基于油菜花粉模板制备ZnAlCe三元复合氧化物多孔材料及其催化性能研究

doi:10.15541/jim20140544

摘要/Abstract

摘要：

采用油菜花粉为生物模板、LDHs晶核溶液为前驱体, 通过共沉淀、辅助微波晶化方法, 经原位生长和煅烧, 简单温和地合成了ZnAlCe三元复合氧化物多孔材料。采用SEM、FT-IR、XRD、EDX、XPS和N₂吸附-脱附分析等对其进行形貌与结构的表征, 并对其催化H₂O₂-α-蒎烯环氧化反应进行了测定。结果表明, ZnAlCe三元复合氧化物能复制花粉模板表面的微纳米结构, 多级孔有序排列, 孔径分布在2~150 nm范围的介孔与大孔尺寸之间, 比表面积达112.94 m²/g, 具有良好的结晶度, 晶型规整; 当α-蒎烯/H₂O₂摩尔比为1: 1.4、催化剂用量为15.0 mg、溶剂(乙酸乙酯/H₂O体积比=4:1)为2 mL、30℃下反应4 h时, α-蒎烯转化率可达61.81%, 产物2, 3-环氧蒎烷、马鞭草烯醇和马鞭草烯酮的选择性分别为40.54%、27.36%、32.10%。

关键词: ZnAlCe三元复合氧化物, 油菜花粉, 生物模板, α-蒎烯氧化

Abstract:

Porous ZnAlCe ternary composite oxide was successfully prepared by a simple and mild technology based on microwave-crystallization and co-precipitation through in situ growth and calcination using rape pollen as biotemplate and LDHs as precursors. Morphology and structure of the as-prepared sample were characterized by SEM, FT-IR, XRD, EDX, XPS and N₂ adsorption and desorption analysis. The results show that the synthesized ZnAlCe ternary composite oxide can copy micro and nano structure of the rape pollen surface and form hierarchical holes with the pore size within 2-150 nm, between mesoporous and macroporous, and the specific surface area at 112.94 m²/g. Moreover, ZnAlCe ternary complex oxide has good crystallinity and crystal structure. The porous complex oxide ZnAlCe was then applied to catalyze α-pinene oxidation using 30wt% hydrogen peroxide as oxidant. It is showed that the α-pinene conversion rate reaches 61.81%, and the selectivity of 2, 3 epoxypinane, verbenol, verbenone is 40.54%, 27.36% and 32.10%, respectively, under the α-pinene/H₂O₂ molar ratio of 1∶1.4 using 15.0 mg ZnAlCe as catalyst being dissolved in 2 mL ethyl acetate/H₂O (volume ratio was 4∶1) at 30℃ for 4 h.

Key words: ZnAlCe ternary complex oxide, rape pollen, biotemplate, α-pinene oxidation

中图分类号:

O611

段胜聪, 孟自珍, 解晶, 陈春霞. 基于油菜花粉模板制备ZnAlCe三元复合氧化物多孔材料及其催化性能研究[J]. 无机材料学报, 2015, 30(4): 420-426.

DUAN Sheng-Cong, MENG Zi-Zhen, XIE Jing, CHEN Chun-Xia. Preparation and Catalytic Property of ZnAlCe Ternary Complex Oxide Porous Materials Based on Rape Pollen Biotemplates[J]. Journal of Inorganic Materials, 2015, 30(4): 420-426.

图/表 11

图1 样品S-1、S-2、S-3、S-4及S-4(催化反应后)的XRD图谱

Fig. 1 XRD patterns of the samples S-1、S-2、S-3、S-4 and S-4 after the catalytic reaction

图2 样品S-1、S-2、S-3、S-4及S-4(催化反应后)的FT-IR图谱

Fig. 2 FT-IR spectra of the samples S-1、S-2、S-3、S-4 and S-4 after the catalytic reaction

图3 样品S-4的EDX图谱

Fig. 3 EDX spectrum of the sample S-4

图4 不同条件下的油菜花粉及以其为模板合成样品的SEM照片

Fig. 4 SEM images of different samples (a) The original morphology of rape pollen; (b) The product after pretreatment of the sample (a) in ethanol; (c) The product after calcination of the sample (b); (d, e) ZnAlCe-LDHs was prepared by using rape pollen as a biotemplate (the sample S-3); (f-h) The product of sample S-4 after calcination of sample S-3; (i) The sample S-4 after the catalytic reaction

图5 样品S-4的XPS图谱

Fig. 5 XPS spectra of the sample S-4

表1 样品S-2、S-4的比表面积与孔径分布

Table1 Specific surface area and pore size of samples S-2 and S-4

Sample	Specific surface area/ (m²•g^-1)	Average pore size /nm	Pore volume /(cm³•g^-1)
S-2	97.6218	14.5704	0.3556
S-4	112.9440	11.7278	0.3311

图6 样品S-4的N2吸附-脱附等温线及孔径分布

Fig. 6 N2 adsorption-desorption isotherm and the pore size distribution of the sample S-4

图7 样品S-4形成过程及其机理图

Fig. 7 Schematic diagram for the formation of the sample S-4

表2 不同催化剂的催化性能比较

Table 2 Comparison of catalytic property of different catalyst

Sample	Conv. /%	Products selectivity/%
Sample	Conv. /%	2, 3-epoxypinane	Verbenol	Verbenone
S-1	31.87	37.29	29.56	33.15
S-2	39.91	39.87	28.52	31.61
S-3	41.76	41.56	25.38	33.06
S-4	48.94	46.34	24.67	28.99

图8 α-蒎烯/H2O2摩尔比对催化性能的影响

Fig. 8 The effect of α-pinene/H2O2 molar ratio on catalytic property Reaction conditions: 136.2 mg α-pinene, 10.0 mg catalyst, 2 mL solvent(V(ethyl acetate):V(water)=4:1), reaction temperature 30℃, reaction period 4 h

图9 催化剂的量对催化性能的影响

Fig. 9 The effect of catalyst amount on catalytic property Reaction conditions: 136.2 mg α-pinene, 158.2 mg 30wt% H2O2, 2 mL solvent(V(ethyl acetate):V(water)=4:1), reaction temperature 30℃, reaction period 4 h

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