Journal of Catalysis最新文献_第2页

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

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

{"title":"Substrate-activated Shvo catalyst for the solvent/promoter-free cyclization of diamines to piperidines and analogues","authors":"Chuanmei Wang , Yihan Zhang , Ting Wang , Yanwei Cao , Zihang Yin , Houyu Tao , Zijun Huang , Dongyun Chen , Xianjie Fang , Jianmei Lu , Lin He","doi":"10.1016/j.jcat.2026.116720","DOIUrl":"10.1016/j.jcat.2026.116720","url":null,"abstract":"<div><div>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 <sup>1</sup>H 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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116720"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095947","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

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

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

{"title":"Metal nitrate in acetonitrile-driven aerobic oxidative cleavage of alkynes to carboxylic acids under mild conditions","authors":"Chao Xie , Zejun Liu , Huichao Wang , Qidong Hou , Hengli Qian , Zhiwei Jiang , Meiting Ju","doi":"10.1016/j.jcat.2026.116719","DOIUrl":"10.1016/j.jcat.2026.116719","url":null,"abstract":"<div><div>The cleavage of C<img>C 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 C<img>C 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 <em>via</em> 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 C<img>C 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 C<img>C bond, with molecular oxygen serving as the terminal oxidant.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116719"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056546","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

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

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

{"title":"Tailoring Au-Cu binary sites for CH4 partial oxidation to CH3OH and C2H5OH","authors":"Jingting Jin , Wenzhi Li , LuLu Zhang , Xiaoyi Liu , Liqun Wang","doi":"10.1016/j.jcat.2026.116745","DOIUrl":"10.1016/j.jcat.2026.116745","url":null,"abstract":"<div><div>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<sub>x</sub>) while enabling the construction of Au-O-Cu sites, and achieved a high alcohol productivity (64.40 and 65.73 μmol/g<sub>cat</sub>/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<sub>4,</sub> 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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116745"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135419","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

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

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

{"title":"Insight into the activation mechanism of methylene C–H bond over Ce–Al composite oxide","authors":"Xiangwei Ren , Yue Zhang , Shuzhen Lyu , Li Wang , Ruichen Liu , Guozhu Liu , Rongrong Zhang","doi":"10.1016/j.jcat.2026.116762","DOIUrl":"10.1016/j.jcat.2026.116762","url":null,"abstract":"<div><div>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 H<sub>2</sub>O<sub>2</sub> production by the anthraquinone process and fine chemical industries, with air at mild conditions. Characterization results show that incorporation of Ce, existing partially in CeAlO<sub>3</sub> 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. <em>In-situ</em> electron paramagnetic resonance measurements and DFT calculations reveal that the Ce–O–Al structure in CeAlO<sub>3</sub> phase promotes the formation of carbon-centered radical R<sup>•</sup> through altering the C–H cleavage mechanism from hydrogen atom transfer to proton-coupled electron transfer (PCET), and superoxide anion radicals (O<sub>2</sub><sup>•−</sup>) formed on oxygen vacancies promote oxidation of R<sup>•</sup>.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116762"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146161097","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

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

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

{"title":"Oxygen-vacancy-enriched MoO3 quantum dots anchored on sulfur-vacancy-rich Zn3In2S6 heterostructures for boosted hydrogen peroxide photosynthesis from pure water","authors":"Cheng-Jie Zheng , Ting Wang , Ren-Chang Zhang , Ke Xu , Zhi-Cai He , Jian Zhang , Guo-Bo Huang , Mingyuan Wang , Guiwu Liu , Wei Chen","doi":"10.1016/j.jcat.2026.116724","DOIUrl":"10.1016/j.jcat.2026.116724","url":null,"abstract":"<div><div>The development of efficient photocatalytic systems for hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) 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 MoO<sub>3</sub> quantum dots (Ov-MoQDs)/sulfur-vacancy-rich Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub> (Sv-ZIS) heterostructures by coupling Sv-ZIS nanosheets with Ov-MoQDs. The optimized 3Ov-MoQDs/Sv-ZIS sample achieves an outstanding H<sub>2</sub>O<sub>2</sub> 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 H<sub>2</sub>O<sub>2</sub> 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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116724"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110688","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

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

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

{"title":"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","authors":"Isabel Poves-Ruiz , Beatriz Sánchez-Page , M. Victoria Jiménez , Miguel Gallegos , Julen Munarriz , Vincenzo Passarelli , Jesús J. Pérez-Torrente","doi":"10.1016/j.jcat.2026.116721","DOIUrl":"10.1016/j.jcat.2026.116721","url":null,"abstract":"<div><div>In-depth studies on the residual hydrosilylation catalytic activity of samples of compound [Cp*RhI{(MeIm)<sub>2</sub>CH<sub>2</sub>}]<sup>+</sup>, bearing an unfunctionalized bis-NHC ligand, lead to the discovery of the excellent catalytic performance of the simple complex [Cp*RhI<sub>2</sub>(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, [η<sup>4</sup>-Cp*H], formed through protonation of the Cp* moiety.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116721"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095953","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

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

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

{"title":"Influence of tailoring acidic sites and silicon distribution of SAPO-11 zeolite via in-situ Zn modification for superior hydroisomerization of Fischer-Tropsch wax","authors":"Fan Shao, Fengzhi Guo, Tianyu Bai, Rongrong Li, Shixuan Guo, Jinxiao Sun, Yasong Zhou, Wenbin Huang, Lu Gong, Gang Wang, Qiang Wei","doi":"10.1016/j.jcat.2026.116716","DOIUrl":"10.1016/j.jcat.2026.116716","url":null,"abstract":"<div><div>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/Al<sub>2</sub>O<sub>3</sub> ratios were synthesized via <em>in-situ</em> doping technique. Characterization results revealed that Zn substitution for Al altered the silicon incorporation environment. The formation of Si-O-Zn bonds (NH<sub>3</sub> adsorption energy = -0.99 eV) indicated weaker acidity than Si-O-Al bonds (−1.44 eV). At ZnO/Al<sub>2</sub>O<sub>3</sub> = 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-C<sub>22</sub> 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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116716"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095946","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

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

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

{"title":"Configuring Co0-Reδ+ cooperative sites for alkali-free hydrogenation of adiponitrile to hexamethylenediamine","authors":"Yi Qin, Wenhao Yang, Hao Liu, Jingjie Luo, Changhai Liang","doi":"10.1016/j.jcat.2026.116744","DOIUrl":"10.1016/j.jcat.2026.116744","url":null,"abstract":"<div><div>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<sub>x</sub> clusters were designed to configure rich Co-ReO<sub>x</sub> interfaces under optimized bimetallic synergy. The anchorage of Co particles on support is benefited in the presence of ReO<sub>x</sub> 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<sup>δ+</sup> to Co to forge the Co<sup>0</sup>-Re<sup>δ+</sup> cooperative pairs and stabilizes the sensitive electron-rich Co sites. The reaction process can be greatly promoted at the interfacial Co<sup>0</sup>-Re<sup>δ+</sup> sites that both the H<sub>2</sub> 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<sub>HMDA</sub>·mol<sub>Co</sub><sup>−1</sup>·h<sup>−1</sup> in the absence of alkali can be achieved by the Co<sub>3</sub>Re<sub>1</sub>/ZnO with stable re-usability and easy regeneration.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116744"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135418","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

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

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

{"title":"Elucidating the role of surface species in CO oxidation catalyzed by boron nitride nanotube supported transition metal oxides","authors":"Jinwon Choi , Mireu Kim , Yeonsu Kwak , Amol Pophali , Gary Halada , Huiting Luo , Gihan Kwon , Insoo Ro , Jaewoo Kim , Miriam Rafailovich , Taejin Kim","doi":"10.1016/j.jcat.2026.116715","DOIUrl":"10.1016/j.jcat.2026.116715","url":null,"abstract":"<div><div>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<sub>x</sub>/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, H<sub>2</sub>-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, <em>in situ</em> DRIFTS, CO-TPSR, reaction-order analysis, and <sup>18</sup>O<sub>2</sub> 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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116715"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072540","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

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

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

{"title":"Ultra-small Au nanocluster supported on modified mesoporous hydroxyapatite for base-free oxidative esterification of alcohols","authors":"Tingting Ge , Zhili Miao , Xiaorui Liu , Ziyan Jia , Chao Liu , Jiahui Huang","doi":"10.1016/j.jcat.2026.116746","DOIUrl":"10.1016/j.jcat.2026.116746","url":null,"abstract":"<div><div>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 Au<sup>0</sup> 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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116746"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129468","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