring mixed-valence PdO_x atomic cluster nests, oxygen vacancies (Vo), and hydroxyl groups was synthesized. Activity tests revealed that 0.4 Pd-def-TiO₂ sample performed best under visible light, producing H₂ at a rate of 3180.66 μmol·g⁻¹·h⁻¹, a 124-fold enhancement over def-TiO₂. Combined characterization and theoretical calculation results showed that Pd-def-TiO₂ formed a “step-like” energy band structure, and the separation and transfer of photogenerated carriers have been optimized in conjunction with Vo and surface hydroxyl groups. Further, HCOOH adsorption was followed by the formation of a bidentate HCOO_BX species, in which one oxygen atom of the adsorbate was hydrogen bonded with a surface hydroxyl group, while the other end was adsorbed onto a Pd⁰ site. This process involved simultaneous electron loss and gain, resulting in a distinctive “valley-shaped” gas-sensing response, thus promoting directional activation of HCOOH, facilitating complete redox reactions. Moreover, photoreduction and Vo (near Pd sites) promoted electron delocalization in mixed-valent Pd²⁺/Pd⁰ species, enabling self-cycling of these active sites, leading to enhanced efficiency and stability during photocatalytic hydrogen evolution from HCOOH. This study contributes to the design of highly efficient and stable catalysts, and advances the understanding of the underlying reaction mechanisms.

HCOOH分解光催化制氢研究为氢能开发提供了科学指导。在本研究中，合成了一种具有混合价PdOx原子簇巢、氧空位（Vo）和羟基的掺杂pd的缺氧TiO2催化剂。活性测试表明，0.4 Pd-def-TiO2样品在可见光下的产氢速率为3180.66 μmol·g−1·h−1，比def-TiO2提高了124倍。结合表征和理论计算结果表明，Pd-def-TiO2形成了“阶梯状”能带结构，并结合Vo和表面羟基优化了光生载流子的分离和转移。此外，HCOOH吸附后形成双齿状HCOOBX，其中吸附物的一个氧原子与表面羟基形成氢键，而另一端被吸附在Pd0位点上。该过程涉及电子的同时损失和获得，导致独特的“谷形”气敏响应，从而促进HCOOH的定向活化，促进完整的氧化还原反应。此外，光还原和Vo（靠近Pd位点）促进了混合价Pd2+/Pd0的电子离域，使这些活性位点能够自循环，从而提高了HCOOH光催化析氢过程的效率和稳定性。该研究有助于设计高效、稳定的催化剂，并促进对潜在反应机理的理解。

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引用次数: 0

Bio-derived quantum dot based luminescent solar concentrator for photocatalytic conversion of fructose to 5-hydroxymethylfurfural via iron(II) complex catalysis 利用铁（II）配合物催化将果糖转化为5-羟甲基糠醛的生物衍生量子点发光太阳能聚光器

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-12 DOI: 10.1016/j.jcat.2026.116701

Mohammad Bashiri, Mona Hosseini-Sarvari

In the present study, a novel benzimidazole ligand was synthesized and used as a precursor for the preparation of iron(II) complex. Following the synthesis, a comprehensive array of experimental investigations was undertaken to explore the structural, photo-electronic, and electrochemical characteristics of the iron(II) complex. The complex was subsequently utilized as an efficient photocatalyst for the selective synthesis of 5-hydroxymethylfurfural (HMF) from fructose. In this catalytic process, a luminescent solar concentrator (LSC) system was employed, further augmented by plant-derived quantum dots. This innovative optical system significantly enhanced the overall efficiency of the photocatalytic reaction. We selected a colorless transparent panel for the LSC device because the emission from the quantum dots falls within the blue region, which overlaps with the absorption spectrum of our complex and can promote the progress of the reaction. The yield of 5-hydroxymethylfurfural from fructose in this continuous flow system under solar irradiation was 91%, whereas in the batch system, a yield of only 70% was achieved under blue light irradiation. Furthermore, this work contributes novel insights into the potential of iron(II) complex-based photocatalysts for driving intricate chemical transformations under environmentally benign and sustainable conditions.

本研究合成了一种新型苯并咪唑配体，并将其作为制备铁（II）配合物的前驱体。在合成之后，进行了一系列全面的实验研究，以探索铁（II）配合物的结构、光电和电化学特性。该配合物随后被用作果糖选择性合成5-羟甲基糠醛（HMF）的有效光催化剂。在该催化过程中，采用了发光太阳能聚光器（LSC）系统，并通过植物衍生的量子点进一步增强。这种创新的光学系统显著提高了光催化反应的整体效率。我们选择了一个无色透明的面板作为LSC器件，因为量子点的发射落在蓝色区域，这与我们的配合物的吸收光谱重叠，可以促进反应的进行。该连续流系统在太阳照射下从果糖中提取5-羟甲基糠醛的收率为91%，而在批处理系统中，蓝光照射下的收率仅为70%。此外，这项工作为铁（II）配合物基光催化剂在环境友好和可持续条件下驱动复杂化学转化的潜力提供了新的见解。

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引用次数: 0

CO2-promoted photocatalytic oxidation of benzylic alcohols over CdS/boron-doped carbon nitride 二氧化碳促进苯甲醇在CdS/硼掺杂氮化碳上的光催化氧化

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-12 DOI: 10.1016/j.jcat.2026.116699

Chenglong Liang , Shuwen Huan , Xiong Chen , Jimmy C. Yu , Meifang Zheng , Sibo Wang

Catalytic oxidation of alcohols to the corresponding carbonyl compounds represents a fundamental transformation in the chemical industry. Herein, we report a novel type-II heterojunction comprising CdS quantum dots (QDs) anchored on boron-doped carbon nitride (BCN) nanosheets is explored for the photocatalytic selective oxidation of benzylic alcohols under an ambient CO₂ atmosphere. The CdS QDs/BCN system manifests substantially enhanced performance, achieving 81% yield of benzaldehyde with 99% selectivity, much higher than either bare BCN or CdS QDs. In this catalytic system, CO₂ is adsorbed and activated at the surface basic sites of CdS QDs/BCN, forming the key carbonate intermediates with benzylic alcohols, which are then selectively oxidized by photoinduced holes, accompanied by the release of CO₂. The protocol demonstrates acceptorless dehydrogenation using CO₂ as an electron shuttle, providing a green and efficient strategy for oxidant-free alcohol oxidation.

醇催化氧化生成相应的羰基化合物代表了化学工业的一个根本转变。在此，我们报道了一种新型ii型异质结，包括锚定在硼掺杂氮化碳（BCN）纳米片上的CdS量子点（QDs），用于在环境CO2气氛下光催化选择性氧化苯基醇。CdS量子点/BCN体系性能显著提高，苯甲醛收率达到81%，选择性达到99%，远高于纯BCN或CdS量子点。在该催化体系中，CO2在CdS QDs/BCN的表面碱性位点被吸附和活化，与苯基醇形成关键的碳酸盐中间体，然后被光诱导孔选择性氧化，同时释放CO2。该方案展示了利用CO2作为电子穿梭的无受体脱氢，为无氧化剂的酒精氧化提供了一种绿色高效的策略。

引用次数: 0

Nitrogen-doped manganese oxide catalysts boost oxidative cyanation of benzyl alcohols 氮掺杂氧化锰催化剂促进苯甲醇氧化氰化反应

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-08 DOI: 10.1016/j.jcat.2026.116688

Liping Tan, Li Fang, Yao Zhang, Jinglin Tong, Yuxin Zhuang, Chunya Li, Lianqing Chen, Shiwei Jin

Environmentally friendly liquid-phase selective oxidation of alcohols with oxygen as oxidant agent is a green strategy for synthesising nitriles and amides. Therein, the design and preparation of heterogeneous catalysts with high activity and selectivity is a hot research topic in this field. Here, we report that nitrogen-doped manganese oxide catalysts have been synthesized by a hydrothermal method, which can oxidize benzyl alcohol to synthesize benzonitrile and benzamide in a cyanide-free environment with high efficiency. As the reaction time and temperature were 6 h and 150 °C, the conversion of benzyl alcohol (feed dosage: 1 mmol) and the selectivity of benzamide were >99 % and 94 %, respectively. The catalyst could be reused at least 5 times without significantly reducing activity. Additionally, the catalyst exhibits broad applicability, capable of catalyzing the cyanidation of various aromatic and aliphatic alcohols. The enhancement in N-MnO₂ catalyst performance is attributed to the introduction of nitrogen, which increases the content of low-valent manganese and oxygen vacancies within the catalyst. It contributes to improved selectivity for benzamide.

以氧为氧化剂的醇类环境友好型液相选择性氧化是合成腈和酰胺的一种绿色策略。其中，设计和制备高活性、高选择性的多相催化剂是该领域的研究热点。本文报道了用水热法合成了氮掺杂氧化锰催化剂，该催化剂可以在无氰环境下高效氧化苯甲醇合成苯腈和苯酰胺。反应时间为6 h，反应温度为150 ℃时，苯甲醇（投料量为1 mmol）的转化率为99 %，苯酰胺的选择性为94 %。该催化剂可重复使用至少5次而不显著降低活性。此外，该催化剂具有广泛的适用性，能够催化各种芳香族和脂肪族醇的氰化反应。N-MnO2催化剂性能的提高主要是由于氮的引入增加了催化剂中低价锰的含量和氧空位。它有助于提高苯甲酰胺的选择性。

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引用次数: 0

Corrigendum to “Robust rGO-supported α-FeOOH/Fe2O3 nanorods catalyst: Unveiling the role of χ-Fe5C2 phase and rGO for exceptional stability in Fischer–Tropsch synthesis”. [J. Catal. 453 (2026) 116584] “稳健的rGO负载α-FeOOH/Fe2O3纳米棒催化剂：揭示χ-Fe5C2相和rGO在费托合成中特殊稳定性的作用”的勘误。[J。Catal. 453 (2026) 116584]

IF 7.3 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-07 DOI: 10.1016/j.jcat.2025.116666

Juan Zhang, Mohamed Abbas, Weibin Fan, Jiangang Chen

The authors regret that the CRediT authorship contribution statement was incomplete in the published version of the article.

作者感到遗憾的是，在文章的发表版本中，信用作者贡献声明不完整。

引用次数: 0

Kinetic study and modeling of the process for the methyl pelargonate synthesis by 1-octene methoxycarbonylation using CO and the catalytic system Pd(OAc)2–PPh3–p-toluenesulfonic acid CO催化体系Pd(OAc)2 - pph3 -对甲苯磺酸催化1-辛烯甲氧羰基化合成对虾精酸甲酯的动力学研究与建模

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-07 DOI: 10.1016/j.jcat.2026.116674

Nadezhda T. Sevostyanova, Sergey A. Batashev, Dar’ya K. Kozlenko

A kinetic study of the 1-octene methoxycarbonylation has been carried out. The target product of the reaction is methyl pelargonate (MP), which is of interest as an intermediate for pharmaceutical syntheses. Using the Pd(OAc)₂/PPh₃/TsOH (TsOH is p-toluenesulfonic acid) as a catalytic system, the 1-octene methoxycarbonylation proceeded regioselectively for MP and was complicated by the formation of only branched esters. Under mild conditions, TOF could achieve values of more than 10^-2 s⁻¹, which opens up the possibility this reaction implementing in industry. A model of reaction selectivity for MP and a kinetic model of the reaction have been obtained. These models are the necessary basis to develop the MP synthesis reactor and the technology for producing this product. Optimal conditions for the 1-octene methoxycarbonylation have been found. The interpretation of the established regularities for the reaction has been given within the framework of the hydride mechanism scheme supplemented by reactions of the low-activity Pd-complexes formation.

对1-辛烯甲氧基羰基化反应进行了动力学研究。该反应的目标产物是过氧化氢甲酯（MP），作为药物合成的中间体很有兴趣。以Pd(OAc)2/PPh3/TsOH （TsOH为对甲苯磺酸）为催化体系，MP的1-辛烯甲氧基羰基化反应是区域选择性的，并且只生成支链酯。在温和的条件下，TOF可以达到10-2 s−1以上的值，这为该反应在工业上实施开辟了可能性。建立了MP的反应选择性模型和反应动力学模型。这些模型是开发MP合成反应器和生产该产品技术的必要依据。找到了1-辛烯甲氧基羰基化反应的最佳条件。在氢化物机理方案的框架内，辅以低活性钯络合物形成的反应，对已建立的反应规律进行了解释。

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引用次数: 0

Synergistic effect of Cu+-Cu0 sites and oxygen vacancies at MOF-derived Cu-ZrO2 interface for the reverse water–gas shift reaction mof衍生Cu- zro2界面上Cu+-Cu0位点和氧空位的协同效应对逆向水气转移反应的影响

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-07 DOI: 10.1016/j.jcat.2026.116679

Huilin Zhou , Yahui Yang , Riying Zeng, Zhenzhen Huang, Qihan Huang, Yidan Li, Lihua Wang

The development of efficient and stable catalysts for the reverse water–gas shift (RWGS) reaction is crucial for mitigating CO₂ emissions. Although cost-effective, conventional copper-based catalysts suffer from valence fluctuations (between Cu⁺ and Cu⁰) and particle sintering. This study developed a Cu/ZrO₂ catalyst via a metal–organic framework (MOF) derivation strategy to enhance the interaction at Cu-ZrO₂ interface and the catalyst stability. Using a bimetallic MOF-818 as a precursor, the Cu/ZrO₂-MOF catalyst was prepared through pyrolysis/reduction. The catalyst exhibited abundant oxygen vacancies (19.1%) and an optimized Cu⁺/Cu⁰ ratio (1.12). Under RWGS conditions, CO₂ conversion reached 39.5% with complete CO selectivity at 450 ℃, surpassing the performance of conventional catalysts. Notably, it showed no significant deactivation over 224 h, including a period under high gas hourly space velocity. Post-reaction characterization confirmed the stability of active sites, which is attributed to the metal-support interaction. Mechanistic studies revealed a synergistic effect at the interface, whereby CO₂ is activated by Cu⁺ sites and oxygen vacancies, while H₂ is dissociated on Cu⁰ sites, which elucidates the synergistic mechanism of interfacial active sites and thus provides a general design strategy for developing sinter-resistant and high-performance Cu-based catalysts.

开发高效、稳定的水气反向变换（RWGS）催化剂对减少二氧化碳排放至关重要。尽管具有成本效益，但传统的铜基催化剂存在价态波动（在Cu+和Cu0之间）和颗粒烧结问题。本研究通过金属-有机骨架（MOF）衍生策略开发了Cu/ZrO2催化剂，以增强Cu-ZrO2界面的相互作用和催化剂的稳定性。以双金属MOF-818为前驱体，通过热解/还原法制备Cu/ZrO2-MOF催化剂。催化剂具有丰富的氧空位（19.1%）和优化的Cu+/Cu0比（1.12）。在RWGS条件下，450℃下CO2转化率达到39.5%，CO选择性完全，超过了常规催化剂的性能。值得注意的是，在224 h内，包括在高气体每小时空间速度下的一段时间内，它没有显示出明显的失活。反应后表征证实了活性位点的稳定性，这归因于金属-载体相互作用。机理研究揭示了界面上的协同效应，即CO2被Cu+位点和氧空位激活，而H2在Cu0位点解离，这阐明了界面活性位点的协同机制，从而为开发抗烧结和高性能的Cu基催化剂提供了总体设计策略。

{"title":"Synergistic effect of Cu+-Cu0 sites and oxygen vacancies at MOF-derived Cu-ZrO2 interface for the reverse water–gas shift reaction","authors":"Huilin Zhou , Yahui Yang , Riying Zeng, Zhenzhen Huang, Qihan Huang, Yidan Li, Lihua Wang","doi":"10.1016/j.jcat.2026.116679","DOIUrl":"10.1016/j.jcat.2026.116679","url":null,"abstract":"<div><div>The development of efficient and stable catalysts for the reverse water–gas shift (RWGS) reaction is crucial for mitigating CO<sub>2</sub> emissions. Although cost-effective, conventional copper-based catalysts suffer from valence fluctuations (between Cu<sup>+</sup> and Cu<sup>0</sup>) and particle sintering. This study developed a Cu/ZrO<sub>2</sub> catalyst via a metal–organic framework (MOF) derivation strategy to enhance the interaction at Cu-ZrO<sub>2</sub> interface and the catalyst stability. Using a bimetallic MOF-818 as a precursor, the Cu/ZrO<sub>2</sub>-MOF catalyst was prepared through pyrolysis/reduction. The catalyst exhibited abundant oxygen vacancies (19.1%) and an optimized Cu<sup>+</sup>/Cu<sup>0</sup> ratio (1.12). Under RWGS conditions, CO<sub>2</sub> conversion reached 39.5% with complete CO selectivity at 450 ℃, surpassing the performance of conventional catalysts. Notably, it showed no significant deactivation over 224 h, including a period under high gas hourly space velocity. Post-reaction characterization confirmed the stability of active sites, which is attributed to the metal-support interaction. Mechanistic studies revealed a synergistic effect at the interface, whereby CO<sub>2</sub> is activated by Cu<sup>+</sup> sites and oxygen vacancies, while H<sub>2</sub> is dissociated on Cu<sup>0</sup> sites,which elucidates the synergistic mechanism of interfacial active sites and thus provides a general design strategy for developing sinter-resistant and high-performance Cu-based catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116679"},"PeriodicalIF":6.5,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908155","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

α-Diimine cobalt complexes bearing axial anagostic interaction: a system for accessing ultra-high molecular weight polybutadiene α-二亚胺钴配合物轴向逆流作用：一种获取超高分子量聚丁二烯的体系

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-07 DOI: 10.1016/j.jcat.2026.116676

Haidong Zhang , Xin Wang , Feng Wang , Xiaohua Wang , Lishuang Ma , Xuequan Zhang , Heng Liu

cis-1,4-Polybutadiene (PBd) with ultra-high molecular weight typically exhibits significantly enhanced mechanical properties, including tear resistance, durability, and tensile strength, etc. Nevertheless, due to inevitable chain transfer reactions during polymerization, achieving such polymers currently remains a major challenge. In this work, we designed a series of α-diimine cobalt complexes featuring axial Co⋯H–C anagostic interactions. When being employed for butadiene polymerization, these complexes not only demonstrated high catalytic activity and excellent cis-1,4-selectivity, but also significantly suppressed chain transfer reactions, enabling the production of polybutadienes with ultra-high molecular weight, markedly exceeding those obtained from cobalt counterparts lacking such interactions.

具有超高分子量的顺式-1,4-聚丁二烯（PBd）通常具有显著增强的机械性能，包括抗撕裂性、耐久性和拉伸强度等。然而，由于聚合过程中不可避免的链转移反应，实现这种聚合物目前仍然是一个主要挑战。在这项工作中，我们设计了一系列具有轴向Co⋯H-C解析相互作用的α-二亚胺钴配合物。当用于丁二烯聚合时，这些配合物不仅表现出高的催化活性和优异的顺式-1,4选择性，而且还能显著抑制链转移反应，从而产生超高分子量的聚丁二烯，明显超过缺乏这种相互作用的钴对应物。

引用次数: 0

Xantphos-derived porous polymer: a robust solid-state ligand for efficient Pd-catalyzed alkoxycarbonylation of alkenes from mono-alcohols to polyols 黄磷衍生的多孔聚合物：一种强大的固体配体，用于高效的pd催化烯烃从单醇到多元醇的烷氧羰基化

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-06 DOI: 10.1016/j.jcat.2026.116677

Yuyong Zhang , Yuanjun Zhao , Yuanyuan Zhu , Yudi Wu , Zhaozhan Wang , Jinglin Mu , Yong Yang

The integration of superior homogeneous catalytic activity with the practical advantages of facile separation and robust recyclability of heterogeneous systems remains a grand challenge. Here, we report a heterogenized bidentate phosphine ligand, constructed by integrating commercial Xantphos into a hypercrosslinked porous polymer, as a versatile platform for Pd-catalyzed alkoxycarbonylation. The tailored polymer, featuring a high surface area, hierarchical pores, and chemical robustness, provides privileged coordination microenvironments. It empowers highly efficient alkoxycarbonylation of diverse alkenes with various alcohols, including monoalcohols, diols, and polyols, to produce valuable esters with activity and selectivity comparable to its homogeneous molecular counterpart. Moreover, the catalytic system enables the in-situ formation of a robust Pd catalyst, wherein Pd nanoparticles are stabilized and uniformly dispersed via strong Pd-P coordination. This resulting catalyst demonstrates exceptional durability, being readily recycled over ten times without significant degradation in performance. This work pioneers a versatile platform for ligand immobilization that effectively bridges homogeneous efficiency with heterogeneous durability, unlocking efficient and sustainable pathways for carbonylation and other ligand-mediate transformations.

将优异的均相催化活性与多相系统的易于分离和强大的可回收性的实际优势相结合仍然是一个巨大的挑战。在这里，我们报道了一种异质双齿膦配体，通过将商业Xantphos整合到超交联多孔聚合物中构建，作为pd催化烷氧羰基化的通用平台。这种定制聚合物具有高表面积、分层孔隙和化学稳定性，提供了优越的配位微环境。它使各种烯烃与各种醇（包括单醇、二醇和多元醇）进行高效的烷氧羰基化反应，产生具有活性和选择性的有价值的酯类，与其同质分子对应物相当。此外，该催化体系能够原位形成强大的Pd催化剂，其中Pd纳米颗粒通过强Pd- p配位稳定并均匀分散。由此产生的催化剂表现出优异的耐久性，易于回收超过十次而不会显著降低性能。这项工作开创了一个多功能的配体固定平台，有效地连接了均匀效率和异质耐久性，为羰基化和其他配体介导的转化打开了有效和可持续的途径。

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引用次数: 0

Design of stable and active (NHC)Pd–phosphine catalysts for the synthesis of high-molecular-weight norbornene-based polymers 合成高分子量降冰片烯基聚合物的稳定和活性（NHC） pd -膦催化剂的设计

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-01-06 DOI: 10.1016/j.jcat.2026.116678

Anna P. Khrychikova , Evgeniya V. Bermesheva , Nadezhda V. Nesterova , Anastasia A. Danshina , Yulia V. Nelyubina , Maxim V. Bermeshev

A series of cationic palladium complexes of the composition [(NHC)Pd(allyl)(PR₃)]⁺BARF⁻ containing N-heterocyclic carbene (NHC) and phosphine ligands of different nature, and a weakly coordinating borate anion were synthesized. Such Pd complexes were for the first time investigated as single-component catalysts for vinyl-addition polymerization of norbornene and its functionalized derivatives. The complexes exhibit high catalytic activity without the need for co-catalysts (to 7·10⁶ g_polymer/mol_Pd h). Polymers synthesized over these Pd complexes in question are characterized by unimodal GPC curves, narrow molecular weight distributions, and linear dependence of the molecular weight on the monomer conversion, which suggests the occurrence of controlled polymerization. It was demonstrated that both the structure of NHC and the nature of phosphine ligand have strong effect on catalytic activity and initiation efficiency. A correlation between Pd—P bond length and the behavior of the complex in the polymerization reaction was revealed, viz.: the shorter Pd—P bond the lower the lability of the phosphine, the initiation efficiency, and the higher the molecular weights of the resulting polymers. As a result, polymerization on the title complexes allows one to obtain polymers with much higher molecular weights compared to polymers synthesized using similar (NHC)Pd systems with other labile ligands. Besides, the synthesized complexes demonstrate high thermal stability and retain their catalytic activity at elevated temperatures. Generally, the presence of the NHC and phosphine ligands in palladium coordination sphere provides a unique balance between the activity, stability, and possibility to obtain high-molecular-weight products. This makes the complexes in hand promising catalysts for targeted synthesis of functional polymeric materials.

合成了一系列由[(NHC)Pd（烯丙基）（PR3）]+BARF−组成的含不同性质n -杂环碳（NHC）和膦配体的阳离子钯配合物，以及弱配位硼酸阴离子。本文首次研究了Pd配合物作为降冰片烯及其功能化衍生物乙烯加成聚合的单组分催化剂。该配合物在不需要助催化剂的情况下表现出较高的催化活性（达到7·106 gpolymer/molPd h）。在这些Pd配合物上合成的聚合物具有单峰GPC曲线、较窄的分子量分布和分子量与单体转化率的线性关系，表明存在可控聚合。结果表明，NHC的结构和膦配体的性质对催化活性和引发效率有很大影响。Pd-P键长度与配合物在聚合反应中的行为存在相关性，即：Pd-P键越短，磷化氢的稳定性越低，引发效率越高，所得聚合物的分子量越高。因此，在标题配合物上的聚合使人们可以获得比使用类似的（NHC）Pd体系与其他不稳定配体合成的聚合物高得多的分子量的聚合物。此外，合成的配合物表现出较高的热稳定性，并在高温下保持其催化活性。通常，钯配位球中NHC和膦配体的存在在活性、稳定性和获得高分子量产物的可能性之间提供了独特的平衡。这使得这些配合物有望成为定向合成功能高分子材料的催化剂。

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引用次数: 0