Reversible transformation between terrace and step sites of Pt nanoparticles on titanium under CO and O2 environments

doi:10.1016/S1872-2067(21)63958-X

Abstract

Abstract:

Understanding the dynamic evolution of active sites of supported metal catalysts during catalysis is fundamentally important for improving its performance, which attracts tremendous research interests in the past decades. There are two main surficial structures for metal catalysts: terrace sites and step sites, which exhibit catalytic activity discrepancy during catalysis. Herein, by using in situ transmission electron microscopy and in situ Fourier transform infrared spectroscopy (FTIR), the transformation between surface terrace and step sites of Pt-TiO₂ catalysts was studied under CO and O₂ environments. We found that the {111} step sites tend to form at {111} terrace under O₂ environment, while these step sites prefer to transform into terrace under CO environment at elevated temperature. Meanwhile, quantitative ratios of terrace/step sites were obtained by in situ FTIR. It was found that this transformation between terrace sites and step sites was reversible during gas treatment cycling of CO and O₂. The selective adsorption of O₂ and CO species at different sites, which stabilized the step/terrace sites, was found to serve as the driving force for active sites transition by density functional theory calculations. Inspired by the in situ results, an enhanced catalytic activity of Pt-TiO₂ catalysts was successfully achieved through tuning surface-active sites by gas treatments.

Key words: In situ transmission electron, microscopy, Surface reconstruction, Metal catalyst, Active site, CO oxidation reaction

Yang Ou, Songda Li, Fei Wang, Xinyi Duan, Wentao Yuan, Hangsheng Yang, Ze Zhang, Yong Wang. Reversible transformation between terrace and step sites of Pt nanoparticles on titanium under CO and O₂ environments[J]. Chinese Journal of Catalysis, 2022, 43(8): 2026-2033.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63958-X

https://www.cjcatal.com/EN/Y2022/V43/I8/2026

Figures/Tables 4

Fig. 1. Structural reconstruction of Pt-TiO2 catalysts under CO and O2 environments. (a-c) show the typical TEM images of one Pt nanoparticle on TiO2 truncated octahedron under O2 at elevated temperatures. (a) 573 K; (b) 673 K; (c) 773 K. The zone axis of TiO2 was near to [111] direction. The gas pressure was 1 bar with 20% O2 in Ar. (d) shows the corresponding schematic model of (a)-(c) viewed from [111] direction of TiO2. (e-g) the typical TEM images of another Pt nanoparticle on TiO2 truncated octahedron under CO at elevated temperatures. (e) 673 K. (f) 773 K. (g) 873 K. The zone axes were [010] for TiO2 and [011] for Pt NP. The gas pressure was 1 bar with 2% CO in Ar. (h) shows the corresponding schematic model of (e)-(g) viewed from [010] direction of TiO2.

Fig. 2. DFT-calculated adsorption energies for O2 and CO molecules adsorbed on various Pt terrace and step sites. Blue, red and black balls are on behalf of platinum, oxygen and carbon atoms, respectively. O2 molecules could spontaneously dissolve at {100} and {111} step sites. The corresponding adsorption energies were listed below the models.

Fig. 3. (a) Contour plot of in situ FTIR spectra of Pt-TiO2 catalysts obtained under CO adsorption at elevated temperature. The sample was pretreated by O2 environment at 573 K for 1 h. White dotted lines point out CO molecules adsorbed on terrace sites (2098-2075 cm?1) and step sites (2075-2000 cm?1). (b) Integrated area of CO molecules adsorbed on terrace and step sites, and mole ratio of CO molecules adsorbed on terrace/step sites at elevated temperatures (283-573 K).

Fig. 4. (a) In situ FTIR spectra of CO saturation adsorption obtained at 303 K, after O2 and CO treatment at 573 K under atmospheric pressure for 1 h, respectively. (b) Quantitative ratios of terrace/step sites at 303 K after gas treatments procedure according to FTIR spectra data. (c) Measured TOF of Pt-TiO2 catalysts at 303 K for CO oxidation reactions after gas treatments.

References

[1]	Y. H. Bing, H. S. Liu, L. Zhang, D. Ghosh, J. J. Zhang, Chem. Soc. Rev., 2010, 39, 2184-2202.
[2]	X. J. Tang, D. H. Fang, L. J. Qu, D. Xu, X. P. Qin, B. W. Qin, W. Song, Z. G. Shao, B. L.Yi, Chin. J. Catal., 2019, 40, 504-514.
[3]	R. J. Farrauto, M. Deeba, S. Alerasool, Nat. Catal., 2019, 2, 603-613.
[4]	L. P. Sheng, Z. X. Ma, S. Y. Chen, J. Z. Lou, C. Y. Li, S. D. Li, Z. Zhang, Y. Wang, H. S.Yang, Chin. J. Catal., 2019, 40, 1070-1077.
[5]	J. D. Wang, H. X. Dai, H. He, Chin. J. Catal., 2011, 32, 1329-1335.
[6]	Z. X. Ma, L. P. Sheng, X. W. Wang, W. T. Yuan, S. Y. Chen, W. Xue, G. R. Han, Z. Zhang, H. S. Yang, Y. H. Lu, Y. Wang, Adv. Mater., 2019, 31, 1903719.
[7]	R. Si, M. Flytzani-Stephanopoulos, Angew. Chem. Int. Ed., 2008, 47, 2884-2887.
[8]	Q. Fu, A. Weber, M. Flytzani-Stephanopoulos, Catal. Lett., 2001, 77, 87-95.
[9]	F. Zhang, M. H. Zeng, R. D. Yappert, J. K. Sun, Y. H. Lee, A. M. Lapointe, B. Peters, M. M. Abu-Omar, S. L. Scott, Science, 2020, 370, 437-441.
[10]	P. Jing, T. Gan, H. Qi, B. Zheng, X. F. Chu, G. Y. Yu, W. F. Yan, Y. C. Zou, W. X. Zhang, G. Liu, Chin. J. Catal., 2019, 40, 214-222.
[11]	W. T. Yuan, B. E. Zhu, K. Fang, X. Y. Li, T. W. Hansen, Y. Ou, H. S. Yang, J. B. Wagner, Y. Gao, Y. Wang, Z. Zhang, Science, 2021, 371, 517-521.
[12]	W. T. Yuan, B. E. Zhu, X. Y. Li, T. W. Hansen, Y. Ou, K. Fang, H. S. Yang, Z. Zhang, J. B. Wagner, Y. Gao, Y. Wang, Science, 2020, 367, 428-430.
[13]	G. X. Li, K. Fang, Y. Ou, W. T. Yuan, H. S. Yang, Z. Zhang, Y. Wang, Prog. Nat. Sci., 2021, 31, 1-13.
[14]	J. Neugebohren, D. Borodin, H. W. Hahn, J. Altschäffel, A. Kandratsenka, D. J. Auerbach, C. T. Campbell, D. Schwarzer, D. J. Harding, A. M. Wodtke, T. N. Kitsopoulos, Nature, 2018, 558, 280-283.
[15]	F. Tao, S. Dag, L. W. Wang, Z. Liu, D. R. Butcher, H. Bluhm, M. Salmeron, G. A. Somorjai, Science, 2010, 327, 850-853.
[16]	K. Honkala, A. Hellman, I. N. Remediakis, A. Logadottir, A. Carlsson, S. Dahl, C. H. Christensen, J. K. Nørskov, Science, 2005, 307, 555-558.
[17]	B. Hammer, O. H. Nielsen, J. K. Nrskov, Catal. Lett., 1997, 46, 31-35.
[18]	S. N. Rashkeev, A. R. Lupini, S. H. Overbury, S. J. Pennycook, S. T. Pantelides, Phys. Rev. B, 2007, 76, 035438.
[19]	T. jiang, D. J. Mowbray, S. Dobrin, H. Falsig, B. Hvolbæk, T. Bligaard, J. K. Nørskov, J. Phys. Chem. C, 2009, 113, 10548-10553.
[20]	H. Falsig, B. Hvolbæk, I. S. Kristensen, T. Jiang, T. Bligaard, C. H. Christensen, J. K. Nørskov, Angew. Chem. Int. Ed., 2008, 47, 4835-4839.
[21]	O. Balmes, G. Prevot, X. Torrelles, E. Lundgren, S. Ferrer, ACS Catal., 2016, 6, 1285-1291.
[22]	M. D. Ackermann, T. M. Pedersen, B. L. M. Hendriksen, O. Robach, S. C. Bobaru, I. Popa, C. Quiros, H. Kim, B. Hammer, S. Ferrer, J. W. M. Frenken, Phys. Rev. Lett., 2005, 95, 255505.
[23]	P. L. Hansen, J. B. Wagner, S. Helveg, J. R. Rostrup-Nielsen, B. S. Clausen, H. Topsøe, Science, 2002, 295, 2053-2055.
[24]	M. Y. Duan, J. Yu, J. Meng, B. E. Zhu, Y. Wang, Y. Gao, Angew. Chem. Int. Ed., 2018, 130, 6574-6579.
[25]	Y. Jiang, H. B. Li, Z. M. Wu, W. Y. Ye, H. Zhang, Y. Wang, C. H. Sun, Z. Zhang, Angew. Chem. Int. Ed., 2016, 55, 12427-12430.
[26]	T. Altantzis, I. Lobato, A. De Backer, A. Beche, Y. Zhang, S. Basak, M. Porcu, Q. Xu, A. Sánchez-Iglesias, L. M. Liz-Marzan, G. Van Tendeloo, S. Van Aert, S. Bals, Nano Lett., 2019, 19, 477-481.
[27]	X. B. Zhang, S. B. Han, B. E. Zhu, G. H. Zhang, X. Y. Li, Y. Gao, Z. X. Wu, B. Yang, Y. F. Liu, W. Baaziz, O. Ersen, M. Gu, J. T. Miller, W. Liu, Nat. Catal., 2020, 3, 411-417.
[28]	S. F. Tan, S. W. Chee, Z. Baraissov, H. M. Jin, T. L. Tan, U. Mirsaidov, Adv. Funct. Mater., 2019, 29, 1903242.
[29]	S. W. Chee, J. M. Arce-Ramos, W. Q. Li, A. Genest, U. Mirsaidov, Nat. Commun., 2020, 11, 2133.
[30]	S. B. Vendelbo, C. F. Elkjaer, H. Falsig, I. Puspitasari, P. Dona, L. Mele, B. Morana, B. J. Nelissen, R. Van Rijn, J. F. Creemer, P. J. Kooyman, S. Helveg, Nat. Mater., 2014, 13, 884-890.
[31]	X. Huang, T. Jones, A. Fedorov, R. Farra, C. Coperet, R. Schlögl, M.-G. Willinger, Adv. Mater., 2021, 33, 2101772.
[32]	Y. Kuwauchi, H. Yoshida, T. Akita, M. Haruta, S. Takeda, Angew. Chem.-Int. Ed., 2012, 51, 7729-7733.
[33]	M. Tang, B. E. Zhu, J. Meng, X. Zhang, W. T. Yuan, Z. Zhang, Y. Gao, Y. Wang, Mater. Today Nano, 2018, 1, 41-46.
[34]	A. Chmielewski, J. Meng, B. E. Zhu, Y. Gao, H. Guesmi, H. Prunier, D. Alloyeau, G. Wang, C. Louis, L. Delannoy, P. Afanasiev, C. Ricolleau, J. Nelayah, ACS Nano, 2019, 13, 2024-2033.
[35]	M. Tang, W. Yuan, Y. Ou, G. X. Li, R. Y. You, S. D. Li, H. S. Yang, Z. Zhang, Y. Wang, ACS Catal., 2020, 10, 14419-14450.
[36]	H. Yoshida, Y. Kuwauchi, J. R. Jinschek, K. Sun, S. Tanaka, M. Kohyama, S. Shimada, M. Haruta, S. Takeda, Science, 2012, 335, 317-319.
[37]	S. F. Liu, H. F. Qi, J. H. Zhou, W. Xu, Y. M. Niu, B. S. Zhang, Y. Zhao, W. Liu, Z. M. Ao, Z. C. Kuang, L. Li, M. Wang, J. H. Wang, ACS Catal., 2021, 11, 6081-6090.
[38]	T. Uchiyama, H. Yoshida, Y. Kuwauchi, S. Ichikawa, S. Shimada, M. Haruta, S. Takeda, Angew. Chem. Int. Ed., 2011, 50, 10157-10160.
[39]	H. Yoshida, K. Matsuura, Y. Kuwauchi, H. Kohno, S. Shimada, M. Haruta, S. Takeda, Appl. Phys. Express, 2011, 4, 065001.
[40]	M. J. Kale, P. Christopher, ACS Catal., 2016, 6, 5599-5609.
[41]	A. N. Liu, X. Liu, L. C. Liu, Y. Pu, K. Guo, W. Tan, S. Gao, Y. D. Luo, S. Yu, R. Si, B. Shan, F. Gao, L. Dong, ACS Catal., 2019, 7759-7768.
[42]	L. Zhou, A. Kandratsenka, C. T. Campbell, A. M. Wodtke, H. Guo, Angew. Chem. Int. Ed., 2019, 58, 6916-6920.
[43]	A. D. Allian, K. Takanabe, K. L. Fujdala, X. H. Hao, T. J. Truex, J. A. Cai, C. Buda, M. Neurock, E. Iglesia, J. Am. Chem. Soc., 2011, 133, 4498-4517.
[44]	J. M. Li, D. S. Xu. Chem. Commun., 2010, 46, 2301-2303.
[45]	M.-H. Yang, P.-C. Chen, M.-C. Tsai, T.-T. Chen, I. C. Chang, H.-T. Chiu, C.-Y. Lee, CrystEngComm, 2013, 15, 2966-2971.
[46]	J. Yoshinobu, N. Tsukahara, F. Yasui, K. Mukai, Y. Yamashita. Phys. Rev. Lett., 2003, 90, 248301.
[47]	H. V. Thang, G. Pacchioni, L. Derita, P. Christopher, J. Catal., 2018, 367, 104-114.
[48]	G. Kresse, J. Furthmüller, Comput. Mater. Sci., 1996, 6, 15-50.
[49]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[50]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[51]	H. J. Monkhorst, J. D. Pack, Phys. Rev. B, 1976, 13, 5188-5192
[52]	Y. Jiang, Z. F. Zhang, W. T. Yuan, X. Zhang, Y. Wang, Z. Zhang, Nano Res., 2018, 11, 42-67.
[53]	J. Jones, H. F. Xiong, A. T. Delariva, E. J. Peterson, H. Pham, S. R. Challa, G. S. Qi, S. Oh, M. H. Wiebenga, X. I. Pereira Hernandez, Y. Wang, A. K. Datye, Science, 2016, 353, 150-154.
[54]	L. Nie, D. H. Mei, H. F. Xiong, B. Peng, Z. B. Ren, X. I. P. Hernandez, A. Delariva, M. Wang, M. H. Engelhard, L. Kovarik, A. K. Datye, Y. Wang, Science, 2017, 358, 1419-1423.
[55]	Y. Zhou, D. E. Doronkin, M. L. Chen, S. Q. Wei, J.-D. Grunwaldt, ACS Catal., 2016, 6, 7799-7809.
[56]	Y. He, J.-C. Liu, L. L. Luo, Y.-G. Wang, J. F. Zhu, Y. G. Du, J. Li, S. X. Mao, C. M. Wang, Proc. Natl. Acad. Sci. U. S. A., 2018, 115, 7700-7705.
[57]	P. Liu, T. T. Wu, J. Madsen, J. Schiøtz, J. Wagner, T. Hansen, Microsc. Microanal., 2020, 26, 2406-2407.
[58]	Y. Y. Li, M. Kottwitz, J. L. Vincent, M. J. Enright, Z. Y. Liu, L. H. Zhang, J. H. Huang, S. D. Senanayake, W. D. Yang, P. A. Crozier, R. G. Nuzzo, A. I. Frenkel, Nat. Commun., 2021, 12, 914.
[59]	T. Avanesian, S. Dai, M. J. Kale, G. W. Graham, X. Q. Pan, P. Christopher, J. Am. Chem. Soc., 2017, 139, 4551-4558.
[60]	L. Derita, S. Dai, K. Lopez-Zepeda, N. Pham, G. W. Graham, X. Q. Pan, P. Christopher, J. Am. Chem. Soc., 2017, 139, 14150-14165.
[61]	C. T. Campbell, G. Ertl, H. Kuipers, J. Segner, J. Chem. Phys., 1980, 73, 5862-5873.
[62]	F. C. Meunier, L. Cardenas, H. Kaper, B. Šmíd, M. Vorokhta, R. Grosjean, D. Aubert, K. Dembélé, T. Lunkenbein, Angew. Chem. Int. Ed., 2021, 60, 3799-3805.
[63]	M. A. Van Spronsen, J. W. M. Frenken, I. M. N. Groot, Chem. Soc. Rev., 2017, 46, 4347-4374.

Reversible transformation between terrace and step sites of Pt nanoparticles on titanium under CO and O₂ environments

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