核壳材料Co3O4@SiO2催化环己基过氧化氢分解

doi:10.15541/jim20210192

摘要/Abstract

摘要：

环己基过氧化氢(CHHP)分解是环己烷无催化氧化工艺制备环己醇和环己酮的重要反应步骤。本研究以Co₃O₄纳米颗粒为内核, 十六烷基三甲基溴化铵(CTAB)为模板剂, 正硅酸四乙酯(TEOS)为硅源, 采用模板法制备了核壳结构材料Co₃O₄@SiO₂。考察了SiO₂壳层制备条件: 乙醇和水的比例、CTAB的浓度和TEOS的用量对核壳材料结构的影响。使用不同技术手段表征材料的结构特征, 在CHHP分解反应中进行材料的催化性能评价和稳定性考察。结果表明, 壳层薄且孔隙率高的材料催化性能更好, 并且核壳结构可以减少钴元素的流失, 催化材料在回收使用过程中出现了不同程度的壳层破碎现象。

关键词: 核壳结构, Co₃O₄@SiO₂, 环己基过氧化氢, 分解

Abstract:

Decomposition of cyclohexyl hydroperoxide (CHHP) is an important step in the preparation of cyclohexanol and cyclohexanone by non-catalytic oxidation of cyclohexane. Using Co₃O₄ nanoparticles as the core, cetyltrimethylammol/lonium bromide (CTAB) as the template and tetraethyl orthosilicate (TEOS) as the silicon source, the core-shell structure material Co₃O₄@SiO₂ was synthesized by template method. The effects of the preparation conditions for SiO₂ shells on the structure of core-shell material were investigated, such as the ratio of ethanol to water, the concentration of CTAB and the amount of TEOS. Textural properties of the materials were characterized by different techniques. Meanwhile, the catalytic performance and stability of the materials were evaluated on the decomposition reaction of CHHP. All results showed that the materials with thin shell and high porosity exhibited a preferable catalytic performance, and the conversion of CHHP was 81.68% and the selectivity of cyclohexanol and cyclohexanone was 70.60% and 34.06%, respectively. This core-shell structure could protect the activity of the core Co₃O₄ and significantly decrease the loss of cobalt element. However, there existed different degree of the fragmentation of SiO₂ shell in the recycling process of Co₃O₄@SiO₂ samples.

Key words: core-shell structure, Co₃O₄@SiO₂, cyclohexyl hydroperoxide, decomposition

中图分类号:

O643

陈小梅, 陈颖, 袁霞. 核壳材料Co₃O₄@SiO₂催化环己基过氧化氢分解[J]. 无机材料学报, 2022, 37(1): 65-71.

CHEN Xiaomei, CHEN Ying, YUAN Xia. Decomposition of Cyclohexyl Hydroperoxide Catalyzed by Core-shell Material Co₃O₄@SiO₂[J]. Journal of Inorganic Materials, 2022, 37(1): 65-71.

图/表 12

图1 催化材料的FT-IR谱图

Fig. 1 FT-IR spectra of catalytic materials

图2 催化材料的XRD图谱

Fig. 2 XRD patterns of catalytic materials

图3 不同乙醇含量制备的Co3O4@SiO2的TEM照片

Fig. 3 TEM images of Co3O4@SiO2 prepared with different ethanol contents (a, b) 30%; (c, d) 50%; (e, f) 90%

图4 不同CTAB浓度制备的Co3O4@SiO2的TEM照片及其壳层厚度统计图

Fig. 4 TEM images and shell thickness statistics of Co3O4@SiO2 prepared with different concentrations of CTAB (a, b) 5 mmol/L; (c, d) 14 mmol/L; (e, f) 25 mmol/L

图 5 不同TEOS用量制备的Co3O4@SiO2的TEM照片及其壳层厚度统计图

Fig. 5 TEM images and shell thickness statistics of Co3O4@SiO2 prepared with different TEOS dosages (a, b) 0.8 mL; (c, d) 1.2 mL; (e, f) 2.0 mL

图6 催化材料的N2物理吸脱附等温线(a)和孔径分布图(b)

Fig. 6 N2 physical adsorption and desorption isotherms (a) and pore size distribution (b) of Co3O4@SiO2 Colorful figures are available on website

表1 催化材料的物理结构特性

Table 1 Physical structural properties of catalytic materials

Sample	n_CTAB/n_TEOS	S_BET/(m²∙g^-1)	D_pore/nm	V_pore/(cm³∙g^-1)
Co₃O₄@SiO₂ (VF_ETOH = 30%)	2.56	332	3.18	0.22
Co₃O₄@SiO₂(VF_ETOH = 50%)	2.56	334	3.18	0.24
Co₃O₄@SiO₂(VF_ETOH = 90%)	2.56	319	2.94	0.18
Co₃O₄@SiO₂(C_CTAB = 5 mmol/L)	0.93	254	2.82	0.16
Co₃O₄@SiO₂(C_CTAB = 25 mmol/L)	4.67	396	2.94	0.21
Co₃O₄@SiO₂ (V_TEOS = 0.8 mL)	3.84	327	2.94	0.18
Co₃O₄@SiO₂(V_TEOS = 2.0 mL)	1.54	486	2.94	0.27

表2 催化材料的Co元素含量

Table 2 Co content of catalytic materials

Entry	Sample	Co content/%
1	Co₃O₄@SiO₂(VF_ETOH = 90%)	39.9
2	Co₃O₄@SiO₂(C_CTAB = 5 mmol/L)	40.1
3	Co₃O₄@SiO₂(C_CTAB = 25 mmol/L)	39.3
4	Co₃O₄@SiO₂(V_TEOS = 0.8 mL)	47.8
5	Co₃O₄@SiO₂(V_TEOS = 2.0 mL)	30.6

表3 催化材料在CHHP分解反应中的催化性能

Table 3 Catalytic performance of catalytic materials in CHHP decomposition reaction

Catalytic material	Con./%	Selectivity/%
Catalytic material	Con./%	A	K	Acid	Ester	A+K
Blank	11.58	162.27	36.16	12.56	14.40	198.43
Co₃O₄	86.83	69.15	38.08	6.73	-15.63	107.23
Co₃O₄@SiO₂(VF_ETOH = 30%)	41.54	66.93	37.70	8.14	-26.54	104.62
Co₃O₄@SiO₂(VF_ETOH = 50%)	60.44	67.73	32.87	7.33	-18.46	100.60
Co₃O₄@SiO₂(VF_ETOH = 90%)	52.62	64.58	30.20	8.54	-25.15	94.79
Co₃O₄@SiO₂(C_CTAB = 5 mmol/L)	55.62	74.72	36.68	6.59	-20.69	111.40
Co₃O₄@SiO₂(C_CTAB =25 mmol/L)	66.68	72.18	31.01	6.83	-15.76	103.19
Co₃O₄@SiO₂(V_TEOS = 0.8 mL)	81.68	70.60	34.06	7.12	-15.97	104.65
Co₃O₄@SiO₂(V_TEOS = 2.0 mL)	73.55	64.75	27.90	6.28	-18.74	92.64

图7 Co3O4@SiO2 (VTEOS = 2.0 mL)反应前后的外观对比图

Fig. 7 Appearance comparison of Co3O4@SiO2(VTEOS = 2.0 mL) before and after the reaction (a) Fresh; (b) 1st cycle

图8 不同催化材料的新鲜及回收样品的反应评价结果

Fig. 8 Reaction evaluation results of fresh and recovered samples catalytic materials

图9 反应5次后回收Co3O4@SiO2(CCTAB=25 mmol/L)的TEM照片

Fig. 9 TEM images of Co3O4@SiO2 (CCTAB=25 mmol/L) recovered after 5 cycles

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核壳材料Co₃O₄@SiO₂催化环己基过氧化氢分解

Decomposition of Cyclohexyl Hydroperoxide Catalyzed by Core-shell Material Co₃O₄@SiO₂

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