准原位XPS和HS-LEIS研究载体对PtCu合金纳米催化剂表面组成的影响

引用本文: 黄俊杰, 宋艳英, 马冬冬, 郑燕萍, 陈明树, 万惠霖. 准原位XPS和HS-LEIS研究载体对PtCu合金纳米催化剂表面组成的影响[J]. 催化学报, 2017, 38(7): 1229-1236. doi: 10.1016/S1872-2067(17)62857-2 shu

Citation: Junjie Huang, Yanying Song, Dongdong Ma, Yanping Zheng, Mingshu Chen, Huilin Wan. The effect of the support on the surface composition of PtCu alloy nanocatalysts:In situ XPS and HS-LEIS studies[J]. Chinese Journal of Catalysis, 2017, 38(7): 1229-1236. doi: 10.1016/S1872-2067(17)62857-2 shu

准原位XPS和HS-LEIS研究载体对PtCu合金纳米催化剂表面组成的影响

厦门大学化学化工学院, 固体表面物理化学国家重点实验室, 醇醚酯化工清洁生产国家工程实验室, 福建厦门 361005
基金项目:
国家重点基础研究发展计划（973计划，2013CB933102）；国家自然科学基金（21273178，21573180，91545204）；厦门卓越生物质柴油有限公司.

摘要: Pt是一类高效、稳定的催化剂，但Pt资源短缺且价格昂贵，限制了其广泛商业化应用.合金化可以使Pt的用量大为减少，且往往能显著提高其催化性能，因而广泛应用于多相催化和电催化.其中PtCu合金是一类很有前景的催化剂，Cu资源丰富、价格低廉，不仅降低了成本，而且由于合金效应提高了催化剂的活性和稳定性.由于合金的粒径、形状、组成及结构是影响其催化性能的重要因素，目前研究大多关注这些特征的可控合成.
然而，大多工业金属催化剂都是负载于氧化物上以提高催化性能，合金纳米粒子的形貌以及表面组成因与载体作用而发生改变，也就是所谓的载体效应.这体现在金属/氧化物界面处，能够促进金属粒子分散、改变其形貌甚至化学态、进而改变其催化性能，其中最具代表性的金属-载体强相互作用.因此，研究不同氧化物载体上合金催化剂的分散度、表面组成、化学态，特别是不同气氛的影响，对明确影响催化剂性能的关键控制因素非常重要.但是由于多相催化剂的复杂性，且表面灵敏的测试手段很少，目前相关报道还不多.近年发展起来的高灵敏度低能离子散射谱（HS-LEIS）是表面层灵敏的测试技术，可以测定最表面层的组成和含量.
本文采用溶剂热共还原法成功制备了均一单相、粒径分布较窄的PtCu_x合金纳米颗粒，并运用浸渍法将其负载在TiO₂载体上，以保证载体上纳米粒子组成的均一性.应用准原位X-射线光电子能谱（XPS）和高HS-LEIS对负载的PtCu合金纳米催化剂在不同条件处理后的表面组成和化学状态进行表征，发现催化剂的表面组成、分布、形貌和化学状态显著受到载体和处理条件的影响，同时得到负载和未负载的催化剂表面组成与体相组成关系的相图.结果表明，PtCu_x/TiO₂催化剂在连续氧化过程中，Cu被氧化并较好在载体表面铺展，Pt-Cu合金状态被破坏，Pt可能主要形成单一金属的纳米粒子，并在界面处形成Pt^δ+.在连续还原过程中，部分被还原的Cu，与Pt形成富Pt合金粒子.催化剂表面层主要是Cu，Pt很少，与体相组成有很大差别，说明载体对Cu的分散起到重要作用.

关键词:

English

The effect of the support on the surface composition of PtCu alloy nanocatalysts:In situ XPS and HS-LEIS studies

State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China
Received Date: 11 April 2017
Revised Date: 12 May 2017
Fund Project:
This work was supported by the National Basic Research Program of China (973 Program, 2013CB933102), the National Natural Science Foundation of China (21273178, 21573180, 91545204), and Xiamen-Zhuoyue Biomass Energy Co. Ltd.

Abstract: Supported PtCu alloys have been broadly applied in heterogeneous catalysis and electrocatalysis owing to their excellent catalytic performance and high CO tolerance. It is important to analyze the outermost surface composition of the supported alloy nanoparticles to understand the nature of the catalytically active sites. In this paper, homogeneous face-centered cubic PtCu nanoparticles with a narrow particle size distribution were successfully fabricated and dispersed on a high-surface-area TiO₂ powder support. The samples were oxidized and reduced in situ and then introduced into the ultrahigh vacuum chamber to measure the topmost surface composition by high-sensitivity low-energy ion scattering spectroscopy, and to determine the oxidation states of the elements by X-ray photoelectron spectroscopy. The surface composition and morphology, elemental distribu-tion, and oxidation states of the components were found to be significantly affected by the support and treatment conditions. The PtCu is de-alloyed upon oxidation with CuO wetting on the TiO₂ sur-face and re-alloyed upon reduction. Phase diagrams of the surface composition and the bulk com-position were plotted and compared for the supported and unsupported materials.

Key words:

1. [1] M. S. Chen, D. Kumar, C. W. Yi, D. W. Goodman, Science, 2005, 310, 291-293.
2. [2] M. S. Chen, D. W. Goodman, Chin. J. Catal., 2008, 29, 1178-1186.
3. [3] T. Komatsu, A. Tamura, J. Catal., 2008, 258, 306-314.
4. [4] D. Liang, J. Gao, J. H. Wang, P. Chen, Y. F. Wei, Z. Y. Hou, Catal. Commun., 2011, 12, 1059-1062.
5. [5] S. H. Zhou, B. Varughese, B. Eichhorn, G. Jackson, K. McIlwrath, Angew. Chem. Int. Ed., 2005, 44, 4539-4543.
6. [6] L. Y. Li, Z. Y. Xu, F. L. Liu, Y. Shao, J. H. Wang, H. Q. Wan, S. R. Zheng, J. Photochem. Photobio. A, 2010, 212, 113-121.
7. [7] J. Knudsen, A. U. Nilekar, R. T. Vang, J. Schnadt, E. L. Kunkes, J. A. Dumesic, M. Mavrikakis, F. Besenbacher, J. Am. Chem. Soc., 2007, 129, 6485-6490.
8. [8] F. Papa, A. Miyazaki, M. Scurtu, A. C. Ianculescu, I. Balint, J. Nano-part. Res., 2014, 16, 2249/1-2249/12.
9. [9] W. J. Kang, R. Li, D. H. Wei, S. L. Xu, S. Y. Wei, H. B. Li, RSC Adv., 2015, 5, 94210-94215.
10. [10] H. Xu, Q. Fu, X. H. Bao, Chin. J. Catal., 2013, 34, 2029-2035.
11. [11] H. D. Zhao, C. Z. Yu, H. J. You, S. C. Yang, Y. Guo, B. J. Ding, X. P. Song, J. Mater. Chem., 2012, 22, 4780-4789.
12. [12] Y. X. Wang, H. J. Zhou, P. C. Sun, T. H. Chen, J. Power Sources, 2014, 245, 663-670.
13. [13] Y. J. Li, F. X. Quan, E. B. Zhu, L. Chen, Y. Huang, C. F. Chen, Nano Res., 2015, 8, 3342-3352.
14. [14] G. L. Zhang, Z. Z. Yang, W. Zhang, H. W. Hu, C. Z. Wang, C. D. Huang, Y. X. Wang, Nanoscale, 2016, 8, 3075-3084.
15. [15] D. Xu, S. Bliznakov, Z. D. Liu, J. Y. Fang, N. Dimitrov, Angew. Chem. Int. Ed., 2010, 49, 1282-1285.
16. [16] X. Y. Zhao, B. B. Luo, R. Long, C. M. Wang, Y. J. Xiong, J. Mater. Chem. A, 2015, 3, 4134-4138.
17. [17] Y. Q. Jiang, Y. Y. Jia, J. W. Zhang, L. Zhang, H. Huang, Z. X. Xie, L. S. Zheng, Chem. Eur. J., 2013, 19, 3119-3124.
18. [18] Y. Y. Jia, Y. Q. Jiang, J. W. Zhang, L. Zhang, Q. L. Chen, Z. X. Xie, L. S. Zheng, J. Am. Chem. Soc., 2014, 136, 3748-3751.
19. [19] J. P. Lai, L. Zhang, W. J. Qi, J. M. Zhao, M. Xu, W. Y. Gao, G. B. Xu, ChemCatChem, 2014, 6, 2253-2257.
20. [20] M. L. Xiao, S. T. Li, X. Zhao, J. B. Zhu, M. Yin, C. P. Liu, W. Xing, ChemCatChem, 2014, 6, 2825-2831.
21. [21] W. Hong, J. Wang, E. Wang, Nano Res., 2015, 8, 2308-2316.
22. [22] B. Y. Xia, H. B. Wu, X. Wang, X. W. Lou, J. Am. Chem. Soc., 2012, 134, 13934-13937.
23. [23] E. Taylor, S. T. Chen, J. Tao, L. J. Wu, Y. M. Zhu, J. Y. Chen, ChemSus-Chem, 2013, 6, 1863-1867.
24. [24] S. F. Fu, C. Z. Zhu, Q. R. Shi, H. B. Xia, D. Du, Y. H. Lin, Nanoscale, 2016, 8, 5076-5081.
25. [25] X. H. Sun, K. Z. Jiang, N. Zhang, S. J. Guo, X. Q. Huang, ACS Nano, 2015, 7, 7634-7640.
26. [26] J. N. Wang, H. X. Dai, H. He, Chin. J. Catal., 2011, 32, 1329-1335.
27. [27] C. M. Wang, S. Bai, Y. J. Xiong, Chin. J. Catal. 2015, 36, 1476-1493.
28. [28] S. J. Tauster, Acc. Chem. Res., 1987, 20, 389-394.
29. [29] Q. Fu, T. Wagner, Surf. Sci. Rep., 2007, 62, 431-498.
30. [30] D. S. Mao, G. Z. Lu, Q. L. Chen, Chin. J. Catal., 2004, 25, 501-510.
31. [31] S. Schauermann, N. Nilius, S. Shaikhutdinov, H. J. Freund, Acc. Chem. Res., 2013, 46, 1673-1681.
32. [32] Q. Fu, F. Yang, X. H. Bao, Acc. Chem. Res., 2013, 46, 1692-1701.
33. [33] X. N. Chen, J. Y. Chen, Y. Zhao, M. S. Chen, H. L. Wan, Chin. J. Catal., 2012, 33, 1901-1905.
34. [34] L. Dong, X. J. Yao, Y. Chen, Chin. J. Catal., 2013, 34, 851-864.
35. [35] X. J. Yao, F. Gao, L. Dong, Chin. J. Catal., 2013, 34, 1975-1985.
36. [36] Y. Y. Jia, J. Y. Su, Z. B. Chen, K. Tan, Q. L. Chen, Z. M. Cao, Y. Q. Jiang, Z. X. Xie, L. S. Zheng, RSC Adv., 2015, 5, 18153-18158.
37. [37] C. D. Wagner, W. M. Riggs, L. E. Davis, J. F. Mouler, G. E. Muilenberg, Handbook of X-ray Photoelectron Spectroscopy, Perkin-elmer Cor-poration, Physical Electronics Division, Eden Prairie, Minnesota, USA, 1979, 190.
38. [38] C. C. Chusuei, D. W. Goodman, X-ray Photoelectron Spectroscopy, In Encyclopedia of Physical Science and Technology, 3rd edition. R. A. Meyers, ed. Academic Press, NY, 2002, 17, 921-938.
39. [39] E. B. Fox, A. F. Lee, K. Wilson, C. S. Song, Top. Catal., 2008, 49, 89-96.
40. [40] S. Cao, J. R. Monnier, C. T. Williams, W. J. Diao, J. R. Regalbuto, J. Catal., 2015, 326, 69-81.
41. [41] S. Alayoglu, G. A. Somorjai, Top. Catal., 2015, 59, 420-438.
42. [42] E. Taglauer, W. Heiland, Appl. Phys., 1976, 9, 261-275.
43. [43] M. Casagrande, S. Lacombe, L. Guillemot, V. A. Esaulov, Surf. Sci. Rep., 2000, 445, L36-L40.
44. [44] H. R. J. ter Veen, T. Kim, I. E. Wachs, H. H. Brongersma, Catal. To-day, 2009, 140, 197-201.
45. [45] Z. Xu, H. M. Zhang, S. S. Liu, B. S. Zhang, H. X. Zhong, D. S. Su, Int. J. Hydrogen Energy, 2012, 37, 17978-17983.
46. [46] N. Barrabés, A. Frare, K. Föttinger, A. Urakawa, J. Llorca, G. Rup-prechter, D. Tichit, Appl. Clay Sci., 2012, 69, 1-10.
47. [47] D. R. Butcher, M. E. Grass, Z. H. Zeng, F. Aksoy, H. Bluhm, W. X. Li, B. S. Mun, G. A. Somorjai, Z. Liu, J. Am. Chem. Soc., 2011, 133, 20319-20325.
48. [48] R. T. Mu, Q. Fu, H. Y. Liu, D. L. Tan, R. S. Zhai, X. H. Bao, Appl. Surf. Sci., 2009, 255, 7296-7301.

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准原位XPS和HS-LEIS研究载体对PtCu合金纳米催化剂表面组成的影响

English

The effect of the support on the surface composition of PtCu alloy nanocatalysts:In situ XPS and HS-LEIS studies

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

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中国化学会秘书处

准原位XPS和HS-LEIS研究载体对PtCu合金纳米催化剂表面组成的影响

English

The effect of the support on the surface composition of PtCu alloy nanocatalysts:In situ XPS and HS-LEIS studies

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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