Citation: Zhang Jian, Wang Liang, Wu Zhiyi, Wang Chengtao, Su Zerui, Xiao Feng-Shou. Rational Design of a Core-Shell Rh@Zeolite Catalyst for Selective Diene Hydrogenation[J]. Acta Physico-Chimica Sinica, ;2020, 36(9): 191200. doi: 10.3866/PKU.WHXB201912001 shu

Rational Design of a Core-Shell Rh@Zeolite Catalyst for Selective Diene Hydrogenation

Zhang Jian ¹ ,
Wang Liang ^2,, ,
Wu Zhiyi ¹ ,
Wang Chengtao ³ ,
Su Zerui ¹ ,
Xiao Feng-Shou ^1,2,3

1.
Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China
2.
Key Lab of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. China
3.
Key Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310028, P. R. China

Corresponding author: Wang Liang, liangwang@zju.edu.cn
Received Date: 2 December 2019
Revised Date: 31 December 2019
Accepted Date: 6 January 2020
Available Online: 14 February 2020
Fund Project: the National Natural Science Foundation of China 91634201the Natural Science Foundation of Zhejiang Province, China LR18B030002the Beijing Advanced Innovation Center for Soft Matter Science, Engineering of the Beijing University of Chemical Technology, China 21530009067the Fundamental Research Funds for the Central Universities, China 2019XZZX004-02the National Natural Science Foundation of China 91645105The project was supported by the National Key Research and Development Program of China 2018YFB0604801The project was supported by the National Key Research and Development Program of China (2018YFB0604801), the National Natural Science Foundation of China (21822203, 91645105, 91634201), the Natural Science Foundation of Zhejiang Province, China (LR18B030002), the Beijing Advanced Innovation Center for Soft Matter Science, Engineering of the Beijing University of Chemical Technology, China (21530009067), and the Fundamental Research Funds for the Central Universities, China (2019XZZX004-02)the National Natural Science Foundation of China 21822203

Selective hydrogenation of dienes and alkynes to monoenes is an important topic of research in the fields of pharmacology and organic synthesis. Catalyst design plays a key role in this process, where a general principle involves controlling the steric diene adsorption by modifying the surface of the metal nanoparticles. For example, upon introducing Bi species into Rh nanoparticles, the resulting RhBi/SiO₂ showed 90% selectivity to 2-hexene, with 95% conversion of 1, 4-hexadiene under ambient conditions, because of the suppressed adsorption of the internal C＝C bond. However, the catalyst activity decreased remarkably; that is, the activity of the unmodified Rh/SiO₂ was about 27 times higher than that of RhBi/SiO₂. Controlled steric adsorption of the diene molecules could also be achieved by the constructing porous channels around the metal nanoparticles. For example, metal-organic framework (ZIF-8) or mesoporous silica (MCM-41) encapsulated noble metals showed high selectivity for the hydrogenation of terminal C＝C bonds. However, these catalysts had poor durability under the thermal/hydrothermal reaction/regeneration conditions. In contrast, zeolites have superior durability under harsh reaction conditions, but they are rarely used in semi-hydrogenation reactions. We recently found that metal nanoparticles fixed within zeolite crystals (e.g., ZSM-5 and Beta) efficiently catalyze the selective hydrogenation of molecules bearing multiple reducible groups. Thus inspired, we developed a catalyst by fixing Rh nanoparticles within zeolite crystals via an inter-zeolite transformation method. The Rh@CHA catalyst was synthesized by introducing Rh species into the parent Y zeolite (Rh@Y) and transformation of the Y zeolite to chabazite (CHA zeolite) under hydrothermal conditions. X-ray diffraction patterns, N₂ sorption isotherms, scanning/transmission electron microscopy images, and model reactions (hydrogenation of probe molecules) confirmed the successful fixation of the Rh nanoparticles inside the CHA zeolite crystals. As expected, the Rh@CHA catalyst was highly selective for the hydrogenation of dienes. For example, Rh@CHA showed a 2-hexene selectivity of 86.7%, with 91.2% conversion of 1, 4-hexadiene. In contrast, the generally supported Rh nanoparticle catalyst (Rh/CHA) showed a low 2-hexene selectivity of 37.2% under identical reaction conditions. Considering that Rh@CHA and Rh/CHA comprise the same CHA zeolite crystals and have similar Rh nanoparticle sizes, the remarkably high selectivity of Rh@CHA is assigned to the steric adsorption of dienes on the Rh surface controlled by the micropores of the CHA zeolite. This work demonstrates that a zeolite-fixed metal core-shell structure is a powerful tool for developing efficient catalysts to be used in diene hydrogenation.
- Heterogeneous catalysis,
- Diene hydrogenation,
- Rh nanoparticle,
- CHA zeolite,
- Core-shell structure,
- Inter-zeolite transformation
1. [1]
  Wang, S.; Zhao, Z. J.; Chang, X.; Zhao, J.; Tian, H.; Yang, C.; Li, M.; Fu, Q.; Mu, R.; Gong, J. Angew. Chem. Int. Ed. 2019, 58, 7668. doi: 10.1002/anie.201903827 doi: 10.1002/anie.201903827
2. [2]
  Yan, H.; Cheng, H.; Yi, H.; Lin, Y.; Yao, T.; Wang, C.; Li, J.; Wei, S.; Lu, J. J. Am. Chem. Soc. 2015, 137, 10484. doi: 10.1021/jacs.5b06485 doi: 10.1021/jacs.5b06485
3. [3]
  Zhao, M.; Yuan, K.; Wang, Y.; Li, G.; Guo, J.; Gu, L.; Hu, W.; Zhao, H.; Tang, Z. Nature 2016, 539, 76. doi: 10.1038/nature19763 doi: 10.1038/nature19763
4. [4]
  Wang, Z.; Zhou, Z.; Zhang, R.; Li, L.; Cheng, Z. M. Acta Phys. -Chim. Sin. 2014, 30, 2315. doi: 10.3866/PKU.WHXB201410152
5. [5]
  Gao, X.; Guo, Z.; Zhou, Y.; Jing, F.; Chu, W. Acta Phys. -Chim. Sin. 2017, 33, 602. doi: 10.3866/PKU.WHXB201611251
6. [6]
  Miyazaki, M.; Furukawa, S.; Komatsu, T. J. Am. Chem. Soc. 2017, 139, 18231. doi: 10.1021/jacs.7b08792 doi: 10.1021/jacs.7b08792
7. [7]
  Lucci, F. R.; Liu, J.; Marcinkowski, M. D.; Yang, M.; Allard, L. F.; Flytzani-Stephanopoulos, M.; Sykes, E. C. H. Nat. Commun. 2015, 6, 8550. doi: 10.1038/ncomms9550 doi: 10.1038/ncomms9550
8. [8]
  Zhang, X.; Shi, H.; Xu, B. Angew. Chem. Int. Ed. 2005, 44, 7132. doi: 10.1002/anie.200502101 doi: 10.1002/anie.200502101
9. [9]
  Lonergan, W. W.; Vlachos, D. G.; Chen, J. G. J. Catal. 2010, 271, 239. doi: 10.1016/j.jcat.2010.01.019 doi: 10.1016/j.jcat.2010.01.019
10. [10]
  Yardimci, D.; Serna, P.; Gates, B. C. ACS Catal. 2012, 2, 2100. doi: 10.1021/cs300475c doi: 10.1021/cs300475c
11. [11]
  Scharnagl, F.; Hertrich, M. F.; Ferretti, F.; Kreyenschulte, C.; Lund, H.; Jackstell, R.; Beller, M. Sci. Adv. 2018, 4, eaau1248. doi: 10.1126/sciadv.aau1248 doi: 10.1126/sciadv.aau1248
12. [12]
  Berhault, G.; Bisson, L.; Thomazeau, C.; Verdon, C.; Uzio, D. Appl. Catal. B 2007, 327, 32. doi: 10.1016/j.apcata.2007.04.028 doi: 10.1016/j.apcata.2007.04.028
13. [13]
  Massard, R.; Uzio, D.; Thomazeau, C.; Pichon, C.; Rousset, J. L.; Bertolini, J. C. J. Catal. 2007, 245, 133. doi: 10.1016/j.jcat.2006.09.014 doi: 10.1016/j.jcat.2006.09.014
14. [14]
  Zhang, X.; Shi, H.; Xu, B. Catal. Today 2007, 122, 330. doi: 10.1016/j.cattod.2007.02.016 doi: 10.1016/j.cattod.2007.02.016
15. [15]
  González, S.; Neyman, K. M.; Shaikhutdinov, S.; Freund, H. J.; Illas, F. J. Phys. Chem. C 2007, 111, 6852. doi: 10.1021/jp071584v doi: 10.1021/jp071584v
16. [16]
  Armbrüster, M.; Behrens, M.; Cinquini, F.; Föttinger, K.; Grin, Y.; Haghofer, A.; Klötzer, B.; Knop-Gericke, A.; Lorenz, H.; Ota, A.; et al. ChemCatChem 2012, 4, 1048. doi: 10.1002/cctc.201200100 doi: 10.1002/cctc.201200100
17. [17]
  McCue, A. J.; McRitchie, C. J.; Shepherd, A. M.; Anderson, J. A. J. Catal. 2014, 319, 127. doi: 10.1016/j.jcat.2014.08.016 doi: 10.1016/j.jcat.2014.08.016
18. [18]
  Zhang, J.; Wang, L.; Shao, Y.; Wang, Y.; Gates, B. C.; Xiao, F. S. Angew. Chem. Int. Ed. 2017, 56, 9747. doi: 10.1002/anie.201703938 doi: 10.1002/anie.201703938
19. [19]
  Stephenson, C. J.; Hupp, J. T.; Farha, O. K. Inorg. Chem. Front. 2015, 2, 448. doi: 10.1039/c5qi00010f doi: 10.1039/c5qi00010f
20. [20]
  Shimazu, S.; Baba, N.; Ichikuni, N.; Uematsu, T. J. Mol. Catal. A: Chem. 2002, 182–183, 343. doi: 10.1016/S1381-1169(01)00508-8 doi: 10.1016/S1381-1169(01)00508-8
21. [21]
  Wang, C.; Wang, L.; Zhang, J.; Wang, H.; Lewis, J. P.; Xiao, F. S. J. Am. Chem. Soc. 2016, 138, 7880. doi: 10.1021/jacs.6b04951 doi: 10.1021/jacs.6b04951
22. [22]
  Chai, Y.; Liu, S.; Zhao, Z. J.; Gong, J.; Dai, W.; Wu, G.; Guan, N.; Li, L. ACS Catal.2018, 8, 8578. doi: 10.1021/acscatal.8b02276 doi: 10.1021/acscatal.8b02276
23. [23]
  Iida, T.; Zanchet, D.; Ohara, K.; Wakihara, T.; Roman-Leshkov, Y. Angew. Chem. Int. Ed.2018, 57, 6454. doi: 10.1002/anie.201800557 doi: 10.1002/anie.201800557
24. [24]
  Van Tendeloo, L.; Gobechiya, E.; Breynaert, E.; Martens, J. A.; Kirschhock, C. E. A. Chem. Commun. 2013, 49, 11737. doi: 10.1039/c3cc47292b doi: 10.1039/c3cc47292b
25. [25]
  Ji, Y.; Deimund, M. A.; Bhawe, Y.; Davis, M. E. ACS Catal. 2015, 5, 4456. doi: 10.1021/acscatal.5b00404 doi: 10.1021/acscatal.5b00404
26. [26]
  Baerlocher, C.; McCusker L. B.; Olson, D. H. Atlas of Zeolite Framework Types, 6th ed.; Elsevier: Radarweg, 2007; pp. 96–97.
1. [1]
  Ruiying Liu , Li Zhao , Baishan Liu , Jiayuan Yu , Yujie Wang , Wanqiang Yu , Di Xin , Chaoqiong Fang , Xuchuan Jiang , Riming Hu , Hong Liu , Weijia Zhou . Modulating pollutant adsorption and peroxymonosulfate activation sites on Co3O4@N,O doped-carbon shell for boosting catalytic degradation activity. Chinese Journal of Structural Chemistry, 2024, 43(8): 100332-100332. doi: 10.1016/j.cjsc.2024.100332
2. [2]
  Min Song , Qian Zhang , Tao Shen , Guanyu Luo , Deli Wang . Surface reconstruction enabled o-PdTe@Pd core-shell electrocatalyst for efficient oxygen reduction reaction. Chinese Chemical Letters, 2024, 35(8): 109083-. doi: 10.1016/j.cclet.2023.109083
3. [3]
  Hua Liu , Jian Zhao , Qi Li , Xiang-Yu Zhang , Zhi-Wei Zheng , Kun Huang , Da-Bin Qin , Bin Zhao . Indium-captured zirconium-porphyrin frameworks displaying rare multi-selectivity for catalytic transfer hydrogenation of aldehydes and ketones. Chinese Chemical Letters, 2025, 36(6): 110593-. doi: 10.1016/j.cclet.2024.110593
4. [4]
  Heng Yang , Zhijie Zhou , Conghui Tang , Feng Chen . Recent advances in heterogeneous hydrosilylation of unsaturated carbon-carbon bonds. Chinese Chemical Letters, 2024, 35(6): 109257-. doi: 10.1016/j.cclet.2023.109257
5. [5]
  Shuai Tang , Zian Wang , Mengyi Zhu , Xinyun Zhao , Xiaoyun Hu , Hua Zhang . Synthesis of organoboron compounds via heterogeneous C–H and C–X borylation. Chinese Chemical Letters, 2025, 36(5): 110503-. doi: 10.1016/j.cclet.2024.110503
6. [6]
  Wen-Jing Li , Jun-Bo Wang , Yu-Heng Liu , Mo Zhang , Zhan-Hui Zhang . Molybdenum-doped carbon nitride as an efficient heterogeneous catalyst for direct amination of nitroarenes with arylboronic acids. Chinese Chemical Letters, 2025, 36(3): 110001-. doi: 10.1016/j.cclet.2024.110001
7. [7]
  Xiao Li , Wanqiang Yu , Yujie Wang , Ruiying Liu , Qingquan Yu , Riming Hu , Xuchuan Jiang , Qingsheng Gao , Hong Liu , Jiayuan Yu , Weijia Zhou . Metal-encapsulated nitrogen-doped carbon nanotube arrays electrode for enhancing sulfion oxidation reaction and hydrogen evolution reaction by regulating of intermediate adsorption. Chinese Chemical Letters, 2024, 35(8): 109166-. doi: 10.1016/j.cclet.2023.109166
8. [8]
  Xian-Fa Jiang , Chongyun Shao , Zhongwen Ouyang , Zhao-Bo Hu , Zhenxing Wang , You Song . Generating electron spin qubit in metal-organic frameworks via spontaneous hydrolysis. Chinese Chemical Letters, 2024, 35(7): 109011-. doi: 10.1016/j.cclet.2023.109011
9. [9]
  Ming Zhong , Xue Guo , Yang Liu , Kun Zhao , Hui Peng , Suijun Liu , Xiaobo Zhang . Molybdenum-glycerate@zeolitic imidazolate framework spheres derived hierarchical nitrogen-doped carbon-encapsulated bimetallic selenides heterostructures for improved lithium-ion storage. Chinese Chemical Letters, 2025, 36(5): 109873-. doi: 10.1016/j.cclet.2024.109873
10. [10]
  Haiyang Peng , Zhipeng Xie , Shuiqing Lu , Da Zhang , Bin Yang , Feng Liang . Dual-functionality composites of polyaniline-coated oxidized carbon nanohorns: Efficient wave absorption and enhanced corrosion resistance. Chinese Chemical Letters, 2025, 36(6): 110818-. doi: 10.1016/j.cclet.2025.110818
11. [11]
  Baokang Geng , Xiang Chu , Li Liu , Lingling Zhang , Shuaishuai Zhang , Xiao Wang , Shuyan Song , Hongjie Zhang . High-efficiency PdNi single-atom alloy catalyst toward cross-coupling reaction. Chinese Chemical Letters, 2024, 35(7): 108924-. doi: 10.1016/j.cclet.2023.108924
12. [12]
  Chengyao Zhao , Jingyuan Liao , Yuxiang Zhu , Yiying Zhang , Lianjie Zhai , Junrong Huang , Hengzhi You . Polystyrene-supported phosphoric-acid catalyzed atroposelective construction of axially chiral N-aryl benzimidazoles. Chinese Chemical Letters, 2025, 36(6): 110337-. doi: 10.1016/j.cclet.2024.110337
13. [13]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
14. [14]
  Shudi Yu , Jie Li , Jiongting Yin , Wanyu Liang , Yangping Zhang , Tianpeng Liu , Mengyun Hu , Yong Wang , Zhengying Wu , Yuefan Zhang , Yukou Du . Built-in electric field and core-shell structure of the reconstructed sulfide heterojunction accelerated water splitting. Chinese Chemical Letters, 2024, 35(12): 110068-. doi: 10.1016/j.cclet.2024.110068
15. [15]
  Jianning Zhang , Yihuai Zhang , Guoxin Ma , Jingchen Zhao , Tao Zhang , Jian Liu . Enhancing hydrothermal stability in Cu/SSZ-13 catalyst for diesel SCR applications through a novel core-shell structure. Chinese Chemical Letters, 2025, 36(7): 110516-. doi: 10.1016/j.cclet.2024.110516
16. [16]
  Yaoyin Lou , Xiaoyang Jerry Huang , Kuang-Min Zhao , Mark J. Douthwaite , Tingting Fan , Fa Lu , Ouardia Akdim , Na Tian , Shigang Sun , Graham J. Hutchings . Stable core-shell Janus BiAg bimetallic catalyst for CO₂ electrolysis into formate. Chinese Chemical Letters, 2025, 36(3): 110300-. doi: 10.1016/j.cclet.2024.110300
17. [17]
  Chen Pu , Daijie Deng , Henan Li , Li Xu . Fe_0.64Ni_0.36@Fe₃NiN Core-Shell Nanostructure Encapsulated in N-Doped Carbon Nanotubes for Rechargeable Zinc-Air Batteries with Ultralong Cycle Stability. Acta Physico-Chimica Sinica, 2024, 40(2): 2304021-0. doi: 10.3866/PKU.WHXB202304021
18. [18]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
19. [19]
  Naihong Wang , Longkang Zhang , Yejun Guan , Peng Wu , Hao Xu . Pt confined in Sn-ECNU-46 zeolite for efficient alkane dehydrogenation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100248-100248. doi: 10.1016/j.cjsc.2024.100248
20. [20]
  Guoliang Liu , Zhiqiang Liu , Anmin Zheng . Modulation of zeolite surface realizes dynamic copper species redispersion. Chinese Journal of Structural Chemistry, 2024, 43(6): 100308-100308. doi: 10.1016/j.cjsc.2024.100308

Get Citation

PDF

XML

Metrics

PDF Downloads(13)
Abstract views(879)
HTML views(134)

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