화학공학소재연구정보센터
Korean Journal of Chemical Engineering, Vol.38, No.8, 1608-1616, August, 2021
Nitrogen-doped graphene loaded non-noble Co catalysts for liquid-phase cyclohexane oxidation with molecular oxygenNitrogen-doped graphene loaded non-noble Co catalysts for liquid-phase cyclohexane oxidation with molecular oxygen
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Selective aerobic oxidation of cyclohexane to cyclohexanone and cyclohexanol (KA oil) with high yield under mild and green conditions is still a significant challenge in the current chemical industry. Herein, nitrogen doped graphene loaded non-noble Co (Co-N-rGO) catalysts, prepared by a facile post-impregnation method, exhibited a high catalytic performance and stability in liquid phase cyclohexane oxidation with molecular oxygen. The experiment and characterization results show that N doping in the catalysts promotes Co metal particle dispersion and induces carbon film coating on Co to prevent leaching and agglomeration. Besides, density functional theory (DFT) calculations show that N doping is beneficial to the O-O bonds breaking in cyclohexyl-hydroperoxides (CHHP), thereby promoting the dissociation of CHHP and enhancing the yield to KA oil. In addition, the catalyst can be easily separated without appreciable loss of catalytic activity after recycling for five times, and show potential industrial application value for the catalytic oxidation of cyclohexane to KA oil in the chemical industry.
  1. Schuchardt U, Cardoso D, Sercheli R, Pereira R, Cruz RS, et al., Appl. Catal. A: Gen., 211, 1 (2001)
  2. Suresh AK, Sharma MM, Sridhar T, Ind. Eng. Chem. Res., 39, 3958 (2000)
  3. Li H, She YB, Wang T, Front. Chem. Sci. Eng., 6, 356 (2012)
  4. Sun L, Liu JH, Luo W, Yang Y, Wang F, Weerakkody C, Suib SL, Mol. Catal., 460, 16 (2018)
  5. Xie CJ, Wang W, Yang YP, Jiang L, Chen YJ, He J, Wang JQ, Mol. Catal., 495, 111134 (2020)
  6. Wu MZ, Zhan WC, Guo Y, Wang YS, Guo YL, Gong XQ, Wang L, Lu GZ, Chinese J. Catal., 37, 184 (2016)
  7. Wu ST, He YR, Wang CH, Zhu CM, Shi J, Chen ZY, Wan Y, Hao F, Xiong W, Liu PL, Luo HA, ACS Appl. Mater. Inter., 12, 26733 (2020)
  8. Xiao Z, Zhan WC, Guo Y, Guo YL, Gong XQ, Lu GZ, Chinese J. Catal., 37, 273 (2016)
  9. Niu XR, Sun YY, Lei ZT, Qin GS, Yang CH, Prog. Nat. Sci-Mater., 30, 35 (2020)
  10. Mo LQ, Huang XF, Huang G, Yuan GP, Wei SJ, ChemistryOpen, 8, 104 (2019)
  11. Alshaheri AA, Tahir MIM, Rahman MBA, Ravoof TBSA, Saleh TA, Chem. Eng. J., 327, 423 (2017)
  12. Zhang P, Wang J, Jia Y, Li WQ, Tan XL, Zhang D, Xu SN, Zhang PP, Wei CD, Miao SD, Appl. Clay Sci., 181, 105226 (2019)
  13. Yuan E, Gu M, Jian P, Korean J. Chem. Eng., 37(7), 1137 (2020)
  14. Ye JH, Tang JJ, Zhao YJ, Wu CD, Inorg. Chem., 59(1), 767 (2020)
  15. Wu PP, Cao YX, Wang Y, Xing W, Zhong ZY, Bai P, Yan ZF, Appl. Surf. Sci., 457, 580 (2018)
  16. Xu C, Jin LL, Wang XZ, Chen YQ, Dai LY, Carbon, 160, 287 (2020)
  17. Navalon S, Dhakshinamoorthy A, Alvaro M, Garcia H, Chem. Rev., 114(12), 6179 (2014)
  18. Long DH, Li W, Ling LC, Miyawaki J, Mochida I, Yoon SH, Langmuir, 26(20), 16096 (2010)
  19. Rao CNR, Sood AK, Subrahmanyam KS, Govindaraj A, Angew. Chem.-Int. Edit., 48, 7752 (2009)
  20. Long JL, Xie XQ, Xu J, Gu Q, Chen LM, Wang XX, ACS Catal., 2, 622 (2012)
  21. Singh AK, Basavaraju KC, Sharma S, Jang S, Park CP, Kim DP, Green Chem, 16, 3024 (2014)
  22. Qin GP, Chen XN, Yang L, Huang HM, ACS Catal., 5, 2882 (2015)
  23. Dhakshinamoorthy A, Primo A, Concepcion P, Alvaro M, Garcia H, Chem. Eur. J., 19, 7547 (2013)
  24. Li XH, Antonietti M, Angew. Chem.-Int. Edit., 52, 4572 (2013)
  25. Bai ZY, Huang RM, Niu L, Zhang Q, Yang L, Zhang JJ, Catalysts, 5, 747 (2015)
  26. Sun W, Gao LF, Feng X, Sun X, Zheng GX, Eur. J. Org. Chem., 2018, 1121 (2018)
  27. He L, Weniger F, Neumann H, Beller M, Angew. Chem.-Int. Edit., 55, 12582 (2016)
  28. Vinayan BP, Ramaprabhu S, J. Mater. Chem. A., 1, 3865 (2013)
  29. Zhou YK, Neyerlin K, Olson TS, Pylypenko S, Bult J, Dinh HN, Gennett T, Shao Z, O’Hayre R, Energy Environ. Sci., 3, 1437 (2010)
  30. Wang C, Zhai P, Zhang ZC, Zhou Y, Zhang JK, Zhang H, Shi ZJ, Han RPS, Huang FQ, Ma D, J. Catal., 334, 42 (2016)
  31. Shi RN, Zhao JX, Liu SS, Sun W, Li HX, Hao PP, Li Z, Ren J, Carbon, 130, 185 (2018)
  32. Favaro M, Agnoli S, Perini L, Durante C, Gennaro A, Granozzi G, Phys. Chem. Chem. Phys., 15, 2923 (2013)
  33. Hummers WS, Offeman RE, J. Am. Chem. Soc., 80, 1339 (1958)
  34. Tian YH, Xu L, Bao J, Qian JC, Su HN, Li HM, Gu HD, Yan C, Li HN, J. Energy Chem., 33, 59 (2019)
  35. Li JR, Zhang RG, Wang BJ, Appl. Surf. Sci., 270, 728 (2013)
  36. Jiang QG, Ao ZM, Chu DW, Jiang Q, J. Phys. Chem. C., 116, 19321 (2012)
  37. Lin Z, Waller G, Liu Y, Liu M, Wong CP, Adv. Eng. Mater., 2, 884 (2012)
  38. Formenti D, Topf C, Junge K, Ragaini F, Beller M, Catal. Sci. Technol., 6, 4473 (2016)
  39. Kumar NA, Nolan H, McEvoy N, Rezvani E, Doyle RL, Lyons MG, Duesberg GS, J. Mater. Chem. A., 1, 4431 (2013)
  40. Liang HW, Bruller S, Dong R, Zhang J, Feng XL, Mullen K, Nat. Commun., 6, 7992 (2015)
  41. Li F, Shu HB, Hu CL, Shi ZY, Liu XT, Liang P, Chen XS, ACS Appl. Mater. Inter., 7, 27405 (2015)
  42. Wang ZL, Hao XF, Jiang Z, Sun XP, Xu D, Wang J, Zhong HX, Meng FL, Zhang XB, J. Am. Chem. Soc., 137(48), 15070 (2015)