Unveiling the self-activation of exsolved LaFe0.9Ru0.1O3 perovskite during the catalytic total oxidation of propane

doi:10.1016/S1872-2067(23)64547-4

Abstract

Abstract:

The exsolution process enables to produce and control the formation of stable and catalytically active nano particles via reductive extraction of uniformly incorporated precious metal ions from a solid oxide solution. Here we consider the simple and stable perovskite LaFeO₃ (LFO) where 10% of Fe on B sites are substituted by ruthenium (LFRO). Hydrogen reduction of LFRO at 800 °C leads to the formation of socketed ruthenium particles whose low-temperature activity in the total propane oxidation reaction at 210 °C is substantially lower than that of the original LFRO. Upon increasing the reaction temperature once to 400 °C, the exsolved catalyst undergoes self-activation so that the activity at 210 °C turns out to be five times higher than that of the original LFRO. High-resolution transmission electron microscopy and nanometer-resolved element mapping, together with averaging characterization methods, including X-ray diffraction and X-ray photoelectron spectroscopy, Raman spectroscopy, and diffuse infrared spectroscopy, unveil that after reduction at 800 °C the exsolved Ru particles are slightly alloyed with Fe and encapsulated by an inert and protecting LaO_x layer. Mild oxidative treatment at 400 °C leads to the removal of the conforming LaO_x layer, while the uncovered RuFe alloy particle transforms to catalytically active oxidic Ru species, with no indication of a separate FeO_x phase. We exemplify with our case study of LaFe_0.9Ru_0.1O₃ that careful redox treatment enables to control the exsolution process and to avoid deactivation. This may be of importance for the whole class of exsolvable materials.

Key words: LaFe_0.9Ru_0.1O₃ perovskite, Exsolution, Redox treatment, RuO₂, Catalytic total oxidation of propane

Yu Wang, Jaime Gallego, Wei Wang, Phillip Timmer, Min Ding, Alexander Spriewald Luciano, Tim Weber, Lorena Glatthaar, Yanglong Guo, Bernd M. Smarsly, Herbert Over. Unveiling the self-activation of exsolved LaFe_0.9Ru_0.1O₃ perovskite during the catalytic total oxidation of propane[J]. Chinese Journal of Catalysis, 2023, 54: 250-264.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64547-4

https://www.cjcatal.com/EN/Y2023/V54/I11/250

Figures/Tables 14

Fig. 1. XRD patterns (a) and enlarged ones (b) of the LFO, LFRO, and LFRO_800R. LaB6 was used as internal standard to calibrate the 2-theta axis.

Table 1 Physicochemical properties of the studied perovskite samples. Pure LFO, LFRO, and LFRO_800R.

Sample	Ru/La+Fe+Ru (mol%) ^a	A_BET (m²·g^-1)	Micro strain^b (%)	Atomic ratio^c(mol%)			Ruⁿ ^c (mol%)
Sample	Ru/La+Fe+Ru (mol%) ^a	A_BET (m²·g^-1)	Micro strain^b (%)	Ru	La	Fe	Ru^α	Ru^β	Ru⁰
LFO	—	9	0.17	0	55	45	—	—	—
LFRO	5.1	12	0.27	8	54	38	79	21	0
LFRO_800R	5.0	11	0.21	13	55	32	0	12	88

Fig. 2. Ru 3d + C 1s XPS spectra for LFO, LFRO, and LFRO_800R. The Ru 3d spectra are decomposed into Ruα (purple), Ruβ (green), and metallic Ru (Ru0, orange).

Fig. 3. Two consecutive light-off curves of LFRO and LFRO_800R for propane combustion reaction. The light-off curve of LFO_1st and LFRO_800R_1st_cooling are also provided for comparison.

Fig. 4. Self‐activation identified with two consecutive propane combustion light-off curves (1st and 2nd) of LFRO_800R_200O, LFRO_800R_300O and LFRO_800R_400O.

Table 2 Catalytic behavior and kinetic parameters of the investigated samples during the first and second catalytic activity test.

Sample	1st					2nd
Sample	T₁₀ (°C)	T₅₀ (°C)	T₉₀ (°C)	STY ^a	E_a (kJ/mol)	T₁₀ (°C)	T₅₀ (°C)	T₉₀ (°C)	STY ^a	E_a (kJ·mol^-1)
LFRO	247	257	302	4.96	118	250	267	305	4.0	94
LFRO_800R	293	304	308	0.27	146	218	230	240	23.5	109
LFRO_800R_200O	285	297	300	0.35	125	220	234	249	20.6	106
LFRO_800R_300O	262	287	294	3.2	111	224	243	254	19.8	95
LFRO_800R_400O	219	235	248	22.3	97	219	235	250	23.0	98

Fig. 5. HRTEM micrographs of the “self-activation” process: LFRO_800R (a), LFRO_800R_200O (b), LFRO_800R_300O (c) and LFRO_800R_400O (d). The reduced sample (LFRO_800R) exhibits core-shell structured particles partially socketed into the parent matrix.

Fig. 6. HAADF-STEM image, EDS elemental mapping image and corresponding line scan results of LFRO_800R (a-d) and LFRO_800R_400O (e-h). The positions for the compositional analysis (orange frame) and line scan measurement (green frame with an arrow) are presented in (c) and (g).

Table 3 Elemental composition of the exsolved particles of LFRO_800R and LFRO_800R_400O.

Sample	La/at%	Fe/at%	Ru/at%
LFRO_800R	11	14	75
LFRO_800R_400O	3	17	80

Fig. 7. Ru 3d XPS spectra of the reduced sample LFRO_800R and after re-oxidation LFRO_800R_200O, LFRO_800R_300O, and LFRO_800R_400O.

Table 4 Physicochemical properties of the re-oxidized LFRO_800R samples.

Sample	Ru/La+Fe+Ru ^a (mol%)	A_BET (m²·g^-1)	d_{(particle size)}^b (nm)	Atomic ratio^c(mol%)			Ruⁿ (mol%)^c
Sample	Ru/La+Fe+Ru ^a (mol%)	A_BET (m²·g^-1)	d_{(particle size)}^b (nm)	Ru	La	Fe	Ru³⁺	Ru^β	Ru⁰
LFRO_800R_200O	5.1	10	11 ± 3	12	55	33	14	41	44
LFRO_800R_300O	4.9	9	10 ± 2	12	54	34	34	55	11
LFRO_800R_400O	5.0	10	12 ± 3	13	53	34	42	58	0

Fig. 8. In-situ CO-adsorption infrared spectra of LFRO, LFRO_800R, LFRO_800R_200O, LFRO_800R_300O and LFRO_800R_400O. The spectral intensities are normalized according to the gaseous CO with its pronounced rotational vibrational bands. The assignment of the spectral features of adsorbed CO are pictorially shown on the right side.

Fig. 9. Structure-activity correlation (STY vs. HRTEM) during propane combustion reaction over studied samples. The schematic model of surface reconstruction of LFRO in reducing atmosphere and oxidizing atmosphere are indicated. LFRO is the as-prepared sample after calcination at 750 °C. LFRO_800R, is the LFRO sample with exsolved particles after reduction at 800 °C for 3 h, LFRO_800R_TO, denote the samples after an oxidative (under 10% O2/Ar) restoration of LFRO_800R at different temperatures T (200 to 400 °C). The activity data are given as STY for a reaction mixture of C3H8: O2: Ar = 1: 9: 90 and a flow rate of 100 mL·min-1, 20 mg of catalyst and a reaction temperature of 210 °C. Orange dots indicate the STY values at 210°C during the first light-off experiment up to 400 °C, while the red dots refer to STY values at 210 °C during the second light-off experiment.

Table 5 Comparison of the catalytic activity of LFRO_800R_400O for propane oxidation with those reported catalysts.

Catalyst	The feed gas	WHSV (mL·h^-1·kg-1 cat)	Reaction temperature (°C)	STY (mol_CO2·h^-1·kg-1 cat)	Ref.
LFRO_800R_400O	1 vol% C₃H₈, 10 vol% O₂, 89 vol% N₂	345000	210	22.3	This Work
Ru/LFO		345000	210	5.5	This Work
Ru/ZrO₂		345000	210	20	[65]
Ru/CeO₂		345000	210	23	[65]
Ru/Al₂O₃		345000	210	17	[65]
Ru/CeO₂-1	0.8 vol% C₃H₈, 2 vol% O₂, 97.8 vol% Ar	150000	170	19	[66]
Pd/CeO₂-R	0.2 vol% C₃H₈, 2 vol% O₂, 97.8 vol% Ar	300000	300	2.1	[67]
Pd/CeO₂-C		300000	300	5.0	[67]
Pd/CeO₂-O		300000	300	43.6	[67]
Pt/ Nb₂O₅		150000	200	19.2	[68]
Pt/ZrO₂		150000	200	5.2	[68]
Pt/ZnO₂		150000	200	1.3	[68]
Pt/SnO₂		150000	200	0.2	[69]
Pt//CeO₂		120000	220	2.0	[69]
Pt//CeO₂-0.5PO_x		120000	220	5.1	[69]
Pt/TiO₂	0.8 vol% C₃H₈, 9.9 vol% O₂, 89.3 vol% N₂	180000	250	39.9	[70]
1Pt/BN	0.2 vol% C₃H₈, 2 vol% O₂, 97.8 vol% N₂	80000	220	7.0	[41]
2Pt-10V/SiO₂	0.2 vol% C₃H₈, 2 vol% O₂, 97.8 vol% N₂	80000	200	30.1	[71]

References

[1]	R. Schlögl, Angew. Chem. Int. Ed., 2015, 54, 3465-3520.
[2]	B. C. Gates, Chem. Rev., 1995, 95, 511-522.
[3]	N. Zheng, G. D. Stucky, J. Am. Chem. Soc., 2006, 128, 14278-14280.
[4]	Y. Nishihata, J. Mizuki, T. Akao, H. Tanaka, M. Uenishi, M. Kimura, T. Okamoto, N. Hamada, Nature, 2002, 418, 164-167.
[5]	K. Kousi, C. Tang, I. S. Metcalfe, D. Neagu, Small, 2021, 17, 2006479.
[6]	D. Neagu, T. S. Oh, D. N. Miller, H. Menard, S. M. Bukhari, S. R. Gamble, R. J. Gorte, J. M. Vohs, J. T. S. Irvine, Nat. Commun., 2015, 6, 8120.
[7]	T. S. Oh, E. K. Rahani, D. Neagu, J. T. S. Irvine, V. B. Shenoy, R. J. Gorte, J. M. Vohs, J. Phys. Chem. Lett., 2015, 6, 5106-5110.
[8]	M. A. Naeem, P. M. Abdala, A. Armutlulu, S. M. Kim, A. Fedorov, C. R. Muller, ACS Catal., 2020, 10, 1923-1937.
[9]	Y. Song, H. Li, M. Xu, G. Yang, W. Wang, R. Ran, W. Zhou, Z. Shao, Small, 2020, 16, 2001859.
[10]	B. Hua, N. Yan, M. Li, Y. Zhang, Y. Sun, J. Li, T. Etsell, P. Sarkar, K. Chuang, J. Luo, Energy Environ. Sci., 2016, 9, 207-215.
[11]	M. B. Katz, G. W. Graham, Y. Duan, H. Liu, C. Adamo, D. G. Schlom, X. Pan, J. Am. Chem. Soc., 2011, 133, 18090-18093.
[12]	J. Zhang, M. R. Gao, J. L. Luo, Chem. Mater., 2020, 32, 5424-5441.
[13]	J. K. Kim, S. Kim, S. Kim, H. J. Kim, K. Kim, W. Jung, J. W. Han, Adv. Mater., 2023, 35, 2203370.
[14]	Y. Yang, J. Li, Y. Sun, Chem. Eng. J., 2022, 440, 135868.
[15]	M. A. Pena, J. L. G. Fierro, Chem. Rev., 2001, 101, 1981-2018.
[16]	S. She, Y. Zhu, X. Wu, Z. Hu, A. Shelke, W. Pong, Y. Chen, Y. Song, M. Liang, C. Chen, H. Wang, W. Zhou, Z. Shao, Adv. Funct. Mater., 2022, 32, 2111091.
[17]	C. Tang, K. Kousi, D. Neagu, I. S. Metcalfe, Chem. Eur. J., 2021, 27, 6666-6675.
[18]	O. Kwon, S. Joo, S. Choi, S. Sengodan, G. Kim, J. Phys. Energy, 2020, 2, 032001.
[19]	Y. Gao, J. Wang, Y. Lyu, K. Lam, F. Ciucci, J. Mater. Chem. A, 2017, 5, 6399-6404.
[20]	B. Zhao, B. Yan, Z. Jiang, S. Yao, Z. Liu, Q. Wu, R. Ran, S. D. Senanayake, D. Weng, J. G. Chen, Chem. Commun., 2018, 54, 7354-7357.
[21]	R. Glaser, T. Zhu, H. Troiani, A. Caneiro, L. Mogni, S. Barnett, J. Mater. Chem. A, 2018, 6, 5193-5201.
[22]	H. Lv, L. Lin, X. Zhang, R. Li, Y. Song, H. Matsumoto, N. Ta, C. Zeng, Q. Fu, G. Wang, X. Bao, Nat. Commun., 2021, 12, 5665.
[23]	N. Hou, T. Yao, P. Li, X. Yao, T. Gan, L. Fan, J. Wang, X. Zhi, Y. Zhao, Y. Li, ACS Appl. Mater. Interfaces, 2019, 11, 6995-7005.
[24]	J. Wang, L. Fu, J. Yang, Z. Liu, J. Myung, K. Wu, Energy Fuels, 2022, 36, 12236-12244.
[25]	B. Koo, K. Kim, J. K. Kim, H. Kwon, J. W. Han, W. Jung, Joule, 2018, 2, 1476-1499.
[26]	Z. Teng, Z. Xiao, G. Yang, L. Guo, X. Yang, R. Ran, W. Wang, W. Zhou, Z. Shao, Mater. Today Energy, 2020, 17, 100458.
[27]	J. Liu, W. Su, J. Rick, S. Yang, C. Pan, J. Lee, J. Chen, B. Hwang, Catal. Sci. Technol., 2016, 6, 3449-3456.
[28]	X. Cao, L. Ke, K. Zhao, X. Yan, X. Wu, N. Yan, Chem. Mater., 2022, 34, 10484-10494.
[29]	W. Lee, J. W. Han, Y. Chen, Z. Cai, B. Yildiz, J. Am. Chem. Soc., 2013, 135, 7909-7925.
[30]	B. P. Barbero, J. A. Gamboa, L. E. Cadus, Appl. Catal. B, 2006, 65, 21-30.
[31]	Y. Yang, L. Zhang, H. Guo, Z. Ding, W. Wang, J. Li, L. Zhou, X. Tu, Y. Qiu, G. Chen, Y. Sun, ACS Appl. Mater. Interfaces, 2022, 14, 30704-30713.
[32]	Z. Wang, Z. Huang, J. T. Brosnhan, S. Zhang, Y. Guo, Y. Guo, L. Wang, W. Zhan, Environ. Sci. Technol., 2019, 53, 5349-5358.
[33]	H. Hao, Z. Liu, F. Zhao, W. Li, Renewable Sustain. Energy Rev., 2016, 62, 521-533.
[34]	H. Xin, L. Lin, R. Li, D. Li, T. Song, R. Wu, Q. Fu, X. Bao, J. Am. Chem. Soc., 2022, 144, 4874-4882.
[35]	H. Tang, Y. Su, B. Zhang, A. F. Lee, M. A. Isaacs, K. Wilson, L. Li, Y. Ren, J. Huang, M. Haruta, B. Qiao, X. Lin, C. Jin, D. Su, J. Wang, T. Zhang, Sci. Adv., 2017, 3, e1700231.
[36]	Y. Jiang, Z. Geng, L. Yuan, Y. Sun, Y. Cong, K. Huang, L. Wang, W. Zhang, ACS Sustainable Chem. Eng., 2018, 6, 11999-12005.
[37]	P. Timmer, T. Weber, L. Glatthaar, H. Over, Inorganics, 2023, 11, 102.
[38]	O. Khalid, A. Spriewald Luciano G,. Drazic, H. Over, ChemCatChem, 2021, 13, 3983-3994.
[39]	Y. Chin, C. Buda, M. Neurock, E. Iglesia, J. Am. Chem. Soc., 2011, 133, 15958-15978.
[40]	Y. Chin, C. Buda, M. Neurock, E. Iglesia, J. Am. Chem. Soc., 2013, 135, 15425-15442.
[41]	Y. Liu, X. Li, W. Liao, A. Jia, Y. Wang, M. Luo, J. Lu, ACS Catal., 2019, 9, 2, 1472-1481.
[42]	E. G. Rini, A. Paul, M. Nasir, R. Amin, M. K. Gupta, R. Mittal, S. Sen, J. Alloys Compd., 2020, 830, 154594.
[43]	H. Chen, C. Lim, M. Zhou, Z. He, X. Sun, X. Li, Y. Ye, T. Tan, H. Zhang, C. Yang, J. W. Han, Y. Chen, Adv. Sci., 2021, 8, 2102713.
[44]	M. C. Weber, M. Guennou, H. J. Zhao, J. Iniguez, R. Vilarinho, A. Almeida, J. A. Moreira, J. Kreisel, Phys. Rev. B, 2016, 94, 214103.
[45]	K. Sultan, M. Ikram, K. Asokan, Vacuum, 2014, 99, 251-258.
[46]	W. Y. Lee, H. J. Yun, J. W. Yoon, J. Alloys Compd., 2014, 583, 320-324.
[47]	W. Gu, J. Liu, M. Hu, F. Wang, Y. Song, ACS Appl. Mater. Interfaces, 2015, 7, 26914-26922.
[48]	D. J. Morgan, Surf. Interface Anal., 2015, 47, 1072-1079.
[49]	H. Over, Chem. Rev., 2012, 112, 3356-3426.
[50]	F. Zaera, ChemCatChem, 2012, 4, 1525-1533.
[51]	F. C. Meunier, J. Phys. Chem. C, 2021, 125, 21810-21823.
[52]	S. Y. Chin, C. T. Williams, M. D. Amiridis, J. Phys. Chem. B, 2006, 110, 871-882.
[53]	J. T. Kiss, R. D. Gonzalez, J. Phys. Chem., 1984, 88, 892-897.
[54]	A. Farkas, G. C. Mellau, H. Over, J. Phys. Chem. C, 2009, 113, 14341-14355.
[55]	T. Tan, Z. Wang, M. Qin, W. Zhong, J. Hu, C. Yang, M. Liu, Adv. Funct. Mater., 2022, 32, 2202878.
[56]	Y. Cong, Z. Geng, Q. Zhu, H. Hou, X. Wu, X. Wang, K. Huang, S. Feng, Angew. Chem. Int. Ed., 2021, 60, 23380-23387.
[57]	Y. Liang, Y. Cui, Y. Chao, N. Han, J. Sunarso, P. Liang, X. He, C. Zhang, S. Liu, Nano Res., 2022, 15, 6977-6986.
[58]	J. Wang, A. Kumar, J. L. Wardini, Z. Zhang, H. Zhou, E. J. Crumlin, J. T. Sadowski, K. B. Woller, W. J. Bowman, J. M. LeBeau, B. Yildiz, Nano Lett., 2022, 22, 5401-5408.
[59]	S. J. Tauster, S. C. Fung, R. T. K. Baker, J. Horsley, Science, 1981, 211, 1121-1125.
[60]	A. Beck, X. Huang, L. Artiglia, M. Zabilskiy, X. Wang, P. Rzepka, D. Palagin, M. G. Willinger, J. A. van Bokhoven, Nat. Commun., 2020, 11, 3220.
[61]	T. Pu, W. Zhang, M. Zhu, Angew. Chem. Int. Ed., 2023, 62, e202212278.
[62]	M. Qin, Y. Xiao, H. Yang, T. Tan, Z. Wang, X. Fan, C. Yang, Appl. Catal. B, 2021, 299, 120613.
[63]	S. Prabhudev, M. Bugnet, G. Z. Zhu, C. Bock, G. A. Botton, ChemCatChem, 2015, 7, 3655-3664.
[64]	H. Zhu, Z. Wu, D. Su, G. M. Veith, H. Lu, P. Zhang, S. Chai, S. Dai, J. Am. Chem. Soc., 2015, 137, 10156-10159.
[65]	Z. Wang, W. Wang, O. Khalid, T. Weber, A. Spriewald Luciano, W. Zhan, B. M. Smarsly, H. Over, ChemCatChem, 2022, 14, e202200149.
[66]	Z. Hu, Z. Wang, Y. Guo, L. Wang, Y. Guo, J. Zhang, W. Zhan, Environ. Sci. Technol., 2018, 52, 9531-9541.
[67]	Z. Hu, X. Liu, D. Meng, Y. Guo, Y. Guo, G. Lu, ACS Catal., 2016, 6, 2265-2279.
[68]	Z. Huang, J. Ding, X. Yang, H. Liu, P. Song, Y. Guo, Y. Guo, L. Wang, W. Zhan, Environ. Sci. Technol., 2022, 56, 17278-17287.
[69]	Z. Huang, S. Cao, J. Yu, X. Tang, Y. Guo, Y. Guo, L. Wang, S. Dai, W. Zhan, Environ. Sci. Technol., 2022, 56, 9661-9671.
[70]	M. S. Avila, C. I. Vignatti, C. R. Apesteguia, T. F. Garetto, Chem. Eng. J., 2014, 241, 52-59.
[71]	W. Liao, Y. Liu, P. Zhao, B. Cen, C. Tang, A. Jia, J. Lu, M. Luo, Appl. Catal. A, 2020, 590, 117337.

Unveiling the self-activation of exsolved LaFe_0.9Ru_0.1O₃ perovskite during the catalytic total oxidation of propane

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 14

References

Related Articles 2

Recommended Articles

Metrics

[1]	Liqing Wu, Qing Liang, Jiayi Zhao, Juan Zhu, Hongnan Jia, Wei Zhang, Ping Cai, Wei Luo. A Bi-doped RuO₂ catalyst for efficient and durable acidic water oxidation [J]. Chinese Journal of Catalysis, 2023, 55(12): 182-190.
[2]	GAO Kang, WEI Mingming, QU Zhenping, FU Qiang, BAO Xinhe. Dynamic structural changes of perovskite-supported metal catalysts during cyclic redox treatments and effect on catalytic CO oxidation [J]. Chinese Journal of Catalysis, 2013, 34(5): 889-897.