Catalytic propane dehydrogenation by anatase supported Ni single-atom catalysts

doi:10.1016/S1872-2067(23)64584-X

Abstract

Abstract:

With the increasing production of propane from shale gas and the growing demand for propylene, propane dehydrogenation (PDH) has gained significant attention as a promising route for the on-purpose production of propylene. As a cheap yet efficient catalyst, Ni-based catalysts have attracted interest because of its ability to activate alkane. Single-atom catalysts (SACs) can maximize the metal atom utilization. Here, we demonstrate that anatase TiO₂ supported Ni SAC (Ni₁/A-TiO₂) exhibits not only superior intrinsic activity and propylene selectivity but also much better stability than the corresponding Ni nanoparticle (NP) catalyst (Ni_NP/A-TiO₂) in PDH reaction at 580 °C. The rate of propylene production on Ni₁/A-TiO₂ is about 1.96 mol_C3H6 g_Ni^-1 h^-1, about 65 times higher than that of Ni_NP/A-TiO₂ sample (0.03 mol_C3H6 g_Ni^-1 h^-1). In combination of high-angle annular dark-field scanning transmission electron microscopy, in-situ diffuse reflectance infrared Fourier transform spectra, in-situ X-ray photoelectron spectroscopy and X-ray absorption spectroscopy characterizations, we confirm that the Ni SAC mainly contains individual Ni atom singly dispersed on the support in positive Ni (II) valence state. In addition, as a result of strong metal-support interaction (SMSI) between Ni NP and TiO₂carrier under reduced conditions, the Ni NPs sites are encapsulated by TiO_x overlayer (~2 nm thick) thus display poor reaction performance.

Key words: Propane dehydrogenation, Single-atom catalysts, Metal atom utilization, Propylene selectivity, Stability

Qian Zhang, Xunzhu Jiang, Yang Su, Yang Zhao, Botao Qiao. Catalytic propane dehydrogenation by anatase supported Ni single-atom catalysts[J]. Chinese Journal of Catalysis, 2024, 57: 105-113.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64584-X

https://www.cjcatal.com/EN/Y2024/V57/I2/105

Figures/Tables 4

Fig. 1. (a-c) The AC-HAADF-STEM images and corresponding EDS mapping of Ni1/A-TiO2-H600 sample, Ni single atoms are highlighted in yellow circles. The AC-HAADF-STEM images (d,e) and size distribution (f) of NiNP/A-TiO2-H600 sample. (g-i) In-situ CO-DRIFT spectra at saturation coverage and followed by helium (He) purge for 30, 60, 90 and 120 s (as labeled) at low temperature (-115 °C) on A-TiO2 and Ni/A-TiO2 catalysts after 600 °C reduction.

Fig. 2. Ni K-edge FT-EXAFS spectra (a), Wavelet transform (WT)-EXAFS of k2-weighted k-space (b) and Ni K-edge XANES spectra (c) of Ni foil, NiO, Ni1/A-TiO2-H600 and NiNP/A-TiO2-H600. (d) In-situ XPS spectra of Ni 2p3/2 for Ni1/A-TiO2-H600 and NiNP/A-TiO2-H600 samples.

Fig. 3. (a) Propane conversion and propene selectivity as a function of time on stream at 580 °C. Conditions: 250 mg catalyst, C3H8/H2/N2 = 1/1/4, WHSV of propane = 2.0 h-1, total flow of 25 mL min-1. EPR spectra (b), Ti 2p (c) and O 1s (d) spectra of pure A-TiO2 and Ni/A-TiO2-H600 samples.

Fig. 4. (a,b) HRTEM images of spent NiNP/A-TiO2 after PDH reaction. (c) In-situ CO-DRIFT spectra at saturation coverage and followed by He purge at low temperature (-115 °C) on spent NiNP/A-TiO2. (d) Propane conversion and propene selectivity over NiNP/A-TiO2 sample with different reduction. Conditions: 580 °C, 250 mg catalyst, C3H8/H2/N2 = 1/1/4, WHSV of propane = 2.0 h-1, total flow of 25 mL min-1. (e) TG analysis and MS signal for the spent catalysts.

References

[1]	D. Akporiaye, S. F. Jensen, U. Olsbye, F. Rohr, E. Rytter, M. Ronnekleiv, A. I. Spjelkavik, Ind. Eng. Chem. Res., 2021, 40, 4741-4748.
[2]	M. Peng, Z. Jia, Z. Gao, M. Xu, D. Cheng, M. Wang, C. Li, L. Wang, X. Cai, Z. Jiang, H. Jiang, N. Wang, D. Xiao, H. Liu, D. Ma, ACS Catal., 2022, 12, 2244-2252.
[3]	J. J. H. B. Sattler, J. Ruiz-Martinez, E. Santillan-Jimenez, B.M. Weckhuysen, Chem. Rev., 2014, 114, 10613-10653.
[4]	T. Otroshchenko, G. Jiang, V. A. Kondratenko, U. Rodemerck, E. V. Kondratenko, Chem. Soc. Rev., 2021, 50, 473-527.
[5]	H. Tian, B. Xu, Chin. J. Catal., 2022, 43, 2173-2182.
[6]	Q. Li, Z. Sui, X. Zhou, D. Chen, Appl. Catal. A, 2011, 398, 18-26.
[7]	S. Sahebdelfar, M. T. Ravanchi, F. Tahriri Zangeneh, S. Mehrazma, S. Rajabi, Chem. Eng. Res. Des., 2012, 90, 1090-1097.
[8]	S. Shen, X. Liu, Y. Guo, Y. Wang, Acta Phys.-Chim. Sin., 2023, 39, 2209043.
[9]	J. J. H. B. Sattler, A. M. Mens, B. M. Weckhuysen, ChemCatChem, 2014, 6, 3139-3145.
[10]	Z. P. Hu, D. Yang, Z. Wang, Z.-Y. Yuan, Chin. J. Catal., 2019, 40, 1233-1254.
[11]	J. Gu, M. Jian, L. Huang, Z. Sun, A. Li, Y. Pan, J. Yang, W. Wen, W. Zhou, Y. Lin, H. J. Wang, X. Liu, L. Wang, X. Shi, X. Huang, L. Cao, S. Chen, X. Zheng, H. Pan, J. Zhu, S. Wei, W. X. Li, J. Lu, Nat. Nanotechnol., 2021, 16, 1141-1149.
[12]	F. Zeng, J. Zhang, R. Xu, R. Zhang, J. Ge, Nano Res., 2022, 15, 5004-5013.
[13]	X. Huang, Y. Ma, L. Zhi, Acta Phys.-Chim. Sin., 2022, 38, 2011050.
[14]	X. Xiong, C. Mao, Z. Yang, Q. Zhang, G. I. N. Waterhouse, L. Gu, T. Zhang, Adv. Energy Mater., 2020, 10. 2002928.
[15]	H. Shi, Y. Li, P. Lu, Z.-S. Wu, Acta Phys.-Chim. Sin., 2021, 37, 2008033.
[16]	G. Zhang, C. Yang, J. T. Miller, ChemCatChem, 2018, 10, 961-964.
[17]	X. Zhou, S. Wu, Y. Luo, L. Zhu, D. He, Energy Fuels, 2022, 37, 450-458.
[18]	T. Wang, X. Cui, K. T. Winther, F. Abild-Pedersen, T. Bligaard, J. K. Nørskov, ACS Catal., 2021, 11, 6290-6297.
[19]	Y. Xu, H. Sang, K. Wang, X. Wang, Appl. Surf. Sci., 2014, 316, 163-170.
[20]	G. Wang, Z. Meng, J. Liu, C. Li, H. Shan, ACS Catal., 2013, 3, 2992-3001.
[21]	Z. Yan, D. W. Goodman, Catal. Lett., 2012, 142, 517-520.
[22]	B. Qiao, A. Wang, X. Yang, L. F. Allard, Z. Jiang, Y. Cui, J. Liu, J. Li, T. Zhang, Nat. Chem., 2011, 3, 634-641.
[23]	X. Cui, F. Shi, Acta Phys.-Chim. Sin., 2021, 37, 2006080.
[24]	S. Ding, Y. Guo, M. J. Hülsey, B. Zhang, H. Asakura, L. Liu, Y. Han, M. Gao, J.-y. Hasegawa, B. Qiao, T. Zhang, N. Yan, Chem, 2019, 5, 3207-3219.
[25]	H. Zhang, W. Tian, X. Duan, H. Sun, Y. Huang, Y. Fang, S. Wang, Chin. J. Catal., 2022, 43, 2301-2315.
[26]	N. Kong, X. Fan, F. Liu, L. Wang, H. Lin, Y. Li, S. T. Lee, ACS Nano, 2020, 14, 5772-5779.
[27]	B. Hu, A. B. Getsoian, N. M. Schweitzer, U. Das, H. Kim, J. Niklas, O. Poluektov, L. A. Curtiss, P. C.Stair, J. T. Miller, A. S. Hock, J. Catal., 2015, 322, 24-37.
[28]	W. Wang, Y. Wu, T. Liu, Y. Zhao, Y. Qu, R. Yang, Z. Xue, Z. Wang, F. Zhou, J. Long, Z. Yang, X. Han, Y. Lin, M. Chen, L. Zheng, H. Zhou, X. Lin, F. Wu, H. Wang, Y. Yang, Y. Li, Y. Dai, Y. Wu, ACS Catal., 2022, 12, 2632-2638.
[29]	N. M. Schweitzer, B. Hu, U. Das, H. Kim, J. Greeley, L. A. Curtiss, P. C. Stair, J. T. Miller, A. S. Hock, ACS Catal., 2014, 4, 1091-1098.
[30]	K. Searles, G. Siddiqi, O. V. Safonova, C. Coperet, Chem. Sci., 2017, 8, 2661-2666.
[31]	V. J. Cybulskis, S. U. Pradhan, J. J. Lovon-Quintana, A. S. Hock, B. Hu, G. Zhang, W. N. Delgass, F. H. Ribeiro, J. T. Miller, Catal. Lett., 2017, 147, 1252-1262.
[32]	B. Hu, N. M. Schweitzer, G. Zhang, S. J. Kraft, D. J. Childers, M. P. Lanci, J. T. Miller, A. S. Hock, ACS Catal., 2015, 5, 3494-3503.
[33]	Z. P. Hu, G. Qin, J. Han, W. Zhang, N. Wang, Y. Zheng, Q. Jiang, T. Ji, Z.Y. Yuan, J. Xiao, Y. Wei, Z. Liu, J. Am. Chem. Soc., 2022, 144, 12127-12137.
[34]	L. Xie, R. Wang, Y. Chai, X. Weng, N. Guan, L. Li, J. Energy Chem., 2021, 63, 262-269.
[35]	S. Song, K. Yang, P. Zhang, Z. Wu, J. Li, H. Su, S. Dai, C. Xu, Z. Li, J. Liu, W. Song, ACS Catal., 2022, 12, 5997-6006.
[36]	R. Ma, J. Gao, J. Kou, D.P. Dean, C. J. Breckner, K. Liang, B. Zhou, J. T. Miller, G. Zou, ACS Catal., 2022, 12, 12607-12616.
[37]	M. Akri, S. Zhao, X. Li, K. Zang, A. F. Lee, M. A. Isaacs, W. Xi, Y. Gangarajula, J. Luo, Y. Ren, Y. T. Cui, L. Li, Y. Su, X. Pan, W. Wen, Y. Pan, K. Wilson, L. Li, B. Qiao, H. Ishii, Y. F. Liao, A. Wang, X. Wang, T. Zhang, Nat. Commun., 2019, 10, 5181.
[38]	M. M. Khan, S. A. Ansari, D. Pradhan, M. O. Ansari, D. H. Han, J. Lee, M. H. Cho, J. Mater. Chem. A, 2014, 2, 637-644.
[39]	L. Xiao, Z. Xie, S. Song, Z. Zhao, M. Ke, W. Song, Z. Zhao, J. Liu, Ind. Eng. Chem. Res., 2021, 60, 1200-1209.
[40]	X. Du, Y. Huang, X. Pan, B. Han, Y. Su, Q. Jiang, M. Li, H. Tang, G. Li, B. Qiao, Nat. Commun., 2020, 11, 5811.
[41]	K. Hadjiivanov, J. Lamotte, J.-C. Lavalley, Langmuir, 1997, 13, 3374-3381.
[42]	K. I. Hadjiivanov, G. N. Vayssilov, Adv. Catal., 2002, 47, 307-511.
[43]	E. Zacharaki, P. Beato, R. R. Tiruvalam, K. J. Andersson, H. Fjellvag, A. O. Sjastad, Langmuir, 2017, 33, 9836-9843.
[44]	J. B. Peri, J. Catal., 1984, 86, 84-94.
[45]	G. Busca, V. Lorenzelli, V. Sanchez Escribano, Chem. Mater., 1992, 4, 595-605.
[46]	C. Resini, T. Venkov, K. Hadjiivanov, S. Presto, P. Riani, R. Marazza, G. Ramis, G. Busca, Appl. Catal. A, 2009, 353, 137-143.
[47]	K. A. Layman, M. E. Bussell, J. Phys. Chem. B, 2004, 108, 10930-10941.
[48]	Z. Xia, H. Zhang, K. Shen, Y. Qu, Z. Jiang, Phys. B, 2018, 542, 12-19.
[49]	L. Liu, P. Zhou, X. Su, Y. Liu, Y. Sun, H. Yang, H. Fu, X. Qu, S. Liu, S. Zheng, Sensor. Actuat. B, 2022, 351, 130983.
[50]	J. F. Marco, J. R. Gancedo, M. Gracia, J. L. Gautier, E. Rios, F. J. Berry, J. Solid State Chem., 2000, 153, 74-81.
[51]	L. Xiang, Y. L. Gong, J. C. Li, Z. W. Wang, Appl. Surf. Sci., 2004, 239, 94-100.
[52]	J. Yang, X. Du, B. Qiao, Chem Catal., 2023, 3, 100424.
[53]	N. Dewangan, J. Ashok, M. Sethia, S. Das, S. Pati, H. Kus, S. Kawi, ChemCatChem, 2019, 11, 4923-4934.
[54]	C. Chen, S. Zhang, Z. Wang, Z.-Y. Yuan, J. Catal., 2020, 383, 77-87.
[55]	T. Cao, X. Dai, F. Li, W. Liu, Y. Bai, Y. Fu, W. Qi, ChemCatChem, 2021, 13, 3067-3073.
[56]	Y. Gao, L. Peng, J. Long, Y. Wu, Y. Dai, Y. Yang, Microporous Mesoporous Mater., 2021, 323, 111187.
[57]	Y. Li, Q. Zhang, S. Fu, V. A. Kondratenko, T. Otroshchenko, S. Bartling, Y. Zhang, A. Zanina, Y. Wang, G. Cui, M. Zhou, Z. Zhao, C. Xu, G. Jiang, E. V. Kondratenko, Chem. Eng. J., 2023, 460, 141778.
[58]	D. Zhao, X. Tian, D. E. Doronkin, S. Han, V. A. Kondratenko, J. D. Grunwaldt, A. Perechodjuk, T. H. Vuong, J. Rabeah, R. Eckelt, U. Rodemerck, D. Linke, G. Jiang, H. Jiao, E. V. Kondratenko, Nature, 2021, 599, 234-238.
[59]	C.-F. Li, X. Guo, Q.-H. Shang, X. Yan, C. Ren, W.-Z. Lang, Y.-J. Guo, Ind. Eng. Chem. Res., 2020, 59, 4377-4387.
[60]	Z. Xie, T. Yu, W. Song, J. Li, Z. Zhao, B. Liu, Z. Gao, D. Li, ACS Catal., 2020, 10, 14678-14693.
[61]	M. Okumura, J. M. Coronado, J. Soria, M. Haruta, J. C. Conesa, J. Catal., 2001, 203, 168-174.
[62]	S. Hashimoto, A. Tanaka, Surf. Interface Anal., 2002, 34, 262-265.
[63]	Z. Liu, J. Wang, K. Wu, A. Xu, M. Jia, APL Mater., 2023, 11, 040701.
[64]	Q. Zhang, M. Akri, Y. Yang, B. Qiao, Cell Rep. Phys. Sci., 2023, 4, 101310.
[65]	T. Saelee, S. Namuangruk, N. Kungwan, A. Junkaew, J. Phys. Chem. C, 2018, 122, 14678-14690.