Journal of Molecular Catalysis A: Chemical最新文献

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Mechanism of CuAAC reaction: In acetic acid and aprotic conditions CuAAC反应机理:在醋酸和非质子条件下
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.11.010
Cihan Özen, Nurcan Şenyurt Tüzün
{"title":"Mechanism of CuAAC reaction: In acetic acid and aprotic conditions","authors":"Cihan Özen,&nbsp;Nurcan Şenyurt Tüzün","doi":"10.1016/j.molcata.2016.11.010","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.010","url":null,"abstract":"<div><p>Protonation of copper-triazolide is a distinctive and final part in CuAAC reaction which has kinetic importance such that it can even affect the product distribution. In the context of this study, the protonation mechanism of copper-triazolide was investigated with quantum mechanical calculations to have a deeper understanding of the mechanism. In aprotic conditions where the alkyne is considered as proton donor, the key finding of DFT calculations performed in this study is that the activation energy barrier for the protonation step is greater than the cycloaddition step. In the absence of a strong proton donor the final protonation step is coupled with the alkyne deprotonation step in the catalytic cycle, which slows down the reaction. A conceivable pathway for acetic acid promoted CuAAC reaction on the basis of experimental and computational studies was also sought. With acetate as ligand, cycloaddition is a facile reaction and the energetics shows that it speeds up the cycloaddition step. Acetic acid in CuAAC reaction provides proton for the final protonation step in the catalytic cycle, decouples the protonation/deprotonation step by acting as a strong proton donor in the last step and facilitates protonation. The energetics presented herein are in accordance with the experimental proposals on rate-determining step in aprotic conditions and decreased reaction times obtained in the experiments in the presence of acetic acid.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2391733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 12
Structure–activity comparison in palladium–N–heterocyclic carbene (NHC) catalyzed arene CH activation- functionalization 钯- n-杂环碳(NHC)催化芳烃活化-功能化的构效比较
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.06.027
Moumita Mondal, Joyanta Choudhury
{"title":"Structure–activity comparison in palladium–N–heterocyclic carbene (NHC) catalyzed arene CH activation- functionalization","authors":"Moumita Mondal,&nbsp;Joyanta Choudhury","doi":"10.1016/j.molcata.2016.06.027","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.06.027","url":null,"abstract":"<div><p>A simple and efficient C<img>H activation catalyst was identified through a model structure-activity screening applied to a noncooperative, nonsymmetric bimetallic palladium(II)-N-heterocyclic carbene complex. Mechanistic studies based on kinetics and DOSY NMR spectroscopy provided the origin of the higher efficiency of the identified catalyst.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.06.027","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2595831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 13
Influence of the functional groups of multiwalled carbon nanotubes on performance of Ru catalysts in sorbitol hydrogenolysis to glycols 多壁碳纳米管官能团对Ru催化剂山梨醇氢解制乙二醇性能的影响
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.11.003
Xingcui Guo , Huihuan Dong , Bin Li , Linlin Dong , Xindong Mu , Xiufang Chen
{"title":"Influence of the functional groups of multiwalled carbon nanotubes on performance of Ru catalysts in sorbitol hydrogenolysis to glycols","authors":"Xingcui Guo ,&nbsp;Huihuan Dong ,&nbsp;Bin Li ,&nbsp;Linlin Dong ,&nbsp;Xindong Mu ,&nbsp;Xiufang Chen","doi":"10.1016/j.molcata.2016.11.003","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.003","url":null,"abstract":"<div><p>Different functional groups (i.e. <img>NH<sub>2</sub>, <img>COOH, <img>OH and nitrogen-doping) modified CNTs (denoted as AMCN, CMCN, HMCN and NMCN, respectively) supported ruthenium catalysts (Ru/AMCN, Ru/CMCN, Ru/HMCN and Ru/NMCN) were prepared by incipient wetness impregnation method. They were fully characterized by XRD, TG, Raman, XPS, TPD and TEM to elucidate the relationship between the physical property and their catalytic performance. TEM results shown that Ru particles were well dispersed on the surface for all the samples with the size of 1.48–1.99<!--> <!-->nm. The effects of functional groups of carbon nanotubes (CNTs), nitrogen doping and base additive types on activity and selectivity of ethylene glycol (EG) and propylene glycol (1,2-PD) were investigated. In addition, the activity and final products distribution were much influenced by the properties of functional groups on CNTs and the type of metal cation of the base promoters, which probably participated in the reaction for accelerating a retro-aldol reaction for C<img>C cleavage. Among the catalysts, Ru supported on AMCN exhibited the best catalytic activities and glycols selectivities than on MCN, CMCN, HMCN and NMCN.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2878505","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 24
Oxidation of aliphatic and aromatic CH bonds by t-BuOOH catalyzed by μ-nitrido diiron phthalocyanine μ-硝基二铁酞菁催化t-BuOOH氧化脂肪和芳香族CH键
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.08.013
Evgeny V. Kudrik , Alexander B. Sorokin
{"title":"Oxidation of aliphatic and aromatic CH bonds by t-BuOOH catalyzed by μ-nitrido diiron phthalocyanine","authors":"Evgeny V. Kudrik ,&nbsp;Alexander B. Sorokin","doi":"10.1016/j.molcata.2016.08.013","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.08.013","url":null,"abstract":"<div><p>Low temperature selective transformation of alkanes to useful products continues to be an important challenge in chemistry and industry. μ-Nitrido diiron phthalocyanines in combination with H<sub>2</sub>O<sub>2</sub> have been recently identified as powerful oxidation catalysts for these challenging reactions due to the formation of ultra-high valent diiron oxo species PcFe(IV)μNFe(IV)<img>O(Pc<sup>+</sup><img>). This very strong <em>two-electron oxidizing</em> species is generated from peroxo complex PcFe(IV)μNFe(III)<img>O<img>O<img>R(Pc) (R<img>H in the case of H<sub>2</sub>O<sub>2</sub>) via <em>heterolytic</em> O<img>O bond cleavage. Therein we show that the evolution of the peroxo diiron complex depends on the peroxide structure. Using <sup>t</sup>BuOOH we have demonstrated the formation of an <em>one-electron oxidizing</em> PcFe(IV)μNFe(IV)<img>O(Pc) and <sup>t</sup>BuO<img> radical via <em>homolytic</em> O<img>O cleavage of the peroxocomplex. The reactivity of the μ-nitrido diiron tetra-<em>t</em>-butylphthalocyanine − <sup>t</sup>BuOOH catalytic system was investigated in the oxidation of different C<img>H bonds in alkanes, olefins, aromatic and alkylaromatic compounds. The main products of cyclohexane oxidation were cyclohexanone and cyclohexanol whereas bicyclohexyl was formed in minor amounts even in the presence of O<sub>2</sub> and <sup>t</sup>BuOOH. Under optimal conditions, the turnover numbers of almost 5300 have been achieved.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.08.013","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2879561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 35
Syntheses of bispyrazolyl monotriazolyl heteroscorpionate platinum(IV) complexes including an unusual Pt-CH2CH2-Pt bridge 含特殊Pt-CH2CH2-Pt桥的双吡唑基单三唑基异蝎酸铂配合物的合成
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.07.002
Katherine D. Lavoie, Bryan E. Frauhiger, Peter S. White, Joseph L. Templeton
{"title":"Syntheses of bispyrazolyl monotriazolyl heteroscorpionate platinum(IV) complexes including an unusual Pt-CH2CH2-Pt bridge","authors":"Katherine D. Lavoie,&nbsp;Bryan E. Frauhiger,&nbsp;Peter S. White,&nbsp;Joseph L. Templeton","doi":"10.1016/j.molcata.2016.07.002","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.07.002","url":null,"abstract":"<div><p>Scorpionate ligands provide the benefit of hemilability while minimizing complete dissociation of the ligand. Previous investigations into Tp′PtL<sub>n</sub>X<sub>m</sub> complexes [Tp′<!--> <!-->=<!--> <!-->hydridotris(3,5-dimethylpyrazolyl)borate] revealed the importance of hemilability as the Tp′ ligand facilitates Pt(II/IV) interconversions. Here we discuss the synthesis and metalation of a series of asymmetric scorpionate ligands bearing two pyrazolyl rings and one triazolyl ring. In addition to utilizing triazole donor arms with differing substituents, we also compare octahedral structures of Pt(IV) complexes with P<!--> <!-->=<!--> <!-->O and C<img>H and B<img>H caps at the pole of the facial tridentate umbrella. Oxidation from Pt(II) to Pt(IV) with electrophilic reagents, simple acids and acid chlorides, leads to isomers in some cases, and the binding properties of the various donor arms dictate the stereochemistry of the products. Investigations into the reactivity of heteroscorpionate tridentate ligands bound to platinum(II) led to C<img>Cl activation reactions with methylene chloride and 1,2-dichloroethane. Isolation of a dinuclear platinum complex bridged by an ethylene unit produced an unusual proton NMR AA′XX′ pattern in the <sup>1</sup>H NMR spectrum due to chirality at each platinum center.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.07.002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2171630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 6
Zeolite Y encaged Ru(III) and Fe(III) complexes for oxidation of styrene, cyclohexene, limonene, and α-pinene: An eye-catching impact of H2SO4 on product selectivity Y型沸石包裹Ru(III)和Fe(III)配合物氧化苯乙烯、环己烯、柠檬烯和α-蒎烯:H2SO4对产物选择性的显著影响
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.11.020
Dinesh R. Godhani, Haresh D. Nakum, Digvijaysinh K. Parmar, Jignasu P. Mehta, Nisheeth C. Desai
{"title":"Zeolite Y encaged Ru(III) and Fe(III) complexes for oxidation of styrene, cyclohexene, limonene, and α-pinene: An eye-catching impact of H2SO4 on product selectivity","authors":"Dinesh R. Godhani,&nbsp;Haresh D. Nakum,&nbsp;Digvijaysinh K. Parmar,&nbsp;Jignasu P. Mehta,&nbsp;Nisheeth C. Desai","doi":"10.1016/j.molcata.2016.11.020","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.020","url":null,"abstract":"<div><p>A novel Ru(III) and Fe(III) complexes of ligands 1 and/or 2 {where 1<!--> <!-->=<!--> <!-->2,2′-((1E,1′E)-((azanediylbis(ethane-2,1-diyl))bis(azanylylidene))bis(methanylylidene))diphenol and 2<!--> <!-->=<!--> <!-->2,2′-((1E,1′E)-((azanediylbis(ethane-2,1-diyl))bis(azanylylidene))bis(methanylylidene)) bis(4-nitrophenol)} have been synthesized as ‘neat’ and zeolite Y encapsulated complexes. These catalysts are characterized by various analytical tools such as FTIR, UV–vis, elemental analysis, ICP-AES, molar conductivity, <sup>1</sup>H- and <sup>13</sup>C NMR, TGA, SEM, AAS, BET, magnetic susceptibility and powder XRD to endorse the complex formation, absence of peripheral redundant ligands and complexes, conservation of zeolite Y morphology and crystallinity, and the encapsulation of complexes without devastation in the zeolite Y framework. Out of these synthesized catalysts, 5Y is found to be a potent candidate for styrene (Conv. 76.1%, TOF: 2130<!--> <!-->h<sup>−1</sup>), cyclohexene (Conv. 84.4%, TOF: 2351<!--> <!-->h<sup>−1</sup>), limonene (Conv. 81.6%, TOF: 2273<!--> <!-->h<sup>−1</sup>), and α-pinene (Conv. 72.6%, TOF: 2023<!--> <!-->h<sup>−1</sup>) oxidation with high selectivity of respective allylic products excluding the styrene oxidation, which undergoes epoxidation only. The addition of H<sub>2</sub>SO<sub>4</sub> in an identical reaction catalyzed by 5Y <em>not only</em> surge the conversion up to 100% in a short time span with high TOF <em>but also</em> increase the selectivity of respective epoxidation products. This switchover in the selectivities could be credited to the presence of H<sub>2</sub>SO<sub>4</sub> that facilitates the heterolytic <img>O<img>O<img> bond cleavage of metal hydroperoxide and stimulates the epoxidation over allylic oxidation. Furthermore, the results establish that the heterogeneous systems are effortlessly recovered and reused without ample drop in the activity and selectivity.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2171639","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 31
Preparation of acetates catalyzed by boric acid and/or tungstophosphoric acid-modified zirconia obtained employing polyethylene glycols as pore-forming agents 以聚乙二醇为成孔剂制备硼酸和/或钨磷酸修饰氧化锆催化的醋酸酯
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.11.004
Lilian Osiglio, Gabriel Sathicq, Luis Pizzio, Gustavo Romanelli, Mirta Blanco
{"title":"Preparation of acetates catalyzed by boric acid and/or tungstophosphoric acid-modified zirconia obtained employing polyethylene glycols as pore-forming agents","authors":"Lilian Osiglio,&nbsp;Gabriel Sathicq,&nbsp;Luis Pizzio,&nbsp;Gustavo Romanelli,&nbsp;Mirta Blanco","doi":"10.1016/j.molcata.2016.11.004","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.004","url":null,"abstract":"<div><p>Zirconia modified with boric acid and/or tungstophosphoric acid calcined at 320<!--> <!-->°C were prepared, characterized and used as catalysts in the production of acetates from diverse alcohols and phenols. Polyethylene glycol (PEG) of different molecular weight (400, 2000, 6000<!--> <!-->Da) were added as low cost pore-forming agents during zirconia synthesis using zirconyl chloride as precursor and ammonium hydroxide as precipitating agent. The zirconias were impregnated with aqueous solutions of boric acid and/or tungstophosphoric acid (TPA). The borated zirconias, zirconias modified with TPA and zirconias doped with both boron and TPA were amorphous mesoporous materials with very strong acid sites, and specific surface areas S<sub>BET</sub> of around 200, 100, and 150<!--> <!-->m<sup>2</sup>/g, respectively. The FT-IR spectra of borated zirconias exhibited the bands of boron species, while the zirconias modified with TPA presented the characteristic bands of tungstophosphate anion, and the zirconias doped with both boron and TPA showed a degradation of the TPA anion, confirmed by <sup>31</sup>P MAS-NMR. The borated zirconias and the zirconias modified with TPA gave excellent selectivity and yield in the 2-phenylethanol esterification with acetic acid. The use of these materials allows obtaining higher or similar results than those reported in the literature. Zirconias doped with both boron and TPA gave lower values, due to the transformation of the [PW<sub>12</sub>O<sub>40</sub>]<sup>3−</sup> Keggin anion in to the [P<sub>2</sub>W<sub>21</sub>O<sub>71</sub>]<sup>6−</sup> and [PW<sub>11</sub>O<sub>39</sub>]<sup>7−</sup> species. The reactivity towards acetylation with acetic acid of different alcohols and phenols using the best catalyst was ordered according to: primary alcohols<!--> <!-->&gt;<!--> <!-->secondary alcohols<!--> <!-->&gt;<!--> <!-->phenols. The reactivity difference of the alcohols and phenols was correlated with the electronic density on the oxygen atom and steric effects.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.004","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"1737690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 7
Effect of gadollunium doping on visible light photocatalytic performance of Ag3PO4: Evaluation of activity in degradation of an anthraquinone dye and mechanism study 钆掺杂对Ag3PO4可见光催化性能的影响:降解蒽醌染料的活性评价及机理研究
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.11.026
E. Ghazalian , N. Ghasemi , A.R. Amani-Ghadim
{"title":"Effect of gadollunium doping on visible light photocatalytic performance of Ag3PO4: Evaluation of activity in degradation of an anthraquinone dye and mechanism study","authors":"E. Ghazalian ,&nbsp;N. Ghasemi ,&nbsp;A.R. Amani-Ghadim","doi":"10.1016/j.molcata.2016.11.026","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.11.026","url":null,"abstract":"<div><p>Gadolinium (Gd)-doped silver orthophosphate (Ag<sub>3</sub>PO<sub>4</sub>) nanoparticles, with spherical morphology, were synthesized by a co-precipitation method and their photocatalytic activities were evaluated in degradation of Reactive Blue 19 (RB19), as a model organic pollutant. The synthesized Ag<sub>3</sub>PO<sub>4</sub> and Gd-doped Ag<sub>3</sub>PO<sub>4</sub> were characterized using X-ray diffraction pattern analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, diffuse reflectance UV–vis spectroscopy and photoluminescence spectroscopy. In comparison with Ag<sub>3</sub>PO<sub>4</sub>, the experimental results revealed a considerable enhancement in photocatalytic activity of Gd-doped Ag<sub>3</sub>PO<sub>4</sub>. The optimum mole fraction of Gd loading in Ag<sub>3</sub>PO<sub>4</sub> was 3%. Lower photocatalytic degradation efficiency of RB19 in the presence of oxalate anion and p-benzoquinone indicated the crucial role of photogenerated holes and superoxide anion-radicals in photocatalysis on Gd-doped Ag<sub>3</sub>PO<sub>4</sub>. The enhancement of photocatalytic activity was attributed to scavenge the photoexcited electrons, and to suppress their recombination with holes and generation of active oxygen species. A nonlinear empirical kinetic model was introduced to predict the apparent first order rate constant (<em>k<sub>app</sub></em>) as a function of operational parameters, including initial RB19 concentration, Gd-doped Ag<sub>3</sub>PO<sub>4</sub> dosage and light intensity. Degradation byproducts were identified using gas chromatography-mass spectrometry and a probable pathway was proposed. Moreover, Gd-doped Ag<sub>3</sub>PO<sub>4</sub> samples displayed adequate reusability after three successive experiments.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.11.026","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"1737691","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 32
Activated vs. pyrolytic carbon as support matrix for chemical functionalization: Efficient heterogeneous non-heme Mn(II) catalysts for alkene oxidation with H2O2 活性碳与热解碳作为化学功能化的支持基质:H2O2氧化烯烃的高效非血红素Mn(II)催化剂
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.08.033
A. Simaioforidou, M. Papastergiou, A. Margellou, D. Petrakis, M. Louloudi
{"title":"Activated vs. pyrolytic carbon as support matrix for chemical functionalization: Efficient heterogeneous non-heme Mn(II) catalysts for alkene oxidation with H2O2","authors":"A. Simaioforidou,&nbsp;M. Papastergiou,&nbsp;A. Margellou,&nbsp;D. Petrakis,&nbsp;M. Louloudi","doi":"10.1016/j.molcata.2016.08.033","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.08.033","url":null,"abstract":"<div><p>Two types of heterogeneous catalytic materials, <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@Cox</strong> and <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@PCox</strong>, have been synthesized and compared by covalent grafting of a catalytically active [<strong>Mn<sup>II</sup>-L<sub>3</sub>imid]</strong> complex on the surface of an oxidized activated carbon (<strong>Cox)</strong> and an oxidized pyrolytic carbon from recycled-tire char (<strong>PCox)</strong>. Both hybrids are non-porous bearing graphitic layers intermixed with disordered sp<sup>2</sup>/sp<sup>3</sup> carbon units. Raman spectra show that (I<sub>D</sub>/I<sub>G</sub>)<sub>activatedcarbon</sub> <!-->&gt;<!--> <!-->(I<sub>D</sub>/I<sub>G</sub>)<sub>pyrolyticcarbon</sub> revealing that oxidized activated carbon(<strong>Cox)</strong> is less graphitized than oxidized pyrolytic carbon (<strong>PCox)</strong>. The <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@Cox</strong> and <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@PCox</strong> catalysts were evaluated for alkene oxidation with H<sub>2</sub>O<sub>2</sub> in the presence of CH<sub>3</sub>COONH<sub>4</sub>. Both showed high selectivity towards epoxides and comparing the achieved yields and TONs, they appear equivalent. However, <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@PCox</strong> catalyst is kinetically faster than the <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@Cox</strong> (accomplishing the catalytic runs in 1.5<!--> <!-->h <em>vs</em>. 5<!--> <!-->h). Thus, despite the similarity in TONs <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@PCox</strong> achieved extremely higher TOFs <strong><em>vs</em>. Mn<sup>II</sup>-L<sub>3</sub>imid@Cox</strong>. Intriguingly, in terms of recyclability, <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@Cox</strong> could be reused for a 2th run showing a ∼20% loss of its catalytic activity, while <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@PCox</strong> practically no recyclable. This phenomenon is discussed in a mechanistic context; interlinking oxidative destruction of the Mn-complex with high TOFs for <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@PCox</strong>, while the low-TOFs of <strong>Mn<sup>II</sup>-L<sub>3</sub>imid@Cox</strong> are preventive for the oxidative destruction of the Mn-complex.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.08.033","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"1737687","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 22
Magnetically recoverable copper oxide catalysts for aerobic allylic oxidation of cyclohexene 磁可回收铜氧化物催化剂用于环己烯的好氧烯丙基氧化
IF 5.062
Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI: 10.1016/j.molcata.2016.07.044
Fernanda Parra da Silva , Renato V. Gonçalves , Liane M. Rossi
{"title":"Magnetically recoverable copper oxide catalysts for aerobic allylic oxidation of cyclohexene","authors":"Fernanda Parra da Silva ,&nbsp;Renato V. Gonçalves ,&nbsp;Liane M. Rossi","doi":"10.1016/j.molcata.2016.07.044","DOIUrl":"https://doi.org/10.1016/j.molcata.2016.07.044","url":null,"abstract":"<div><p>Magnetically recoverable copper oxide catalysts prepared by sol-immobilization method exhibited interesting properties for the allylic oxidation of cyclohexene with molecular oxygen as the sole oxidant. The catalysts were prepared by immobilization of pre-synthesized PVA (polyvinyl alcohol)-stabilized Cu<sub>2</sub>O nanoparticles (NPs) on a magnetically recoverable support; the catalyst was further oxidized to CuO NPs after calcination at 600<!--> <!-->°C. Both catalysts can selectively oxidize cyclohexene through allylic oxidation to give 2-cyclohexene-1-one as the main product, but CuO was identified as the most active species providing 90% cyclohexene conversion and 96% selectivity for allylic products under 100<!--> <!-->°C and 4<!--> <!-->bar pressure of O<sub>2</sub> for 6<!--> <!-->h of reaction time. The catalysts were magnetically recovered without metal leaching and could be reused in at least six consecutive runs.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":null,"pages":null},"PeriodicalIF":5.062,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.07.044","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2391730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 23
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