无额外供氢体下负载型MoFeO<sub><i>x</i></sub>催化剂催化甘油制丙烯醇

引用本文: 兰海, 肖熙, 袁善良, 张彪, 周桂林, 蒋毅. 无额外供氢体下负载型MoFeO_x催化剂催化甘油制丙烯醇[J]. 物理化学学报, 2017, 33(11): 2301-2309. doi: 10.3866/PKU.WHXB201705261 shu

Citation: LAN Hai, XIAO Xi, YUAN Shan-Liang, ZHANG Biao, ZHOU Gui-Lin, JIANG Yi. MoFeO_x-Supported Catalysts for the Catalytic Conversion of Glycerol to Allyl Alcohol without External Hydrogen Donors[J]. Acta Physico-Chimica Sinica, 2017, 33(11): 2301-2309. doi: 10.3866/PKU.WHXB201705261 shu

无额外供氢体下负载型MoFeO_x催化剂催化甘油制丙烯醇

兰海 ^1,2, ,
肖熙 ^1,2, ,
袁善良 ^1,2, ,
张彪 ^1, ,
周桂林 ^3, ,
蒋毅 ^1,

1.
中国科学院成都有机化学研究所, 成都 610041;
2.
中国科学院大学, 北京 100049;
3.
重庆工商大学, 环境与资源学院, 材料科学与工程系, 催化与功能有机分子重庆市重点实验室, 重庆 400067
基金项目:
中国科学院“西部之光”项目

摘要: 采用浸渍法制备MoFe/X（X=SnO₂，ZrO₂，CeO₂，TiO₂，CNTs，MgO）以及MoFe氧化物催化剂用于甘油气-固相催化转化制丙烯醇。通过XRD、BET、XPS、H₂-TPR和NH₃-TPD表征，MoFe主要由晶相Fe₂O₃和Fe₂（MoO₄）₃组成而MoFe/X主要为高分散态的Fe、Mo氧化物（Fe³⁺、Mo⁶⁺），其表面均只存在弱酸中心；所采用载体由于自身性质（比表面积和酸碱性）差异与Mo、Fe氧化物之间存在不同的相互作用，进而有效地调控了MoFe/X的表面弱酸强度、酸浓度和可还原性能。所制备催化剂对甘油制丙烯醇的催化性能（收率）依次为：MoFe/TiO₂ > MoFe/CeO₂ > MoFe/ZrO₂ > MoFe/CNTs >> MoFe/SnO₂ > MoFe >> MoFe/MgO。340℃时，MoFe/TiO₂上甘油的转化率达到83.4%，丙烯醇的选择性和收率分别达到26.7%和22.3%；同时其展现出优于MoFe/CeO₂、MoFe/ZrO₂和MoFe/CNTs的稳定性。甘油转化率与催化剂表面弱酸中心浓度呈正相关性，而丙烯醇的生成则与氧化中心（非酸中心）密切相关。甘油转化率和丙烯醇选择性在MoFe/X上随反应温度变化而呈现相悖的变化趋势。

关键词:

English

MoFeO_x-Supported Catalysts for the Catalytic Conversion of Glycerol to Allyl Alcohol without External Hydrogen Donors

1.
Chengdu Institute of Organic Chemistry, Chinese Academy of Science, Chengdu 610041, P. R. China;
2.
University of Chinese Academy of Science, Beijing 100049, P. R. China;
3.
Chongqing Key Laboratory of Catalysis & Environmental New Materials, Department of Materials Science and Engineering, College of Environment and Resources, Chongqing Technology and Business University, Chongqing 400067, P. R. China
Received Date: 19 April 2017
Revised Date: 19 May 2017
Fund Project:
The project was supported by CAS “light of West China” Program 2015

Abstract: Supported MoFe/X (X=SnO₂, ZrO₂, CeO₂, TiO₂, CNTs (Carbon nano-tubes)), MgO and MoFe oxide catalysts were prepared for use in the catalytic conversion of glycerol to allyl alcohol. The prepared catalysts were characterized by XRD, BET, XPS, H₂-TPR, and NH₃-TPD. The results showed that Fe and Mo oxides with high chemical value (Fe³⁺ and Mo⁶⁺) predominated in MoFe/X MoFe oxide catalysts, which exhibited only weakly acidic properties. The applied supports with different physicochemical characteristics showed distinct interactions with Mo and Fe oxides, modifying the concentration of surface weak acid site, acid strength, and reducibility of MoFe/X oxide catalysts. The catalysts, based on their catalytic performance for glycerol conversion to allyl alcohol, can be ranked in terms of allyl alcohol yield as MoFe/TiO₂ > MoFe/CeO₂ > MoFe/ZrO₂ > MoFe/CNTs >> MoFe/SnO₂ > MoFe >> MoFe/MgO. Over the MoFe/TiO₂, a maximum allyl alcohol yield of 22.3% was from glycerol conversion of 83.4%, which had a selectivity of 26.7%. The MoFe/TiO₂ also showed higher catalytic stability than the MoFe/CeO₂, MoFe/ZrO₂, and MoFe/CNTs oxide catalysts. The glycerol conversion showed positive relationship with the surface weak acid concentration of MoFe and MoFe/X catalysts, while the allyl alcohol was produced over the redox sites (non-acid sites) of catalysts. With increasing reaction temperature, the glycerol conversion increased, while the allyl alcohol selectivity decreased, over the MoFe/X oxide catalysts.

Key words:

1. [1]
  (1) Yang, F. X.; Hanna, M. A.; Sun, R. C. Biotechnol. Biofuels 2012, 5, 13. doi: 10.1186/1754-6834-5-13
2. [2]
  (2) Anwar, U. F. Fuel 2008, 87 (3), 265. doi: 10.1016/j.fuel.2007.05.003
3. [3]
  (3) Wang, Y. L.; Zhou, J. X.; Guo, X. W. RSC Adv. 2015, 5 (91), 74611. doi: 10.1039/C5RA11957J
4. [4]
  (4) Zheng, Y. G.; Chen, X. L.; Shen, Y. C. Chem. Rev. 2010, 110 (3), 1807. doi: 10.1021/cr100058u
5. [5]
  (5) Nakagawa, Y.; Tomishige, K. Catal. Sci. Technol. 2011, 1 (2), 179. doi: 10.1039/C0CY00054J
6. [6]
  (6) Zhou, C. H.; Beltramini, J. N.; Fan, Y. X.; Lu, G. Q. Chem. Soc. Rev.2008, 37 (3), 527. doi: 10.1039/B707343G
7. [7]
  (7) Tran, N. H.; Kannangara, G. S. K. Chem. Soc. Rev. 2013, 42 (24), 9454. doi: 10.1039/C3CS60227C
8. [8]
  (8) Bagheri, S.; Julkapli, N. M.; Yehye, W. A. Renew. Sust. Energ. Rev.2015, 41, 113. doi: 10.1016/j.rser.2014.08.031
9. [9]
  (9) Xiao, W. Y.; Wang, F.; Xiao, G. M. RSC Adv. 2015, 5 (78), 63697. doi: 10.1039/C5RA07593A
10. [10]
  (10) NPCS Board of Consultants & Engineers. Industrial Alcohol Technology Handbook; Asia Pacific Business Press Inc.: Delhi, India, 2010; pp 56–78.
11. [11]
  (11) Arceo, E.; Marsden, P.; Bergman, R. G.; Ellman, J. A. Chem. Commun. 2009, 23, 3357. doi: 10.1039/B907746D
12. [12]
  (12) Tazawa, S.; Ota, N.; Tamura, M.; Nakagawa, Y.; Okumura, K.; Tomishige, K. ACS Catal. 2016, 6, 6393. doi: 10.1021/acscatal.6b01864
13. [13]
  (13) Lari, G. M.; Chen, Z. P.; Mondelli, C.; Pérez-Ramírez, J. ChemCatChem 2017, 9, 1. doi:10.1002/cctc.201601635
14. [14]
  (14) Liu, Y.; Tüysüz, H.; Jia, C. J.; Schwickardi, M. Chem. Commun. 2010, 46 (8), 1238. doi: 10.1039/B921648K
15. [15]
  (15) Konak, A.; Tag, T.; Nakamur, A.; Masud, T. Appl. Catal. B Environ. 2014, 146, 267. doi: 10.1016/j.apcatb.2013.03.007
16. [16]
  (16) Sánchez, G.; Friggieri, J.; Stockenhuber, M. Catal. Sci. Technol. 2014, 4 (9), 3090. doi: 10.1039/C4CY00407H
17. [17]
  (17) Sánchez, G.; Dlugogorski, B. Z.; Kennedy, E. M. Appl. Catal. A Gen. 2016, 509, 130. doi: 10.1016/j.apcata.2015.09.039
18. [18]
  (18) Sánchez, G.; Friggieri, J.; Stockenhuber, M. Appl. Catal. B Environ. 2014, 152-153, 117. doi: 10.1016/j.apcatb.2014.01.019
19. [19]
  (19) Suprun, W.; Lutecki, M.; Haber, T.; Papp, H. J. Mol. Catal. A Chem. 2009, 309 (1–2), 71. doi: 10.1016/j.molcata.2009.04.017
20. [20]
  (20) Deutsch, J.; Martin, A.; Lieske, H. J. Catal. 2007, 245 (2), 428. doi: 10.1016/j.jcat.2006.11.006
21. [21]
  (21) Clacens, J. M.; Pouilloux, Y.; Barrault, J. Appl. Catal. A Gen. 2002, 227 (1–2), 181. doi: 10.1016/S0926-860X(01)00920-6
22. [22]
  (22) Ülgenm, A. Conversion of Glycerol to the ValuableIntermediates Acrolein and Allyl alcohol in the Presence ofHeterogeneous Catalysts. Ph.D. Dissertation, RWTH AachenUniversity, Aachen, Germany, 2009, p. 137.
23. [23]
  (23) Wu, C. T.; Yu, K. M. K.; Liao, F. L.; Young, N.; Nellist, P.; Dent, A.; Kroner, A.; Tsang, S. C. E. Nat. Commun. 2015, 3, 1050. doi: 10.1038/NCHEM.2345
24. [24]
  (24) Athmane, B.; Ioana, F.; Bertrand, D.; Maxime, B.; Philippe, T. Microporous Mesoporous Mater. 2012, 155, 131. doi: 10.1016/j.micromeso.2012.01.028
25. [25]
  (25) Liu, Z. M.; Su, H.; Chen, B. H.; Li, J. H. Chem. Eng. J. 2016, 299, 255. doi: 10.1016/j.cej.2016.04.100
26. [26]
  (26) Tang, D. D.; Zhang, G. K. Chem. Eng. J. 2016, 238, 721. doi: 10.1016/j.cej.2015.08.019
27. [27]
  (27) Li, H. C.; Li K. Z.; Wang, H.; Zhu, X.; Cheng, X. M.; Zhai, K. Appl. Surf. Sci. 2016, 390, 513. doi: 10.1016/j.apsusc.2016.08.122
28. [28]
  (28) Kaew-arpha, T.; Mickaël, C.; Louise, J. D.; Olivier, G. Appl. Catal. B Environ. 2014, 145, 126. doi: 10.1016/j.apcatb.2013.01.043
29. [29]
  (29) Dias, A. P. S.; Rozanov, V.V.; Portela, M. F. Appl. Catal. A Gen. 2008, 345 (2), 185. doi: 10.1016/j.apcata.2008.04.040
30. [30]
  (30) Deshmanea, V. G.; Owen, S. L.; Abrokwah, R. Y.; Kuila, D. J. Mol. Catal. A Chem. 2015, 408, 202. doi: 10.1016/j.molcata.2015.07.023
31. [31]
  (31) Titus, J.; Roussière, T.; Wasserschaff, G.; Schunk, S.; Milanovc, A.; Schwabc, E.; Gläser, G. R. Catal. Today 2016, 270, 68. doi: 10.1016/j.cattod.2015.09.027
32. [32]
  (32) Zhou, G. L.; Lan, H.; Gao, T. T.; Xie, H. M. Chem. Eng. J. 2014, 246, 53. doi: 10.1016/j.cej.2014.02.059

扫一扫看文章

计量

PDF下载量: 1
文章访问数: 534
HTML全文浏览量: 36

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

无额外供氢体下负载型MoFeO_x催化剂催化甘油制丙烯醇

English

MoFeO_x-Supported Catalysts for the Catalytic Conversion of Glycerol to Allyl Alcohol without External Hydrogen Donors

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

无额外供氢体下负载型MoFeOx催化剂催化甘油制丙烯醇

English

MoFeOx-Supported Catalysts for the Catalytic Conversion of Glycerol to Allyl Alcohol without External Hydrogen Donors

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

无额外供氢体下负载型MoFeO_x催化剂催化甘油制丙烯醇

MoFeO_x-Supported Catalysts for the Catalytic Conversion of Glycerol to Allyl Alcohol without External Hydrogen Donors

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs