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Deoxydehydration with Molecular Hydrogen over CeriaSupported Rhenium Catalyst with Gold Promoter Shuhei Tazawa, Nobuhiko Ota, Masazumi Tamura, Yoshinao Nakagawa, Kazu Okumura, and Keiichi Tomishige ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.6b01864 • Publication Date (Web): 23 Aug 2016 Downloaded from http://pubs.acs.org on August 25, 2016
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ACS Catalysis
Deoxydehydration with Molecular Hydrogen over Ceria-Supported Rhenium Catalyst with Gold Promoter Shuhei Tazawa,† Nobuhiko Ota,† Masazumi Tamura,†§ Yoshinao Nakagawa,*†§ Kazu Okumura,‡ Keiichi Tomishige*†§ †
Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, Aoba 6-6-07, Aramaki, Aoba-ku, Sendai 980-8579, Japan ‡ Department of Applied Chemistry, Faculty of Engineering, Kogakuin University Nakano-machi 2665-1, Hachioji, Tokyo 192-0015, Japan §
Research Center for Rare Metal and Green Innovation, Tohoku University, Aoba 468-1, Aramaki, Aoba-ku, Sendai 9808579, Japan
ABSTRACT: Gold nanoparticles co-catalyst and ceria support catalyst enabled the use of H2 as a reductant for Re-catalyzed deoxydehydration (DODH), converting vicinal diols to olefins with higher activity than homogeneous Re catalysts using non-H2 reductants and with comparable selectivity. The suitable particle size (~10 nm) of Au in ReOx-Au/CeO2 catalyst was especially effective for activating H2 while retaining the C=C bond in DODH products. Glycerol was converted to allyl alcohol in 91% yield and the TON per Re atom reached 300. This system is applicable to other substrates such as erythritol (81% yield of 1,3-butadiene). KEYWORDS: heterogeneous catalysis, rhenium oxide, gold, deoxydehydration, glycerol
Catalytic removal of oxygen atoms from highly functionalized molecules has attracted much attention, especially in the field of biomass conversions.1 Among the products, unsaturated compounds are difficult to produce but are very attractive since olefinic compounds are especially important platform chemicals which are still produced primarily from petroleum resources.2-4 One of the most promising reactions is allyl alcohol production from glycerol. Allyl alcohol is currently synthesized by the hydrolysis of allyl chloride5 and it is a versatile intermediate for various useful chemicals such as agrochemicals, resin, medicine, perfume and so forth.6 Glycerol is one of the most important building blocks in the biomass-derived resources, since enormous amount of glycerol is co-produced by the biodiesel production process from vegetable oils.7,8. However, only a few systems of glycerol conversion to allyl alcohol with cheap reductant were reported: Konaka et al. reported 27% yield of allyl alcohol using K/ZrO2-FeOx catalyst without external reductant at 623 K.8 Sánchez et al. reported 19.5% yield of allyl alcohol using Fe/alumina catalyst and formic acid as a reductant at 613 K.9 In recent years, increasing interest has been paid to deoxydehydration (DODH) which typically uses Re catalyst and enables one step transformation of vicinal hydroxyl groups into C=C bond (Scheme 1).10,11 Shiramizu and Toste reported direct transformation of biomass derivatives such as sugar alcohols into corresponding DODH products including glycerol to allyl alcohol (90% yield; TON = 36) by a homogeneous Re catalyst (CH3ReO3) and a secondary alcohol as a reductant.12 Although many homogeneous catalysts with various reductants for DODH have been reported,13-18 application of heterogeneous catalysts and use of H2 is still under development.19,20
Scheme 1. A Generalized Scheme for DODH Reaction (Red=reductant, RedO=oxidized reductant). R HO
R' OH
Red
RedO + H2O R
R'
Catalyst
Recently, ReOx/TiO2 was reported as the first stable heterogeneous catalyst for DODH.21 However, there is room for improvement in the catalytic performance (58% yield of allyl alcohol from glycerol with 3-octanol reductant; TON = 18). We have very recently reported an efficient system of simultaneous removal of vicinal hydroxyl groups such as glycerol to 1-propanol with H2 and ReOx-Pd/CeO2 as the reductant and a heterogeneous combination of DODH + hydrogenation.22,23 In this catalyst, ReOx were highly dispersed in an atomic level on the surface of CeO2 which stabilizes the active high-valent isolated Re species. The role of Pd is to activate H2 and to promote the reduction of Re species, however, Pd is also a very effective hydrogenation catalyst, and olefinic products was not obtained. In order to obtain olefinic products, the component with the promotion of the Re reduction and without hydrogenation activity is necessary. We found that Au particles with an appropriate size are very effective component, and ReOx-Au/CeO2 catalyst can efficiently convert glycerol to allyl alcohol. This system can be applied to other substrates including erythritol. Erythritol is manufactured in a large scale by fermentation and its DODH product, 1,3-butadiene, is a very important chemical in industry.24-30
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Table 1. Reduction of Glycerol over Various ReOx-impM0.3/CeO2 Catalystsa Entry
Catalyst
Conv. [%]
Selectivity [%] Allyl alcohol
1-Propanol
1,2-Propanediol
1,3-Propanediol
Propanal
Hydrocarbon
Others
1
ReOx-impRu0.3/CeO2
23
1
92
2
