杂多酸的共价负载及其对四氢噻吩氧化性能研究

doi:10.11949/0438-1157.20191160

摘要/Abstract

摘要：

首先采用改进的Hummers法制备氧化石墨烯（GO），用3-氨丙基三甲氧基硅氧烷（KH540）对GO进行表面改性，制得氨基改性氧化石墨烯NH₂-GO。然后，通过γ-(2,3-环氧丙基) 三甲氧基硅烷对单缺位的Dawson型磷钨酸盐K₁₀[α-P₂W₁₇O₆₁]·20H₂O（P₂W₁₇）进行环氧基改性，制得环氧基改性的EPO-P₂W₁₇。最后，借助NH₂-GO与EPO-P₂W₁₇之间的席夫碱反应实现P₂W₁₇在GO上的共价固载，制得复合催化剂P₂W₁₇/GO。采用FT-IR、UV-Vis、TG、XPS、TEM等对复合材料的结构和组成进行了表征。以四氢噻吩（THT）作为催化评价的对象，初步考察了P₂W₁₇/GO的催化氧化活性。实验结果表明，共价负载在GO上的P₂W₁₇分散性良好，且复合催化剂P₂W₁₇/GO对THT表现出良好的催化活性和高的选择性。较小的P₂W₁₇/GO用量（0.02 g）下，以H₂O₂为氧化剂，反应75 min，THT转化率达100%；相对于EPO-P₂W₁₇，其催化活性提高了1.7倍；其催化H₂O₂氧化THT的过程符合准一级动力学模型。此外，该催化剂具有良好的重复使用性。

关键词: 氧化石墨烯, Dawson型磷钨酸盐, 共价键合, 催化, 氧化脱硫

Abstract:

Firstly, the graphene oxide (GO) was prepared by the modified Hummers method, and modified with 3-aminopropyltrimethoxysilane to obtain NH₂-GO containing amino groups. Then, the single lacunary Dawson type tungstophosphate K₁₀[α-P₂W₁₇O₆₁]·20H₂O (P₂W₁₇) was modified with γ-(2,3-epoxypropoxy) propyltrimethoxysilane (EPO) to prepare EPO-P₂W₁₇ containing epoxy groups. Finally, P₂W₁₇ was covalently bonded onto GO through the reaction of EPO-P₂W₁₇ with NH₂-GO to prepare P₂W₁₇/GO composite catalysts. The structure and composition of the composites were characterized by FT-IR, UV-Vis, TG, XPS, TEM, etc. Tetrahydrothiophene (THT) was used as the object of catalytic evaluation, and the catalytic oxidation activity of P₂W₁₇/GO was initially investigated. The results show that P₂W₁₇ covalent-supported on GO is well dispersed. And the oxidation process of THT catalyzed by P₂W₁₇/GO using H₂O₂ presented the high efficiency and selectivity. The conversion of THT could reach 100% at 75 min with H₂O₂ as oxidant under a small amount of P₂W₁₇/GO (0.02 g), and its catalytic activity is 1.7 times higher than that of EPO-P₂W₁₇. The catalytic oxidation of THT by P₂W₁₇/GO follows the quasi-first order kinetic model. More attractively, P₂W₁₇/GO could be well reused several times, stemming from the strong covalent bonding between P₂W₁₇ and GO surface.

Key words: graphene oxide, Dawson phosphotungstic acid, covalent immobilization, catalysis, oxidative desulfurization

中图分类号:

O 643.32

刘叶峰, 左鹏, 李瑞琪, 焦纬洲, 王蕊欣. 杂多酸的共价负载及其对四氢噻吩氧化性能研究[J]. 化工学报, 2020, 71(4): 1627-1636.

Yefeng LIU, Peng ZUO, Ruiqi LI, Weizhou JIAO, Ruixin WANG. Covalently supported polyoxometalate and its catalytic oxidative desulfurization of tetrahydrothiophene[J]. CIESC Journal, 2020, 71(4): 1627-1636.

图/表 11

图1 在GO表面共价固载P2W17的化学反应过程

Fig.1 Covalent loading process of P2W17 on GO surface

图2 GO、NH2-P2W17、EPO-P2W17和P2W17/GO的红外光谱图

Fig.2 FT-IR spectra of GO,NH2-P2W17,EPO-P2W17 and P2W17/GO

图3 P2W17、EPO-P2W17、新制备P2W17/GO和回收的P2W17/GO的紫外-可见漫反射光谱图

Fig.3 UV-Vis diffuse reflectance spectra of P2W17,EPO-P2W17,freshly prepared P2W17/GO and recovered P2W17/GO

图4 P2W17/GO的XPS谱图（a）及其W 4f（b）和P 2p（c）的高分辨谱图

Fig.4 XPS spectra of P2W17/GO (a) and high-resolution spectra of W4f (b) and P 2p (c)

图5 GO的AFM图(a)和GO的片层厚度图(b)；GO（c）和P2W17/GO（d）的TEM图

Fig.5 AFM images of GO (a) and height of GO (b); TEM images of GO (c) and P2W17/GO (d)

图6 NH2-GO和P2W17/GO的热失重曲线图

Fig.6 TGA curves of NH2-GOand P2W17/GO

图7 不同体系催化氧化THT的曲线图（a），伪一级动力学曲线（b），P2W17/GO催化氧化THT过程的HPLC图（c）

Fig.7 THT oxidation conversion as functions of reaction time curve with different catalytic systems(a); pseudo-first-order kinetic curves(b); HPLC chromatograms of oxidation process of THT by P2W17/GO (c)

图8 P2W17/GO催化氧化THT的反应机理示意图

Fig.8 Schematic diagram of possible mechanism of catalytic oxidation process of THT by P2W17/GO

图9 P2W17/GO不同用量下THT的催化氧化曲线（a）和伪一级动力学曲线（b）

Fig.9 Catalytic oxidation curves of THT different dosages under P2W17/GO(a) and pseudo-first-order kinetic curves(b)

图10 不同H2O2下的催化氧化曲线

Fig.10 Catalytic oxidation curves of THT underdifferent hydrogen peroxide dosages

图11 P2W17/GO催化氧化THT的重复使用性

Fig.11 Stability of P2W17/GO during catalytic oxidation process of THT after recovery

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