Journal of Catalysis最新文献

Access to cyclobutane–fused dihydrobenzothiophenes via gold–mediated photocatalyzed [2+2]–cycloaddition reactions 通过金介导的光催化[2+2]-环加成反应获得环丁烷融合二氢苯并噻吩

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2024-11-21 DOI: 10.1016/j.jcat.2024.115850

Ekaterina A. Martynova, Vladislav V. Voloshkin, Marco Villa, Antonio Fiorentino, Marek Beliš, Kristof Van Hecke, Paola Ceroni, Steven P. Nolan

引用次数: 0

Homogeneous and heterogeneous selective oxidation of ethyl lactate regulated by a novel vanadium complex 新型钒络合物调节乳酸乙酯的均相和异相选择性氧化作用

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2024-11-19 DOI: 10.1016/j.jcat.2024.115849

Yi Zhang, Shengyun Liao, Haitao Zhu, Qian Zhao, Jiaxin Zheng, Shuxian Ge, Jiaojiao Shi, Xinli Tong

{"title":"Homogeneous and heterogeneous selective oxidation of ethyl lactate regulated by a novel vanadium complex","authors":"Yi Zhang, Shengyun Liao, Haitao Zhu, Qian Zhao, Jiaxin Zheng, Shuxian Ge, Jiaojiao Shi, Xinli Tong","doi":"10.1016/j.jcat.2024.115849","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115849","url":null,"abstract":"As a green and sustainable alternative for producing ethyl pyruvate (EP), the selective aerobic oxidation of ethyl lactate (EL) is still facing issues such as low catalytic efficiency, harsh reaction conditions and catalyst instability. Herein, a novel crystalline vanadium-based coordination compound (VTC=VPTPYCl2(H2O), PTPY = 4′-phenyl-2,2′:6′,2′’-terpyridine) has been designed and synthesized. A highly efficient homogeneous catalytic system (VTC-400-O2-CH3CN, 400 represents the activation temperature) and a recyclable heterogeneous system (VTC-500-O2-CH3CN) for the liquid-phase conversion of EL to EP are developed using molecular oxygen as oxidant through activating VTC at different temperature. In VTC-400-O2-CH3CN system, EL can be completely converted within 4 h, and the yield of EP is 77.8 %, which outperforms the state-of-art reported catalytic system. Meanwhile, the heterogeneous VTC-500 catalyst can also promote the full conversion of EL within 4 h, and its activity remains basically unchanged after being used for 10 times. Structural characterization reveals that the soluble VTC breaks the weak coordination V-Cl bonds at a lower activation temperature of 400 ° C to expose more vanadium-based catalytic sites, but the framework of ligand remains intact. However, the organic derived carbon skeleton at higher temperature of 500 ° C can effectively confine the V-based active species and prevent the dissolution of the catalyst, which impels the transition of the homogeneous to heterogeneous catalytic system.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"99 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673737","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

Unravelling the mechanistic ‘Black Box’ of heterogeneous condensation reactions catalyzed by aminosilicas 揭开氨基硅酸催化的异质缩合反应的机理 "黑匣子

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2024-11-16 DOI: 10.1016/j.jcat.2024.115852

Parijat Borah, Preeti Nanda Sahu, Anik Sen, Miquel A. Pericàs

{"title":"Unravelling the mechanistic ‘Black Box’ of heterogeneous condensation reactions catalyzed by aminosilicas","authors":"Parijat Borah, Preeti Nanda Sahu, Anik Sen, Miquel A. Pericàs","doi":"10.1016/j.jcat.2024.115852","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115852","url":null,"abstract":"Primary amino-functionalized silicas (H2N-SiO2) are well known acid-base cooperative catalysts for many organic transformations, including carbon–carbon (C–C) bond forming condensation reactions, and much attention has been devoted to the elucidation of their action mode. However, to our surprise, the mechanism of Henry reactions and Knoevenagel condensations catalyzed by H2N-SiO2 is still paradoxical, and the identity of the actual base species, transition states, reactivity, and product selectivity, remain as debatable topics of discussion. Herein we propose a brand-new reaction mechanism for H2N-SiO2-catalyzed Henry reactions that overcomes all prior inconsistencies. With the aid of Hammett analysis and density functional theory (DFT) calculations, we have effectively identified several critical transition states and are able to explain reactivity and product selectivity. This study revealed that H2N-SiO2 catalyzed Henry reactions of aldehydes and nitro compounds follow the imine mechanism to afford olefin adducts as only possible products. In addition, we utilized our findings to comprehend the mechanism of Knoevenagel condensation, a comparable reaction, dispelling a more than two-decade old misconception regarding the nature of the active base involved.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"17 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642597","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

Promoting role of residual organic structure directing agent in skeletal butene isomerization over ferrierite 残余有机结构引导剂在铁氧体上的骨架丁烯异构化中的促进作用

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2024-11-16 DOI: 10.1016/j.jcat.2024.115847

Karoline L. Hebisch, Pawel A. Chmielniak, Violet A. Cutler, Rick B. Watson, Kinga Gołąbek, Carsten Sievers

{"title":"Promoting role of residual organic structure directing agent in skeletal butene isomerization over ferrierite","authors":"Karoline L. Hebisch, Pawel A. Chmielniak, Violet A. Cutler, Rick B. Watson, Kinga Gołąbek, Carsten Sievers","doi":"10.1016/j.jcat.2024.115847","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115847","url":null,"abstract":"This work examines how acid site concentration (FT-IR) and strength (NH3-TPD) as well as pore mouth accessibility modulate the activity of the microporous zeolite ferrierite (H-FER) during the skeletal isomerization of 1-butene to iso-butene. Restricting the accessibility of catalyst pores and strong acid sites is achieved by selective oxidation of residual organic structure directing agent (OSDA) through precise control of calcination conditions. Because this reaction is mediated by catalytically active carbonaceous deposits, residual OSDA affects their formation. This work demonstrates that small amounts of residual OSDA (∼ 0.2 wt%) are beneficial to the reaction under industrially relevant reaction conditions in three ways. Selective poisoning of strong BAS with OSDA nearly halves the amount of dimerization and cracking byproducts and improves catalyst lifetime. Simultaneously, carbonaceous fragments of the OSDA act as coke precursors and help shorten the startup time. Hence, catalyst lifetime may be significantly improved through both optimal pre-treatment conditions and by designing catalysts with an increased number of accessible pore mouths.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"7 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142645846","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

Magnesium oxide-supported potassium hydride as a transition-metal-free catalyst for the selective hydrogenation of alkynes 氧化镁支撑的氢化钾作为炔烃选择性氢化的无过渡金属催化剂

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2024-11-16 DOI: 10.1016/j.jcat.2024.115851

Xilun Zhang, Hongliang Liang, Fei Chang

{"title":"Magnesium oxide-supported potassium hydride as a transition-metal-free catalyst for the selective hydrogenation of alkynes","authors":"Xilun Zhang, Hongliang Liang, Fei Chang","doi":"10.1016/j.jcat.2024.115851","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115851","url":null,"abstract":"Catalytic hydrogenation of alkynes to alkenes is pivotal in both petrochemical and fine chemical industries. Its implementation relies on the use of transition metals, especially those precious Pd-based catalysts. In this work, we utilize a melt infiltration method to prepare magnesium oxide-supported potassium hydride (KH/MgO), which is illustrated as a transition-metal-free catalyst for selective hydrogenation of alkynes. H2-D2 exchange experiment proves that dihydrogen activation and dissociation on KH/MgO is plausible at room temperature and ambient pressure. KH/MgO catalyzes hydrogenation of diphenylacetylene (DPA) already at 40 ℃, implying its high intrinsic activity at very mild conditions. Under an optimized condition of 80°C, 2 bar H2, and 40 h, 75 % conversion of DPA is achieved, affording 82 % selectivity to stilbenes. Mechanistic study suggests that surface hydride on KH/MgO plays an important role toward dihydrogen activation, and involved in the hydrogenation step to form stilbenes. This work shows the promise for using light metal hydrides consisting of earth-abundant elements as alternative hydrogenation catalysts.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"166 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642599","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 selectivity in furfural hydrogenolysis over NiCoAl catalyst through a simple rinsing process 通过简单的漂洗工艺调整镍钴铝催化剂在糠醛氢解过程中的选择性

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2024-11-15 DOI: 10.1016/j.jcat.2024.115845

Zepeng Zhao, Wenguang Zhou, Guozhang Chang, Lungang Chen, Chenguang Wang, Yuhe Liao, Jinxing Long, Longlong Ma, Yong Liu

{"title":"Tailoring selectivity in furfural hydrogenolysis over NiCoAl catalyst through a simple rinsing process","authors":"Zepeng Zhao, Wenguang Zhou, Guozhang Chang, Lungang Chen, Chenguang Wang, Yuhe Liao, Jinxing Long, Longlong Ma, Yong Liu","doi":"10.1016/j.jcat.2024.115845","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115845","url":null,"abstract":"In this study, the structure–activity relationships were investigated in converting biomass-derived furfural into cyclopentanone (CPO) or tetrahydrofuran alcohol (THFA) using a rinsing method to modulate the NiCoAl catalyst. Characterization of two catalysts, NiCoAl (without rinsing) and NiCoAl-R (with rinsing), reveals differences in morphology, composition, and acidity. Rinsing induced a transition from agglomerate to layered structure in NiCoAl-R, which exhibited higher acid strength and improved Lewis to Brønsted acid ratio. NiCoAl-R contained a high percentage of metal oxides, while NiCoAl had a high percentage of metallic species on its surface. These distinctions resulted in varied performance in FFA hydrogenolysis, with NiCoAl-R favoring CPO formation and NiCoAl facilitating THFA production. In situ DRIFTS experiments reveals differing furfural sorption states, and DFT calculations highlighted the higher activity of metal oxides in ring-opening reactions. This investigation elucidates the intricate relationship between catalyst properties and performance, offering insights for tailored catalyst design in biomass conversion.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"7 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637514","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

N, P co-doped porous biochar supported electron deficient Niδ+ for domino reductive amination and amidation of levulinic acid with nitroarenes to N-substituted pyrrolidones using methyl formate N、P 共掺多孔生物炭支持缺电子的 Niδ+，用于利用甲酸甲酯将乙酰丙酸与硝基烯烃进行多米诺还原胺化和酰胺化，生成 N-取代的吡咯烷酮

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2024-11-15 DOI: 10.1016/j.jcat.2024.115848

Honghui Gong, Longxing Wei, Qi Li, Fei Wang, Yihan Jin, Xiaojing Zhang, Kexin Guo, Yuan Ma, Xian-Lei Shi

{"title":"N, P co-doped porous biochar supported electron deficient Niδ+ for domino reductive amination and amidation of levulinic acid with nitroarenes to N-substituted pyrrolidones using methyl formate","authors":"Honghui Gong, Longxing Wei, Qi Li, Fei Wang, Yihan Jin, Xiaojing Zhang, Kexin Guo, Yuan Ma, Xian-Lei Shi","doi":"10.1016/j.jcat.2024.115848","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115848","url":null,"abstract":"The synthesis of N-substituted pyrrolidones starting from biomass-derived levulinic acid (LA) and nitroarenes is a highly attractive route for LA valorization, but still faces challenges. Herein, we report an electron deficient Niδ+ catalyst (Ni2P/NPCB-600) prepared by doping N and P into coffee biochar using a one-pot carbonization method. Ni2P/NPCB-600 shows outperform catalytic performance compared with the corresponding metallic Ni catalysts (Ni/CB-600 and Ni/NPCB-600) in the domino reductive amination and amidation of LA with nitroarenes. Characterization and controlled experiments demonstrate that the high catalytic activity and selectivity of Ni2P/NPCB-600 are mainly attributed to the formation of electron deficient Niδ+ (Ni2δ+-Pδ-), which could promote the decomposition of methyl formate, and the adsorption and activation of C=O bonds in LA during the domino reactions. Furthermore, Ni2P/NPCB-600 also shows good substrate scope, various N-substituted pyrrolidones can be directly synthesized from LA and different nitroarenes with good to excellent yields (87.5–99 %). This study provides a potential pathway for efficiently producing N-substituted pyrrolidones by adjusting the electron density of Ni.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"248 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642977","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

Surface self-modification of TiO2 for enhanced photocatalytic toluene oxidation via photothermal effect 通过光热效应对 TiO2 进行表面自修饰以增强其光催化甲苯氧化能力

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2024-11-13 DOI: 10.1016/j.jcat.2024.115846

Jinyu Li , Sunzai Ke , Jiayu Yi , Xiang Li , Lijuan Shen , Ruidan Zhang , Min-Quan Yang

{"title":"Surface self-modification of TiO2 for enhanced photocatalytic toluene oxidation via photothermal effect","authors":"Jinyu Li , Sunzai Ke , Jiayu Yi , Xiang Li , Lijuan Shen , Ruidan Zhang , Min-Quan Yang","doi":"10.1016/j.jcat.2024.115846","DOIUrl":"10.1016/j.jcat.2024.115846","url":null,"abstract":"<div><div>Surface modification plays an important role in extending light absorption and enhancing the catalytic performance of semiconductor photocatalysts. However, most current studies focus on pre-modification of the semiconductors before reaction, while surface self-modification of catalyst during photocatalytic reaction process is often neglected. Here, we report the surface self-modification of TiO2 catalyst during photocatalytic oxidation of toluene under UV light irradiation, which changes the colour of TiO2 from white to yellow, and effectively extends its light absorption range into visible light region. The absorbed visible light is primarily released as thermal energy, significantly increasing the temperature of the catalytic system. Mechanistic studies reveal that the temperature elevation facilitates the separation of photogenerated charge carriers in TiO2 and promotes the generation of •O2−, consequently accelerating the surface redox reactions. The surface self-modified TiO2 exhibits an enhanced photothermal catalytic benzaldehyde generation of 4485 μmol g−1 h−1 under UV–visible light irradiation, which surpasses the UV-driven activity by a factor of 1.9. This study offers new perspectives on the surface modification of semiconductor photocatalysts during organic transformations. It is anticipated to trigger increased research attention to this effect, ultimately advancing solar-to-chemical energy conversion.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"440 ","pages":"Article 115846"},"PeriodicalIF":6.5,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601719","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

Palladium-catalyzed difluoroalkylative carbonylation of unactivated alkenes toward γ-Lactams 钯催化未活化烯烃的二氟烷基化羰基化反应生成 γ-内酰胺

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2024-11-13 DOI: 10.1016/j.jcat.2024.115839

Xin Qi , Yuanrui Wang , Xiao-Feng Wu

引用次数: 0

Selective adsorption and hydrogenolysis of C-OH bond in biomass derived furanic compounds over Ni-TT-Nb2O5 Ni-TT-Nb2O5 对生物质衍生呋喃化合物中 C-OH 键的选择性吸附和氢解作用

IF 7.3 1区化学

Journal of Catalysis Pub Date : 2024-11-12 DOI: 10.1016/j.jcat.2024.115844

Zhendong Yu, Zihao Qin, Hongyuan Liu, Shaoyu Yuan, Renjie Huang, Binglin Chen, Zheng Li, Lu Lin, Carol Sze Ki Lin, Xianhai Zeng

{"title":"Selective adsorption and hydrogenolysis of C-OH bond in biomass derived furanic compounds over Ni-TT-Nb2O5","authors":"Zhendong Yu, Zihao Qin, Hongyuan Liu, Shaoyu Yuan, Renjie Huang, Binglin Chen, Zheng Li, Lu Lin, Carol Sze Ki Lin, Xianhai Zeng","doi":"10.1016/j.jcat.2024.115844","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115844","url":null,"abstract":"The selective hydrogenolysis of C-OH in renewable furanic compounds to corresponding high-value products has been attractive yet challenging, and the mechanism remains vague. Herein, a non-noble catalyst (Ni-TT-Nb2O5) was prepared to address this challenge. Batch and continuous reaction results show that Ni-TT-Nb2O5 can selectively hydrodeoxygenate 5-hdyroxymethylfurfural to 5-methylfurfural with a very high selectivity of 99 %. Moreover, Ni-TT-Nb2O5 can also selectively hydrodeoxygenate various furanic, benzenoid and aliphatic alcohols, achieving up to > 95 % selectivity. In-situ FTIR and DFT calculations showed that compared with other Ni-supported (supports = Al2O3, CeO2, SiO2, ZrO2) catalysts, HMF was adsorbed on Ni-TT-Nb2O5 surface via parallel mode exclusively, and the C-OH bond was easier to be activated. This work therefore explained the mechanism of selective hydrogenolysis of C-OH in HMF over Ni-TT-Nb2O5, and offered an advanced approach for the upgrading of C-OH-containing furanic compounds as well as benzenoid and aliphatic alcohols.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"16 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601723","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