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The Low Temperature Solvent-Free Aerobic Oxidation of Cyclohexene to Cyclohexane Diol Over Highly Active Au/Graphite and Au/Graphene Catalysts

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The Low Temperature Solvent-Free Aerobic Oxidation of Cyclohexene to Cyclohexane Diol Over Highly Active Au/Graphite and Au/Graphene Catalysts catalysts Article The Low Temperature Solvent-Free Aerobic Oxidation of Cyclohexene to Cyclohexane Diol over Highly Active Au/Graphite and Au/Graphene Catalysts Owen Rogers 1, Samuel Pattisson 1, Joseph Macginley 1 ID , Rebecca V. Engel 1, Keith Whiston 2, Stuart H. Taylor 1,* ID and Graham J. Hutchings 1,* ID 1 Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK; [email protected] (O.R.); [email protected] (S.P.); [email protected] (J.M.); [email protected] (R.V.E.) 2 INVISTA Performance Technologies, the Wilton Centre, Wilton, Redcar TS10 4RF, UK; [email protected] * Correspondence: [email protected] (S.H.T.); [email protected] (G.J.H.); Tel.: +44-2920-874-062 (S.H.T.); +44-2920-874-059 (G.J.H.) Received: 2 July 2018; Accepted: 28 July 2018; Published: 31 July 2018 Abstract: The selectivity and activity of gold-catalysts supported on graphite and graphene have been compared in the oxidation of cyclohexene. These catalysts were prepared via impregnation and sol immobilisation methods, and tested using solventless and radical initiator-free reaction conditions. The selectivity of these catalysts has been directed towards cyclohexene epoxide using WO3 as a co-catalyst and further to cyclohexane diol by the addition of water, achieving a maximum selectivity of 17% to the diol. The sol immobilisation catalysts were more reproducible and far more active, however, selectivity towards the diol was lower than for the impregnation catalyst. The results suggest that formation of cyclohexane diol through solventless oxidation of cyclohexene is limited by a number of factors, such as the formation of an allylic hydroperoxyl species as well as the amount of in situ generated water. Keywords: cyclohexene; cyclohexane diol; adipic acid; catalytic oxidation; gold; graphene 1. Introduction In recent decades, the impact of chemistry on society has largely been influenced by its capacity to make new molecules in an environmentally considerate and sustainable way. This has led to the development of catalysts with increasing efficiency and selectivity, which, when combined with the improvements in reaction engineering and purification methods, leads to greater atom economies and energy efficiencies [1]. The industrial production of adipic acid historically relies on the aerobic oxidation of cyclohexane at 125–165 ◦C and 8–15 atm, usually in the presence of a homogenous cobalt-based catalyst. The resulting product mixture of cyclohexanol and cyclohexanone, known as KA oil, is then oxidised by nitric acid to adipic acid [2,3]. Alternative technology based on cyclohexene as a raw material for cyclohexanol synthesis is also now practiced commercially, with the product still being converted to adipic acid using nitric acid oxidation. The process for producing adipic acid from KA oil via nitric acid oxidation historically produced 400,000 metric tons of N2O globally. N2O has a global warming potential approximately 300 times that of CO2 [4]. However, recent catalytic and thermal abatement of these emissions within both adipic acid and nitric acid processes has resulted in very significant reductions in attendant N2O emissions, and therefore of their environmental significance. Catalysts 2018, 8, 311; doi:10.3390/catal8080311 www.mdpi.com/journal/catalysts Catalysts 2018, 8, 311 2 of 10 However, in principle, processes for adipic acid synthesis that avoid the use of nitric acid as an oxidant eliminate concerns with N2O emissions [5–7] and offer a higher atom economy. Routes to adipic acid based on aerobic oxidation with air as the terminal oxidant are therefore of continuing research interest. The possibility of using cyclohexene as a feedstock has lately become an option because of recent improvements in the partial hydrogenation of benzene to cyclohexene in the Asahi process [8]. The higher reactivity of cyclohexene allows it to be oxidised at lower temperatures by oxidants such as O2 and hydrogen peroxide, and therefore avoids N2O formation when using nitric acid. The first step in forming adipic acid from cyclohexene is epoxidation of the alkene, which can subsequently undergo hydrolysis to form cyclohexane diol. The diol can then be converted into adipic acid through the oxidative cleavage of the C–C bond, as demonstrated by Obara et al. [9] and Rozhko et al. [10] However, the prospect of achieving the one-step conversion of cyclohexene to adipic acid is hindered by the low miscibility of cyclohexane diol in cyclohexene, therefore, a second step would be required to form adipic acid. Current epoxidations of cyclohexene require the use of stoichiometric oxygen donors such as chromates, permanganates, and periodates, which could result in complex heat management needs and by-products that are harmful to the environment [11]. Peroxides are also commonly used to act as radical initiators [12] or stoichiometric oxidants, however, these can increase the cost of the process and produce unwanted waste [13]. High yields of cyclohexene oxide are also mostly achieved using specific solvents, which can become uneconomical and contribute to the high levels of waste produced [14]. Therefore, the most sustainable alternative would be to run the reaction under solventless conditions using air [15] or oxygen [16] as the oxidant. However, this leads to lower selectivity where mainly products of allylic oxidation are observed [17,18]. In previous work, Sato et al. achieved the one-pot solventless oxidation of cyclohexene to adipic acid in the presence of an Na2WO4·2H2O catalyst, a phase transfer catalyst, and 30% hydrogen peroxide [19]. This produced a 90% yield of adipic acid after 8 h at 90 ◦C in air. However, this reaction required 4.0 to 4.4 molar equivalents of H2O2 to cyclohexene. This ratio renders the process uneconomical on an industrial scale because of the expense of using hydrogen peroxide in these relative amounts. The presence of a toxic phase transfer catalyst is also a major drawback of this approach. Gold nanoparticles have been shown to be active in a number of reactions, despite being originally considered chemically inactive. Since the pioneering work on gold nanoparticles by Haruta and Hutchings [20,21], gold has been shown to be active in several reactions, namely, low-temperature CO oxidation [22,23], C–C bond coupling [24,25], selective hydrogenation [26–28], and oxidations [29,30]. Ovoshchnikov et al. assessed the reactivity of Au-based catalysts for cyclohexene oxidations using solvent-free and initiator-free conditions [31]. It was found that the selectivity of the oxidations could be altered from allylic products to the epoxide via the choice of co-catalyst. A WO3 co-catalyst was found to shift the selectivity towards cyclohexene oxide, while MIL-101 catalysed conversion of cyclohexenyl hydroperoxide to the allylic products. Using a WO3 and Au/SiO2 system, they could achieve 50% conversion and 26% selectivity towards the epoxide as the main product at 65 ◦C and 1 atm O2. WO3 achieves this by promoting the reaction between cyclohexenyl hydroperoxide and cyclohexene to create cyclohexene oxide and 2-cyclohexen-1-ol, as shown in Scheme1. As a result of these findings, herein we present an investigation into the selective oxidation of cyclohexene under solventless and radical initiator free conditions to target cyclohexanediol with Au-based catalysts. Catalysts 2018, 8, 311 3 of 10 Catalysts 2018, 8, x FOR PEER REVIEW 3 of 10 Scheme 1. Proposed mechanism by Ovoshchnikov et al. for cyclohexene oxidation [31]. [31]. 2. Results The aim of this work was to modify conditions used by Ovoshchnikov et al. in order to achieve further oxidation of the epoxide to yieldyield cyclohexanecyclohexane diol. For For all all catalysts, the the Au content was maintained at at 1 1 wt wt % % with with either either a agraphite graphite or or graphene graphene support. support. The The catalysts catalysts were were prepared prepared via viaan impregnationan impregnation method method or ora sol a sol immobilisation immobilisation me methodthod and and then then analysed analysed by by TEM (transmission electron microscopy) and STEM (scanning transmissi transmissionon electron microscopy) techniques to quantify nanoparticle size and establish a relationship between nanoparticle size and selectivity to the desired ◦ products. Unless Unless otherwise otherwise stated, stated, all all reactions reactions were were run run at at 3 bar O 2 atat 60 60 °CC for for 24 24 h, h, with 0.1 g of catalyst (5.08 × 1010−6− Au6 Au mol mol %). %). The The results results are are presented presented in in Table Table 1.1 . a Table 1. Performance of catalysts in cyclohexene oxidation a. SelectivitySelectivity (%) (%) CatalystCatalyst ConversionConversion (%) (%) Cy–OxideCy–Oxide Cy–OlCy–Ol Cy–OneCy–One Cy–DiolCy–Diol Blank - 1.7 3.2 41.6 47.5 2.3 Blank - 1.7 3.2 41.6 47.5 2.3 GraphiteGraphite -- 0.60.6 3.63.6 20.120.1 29.229.2 2.72.7 GrapheneGraphene -- 4.34.3 13.413.4 26.926.9 48.748.7 0.10.1 WOWO3 -- 10.310.3 37.037.0 39.539.5 12.412.4 5.25.2 II 8.58.5 13.713.7 17.317.3 38.438.4 1.41.4 1%1% Au/graphite Au/graphite SS 61.461.4 3.93.9 15.615.6 55.355.3 4.54.5 b II 17.717.7 29.829.8 31.131.1 22.222.2 5.15.1 1%1% Au/graphite Au/graphite ++ WOWO33 b SS 75.275.2 0.40.4 16.416.4 37.037.0 13.713.7 II 25.925.9 10.110.1 18.218.2 53.353.3 3.13.1 1%1% Au/graphene Au/graphene SS 73.273.2 0.00.0 18.618.6 56.056.0 7.87.8 b II 41.641.6 7.17.1 21.321.3 46.446.4 5.25.2 1%1% Au/graphene Au/graphene ++ WOWO33 b SS 76.176.1 0.00.0 17.017.0 48.848.8 9.09.0 a a Reactionconditions: conditions: cyclohexene cyclohexene (10 (10 mL), mL), n-decane n-decane (1 mL) (1 as mL) an internalas an internal standard, st catalystandard, (0.1 catalyst g), O2 (0.1(3 atm), g), 60 ◦C, 24 h, glass reactor.
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