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Corresponding Author

Jian-xin LI(jxli@tjpu.edu.cn)

Abstract

Cyclohexanone and cyclohexanol (KA oil) obtained from highly selective oxidation of cyclohexane (CHA) show important industrial value and application prospects. In this work, the intermittent electrodeposition was developed to prepare nano-MnOx catalyst loading porous tubular titanium membrane electrode (MnOx/Ti), which was employed to constitute an electro-catalytic membrane reactor (ECMR) for the oxidation of cyclohexane to produce cyclohexanol and cyclohexanone. The surface morphology, crystal structure and electrochemical property of the catalysts were characterized by FESEM, XRD and electrochemical workstation, respectively. The results show that the catalyst prepared by the intermittent electrodeposition displayed nano-flower-like γ-MnO2. Compared with titanium membrane, the MnOx/Ti electrocatalytic membrane exhibited better electrochemical performance and mass transfer performance. Furthermore, the ECMR was constructed by using the MnOx/Ti electrocatalytic membrane as the anode and the stainless steel mesh as the cathode. When the initial concentration of cyclohexane was 30 mmol·L-1, the reaction temperature was 30oC, the residence time was 34.3 min and the current density was 2.3 mA·cm-2. The cyclohexane conversion rate reached 25.6% and the total selectivity of KA oil exceeded 99%. Simultaneously, the ECMR with MnOx/Ti electrode showed a good stability during the oxidation of cyclohexane.

Graphical Abstract

Keywords

intermittent electrodeposition, MnOx/Ti electrocatalytic membrane, electrocatalytic membrane reactor, cyclohexane oxidation, cyclohexanol and cyclohexanone

Publication Date

2020-06-28

Online Available Date

2019-04-25

Revised Date

2019-04-18

Received Date

2019-03-12

References

[1] Alshehri A A, Alhanash A M, Eissa M, et al. New catalysts with dual-functionality for cyclohexane selective oxidation[J]. Applied Catalysis A General, 2018,554:71-79.

[2] Yu A P, Chen Z W, Maric R, et al. Electrochemical supercapacitors for energy storage and delivery: advanced materials, technologies and applications[J]. Applied Energy, 2015,153(SI):1-2.

[3] Loncarevic D, Krstic J, Dostanic J, et al. Cyclohexane oxidation and cyclohexyl hydroperoxide decomposition by poly(4-vinylpyridine-co-divinylbenzene) supported cobalt and chromium complexes[J]. Chemical Engineering Journal, 2010,157(1):181-188.

[4] Makgwane P R, Ray S S. Efficient room temperature oxidation of cyclohexane over highly active hetero-mixed WO3/V2O5 oxide catalyst[J]. Catalysis Communication 2014,54:118-123.
doi: 10.1016/j.catcom.2014.05.031 URL

[5] Selvamani a, Selvaraj M, Gurulakshmi M, et al. Selective oxidation of cyclohexane using Ce1-xMnxO2 nanocatalysts[J]. Journal of Nanoscience & Nanotechnology, 2014,14(4):2864-2870.
doi: 10.1166/jnn.2014.8637 URL pmid: 24734702

[6] Zabihi M, Khorasheh F, Shayegan J. Supported copper and cobalt oxides on activated carbon for simultaneous oxidation of toluene and cyclohexane in air[J]. RSC Advances, 2014,5(7):5107-5122.
doi: 10.1039/C4RA14430A URL

[7] Wang L B, Zhao S T, Liu C X, et al. Aerobic oxidation of cyclohexane on catalysts based on twinned and single-crystal Au75Pd25 bimetallic nanocrystals[J]. Nano Letters, 2015,15(5):2875-2880.
doi: 10.1021/nl5045132 URL pmid: 25839191

[8] Yu H, Peng F, Tan J, et al. Selective catalysis of the aerobic oxidation of cyclohexane in the liquid phase by carbon nanotubes[J]. Angewandte Chemie International Edition, 2011,50(17):3978-3982.
doi: 10.1002/anie.201007932 URL pmid: 21433233

[9] Yang X X, Yu H, Peng F, et al. Confined iron nanowires enhance the catalytic activity of carbon nanotubes in the aerobic oxidation of cyclohexane[J]. ChemSusChem, 2012,5(7):1213-1217.
doi: 10.1002/cssc.201100807 URL pmid: 22488987

[10] Li J, Shi Y, Xu L, et al. Selective oxidation of cyclohexane over transition-metal-incorporated HMS in a solvent-free system[J]. Industrial & Engineering Chemistry Research, 2010,49(11):5392-5399.

[11] Fei F, Chen L, Zhao C L, et al. Distribution of chlorpyrifos in rice paddy environment and its potential dietary risk[J]. Journal of Environmental Sciences, 2015,35(9):101-107.
doi: 10.1016/j.jes.2015.02.015 URL

[12] Zhong W Z, Qiao T, Dai J, et al. Visible-light-responsive sulfated vanadium-doped TS-1 with hollow structure: Enhanced photocatalytic activity in selective oxidation of cyclohexane[J]. Journal of Catalysis, 2015,330:208-221.

[13] Xu L X, He C H, Zhu M Q, et al. Silica-supported gold catalyst modified by doping with titania for cyclohexane oxidation[J]. Catalysis Letters, 2007,118(3/4):248-253.
doi: 10.1007/s10562-007-9178-6 URL

[14] Mishra G S, Sinha S. Oxidation of cyclohexane with molecular oxygen catalyzed by SiO2 supported palladium catalysts[J]. Catalysis Letters, 2008,125(1/2):139-144.
doi: 10.1007/s10562-008-9535-0 URL

[15] Li L( 李乐), Wang H( 王虹), Ma R H( 马荣花), et al. Preparation of nano-manganite loaded titanium electocatalytic membrane electrode for phenolic wastewater treatment[J]. Journal of Electrochemistryl( 电化学), 2018,24(4):309-318.

[16] Fang X, Yin Z, Wang H, et al. Controllable oxidation of cyclohexane to cyclohexanol and cyclohexanone by a nano-MnOx/Ti electrocatalytic membrane reactor[J]. Journal of Catalysis, 2015,329:187-194.
doi: 10.1016/j.jcat.2015.05.004 URL

[17] Xiao Z, Zhan W C, Guo Y, et al. The synjournal of Codoped SAPO-5 molecular sieve and its performance in the oxidation of cyclohexane with molecular oxygen[J]. Chinese Journal of Catalysis, 2016,37(2):273-280.
doi: 10.1016/S1872-2067(15)61014-2 URL

[18] Hereijgers B P C, Weckhuysen B M. Aerobic oxidation of cyclohexane by gold-based catalysts: new mechanistic insight by thorough product analysis[J]. Journal of Catalysis, 2013,270(1):16-25.
doi: 10.1016/j.jcat.2009.12.003 URL

[19] Liu H U, Cui Z F. Optimization of operating conditions for glucose oxidation in an enzymatic membrane bioreactor[J]. Journal of Membrane Science, 2007. 302(1):180-187.
doi: 10.1016/j.memsci.2007.06.044 URL

[20] Yoshida J I, Kim H, Nagaki A. Green and sustainable chemical synjournal using flow microreactors[J]. ChemSus-Chem, 2011,4(3):331-340.

[21] Qi Y B, Zhang Y J, Yin Z, et al. Effect of solvent on conversion and selectivity during the selective oxidation of cyclohexane by nano-5/Ti membrane electrode[J]. Journal of The Electrochemical Society, 2018,165(9):460-465.

[22] Clarke C J, Browning G J, Donne S W. An RDE and RRDE study into the electrodeposition of manganese dioxide[J]. Electrochimica Acta, 2006,51(26):5773-5784.

[23] Huang Y, Yan H J, Tong Y J. Electrocatalytic determination of reduced glutathione using rutin as a mediator at acetylene black spiked carbon paste electrode[J]. Journal of Electroanalytical Chemistry, 2015,743:25-30.

[24] Wu M Z, Zhan W C, Guo Y, et al. Solvent-free selective oxidation of cyclohexane with molecular oxygen over manganese oxides: Effect of the calcination temperature[J]. Chinese Journal of Catalysis, 2016,37(1):184-192.

[25] Wu M Z, Zhan W C, Guo Y L, et al. An effective Mn-Co mixed oxide catalyst for the solvent-free selective oxidation of cyclohexane with molecular oxygen[J]. Applied Catalysis A - General, 2016,523:97-106.

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