EnhancedStability of Nickel Phyllosilicate Anchored Ni/SiO₂ Catalyst forLiquid-Phase Hydrogenation and Hydrodeoxygenation

Abstract

Theaggregation and leaching of nanoparticles often reduce catalytic activity andhinder the long-term application of catalysts. Here, we synthesis a hollowNi/SiO₂-AEH catalyst with small Ni nanoparticles (NPs) encapsulatedby nickel phyllosilicate (NiPS) via an ammonia evaporation-hydrothermal method.Compared with the Ni/SiO₂-AE only synthesized via ammoniaevaporation method, the Ni/SiO₂-AEH catalyst after furtherhydrothermal treatment possesses more nickel phyllosilicate (NiPS) species,which enhances the stability of Ni NPs through the strong metal-support bonding(Si-O-Ni) in NiPS. By controlling the size of Ni NPs to 3.6nm along with the presence of NiPS, we find that Ni/SiO₂-AEHdisplays superior catalytic performance for maleic anhydride (MA) hydrogenationand vanillin hydrodeoxygenation, achieving yields of 97% for succinic anhydride(SA) and 99% for 2-methoxy-4-methylphenol (MMP), respectively. Importantly, thedeactivation of Ni/SiO₂-AEH is remarkably suppressed, with only a slightdecrease in activity after five or six runs. The excellent catalytic activityand stability of phyllosilicate materials imply an extensive application inother industrial catalytic reactions.

Keywords

Nickel phyllosilicate / Hollow structure / Hydrodeoxygenation / Hydrogenation / Maleic anhydride / Vanillin

Supplementary Materials

The following supporting information can be found at: https://www.sciepublish.com/article/pii/852, Figure S1: Textural characterization of SiO₂, Ni/SiO₂-IM, Ni/SiO₂-AE and Ni/SiO₂-AEH. (a) Adsorption-desorption isotherms and (b) pore size distributions; Figure S2: Characterization of Ni/SiO₂-IM. (a) TEM image and (b) partial enlarged picture. Inset in (b) is the corresponding particle size distribution; Figure S3: H₂-TPD profiles of Ni/SiO₂-IM, Ni/SiO₂-AE and Ni/SiO₂-AEH; Figure S4: Catalytic performance of Ni/SiO₂-AEH versus reaction temperature (0.2 g MA, 10 mg Ni/SiO2-AEH, 2.5 MPa H2, 3 h); Figure S5: Time courses for the catalytic conversion of vanillin over Ni/SiO₂-AEH catalyst. Reaction conditions: 15 mg catalyst,152 mg vanillin, 10 mL dioxane, 100 °C, 2 MPa H₂; Figure S6: Morphology characterization of spent Ni/SiO₂-AE and Ni/SiO₂-AEH catalysts: (a) SEM and (c) TEM images of Ni/SiO₂-AE after four runs; (b) SEM and (d) TEM images of Ni/SiO₂-AEH after six runs; Figure S7: Characterization of fresh and spent Ni/SiO₂-AEH-800 catalyst. (a) TEM image and (b) partial enlarged picture of fresh Ni/SiO₂-AEH-800 catalyst; (c) TEM image and (d) partial enlarged picture of Ni/SiO₂-AEH-800 catalyst after three runs. Inset in (b) is the corresponding particle size distribution; Figure S8: (a) Recycling test of the Ni/SiO₂-AEH-800 catalyst. Reaction condition: 10 mg catalyst, 250 mg MA, 2 mL 1,4-dioxane, 80 °C, 2.5 MPa H₂, 3 h. (b) XRD patterns of fresh and spent Ni/SiO₂-AEH-800 catalysts; Figure S9: TEM images of Cu/SiO₂-IM (a, b). Inset in (b) is the particle size distribution; Figure S10: Physical characterization of Cu-based catalysts. (a) XRD patterns of Cu/SiO₂-IM, Cu/SiO₂-AE and Cu/SiO₂-AEH; (b) FT-IR spectra of Cu/SiO₂-IM, Cu/SiO₂-AE and Cu/SiO₂-AEH catalysts; (c) H₂-TPR profiles of CuO/SiO₂-IM, CuO/SiO₂-AE and CuO/SiO₂-AEH and (d) Cu 2p photoelectron spectrum of Cu/SiO₂-IM, Cu/SiO₂-AE and Cu/SiO₂-AEH catalysts; Figure S11: The hydrogenation performance of MA over Cu-based catalysts. (a) Catalytic evaluation of Cu/SiO₂, Cu/SiO₂-AE and Cu/SiO₂-AEH catalysts; Reaction conditions: 20 mg cat., 100 mg MA, 2 mL dioxane, 150 °C, 3 MPa H₂, 3 h. (b) Catalytic performance of Cu/SiO₂-AEH versus reaction temperature; Figure S12: Electron microscopic characterization of Cu/SiO₂-AEH after fifth run. (a) TEM image, (b) HRTEM-HAADF image and (c-e) corresponding HRTEM-STEM mapping of Cu, Si and O; Figure S13: Electron microscopic characterization of Cu/SiO₂-AE after fifth run. (a) TEM image, (b) HRTEM-HAADF image and (c-e) corresponding HRTEM-STEM mapping of Cu, Si and O; Figure S14: XRD patterns of (a) Cu₈Ni₂/SiO₂-AE, (b) Cu₈Ni₂/SiO₂-AEH, (c) Cu₅Ni₅/SiO₂-AE, (d) Cu₅Ni₅/SiO₂-AEH, (e) Cu₂Ni₈/SiO₂-AE and (f) Cu₂Ni₈/SiO₂-AEH; Figure S15: TEM images of (a) Cu₈Ni₂/SiO₂-AE; (b) Cu₈Ni₂/SiO₂-AEH; (c). Cu₅Ni₅/SiO₂-AE; (d) Cu₅Ni₅/SiO₂-AEH; (e) Cu₂Ni₈/SiO₂-AE and (f) Cu₂Ni₈/SiO₂-AEH and corresponding enlarged images (a′-f′); Figure S16: Reaction studies on MA hydrogenolysis. (a) Catalytic evaluation of (a′) Cu₈Ni₂/SiO₂-AEH, (b′) Cu₅Ni₅/SiO₂-AEH, (c′) Cu₂Ni₈/SiO₂- AEH, (d′) Ni/SiO₂- AEH, (e′) Cu₈Ni₂/SiO₂-AE, (f′) Cu₅Ni₅/SiO₂-AE, (g′) Cu₂Ni₈/SiO₂-AE and (h′) Ni/SiO₂-AE. Reaction conditions: 10 mg cat., 200 mg MA, 2 mL dioxane, 80 °C, 2 MPa H₂, 2.5 h. (b) Catalytic evaluation of (a′) Cu₈Ni₂/SiO₂-AEH, (b′) Cu₅Ni₅/SiO₂-AEH, (c′) Cu₂Ni₈/SiO₂-AEH and (d′) Ni/SiO₂-AEH. Reaction conditions: 10 mg cat., 200 mg MA, 2 ml dioxane, 200 °C, 2 MPa H₂, 2.5 h; Table S1: BET surface areas and pore structure parameters of Ni-based catalysts; Table S2: Characterization of active metal Ni in as-synthesized catalysts; Table S3: O 1s binding energy and surface Ni oxides proportion of as-synthesized Ni based catalysts; Table S4: Comparison of the catalytic performance of different reported MA hydrogenation catalysts; Table S5: Comparison of the catalytic performance of different reported vanillin HDO catalysts; Table S6: BET surface areas and pore structure parameters of Cu-based samples; Table S7: Characterization of active metal Cu in obtained catalysts.

Acknowledgments

This project is supported by the Natural Science Foundation of Hubei Province, China (No. 2024AFB205). The authors would like to highly appreciate Yong Wang, Shanjun Mao and Xuefeng Li from Zhejiang University for providing experimental facilities, valuable suggestions, as well as their critical discussions throughout this research.

Author Contributions

Experimental designing, data collection and analysis, writing manuscript, H.N.; supervision, Z.D., C.C. and S.H.; formal analysis, H.N.; investigation, H.N. and Z.D.; editing, S.H.; conceptualization, H.N. All authors have read and agreed to the published version of the manuscript.

Ethics Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data will be made available on request.

Funding

This research was funded by the Natural Science Foundation of Hubei Province, China (No. 2024AFB205).

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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