Preparation of Cu/MgO catalysts for γ-valerolactone hydrogenation to 1, 4-pentanediol by MOCVD
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摘要: 以Cu (acac)2为金属有机铜前体, 层状MgO为载体, 采用金属有机化学气相沉积方法 (MOCVD) 制备了Cu/MgO催化剂, 并通过X射线衍射 (XRD)、傅里叶变换红外光谱 (FT-IR)、场发射扫描电镜 (FE-SEM)、透射电子显微镜 (TEM) 和N2物理吸附等方法对Cu/MgO催化剂结构进行表征.结果表明, 有机铜前体沉积在了MgO上, 并且在沉积后, 载体MgO的晶体结构仍然保留完整.利用生物质平台分子γ-戊内酯加氢反应来评价Cu/MgO催化剂的催化性能.研究表明, 在473 K和10 MPa反应条件下, 18% Cu/MgO催化剂表现出优异的催化活性 (90.5%) 和1, 4-戊二醇选择性 (94.4%), 且催化剂循环三次, 催化活性没有显著降低.Abstract: The laminar MgO with high specific area and the organometallic precursor Cu (acac)2 were used for the successful synthesis of Cu/MgO catalysts by metal-organic chemical vapor deposition (MOCVD) method. The copper supported on MgO catalysts were characterized by means of X-ray diffraction, Fourier-transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and N2-physisorption. Characterization results indicated that the organic precursor was successfully deposited onto MgO and the crystal structure of MgO remained intact after deposition. The hydrogenation of γ-valerolactone (γ-GVL) was employed to evaluate the catalytic performance of the Cu/MgO catalysts. It was found that the 18% Cu/MgO catalyst exhibited excellent catalytic activity (90.5%) and selectivity (94.4%) for 1, 4-PDO at 473 K and 10 MPa, and the catalytic activity of Cu/MgO did not diminish significantly after cycling for three times.
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Key words:
- Cu/MgO /
- MOCVD /
- γ-valerolactone /
- hydrogenation /
- 1, 4-PDO
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Figure 1 Reaction pathways of the conversion of γ-GVL to value-added chemicals and fuels
Figure 5 N2 adsorption-desorption isotherms of the MgO and Cu/MgO catalysts with different metal loadings after reduced at 573 K
Figure 6 XRD patterns of (a) MgO, (b) 6% Cu/MgO, (c) 9% Cu/MgO, (d) 12% Cu/MgO, and (e) 18% Cu/MgO
Figure 7 TEM images of (a), (b) 18% Cu/MgO before reaction, (c), (d) 18% Cu/MgO after reaction
Figure 8 Effect of reaction temperature (a) and H2 pressure (b) on conversion and selectivity over Cu/MgO reaction conditions: 0.4 g Cu/MgO (18% Cu), 2.5% dioxane solution of γ-GVL 20 g, 10 h (a) 8.0 MPa of H2 pressure and (b) 473 K
Figure 9 XRD patterns of (a) 18% Cu/MgO, (b) 18% Cu/MgO after reaction, (c) 18% Cu/MgO treated at 773 K in air after reaction, (d) reduced 18% Cu/MgO after the treatment of (c) sample
Figure 10 Reusability of Cu/MgO catalyst in dioxane reaction conditions: 473 K, 8.0 MPa H2 pressure, 0.4 g Cu/MgO (18% Cu), 2.5% dioxane solution of γ-GVL 20 g, 10 h
Table 1 Hydrogenation of γ-GVL with various loads copper-catalysts in dioxane
Entry Metal loading w/% Conversion x/% Selectivity s/% 1, 4-PDO 2-MTHF n-pentanol 1 0 0 0 0 0 2 6 71.4 78.8 8.3 7.4 3 9 75.0 85.7 5.9 3.0 4 12 78.5 65.0 14.1 16.0 5 18 80.0 61.5 17.7 18.3 reaction conditions: 8.0 MPa H2 pressure, 513 K, 0.4 g Cu/MgO, 2.5% dioxane solution of γ-GVL 20 g, 10 h 
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Table 2 Cu content of the catalysts after reaction by ICP
Sample Fresh Used1 Used2 Used3 Cu content w/% 18.0 13.5 10.8 9.1
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