Highly stable encapsulated Ni catalyst for phenol hydrogenation: Synthesis and mechanistic insight

doi:10.1016/S1872-2067(26)65220-5

Abstract

Abstract:

Hydrogenation of biomass-derived phenol to cyclohexanol represents a sustainable pathway for cyclohexanol production. Although supported Ni catalysts exhibit potential for fixed-bed applications, traditional systems suffer from rapid deactivation. Herein, we demonstrate a highly stable encapsulated Ni@silicalite-1 catalyst synthesized via chelator-free hydrothermal route. Compared to conventional impregnated Ni/silicalite-1 counterparts, Ni@silicalite-1 maintains exceptional operational stability beyond 100 h with sustained phenol conversion exceeding 90% and cyclohexanol selectivity over 95% under continuous-flow conditions. Characterization results including X-ray absorption spectroscopy, in-situ diffuse reflectance infrared Fourier transform spectroscopy and high angle annular dark field scanning transmission electron microscopy reveal that ultrafine Ni nanoparticles (~2.34 nm) anchored via Ni-O-Si interfacial bonds constitute the active sites, conferring dual resistance to thermal sintering and carbon deposition under reaction conditions. Mechanistic studies tracking silicalite-1 crystallization demonstrate that amorphous nickel silicate precursors gradually transform into spatially confined Ni nanoparticles driven by the organic template. This work establishes a universal paradigm for constructing sintering-resistant metal-zeolite catalysts through nanoscale engineering of metal-support interfaces.

Key words: Hydrogenation, Phenol, Cyclohexanol, Nickel-based catalyst, In-situ synthesis

Maochen Qian, Wen Liu, Xinbao Zhang, Xiangxue Zhu, Xiujie Li. Highly stable encapsulated Ni catalyst for phenol hydrogenation: Synthesis and mechanistic insight[J]. Chinese Journal of Catalysis, 2026, 91: 351-364.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65220-5

https://www.cjcatal.com/EN/Y2026/V91/I12/351

Figures/Tables 8

Fig. 1. General properties of different samples. (A) XRD patterns. (B) H2-TPR profiles. (C) Ni 2p3/2 XPS spectra. (D) UV-Raman spectra. (E) UV-vis spectra. Fourier transform of K3-weighted EXAFS spectra at R space (F) and Wavelet transforms (G,H) from experimental data.

Fig. 2. HAADF-STEM images and TEM-EDS mappings of NiO@S-1 (A), Ni@S-1-500C-R (B), NiO/S-1 (C), and Ni/S-1-500C-R (D).

Fig. 3. Catalytic performance of Ni@S-1 and Ni/S-1 in phenol hydrogenation: Phenol conversion and selectivity for cyclohexanol (A) and distribution of by-products (B) and long-term durability tests (C) of Ni@S-1. Reaction conditions: 155 °C, 2.0 MPa, WHSV: 3.0 h-1 or 1.0 h-1.

Fig. 4. Catalytic hydrogenation performance of Ni@S-1 for phenol and its derived compounds. a Reaction conditions: substrate (0.25 g), catalyst (0.05 g), isopropanol (5 mL), 150 °C, 1 MPa H2, 3 h. b Reaction conditions: substrate (0.15 g), catalyst (0.05 g), isopropanol (5 mL), 180 °C, 2 MPa H2, 5 h. c Reaction conditions: substrate (0.15 g), catalyst (0.05 g), isopropanol (5 mL), 150 °C, 2 MPa H2, 4 h. d Reaction conditions: substrate (0.15 g), catalyst (0.05 g), isopropanol (5 mL), 180 °C, 2 MPa H2, 7 h. e Reaction conditions: substrate (0.15 g), catalyst (0.05 g), isopropanol (5 mL), 220 °C, 1 MPa H2, 8 h.

Fig. 5. In-situ DRIFTS of cyclohexanol desorption during programmed temperature desorption experiments (A,B) and corresponding contour plots (C, D) within the characteristic cyclohexanol vibrational bands for Ni@S-1 and Ni/S-1. (E,F) Evolution of the cyclohexanone absorption region for Ni/S-1 before and after reaction.

Fig. 6. (A,B) HAADF-STEM observation of the spent Ni@S-1 and Ni/S-1 catalysts and their corresponding element maps. (C) UV-Raman spectra comparing the carbon deposits on the spent catalysts. (D) GC-MS spectrum of catalyst leachate after reaction. (E,F) TG and DTG curves of the spent catalysts.

Fig. 7. XRD patterns (A), H2-TPR profiles (B), IR spectra in the hydroxyl vibration region (C), and UV-Raman spectra (D) of NiO@S-1 after different crystallization time. (E) Possible nickel dispersion mechanism during in-situ zeolite synthesis, HAADF-STEM images and the corresponding element mapping and catalytic performance of Ni@S-1 after different crystallization time.

Fig. 8. TG-MS profiles (A,B) and in-situ DRIFT spectra in hydroxyl region (C,D) and C-H vibration region (E,F) of the as-synthesized S-1 and NiO@S-1.

References

[1]	Y. Yang, Z. Ren, S. Zhou, M. Wei, ACS Catal., 2021, 11, 6440-6454.
[2]	P. Yan, P. Tian, K. Li, M. A. Cohen Stuart, J. Wang, X. Yu, S. Zhou, Chem. Eng. J., 2020, 397, 125484.
[3]	Q. Meng, M. Hou, H. Liu, J. Song, B. Han, Nat. Commun., 2017, 8, 14190.
[4]	L. Chen, A. P. van Muyden, X. Cui, G. Laurenczy, P. J. Dyson, Green Chem., 2020, 22, 3069-3073.
[5]	G. Xue, L. Yin, S. Shao, G. Li, Nanotechnology, 2022, 33, 072003.
[6]	W. Cao, Z. Li, Y. Zhang, P. Fu, Energy Fuels, 2024, 38, 23246-23267.
[7]	G. Begum, R. Chilivery, K. K. Gudimella, S. Mohanapriya, M. Baithy, ChemCatChem, 2025, 17, e01116.
[8]	X. Cui, A.-E. Surkus, K. Junge, C. Topf, J. Radnik, C. Kreyenschulte, M. Beller, Nat. Commun., 2016, 7, 11326.
[9]	S.-C. Qi, L. Zhang, H. Einaga, S. Kudo, K. Norinaga, J.-I. Hayashi, J. Mater. Chem. A, 2017, 5, 3948-3965.
[10]	X. Kong, Y. Gong, S. Mao, Y. Wang, ChemNanoMat, 2018, 4, 432-450.
[11]	K. V. R. Chary, D. Naresh, V. Vishwanathan, M. Sadakane, W. Ueda, Catal. Commun., 2007, 8, 471-477.
[12]	H. Xia, H. Tan, H. Cui, F. Song, Y. Zhang, R. Zhao, Z.-N. Chen, W. Yi, Z. Li, Catal. Sci. Technol., 2021, 11, 1881-1887.
[13]	H. Zhang, A. Han, K. Okumura, L. Zhong, S. Li, S. Jaenicke, G.-K. Chuah, J. Catal., 2018, 364, 354-365.
[14]	F. Martinez-Espinar, P. Blondeau, P. Nolis, B. Chaudret, C. Claver, S. Castillón, C. Godard, J. Catal., 2017, 354, 113-127.
[15]	Z. Zhang, L. Ding, J. Gu, Y. Li, N. Xue, L. Peng, Y. Zhu, W. Ding, Catal. Sci. Technol., 2017, 7, 5953-5963.
[16]	I. E. Ertas, M. Gulcan, A. Bulut, M. Yurderi, M. Zahmakiran, Microporous Mesoporous Mater., 2016, 226, 94-103.
[17]	J. He, X.-H. Lu, Y. Shen, R. Jing, R.-F. Nie, D. Zhou, Q.-H. Xia, Mol. Catal., 2017, 440, 87-95.
[18]	J. Shen, J. Shang, X. Tian, M. Ding, Chem. Eng. J., 2024, 497, 154813.
[19]	L. Guo, X. Chen, S. Zhou, X. Yu, C. Qiao, Y. Tian, Fuel, 2024, 366, 131384.
[20]	L. Wang, L. Wang, X. Meng, F. Xiao, Adv. Mater., 2019, 31, 1901905.
[21]	M. Tao, C. Zhou, Y. Shi, X. Meng, J. Gu, W. Gao, Z. Xin, RSC Adv., 2020, 10, 20852-20861.
[22]	Y. Shi, S. Wang, Y. Li, F. Yang, H. Yu, Y. Chu, T. Li, H. Yin, Materials, 2022, 15, 3044.
[23]	Y. Tian, M. Gao, H. Xie, S. Xu, M. Ye, Z. Liu, J. Am. Chem. Soc., 2024, 146, 4958-4972.
[24]	Q. Zhu, G. Wang, J. Liu, L. Su, C. Li, ACS Appl. Mater. Interfaces, 2017, 9, 30711-30721.
[25]	S. V. Konnov, D. V. Bruter, V. S. Pavlov, I. I. Ivanova, Inorg. Chem. Front., 2024, 11, 3669-3706.
[26]	G. Liu, Y. Tian, B. Zhang, L. Wang, X. Zhang, J. Hazard. Mater., 2019, 367, 568-576.
[27]	L. Liu, M. Lopez-Haro, J. A. Perez-Omil, M. Boronat, J. J. Calvino, A. Corma, Nat. Commun., 2022, 13, 821.
[28]	H. Wu, H. Wang, Y. Lv, Y. Wu, Y. Wang, Q. Luo, Y. Hui, L. Liu, M. Zhang, K. Hou, L. Li, J. Zeng, W. Dai, L. Wang, F.-S. Xiao, Angew. Chem. Int. Ed., 2025, 64, e202420306.
[29]	R. Khare, R. Weindl, S. Kim, L. Kovarik, A. Jentys, K. Reuter, J. A. Lercher, JACS Au, 2025, 5, 890-901.
[30]	L. Tai, R. Hamidi, B. de Caprariis, M. Damizia, L. Paglia, M. Scarsella, R. Karimzadeh, P. De Filippis, Renewable Energy, 2022, 182, 647-658.
[31]	A. Rafiani, D. Aulia, G. T. M. Kadja, Case Stud. Chem. Environ. Eng., 2024, 9, 100717.
[32]	Q. Zhang, S. Gao, J. Yu, Chem. Rev., 2023, 123, 6039-6106.
[33]	S. Karimi, F. Meshkani, M. Rezaei, A. Rastegarpanah, Powder Technol., 2024, 443, 119896.
[34]	Y. Pei, X. Qiu, L. Wang, S. Kawi, Fuel, 2025, 390, 134651.
[35]	A. R. Richard, M. Fan, ACS Catal., 2017, 7, 5679-5692.
[36]	B. Lu, Y. Ju, T. Abe, K. Kawamoto, RSC Adv., 2015, 5, 56444-56454.
[37]	C.-H. Chen, H.-K. Chen, W.-H. Huang, C.-L. Chen, K. Choojun, T. Sooknoi, H.-K. Tian, Y.-C. Lin, Green Chem., 2023, 25, 7582-7597.
[38]	L. Xu, Y. Yuan, Q. Han, L. Dong, L. Chen, X. Zhang, L. Xu, Catal. Sci. Technol., 2020, 10, 7904-7913.
[39]	Y. Zhang, S. Li, Y. Fu, L. Zheng, H. Li, W. Kong, B. Pan, J. Li, J. Zhang, Y. Sun, Appl. Catal. B, 2024, 350, 123903.
[40]	F. Chandoul, H. Moussa, K. Jouini, A. Boukhachem, F. Hosni, M. S. Fayache, R. Schneider, J. Mater. Sci. Mater. Electron., 2019, 30, 348-358.
[41]	X. Kong, Y. Zhu, H. Zheng, X. Li, Y. Zhu, Y.-W. Li, ACS Catal., 2015, 5, 5914-5920.
[42]	T. Sasaki, N. Ichikuni, T. Hara, S. Shimazu, Catal. Today, 2018, 307, 29-34.
[43]	P. Yan, S. Xi, H. Peng, D. R. G. Mitchell, L. Harvey, M. Drewery, E. M. Kennedy, Z. Zhu, G. Sankar, M. Stockenhuber, J. Am. Chem. Soc., 2023, 145, 9718-9728.
[44]	K. Kirkwood, S. D. Jackson, Catalysts, 2020, 10, 584.
[45]	F. Morteo-Flores, M. Quayle, A. Salom-Català, M. Pera-Titus, A. Roldan, ChemCatChem, 2023, 15, e202300671.
[46]	X. Liu, W. An, Y. Wang, C. H. Turner, D. E. Resasco, Catal. Sci. Technol., 2018, 8, 2146-2158.
[47]	X. Wang, C. Yang, P. Wang, C. Shen, Chem. Eng. J., 2023, 470, 144195.
[48]	R. Trane-Restrup, A. D. Jensen, Appl. Catal. B, 2015, 165, 117-127.
[49]	P. Rzepka, D. Sheptyakov, C. Wang, J. A. van Bokhoven, V. Paunović, ACS Catal., 2024, 14, 5593-5604.
[50]	Q. Zhang, Z. Jiang, Y. Zhang, X. Xu, Y. Yang, Y. Qin, L. Song, Y. Mei, Y. Zu, Appl. Catal. B, 2025, 362, 124722.