铜-氧化铈界面:几何及电子结构

引用本文: 周燕, 陈阿玲, 宁静, 申文杰. 铜-氧化铈界面:几何及电子结构[J]. 催化学报, 2020, 41(6): 928-937. doi: 10.1016/S1872-2067(20)63540-9 shu

Citation: Yan Zhou, Aling Chen, Jing Ning, Wenjie Shen. Electronic and geometric structure of the copper-ceria interface on Cu/CeO₂ catalysts[J]. Chinese Journal of Catalysis, 2020, 41(6): 928-937. doi: 10.1016/S1872-2067(20)63540-9 shu

铜-氧化铈界面:几何及电子结构

中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连 116023
基金项目:
国家自然科学基金（21761132031，21533009，91645107，21621063）.

摘要: 纳米催化材料的性能主要由粒子尺寸、形貌和界面决定，即活性位点的电子及几何结构.尺寸、形貌可控的纳米催化材料的合成及其反应性能的研究，即催化剂的构效关系，一直是催化领域的研究热点.氧化物负载的金属催化剂广泛应用于多相催化反应过程.基于氧化铈优异的氧化还原性能，Cu/CeO₂催化剂在CO氧化、N₂O消除、水气变换、甲醇合成等反应中表现出优异性能.其中，通过铜物种与氧化铈表面化学键合形成的金属-载体界面通常被认为是催化活性中心.铜物种和氧化铈的相互作用主要体现在氧化铈固定铜物种，而铜物种促进氧化铈的氧化还原能力，涉及Cu²⁺/Cu⁺/Cu⁰和Ce³⁺/Ce⁴⁺之间电子的传输和转移.
Cu/CeO₂催化剂活性位的原子结构与金属-载体相互作用程度密切相关.氧化铈形貌和铜负载量是决定界面电子和几何结构的重要因素.常见的纳米氧化铈形貌包括纳米粒子（多面体）、纳米棒和纳米立方体，可分别选择性暴露（111）、（110）和（100）晶面；这些晶面上原子配位环境和化学性能决定了铜-氧化铈的键合方式和界面结构.与暴露{100}晶面的纳米立方体相比，主要暴露{100}/{110}镜面的氧化铈纳米棒、暴露{111}/{100}晶面的纳米粒子与铜物种具有更强的金属-载体相互作用程度，也更有利于铜物种的分散.铜的负载量也显著影响铜物种在特定氧化铈表面的分散度和化学状态；随着铜负载量的增加，可在氧化铈表面形成层状铜、铜团簇和铜纳米粒子.通常情况下，低负载量有利于单层、双层铜物种的形成，高负载量时则出现多层铜和铜纳米粒子.催化活性位通常是由铜原子与氧化铈上的氧空穴相互作用产生，与氧化铈表面氧空穴的数量和密度密切相关，即氧化铈形貌.
本文总结了Cu/CeO₂催化剂的研究进展，讨论了氧化铈形貌和铜负载量对铜物种分散度和化学状态的影响规律，总结了铜氧化铈界面结构的多维度表征结果，比较了Cu/CeO₂催化剂在CO氧化、水气变换及甲醇合成中的活性位结构和反应机制.

关键词:

English

Electronic and geometric structure of the copper-ceria interface on Cu/CeO₂ catalysts

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
Received Date: 21 October 2019
Revised Date: 29 November 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21761132031, 21533009, 91645107, 21621063).

Abstract: The atomic structure of the active sites in Cu/CeO₂ catalystsis intimately associated with the copper-ceria interaction. Both the shape of ceria and the loading of copper affect the chemical bonding of copper species on ceria surfaces and the electronic and geometric character of the relevant interfaces. Nanostructured ceria, including particles (polyhedra), rods, and cubes, provides anchoring sites for the copper species. The atomic arrangements and chemical properties of the (111), (110) and (100) facets, preferentially exposed depending on the shape of ceria, govern the copper-ceria interactions and in turn determine their catalytic properties. Also, the metal loading significantly influences the dispersion of copper species on ceria with a specific shape, forming copper layers, clusters, and nanoparticles. Lower copper contents result in copper monolayers and/or bilayers while higher copper loadings lead to multi-layered clusters and faceted particles. The active sites are usually generated via interactions between the copper atoms in the metal species and the oxygen vacancies on ceria, which is closely linked to the number and density of surface oxygen vacancies dominated by the shape of ceria.

Key words:

1. [1] W. Liu, M. Flytzani-Stephanopoulos, J. Catal., 1995, 153, 304-316.
2. [2] K. Zhou, R. Xu, X. Sun, H. Chen, Q. Tian, D. Shen, Y. Li, Catal. Lett., 2005, 101, 169-173.
3. [3] A. P. Jia, G. S. Hu, L. Meng, Y. L. Xie, J. Q. Lu, M. F. Luo, J. Catal., 2012, 289, 199-209.
4. [4] S. Yao, K. Mudiyanselage, W. Xu, A. C. Johnston-Peck, J. C. Hanson, T. Wu, D. Stacchiola, J. A. Rodriguez, H. Zhao, K. A. Beyer, K. W. Chapman, P. J. Chupas, A. Martínez-Arias, R. Si, T. B. Bolin, W. Liu, S. D. Senanayake, ACS Catal., 2014, 4, 1650-1661.
5. [5] W. W. Wang, W. Z. Yu, P. P. Du, H. Xu, Z. Jin, R. Si, C. Ma, S. Shi, C. J. Jia, C. H. Yan, ACS Catal., 2017, 7, 1313-1329.
6. [6] M. Lykaki, E. Pachatouridou, S. A. C. Carabineiro, E. Iliopoulou, C. Andriopoulou, N. Kallithrakas-Kontos, S. Boghosian, M. Konsolakis, Appl. Catal. B, 2018, 230, 18-28.
7. [7] S. A. Mock, E. T. Zell, S. T. Hossain, R. Wang, ChemCatChem, 2018, 10, 311-319.
8. [8] H. Zhou, Z. Huang, C. Sun, F. Qin, D. Xiong, W. Shen, H. Xu, Appl. Catal. B, 2012, 125, 492-498.
9. [9] M. Zabilskiy, P. Djinović, E. Tchernychova, O. P. Tkachenko, L. M. Kustov, A. Pintar, ACS Catal., 2015, 5, 5357-5365.
10. [10] M. Zabilskiy, P. Djinović, E. Tchernychova, A. Pintar, Appl. Catal. B, 2016, 197, 146-158.
11. [11] L. Liu, Z. Yao, Y. Deng, F. Gao, B. Liu, L. Dong, ChemCatChem, 2011, 3, 978-989.
12. [12] X. Yao, F. Gao, Q. Yu, L. Qi, C. Tang, L. Dong, Y. Chen, Catal. Sci. Technol., 2013, 3, 1355-1366.
13. [13] Y. Bai, X. Bian, W. Wu, Appl. Surf. Sci., 2019, 463, 435-444.
14. [14] A. Martínez-Arias, D. Gamarra, M. Fernández-García, A. Hornés, P. Bera, Z. Koppány, Z. Schay, Catal. Today, 2009, 143, 211-217.
15. [15] D. Gamarra, A. López Cámara, M. Monte, S. B. Rasmussen, L. E. Chinchilla, A. B. Hungría, G. Munuera, N. Gyorffy, Z. Schay, V. Cortés Corberán, J. C. Conesa, A. Martínez-Arias, Appl. Catal. B, 2013, 130-131, 224-238.
16. [16] A. Martínez-Arias, D. Gamarra, A. Hungría, M. Fernández-García, G. Munuera, A. Hornés, P. Bera, J. Conesa, A. Cámara, Catalysts, 2013, 3, 378-400.
17. [17] M. Monte, D. Gamarra, A. López Cámara, S. B. Rasmussen, N. Gyorffy, Z. Schay, A. Martínez-Arias, J. C. Conesa, Catal. Today, 2014, 229, 104-113.
18. [18] X. Guo, R. Zhou, Catal. Sci. Technol., 2016, 6, 3862-3871.
19. [19] S. Y. Yao, W. Q. Xu, A. C. Johnston-Peck, F. Z. Zhao, Z. Y. Liu, S. Luo, S. D. Senanayake, A. Martínez-Arias, W. J. Liu, J. A. Rodriguez, Phys. Chem. Chem. Phys., 2014, 16, 17183-17195.
20. [20] C. Chen, Y. Zhan, J. Zhou, D. Li, Y. Zhang, X. Lin, L. Jiang, Q. Zheng, ChemPhysChem, 2018, 19, 1448-1455.
21. [21] A. Chen, X. Yu, Y. Zhou, S. Miao, Y. Li, S. Kuld, J. Sehested, J. Liu, T. Aoki, S. Hong, M. F. Camellone, S. Fabris, J. Ning, C. Jin, C. Yang, A. Nefedov, C. Wöll, Y. Wang, W. Shen, Nat. Catal., 2019, 2, 334-341.
22. [22] W. Shen, Y. Ichihashi, Y. Matsumara, Catal. Lett., 2002, 79, 125-127.
23. [23] J. Graciani, K. Mudiyanselage, F. Xu, A. E. Baber, J. Evans, S. D. Senanayake, D. J. Stacchiola, P. Liu, J. Hrbek, J. F. Sanz, J. A. Rodriguez, Science, 2014, 345, 546-550.
24. [24] L. G. A. van de Water, S. K. Wilkinson, R. A. P. Smith, M. J. Watson, J. Catal., 2018, 364, 57-68.
25. [25] Y. Liu, T. Hayakawa, K. Suzuki, S. Hamakawa, T. Tsunoda, T. Ishii, M. Kumagai, Appl. Catal. A, 2002, 223, 137-145.
26. [26] S. Sa, H. Silva, L. Brandao, J.M. Sousa, A. Mendes, Appl. Catal. B, 2010, 99, 43-57.
27. [27] S.-C. Yang, W.-N. Su, S. D. Lin, J. Ricka, B.-J. Hwang, Catal. Sci. Technol., 2012, 2, 807-812.
28. [28] S. D. Senanayake, D. Stacchiola, J. A. Rodriguez, Acc. Chem. Res., 2013, 46, 1702-1711.
29. [29] A. López Cámara, S. Chansai, C. Hardacre, A. Martínez-Arias, Int. J. Hydrogen Energy, 2014, 39, 4095-4101.
30. [30] J. A. Rodriguez, P. Liu, D. J. Stacchiola, S. D. Senanayake, M. G. White, J. G. Chen, ACS Catal., 2015, 5, 6696-6706.
31. [31] S. Chen, L. Li, W. Hu, X. Huang, Q. Li, Y. Xu, Y. Zuo, G. Li, ACS Appl. Mater. Interfaces, 2015, 7, 22999-23007.
32. [32] M. Konsolakis, Appl. Catal. B, 2016, 198, 49-66.
33. [33] L. Lin, S. Yao, Z. Liu, F. Zhang, N. Li, D. Vovchok, A. Martínez-Arias, R. Castañeda, J. Lin, S. D. Senanayake, D. Su, D. Ma, J. A. Rodriguez, J. Phys. Chem. C, 2018, 122, 12934-12943.
34. [34] A. Martínez-Arias, M. Ferńandez-García, J. Soria, J. C. Conesa, J. Catal., 1999, 182, 367-377.
35. [35] K. Mudiyanselage, S. D. Senanayake, L. Feria, S. Kundu, A. E. Baber, J. Graciani, A. B. Vidal, S. Agnoli, J. Evans, R. Chang, S. Axnanda, Z. Liu, J. F. Sanz, P. Liu, J. A. Rodriguez, D. J. Stacchiola, Angew. Chem. Int. Ed., 2013, 52, 5101-5105.
36. [36] M. M. Branda, N. C. Hernández, J. F. Sanz, F. Illas, J. Phys. Chem. C, 2010, 114, 1934-1931.
37. [37] L. Szabova, M. F. Camellone, M. Huang, V. Matolin, S. Fabris, J. Chem. Phys., 2010, 133, 234705.
38. [38] Z. Ren, N. Liu, B. Chen, J. Li, D. Mei, J. Phys. Chem. C, 2018, 122, 27402-27411.
39. [39] J. Han, H. J. Kim, S. Yoon, H. Lee, J. Mol. Catal. A, 2011, 335, 82-88.
40. [40] J. Paier, C. Penschke, J. Sauer, Chem. Rev., 2013, 113, 3949−3985.
41. [41] M. Nolan, J. E. Fearon, G. W. Watson, Solid State Ionics, 2006, 177, 3069-3074.
42. [42] P. Gawade, B. Mirkelamoglu, U. S. Ozkan, J. Phys. Chem. C, 2010, 114, 18173-18181.
43. [43] R. Si, J. Raitano, N. Yi, L. H. Zhang, S. W. Chan, M. Flytzani-Stephanopoulos, Catal. Today, 2012, 180, 68-80.
44. [44] Z. Ren, F. Peng, J. Li, X. Liang, B. Chen, Catalysts, 2017, 7, 48.
45. [45] A. Trovarelli, Catal. Rev. Sci. Eng., 1996, 38, 439-520.
46. [46] N. Ta, J. Liu, W. Shen, Chin. J. Catal., 2013, 34, 838-850.
47. [47] Y. Li, W. Shen, Chem. Soc. Rev., 2014, 43, 1543-1574.
48. [48] T. Montini, M. Melchionna, M. Monai, P. Fornasiero, Chem. Rev., 2016, 116, 5987-6041.
49. [49] A. Trovarelli, J. Llorca, ACS Catal., 2017, 7, 4716-4735.
50. [50] H. X. Mai, L. D. Sun, Y. W. Zhang, R. Si, W. Feng, H. P. Zhang, H. C. Liu, C. H. Yan, J. Phys. Chem. B, 2005, 109, 24380-24385.
51. [51] X. W. Liu, K. B. Zhou, L. Wang, B. Y. Wang, Y. D. Li, J. Am. Chem. Soc., 2009, 131, 3140-3141.
52. [52] S. Agarwal, L. Lefferts, B. L. Mojet, D. Ligthart, E. J. M. Hensen, D. R. G. Mitchell, W. J. Erasmus, B. G. Anderson, E. J. Olivier, J. H. Neethling, A. K. Datye, ChemSusChem, 2013, 6, 1898-1906.
53. [53] Z. X. Yang, T. K. Woo, M. Baudin, K. Hermansson, J. Chem. Phys., 2004, 120, 7741-7749.
54. [54] Z. L. Wu, M. J. Li, J. Howe, H. M. Meyer, S. H. Overbury, Langmuir, 2010, 26, 16595-16606.
55. [55] D. Gamarra, G. Munuera, A. B. Hungría, M. Fernández-García, J. C. Conesa, P. A. Midgley, X. Q. Wang, J. C. Hanson, J. A. Rodríguez, A. Martínez-Arias, J. Phys. Chem. C, 2007, 111, 11026-11038.
56. [56] J. Sofia, J. C. Conesa, A. Martínez-Arias, J. M. Coronado, Solid State Ionics, 1993, 63-65, 755-761.
57. [57] L. Dong, X. Yao, Y. Chen, Chin. J. Catal., 2013, 34, 851-864.
58. [58] W. W. Wang, P. P. Du, S. H. Zou, H. Y. He, R. X. Wang, Z. Jin, S. Shi, Y. Y. Huang, R. Si, Q. S. Song, C. J. Jia, C. H. Yan, ACS Catal., 2015, 5, 2088-2099.
59. [59] S. A. Mock, S. E. Sharp, T. R. Stoner, M. J. Radetic, E. T. Zell, R. Wang, J. Colloid Interface Sci., 2016, 466, 261-267.
60. [60] J. Ning, Y. Zhou, A. Chen, Y. Li, S. Miao, W. Shen, Catal. Today, 2019, https://doi.org/10.1016/j.cattod.2019.07.048.
61. [61] T. E. James, S. L. Hemmingson, C. T. Campbell, ACS Catal., 2015, 5, 5673-5678.
62. [62] T. E. James, S. L. Hemmingson, T. Ito, C. T. Campbell, J. Phys. Chem. C, 2015, 119, 17209-17217.
63. [63] Z. Yang, L. Xie, D. Ma, G. Wang, J. Phys. Chem. C, 2011, 115, 6730-6740.
64. [64] W. Liu, M. Flytzani-Stephanopoulos, J. Catal., 1995, 153, 317-332.
65. [65] W. Z. Yu, W. W. Wang, S. Q. Li, X. P. Fu, X. Wang, K. Wu, R. Si, C. Ma, C. J. Jia, C. H. Yan, J. Am. Chem. Soc., 2019, 141, 17548-17557.
66. [66] G. Avgouropoulos, T. Ioannides, Appl. Catal. A, 2003, 244, 155-167.
67. [67] M. Monte, G. Munuera, D. Costa, J. C. Conesa, A. Martínez-Arias, Phys. Chem. Chem. Phys., 2015, 17, 29995-30004.
68. [68] F. Zhao, Z. Liu, W. Xu, S. Yao, R. Si, A. C. Johnston-Peck, A. Martínez-Arias, J. C. Hanson, S. D. Senanayake, J. A. Rodriguez, Catal. Lett., 2015, 145, 808-815.
69. [69] X. Wang, J. A. Rodriguez, J. C. Hanson, D. Gamarra, A. Martínez-Arias, M. Fernández-García, J. Phys. Chem. B, 2006, 110, 428-434.
70. [70] R. M. Nix, T. Rayment, R. M. Lambert, J. R. Jennings, G. Owen, J. Catal., 1987, 106, 216-234.
71. [71] W. Shen, Y. Ichihashi, Y. Matsumura, Appl. Catal. A, 2005, 282, 221-226.
72. [72] B. Ouyang, W. Tan, B. Liu, Catal. Commun., 2017, 95, 36-39.

扫一扫看文章

计量

PDF下载量: 45
文章访问数: 1434
HTML全文浏览量: 344

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

铜-氧化铈界面:几何及电子结构

English

Electronic and geometric structure of the copper-ceria interface on Cu/CeO₂ 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

铜-氧化铈界面:几何及电子结构

English

Electronic and geometric structure of the copper-ceria interface on Cu/CeO2 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

Electronic and geometric structure of the copper-ceria interface on Cu/CeO₂ catalysts

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs