单原子催化剂的制备、表征及催化性能

引用本文: 王丽琼, 黄亮, 梁峰, 刘思敏, 王玉华, 张海军. 单原子催化剂的制备、表征及催化性能[J]. 催化学报, 2017, 38(9): 1528-1539. doi: 10.1016/S1872-2067(17)62770-0 shu

Citation: Liqiong Wang, Liang Huang, Feng Liang, Simin Liu, Yuhua Wang, Haijun Zhang. Preparation, characterization and catalytic performance of single-atom catalysts[J]. Chinese Journal of Catalysis, 2017, 38(9): 1528-1539. doi: 10.1016/S1872-2067(17)62770-0 shu

单原子催化剂的制备、表征及催化性能

王丽琼 ^a, ,
黄亮 ^a, ,
梁峰 ^b, ,
刘思敏 ^b, ,
王玉华 ^c, ,
张海军 ^a,

a 武汉科技大学耐火材料与冶金国家重点实验室, 湖北武汉 430081;
b 武汉科技大学化学与化工学院, 湖北武汉 430081;
c 武汉科技大学冶金工业过程系统科学湖北省重点实验室, 湖北武汉 430081
基金项目:
国家自然科学基金（51472184，51472185）；湖北省科技支撑计划对外科技合作项目（2013BHE003）；湖北省教育厅高等学校优秀中青年科技创新团队计划（T201602）.

摘要: 单原子催化剂（SACs）是指金属以单原子形式均匀分散在载体上形成的具有优异催化性能的催化剂.与传统载体型催化剂相比，SACs具有活性高、选择性好及贵金属利用率高等优点，在氧化反应、加氢反应、水煤气变换、光催化制氢以及电化学催化等领域都具有广泛应用，是目前催化领域的研究热点之一.常见的SACs制备方法有共沉淀法、浸渍法、置换反应法、原子层沉积法以及反奥斯瓦尔德熟化法等.实验及理论研究表明，单原子催化剂高的活性和选择性可归因于活性金属原子和载体之间的相互作用及由此引起的电子结构改变.载体是影响单原子催化剂性能的重要因素之一.目前常用的SACs载体有金属氧化物、二维材料和金属纳米团簇等，本文着重综述了这三种负载型SACs的制备、表征、催化性能及催化机理，并概述了SACs未来可能的发展方向和应用.
研究表明，共沉淀法、湿浸渍法和反奥斯瓦尔德熟化法等方法可用来制备氧化物负载的SACs.高角环形暗场像-扫描透射电子显微镜（HAADF-STEM）表明金属是以单原子形式均匀分散在载体上，近边X射线吸收精细结构（XANES）结果表明金属原子与载体之间存在着强相互作用.实验和理论研究均表明该类催化剂在CO氧化反应、水煤气转化及乙炔加氢生成乙烯等反应中具有高的催化活性和稳定性.采用化学气相沉积法和原子层沉积法等方法可以将金属原子稳定地负载在具有缺陷活性位点的石墨烯、MXene及六方氮化硼等二维材料上并相应制备出SACs.X射线吸收精细结构谱（EXAFS）和XANES分析表明样品中金属以单原子形式存在，而且金属原子与载体之间也存在着强相互作用，理论计算表明金属原子与二维载体之间的电荷转移是SACs活性高的主要原因.置换反应法和连续还原法是制备溶胶型SACs的有效方法，其中置换反应法可将活性金属原子原位组装在金属模板团簇的顶点位置，连续还原法可将活性原子负载于金属模板团簇的表面.DFT计算表明活性原子和金属模板团簇之间存在电荷转移效应，这是溶胶型SACs具有非常高的催化活性的主要原因.
SACs下一步的研究方向可能是：（1）研究开发新型SACs，尽可能提高催化剂中活性金属原子的含量；（2）深入研究SACs的结构、活性以及催化机理之间的关系；（3）尝试将SACs大规模应用于工业催化.

关键词:

English

Preparation, characterization and catalytic performance of single-atom catalysts

a The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China;
b School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China;
c Hubei Province Key Laboratory of Science in Metallurgical Process, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China
Received Date: 29 October 2016
Revised Date: 19 December 2016
Fund Project:
This work was supported by the National Natural Science Foundation of China (51472184 and 51472185), the Science and Technology Support Pro-gram of Hubei Province (2013BHE003), and the Program for Innovative Teams of Outstanding Young and Middle-Aged Researchers in the Higher Education Institutions of Hubei Province (T201602).

Abstract: Supported and colloidal single-atom catalysts (SACs), which possess excellent catalytic properties, are particularly important in both fundamental studies and practical applications. The progress made in the preparation methods, characterization, catalytic performances and mechanisms of SACs anchored to metal oxides, two-dimensional materials and the surface of metal nanoclusters (NCs) are reviewed. The different techniques for SAC fabrication, including conventional solution methods based on co-precipitation, incipient wetness co-impregnation, and the chemical vapor deposition method, as well as the newer atom layer deposition (ALD) and galvanic replacement methods, are summarized. The main results from experimental and theoretical studies of various catalytic reac-tions over SACs, including oxidation reactions, hydrogenation, water gas shift, photocatalytic H₂ evolution and electrochemical reactions, are also discussed. Moreover, the electronic properties of the single atoms and their interactions with the supports are described to assist in understanding the origin of the high catalytic activity and selectivity of SACs. Finally, possible future research di-rections of SACs and their applications are proposed.

Key words:

1. [1] P. Wang, H. Z. Liu, J. R. Niu, R. Li, J. Ma, Catal. Sci. Technol., 2014, 4, 1333-1339.
2. [2] Z. Balogh, G. Halasi, B. Korbély, K. Hernadi, Appl. Catal. A, 2008, 344, 191-197.
3. [3] M. Lewandowski, G. S. Babu, M. Vezzoli, M. D. Jones, R. E. Owen, D. Mattia, P. Plucinski, E. Mikolajska, A. Ochenduszko, D. C. Apperley, Catal. Commun., 2014, 49, 25-28.
4. [4] H. J. You, S. C. Yang, B. J. Ding, H. Yang, Chem. Soc. Rev., 2013, 42, 2880-2904.
5. [5] G. Halasi, I. Ugrai, F. Solymosi, J. Catal., 2011, 281, 309-317.
6. [6] M. H. Liu, W. Y. Yu, H. F. Liu. J. Mol. Catal. A, 1999, 138, 295-303.
7. [7] H. J. Zhang, W. Q. Li, Y. J. Gu, S. W. Zhang, J. Nanosci. Nanotechnol., 2014, 14, 5743-5751.
8. [8] H. J. Zhang, N. Toshima, J. Colloid Interface Sci., 2013, 394, 166-176.
9. [9] H. J. Zhang, M. Okumura, N. Toshima, J. Phys. Chem. C, 2011, 115, 14883-14891.
10. [10] S. Vajda, M. J. Pellin, J. P. Greeley, C. L. Marshall, L. A. Curtiss, G. A. Ballentine, J. W. Elam, S. Catillon-Mucherie, P. C. Redfern, F. Mehmood, P. Zapol, Nat. Mater., 2009, 8, 213-216.
11. [11] J. Lin, B. T. Qiao, N. Li, L. Li, X. C. Sun, J. Y. Liu, X. D. Wang, T. Zhang, Chem. Commun., 2015, 51, 7911-7914.
12. [12] M. Turner, V. B. Golovko, O. P. Vaughan, P. Abdulkin, A. Ber-enguer-Murcia, M. S. Tikhov, B. F. Johnson, R. M. Lambert, Nature, 2008, 454, 981-983.
13. [13] X. F. Yang, A. Q. Wang, B. T. Qiao, J. Li, J. Y. Liu, T. Zhang, Acc. Chem. Res., 2013, 46, 1740-1748.
14. [14] P. P. Hao, Y. Y. Jin, J. Ren, Z. Li, Prog. Chem., 2015, 27, 1689-1704.
15. [15] B. Long, Y. Tang, J. Li, Nano Res., 2016, 9, 3868-3880.
16. [16] P. Wu, P. Du, H. Zhang, C. X. Cai, Phys. Chem. Chem. Phys., 2015, 17, 1441-1449.
17. [17] B. L. He, J. S. Shen, Z. X. Tian, Phys. Chem. Chem. Phys., 2016, 18, 24261-24269.
18. [18] J. X. Liang, X. Yang, A. Q. Wang, T. Zhang, J. Li, Catal. Sci. Technol., 2016, 6, 6886-6892.
19. [19] H. J. Zhang, T. Watanabe, M. Okumura, M. Haruta, N. Toshima, Nat. Mater., 2012, 11, 49-52.
20. [20] B. T. Qiao, A. Q. Wang, X. F. Yang, L. F. Allard, Z. Jiang, Y. T. Cui, J. Y. Liu, J. Li, T. Zhang, Nat. Chem., 2011, 3, 634-641.
21. [21] X. R. Cao, Y. F. Ji, Y. Luo, J. Phys. Chem. C, 2015, 119, 1016-1023.
22. [22] G. Vile, D. Albani, M. Nachtegaal, Z. P. Chen, D. Dontsova, M. Anto-nietti, N. Lopez, J. Perez-Ramirez, Angew. Chem. Int. Ed., 2015, 54, 11265-11269.
23. [23] G. X. Pei, X. Y. Liu, A. Q. Wang, A. F. Lee, M. A. Isaacs, L. Li, X. L. Pan, X. F. Yang, X. D. Wang, Z. J. Tai, K. Wilson, T. Zhang, ACS Catal., 2015, 5, 3717-3725.
24. [24] G. Kyriakou, M. B. Boucher, A. D. Jewell, E. A. Lewis, T. J. Lawton, A. E. Baber, H. L. Tierney, M. Flytzani-Stephanopoulos, E. C. Sykes, Science, 2012, 335, 1209-1212.
25. [25] J. Lin, A. Q. Wang, B. T. Qiao, X. Y. Liu, X. F. Yang, X. D. Wang, J. X. Liang, J. Li, J. Y. Liu, T. Zhang, J. Am. Chem. Soc., 2013, 135, 15314-15317.
26. [26] K. Ding, A. Gulec, A. M. Johnson, N. M. Schweitzer, G. D. Stucky, L. D. Marks, P. C. Stair, Science, 2015, 350, 189-192.
27. [27] X. G. Li, W. T. Bi, L. Zhang, S. Tao, W. S. Chu, Q. Zhang, Y. Luo, C. Z. Wu, Y. Xie, Adv. Mater., 2016, 28, 2427-2431.
28. [28] H. T. Wang, Q. X. Wang, Y. C. Cheng, K. Li, Y. B. Yao, Q. Zhang, C. Z. Dong, P. Wang, U. Schwingenschlogl, W. Yang, X. X. Zhang, Nano Lett., 2012, 12141-144.
29. [29] W. L. Wang, E. J. G. Santos, B. Jiang, E. D. Cubuk, C. Ophus, A. Cen-teno, A. Pesquera, A. Zurutuza, J. Ciston, R. Westervelt, E. Kaxiras, Nano Lett., 2014, 14, 450-455.
30. [30] S. Yang, Y. J. Tak, J. Kim, A. Soon, H. Lee, ACS Catal., 2017, 7, 1301-1307.
31. [31] S. Yang, J. Kim, Y. J. Tak, A. Soon, H. Lee, Angew. Chem. Int. Ed., 2016, 55, 2058-2062.
32. [32] J. Xing, J. F. Chen, Y. H. Li, W. T. Yuan, Y. Zhou, L. R. Zheng, H. F. Wang, P. Hu, Y. Wang, H. J. Zhao, Y. Wang, H. G. Yang, Chemistry, 2014, 20, 2138-2144.
33. [33] B. T. Qiao, J. Lin, A. Q. Wang, Y. Chen, T. Zhang, J. Y. Liu, Chinese J. Catal., 2015, 36, 1505-1511.
34. [34] B. T. Qiao, J. X. Liang, A. Q. Wang, C. Q. Xu, J. Li, T. Zhang, J. Y. Liu, Nano Res., 2015, 8, 2913-2924.
35. [35] Y. Sato, Y. Soma, T. Miyao, S. Naito, Appl. Catal. A, 2006, 304, 78-85.
36. [36] L. L. Zhang, A. Q. Wang, J. T. Miller, X. Y. Liu, X. F. Yang, W. T. Wang, L. Li, Y. Q. Huang, C. Y. Mou, T. Zhang, ACS Catal., 2014, 4, 1546-1553.
37. [37] M. Moses-DeBusk, M. Yoon, L. F. Allard, D. R. Mullins, Z. L. Wu, X. F. Yang, G. Veith, G. M. Stocks, C. K. Narula, J. Am. Chem. Soc., 2013, 135, 12634-12645.
38. [38] X. K. Gu, B. T. Qiao, C. Q. Huang, W. C. Ding, K. J. Sun, E. S. Zhan, T. Zhang, J. Y. Liu, W. X. Li, ACS Catal., 2014, 4, 3886-3890.
39. [39] P. P. Hu, Z. W. Huang, Z. Amghouz, M. Makkee, F. Xu, F. Kapteijn, A. Dikhtiarenko, Y. X. Chen, X. Gu, X. F. Tang, Angew. Chem. Int. Ed., 2014, 53, 3418-3421.
40. [40] P. X. Liu, Y. Zhao, R. X. Qin, S. G. Mo, G. X. Chen, L. Gu, D. M. Chevrier, P. Zhang, Q. Guo, D. D. Zang, B. H. Wu, G. Fu, N. F. Zheng, Science, 2016, 352, 797-800.
41. [41] D. H. Deng, K. S. Novoselov, Q. Fu, N. F. Zheng, Z. Q. Tian, X. H. Bao, Nat. Nanotechnol., 2016, 11, 218-230.
42. [42] S. Z. Butler, S. M. Hollen, L. Y. Cao, Y. Cui, J. A. Gupta, H. R. Gutierrez, T. F. Heinz, S. S. Hong, J. X. Huang, A. F. Ismach, E. John-ston-Halperin, M. Kuno, V. V. Plashnitsa, R. D. Robinson, R. S. Ruoff, S. Salahuddin, J. Shan, L. Shi, M. G. Spencer, M. Terrones, W. Windl, J. E. Goldberger, ACS Nano, 2013, 7, 2898-2926.
43. [43] H. J. Qiu, Y. Ito, W. Cong, Y. Tan, P. Liu, A. Hirata, T. Fujita, Z. Tang, M. Chen, Angew. Chem. Int. Ed., 2015, 54, 14031-14035.
44. [44] S. H. Sun, G. X. Zhang, N. Gauquelin, N. Chen, J. G. Zhou, S. L. Yang, W. F. Chen, X. B. Meng, D. S. Geng, M. N. Banis, R. Y. Li, S. Y. Ye, S. Knights, G. A. Botton, T. K. Sham, X. L. Sun, Sci. Rep., 2013, 3, 1755-1763.
45. [45] H. Yan, H. Cheng, H. Yi, Y. Lin, T. Yao, C. L. Wang, J. J. Li, S. Q. Wei, J. L. Lu, J. Am. Chem. Soc., 2015, 137, 10484-10487.
46. [46] G. P. Gao, Y. Jiao, E. R. Waclawik, A. J. Du, J. Am. Chem. Soc., 2016, 138, 6292-6297.
47. [47] P. Zhao, Y. Su, Y. Zhang, S. J. Li, G. Chen, Chem. Phys. Lett., 2011, 515, 159-162.
48. [48] S. Lin, X. X. Ye, R. S. Johnson, H. Guo, J. Phys. Chem. C, 2013, 117, 17319-17326.
49. [49] X. Zhang, J. C. Lei, D. H. Wu, X. D. Zhao, Y. Jing, Z. Zhou, J. Mater. Chem. A, 2016, 4, 4871-4876.
50. [50] Y. Wang, H. Yuan, Y. F. Li, Z. F. Chen, Nanoscale, 2015, 7, 11633-11641.
51. [51] Y. F. Li, Z. Zhou, G. T. Yu, W. Chen, Z. F. Chen, J. Phys. Chem. C, 2010, 114, 6250-6254.
52. [52] J. Halim, S. Kota, M. R. Lukatskaya, M. Naguib, M. Q. Zhao, E. J. Moon, J. Pitock, J. Nanda, S. J. May, Y. Gogotsi, M. W. Barsoum, Adv. Funct. Mater., 2016, 26, 3118-3127.
53. [53] Q. K. Hu, D. D. Sun, Q. H. Wu, H. Y. Wang, L. B. Wang, B. Z. Liu, A. G. Zhou, J. L. He, J. Phys. Chem. A, 2013, 117, 14253-14260.
54. [54] Y. Wang, X. C. Wang, M. Antonietti, Angew. Chem. Int. Ed., 2012, 51, 68-89.
55. [55] G. Gao, Y. Jiao, E. R. Waclawik, A. Du, J. Am. Chem. Soc., 2016, 138, 6292-6297.
56. [56] H. J. Zhang, Y. N. Cao, L. L. Lu, Z. Cheng, S. W. Zhang, Metall. Mater. Trans. B, 2014, 46, 523-530.
57. [57] H. J. Zhang, N. Toshima, Catal. Sci. Technol., 2013, 3, 268-278.
58. [58] H. J. Zhang, N. Toshima, K. Takasaki, M. Okumura, J. Alloys Comp., 2014, 586, 462-468.
59. [59] H. J. Zhang, J. Okuni, N. Toshima, J. Colloid Interface Sci., 2011, 354, 131-138.
60. [60] C. P. Jiao, Z. L. Huang, X. F. Wang, H. J. Zhang, L. L. Lu, S. W. Zhang, RSC Adv., 2015, 5, 34364-34371.
61. [61] D. C. Kong, Y. J. Gu, S. Xiang, P. Wang, J. Cheng, H. J. Zhang, S. W. Zhang, Chem. J. Chin. Univ., 2013, 34, 2377-2382.
62. [62] X. F. Wang, S. R. Sun, Z. L. Huang, H. J. Zhang, S. W. Zhang, Int. J. Hydrogen Energy, 2014, 39, 905-916.
63. [63] X. Y. Zhou, W. Q. Li, W. Li, L. Su, W. G. Zha, Z. N. Zhou, H. J. Zhang, L. L. Lu, S. W. Zhang, F. L. Li, Chem. Online, 2015, 78, 237-241.
64. [64] W. G. Zhao, L. Su, Z. N. Zhou, H. J. Zhang, L. L. Lu, S. W. Zhang, Acta Phys.-Chim. Sin., 2015, 31, 145-152.
65. [65] X. F. Wang, Y. N. Cao, S. R. Sun, Z. L. Huang, H. J. Zhang, S. W. Zhang, Rare Metal Mater. Eng., 2015, 44, 753-758.
66. [66] H. J. Zhang, X. G. Deng, C. P. Jiao, L. L. Lu, S. W. Zhang, Mater. Res. Bull., 2016, 79, 29-35.
67. [67] H. J. Zhang, N. Toshima, J. Nanosci. Nanotechnol., 2013, 13, 5405-5412.
68. [68] H. J. Zhang, T. Watanabe, M. Okumura, M. Haruta, N. Toshima, J. Catal., 2013, 305, 7-18.
69. [69] H. J. Zhang, L. L. Lu, K. Kawashima, M. Okumura, M. Haruta, N. Toshima, Adv. Mater., 2015, 27, 1383-1388.
70. [70] H. J. Zhang, L. Q. Wang, L. L. Lu, N. Toshima, Sci. Rep., 2016, 6, 30752-30762.
71. [71] T. Nakamura, Y. Tsukahara, T. Yamauchi, H. Mori, Y. Wada, Chem. Lett., 2007, 36, 154-155.
72. [72] C. P. Jiao, Z. L. Huang, H. J. Zhang, S. W. Zhang, Prog. Chem., 2015, 27, 472-481.
73. [73] Z. Ban, Y. A. Barnakov, F. Li, V. O. Golub, C. J. O'Connor, J. Mater. Chem., 2005, 15, 4660-4662.
74. [74] J. Yang, J. Y. Lee, H. P. Too, J. Phys. Chem. B, 2005, 109, 19208-19212.
75. [75] H. J. Zhang, K. Kawashima, M. Okumura, N. Toshima, J. Mater. Chem. A, 2014, 2, 13498-13508.
76. [76] J. S. Jirkovsky, I. Panas, E. Ahlberg, M. Halasa, S. Romani, D. J. Schiffrin, J. Am. Chem. Soc., 2011, 133, 19432-19441.
77. [77] H. J. Zhang, N. Toshima, Appl. Catal. A, 2011, 400, 9-13.
78. [78] H. J. Zhang, L. L. Lu, Y. N. Cao, S. Du, Z. Cheng, S. W. Zhang, Mater. Res. Bull., 2014, 49, 393-398.
79. [79] W. Q. Li, W. G. Zhao, X. Y. Zhou, L. Su, H. J. Zhang, L. L. Lu, S. W. Zhang, Chem. J. Chin. Univ., 2014, 35, 2164-2169.
80. [80] M. S. Bootharaju, C. P. Joshi, M. R. Parida, O. F. Mohammed, O. M. Bakr, Angew. Chem. Int. Ed., 2016, 55, 922-926.
81. [81] S. X. Liang, C. Hao, Y. T. Shi, ChemCatChem, 2015, 7, 2559-2567.

扫一扫看文章

计量

PDF下载量: 449
文章访问数: 8896
HTML全文浏览量: 3831

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

单原子催化剂的制备、表征及催化性能

English

Preparation, characterization and catalytic performance of single-atom catalysts

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

单原子催化剂的制备、表征及催化性能

English

Preparation, characterization and catalytic performance of single-atom catalysts

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

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs