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Aerobic Catalytic Oxidation of Cyclohexene Over Tizrco Catalysts

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Aerobic Catalytic Oxidation of Cyclohexene Over Tizrco Catalysts catalysts Article Aerobic Catalytic Oxidation of Cyclohexene over TiZrCo Catalysts Tong Liu 1,2,3, Haiyang Cheng 1,2,*, Weiwei Lin 1,2, Chao Zhang 1,2, Yancun Yu 1,2 and Fengyu Zhao 1,2,* 1 State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China; [email protected] (T.L.); [email protected] (W.L.); [email protected] (C.Z.); [email protected] (Y.Y.) 2 Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China 3 University of Chinese Academy of Sciences, Beijing 100049, China * Correspondence: [email protected] (H.C.); [email protected] (F.Z.); Tel.: +86-431-8526-2454 (H.C.); Tel./Fax: +86-431-8526-2410 (F.Z.) Academic Editor: Michalis Konsolakis Received: 8 December 2015; Accepted: 12 January 2016; Published: 29 January 2016 Abstract: The aerobic oxidation of hydrocarbon is of great significance from the viewpoints of both fundamental and industry studies as it can transfer the petrochemical feedstock into valuable chemicals. In this work, we investigated the aerobic oxidation of cyclohexene over TiZrCo catalysts, in which 2-cyclohexen-1-one was produced with a high selectivity of 57.6% at a conversion of 92.2%, which are comparable to the best results reported for the aerobic oxidation of cyclohexene over heterogeneous catalysts. The influences of kinds of solvent, substrate concentration and reaction temperature were evaluated. Moreover, the catalytic performance of the TiZrCo catalyst and the main catalytic active species were also discussed. The results of SEM, XRD and XPS suggested that the surface CoO and Co3O4 species are the catalytic active species and contribute to the high activity and selectivity in the present cyclohexene oxidation. The present catalytic system should have wide applications in the aerobic oxidation of hydrocarbons. Keywords: aerobic oxidation; heterogeneous catalyst; cyclohexene; TiZrCo 1. Introduction The selective oxidation of hydrocarbon is of great importance in the chemical industry, and the oxidation of alkenes to value-added chemicals has been paid more attention [1–4]. For example, 2-cyclohexen-1-one, which can be produced from oxidation of the C–H bond at the allylic site of cyclohexene, is one of the important fine chemicals because it is widely used in the manufacture of perfumes, pharmaceuticals, dyestuff and agrochemicals [5–7]. However, the yield of 2-cyclohexen-1-one produced from cyclohexene oxidation is quite low due to the existence of two active sites (C–H and C=C bond) on the cyclohexene molecule [8]. Thus, it is still a great challenge to enhance the selectivity of 2-cyclohexen-1-one by designing an efficient catalyst. For oxidation of cyclohexene, the traditional oxidants are iodosylbenzene, sodium hypochlorite, chromium trioxide, t-butyl hydroperoxide, H2O2, etc. These strong oxidants can improve the oxidation rate and increase the yield of product, but they are expensive and harmful to the environment. Therefore, developing a green oxidation process is of importance in view of the academic research and industrial application. Recently, the oxidation with molecular oxygen as an oxidant has received much attention as it is a cheap, abundant and environmentally benign process and some achievements have been obtained [9–13]. For example, the ionic liquids with metal chelate anion [C10mim][Co(F6-acac)3] exhibited high catalytic Catalysts 2016, 6, 24; doi:10.3390/catal6020024 www.mdpi.com/journal/catalysts Catalysts 2016, 6, 24 2 of 9 Catalysts 2016, 6, 24 2 of 9 activitycatalytic foractivity the allylic for the oxidation allylic ofoxidation cyclohexene of cyclohexene in the absence in the of solventabsence with of solvent a high selectivitywith a high of ´ 81%selectivity to 2-cyclohexen-1-one of 81% to 2-cyclohexen at a conversion-1-one of at 100% a conversion [10], and the of Cu-[cationic 100% [10], salphen][Br and the Cu]2-[cationiccomplex presentedsalphen][Br a− selectivity]2 complex of presented 64.1% to 2-cyclohexen-1-onea selectivity of 64.1% at to a 100%2-cyclohexen conversion-1-one for at the a aerobic100% conversion oxidation offor cyclohexene the aerobic inoxidation acetonitrile of cyclohexene [11]. Although in acetonitrile these homogeneous [11]. Although catalysts these are efficienthomogeneous for the catalysts selective allylicare efficient oxidation for the of cyclohexene,selective allylic their oxidation industrial of applicationcyclohexene, is limitedtheir industrial due to the application difficult separation, is limited anddue theto the residual difficult metal separation, ions will and affect the the residual quality metal of the ions product. will affect Hence, the quality heterogeneous of the product. catalysts Hence, have beenheterogeneous developed catalysts by immobilizing have been metal developed complexes by immobilizing on solid supports, metal suchcomplexes as resinate-immobilized on solid supports, Co(II),such as which resinate exhibited-immobilized high catalytic Co(II), activitywhich exhibited with a 44.4% high selectivity catalytic activity to 2-cyclohexen-1-one with a 44.4% selectivity at a 94.5% conversionto 2-cyclohexen of cyclohexene-1-one at a [ 1294.5%]. Core-shell conversion type of Fe 3cyclohexeneO4@chitosan-Schiff [12]. Core base-immobilized-shell type Fe3O Co(II),4@chitosan Cu(II)- andSchiff Mn(II) base- complexesimmobilized were Co(II), also reportedCu(II) and active Mn(II) for thecomplexes cyclohexene were oxidation,also reported and aactive selectivity for the of 77.2%cyclohexene to 2-cyclohexen-1-one oxidation, and a selectivity was obtained of 77.2% at a to conversion 2-cyclohexen of 46.8%-1-one [ 13was]. obtained On the other at a conversion hand, the supportedof 46.8% [13] transition. On the metalother orhand, oxides the weresupported also employed transition as metal heterogeneous or oxides were catalysts also foremployed the allylic as oxidationheterogeneous of cyclohexene catalysts for [6 the,14 –allylic20]. Recently,oxidation Au of cyclohexene nanoparticles [6,14 supported–20]. Recently, on modified Au nanoparticles bentonite andsupported silica gave on modified a high conversion bentonite and (92%) silica and ga anve excellenta high conversion selectivity (92%) (97%) and to an 2-cyclohexen-1-one excellent selectivity in the(97%) aerobic to 2-cyclohexen oxidation- of1-one cyclohexene in the aerobic without oxidation solvent of [cyclohexene21]. It was alsowithout reported solvent that [21] PdO/SBA-15. It was also wasreported an active that PdO/SBA catalyst for-15 the was oxidation an active of catalyst cyclohexene for the inoxidation acetonitrile, of cyclohexene and a conversion in acetonitrile, of 56% and a selectivityconversion ofof 82%56% toand 2-cyclohexen-1-one a selectivity of 82% were to 2 obtained-cyclohexen [6].-1 In-one addition, were obtained nitrogen-doped [6]. In addition, carbon nanotubes,nitrogen-doped and graphiticcarbon nanotubes, carbon nitride-supported and graphitic carbon FeO and nitride CoO-supported were also effectiveFeO andcatalysts CoO were for also the oxidationeffective catalysts of cyclohexene for the oxidation [14,22]. Until of cyclohexene now, it was [14,22] still a hot. Until topic now, to design it was astill heterogeneous a hot topic to catalyst design fora heterogeneous the aerobic allylic catalyst oxidation for the of aerobic cyclohexene. allylic oxidation of cyclohexene. In our previous previous work, work, we we found found that that Ti Ti-Zr-Co-Zr-Co metallic metallic catal catalystyst was was effective effective for for the the oxidation oxidation of ofcyclohexane cyclohexane and and ethylbenzene ethylbenzene [23 [23–25–25], ],in in which which cyclohexanol cyclohexanol and and cyclohexanone cyclohexanone were produced with a high selectivity of of 90% 90% at at a a conversion conversion around around 7% 7%,, and and acetophenone acetophenone was was produced produced with with a a69.2% 69.2% selectivity selectivity at ata high a high co conversionnversion of of61.9%. 61.9%. The The Ti- Ti-Zr-CoZr-Co metallic metallic catalyst catalyst is simple is simple and and cheap cheap in inproduction production and and sturdy sturdy to towearing wearing in inthe the utilization, utilization, as ascompared compared to tothose those reported reported catalysts catalysts such such as asmetal metal-organic-organic complex, complex, metal metal nanoparticles nanoparticles and and nanocarbon nanocarbon materials. materials. Therefore, Therefore, it inspires it inspires us usto tostudy study itsits efficiency efficiency in in catalyzing catalyzing other other hydrocarbon hydrocarbon oxidations oxidations.. In In the the present present work, work, the catalytic performancesperformances of of the the Ti Ti-Zr-Co-Zr-Co cata catalystslysts were were discussed discussed for for the the aerobic aerobic oxidation oxidation of cyclohexene. of cyclohexene. We Wefound found that that2-cyclohexen 2-cyclohexen-1-one-1-one was produced was produced with a withhigh aselectivity high selectivity of 57.6% of at 57.6% a conversion at a conversion of 92.2%, ofwhich 92.2%, are which comparable are comparable to the best to theresults best resultsreported reported for the foraerobic the aerobic oxidation oxidation of cyclohexene of cyclohexene over overheterogeneous heterogeneous catalysts catalysts.. It was It was confirmed confirmed the the surface surface CoO CoO and and Co Co3O3O4 4actedacted as as the the catalytic catalytic active sites and contributedcontributed
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