Citation: Cai-Li WANG, Bo-Yong YE, Han WANG, Song-Lin WANG, Lei YANG, Zhao-Yin HOU. Preparation and application in the hydrogenation of dimethyl terephthalate of Ru@G-CS catalyst[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(11): 2091-2102. doi: 10.11862/CJIC.2023.174 shu

Preparation and application in the hydrogenation of dimethyl terephthalate of Ru@G-CS catalyst

Cai-Li WANG ¹ ,
Bo-Yong YE ¹ ,
Han WANG ² ,
Song-Lin WANG ² ,
Lei YANG ² ,
Zhao-Yin HOU ^{1, 2,,}

1.
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemistry, Zhejiang University, Hangzhou 310058, China
2.
Zhejiang Hengyi Petrochemical Research Institute Co., Ltd., Hangzhou 311200, China

Corresponding author: Zhao-Yin HOU, zyhou@zju.edu.cn
Received Date: 20 May 2023
Revised Date: 17 September 2023

Figures(14)

A series of nitrogen-doped graphene-coated Ru-based catalysts (Ru@G-CS) were prepared using glucose, melamine, and RuCl₃ as raw materials in a facile one-step pyrolysis method at 700℃ with a varied mass ratio of glucose/melamine in feed. The composition, structure, and surface morphology of these catalysts were characterized with powder X-ray diffraction, Raman spectroscopy, N₂ adsorption-desorption, X-ray photoelectron spectroscopy, scanning electron microscope, and transmission electron microscope. Characterization results showed that nitrogen in the graphene skeleton can promote the dispersion of Ru, and there was also a strong interaction between nitrogen and loaded Ru. Ru@G-CS(1:4) catalyst (with the mass ratio of glucose/melamine in feed was 1:4) possesses the highest surface area (429 m²·g^-1), biggest pore volume (0.45 cm³·g^-1) and highly dispersed Ru particles (about 1 nm) that encapsulated in 1-2 layered graphene film. At the same time, the detected w_Ru⁰/w_{Ru^{4 +}} (73.6/26.4), I_D/I_G (1.30) and I_2D/I_G (0.32) reached their maximum in Ru@G-CS(1:4). These catalysts were tested in dimethyl terephthalate (DMT) hydrogenation to 1,4-cyclohexane dimethyl dicarboxylate (DMCD) under mild conditions and compared with those traditional carriers (HZSM-5, Al₂O₃, MgO, ZnO) supported Ru catalysts. Ru@G-CS(1:4) exhibited high activity and stability at 160℃, 2.5 MPa H₂, m_DMT/m_Ru=833, the detected conversion of DMT reached 100% and the selectivity of DMCD remained higher than 98.5% within 4 h. The calculated turnover frequency of each Ru was 233.4 h^-1. More importantly, Ru@G-CS(1:4) could maintain its performance at least in 10 cycles. It was concluded that the electron-structure synergistic effect might be the main reason for the excellent activity and stability of Ru@G-CS(1:4).
- dimethyl terephthalate,
- dimethyl 1,4-cyclohexanedicarboxylate,
- hydrogenation,
- graphene,
- Ru
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