Journal of Catalysis最新文献_第2页

Metal nitrate in acetonitrile-driven aerobic oxidative cleavage of alkynes to carboxylic acids under mild conditions 金属硝酸盐在乙腈驱动的有氧氧化裂解条件下生成羧酸

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-01-27 DOI: 10.1016/j.jcat.2026.116719

Chao Xie , Zejun Liu , Huichao Wang , Qidong Hou , Hengli Qian , Zhiwei Jiang , Meiting Ju

The cleavage of CC bond in alkynes represents a promising strategy for the functional group transformation of alkyne compounds. However, balancing reactivity and selectivity remains a significant challenge due to its high bond dissociation energy and the inherently complex reaction pathways involved. In this work, we report a mild aerobic oxidative cleavage protocol for alkyne CC bonds using commercially available nitrates as catalysts in acetonitrile, affording carboxylic acids in good to excellent yields. This approach exhibits broad functional group tolerance, being applicable to both unactivated alkynes and substrates bearing oxidation-sensitive groups. Mechanistic investigations via EPR, FT-IR, and NMR spectroscopy reveal that the excellent catalytic performance stems from the formation of coordination intermediates between the alkyne and metal nitrate. These intermediates are stabilized by acetonitrile through ion–dipole interactions—a stabilization effect that not only promotes alkyne activation and facilitates oxygen atom transfer (OAT) from nitrate to the CC bond but also drives the reduction of nitrate to nitrogen oxides. These nitrogen oxides subsequently act as free-radical initiators to trigger a chain reaction, accelerating the oxidative cleavage of the CC bond, with molecular oxygen serving as the terminal oxidant.

烷烃中CC键的裂解为烷烃化合物的官能团转化提供了一种强有力的策略，但由于其高键解离能和固有的复杂反应途径，很难平衡反应性和选择性。在这项工作中，我们报道了在乙腈中使用市售硝酸盐对炔CC键进行温和的有氧氧化裂解，从而形成收率良好到优异的羧酸。这种方法显示了广泛的官能团耐受性，适用于那些未活化的炔和含有氧化敏感基团的底物。通过EPR， FT-IR和NMR测量的机理研究表明，优异的催化性能源于炔和硝酸锌之间形成的配位中间体，通过离子偶极子相互作用被乙腈稳定。这种稳定性促进炔活化，促进氧原子从硝酸盐转移到CC键，并将硝酸盐还原为氮氧化物，氮氧化物随后作为自由基引发剂触发链式反应，加速CC键的氧化裂解，分子氧作为末端氧化剂。

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引用次数: 0

Substrate-activated Shvo catalyst for the solvent/promoter-free cyclization of diamines to piperidines and analogues 无溶剂/促进剂的二胺环化成哌啶和类似物的底物活化Shvo催化剂

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.2026.116720

Chuanmei Wang , Yihan Zhang , Ting Wang , Yanwei Cao , Zihang Yin , Houyu Tao , Zijun Huang , Dongyun Chen , Xianjie Fang , Jianmei Lu , Lin He

Piperidine derivatives serve as crucial synthetic building blocks for pharmaceuticals and agrochemicals. With breakthroughs in the production capacity of diamines (such as 2-methylpentanediamine and 1,5-pentanediamine), employing cyclization strategies to access piperidine frameworks has garnered increasing attention. Herein, we report an efficient strategy to rapidly access piperidines via a “hydrogen-borrowing” mechanism over Shvo Ru catalysis without any additives. Firstly, the interaction between the Shvo Ru complex and diamines was investigated by ¹H NMR, FT-IR, mass spectrometry, and DFT calculations, revealing the role of diamines in dissociating the Shvo pre-catalyst and facilitating the formation of reactive intermediates. Based on this observation, Shvo-based catalysts with efficient activity for the solvent/promoter-free cyclization of diamines to piperidines were developed. This catalytic system is applicable not only to 100-gram scale-up synthesis with a record-high turnover number (TON) of 8645 and excellent selectivity (>99%), but also remains stable for over 4 cycles without significant loss of activity. Finally, the catalytic mechanism of the Shvo Ru-mediated, solvent/promoter-free cyclization of diamines to piperidines was proposed by DFT calculations and control experiments.

哌啶衍生物是药品和农用化学品的重要合成基石。随着二胺（如2-甲基戊二胺和1,5-戊二胺）生产能力的突破，采用环化策略获得哌啶框架越来越受到关注。在此，我们报告了一种有效的策略，通过“借氢”机制，在没有任何添加剂的情况下，通过Shvo Ru催化快速获得哌啶。首先，通过1H NMR， FT-IR，质谱分析和DFT计算研究了Shvo Ru配合物与二胺的相互作用，揭示了二胺在分离Shvo预催化剂和促进反应中间体形成中的作用。在此基础上，开发了具有高效活性的shvo基催化剂，用于无溶剂/促进剂环化二胺生成哌替啶。该催化体系不仅适用于100克规模合成，具有创纪录的8645周转率（TON）和优异的选择性（>99%），而且在4个循环以上保持稳定而没有明显的活性损失。最后，通过离散傅立叶变换计算和控制实验，提出了双胺无溶剂/促进剂环化生成哌啶的催化机理。

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引用次数: 0

Tailoring Au-Cu binary sites for CH4 partial oxidation to CH3OH and C2H5OH 为CH4部分氧化生成CH3OH和C2H5OH裁剪Au-Cu二元位

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.2026.116745

Jingting Jin , Wenzhi Li , LuLu Zhang , Xiaoyi Liu , Liqun Wang

Using monometallic copper (Cu) catalysts to selectively oxidize methane into clean fuels such as alcohols holds profound practical importance. However, Cu species remain constrained by insufficient methane activation at low temperature and over-oxidation with elevated temperature. This work proposed a strategy employing chemical reduction to enhance the homogeneity of active species, eliminating the harmful copper oxide species (CuO_x) while enabling the construction of Au-O-Cu sites, and achieved a high alcohol productivity (64.40 and 65.73 μmol/g_cat/h for methanol and ethanol, respectively) and selectivity (83.75%) under continuous flow at 250 °C. It is evidenced that the incorporation of gold (Au) promoted the polarization of adjacent Cu atoms’ d-orbitals, strengthening their coupling with methane and molecular oxygen. This electronic modulation concurrently downshifts Cu’s d-band center, weakening the adsorption strength of key intermediates, thus boosting the selectivity. Additionally, a catalytic domain with high electron localization emerged around the Au atom, providing additional anchoring sites for extra *CH_4, which contributed to the co-formation of ethanol. These findings offered a viable strategy to circumvent the bottlenecks of conventional Cu-based catalysts, showcased the considerable potential of noble metal-transition metal synergy, and paved a solid pathway for designing advanced catalysts for methane conversion.

使用单金属铜（Cu）催化剂选择性地将甲烷氧化为清洁燃料，如酒精，具有深远的实际意义。然而，Cu在低温下仍然受到甲烷活化不足和高温下过度氧化的限制。本研究提出了一种化学还原策略，以提高活性物质的均匀性，消除了有害的氧化铜物质（CuOx），同时促进了Au-O-Cu位点的构建，在250°C连续流动下，甲醇和乙醇的醇产率分别为64.40和65.73 μmol/gcat/h，选择性为83.75%。结果表明，金（Au）的加入促进了相邻Cu原子d轨道的极化，加强了它们与甲烷和分子氧的耦合。这种电子调制同时降低了Cu的d波段中心，减弱了关键中间体的吸附强度，从而提高了选择性。此外，在Au原子周围出现了一个具有高电子定位的催化结构域，为额外的*CH4提供了额外的锚定位点，这有助于乙醇的共形成。这些发现为克服传统cu基催化剂的瓶颈提供了可行的策略，展示了贵金属-过渡金属协同作用的巨大潜力，并为设计先进的甲烷转化催化剂铺平了坚实的道路。

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引用次数: 0

Insight into the activation mechanism of methylene C–H bond over Ce–Al composite oxide Ce-Al复合氧化物上亚甲基C-H键活化机理的探讨

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-11 DOI: 10.1016/j.jcat.2026.116762

Xiangwei Ren , Yue Zhang , Shuzhen Lyu , Li Wang , Ruichen Liu , Guozhu Liu , Rongrong Zhang

Oxidation of methylene compounds remains a critical challenge due to the difficult activation of C–H bond. Herein, Ce–Al composite oxide was prepared and employed for oxidation of 2-alkyl-anthrone and anthracene to corresponding anthraquinone (AQ) which is used widely in the H₂O₂ production by the anthraquinone process and fine chemical industries, with air at mild conditions. Characterization results show that incorporation of Ce, existing partially in CeAlO₃ phase, results in the generation of oxygen vacancies and enhancement of reducibility. The optimal Ce–Al composite oxide (10%CeAl) exhibits superior performance in oxidation of 2-alkyl-anthrone and anthracene to AQ. The conversion of 100% could be achieved for 2-alkyl-anthrone to AQ at reaction time of 8 h and for 2-alkyl-anthracene to AQ at 15 h over 10%CeAl, with 100% selectivity. In-situ electron paramagnetic resonance measurements and DFT calculations reveal that the Ce–O–Al structure in CeAlO₃ phase promotes the formation of carbon-centered radical R^• through altering the C–H cleavage mechanism from hydrogen atom transfer to proton-coupled electron transfer (PCET), and superoxide anion radicals (O₂^•−) formed on oxygen vacancies promote oxidation of R^•.

由于C-H键难以激活，亚甲基化合物的氧化仍然是一个关键的挑战。本文制备了Ce-Al复合氧化物，并将其用于在温和空气条件下将2-烷基蒽酮和蒽酮氧化为蒽醌（AQ），蒽醌在蒽醌工艺和精细化工生产H2O2中广泛使用。表征结果表明，部分存在于CeAlO3相中的Ce的掺入导致了氧空位的生成和还原性的增强。最佳的Ce-Al复合氧化物（10%CeAl）在2-烷基蒽醌和蒽醌的氧化反应中表现出优异的性能，反应时间为8 h， 2-烷基蒽醌的转化率为100%，反应时间为15 h， 2-烷基蒽醌的转化率为100%，选择性为100%。原位电子顺磁共振测量和DFT计算表明，CeAlO3相中的Ce-O-Al结构通过改变C-H裂解机制，从氢原子转移到质子耦合电子转移（PCET），促进了碳中心自由基R•的形成，氧空位上形成的超氧阴离子自由基（O2•−）促进了R•的氧化。

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引用次数: 0

Oxygen-vacancy-enriched MoO3 quantum dots anchored on sulfur-vacancy-rich Zn3In2S6 heterostructures for boosted hydrogen peroxide photosynthesis from pure water 富氧空位MoO3量子点锚定在富硫空位Zn3In2S6异质结构上，促进纯水过氧化氢光合作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.jcat.2026.116724

Cheng-Jie Zheng , Ting Wang , Ren-Chang Zhang , Ke Xu , Zhi-Cai He , Jian Zhang , Guo-Bo Huang , Mingyuan Wang , Guiwu Liu , Wei Chen

The development of efficient photocatalytic systems for hydrogen peroxide (H₂O₂) production from pure water remains a huge challenge due to rapid charge recombination and insufficient redox capability in single-component photocatalysts. Herein, we successfully constructed the S-scheme oxygen-vacancy-enriched MoO₃ quantum dots (Ov-MoQDs)/sulfur-vacancy-rich Zn₃In₂S₆ (Sv-ZIS) heterostructures by coupling Sv-ZIS nanosheets with Ov-MoQDs. The optimized 3Ov-MoQDs/Sv-ZIS sample achieves an outstanding H₂O₂ production rate of 85.8 ± 3.1 μM under visible light illumination for 1 h in the pure water, which is about 3.5 and 45.1 times higher than those of Sv-ZIS and Ov-MoQDs, respectively. Through comprehensive in situ and ex situ characterizations combined with theoretical calculations, we demonstrate that the enhanced activity stems from efficient charge separation and transfer across the heterogeneous interfaces via an S-scheme mechanism. Furthermore, the H₂O₂ photosynthesis over Ov-MoQDs/Sv-ZIS heterostructures is found to proceed through a two-step single-electron oxygen reduction reaction (ORR) pathway. This work provides valuable insights into the rational design of advanced heterostructured photocatalysts for sustainable chemical synthesis.

由于单组分光催化剂的快速电荷重组和氧化还原能力不足，开发用于纯水生产过氧化氢（H2O2）的高效光催化系统仍然是一个巨大的挑战。本文通过将s - zis纳米片与Ov-MoQDs耦合，成功构建了富氧空位MoO3量子点(Ov-MoQDs)/富硫空位Zn3In2S6 （Sv-ZIS）异质结构。优化后的3Ov-MoQDs/Sv-ZIS样品在纯水中可见光照射1 h， H2O2产率为85.8 ± 3.1 μM，分别是Sv-ZIS和Ov-MoQDs的3.5倍和45.1倍。通过综合的原位和非原位表征结合理论计算，我们证明了活性的增强源于通过S-scheme机制在异质界面上有效的电荷分离和转移。此外，发现Ov-MoQDs/Sv-ZIS异质结构上的H2O2光合作用通过两步单电子氧还原反应（ORR）途径进行。这项工作为合理设计用于可持续化学合成的先进异质结构光催化剂提供了有价值的见解。

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引用次数: 0

Mechanistic Insights on the β-(Z) alkyne hydrosilylation by a NHC-based Cp*Rh(III) catalyst: from catalyst design to an alternative model for H-Si activation 基于nhc的Cp*Rh（III）催化剂对β-(Z)炔氢硅化反应的机理研究：从催化剂设计到H-Si活化的替代模型

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.2026.116721

Isabel Poves-Ruiz , Beatriz Sánchez-Page , M. Victoria Jiménez , Miguel Gallegos , Julen Munarriz , Vincenzo Passarelli , Jesús J. Pérez-Torrente

In-depth studies on the residual hydrosilylation catalytic activity of samples of compound [Cp*RhI{(MeIm)₂CH₂}]⁺, bearing an unfunctionalized bis-NHC ligand, lead to the discovery of the excellent catalytic performance of the simple complex [Cp*RhI₂(IMe)] (IMe = 1,3-dimethylimidozol-2-ylidene). This compound efficiently catalyzes the hydrosilylation of wide a range of terminal alkynes, with complete regio- and stereoselectivity toward the thermodynamically less stable β-(Z)-vinylsilane isomer. The reaction mechanism has been explored by DFT calculations. The reaction seems to proceed through an ionic outer-sphere mechanism, involving heterolytic activation of the hydrosilane assisted by the rhodium center and a solvent molecule (acetone). In the absence of acetone, a metal–ligand cooperation reaction pathway is proposed, in which the Cp* ligand acts as a proton-relay within the coordination sphere of the Rh(III) center. The cooperative activation of the hydrosilane by the metallocene moiety of the catalyst precursor generates a reactive Rh(I)–silyl intermediate bearing a pentamethylcyclopenta-1,3-diene ligand, [η⁴-Cp*H], formed through protonation of the Cp* moiety.

深入研究了含非官能化双nhc配体的化合物[Cp*RhI{(MeIm)2CH2}]+样品的残余硅氢化催化活性，发现了简单配合物[Cp*RhI2(IMe)] （IMe = 1,3-二甲基咪唑啉-2-酰基）具有优异的催化性能。该化合物能有效催化多种末端炔的硅氢化反应，对热力学不稳定的β-(Z)-乙烯基硅烷异构体具有完全的区域选择性和立体选择性。通过DFT计算探讨了反应机理。该反应似乎是通过离子外球机制进行的，包括氢硅烷在铑中心和溶剂分子（丙酮）的帮助下的异裂解活化。在没有丙酮的情况下，提出了一种金属-配体协同反应途径，其中Cp*配体在Rh（III）中心的配位球内充当质子中继。催化剂前驱体的茂金属部分对氢硅烷的协同活化产生反应性的Rh(I) -硅基中间体，通过Cp*部分的质子化形成五甲基环五-1,3-二烯配体[η4-Cp*H]。

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引用次数: 0

Influence of tailoring acidic sites and silicon distribution of SAPO-11 zeolite via in-situ Zn modification for superior hydroisomerization of Fischer-Tropsch wax 原位锌改性对SAPO-11沸石酸性位和硅分布对费托蜡加氢异构化的影响

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-01-30 DOI: 10.1016/j.jcat.2026.116716

Fan Shao, Fengzhi Guo, Tianyu Bai, Rongrong Li, Shixuan Guo, Jinxiao Sun, Yasong Zhou, Wenbin Huang, Lu Gong, Gang Wang, Qiang Wei

Improving the performance of hydroisomerization catalysts for jet fuel production remains a considerable challenge, due to the difficulty in precisely controlling the balance between metal and acid functions. Although zinc modification offers a promising strategy to enhance the synergy, the underlying mechanistic understanding of Zn-induced framework repair and reconstruction remains unclear, blocking the rational design of bifunctional catalysts. In this work, A series of Zn-modified SAPO-11 zeolites with tunable ZnO/Al₂O₃ ratios were synthesized via in-situ doping technique. Characterization results revealed that Zn substitution for Al altered the silicon incorporation environment. The formation of Si-O-Zn bonds (NH₃ adsorption energy = -0.99 eV) indicated weaker acidity than Si-O-Al bonds (−1.44 eV). At ZnO/Al₂O₃ = 0.5% doping, isolated P-O-Zn bonds promoted the dispersion and dissolution of large silicon islands (Si(4Si)), increasing weak Brønsted acid sites. At higher Zn doping, the mechanism shifted inducing Si redistribution and forming medium-strong Brønsted acid sites. Namely, a dual role of Zn was identified as framework repair at low loading and framework reconstruction at high loading. The weakened and dispersed acidity enhanced Pt dispersion and reducibility, enabling Pt/(0.75ZnSAPO-11 + ASA) catalyst to deliver the highest iso-C₂₂ yield (30.9%) and selectivity (58.7%), with double-branched isomer yield (10.8%) and selectivity (20.6%). This work highlights the underlying mechanism of Zn modification in catalyst framework, and demonstrates its implications for enhancing the industrial application of Zn-modified catalysts in Fischer-Tropsch wax upgrading and jet fuel cold-flow performance.

由于难以精确控制金属和酸功能之间的平衡，提高用于喷气燃料生产的加氢异构化催化剂的性能仍然是一个相当大的挑战。尽管锌改性提供了一种很有希望的增强协同作用的策略，但锌诱导的框架修复和重建的潜在机制尚不清楚，这阻碍了双功能催化剂的合理设计。本文采用原位掺杂技术合成了一系列ZnO/Al2O3可调的ZnO改性SAPO-11分子筛。表征结果表明，Zn取代Al改变了硅的掺入环境。Si-O-Zn键的形成（NH3吸附能= -0.99 eV）表明酸性弱于Si-O-Al键（- 1.44 eV）。在ZnO/Al2O3 = 0.5%掺杂时，分离的P-O-Zn键促进了大硅岛（Si(4Si)）的分散和溶解，增加了弱Brønsted酸位。在高Zn掺杂下，诱导Si重分布和形成中强Brønsted酸位的机理发生转变。即锌在低负荷下具有骨架修复作用，在高负荷下具有骨架重建作用。减弱和分散的酸度增强了Pt的分散性和还原性，使Pt/(0.75ZnSAPO-11 + ASA)催化剂具有最高的iso-C22产率（30.9%）和选择性（58.7%），双支异构体产率（10.8%）和选择性（20.6%）。本研究强调了锌在催化剂框架中的修饰机理，并论证了其对加强锌修饰催化剂在费托蜡升级和喷气燃料冷流性能方面的工业应用的意义。

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引用次数: 0

Configuring Co0-Reδ+ cooperative sites for alkali-free hydrogenation of adiponitrile to hexamethylenediamine 配置自己腈无碱加氢制六亚甲二胺的Co0-Reδ+配合位点

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-07 DOI: 10.1016/j.jcat.2026.116744

Yi Qin, Wenhao Yang, Hao Liu, Jingjie Luo, Changhai Liang

Synthesis of hexamethylenediamine (HMDA), the crucial monomer for polyamides, is a significant catalyst process and can be proceeded by selectively hydrogenating the adiponitrile (ADN). Fine Co particles decorated by ReO_x clusters were designed to configure rich Co-ReO_x interfaces under optimized bimetallic synergy. The anchorage of Co particles on support is benefited in the presence of ReO_x cluster with the Re atoms migrating onto the surface and into the lattices of cobalt. Modulation on the electronic environment occurs by electrons delivering from Re^δ+ to Co to forge the Co⁰-Re^δ+ cooperative pairs and stabilizes the sensitive electron-rich Co sites. The reaction process can be greatly promoted at the interfacial Co⁰-Re^δ+ sites that both the H₂ dissociation energy and the adsorption energy for reactant and intermediate are greatly tuned to cater to the high selectivity towards HMDA. The HMDA yield of 87.5% with a rate of 3.60 mol_HMDA·mol_Co⁻¹·h⁻¹ in the absence of alkali can be achieved by the Co₃Re₁/ZnO with stable re-usability and easy regeneration.

聚酰胺的关键单体己二胺（HMDA）的合成是一个重要的催化过程，可通过选择性氢化己二腈（ADN）进行。在优化的双金属协同作用下，设计了由ReOx团簇修饰的细Co颗粒，以配置丰富的Co-ReOx界面。ReOx簇的存在有利于Co颗粒在载体上的锚定，Re原子迁移到钴的表面和晶格中。电子环境发生调制，电子从Reδ+传递到Co，形成Co -Reδ+合作对，稳定敏感的富电子Co位。在Co0-Reδ+的界面位置上，H2的解离能以及对反应物和中间体的吸附能都被极大地调整以适应对HMDA的高选择性，从而极大地促进了反应过程。在无碱条件下，Co3Re1/ZnO的HMDA产率为3.60 molHMDA·molCo−1·h−1，可达87.5%，且可重复使用，易于再生。

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引用次数: 0

Elucidating the role of surface species in CO oxidation catalyzed by boron nitride nanotube supported transition metal oxides 氮化硼纳米管负载过渡金属氧化物催化CO氧化过程中表面物质的作用

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-01-28 DOI: 10.1016/j.jcat.2026.116715

Jinwon Choi , Mireu Kim , Yeonsu Kwak , Amol Pophali , Gary Halada , Huiting Luo , Gihan Kwon , Insoo Ro , Jaewoo Kim , Miriam Rafailovich , Taejin Kim

Boron nitride nanotube (BNNT) is considered a highly promising catalyst support due to its outstanding thermal stability and chemical inertness. These characteristics make BNNT an attractive alternative for high-temperature applications. However, most studies to date have focused on incorporating platinum group metals (PGMs) to achieve high activity. Although BNNT-supported PGM catalysts are highly effective, their scarcity and high cost hinder widespread use in industrial processes. In this study, BNNT-supported transition metal oxides (TMO_x/BNNT; TM = Fe, Co, Ni, and Cu) catalysts were investigated, and CO oxidation was applied as a model reaction to evaluate their catalytic performance. Several characterization techniques, including SEM-EDX, TEM, SXRD, H₂-TPR, and XPS, were employed to examine their physicochemical properties. Notably, the particle size of the metal oxides differed significantly depending on the metal type. This variation is primarily attributed to the inherent metal–support interactions and the thermodynamic stability of each oxide during synthesis. These properties also affected catalytic activity, and various parameters, such as oxygen mobility and redox behavior, played important roles in determining performance. Finally, in situ DRIFTS, CO-TPSR, reaction-order analysis, and ¹⁸O₂ isotope-labeling experiment were used to investigate the reaction mechanism. The findings provide insights into the design of cost-effective BNNT-supported catalysts and highlight their potential applicability in oxidation reactions.

氮化硼纳米管（BNNT）由于其优异的热稳定性和化学惰性被认为是一种很有前途的催化剂载体。这些特性使BNNT成为高温应用的有吸引力的替代品。然而，迄今为止，大多数研究都集中在加入铂族金属（PGMs）以获得高活性。虽然bnnt负载的PGM催化剂非常有效，但其稀缺性和高成本阻碍了其在工业过程中的广泛应用。本研究研究了BNNT负载的过渡金属氧化物（TMOx/BNNT; TM = Fe, Co, Ni, and Cu）催化剂，并以Co氧化反应作为模型反应来评价其催化性能。采用SEM-EDX、TEM、SXRD、H2-TPR和XPS等表征技术对其理化性质进行了表征。值得注意的是，金属氧化物的颗粒大小因金属类型的不同而有显著差异。这种变化主要归因于合成过程中固有的金属-载体相互作用和每种氧化物的热力学稳定性。这些性质也影响催化活性，而各种参数，如氧迁移率和氧化还原行为，在决定性能方面起着重要作用。最后，采用原位漂移、CO-TPSR、反应顺序分析和18O2同位素标记实验对反应机理进行了探讨。这些发现为设计具有成本效益的bnnt负载催化剂提供了见解，并强调了它们在氧化反应中的潜在适用性。

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引用次数: 0

Ultra-small Au nanocluster supported on modified mesoporous hydroxyapatite for base-free oxidative esterification of alcohols 改性介孔羟基磷灰石支撑的超小金纳米团簇用于醇的无碱氧化酯化反应

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.2026.116746

Tingting Ge , Zhili Miao , Xiaorui Liu , Ziyan Jia , Chao Liu , Jiahui Huang

The oxidative esterification of alcohols is a key transformation in fine chemical synthesis and green chemistry. However, supported Au catalysts often suffer from nanoparticle agglomeration, leading to a significant loss of activity. Here, we report that Zn-doped hydroxyapatite (ZnHAP) can effectively stabilize ultra-small Au nanoclusters through Au-support interactions, even after high-temperature calcination at 400 ℃. The resulting Au/ZnHAP catalyst, with an ultralow Au loading of 0.25 wt%, exhibits outstanding performance in the base-free oxidative esterification of benzyl alcohol (Conv. 99%, Sele. 95%). Mechanistic investigations reveal that Zn incorporation into HAP modulates the surface basicity, thereby enhancing substrate adsorption and accelerating the key oxidative dehydrogenation step of the hemiacetal intermediate. Moreover, the increased Au⁰ fraction induced by higher calcination temperatures further promotes benzyl alcohol activation. Consequently, under base-free conditions, the ester formation rate is governed by both the number of exposed Au active sites and the balanced distribution of surface acid–base sites. This work provides new mechanistic insights and practical guidance for the rational design of efficient, base-free oxidative esterification catalysts based on supported Au systems.

醇类化合物的氧化酯化反应是精细化学合成和绿色化学的一个重要转变。然而，负载型金催化剂经常受到纳米颗粒团聚的影响，导致活性的显著损失。本文报道了掺锌羟基磷灰石（ZnHAP）即使在400 ℃高温煅烧后，也能通过Au-载体相互作用有效地稳定超小金纳米团簇。所制备的Au/ZnHAP催化剂的Au负载率为0.25 wt%，在苯甲醇的无碱氧化酯化反应中表现出优异的性能（Conv. 99%, Sele. 95%）。机理研究表明，锌掺入HAP可调节表面碱度，从而增强底物吸附，加速半缩醛中间体氧化脱氢的关键步骤。此外，较高的焙烧温度引起的Au0分数的增加进一步促进了苯甲醇的活化。因此，在无碱条件下，酯的形成速率由暴露的Au活性位点的数量和表面酸碱位点的平衡分布共同决定。这项工作为合理设计高效、无碱的负载型金体系氧化酯化催化剂提供了新的机理见解和实践指导。

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引用次数: 0