Sn1Pt single-atom alloy evolved stable PtSn/nano-Al2O3 catalyst for propane dehydrogenation

doi:10.1016/S1872-2067(23)64402-X

Abstract

Abstract:

The PtSn/Al₂O₃ is a prototypical industrial catalyst for propane dehydrogenation (PDH). However, the local structures of the active sites are still inconclusive under the operation conditions. Herein, the evolutions of the Pt-Sn active centers supported on nano-Al₂O₃ are definitely discerned at the atomic level during PDH reaction. By combining complementary in situ characterizations and theoretical calculations, we demonstrate that a highly productive Sn₁Pt single-atom alloy (47.6 mol_C3H6 g_Pt^-1 h^-1) forms after the reduction, and thereby self-assembles to the Pt₃Sn intermetallic compound during the reaction, which exhibits a rather stable performance (k_d-10~40h: 0.0026 h^-1). Intriguingly, the results of in situ diffuse reflectance infrared Fourier-transform spectroscopy further corroborate that the adjacent Pt atoms with terrace sites aggravating the coke deposition can be circumvented through this single-atom alloy mediated reconstruction. Our findings depict an unprecedented evolution process of the active sites of the PtSn/Al₂O₃, and afford an effectual nanostructure engineering pathway for stable PDH catalysts.

Key words: Propane dehydrogenation, Propylene, Pt-Sn catalyst, Reconstruction, Single-atom alloy

Yanan Xing, Leilei Kang, Jingyuan Ma, Qike Jiang, Yang Su, Shengxin Zhang, Xiaoyan Xu, Lin Li, Aiqin Wang, Zhi-Pan Liu, Sicong Ma, Xiao Yan Liu, Tao Zhang. Sn₁Pt single-atom alloy evolved stable PtSn/nano-Al₂O₃ catalyst for propane dehydrogenation[J]. Chinese Journal of Catalysis, 2023, 48: 164-174.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64402-X

https://www.cjcatal.com/EN/Y2023/V48/I5/164

Figures/Tables 6

Fig. 1. (a) Propane conversion (solid) and propylene selectivity (hollow) with time on stream for the 0.1Pt/nano-Al2O3 (green triangle), 0.1Pt1Sn/nano-Al2O3 (blue circle) and 0.5Pt1Sn/nano-Al2O3 (red square) catalysts. (b) The productivities and deactivation rate constants (kd) of the 0.1Pt1Sn/nano-Al2O3 and 0.5Pt1Sn/nano-Al2O3 at different stages in Fig. 1(a). (c) Initial productivity for representative PtSn-based PDH catalysts studied in the literatures. Numbers in brackets are corresponding to the row numbers in Table S2.

Fig. 2. AC-HAADF-STEM images of the 0.1Pt1Sn/nano-Al2O3 after the calcination (a), reduction (b) and PDH reaction (c). The insets are the corresponding size distribution of the metal nanoparticles. The EDS mappings of the 0.1Pt1Sn/nano-Al2O3 after the reduction (d-f) and PDH reaction (g-i) for 12 h.

Fig. 3. In situ XPS spectra of Sn 3d5/2 of the 0.1Pt1Sn/nano-Al2O3 (a) and the 0.5Pt1Sn/nano-Al2O3 (b) under 20 vol% H2/Ar at 600 °C for 2 h reduction. Normalized in situ XANES spectra at the Pt L3-edge (c) and Sn K-edge (e), as well as the corresponding k2-weighted Fourier transform spectra at the Pt L3-edge (d) and Sn K-edge (f) (without phase correction) of the 0.1Pt1Sn/nano-Al2O3 during PDH reaction. The Pt foil, Sn foil, SnO and SnO2 were provided as references.

Table 1 Fitting results of the EXAFS data of the 0.1Pt1Sn/nano-Al2O3 catalyst and the references.

Sample	Shell	N	R (Å)	σ² (×10^-2 Å²)	ΔE₀ (eV)	R-factor (%)
Pt foil	Pt-Pt	12.0	2.76	0.4	6.8	0.3
Sn foil	Sn-Sn	8.0	3.01	1.2	2.2	0.1
0.1Pt1Sn-reduction	Pt-O	0.4	1.94	0.3	1.0	3.1
	Pt-Pt	3.9	2.75	0.6	1.0	—
	Pt-Sn	1.4	2.66	0.7	1.0	—
	Sn-O	1.4	2.12	1.4	2.1	3.6
	Sn-Pt	1.4	2.66	0.8	-19.5	—
0.1Pt1Sn-reaction 3 h	Pt-O	0.7	2.12	0.3	15.4	0.1
	Pt-Pt	4.0	2.75	1.3	7.7	—
	Pt-Sn	1.7	2.81	1.3	7.7	—
0.1Pt1Sn-reaction17.5 h	Pt-O	0.6	2.06	0.3	9.5	0.6
	Pt-Pt	4.6	2.76	1.1	5.6	—
	Pt-Sn	1.6	2.80	1.2	5.6	—

Fig. 4. The DFT results of PDH reaction on PtSn/Al2O3. (a) The energy variation trajectory during SSW-DFT simulation for Pt6Sn3 cluster global optimization on Al2O3 (110) surface. Gibbs free energy profiles (b) and the corresponding structures (c) of the transition states during the PDH process. (d) The variation of reaction rate during microkinetics simulation for PDH reaction on Sn1Pt SAA and Pt3Sn (111) surface at 873 K and 1 bar 14 vol% C3H8 and 14 vol% H2 pressure. The asterisk indicates the adsorption state. The reaction snapshots are shown with the Pt, Sn, Al, O, C and H in cyan, light gray, pink, red, grey and white colours, respectively.

Fig. 5. In situ CO-DRIFTS of the 0.1Pt1Sn/nano-Al2O3 (a), and 0.5Pt1Sn/nano-Al2O3 (b). As a comparison, the corresponding monometallic counterparts were used as references. (c) Schematic illustration of the evolution of PtSn/nano-Al2O3 catalysts during PDH reaction.

References

[1]	M. Monai, M. Gambino, S. Wannakao, B. M. Weckhuysen, Chem. Soc. Rev., 2021, 50, 11503-11529.
[2]	M. Martino, E. Meloni, G. Festa, V. Palma, Catal., 2021, 11, 1070.
[3]	J. H. Carter, T. Bere, J. R. Pitchers, D. G. Hewes, B. D. Vandegehuchte, C. J. Kiely, S. H. Taylor, G. J. Hutchings, Green Chem., 2021, 23, 9747-9799.
[4]	Q. Sun, N. Wang, Q. Fan, L. Zeng, A. Mayoral, S. Miao, R. Yang, Z. Jiang, W. Zhou, J. Zhang, T. Zhang, J. Xu, P. Zhang, J. Cheng, D. C. Yang, R. Jia, L. Li, Q. Zhang, Y. Wang, O. Terasaki, J. Yu, Angew. Chem. Int. Ed., 2020, 59, 19450-19459.
[5]	W. S. Yang, L. W. Lin, Y. N. Fan, J. L. Zang, Catal. Lett., 1992, 12, 267-275.
[6]	L. Liu, M. Lopez-Haro, C. W. Lopes, S. Rojas-Buzo, P. Concepcion, R. Manzorro, L. Simonelli, A. Sattler, P. Serna, J. J. Calvino, A. Corma, Nat. Catal., 2020, 3, 628-638.
[7]	J. Zhang, Y. Deng, X. Cai, Y. Chen, M. Peng, Z. Jia, Z. Jiang, P. Ren, S. Yao, J. Xie, D. Xiao, X. Wen, N. Wang, H. Liu, D. Ma, ACS Catal., 2019, 9, 5998-6005.
[8]	H. Zhu, D. H. Anjum, Q. Wang, E. Abou-Hamad, L. Emsley, H. Dong, P. Laveille, L. Li, A. K. Samal, J. M. Basset, J. Catal., 2014, 320, 52-62.
[9]	X. Zhu, T. Wang, Z. Xu, Y. Yue, M. Lin, H. Zhu, J. Energy Chem., 2022, 65, 293-301.
[10]	A. W. Hauser, J. Gomes, M. Bajdich, M. Head-Gordon, A. T. Bell, Phys. Chem. Chem. Phys., 2013, 15, 20727-20734.
[11]	J. Wang, X. Chang, S. Chen, G. Sun, X. Zhou, E. Vovk, Y. Yang, W. Deng, Z. J. Zhao, R. Mu, C. Pei, J. Gong, ACS Catal., 2021, 11, 4401-4410.
[12]	A. H. Motagamwala, R. Almallahi, J. Wortman, V. O. Igenegbai, S. Linic, Science, 2021, 373, 217-222.
[13]	H. Xiong, S. Lin, J. Goetze, P. Pletcher, H. Guo, L. Kovarik, K. Artyushkova, B. M. Weckhuysen, A. K. Datye, Angew. Chem. Int. Ed., 2017, 56, 8986-8991.
[14]	L. Deng, H. Miura, T. Shishido, Z. Wang, S. Hosokawa, K. Teramura, T. Tanaka, J. Catal., 2018, 365, 277-291.
[15]	E. Merlen, P. Beccat, J. C. Bertolini, P. Delichere, N. Zanier, B. Dldillon, J. Catal., 1996, 159, 178-188.
[16]	Z. P. Hu, D. D. Yang, Z. Wang, Z. Y. Yuan, Chin. J. Catal., 2019, 40, 1233-1254.
[17]	A. Iglesias-Juez, A. M. Beale, K. Maaijen, T. C. Weng, P. Glatzel, B. M. Weckhuysen, J. Catal., 2010, 276, 268-279.
[18]	G. Sun, Z. J. Zhao, R. Mu, S. Zha, L. Li, S. Chen, K. Zang, J. Luo, Z. Li, S. C. Purdy, A. J. Kropf, J. T. Miller, L. Zeng, J. Gong, Nat. Commun., 2018, 9, 4454-4462.
[19]	S. Chen, C. Pei, G. Sun, Z. J. Zhao, J. Gong, Acc. Mater. Res., 2020, 1, 30-40.
[20]	L. Liu, M. Lopez-Haro, C. W. Lopes, C. Li, P. Concepcion, L. Simonelli, J. J. Calvino, A. Corma, Nat. Mater., 2019, 18, 866-873.
[21]	I. Lezcano-González, P. Cong, E. Campbell, M. Panchal, M. Agote-Aran, V. Celorrio, Q. He, R. Oord, B. M. Weckhuysen, A. M. Beale, ChemCatChem, 2022, 14, e202101828.
[22]	T. Wang, Z. Xu, Y. Yue, T. Wang, M. Lin, H. Zhu, Chin. J. Chem. Eng., 2022, 41, 384-391.
[23]	J. Zhu, R. Osuga, R. Ishikawa, N. Shibata, Y. Ikuhara, J. N. Kondo, M. Ogura, J. Yu, T. Wakihara, Z. Liu, T. Okubo, Angew. Chem. Int. Ed., 2020, 59, 19669-19674.
[24]	Z. Xu, R. Xu, Y. Yue, P. Yuan, X. Bao, E. Abou-Hamad, J. M. Basset, H. Zhu, J. Catal., 2019, 374, 391-400.
[25]	L. Shi, G. M. Deng, W. C. Li, S. Miao, Q. N. Wang, W. P. Zhang, A. H. Lu, Angew. Chem. Int. Ed., 2015, 54, 13994-13998.
[26]	Y. Zhu, Z. An, H. Song, X. Xiang, W. Yan, J. He, ACS Catal., 2017, 7, 6973-6978.
[27]	Z. Xu, Y. Yue, X. Bao, Z. Xie, H. Zhu, ACS Catal., 2019, 10, 818-828.
[28]	P. Yin, S. Hu, K. Qian, Z. Wei, L. L. Zhang, Y. Lin, W. Huang, H. Xiong, W. X. Li, H. W. Liang, Nat. Commun., 2021, 12, 4865-4874.
[29]	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.
[30]	H. N. Pham, J. J. Sattler, B. M. Weckhuysen, A. K. Datye, ACS Catal., 2016, 6, 2257-2264.
[31]	H. S. Yu, X. J. Wei, J. Li, S. J. Gu, S. Zhang, L. H. Wang, J. Y. Ma, L. N. Li, Q. Gao, R. Si, F. F. Sun, Y. Wang, F. Song, H. J. Xu, X. H. Yu, Y. Zou, J. Q. Wang, Z. Jiang, Y. Y. Huang, Nucl. Sci. Tech., 2015, 26, 050102.
[32]	Y. Uemura, Y. Inada, K. K. Bando, T. Sasaki, N. Kamiuchi, K. Eguchi, A. Yagishita, M. Nomura, M. Tada, Y. Iwasawa, J. Phys. Chem. C, 2011, 115, 5823-5833.
[33]	B. Ravel, M. Newville, J. Synchrotron Radiat., 2005, 12, 537-541.
[34]	S. D. Huang, C. Shang, P. L. Kang, X. J. Zhang, Z. P. Liu, WIREs Comput. Mol. Sci., 2019, 9, e1415.
[35]	Y. Li, C. M. Lousada, P. A. Korzhavyi, J. Appl. Phys., 2014, 115, 203514.
[36]	G. Kresse, J. Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[37]	P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[38]	G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[39]	J. P. Perdew, Y. Wang, Phys. Rev. B, 1992, 45, 13244-13249.
[40]	S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys., 2010, 132, 154104.
[41]	N. Kaylor, R. J. Davis, J. Catal., 2018, 367, 181-193.
[42]	C. Sun, J. Luo, M. Cao, P. Zheng, G. Li, J. Bu, Z. Cao, S. Chen, X. Xie, J. Energy Chem., 2018, 27, 311-318.
[43]	X. Fan, J. Li, Z. Zhao, Y. Wei, J. Liu, A. Duan, G. Jiang, Catal. Sci. Technol., 2015, 5, 339-350.
[44]	Q. Yu, T. Yu, H. Chen, G. Fang, X. Pan, X. Bao, J. Energy Chem., 2020, 41, 93-99.
[45]	M. Liu, W. Tang, Z. Xie, H. Yu, H. Yin, Y. Xu, S. Zhao, S. Zhou, ACS Catal., 2017, 7, 1583-1591.
[46]	W. Zhang, H. Wang, J. Jiang, Z. Sui, Y. Zhu, D. Chen, X. Zhou, ACS Catal., 2020, 10, 12932-12942.
[47]	Y. Chen, Y. Feng, L. Li, J. Liu, X. Pan, W. Liu, F. Wei, Y. Cui, B. Qiao, X. Sun, X. Li, J. Lin, S. Lin, X. Wang, T. Zhang, ACS Catal., 2020, 10, 8815-8824.
[48]	H. Rong, Z. Niu, Y. Zhao, H. Cheng, Z. Li, L. Ma, J. Li, S. Wei, Y. Li, Chem. Eur. J., 2015, 21, 12034-12041.
[49]	G. J. Siri, J. M. Ramallo-Lopez, M. L. Casella, J. L. G. Fierro, F. G. Requejo, O. A. Ferretti, Appl. Catal. A: Gen., 2005, 278, 239-249.
[50]	S. Ma, Z.-P. Liu, Nat. Commun., 2022, 13, 2716-2723.
[51]	M. J. Kale, P. Christopher, ACS Catal., 2016, 6, 5599-5609.
[52]	Y. Nakaya, F. Xing, H. Ham, K. I. Shimizu, S. Furukawa, Angew. Chem. Int. Ed., 2021, 60, 19715-19719.
[53]	S. Chen, X. Chang, G. Sun, T. Zhang, Y. Xu, Y. Wang, C. Pei, J. Gong, Chem. Soc. Rev., 2021, 50, 3315-3354.
[54]	X. Liu, A. Wang, L. Li, T. Zhang, C. Mou, J. Lee, J. Catal., 2016, 278, 288-296.
[55]	X. Liu, A. Wang, X. Yang, T. Zhang, C. Mou, D. Su, J. Li, Chem. Mater., 2009, 21, 410-418.
[56]	B. K. S. Vu, M. B. Ahn, I. Y. Suh, Y. W. Suh, D. J. Kim, W. I. Koh, H. L. Choi, Y. G. Shin, E. Woo, Appl. Catal. A, 2011, 400, 25-33.
[57]	L. W. Lin, T. Zhang, J. L. Zang, Z. S. Xu, Appl. Catal., 1990, 67, 11-23.

Sn₁Pt single-atom alloy evolved stable PtSn/nano-Al₂O₃ catalyst for propane dehydrogenation

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