Journal of Catalysis最新文献

英文中文

Selective hydrogenation of quinoline catalyzed by Ni/TiO2-Al2O3: role of TiO2 in promoting hydrogen spillover Ni/TiO2- al2o3催化喹啉选择性加氢：TiO2促进氢溢出的作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-06 DOI: 10.1016/j.jcat.2026.116730

Hong Zhao , Tongtong Fan , Chuang Liu , Huaguang Tong , Tong Li , Jiantai Ma , Zhengping Dong

Efficient hydrogen activation and spillover remain critical challenges limiting the hydrogenation efficiency of heterogeneous catalytic systems. To address this limitation, we developed a TiO₂ modification strategy involving the in-situ formation of reducible TiO₂ on Al₂O₃, resulting in a Ni/TiO₂-Al₂O₃ catalyst with enhanced hydrogen spillover efficiency. The modified catalyst exhibits significantly improved activity for the selective hydrogenation of quinoline under identical reaction conditions. Comprehensive characterization and experimental results demonstrate that TiO₂ incorporation facilitates H₂ activation and generates abundant hydrogen migration pathways, thereby increasing the concentration of active hydrogen species on the Al₂O₃ surface. DFT calculations further confirm that the hydrogen migration barrier at the TiO₂-Al₂O₃ interface is lower than that of pure Al₂O₃, offering theoretical support for the enhanced spillover efficiency. Meanwhile, the spatial separation between quinoline adsorption sites, Lewis acid of Al₂O₃ and hydrogen activation sites, Ni nanoparticles, directly drive the enhanced hydrogenation performance. Furthermore, the use of an i-PrOH/ H₂O mixed solvent significantly enhances catalysis, as water mediates the spillover of active hydrogen species from the catalyst into the aqueous phase, where they participate in the reaction via a Grotthuss proton-hopping mechanism, as evidenced by NMR. Delayed feeding experiments demonstrate that hydrogen stored in the aqueous phase can still drive quinoline hydrogenation even after H₂ removal, highlighting the importance of both solid- and liquid-phase hydrogen transfer. This dual-phase spillover strategy offers a promising avenue for designing highly efficient heterogeneous catalytic hydrogenation systems.

有效的氢活化和溢出仍然是限制多相催化系统加氢效率的关键挑战。为了解决这一限制，我们开发了一种TiO2改性策略，包括在Al2O3上原位形成可还原的TiO2，从而产生具有增强氢溢出效率的Ni/TiO2-Al2O3催化剂。在相同的反应条件下，改性后的催化剂对喹啉的选择性加氢反应活性显著提高。综合表征和实验结果表明，TiO2的掺入促进了H2的活化，产生了丰富的氢迁移途径，从而增加了Al2O3表面活性氢的浓度。DFT计算进一步证实了TiO2-Al2O3界面处的氢迁移势垒低于纯Al2O3，为提高溢出效率提供了理论支持。同时，喹啉吸附位点Al2O3的Lewis酸与氢活化位点Ni纳米粒子之间的空间分离直接驱动了加氢性能的增强。此外，i-PrOH/ H2O混合溶剂的使用显著增强了催化作用，因为水介导活性氢从催化剂溢出到水相，在那里它们通过Grotthuss质子跳跃机制参与反应，核磁共振证实了这一点。延迟加料实验表明，即使在H2去除后，储存在水相中的氢仍然可以驱动喹啉加氢，这突出了固相和液相氢转移的重要性。这种双相溢出策略为设计高效的多相催化加氢系统提供了一条有前途的途径。

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引用次数: 0

Step-by-step elucidation of the role of platinum in a co-impregnated Co/SiO2 Fischer–Tropsch catalyst 逐步阐明铂在共浸渍Co/SiO2费托催化剂中的作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-10 DOI: 10.1016/j.jcat.2026.116757

Sandeeran Govender, Sinqobile V.L. Mahlaba, Eric van Steen

Platinum is a well-known reduction promoter for cobalt-based catalysts resulting in a higher degree of reduction, and an improved activity. Here, the role of platinum in a co-impregnated Pt-Co/SiO₂ catalyst (Co-loading: 10 wt-%; Pt-loading: 0–0.44 wt-%) is investigated in depth. The addition of more platinum to the catalyst formulation results in an increased formation of Co₃O₄ in the calcined catalyst, progressively fewer reduction features in the TPR profiles, and yet a decreasing hydrogen uptake after peaking at 0.05 wt-% Pt. The metallic cobalt particle appears to become richer in smaller hcp-cobalt crystallites upon platinum incorporation. The calculated initial TOF increases strongly with increasing platinum loading possibly due to electronic promotion, however the cobalt time yield plateaus as a function of the platinum loading because of the decreasing metal dispersion. The intrinsic deactivation becomes stronger at high platinum loading which is postulated to be linked to increased carbon deposition. The product selectivity appears to be primarily affected by the conversion level rather than the level of platinum promotion.

铂是一种众所周知的钴基催化剂的还原助剂，其还原程度较高，活性也有所提高。本文深入研究了铂在共浸渍Pt-Co/SiO2催化剂中的作用（共载量：10 wt-%；共载量：0-0.44 wt-%）。在催化剂配方中加入更多的铂，会导致煅烧催化剂中Co3O4的形成增加，TPR曲线上的还原特征逐渐减少，但在0.05 wt-% Pt达到峰值后，氢吸收量却在下降。在铂的加入后，金属钴颗粒中更小的hcp-钴晶体变得更丰富。计算出的初始TOF随着铂加载量的增加而增加，这可能是由于电子促进的作用，然而钴产率随着铂加载量的增加而趋于平稳，这是由于金属弥散度的减少。在高铂负载下，本征失活变得更强，这被认为与碳沉积增加有关。产品选择性似乎主要受转化水平的影响，而不是白金推广水平的影响。

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引用次数: 0

Insight into the crucial role of carbon in LaFeO3@C composites for liquid-phase aerobic oxidation of benzyl alcohol to benzaldehyde 洞察碳在LaFeO3@C复合材料中对苯甲醇液相好氧氧化制苯甲醛的关键作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-06 DOI: 10.1016/j.jcat.2026.116747

Wenwen Xiao , Joshua Gorimbo , Qingye Zhao , Zhiyan He , Shuai Lyu , Ping Xiao , Yali Yao , Junjiang Zhu

Adsorption, reaction and desorption are three primary steps of a catalytic reaction, and a potential catalyst should thus have large surface area to adsorb reactants, efficient active sites to convert reactants and good ability to eliminate products. To achieve this goal, we herein report the fabrication of porous carbon-coated perovskite catalyst, LaFeO₃@C, for liquid-phase oxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) using O₂ as oxidant. The large surface area and rich pores of porous carbon facilitate the adsorption and transport of reactants (BzOH and O₂) from solution to the active sites of LaFeO₃, the oxygen vacancies of LaFeO₃ generated by carbon reduction improve the reaction rate between BzOH and O₂, and the hydrophobic surface oxygen functional groups (SOFGs) formed on the porous carbon promote the removal of by-product water from the active sites. Catalytic tests indicated that LaFeO₃ and carbon individually showed negligible activity for the reaction, while an abrupt increase in the activity was observed upon their integration, especially for LaFeO₃@C heated in air at 350 °C for 60 min (denoted as LFO@C-60), which showed a reaction rate of 0.57 mmol·g⁻¹·h⁻¹ after 3 h of reaction time, owing to its appropriate surface area, mesopores, oxygen vacancies and hydrophobic SOFGs. The results provide a novel strategy to fabricate perovskite oxide catalysts for liquid-phase reactions via porous carbon coating.

吸附、反应和解吸是催化反应的三个基本步骤，因此一个潜在的催化剂应该具有大的表面积来吸附反应物，高效的活性位点来转化反应物，以及良好的消除产物的能力。为了实现这一目标，本文报道了制备多孔碳包覆钙钛矿催化剂LaFeO3@C，用于以O2为氧化剂液相氧化苯甲醇（BzOH）为苯甲醛（BzH）。多孔碳的大表面积和丰富的孔隙有利于反应物（BzOH和O2）从溶液中吸附和运输到LaFeO3的活性位点，碳还原产生的LaFeO3的氧空位提高了BzOH和O2的反应速率，多孔碳上形成的疏水表面氧官能团（SOFGs）促进了活性位点副产物水的去除。催化实验表明，LaFeO3和碳单独的反应活性可以忽略不计，而当它们结合在一起时，活性突然增加，特别是LaFeO3@C在空气中350°C加热60 min（记为LFO@C-60），由于其合适的表面积、介孔、氧空位和疏水SOFGs，反应时间3 h后反应速率为0.57 mmol·g−1·h−1。研究结果为通过多孔碳涂层制备液相反应用钙钛矿氧化物催化剂提供了一种新思路。

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引用次数: 0

Layered double hydroxides enabled efficient electrocatalytic oxidative cleavage of C(OH)−C bonds 层状双氢氧化物实现了C(OH)−C键的高效电催化氧化裂解

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-01-31 DOI: 10.1016/j.jcat.2026.116728

Yiyuan Zhang, Xianhong Wu, Jinjie Lin, Hanyang Chen, Run-Cang Sun

The electrochemical oxidative cleavage of C(OH)-C bonds facilitates the conversion of lignin-derived secondary alcohols and ketones into valuable carboxylates in a mild and environmentally friendly manner. In this study, we present efficient and cost-effective FeNi layered double-hydroxide (LDH) nanosheets created through a one-step galvanostatic electrodeposition on nickel foam (NF). The FeNi-LDH/NF shows a high activity for α-phenethyl alcohol (α-PEA) electrooxidation reaction leading to low potential 1.489 V vs. RHE to reach a current density of 100 mA cm⁻², α-PEA was almost completely transformed, and the yield of benzoic acid (BA) was high (> 95%). Both theory and experiments show that α-PEA is first oxidized to acetophenone and then to benzoic acid. The dehydrogenation and oxygenation of the C–H bond is the rate-limiting step of the reaction. In addition, an energy-saving and multifunctional flow electrolytic cell has been developed successfully, througn coupling α-PEA electrooxidation reaction with hydrogen evolution reaction, with FeNi-LDH/NF as dual-functional electrocatalyst. The flow electrolytic cell can operate stably for 200 h.

C(OH)-C键的电化学氧化裂解有助于木质素衍生的仲醇和酮以温和和环保的方式转化为有价值的羧酸盐。在这项研究中，我们通过一步恒流电沉积在泡沫镍（NF）上制备了高效且具有成本效益的FeNi层状双氢氧化物（LDH）纳米片。FeNi-LDH/NF对α-苯乙醇（α-PEA）具有较高的电氧化反应活性，相对于RHE电位为1.489 V，电流密度为100 mA cm−2，α-PEA几乎完全转化，苯甲酸（BA）收率高（95%）。理论和实验都表明，α-PEA首先被氧化为苯乙酮，然后被氧化为苯甲酸。C-H键的脱氢和氧化是反应的限速步骤。此外，通过α-PEA电氧化反应与析氢反应耦合，以FeNi-LDH/NF为双功能电催化剂，成功研制出节能多功能流动电解槽。流动电解槽可稳定运行200 h。

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引用次数: 0

Alkaline oxide clusters inside zeolites catalyze the selective synthesis of ethyl methyl carbonate 沸石内碱性氧化物团簇催化选择性合成碳酸甲酯

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-02 DOI: 10.1016/j.jcat.2026.116729

Yongkun Zheng, Nacho Solá-Ferrer, Lluís Martínez-Belenguer, Belén Lerma-Berlanga, Antonio Leyva-Pérez

Ethyl methyl carbonate (EMC), as the simplest asymmetric carbonate, is considered a unique green liquid organic compound for lithium batteries (electrolyte) and gasoline blending (octane enhancer additive), with properties between dimethyl and diethyl carbonate. In accordance, its chemical production is expected to boost during the coming years, despite green chemical syntheses for EMC are still to be developed. Here we show the selective synthesis of EMC from DMC and ethanol with one of the cheapest commercially available solids, i.e. zeolites, as a heterogeneous catalyst for the reaction, surpassing most of the current soluble catalysts employed for this reaction. While a pristine commercial zeolite such as NaX already shows a significant catalytic activity (65% conversion, 91% selectivity to EMC) without any pre-activation treatment, is recoverable and reusable, and can be implemented in batch and in flow, the incorporation of alkaline oxide clusters inside the zeolitic framework, i.e. K₂O, boosts the catalytic activity not only for the NaX zeolite but also for the parent H-USY and NaY zeolites, otherwise barely catalytically active for the reaction, to give yields up to >99% and ≈80% selectivity to EMC. These results bring a sustainable and cheap catalytic system for the production of EMC.

碳酸甲酯（EMC）是最简单的不对称碳酸盐，是锂电池（电解质）和汽油混合（辛烷值增强剂添加剂）中独特的绿色液体有机化合物，其性能介于碳酸二甲基和碳酸二乙酯之间。因此，尽管EMC的绿色化学合成仍有待开发，但其化学品生产预计将在未来几年内增加。在这里，我们展示了从DMC和乙醇中选择性合成EMC，其中一种最便宜的商业固体，即沸石，作为反应的非均相催化剂，超过了目前用于该反应的大多数可溶性催化剂。虽然原始的商业沸石，如NaX，在没有任何预活化处理的情况下已经显示出显著的催化活性（65%的转化率，91%的EMC选择性），是可回收和可重复使用的，并且可以在批量和流动中实现，但在沸石框架内加入碱性氧化物团簇，即K2O，不仅提高了NaX沸石的催化活性，而且提高了母体H-USY和NaY沸石的催化活性，否则几乎没有催化活性。对电磁兼容的选择性可达99%和约80%。这些结果为电磁兼容的生产提供了一个可持续的、廉价的催化体系。

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引用次数: 0

Direct synthesis of phenyl isocyanate by carbonylation of nitrobenzene, catalyzed by palladium/phenanthroline complexes: promoting effect of phosphorus acids 钯/菲罗啉配合物催化硝基苯羰基化直接合成异氰酸苯酯：磷酸的促进作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-09 DOI: 10.1016/j.jcat.2026.116753

Doaa R. Ramadan , Manar Ahmed Fouad , Francesco Ferretti , Alessandro Gardelli , Artur Brotons Rufes , Chiara Costabile , Fabio Ragaini

The synthesis of aryl isocyanates by direct carbonylation of nitroarenes is the most straightforward alternative to the current technology, which involves the use of very toxic phosgene at one stage of the process. However, it faces several problems and has been little investigated in recent years. By taking advantage of our previous studies on the related carbonylation reaction yielding carbamates, we herein report that the use of phosphorus acids, diphenylphosphinic acid in particular, as promoters for the palladium/phenanthroline catalytic system, allows an improvement in activity and turnover number of almost one order of magnitude with respect to the best results previously reported. The effect of several experimental variables was investigated. Mechanistic investigations indicates that the enhanced activity is not associated with pathways involving water-assisted processes or aniline intermediates.

通过硝基芳烃的直接羰基化来合成芳基异氰酸酯是目前技术的最直接的替代方法，目前的技术在工艺的一个阶段需要使用剧毒的光气。然而，它面临着一些问题，近年来研究很少。利用我们之前对产氨基甲酸酯的相关羰基化反应的研究，我们在此报道，使用磷酸，特别是二苯基膦酸作为钯/菲罗啉催化体系的促进剂，可以使活性和周转率比之前报道的最佳结果提高近一个数量级。研究了几个实验变量的影响。机制研究表明，增强的活性与涉及水辅助过程或苯胺中间体的途径无关。

引用次数: 0

Realize the non-radical selective dehydrogenation of amine on TiO2 photoanode with uniformly coated Ni(OH)2 nano-layer 均匀涂覆Ni(OH)2纳米层，在TiO2光阳极上实现胺的非自由基选择性脱氢

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-04 DOI: 10.1016/j.jcat.2026.116735

Shaohua He , Jie Yang , Ge Tian , Sipeng Yang , Mengyu Duan , Shaorui Jian , Shirong Kang , Jianjiang Lu , Chuncheng Chen

The photoelectrocatalytic (PEC) oxidation represents an efficient route for the degradation of organic pollutants and transformation of organic chemicals. However, the PEC direct oxidation on TiO₂ photoanode suffers from low current efficiency and poor selectivity because of the intrinsic radical characteristics. We realize the high-efficient and selective oxidation of organic amine to nitrile by covering the TiO₂ photoanode with a uniform Ni(OH)₂ nano-layer. It is found that on bare TiO₂ photoanode, the oxidation of model substrate benzylamine leads to the formation of benzaldehyde as the main products with a selectivity of 35% and a Faradaic efficiency (FE) of only 7%. By contrast, on the Ni(OH)₂-covered TiO₂, the selective dehydrogenation of benzylamine to benzonitrile becomes the dominant process with a selectivity of > 99% and FE value exceeding 80%. The detailed experiments by operando EPR, XPS, UV–vis, and Raman spectroscopy reveals that the presence of Ni(OH)₂ nano-layer on the surface of TiO₂ successfully shifts the reaction pathway from traditional radical-driven oxidation to a predominantly non-radical mechanism. The high-valent Ni species (NiOOH), rather than radical, is the key reactive intermediate for the selective dehydrogenation of amine. This work provides a new strategy for PEC valorization of wastewater pollutants, achieving simultaneous pollutants highly selective conversion and chemical energy recovery.

光电催化氧化是有机污染物降解和有机化学品转化的有效途径。然而，由于其固有的自由基特性，PEC在TiO2光阳极上的直接氧化存在电流效率低、选择性差的问题。我们通过在TiO2光阳极表面覆盖均匀的Ni(OH)2纳米层，实现了有机胺高效选择性氧化成腈。在裸TiO2光阳极上，模型底物苄胺氧化生成苯甲醛为主要产物，选择性为35%，法拉第效率（FE）仅为7%。而在Ni(OH)2包覆的TiO2上，苯胺选择性脱氢制苯腈成为主导过程，选择性达到99%，FE值超过80%。通过EPR、XPS、UV-vis和拉曼光谱的详细实验表明，TiO2表面Ni(OH)2纳米层的存在成功地将反应途径从传统的自由基驱动氧化转变为以非自由基为主的氧化机制。高价镍（NiOOH），而不是自由基，是胺选择性脱氢的关键反应中间体。本研究为废水污染物的PEC增值提供了一种新的策略，实现了污染物的高选择性转化和化学能回收。

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引用次数: 0

Carbon chain engineering in boron nitride catalysts unlocks propane dehydrogenation performance via atomic scale modulation 氮化硼催化剂中的碳链工程通过原子尺度调制解锁丙烷脱氢性能

IF 7.3 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-24 DOI: 10.1016/j.jcat.2026.116847

HuiJie Wang, WeiHang Xu, XiaoYing Sun, Zhan Yu, Zhen Zhao, Bo Li

引用次数: 0

Direct aerobic dehydrocyclization of alkyl alcohols to pyrimidines enabled by subnanometric Co clusters 亚纳米Co团簇使烷基醇直接有氧脱氢成嘧啶

IF 7.3 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-21 DOI: 10.1016/j.jcat.2026.116838

Yang Cao, Jie Fang, Guo-Ping Lu, Yamei Lin, Xing Zhang

引用次数: 0

N-formylation dominated reductive cyclization of CO2 mediated by a metal-free frustrated Lewis pair-functionalized covalent organic framework n -甲酰化主导的二氧化碳的还原环化介导的无金属受挫刘易斯对功能化共价有机框架

IF 7.3 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-03-21 DOI: 10.1016/j.jcat.2026.116841

Xuan Wu, Mingcai Zhang, Zhengmei Wang, Qinghao Wang, Xiaolong Hao, Jincai Wu, Xiaobo Pan

引用次数: 0

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