Au NPs/Cu-TCPP材料的构筑及其催化薄荷醇氧化的研究  

Preparation of Au NPs/Cu-TCPP material and its performance in catalytic oxidation of menthol

作　　者：李世叶 张剑[2] 王杰 杨超 张晋 成世兴 Shiye Li;Jian Zhang;Jie Wang;Chao Yang;Jin Zhang;Shixing Cheng(School of Chemical Engineering,Shanxi Institute of Science and Technology,Jincheng,Shanxi 048000,China;School of Chemistry and Chemical Engineering,Shanxi University,Taiyuan,Shanxi 030006,China)

机构地区：[1]山西科技学院化学工程学院,山西晋城048000 [2]山西大学化学化工学院,山西太原030006

出　　处：《日用化学工业（中英文）》2024年第11期1330-1338,共9页China Surfactant Detergent & Cosmetics

基　　金：山西省基础研究计划青年项目(自由探索类)(202303021212302,202303021212303,202303021212304)。

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(NO_(3))_(2)·3H_(2)O)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CH_(3)CH_(2)OH(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(Me CN)为溶剂,氨基酸咪唑离子液体([C_(4)mim]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。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-TCPPnanosheets(X=Pd NPs,Pt NPs and Au NPs).In this work,Cu-TCPP nanosheets were synthesized by hydrothermal method,in which Cu(NO_(3))_(2)·3H_(2)O was used as the metal salt,TCPP(4-carboxyporphyrin)was used as the organic ligand,and a mixed solution of DMF and CH_(3)CH_(2)OH(V_(DMF)/V_(CH3CH2OH)=3:1)was used as the solvent.Then Au NPs were loaded onto Cu-TCPPnanosheets 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[C_(4)mim]Cys as cocatalyst,Au NPs/Cu-TCPPcatalyzed 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.

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 

分 类 号：TQ032[化学工程]