Au NPs/Cu-TCPP材料的构筑及其催化薄荷醇氧化的研究

doi:10.3969/j.issn.2097-2806.2024.11.006

摘要/Abstract

摘要：

二维纳米片具有大的比表面积和高孔隙率的特征，这使得其可以承载更多的活性中心，从而提高该材料的催化性能。如Cu-TCPP纳米片，拥有大的比表面积，可用于负载Pd NPs、Pt NPs以及Au NPs，以获得X NPs/Cu-TCPP纳米片（X=Pd NPs、Pt NPs和Au NPs）。本研究首先通过水热法，以三水合硝酸铜（Cu（NO₃） ₂·3H₂O）为金属盐，4-羧基卟啉（TCPP）为有机配体，N,N-二甲基甲酰胺（DMF）和CH₃CH₂OH（体积比3∶1）的混合溶液作为溶剂，合成Cu-TCPP纳米片。随后，采用还原法将Au NPs负载到Cu-TCPP纳米片上，形成Au NPs/Cu-TCPP纳米片，用于催化薄荷醇进行选择性氧化反应。在反应中，以叔丁基过氧化氢（TBHP）为氧化剂，乙腈（MeCN）为溶剂，氨基酸咪唑离子液体（[C₄mim]Cys）为助催化剂，Au NPs/Cu-TCPP催化薄荷醇进行选择性氧化，生成薄荷酮。在50 ℃下反应18 h，薄荷醇的转化率和薄荷酮的选择性和产率都达到最高，分别为70.2%，99.9%和69.5%，该方法不仅将薄荷醇转化为高选择性的薄荷酮，而且操作简便，绿色环保，符合当前绿色化工发展的要求。

关键词: 二维纳米片, Au NPs/Cu-TCPP纳米片, 薄荷醇, 选择性氧化, 薄荷酮

Abstract:

Two-dimensional nanosheets have the characteristics of large specific surface area and high porosity, which allow them to support more active centers, thus improving the catalytic performance of the material. For example, Cu-TCPP nanosheets have large specific surface area and can be loaded with Pd nanoparticles （NPs）, Pt NPs and Au NPs to obtain X NPs/Cu-TCPP nanosheets （X=Pd NPs, Pt NPs and Au NPs）. In this work, Cu-TCPP nanosheets were synthesized by hydrothermal method, in which Cu（NO₃） ₂·3H₂O was used as the metal salt, TCPP （4-carboxyporphyrin） was used as the organic ligand, and a mixed solution of DMF and CH₃CH₂OH （V_DMF/V_CH3CH2OH=3∶1） was used as the solvent. Then Au NPs were loaded onto Cu-TCPP nanosheets by reduction method to form Au NPs/Cu-TCPP nanosheets, which were employed to catalyze the selective oxidation of menthol. In the reaction, with tert-butyl hydroperoxide （TBHP） as oxidant, acetonitrile （MeCN） as solvent, and the amino acid imidazolium ionic liquid [C₄mim]Cys as cocatalyst, Au NPs/Cu-TCPP catalyzed the selective oxidation of menthol to obtain menthone. After reacting at 50 ℃ for 18 h, the conversion of menthol was up to 70.2%, the selectivity and yield of menthone could reach 99.9% and 69.5%. This method not only highly selectively convert menthol to menthone, but also was easy to operate and environmentally friendly, which could meet the current development requirements of the green chemical industry.

Key words: two-dimensional nanosheet, Au NPs/Cu-TCPP nanosheet, menthol, selective oxidation, menthone

中图分类号:

TQ032

李世叶, 张剑, 王杰, 杨超, 张晋, 成世兴. Au NPs/Cu-TCPP材料的构筑及其催化薄荷醇氧化的研究[J]. 日用化学工业（中英文）, 2024, 54(11): 1330-1338.

Shiye Li, Jian Zhang, Jie Wang, Chao Yang, Jin Zhang, Shixing Cheng. Preparation of Au NPs/Cu-TCPP material and its performance in catalytic oxidation of menthol[J]. China Surfactant Detergent & Cosmetics, 2024, 54(11): 1330-1338.

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Entry	Catalyst/mg	Solvent/mL	Conv./%	Sel./%	Yield/%
1	Au NPs/ Cu-TCPP	MeCN（1.0）	24.5	>99	23.6
2		MeCN（2.0）	45.9	>99	44.9
3		MeCN（3.0）	30.4	>99	29.8
4		MeCN（4.0）	20.3	>99	19.7
5		MeCN（5.0）	8.2	>99	7.6
6		EA（2.0）	7.8	>99	7.2
7		THF（2.0）	1.8	>99	1.2
8		DMF（2.0）	9.9	>99	9.5
9		Ethanol（2.0）	1.7	>99	1.3
10		DMSO（2.0）	6.0	>99	5.6
11	Cu-TCPP	MeCN（2.0）	10.6	>99	9.8

Entry	IL	Conv./%	Sel./%	Yield/%
1	0.01 mmol [C₄mim]Cys	17.2	>99	16.9
2	0.025 mmol [C₄mim]Cys	28.9	>99	28.2
3	0.03 mmol [C₄mim]Cys	37.9	>99	37.2
4	0.05 mmol [C₄mim]Cys	45.9	>99	44.9
5	0.075 mmol [C₄mim]Cys	38.9	>99	38.0
6	0.10 mmol [C₄mim]Cy	27.7	>99	27.2
7	0.05 mmol [C₄mim]HSO₄	22.4	>99	22.0
8	0.05 mmol [C₄mim]Cl	17.8	>99	17.3
9	0.05 mmol [C₄mim]Ala	6.6	>99	5.9
10	0.05 mmol [C₄mim]Pro	20.3	>99	19.8
11	no	5.7	>99	5.2

Entry	Type of oxidants	Conv./%	Sel./%	Yield/%
1	TBHP	45.9	>99	44.9
2	DTBP	14.2	>99	13.6
3	BPO	6.7	>99	5.9
4	M-CPBA	2.4	>99	1.6
5	O₂	17.2	>99	16.8
6	H₂O₂	26.7	>99	26.2