Research Note pubs.acs.org/IECR
Zirconia-Supported Ruthenium Catalyst for Efficient Aerobic Oxidation of Alcohols to Aldehydes Yo-Han Kim,† Seung-Kyu Hwang,‡ Jung Won Kim,*,‡ and Yoon-Sik Lee*,† †
School of Chemical and Biological Engineering, Seoul National University, 1 Gwanak-Ro, Gwanak-Gu, Seoul 151-742, Republic of Korea ‡ Department of Chemical Engineering, Kangwon National University at Samcheok, 1 Joonang-Ro, Samcheok, Kangwon 245-711, Republic of Korea S Supporting Information *
ABSTRACT: We have developed the supported ruthenium catalyst (Ru(OH)x/ZrO2) that shows highly efficient catalytic performance for the oxidation of activated, nonactivated, and heterocyclic alcohols with only 1 atm of molecular oxygen as a green oxidant. The ruthenium active site gave excellent aerobic alcohol oxidation reaction (turnover number (TON) = 63 000). The catalyst was easily recovered after the reaction and could be reused without a significant loss of its catalytic performance.
1. INTRODUCTION A catalytic oxidation of alcohols to the corresponding ketones or aldehydes has received noticeable attention and is one of the most important reactions both in organic synthesis and in fine chemical industry.1−4 Traditional methods for the oxidation of alcohols require stoichiometric amount of metal oxidants (e.g., dichromate and permanganate), which are expensive, highly toxic, or produce large amounts of harmful metal salts as waste.4,5 For this reason, environmentally friendly systems that use “greener oxidants”, such as molecular oxygen or hydrogen peroxide as a sole oxidant, have been developed to reduce the chemical waste.6−10 Although homogeneous transition-metal catalysts have been reported for the oxidation of alcohols with molecular oxygen, they need additives such as bases (as hydrogen acceptors) and/or co-catalysts and have not been applied for aerobic oxidation of a wide range of alcohols.11−15 Therefore, the heterogeneous catalytic aerobic oxidation is desirable for decreasing the environmental burden by the reuse and easy separation of the catalysts. The heterogeneous catalysts generally suffer from lower catalytic activity than their counterparts, homogeneous catalysts. Much effort has been made to overcome the problem in heterogeneous catalytic system.1 Various heterogeneous catalysts containing transition metals, such as Au, Pd, and Ru have also been developed for aerobic alcohol oxidation reaction using molecular oxygen. These metal nanoparticle (NP) catalysts were supported on various solid materials. Pd NPs have been loaded on carbon,16 alumina,17 hydroxyapatite (HAP),18 and SiO2−Al2O3 mixed oxide19 for aerobic benzyl alcohol oxidation. The supported Pd catalysts showed sufficiently good turnover frequencies (TOFs) from 684 h−1 to 10 080 h−1. However, they produced the corresponding benzaldehyde with a selectivity of 98%). Alicyclic alcohol such as cyclopentanol was selectively oxidized to the corresponding cyclic ketone (entry
12). Ru(OH)x/ZrO2 performed well in the oxidation of alcohols containing heteroatoms such as oxygen (entry 13), sulfur (entry 14), and nitrogen (entry 15) to the corresponding carbonyl compounds with high yields. The TOF reached to 200 h−1, which is significantly higher than those with previously reported heterogeneous catalysts like Ru/Ni(OH)2 (TOF = 66 12550
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Research Note
h−1),24 Ru/HAP (TOF = 2 h−1),18 Ru/alumina (TOF = 40 h−1),5 and Ru/Mg−LaO (TOF = 2 h−1).34 The heterogeneous catalytic system without solvents would be more practical for developing industrial process. Solvent-free oxidation of benzyl alcohol with Ru(OH)x /ZrO 2 was demonstrated at 100 °C and the turnover number (TON) reached 63 000 (eq 1). The Ru(OH)x/ZrO2 catalyst could be easily removed from the reaction mixture by a simple filtration method, and recycled ten times without significant loss of its original catalytic performance (see the recycling result in Figure S3 in the Supporting Information). In addition, ruthenium species were not detected from the reaction supernatant via ICP-AES analysis.
microscopy images were supported by National Center for Interuniversity Research Facilities at Seoul National University.
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3. CONCLUSION Ru(OH)x/ZrO2 is an efficient heterogeneous catalyst for selective aerobic alcohol oxidation. The highly active ruthenium active site (Ru−OH) was well-deposited on the surface of ZrO2 without forming any ruthenium oxide or ruthenium metal nanoparticles. The ruthenium active site promoted excellent aerobic alcohol oxidation reaction (turnover number (TON) = 63 000), because of the surface chemical environment on ZrO2 having unsaturated Lewis acid−base pairs. The catalyst can be separated easily and recycled 10 times without any loss of catalytic performance. Our results with Ru(OH)x/ZrO2 catalyst will facilitate the development of green chemical processes for industrial alcohol oxidation.
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ASSOCIATED CONTENT
S Supporting Information *
Materials and general experimental procedures were given in detail. XRD patterns of Ru(OH)x/ZrO2 fabricated from commercially available ZrO2 and fresh ZrO2 were taken at 10°−70° (2θ). XPS spectra of Ru(OH)x/ZrO2 were obtained at Ru 3d and O 1s. The results of aerobic benzyl alcohol oxidation were obtained by using our catalyst and various commercially available Ru catalysts. The catalytic performance of Ru(OH)x/ZrO2 for aerobic benzyl alcohol oxidation reaction was shown after each recycling test over 10 times. This material is available free of charge via the Internet at http://pubs.acs. org/.
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REFERENCES
AUTHOR INFORMATION
Corresponding Authors
*Tel.: +82-2-880-7073. Fax: +82-2-876-9625. E-mail: jwemye@ kangwon.ac.kr (J. W. Kim). *Tel.: +82-2-880-7073. Fax: +82-2-876-9625. E-mail: yslee@ snu.ac.kr (Y.-S. Lee). Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by the Brain Korea 21 Plus (BK21 Plus) program, Ministry of Education (5261-20130100), and National Research Foundation in Korea (NRF). This research was also supported by National Research Foundation of Korea (No. NRF-2012R1A1A1041991). The transmission electron 12551
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