Citation: Li Huabo, Cui Yuanyuan, Liu Yixin, Dai Wei-Lin. Promotional Effect of Cr on Cu/SiO₂ Catalyst for the Production of Methanol from Carbonate Hydrogenation[J]. Acta Chimica Sinica, ;2019, 77(4): 371-378. doi: 10.6023/A19010012 shu

Promotional Effect of Cr on Cu/SiO₂ Catalyst for the Production of Methanol from Carbonate Hydrogenation

Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200438

Corresponding author: Dai Wei-Lin, wldai@fudan.edu.cn
Received Date: 5 January 2019
Available Online: 7 April 2019
Fund Project: the Science and Technology Commission of Shanghai Municipality 08DZ2270500the National Natural Science Foundation of China 21373054Project supported by the National Natural Science Foundation of China (No. 21373054) and the Science and Technology Commission of Shanghai Municipality (No. 08DZ2270500)

Figures(7)

Recently, it has been widely reported that CO₂ was utilized to produce valuable chemical feedstock with copper/zinc and metal oxide based catalysts, yet harsh conditions (high pressure and high temperature, etc.) are still essential for the activity and selectivity. Compared with the harsh conditions required in the direct conversion of CO₂ to achieve high selectivity and activity, mild conditions in the indirect conversion of CO₂ through the carbonate intermediate provides an alternative. Since CO₂ can be easily transferred to carbonate under mild and even atmospheric pressure of CO₂ in many reports, hydrogenation of carbonates to methanol at ambient condition presents an attractive strategy for the indirect conversion of CO₂ with higher catalytic activity. In our previous work, we have reported that Cu/SiO₂ catalyst achieved satisfying performance for the hydrogenation of diethyl carbonate with poor stability at long term running due to the agglomeration of active metal. Herein, we present that the catalytic activity and stability of the catalysts in the hydrogenation of carbonates could be efficiently improved by the addition of Cr. In this research, various Cr-promoted Cr_x-Cu/SiO₂ catalysts were synthesized through an ammonia evaporation method. The effect of added Cr on the catalytic performance was investigated by the hydrogenation of diethyl carbonate (DEC) as a probe reaction system. The results showed that the Cr_x-Cu/SiO₂ catalyst with 3 wt% Cr performed the preferable activity. Under the reaction conditions of temperature of 503 K, hydrogen pressure of 2.5 MPa and liquid hourly space velocity (LHSV) of 1.0 h^-1, the conversion of DEC could be 99%, while the selectivity of product methanol (86.2%) and space-time yields (STY) of methanol (5.6 mmol_MeOH·g_cat^-1·h^-1) were enhanced significantly. The physicochemical properties of Cr_x-Cu/SiO₂ catalysts were characterized by X-ray diffraction (XRD), N₂ physical adsorption and desorption, transmission electron microscopy (TEM), H₂ temperature-programmed reduction (H₂-TPR) and in-situ diffuse reflection infrared Fourier transform spectroscopy (In-situ DRIFTS). The results revealed that the dispersion of active copper species was significantly improved. The copper chromite species formed by the interaction of copper and chromium could optimize the distribution of Cu(0) and Cu(Ⅰ) and regulate adsorption construction of reactant, efficiently improving the catalytic performance and stability for the hydrogenation of diethyl carbonate to methanol.
- Cr_x-Cu/SiO₂,
- carbonate,
- hydrogenation,
- dispersion,
- promotional effect
1. [1]
2. [2]
  Behrens, M.; Studt, F.; Kasatkin, I.; Kuhl, S.; Havecker, M.; Abild-Pedersen, F.; Zander, S.; Girgsdies, F.; Kurr, P.; Kniep, B.-L.; Tovar, M.; Fischer, R. W.; Norskov, J. K.; Schlogl, R. Science 2012, 336, 893. doi: 10.1126/science.1219831
3. [3]
  (a) Balaraman, E.; Gunanathan, C.; Zhang, J.; Shimon, L.; Milstein, D. Nat. Chem. 2011, 3, 609;(b) Balaraman, E.; Ben-David, Y.; Milstein, D. Angew. Chem., Int. Ed. 2011, 50, 11702;(c) Han, Z. B.; Rong, L. C.; Wu, J.; Zhang, L.; Wang, Z.; Ding, K. L. Angew. Chem., Int. Ed. 2012, 51, 13041.
4. [4]
  (a) Chen, X.; Cui, Y. Y.; Wen, C.; Wang, B.; Dai, W.-L. Chem. Commun. 2015, 51, 13776;(b) Lian, C.; Ren, F. M.; Liu, Y. X.; Zhao, G. F.; Ji, Y. J.; Rong, H. P.; Jia, W.; Ma, L.; Lu, H. Y.; Wang, D. S.; Li, Y. D. Chem. Commun. 2015, 51, 1252;(c) Tamura, M.; Kitanaka, T.; Nakagawa, Y.; Tomishige, K. ACS Catal. 2016, 6, 376;(d) Cui, Y. Y.; Dai, W.-L. Catal. Sci. Technol. 2016, 6, 7752.
5. [5]
  (a) Wen, C.; Cui, Y. Y.; Dai, W.-L; Xie, S. H.; Fan, K. N. Chem. Commun. 2013, 49, 5195;(b) Ye, R.-P.; Lin, L.; Li, Q. H.; Zhou, Z. F.; Wang, T. T.; Russell, C.; Adidharma, H.; Xu, Z. H; Yao, Y.-G.; Fan, M. H. Catal. Sci. Technol. 2018, 8, 3428.
6. [6]
7. [7]
  Yin, A. Y.; Wen, C.; Guo, X. Y.; Dai, W.-L.; Fan, K. N. J. Catal. 2011, 280, 77. doi: 10.1016/j.jcat.2011.03.006
8. [8]
  (a) Kim, N. D.; Oh, S.; Joo, J. B; Jung, K.; Yi, J. H. Top Catal. 2010, 53, 517;(b) Xiao, Z. H.; Ma, Z. Q.; Wang, X. K.; Williams, C.; Liang, C. H. Ind. Eng. Chem. Res. 2011, 50, 2031.
9. [9]
  Tsoncheva, T.; Järn, M.; Paneva, D.; Dimitrov, M.; Mitov, I. Micropor. Mesopor. Mat. 2011, 137, 56. doi: 10.1016/j.micromeso.2010.08.021
10. [10]
  Dragoi, B.; Ungureanu, A.; Chirieac, A.; Hulea, V.; Royer, S.; Dumitriu, E. Catal. Sci. Technol. 2013, 3, 2319. doi: 10.1039/c3cy00198a
11. [11]
  Wang, J. Q.; Chernavskii, P.; Khodakov, A.; Wang, Y. J. Catal. 2012, 286, 51. doi: 10.1016/j.jcat.2011.10.012
12. [12]
  Yin, A. Y.; Guo, X. Y.; Dai, W. -L.; Fan, K. N. Acta Chim. Sinica 2009, 67, 1731.
13. [13]
  Yin, A. Y.; Guo, X. Y.; Dai, W.-L.; Fan, K. N. J. Phys. Chem. C 2009, 113, 11003.
14. [14]
  (a) Wang, Y.; Shen, Y. L.; Zhao, Y. J.; Lv, J.; Wang, S. P.; Ma, X. B. ACS Catal. 2015, 5, 6200;(b) Zhao, Y. J.; Li, S. M.; Wang, Y.; Shan, B.; Zhang, J.; Wang, S. P.; Ma, X. B. Chem. Eng. J. 2017, 313, 759.
15. [15]
  Guo, X. L.; Chen, X.; Su, D. S.; Liang, C. H. Acta Chim. Sinica 2018, 76, 22. doi: 10.3866/PKU.WHXB201706302
16. [16]
  Liang, C. H.; Ma, Z. Q.; Ding, L.; Qiu, J. S. Catal. Lett. 2009, 130, 169. doi: 10.1007/s10562-009-9844-y
17. [17]
  Zheng, X. L.; Lin, H. Q.; Zheng, J. W.; Duan, X. P.; Yuan, Y. Z. ACS Catal. 2013, 3, 2738. doi: 10.1021/cs400574v
18. [18]
  Zhang, M. H.; Li, G. M.; Jiang, H. X.; Zhang, J. Y. Catal. Lett. 2011, 141, 1104. doi: 10.1007/s10562-011-0635-x
19. [19]
  Yurieva, T. M.; Plyasova, L. M.; Makarova, O. Y.; Krieger, T. A. J. Mol. Catal. A:Chem. 1996, 113, 455. doi: 10.1016/S1381-1169(96)00272-5
20. [20]
  Khassin, A. A.; Kustova, G. N.; Jobic, H.; Yurieva, T. M.; Chesalov, Y. A.; Filonenko, G. A.; Plyasova, L. M.; Parmon, V. N. Phys. Chem. Chem. Phys. 2009, 11, 6090. doi: 10.1039/b821381j
21. [21]
  Xiao, Z. H.; Wang, X. K.; Xiu, J. H.; Wang, Y. M.; Williams, C.; Liang, C. H. Catal. Today 2014, 234, 200. doi: 10.1016/j.cattod.2014.02.025
22. [22]
  (a) Choi, K.; Vannice, M. J. Catal. 1991, 131, 22;(b) Fisher, I. A.; Bell, A. T. J. Catal. 1998, 178, 153;(c) Zhu, S. H.; Gao, X. Q.; Zhu, Y. L.; Fan, W. B.; Wang, J. G.; Li, Y. W. Catal. Sci. Technol. 2015, 5, 1169.
23. [23]
  Ge, X.; Zou, H.; Wang, J.; Shen, J. Y. React. Kinet. Catal. Lett. 2005, 85, 253. doi: 10.1007/s11144-005-0268-4
24. [24]
  Boccuzzi, F.; Chiorino, A.; Tsubota, S.; Haruta, M. J. Phys. Chem. 1996, 100, 3625. doi: 10.1021/jp952259n
25. [25]
  (a) Gong, J. L.; Yue, H. R.; Zhao, Y. J.; Zhao, S.; Zhao, L.; Lv, J.; Wang, S. P.; Ma, X. B. J. Am. Chem. Soc. 2012, 134, 13922;(b) Yue, H. R.; Zhao, Y. J.; Ma, X. B.; Gong, J. L. Chem. Soc. Rev. 2012, 41, 4218;(c) Zheng, J. W.; Zhou, J. F.; Lin, H. Q.; Duan, X. P.; Williams, C.; Yuan, Y. Z. J. Phys. Chem. C 2015, 119, 13758.
26. [26]
  Garcilaso, V.; Barrientos, J.; Bobadilla, L. F.; Laguna, O. H.; Boutonnet, M.; Centeno, M. A.; Odriozola, J. A. Renew. Energ. 2019, 132, 1141. doi: 10.1016/j.renene.2018.08.080
27. [27]
  Bechara, R.; Wrobel, G.; Daage, M.; Bonnelle, J. P. Appl. Catal. 1985, 16, 15. doi: 10.1016/S0166-9834(00)84066-X
28. [28]
  He, Z.; Lin, H. Q.; He, P.; Yuan, Y. Z. J. Catal. 2011, 277, 54. doi: 10.1016/j.jcat.2010.10.010
29. [29]
  Zhou, G. B.; Tan, X. H.; Dou, R. F.; Pei, Y.; Fan, K. N.; Qiao, M. H.; Sun, B.; Zong, B. N. Sci. China:Chem. 2014, 44, 121.
1. [1]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
2. [2]
  Shipeng WANG , Shangyu XIE , Luxian LIANG , Xuehong WANG , Jie WEI , Deqiang WANG . Piezoelectric effect of Mn, Bi co-doped sodium niobate for promoting cell proliferation and bacteriostasis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1919-1931. doi: 10.11862/CJIC.20240094
3. [3]
  Cheng PENG , Jianwei WEI , Yating CHEN , Nan HU , Hui ZENG . First principles investigation about interference effects of electronic and optical properties of inorganic and lead-free perovskite Cs₃Bi₂X₉ (X=Cl, Br, I). Chinese Journal of Inorganic Chemistry, 2024, 40(3): 555-560. doi: 10.11862/CJIC.20230282
4. [4]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . 表面硫物种对钯-硫纳米片加氢性能的影响. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-. doi: 10.3866/PKU.WHXB202309043
5. [5]
  Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, 2024, 39(11): 232-240. doi: 10.3866/PKU.DXHX202402057
6. [6]
  Xinpin Pan , Yongjian Cui , Zhe Wang , Bowen Li , Hailong Wang , Jian Hao , Feng Li , Jing Li . Robust chemo-mechanical stability of additives-free SiO₂ anode realized by honeycomb nanolattice for high performance Li-ion batteries. Chinese Chemical Letters, 2024, 35(10): 109567-. doi: 10.1016/j.cclet.2024.109567
7. [7]
  Peipei Sun , Jinyuan Zhang , Yanhua Song , Zhao Mo , Zhigang Chen , Hui Xu . 引入内建电场增强光载流子分离以促进H₂的生产. Acta Physico-Chimica Sinica, 2024, 40(11): 2311001-. doi: 10.3866/PKU.WHXB202311001
8. [8]
  Jianyin He , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . ZnCoP/CdLa₂S₄肖特基异质结的构建促进光催化产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2404030-. doi: 10.3866/PKU.WHXB202404030
9. [9]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276
10. [10]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-. doi: 10.3866/PKU.WHXB202312007
11. [11]
  Changyan Sun , Hualei Zhou , Bin Dong . Application of “PBL” Teaching Mode in Inorganic Chemistry Experimental Education in the Perspective of Course Ideology and Politics: Taking Preparation of Manganese Carbonate as an Example. University Chemistry, 2024, 39(11): 378-383. doi: 10.12461/PKU.DXHX202402016
12. [12]
  Yaling Chen . Basic Theory and Competitive Exam Analysis of Dynamic Isotope Effect. University Chemistry, 2024, 39(8): 403-410. doi: 10.3866/PKU.DXHX202311093
13. [13]
  YanYuan Jia , Rong Rong , Jie Liu , Jing Guo , GuoYu Jiang , Shuo Guo . Unity is Strength, and Independence Shines: A Science Popularization Experiment on AIE and ACQ Effects. University Chemistry, 2024, 39(9): 349-358. doi: 10.12461/PKU.DXHX202402035
14. [14]
  Ling Liu , Haibin Wang , Genrong Qiang . Curriculum Ideological and Political Design for the Comprehensive Preparation Experiment of Ethyl Benzoate Synthesized from Benzyl Alcohol. University Chemistry, 2024, 39(2): 94-98. doi: 10.3866/PKU.DXHX202304080
15. [15]
  Shuying Zhu , Shuting Wu , Ou Zheng . Improvement and Expansion of the Experiment for Determining the Rate Constant of the Saponification Reaction of Ethyl Acetate. University Chemistry, 2024, 39(4): 107-113. doi: 10.3866/PKU.DXHX202310117
16. [16]
  Ruitong Zhang , Zhiqiang Zeng , Xiaoguang Zhang . Improvement of Ethyl Acetate Saponification Reaction and Iodine Clock Reaction Experiments. University Chemistry, 2024, 39(8): 197-203. doi: 10.3866/PKU.DXHX202312004
17. [17]
  Ping Song , Nan Zhang , Jie Wang , Rui Yan , Zhiqiang Wang , Yingxue Jin . Experimental Teaching Design on Synthesis and Antitumor Activity Study of Cu-Pyropheophorbide-a Methyl Ester. University Chemistry, 2024, 39(6): 278-286. doi: 10.3866/PKU.DXHX202310087
18. [18]
  Bingliang Li , Yuying Han , Dianyang Li , Dandan Liu , Wenbin Shang . One-Step Synthesis of Benorilate Guided by Green Chemistry Principles and in vivo Dynamic Evaluation. University Chemistry, 2024, 39(6): 342-349. doi: 10.3866/PKU.DXHX202311070
19. [19]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
20. [20]
  Jin CHANG . Supercapacitor performance and first-principles calculation study of Co-doping Ni(OH)₂. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1697-1707. doi: 10.11862/CJIC.20240108

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(1503)
HTML views(201)

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

Promotional Effect of Cr on Cu/SiO2 Catalyst for the Production of Methanol from Carbonate Hydrogenation

Metrics

通讯作者: 陈斌, bchen63@163.com

Promotional Effect of Cr on Cu/SiO₂ Catalyst for the Production of Methanol from Carbonate Hydrogenation