Coking-resistant CeAlO3-Socketed Nickel Nanocatalysts for dry reforming of methane

doi:10.1016/S1872-2067(26)65063-2

Abstract

Abstract:

Nickel-based catalysts are regarded as the most promising candidates for industrial dry reforming of methane (DRM), yet severe coking and metal sintering impede their commercial viability. Herein, we report a CeAlO₃-socketed Ni nanocatalyst with extensive Ni-CeAlO₃ interfaces, demonstrating coke-free stability with no deactivation over 500 h test at 700 °C for a feed of CH₄/CO₂ = 1/1 (undiluted). The socket-structured catalyst was obtained via H₂-reduction-triggered Ni exsolution and simultaneous formation of CeAlO₃ from a Ce₁Al_0.95Ni_0.05O_x composite oxide. A socketed structure featuring extensive Ni-CeAlO₃ interface was achieved upon reduction at 750 °C, which essentially modulated the catalytic activation kinetics of both CO₂ and CH₄. In-situ diffused reflectance infrared Fourier transformed spectroscopy and isotope-labeling experiments were performed to gain insight into the interfacial catalysis, revealing that CO₂ was preferentially activated at the Ni-CeAlO₃ interface to form CO and O*, and CH₄ was subsequently oxidized by O* to form H₂ and another CO through formation of CH₃O* intermediates. Such tandem reaction pathway led to stoichiometric conversion of CO₂ and CH₄ molecules thereby imparting our catalyst to high coking resistance. Our findings shed light on the rational design of a valid Ni-based DRM catalyst with substantial potential for industrial application.

Key words: Dry reforming of methane, Coking resistance, Nickel catalyst, Interface catalysis, CeAlO₃

Zhongchen Ma, Meiyi Yin, Run Xu, Rongjun Zhang, Tian Lan, Wenli Gu, Guoqing Chen, Yong Lu. Coking-resistant CeAlO₃-Socketed Nickel Nanocatalysts for dry reforming of methane[J]. Chinese Journal of Catalysis, 2026, 87: 363-375.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65063-2

https://www.cjcatal.com/EN/Y2026/V87/I8/363

Figures/Tables 5

Fig. 1. Reduction induced Ni exsolution from Ce1Al0.95Ni0.05Ox composite oxide. (a) XRD patterns and local enlarged patterns of Ce1Al0.95Ni0.05Ox and Ce1Al0.95Ni0.05Ox-T catalysts (T, reduction temperature). (b) Crystallite sizes of CeAlO3 in the Ce1Al0.95Ni0.05Ox-T catalysts, derived from XRD patterns. (c) TEM images of representative Ce1Al0.95Ni0.05Ox-T catalysts. (d) Schematic illustration of the exsolution degree of nickel nanoparticles against reduction temperatures, based on TEM images. (e) SEM images of the Ce1Al0.95Ni0.05Ox-T catalysts.

Fig. 2. Structural characterization of exsolved Ni nanoparticles. (a) XRD patterns and local enlarged patterns of fresh and reduced catalysts. (b) H2 pulse chemisorption-MS profiles of the Ce1Al0.95Ni0.05Ox-750 and Ni/CeAlO3-750 catalysts. (c) TEM image of the Ni/CeAlO3-750 catalyst. (d) AC-STEM image of the Ce1Al0.95Ni0.05Ox-750 catalyst and EDS line mapping images (inset) across the region outlined by red dashed line. (e) Ball-and-stick model of the Ni-CeAlO3 interface. (f) Schematic illustration of the particle-substrate interface for deposited and exsolved Ni nanoparticles.

Fig. 3. Catalytic performance of Ce1Al0.95Ni0.05Ox-T and Ni/CeAlO3-750 catalysts for the DRM reaction and characterization of the used catalysts. (a) CH4 and CO2 conversions during 100-h DRM reaction test. XRD patterns and local enlarged patterns (b), TG profiles (c), and O2-TPO-MS profiles (d) of the used catalysts. (e) 500-h DRM reaction stability test of the Ce1Al0.95Ni0.05Ox-750 catalyst. Reaction conditions: 700 °C, CH4/CO2 = 1/1, GHSV = 15 L gcat−1 h−1, and 1 bar.

Fig. 4. Insights into CH4 and CO2 activations at the Ni-CeAlO3 interface. CH4-TPSR-MS (a), CO2-TPSR-MS (b), and CO2/CH4-TPSR-MS (c) profiles for the Ce1Al0.95Ni0.05Ox-750 and Ni/CeAlO3-750 catalysts.

Fig. 5. Interfacial catalysis for DRM reaction. (a) 13CO2/CH4-TPSR-MS profiles for Ce1Al0.95Ni0.05Ox-750 in a flow of 13CO2/CH4/He (1/1/8) at 30 mL min−1. (b) 13CO2/CH4-constant temperature pulse reaction over Ni/CeAlO3-750 and Ce1Al0.95Ni0.05Ox-750 catalysts at 750 °C, with each pulse of 0.5 mL of 13CO2/CH4/He (1/1/8) carried by He at 20 mL min−1. In-situ DRIFT spectra collected over Ce1Al0.95Ni0.05Ox-750 catalyst under static-state CO2/CH4/He (1/1/8) atmosphere at 700 °C (c,d), and under continuous CO2/He (1/9) flow at 20 mL min−1 first for 15 min at 700 °C followed by He purging for 15 min, and then exposed to continuous flow of CH4/He (1/9) at 20 mL min−1 for another 15 min at 700 °C (e,f).

References

[1]	J. Tollefson, Nature, 2017, 551, 283-283.
[2]	C. B. Field, K. J. Mach, Science, 2017, 356, 706-707.
[3]	M. He, Y. Sun, B. Han, Angew. Chem. Int. Ed., 2022, 61, e202112835.
[4]	Y. Xiao, K. Xie, Angew. Chem. Int. Ed., 2022, 61, e202113079.
[5]	X. Guo, G. Fang, G. Li, H. Ma, H. Fan, L. Yu, C. Ma, X. Wu, D. Deng, M. Wei, D. Tan, R. Si, S. Zhang, J. Li, L. Sun, Z. Tang, X. Pan, X. Bao, Science, 2014, 344, 616-619.
[6]	Y. Song, E. Ozdemir, S. Ramesh, A. Adishev, S. Subramanian, A. Harale, M. Albuali, B. A. Fadhel, A. Jamal, D. Moon, S. H. Choi, C. T. Yavuz, Science, 2020, 367, 777-781.
[7]	L. C. Buelens, V. V. Galvita, H. Poelman, C. Detavernier, G. B. Marin, Science, 2016, 354, 449-452.
[8]	S. J. Davis, N. S. Lewis, M. Shaner, S. Aggarwal, D. Arent, I. L. Azevedo, S. M. Benson, T. Bradley, J. Brouwer, Y.-M. Chiang, C. T. M. Clack, A. Cohen, S. Doig, J. Edmonds, P. Fennell, C. B. Field, B. Hannegan, B.-M. Hodge, M. I. Hoffert, E. Ingersoll, P. Jaramillo, K. S. Lackner, K. J. Mach, M. Mastrandrea, J. Ogden, P. F. Peterson, D. L. Sanchez, D. Sperling, J. Stagner, J. E. Trancik, C.-J. Yang, K. Caldeira, Science, 2018, 360, eaas9793.
[9]	J. Yu, X. Yang, Y. Jia, Z.-Q. Wang, W. Li, Y. Jiang, S. Dai, W. Zhan, Nat. Commun., 2024, 15, 10229.
[10]	A. J. Martín, S. Mitchell, C. Mondelli, S. Jaydev, J. Pérez-Ramírez, Nat. Catal., 2022, 5, 854-866.
[11]	D. Pakhare, J. Spivey, Chem. Soc. Rev., 2014, 43, 7813-7837.
[12]	J. J. Torrez-Herrera, S. A. Korili, A. Gil, Catal. Rev., 2023, 65, 1300-1357.
[13]	M. Peng, C. Li, Z. Wang, M. Wang, Q. Zhang, B. Xu, M. Li, D. Ma, Chem. Rev., 2025, 125, 2371-2439.
[14]	C. Xie, Z. Niu, D. Kim, M. Li, P. Yang, Chem. Rev., 2020, 120, 1184-1249.
[15]	W. Gao, Z. D. Hood, M. Chi, Acc. Chem. Res., 2017, 50, 787-795.
[16]	Y. Pan, C. Zhang, Z. Liu, C. Chen, Y. Li, Matter, 2020, 2, 78-110.
[17]	I. Langmuir, J. Am. Chem. Soc., 1916, 38, 2221-2295.
[18]	G. Chen, Y. Zhao, G. Fu, P. N. Duchesne, L. Gu, Y. Zheng, X. Weng, M. Chen, P. Zhang, C.-W. Pao, J.-F. Lee, N. Zheng, Science, 2014, 344, 495-499.
[19]	I. X. Green, W. Tang, M. McEntee, M. Neurock, J. T. Yates Jr, J. Am. Chem. Soc., 2012, 134, 12717-12723.
[20]	D. Neagu, T.-S. Oh, D. N. Miller, H. Ménard, S. M. Bukhari, S. R. Gamble, R. J. Gorte, J. M. Vohs, J. T. S. Irvine, Nat. Commun., 2015, 6, 8120.
[21]	D. Neagu, V. Kyriakou, I.-L. Roiban, M. Aouine, C. Tang, A. Caravaca, K. Kousi, I. Schreur-Piet, I. S. Metcalfe, P. Vernoux, M. N. Tsampas, ACS Nano, 2019, 13, 12996-13005.
[22]	S. Kim, S. Nam, W. Jung, H. Kim, Y. Choi, H. Kim, ACS Catal., 2025, 15, 6812-6825.
[23]	J. Oh, S. Joo, C. Lim, H. J. Kim, F. Ciucci, J.-Q. Wang, J. W. Han, G. Kim, Angew. Chem. Int. Ed., 2022, 61, e202204990.
[24]	T. W. van Deelen, C. Hernández Mejía, K. P. de Jong, Nat. Catal., 2019, 2, 955-970.
[25]	S. Joo, K. Kim, O. Kwon, J. Oh, H. J. Kim, L. Zhang, J. Zhou, J.-Q. Wang, H. Y. Jeong, J. W. Han, G. Kim, Angew. Chem. Int. Ed., 2021, 60, 15912-15919.
[26]	K. Kim, B. Koo, Y.-R. Jo, S. Lee, J. K. Kim, B.-J. Kim, W. Jung, J. W. Han, Energy Environ. Sci., 2020, 13, 3404-3411.
[27]	S. A. Horlick, Y.-L. Huang, I. A. Robinson, E. D. Wachsman, Nano Energy, 2021, 87, 106193.
[28]	X. Ding, Y. Yang, Z. Li, P. Huang, X. Liu, Y. Guo, Y. Wang, ACS Catal., 2023, 13, 15535-15545.
[29]	Y. Tang, Y. Wei, Z. Wang, S. Zhang, Y. Li, L. Nguyen, Y. Li, Y. Zhou, W. Shen, F. F. Tao, P. Hu, J. Am. Chem. Soc., 2019, 141, 7283-7293.
[30]	A. Manabayeva, P. Mäki-Arvela, Z. Vajglová, M. Martinez-Klimov, O. Yevdokimova, A. Peuronen, M. Lastusaari, T. Tirri, K. Kassymkan, T. S. Baizhumanova, M. Zhumabek, R. O. Sarsenova, Z. T. Zheksenbaeva, G. N. Kaumenova, V. Russo, D. Y. Murzin, S. A. Tungatarova, Ind. Eng. Chem. Res., 2023, 62, 20588-20607.
[31]	R. Schmitt, A. Nenning, O. Kraynis, R. Korobko, A. I. Frenkel, I. Lubomirsky, S. M. Haile, J. L. M. Rupp, Chem. Soc. Rev., 2020, 49, 554-592.
[32]	T. Montini, M. Melchionna, M. Monai, P. Fornasiero, Chem. Rev., 2016, 116, 5987-6041.
[33]	T. Staudt, Y. Lykhach, N. Tsud, T. Skála, K. C. Prince, V. Matolín, J. Libuda, J. Catal., 2010, 275, 181-185.
[34]	Y. Zhang, N. Cao, K. Wang, M. Yan, X. Zhang, P. Xie, ACS Catal., 2025, 15, 8833-8845.
[35]	W. Chen, G. Zhao, Q. Xue, L. Chen, Y. Lu, Appl. Catal. B, 2013, 136-137, 260-268.
[36]	S. Helveg, C. López-Cartes, J. Sehested, P. L. Hansen, B. S. Clausen, J. R. Rostrup-Nielsen, F. Abild-Pedersen, J. K. Nørskov, Nature, 2004, 427, 426-429.
[37]	J.-W. Snoeck, G. F. Froment, M. Fowles, J. Catal., 1997, 169, 240-249.
[38]	S. Saadi, F. Abild-Pedersen, S. Helveg, J. Sehested, B. Hinnemann, C. C. Appel, J. K. Nørskov, J. Phys. Chem. C, 2010, 114, 11221-11227.
[39]	J. Lucas, N. S. Padmanabha Naveen, M. J. Janik, K. Alexopoulos, G. Noh, D. Aireddy, K. Ding, J. A. Dorman, K. M. Dooley, ACS Catal., 2024, 14, 9115-9133.
[40]	Z. Liu, P. Lustemberg, R. A. Gutiérrez, J. J. Carey, R. M. Palomino, M. Vorokhta, D. C. Grinter, P. J. Ramírez, V. Matolín, M. Nolan, M. V. Ganduglia-Pirovano, S. D. Senanayake, J. A. Rodriguez, Angew. Chem. Int. Ed., 2017, 56, 13041-13046.
[41]	J. Fan, W.-C. Li, L. He, B. He, F. Tang, Z. Liu, D. Wang, X. Liu, L. Chen, A.-H. Lu, ACS Catal., 2024, 14, 17748-17759.
[42]	H. Xiong, Y. Dong, C. Hu, Y. Chen, H. Liu, R. Long, T. Kong, Y. Xiong, J. Am. Chem. Soc., 2024, 146, 9465-9475.
[43]	H. Wang, G. Cui, H. Lu, Z. Li, L. Wang, H. Meng, J. Li, H. Yan, Y. Yang, M. Wei, Nat. Commun., 2024, 15, 3765.
[44]	Z. Liu, F. Zhang, N. Rui, X. Li, L. Lin, L. E. Betancourt, D. Su, W. Xu, J. Cen, K. Attenkofer, H. Idriss, J. A. Rodriguez, S. D. Senanayake, ACS Catal., 2019, 9, 3349-3359.
[45]	J. Li, J. Zhao, S. Wang, K.-S. Peng, B. Su, K. Liu, S.-F. Hung, M. Huang, G. Zhang, H. Zhang, X. Wang, J. Am. Chem. Soc., 2025, 147, 14705-14714.

Coking-resistant CeAlO₃-Socketed Nickel Nanocatalysts for dry reforming of methane

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 5

References

Related Articles 15

Recommended Articles

Metrics

[1]	Xiaofeng Yan, Yuxuan Meng, Yuefan Tuo, Yao Xue, Qianrui Yang, Zhengkun Luo, Yilong Yan, Meng Lin, Yufei Zhao, Xianguang Meng. Mn-Zn-O active phase promoted Ni-Co nanometal exsolved from MgO-based oxide for photothermal dry reforming of methane [J]. Chinese Journal of Catalysis, 2026, 85(6): 298-309.
[2]	Xiaoxiao Xing, Peiwen Wu, Yiru Zou, Zhaozeng Gao, Zhendong Yu, Minmeng Tang, Yanhong Chao, Wenshuai Zhu, Zhichang Liu, Chunming Xu. Biphasic interface engineering: A machine learning-guided strategy for optimizing selective oxidative desulfurization of FCC slurry oil [J]. Chinese Journal of Catalysis, 2026, 84(5): 375-389.
[3]	Wang Qiuyue, Yang Chenyu, Zhu Shenggan, Zhang Yuansen, Wang Xuan, Li Yongting, Ding Weiping, Guo Xuefeng. Interface engineering of oxygen-vacancy-rich MgO/Ni@NiAlO enables low-temperature coke-free methane dry reforming [J]. Chinese Journal of Catalysis, 2025, 75(8): 9-20.
[4]	Ya-Hui Li, Yu Chen, Jin-Yu Guo, Rui Wang, Shu-Na Zhao, Gang Li, Shuang-Quan Zang. Engineering coordination microenvironments of polypyridine Ni catalysts embedded in covalent organic frameworks for efficient CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2025, 74(7): 155-166.
[5]	Yiming Lei, Jinhua Ye, Jordi García-Antón, Huimin Liu. Recent advances in the built-in electric-field-assisted photocatalytic dry reforming of methane [J]. Chinese Journal of Catalysis, 2023, 53(10): 72-101.
[6]	Hongmei Ai, Hongyuan Yang, Qing Liu, Guoming Zhao, Jing Yang, Fangna Gu. ZrO₂-modified Ni/LaAl₁₁O₁₈ catalyst for CO methanation:Effects of catalyst structure on catalytic performance [J]. Chinese Journal of Catalysis, 2018, 39(2): 297-308.
[7]	M. Y. Lee, J. S. Nam, J. H. Seo. Synthesis of Ni-CeO₂ catalyst for the partial oxidation of methane using RF thermal plasma [J]. Chinese Journal of Catalysis, 2016, 37(5): 743-749.
[8]	Weizuo Li, Zhongkui Zhao, Yanhua Jiao, Guiru Wang. Morphology effect of zirconia support on the catalytic performance of supported Ni catalysts for dry reforming of methane [J]. Chinese Journal of Catalysis, 2016, 37(12): 2122-2133.
[9]	M. A. Goula, N. D. Charisiou, K. N. Papageridis, G. Siakavelas. Influence of the synthesis method parameters used to prepare nickel-based catalysts on the catalytic performance for the glycerol steam reforming reaction [J]. Chinese Journal of Catalysis, 2016, 37(11): 1949-1965.
[10]	Junjie Zhang, Fang Lu, Weiqiang Yu, Rui Lu, Jie Xu. Effects of alkaline additives on the formation of lactic acid in sorbitol hydrogenolysis over Ni/C catalyst [J]. Chinese Journal of Catalysis, 2016, 37(1): 177-183.
[11]	Xuejun Xu, Qiang Fu, Xinhe Bao. MoO_x-promoted Pt catalysts for the water gas shift reaction at low temperatures [J]. Chinese Journal of Catalysis, 2015, 36(5): 750-756.
[12]	Jiubiao Hu, Changlin Yu, Yadong Bi, Longfu Wei, Jianchai Chen, Xirong Chen. Preparation and characterization of Ni/CeO₂-SiO₂ catalysts and their performance in catalytic partial oxidation of methane to syngas [J]. Chinese Journal of Catalysis, 2014, 35(1): 8-20.
[13]	Xiaojuan Hu, Wenjun Yan, Weihua Ding, Jian Yu, Yan Huang. Bifunctional palladium composite membrane for hydrogen separation and catalytic CO methanation [J]. Chinese Journal of Catalysis, 2013, 34(9): 1720-1729.
[14]	ZHAO Yonghui, LI Shenggang, SUN Yuhan. Theoretical study on the dissociative adsorption of CH₄ on Pd-doped Ni surfaces [J]. Chinese Journal of Catalysis, 2013, 34(5): 911-922.
[15]	Anis H. FAKEEHA, Wasim U. KHAN, Ahmed S. AL-FATESH, Ahmed E. ABASAEED. Stabilities of zeolite-supported Ni catalysts for dry reforming of methane [J]. Chinese Journal of Catalysis, 2013, 34(4): 764-768.