Preparation and Catalytic Property of ZnAlCe Ternary Complex Oxide Porous Materials Based on Rape Pollen Biotemplates

doi:10.15541/jim20140544

Abstract

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

CLC Number:

O611

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.

Figures/Tables 11

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

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

Fig. 3 EDX spectrum of the sample S-4

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

Fig. 5 XPS spectra of the sample S-4

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

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

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

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

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

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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