铂纳米粒子与氧化铁载体协同作用促进芳香硝基化合物温和条件下选择加氢

引用本文: 景培, 甘涛, 戚卉, 郑彬, 初学峰, 于贵阳, 闫文付, 邹永存, 张文祥, 刘钢. 铂纳米粒子与氧化铁载体协同作用促进芳香硝基化合物温和条件下选择加氢[J]. 催化学报, 2019, 40(2): 214-222. doi: S1872-2067(19)63276-6 shu

Citation: Pei Jing, Tao Gan, Hui Qi, Bin Zheng, Xuefeng Chu, Guiyang Yu, Wenfu Yan, Yongcun Zou, Wenxiang Zhang, Gang Liu. Synergism of Pt nanoparticles and iron oxide support for chemoselective hydrogenation of nitroarenes under mild conditions[J]. Chinese Journal of Catalysis, 2019, 40(2): 214-222. doi: S1872-2067(19)63276-6 shu

铂纳米粒子与氧化铁载体协同作用促进芳香硝基化合物温和条件下选择加氢

景培 ^a, ,
甘涛 ^a, ,
戚卉 ^b, ,
郑彬 ^a, ,
初学峰 ^c, ,
于贵阳 ^a, ,
闫文付 ^a, ,
邹永存 ^a, ,
张文祥 ^a, ,
刘钢 ^a,

a 吉林大学化学学院, 无机合成与制备化学国家重点实验室, 吉林长春 130012;
b 吉林大学第二医院, 吉林长春 130041;
c 吉林建筑大学电气与电子信息工程学院, 吉林省建筑电气综合节能重点实验室, 吉林长春 130041
基金项目:
国家自然科学基金（21473073，21473074）；吉林省科技发展计划（20170101171JC，20180201068SF）；吉林省教育厅"十三五"科学技术研究项目（2016403）；无机合成和制备化学国家重点实验室开放项目（201703）.

摘要: 负载型Pt基催化剂是一类重要的工业催化剂，在很多还原和氧化反应中都表现出很高的催化活性，但高昂的价格一直制约着Pt基催化剂的大规模应用.另外，Pt活性位点对有机化合物不同基团的区分性差，通常造成目的产物的选择性较低.以人们熟知的芳香硝基化合物加氢为例，当有其它易还原基团如C=C、C=O、-X等存在时，在硝基加氢的同时，这些基团也不同程度地被还原.在已报道的工作中，通过合理设计Pt活性中心结构、改善Pt周围环境以及在反应中添加无机盐或有机化合物等方法，芳香硝基化合物加氢的选择性获得大幅提升，但催化剂活性对Pt负载量的依赖性仍然很高，降低催化剂中的Pt活性位数量会显著降低催化剂活性.此外，Pt纳米粒子在反应过程中的聚集以及氧化物载体在强还原气氛下的性能变化等对催化剂的稳定性产生很大影响.
本文工作中我们尝试发挥载体在反应中的作用，实现氢解离和反应物加氢活性中心在空间上分离，从而降低Pt的负载量.工作思路主要是基于氢溢流的基本原理，其难点在于高效氢解离活性中心的设计和载体的选择，后者需满足活泼氢物种的输运和硝基基团的有效吸附.为了实现上述目标，本文采用胶体法制备了3-4nm的Pt粒子，该方法可以有效地控制Pt纳米粒子的尺寸以及在载体上的分散状态，从而形成大量的Pt⁰活性位，实现高效氢解离.在充分考虑载体的氧化还原性和表面碱性质（给电子能力）的基础上，我们筛选了多种氧化物作为载体.反应结果显示，Pt/α-Fe₂O₃在Pt负载量仅为0.2wt%时即表现出很高的芳香硝基化合物加氢催化活性和选择性，并且该反应可在相当温和的条件（30℃，5bar H₂）下进行.在经过多次循环反应后，Pt纳米粒子的尺寸、分散状态以及α-Fe₂O₃载体的物相等均未发生变化，催化剂表现出很高的稳定性.
Pt纳米粒子的高效氢解离能力是催化剂实现高活性的重要因素之一，而α-Fe₂O₃的表面性质也同样发挥了重要作用，其表面一定数量的氧空位具有较强的给电子能力，可以与具有较强吸电子能力的硝基基团作用，实现反应物的高效吸附；载体表面适当的氧化还原性有利于活泼氢的输运，在与Pt纳米粒子的协同作用下实现了温和条件下芳香硝基化合物的选择性加氢.本工作显著降低了Pt的使用量，实现了非常温和条件下的稳定、高效加氢，可为低成本Pt基催化剂的设计提供借鉴.

关键词:

English

Synergism of Pt nanoparticles and iron oxide support for chemoselective hydrogenation of nitroarenes under mild conditions

a State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, Jilin, China;
b The Second Hospital of Jilin University, Changchun 130041, Jilin, China;
c Provincial Key Laboratory of Architectural Electricity & Comprehensive Energy Saving, School of Electrical and Electronic Information Engineering, Jilin Jianzhu University, Changchun 130118, Jilin, China
Received Date: 18 December 2018
Revised Date: 20 December 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (21473073, 21473074), "13th Five-Year" Science and Technology Research of the Education Department of Jilin Province (2016403), the Development Project of Science and Technology of Jilin Province (20170101171JC, 20180201068SF), and the Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry (201703).

Abstract: An efficient and low-cost supported Pt catalyst for hydrogenation of niroarenes was prepared with colloid Pt precursors and α-Fe₂O₃ as a support. The catalyst with Pt content as low as 0.2 wt% exhibits high activities, chemoselectivities and stability in the hydrogenation of nitrobenzene and a variety of niroarenes. The conversion of nitrobenzene can reach 3170 mol_conv h^-1 mol_Pt^-1 under mild conditions (30℃, 5 bar), which is much higher than that of commercial Pt/C catalyst and many reported catalysts under similar reaction conditions. The spatial separation of the active sites for H₂ dissociation and hydrogenation should be responsible for the high chemoselectivity, which decreases the contact possibility between the reducible groups of nitroarenes and Pt nanoparticles. The unique surface properties of α-Fe₂O₃ play an important role in the reaction process. It provides active sites for hydrogen spillover and reactant adsorption, and ultimately completes the hydrogenation of the nitro group on the catalyst surface.

Key words:

1. [1] E. Schmidt, A. Vargas, T. Mallat, A. Baiker, J. Am. Chem. Soc., 2009, 131, 12358-12367.
2. [2] W. Y. Cui, D. Xue, N. D. Tan, B. Zheng, M. J. Jia, W. X. Zhang, Chin. J. Catal., 2018, 39, 1534-1542.
3. [3] J. J. Liu, S. H. Zou, J. C. Wu, H. Kobayashi, H. T. Zhao, J. Fan, Chin. J. Catal., 2018, 39, 1081-1089.
4. [4] B. Zheng, S. J. Wu, X. W. Yang, M. J. Jia, W. X. Zhang, G. Liu, ACS. Appl. Mater. Inter., 2016, 8, 26683-26689.
5. [5] P. P. Ye, A. J. Gellman, J. Am. Chem. Soc., 2008, 130, 8518-8526.
6. [6] G. C. da Silva, M. R. Fernandes, E. A. Ticianelli, ACS. Catal., 2018, 8, 2081-2092.
7. [7] Z. J. Chen, J. Y. Chen, Y. W. Li, Chin. J. Catal., 2017, 38, 1108-1126.
8. [8] S. Anantharaj, P. E. Karthik, B. Subramanian, S. Kundu, ACS. Catal., 2016, 6, 4660-4672.
9. [9] Y. L. Sui, S. B. Liu, T. F. Li, Q. X. Liu, T. Jiang, Y. F. Guo, J. L. Luo, J. Catal., 2017, 353, 250-255.
10. [10] L. L. Geng, M. Zhang, W. X. Zhang, M. J. Jia, W. F. Yan, G. Liu, Catal. Sci. Technol., 2015, 5, 3097-3102.
11. [11] R. V. Jagadeesh, A. E. Surkus, H. Junge, M-M. Pohl, J. Radnik, J. Rabeah, H. Huan, V. Schünemann, A. Brückner, M. Beller, Science, 2013, 342, 1073-1076.
12. [12] Y. J. Shu, T. Chen, H. C. Chan, L. F. Xie, Q. S. Gao, Chem-Asian. J., 2018, 13, 3737-3744.
13. [13] Q. M. Hu, S. Wang, Z. Gao, Y. Q. Li, Q. Zhang, Q. Xiang, Y. Qin, Appl. Catal. B:Environ., 2017, 218, 591-599.
14. [14] M. W. Zhu, B. Huang, Q. Shao, Y. C. Pi, Y. Qian, X. Q. Huang, ChemCatChem., 2018, 10, 3214-3218.
15. [15] W. Shi, B. S. Zhang, Y. M. Lin, Q. Wang, Q. Zhang, D. S. Su, ACS. Catal., 2016, 6, 7844-7854.
16. [16] P. Lara, K. Philippot, Catal. Sci. Technol., 2014, 4, 2445-2465.
17. [17] G. Vilé, D. Albani, N. Almora-Barrios, N. López, J. Pérez-Ramírez, ChemCatChem., 2016, 8, 21-33.
18. [18] J. Wang, Y. J. Zhang, J. Y. Diao, J. Y. Zhang, H. Y. Liu, D. S.Su, Chin. J. Catal., 2018, 39, 79-87.
19. [19] K. Möbus, D. Wolf, H. Benischke, U. Dittmeier, K. Simon, U. Packruhn, R. Jantke, S. Weidlich, C. Weber, B. S. Chen, Top. Catal., 2010, 53, 1126-1131.
20. [20] M. Makosch, W-I. Lin, V. Bumbálek, J. Sá, J. W. Medlin, K. Hungerbühler, J. A. van Bokhoven, ACS. Catal., 2012, 2, 2079-2081.
21. [21] K-i. Shimizu, Y. Miyamoto, A. Satsuma, J. Catal., 2010, 270, 86-94.
22. [22] K-i. Shimizu, Y. Miyamoto, T. Kawasaki, T. Tanji, Y. Tai, A. Satsuma, J. Phys. Chem. C., 2009, 113, 17803-17810.
23. [23] T. Mitsudome, Y. Mikami, M. Matoba, T. Mizugaki, K. Jitsukawa, K. Kaneda, Angew. Chem. Int. Ed., 2012, 51, 136-139.
24. [24] H. S. Wei, X. Y. Liu, A. Q. Wang, L. L. Zhang, B. T. Qiao, X. F. Yang, Y. Q. Huang, S. Miao, J. Y. Liu, T. Zhang, Nat. Commun., 2014, 5, 5634-5641.
25. [25] A. Corma, P. Serna, P. Concepcion, J. J. Calvino, J. Am. Chem. Soc., 2008, 130, 8748-8753.
26. [26] S. Zhang, C. R. Chang, Z. Q. Huang, J. Li, Z. M. Wu, Y. Y. Ma, Z. Y. Zhang, Y. Wang, Y. Q. Qu, J. Am. Chem. Soc., 2016, 138, 2629-2637.
27. [27] L. Wang, E. J. Guan, J. Zhang, J. H. Yang, Y. H. Zhu, Y. Han, M. Yang, C. Cen, G. Fu, B. C. Gates, F. S. Xiao, Nat. Commun., 2018, 9, 1362-1369.
28. [28] H. S. Wei, Y. J. Ren, A. Q. Wang, X. Y. Liu, X. Liu, L. L. Zhang, S. Miao, L. Li, J. Y. Liu, J. H. Wang, G. F. Wang, D. S. Su, T. Zhang, Chem. Sci., 2017, 8, 5126-5131.
29. [29] B. Zhang, H. Asakura, J. Zhang, J. G. Zhang, S. De, N. Yan, Angew. Chem. Int. Ed., 2016, 55, 8319-8323.
30. [30] W. Karim, C. Spreafico, A. Kleibert, J. Gobrecht, J. VandeVondele, Y. Ekinci, J. A. van Bokhoven, Nature, 2017, 541, 68-71.
31. [31] L. R. Merte, G. Peng, R. Bechstein, F. Rieboldt, C. A. Farberow, L. C. Grabow, W. Kudernatsch, S. Wendt, E. Laegsgaard, M. Mavrikakis, F. Besenbacher, Science, 2012, 336, 889-893.
32. [32] R. Prins, Chem. Rev., 2012, 112, 2714-2738.
33. [33] B. Zheng, G. Liu, L. L. Geng, J. Y. Cui, S. J. Wu, P. Wu, M. J. Jia, W. F. Yan, W. X. Zhang, Catal. Sci. Technol., 2016, 6, 1546-1554.
34. [34] A. Corma, P. Serna, H. Garcia, J. Am. Chem. Soc., 2007, 129, 6358-6359.
35. [35] M. Boronat, P. Concepcion, A. Corma, S. Gonzalez, F. Illas, P. Serna, J. Am. Chem. Soc., 2007, 129, 16230-16237.
36. [36] J. L. Song, G. Y. Yu, X. Li, X. W. Yang, W. X. Zhang, W. F. Yan, G. Liu, Chin. J. Catal., 2018, 39, 309-318.
37. [37] L. Q. Liu, F. Zhou, L. G. Wang, X. J. Qi, F. Shi, Y. Q. Deng, J. Catal., 2010, 274, 1-10.
38. [38] Z. Z. Yang, N. Zhang, Y. Cao, M. C. Gong, M. Zhao, Y. Q. Chen, Catal. Sci. Technol., 2014, 4, 3032-3043.
39. [39] R. Ahmadi, M. K. Amini, J. C. Bennett, J. Catal., 2012, 292, 81-89.
40. [40] E. Ivanova, M. Mihaylov, F. Thibault-Starzyk, M. Daturi, K. Hadjiivanov, J. Mol. Catal. A, 2007, 274, 179-184.
41. [41] S. Shen, X. L. Wang, Q. Ding, S. Q. Jin, Z. C. Feng, C. Li, Chin. J. Catal., 2014, 35, 1900-1906.
42. [42] G. Richner, J. A. van Bokhoven, Y. M. Neuhold, M. Makosch, K. Hungerbuhler, Phys. Chem. Chem. Phys., 2011, 13, 12463-12471.
43. [43] S. Meijers, V. Ponec, J. Catal., 1996, 160, 1-9.
44. [44] D. Flak, Q. Chen, B. S. Mun, Z. Liu, M. Rękas, A. Braun, Appl. Surf. Sci., 2018, 455, 1019-1028.
45. [45] S. Sultana, S. Mansingh, K. M. Parida, J. Mater. Chem. A., 2018, 6, 11377-11389.
46. [46] L. L. Geng, J. L. Song, B. Zheng, S. J. Wu, W. X. Zhang, M. J. Jia, G. Liu, Chin. J. Catal., 2016, 37, 1451-1460.

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沈阳化工大学材料科学与工程学院沈阳 110142

铂纳米粒子与氧化铁载体协同作用促进芳香硝基化合物温和条件下选择加氢

English

Synergism of Pt nanoparticles and iron oxide support for chemoselective hydrogenation of nitroarenes under mild conditions

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

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

铂纳米粒子与氧化铁载体协同作用促进芳香硝基化合物温和条件下选择加氢

English

Synergism of Pt nanoparticles and iron oxide support for chemoselective hydrogenation of nitroarenes under mild conditions

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？

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