화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.86, 220-231, June, 2020
DOI10.1016/j.jiec.2020.03.008  Export Citation
Zr-based metal.organic frameworks drived Rh.Mn catalysts for highly selective CO hydrogenation to C2 oxygenates
Xiaoya Xue, Jun Yu†, Ying Han, Xiuzhen Xiao, Zhangping Shi1, Haifang Mao, and Dongsen Mao†
  • Research Institute of Applied Catalysis, School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China
  • 1State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, SINOPEC Shanghai Research Institute of Petrochemical Technology, Shanghai, 201208, China
E-mail:,
A series of Zr-based metal-organic frameworks (UiO-66) supported Rh.Mn catalysts with various metal loadings were prepared by using a co-impregnation method, and the catalytic activities were investigated for the direct synthesis of ethanol-based C2 + oxygenates from CO hydrogenation. The catalysts were comprehensively characterized by means of N2 sorption, XRD, TEM, XPS, H2-TPR, and DRIFT. The structural and textural properties of the catalysts show clearly that the overall framework structure of UiO-66 can be beneficial to the high dispersion of supported metals, but the synergistic effect of Rh and Mn would be influenced by the metal loading or Mn/Rh ratio. When the loadings of Rh and Mn reached 3 wt.% and 3 wt.%, the catalyst has the best catalytic activity with the highest yield of C2 + oxygenates of 200.1 g/(kg h), which can be attributed to the enhanced CO dissociation ability of Rh sites and weaker Rh-CO band strength.
Keywords:UiO-66;Rh-Mn catalyst;CO hydrogenation;Ethanol
  1. Luk HT, Mondelli C, Ferre DC, Stewart JA, Perez-Ramirez J, Chem. Soc. Rev., 46, 1358 (2017)
  2. Zhang R, Liu F, Wang BJ, Catal. Sci. Technol., 6, 8036 (2016)
  3. Deng J, Li MM, Wang Y, Green. Chem., 18, 4824 (2016)
  4. Zhao L, Mu XL, Liu TS, Fang KG, Cat. Sci. Technol., 8, 2066 (2018)
  5. Sachtler WMH, Ichikawa M, J. Phys. Chem., 90, 4752 (1986)
  6. Lin PZ, Liang DB, Luo HY, Xu CH, Zhou HW, Huang SY, Lin LW, Appl. Catal. A: Gen., 131(2), 207 (1995)
  7. Yin HM, Ding YJ, Luo HY, Zhu HJ, He DP, Xiong JM, Lin LW, Appl. Catal. A: Gen., 243(1), 155 (2003)
  8. Wang Y, Luo HY, Liang DB, Bao XH, J. Catal., 196(1), 46 (2000)
  9. Mao W, Su JJ, Zhang ZP, Xu XC, Fu DL, Dai WW, Xu J, Zhou XG, Han YF, Chem. Eng. Sci., 135, 301 (2015)
  10. Yu J, Mao DS, Han LP, Guo QS, Lu GZ, J. Mol. Catal. A-Chem., 367, 38 (2013)
  11. Yu J, Mao DS, Ding D, Lu GZ, RSC Adv., 6, 76736 (2016)
  12. Liu YF, Zhang LF, Goltl F, Ball MR, Hermans I, Kuech TF, Mavrikakis M, Dumesic JA, ACS Catal., 8, 10707 (2018)
  13. Zhang RG, Peng M, Wang BJ, Catal. Sci. Technol., 7, 1073 (2017)
  14. Xu DD, Zhang HT, Ma HF, Qian WX, Ying WY, Catal. Commun., 98, 90 (2017)
  15. Haider MA, Gogate MR, Davis RJ, J. Catal., 261(1), 9 (2009)
  16. Gogate MR, Davis RJ, Catal. Commun., 11, 901 (2010)
  17. Yu J, Yu JH, Shi ZP, Guo QS, Xiao XZ, Mao MF, Mao DS, Catal. Sci. Technol., 9, 3675 (2019)
  18. Guglielminotti E, Pinna F, Rigoni M, Strukul G, Zanderighi L, J. Mol. Catal. A-Chem., 103, 105 (1995)
  19. Fan ZL, Chen W, Pan XL, Bao XH, Catal. Today, 147(2), 86 (2009)
  20. Chen GC, Guo CY, Zhang XH, Huang ZJ, Yuan GQ, Fuel Process. Technol., 92(3), 456 (2011)
  21. Won BD, Jeong MH, Kim MH, Chung CH, Moon DJ, Suh YW, Baik JH, Bae JW, Microporous Mesoporous Mater., 255, 44 (2018)
  22. Yang CS, Mu RT, Wang GS, Song JM, Tian H, Zhao ZJ, Gong JL, Chem. Sci., 10, 3161 (2019)
  23. Yang D, Odoh SO, Wang TC, Farha OK, Hupp JT, Cramer CJ, Gagliardi L, Gates BC, J. Am. Chem. Soc., 137(23), 7391 (2015)
  24. Yang D, Odoh SO, Borycz J, Wang TC, Farha OK, Hupp JT, Cramer CJ, Gagliardi L, Gates BC, ACS Catal., 6, 235 (2015)
  25. Na K, Choi KM, Yaghi OM, Somorjai GA, Nano Lett., 14, 5979 (2014)
  26. An B, Zhang JZ, Cheng K, Ji PF, Wang C, Lin WB, J. Am. Chem. Soc., 139(10), 3834 (2017)
  27. Katz MJ, Brown ZJ, Colon YJ, Siu PW, Scheidt KA, Snurr RQ, Hupp JT, Farha OK, Chem. Commun., 49, 9449 (2013)
  28. Yu J, Mao D, Han L, Guo Q, Lu G, J. Ind. Eng. Chem., 19(3), 806 (2013)
  29. Yu J, Mao DS, Lu GZ, Guo QS, Han LP, Catal. Commun., 24, 25 (2012)
  30. Han LP, Mao DS, Yu J, Guo QS, Lu GZ, Catal. Commun., 23, 20 (2012)
  31. Cavka JH, Jakobsen S, Olsbye U, Guillou N, Lamberti C, Bordiga S, Lillerud KP, J. Am. Chem. Soc., 130(42), 13850 (2008)
  32. Hu ZG, Peng YW, Kang ZX, Qian YH, Zhao D, Inorg. Chem., 54(10), 4862 (2015)
  33. Parres-Esclapez S, Such-Basanez I, Illan-Gomez MJ, de Lecea CSM, Bueno-Lopez A, J. Catal., 276(2), 390 (2010)
  34. Reyes P, Concha I, Pecchi G, Fierro JLG, J. Mol. Catal. A-Chem., 129, 269 (1998)
  35. Eriksson S, Rojas S, Boutonnet M, Fierro JLG, Appl. Catal. A: Gen., 326(1), 8 (2007)
  36. Rungtaweevoranit B, Baek J, Araujo JR, Archanjo BS, Choi KM, Yaghi OM, Somorjai GA, Nano Lett., 16, 7645 (2016)
  37. Ning LM, Liao SY, Cui HG, Yu LH, Tong XL, ACS Sustain. Chem. Eng., 6, 135 (2018)
  38. Jiang D, Ding Y, Pan Z, Li X, Jiao G, Li J, Chen W, Luo H, Appl. Catal. A: Gen., 331, 70 (2007)
  39. Yu J, Mao DS, Han LP, Guo QS, Lu GZ, Fuel Process. Technol., 106, 344 (2013)
  40. Yang AC, Garland CW, J. Phys. Chem., 61, 1504 (1957)
  41. Solymosi F, Pasztor M, J. Phys. Chem., 89, 4789 (1985)
  42. Gao J, Mo XH, Chien ACY, Torres W, Goodwin JG, J. Catal., 262(1), 119 (2009)
  43. Choi Y, Liu P, J. Am. Chem. Soc., 131(36), 13054 (2009)
  44. Ojeda M, Granados ML, Rojas S, Terreros P, Garcia-Garcia FJ, Fierro JLG, Appl. Catal. A: Gen., 261(1), 47 (2004)