Citation: SUN Hai-Jie, LI Yong-Yu, LI Shuai-Hui, ZHANG Yuan-Xin, LIU Shou-Chang, LIU Zhong-Yi, REN Bao-Zeng. ZnSO₄ and La₂O₃ as Co-Modifier of the Monoclinic Ru Catalyst for Selective Hydrogenation of Benzene to Cyclohexene[J]. Acta Physico-Chimica Sinica, ;2014, 30(7): 1332-1340. doi: 10.3866/PKU.WHXB201405072 shu

ZnSO₄ and La₂O₃ as Co-Modifier of the Monoclinic Ru Catalyst for Selective Hydrogenation of Benzene to Cyclohexene

1.
1. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R. China;
2. Institute of Environmental and Catalytic Engineering, Department of Chemistry, Zhengzhou Normal University, Zhengzhou 450044, P. R. China;
3. School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, P. R. China

Received Date: 28 February 2014
Available Online: 7 May 2014
Fund Project:

A nano-scale monometallic Ru(0) catalyst was prepared by the precipitation method, and the effect of using ZnSO₄ and La₂O₃ as co-modifiers on the performance of the catalyst for selective hydrogenation of benzene to cyclohexene was investigated. The catalysts before and after hydrogenation were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), transmission electron microscopy (TEM), and N₂-physisorption. It was found that increasing the amount of alkaline La₂O₃ increased the amount of the ((Zn(OH)₂)₃(ZnSO₄)(H₂O)_x (x=1, 3) salt formed by the hydrolysis of ZnSO₄, which resulted in a gradual decrease of the activity of the Ru(0) catalyst and a gradual increase of the selectivity for cyclohexene. When the molar ratio of La₂O₃/Ru was 0.075, cyclohexene selectivity of 75.2% and cyclohexene yield of 58.4% at a benzene conversion of 77.6% were achieved in 25 min over the Ru(0) catalyst in the presence of ZnSO₄. Moreover, this catalytic system had od reusability. The mass transfer calculation results indicated that the liquid-solid diffusion constraints and pore diffusion limitations could all be ignored. This suggested that the high cyclohexene selectivity and cyclohexene yield could not be simply ascribed to physical effects, and were closely related to the catalyst structure and the catalytic system. Based on the experimental results, we suggest that the surface of the Ru(0) catalyst on which the (Zn(OH)₂)₃(ZnSO₄)(H₂O)_x (x= 1, 3) salt chemisorbed had two types of active sites for activating the benzene molecules: Ru⁰ and Zn²⁺. The ability of Zn²⁺ to activate benzene was much weaker than that of Ru⁰ owing to some electron transfer from Zn²⁺ to Ru⁰, which was confirmed by the XPS and AES results. Furthermore, Zn²⁺ could cover some of the Ru active sites because Ru and Zn²⁺ have similar atomic radii, which decreased the number of Ru⁰ active sites for activating H₂ molecules. As a result, the benzene activated on Zn²⁺ could only be hydrogenated to cyclohexene, and the activity of the Ru(0) catalyst decreased. A dual active site model is proposed, for the first time, to explain the reaction of benzene hydrogenation over the Ru-based catalyst, and Hückel molecular orbital theory was used to show the reasonableness of the model.
- Benzene,
- Selective hydrogenation,
- Cyclohexene,
- Ruthenium,
- Znic,
- Lanthanum
1. [1]
  
  (1) Lu, F.; Liu, J.; Xu, J. Prog. Chem. 2003, 15, 338. [路芳, 刘菁, 徐杰. 化学进展, 2003, 15, 338.]
2. [2]
  (2) Sun, H. J.; Chen, Z. H.; Guo,W.; Zhou, X. L.; Liu, Z. Y.; Liu, S. C. Chin. J. Chem. 2011, 29, 369. doi: 10.1002/cjoc.201190092
3. [3]
  (3) Surawanshi, P. T.; Mahajani, V. V. J. Chem. Tech. Biotechnol. 1997, 69, 154.
4. [4]
  (4) Nagahara, H.; Ono, M.; Konishi, M.; Fukuoka, Y. Appl. Surf. Sci. 1997, 121 -122, 448.
5. [5]
  (5) Wu, J. M.; Yang, Y. F.; Chen, J. L. Chem. Ind. Eng. Prog. 2003, 22, 295. [吴济民, 杨炎锋, 陈聚良. 化工进展, 2003, 22, 295.]
6. [6]
  (6) Ning, J. B.; Xu, J.; Liu, J.; Lu, F. Catal. Lett. 2006, 109, 175. doi: 10.1007/s10562-006-0075-1
7. [7]
  (7) Sun, H. J.;Wang, H. X.; Jiang, H. B.; Li, S. H.; Liu, S. C.; Liu, Z. Y.; Yuan, X. M.; Yang, K. J. Appl. Catal. A: Gen. 2013, 450, 160. doi: 10.1016/j.apcata.2012.10.016
8. [8]
  (8) Sun, H. J.; Pan, Y. J.; Jiang, H. B.; Li, S. H.; Zhang, Y. X.; Liu, S. C.; Liu, Z. Y. Appl. Catal. A: Gen. 2013, 464 -465, 1.
9. [9]
  (9) Sun, H. J.; Jiang, H. B.; Li, S. H.;Wang, H. X.; Pan, Y. J.; Dong, Y. Y.; Liu, S. C.; Liu, Z. Y. Chin. J. Catal. 2013, 34, 684. [孙海杰, 江厚兵, 李帅辉, 王红霞, 潘雅洁, 董莹莹, 刘寿长. 刘仲毅. 催化学报, 2013, 34, 684.] doi: 10.1016/S1872-2067(11)60489-0
10. [10]
  (10) Sun, H. J.; Pan, Y. J.; Li, S. H.; Zhang, Y. X.; Dong, Y. Y.; Liu, S. C.; Liu. Z. Y. J. Energy Chem. 2013, 22, 710. doi: 10.1016/S2095-4956(13)60094-7
11. [11]
  (11) Sun, H. J.; Dong, Y. Y.; Li, S. H.; Jiang, H. B.; Zhang, Y. X.; Liu, Z. Y.; Liu, S. C. J. Mol. Catal. A: Chem. 2013, 368 -369, 119.
12. [12]
  (12) Sun, H. J.; Li, S. H.; Zhang, Y. X.; Jiang, H. B.; Qu, L. L.; Liu, S. C.; Liu, Z. Y. Chin. J. Catal. 2013, 34, 1482. [孙海杰, 李帅辉, 张元馨, 江厚兵, 曲良龙, 刘寿长, 刘仲毅. 催化学报, 2013, 34, 1482.]
13. [13]
  (13) Zhang, P.;Wu, T. B.; Jiang, T.;Wang,W. T.; Liu, H. Z.; Fan, H. L.; Zhang, Z. F.; Han, B. X. Green Chem. 2012, 15, 152. doi:10.1016/S1872-2067(12)60637-8
14. [14]
  (14) Tan, X. H.; Zhou, G. B.; Dou, R. F.; Pei, Y.; Fan, K. N.; Qiao, M. H.; Sun, B.; Zong, B. N. Acta Phys. -Chim. Sin. 2014, 30, 932. [谭晓荷, 周功兵, 窦镕飞, 裴燕, 范康年, 乔明华, 孙斌, 宗保宁. 物理化学学报, 2014, 30, 932.]
15. [15]
  (15) Liu, J. L.; Zhu, Y.; Liu, J.; Pei, Y.; Li, Z. H.; Li, H.; Li, H. X.; Qiao, M. H.; Fan, K. N. J. Catal. 2009, 268, 100. doi: 10.1016/j.jcat.2009.09.007
16. [16]
  (16) Fan, G. Y.; Li, R. X.; Li, X. J.; Chen, H. Catal. Commun. 2008, 9, 1394. doi: 10.1016/j.catcom.2007.11.039
17. [17]
  (17) Sun, H. J.; Jiang, H. B.; Li, S. H.; Dong, Y. Y.;Wang, H. X.; Pan, Y. J.; Liu, S. C.; Tang, M. S.; Liu, Z. Y. Chem. Eng. J. 2013, 218, 415. doi: 10.1016/j.cej.2012.12.041
18. [18]
  (18) Struijk, J.; d′Angremond, M.; Lucas-de Regt,W. J. M.; Scholten, J. J. F. Appl. Catal. A: Gen, 1992, 83, 263. doi:10.1016/0926-860X(92)85039-E
19. [19]
  (19) Milone, C.; Neri, G.; Donato, A.; Musolino, M. G.; Mercadante, L. J. Catal. 1996, 159, 253. doi: 10.1006/jcat.1996.0086
20. [20]
  (20) Folksson, B. Acta Chim. Scand. 1973, 27, 287. doi: 10.3891/acta. chem.scand.27-0287
21. [21]
  (21) Nyholm, R.; Martensson, N. J. Phys. C 1980, 13, 1279.
22. [22]
  (22) Moretti, G.; Fierro, G.; Lo Jacono, M.; Porta, P. Surf. Interface Anal. 1989, 14, 325.
23. [23]
  (23) Ramos-Fernández, E. V.; Ferreira, A. F. P.; Sepúlveda-Escribano, A.; Kapteijn, F.; Rodríguez-Reinoso, F. J. Catal. 2008, 258, 52. doi: 10.1016/j.jcat.2008.05.025
24. [24]
  (24) Su, F. B.; Lee, F. Y.; Lv, L.; Liu, J.; Tian, X. N.; Zhao, X. S. Adv. Funct. Mater. 2007, 17, 1926.
25. [25]
  (25) Hu, S. C.; Chen, Y.W. Ind. Eng. Chem. Res. 1997, 36, 5153. doi: 10.1021/ie970300y
26. [26]
  (26) Liu, H. Z.; Jiang, T.; Han, B. X.; Liang, S. G.; Zhou, Y. X. Science 2009, 326, 1250. doi: 10.1126/science.1179713
27. [27]
  (27) Marchi, A. J.; rdo, D. A.; Trasrti, A. F.; Apesteguía, C. R. Appl. Catal. A: Gen. 2003, 249, 53. doi: 10.1016/S0926-860X(03)00199-6
1. [1]
  Lu XU , Chengyu ZHANG , Wenjuan JI , Haiying YANG , Yunlong FU . Zinc metal-organic framework with high-density free carboxyl oxygen functionalized pore walls for targeted electrochemical sensing of paracetamol. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 907-918. doi: 10.11862/CJIC.20230431
2. [2]
  Xiaoling LUO , Pintian ZOU , Xiaoyan WANG , Zheng LIU , Xiangfei KONG , Qun TANG , Sheng WANG . Synthesis, crystal structures, and properties of lanthanide metal-organic frameworks based on 2, 5-dibromoterephthalic acid ligand. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1143-1150. doi: 10.11862/CJIC.20230271
3. [3]
  Xuefei Zhao , Xuhong Hu , Zhenhua Jia . 理论与计算化学在傅-克烷基化反应教学中的应用. University Chemistry, 2025, 40(8): 360-367. doi: 10.12461/PKU.DXHX202410008
4. [4]
  Anqiu LIU , Long LIN , Dezhi ZHANG , Junyu LEI , Kefeng WANG , Wei ZHANG , Junpeng ZHUANG , Haijun HAO . Synthesis, structures, and catalytic activity of aluminum and zinc complexes chelated by 2-((2,6-dimethylphenyl)amino)ethanolate. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 791-798. doi: 10.11862/CJIC.20230424
5. [5]
  Hui-Ying Chen , Hao-Lin Zhu , Pei-Qin Liao , Xiao-Ming Chen . Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2306046-0. doi: 10.3866/PKU.WHXB202306046
6. [6]
  Shuhong Xiang , Lv Yang , Yingsheng Xu , Guoxin Cao , Hongjian Zhou . Selective electrosorption of Cs(Ⅰ) from high-salinity radioactive wastewater using CNT-interspersed potassium zinc ferrocyanide electrodes. Acta Physico-Chimica Sinica, 2025, 41(9): 100097-0. doi: 10.1016/j.actphy.2025.100097
7. [7]
  Feifei Yang , Wei Zhou , Chaoran Yang , Tianyu Zhang , Yanqiang Huang . Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst. Acta Physico-Chimica Sinica, 2024, 40(7): 2308017-0. doi: 10.3866/PKU.WHXB202308017
8. [8]
  Fa Wang , Yu Chen , Hui Chao . Ruthenium(II) Complexes as Photoactivated Chemo-Prodrugs for Hypoxic Tumor Therapy. University Chemistry, 2025, 40(7): 200-212. doi: 10.12461/PKU.DXHX202410024
9. [9]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
10. [10]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
11. [11]
  Hailang JIA , Pengcheng JI , Hongcheng LI . Preparation and performance of nickel doped ruthenium dioxide electrocatalyst for oxygen evolution. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1632-1640. doi: 10.11862/CJIC.20240398
12. [12]
  Zhaoyang WANG , Chun YANG , Yaoyao Song , Na HAN , Xiaomeng LIU , Qinglun WANG . Lanthanide(Ⅲ) complexes derived from 4′-(2-pyridyl)-2, 2′∶6′, 2″-terpyridine: Crystal structures, fluorescent and magnetic properties. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1442-1451. doi: 10.11862/CJIC.20240114
13. [13]
  Wenqi Gao , Xiaoyan Fan , Feixiang Wang , Zhuojun Fu , Jing Zhang , Enlai Hu , Peijun Gong . Exploring Nernst Equation Factors and Applications of Solid Zinc-Air Battery. University Chemistry, 2024, 39(5): 98-107. doi: 10.3866/PKU.DXHX202310026
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]
  Feng Sha , Xinyan Wu , Ping Hu , Wenqing Zhang , Xiaoyang Luan , Yunfei Ma . Design of Course Ideology and Politics for the Comprehensive Organic Synthesis Experiment of Benzocaine. University Chemistry, 2024, 39(2): 110-115. doi: 10.3866/PKU.DXHX202307082
16. [16]
  Wanmin Cheng , Juan Du , Peiwen Liu , Yiyun Jiang , Hong Jiang . Photoinitiated Grignard Reagent Synthesis and Experimental Improvement in Triphenylmethanol Preparation. University Chemistry, 2024, 39(5): 238-242. doi: 10.3866/PKU.DXHX202311066
17. [17]
  Liangzhen Hu , Li Ni , Ziyi Liu , Xiaohui Zhang , Bo Qin , Yan Xiong . A Green Chemistry Experiment on Electrochemical Synthesis of Benzophenone. University Chemistry, 2024, 39(6): 350-356. doi: 10.3866/PKU.DXHX202312001
18. [18]
  Yahui HAN , Jinjin ZHAO , Ning REN , Jianjun ZHANG . Synthesis, crystal structure, thermal decomposition mechanism, and fluorescence properties of benzoic acid and 4-hydroxy-2, 2′: 6′, 2″-terpyridine lanthanide complexes. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 969-982. doi: 10.11862/CJIC.20240395
19. [19]
  Shahua Huang , Xiaoming Guo , Lin Lin , Guangping Chang , Sheng Han , Zuxin Zhou . Application of “Integration of Industry and Education” in Engineering Chemistry: Improvement of the Pesticide Fipronil Production. University Chemistry, 2024, 39(3): 199-204. doi: 10.3866/PKU.DXHX202309064
20. [20]
  Jingyu Cai , Xiaoyu Miao , Yulai Zhao , Longqiang Xiao . Exploratory Teaching Experiment Design of FeOOH-RGO Aerogel for Photocatalytic Benzene to Phenol. University Chemistry, 2024, 39(4): 169-177. doi: 10.3866/PKU.DXHX202311028

Get Citation

PDF

XML

Metrics

PDF Downloads(494)
Abstract views(878)
HTML views(10)

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

ZnSO4 and La2O3 as Co-Modifier of the Monoclinic Ru Catalyst for Selective Hydrogenation of Benzene to Cyclohexene

Metrics

通讯作者: 陈斌, bchen63@163.com

ZnSO₄ and La₂O₃ as Co-Modifier of the Monoclinic Ru Catalyst for Selective Hydrogenation of Benzene to Cyclohexene