介孔碳载体与二氧化钛在环境光催化条件下的高选择性环氧化苯乙烯

guangjian wang, Hongyu Gao, Fangfang Kang, Y. Zi
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摘要

本文的主要目的是基于环境友好化学的基本原理,设计一种新型结构的介孔碳复合材料,开发经济、绿色的环境条件下氧化苯乙烯等常见化学反应中间体的光催化工艺。以三嵌段共聚物为模板剂,采用常规水热法制备有序介孔二氧化硅,然后在硫酸处理的介孔二氧化硅中加入蔗糖,利用反复制效应对介孔二氧化硅进行炭化和去除模板,采用简单模板法合成有序介孔碳材料。以不同含量的钛酸四丁酯为原料,在氮气气氛下,在700℃下浸渍烧结2h,制备了钛酸四丁酯脱除和二氧化钛结晶的复合介孔碳材料。采用x射线衍射、傅里叶变换红外光谱、拉曼光谱、扫描电镜和高分辨率透射电镜等对复合催化剂进行了表征。制备的碳材料的结构和形态表明,TiO2插入后仍保持了典型的有序介孔结构,TiO2的活性组分均匀分布在介孔碳通道中。对H2O2与苯乙烯的摩尔比、反应时间、溶剂、催化剂用量等多种反应参数进行了较长时间的优化,以H2O2为氧化剂,在光照射下制备复合催化剂进行苯乙烯环氧化反应。结果表明,在室温、苯乙烯用量为0.50g、H2O2用量为2.00g (30%wt%)、催化剂用量为0.200g、反应时间为3h的光催化条件下,反应转化率达到30%以上,选择性90%。这种环境条件下的绿色光催化氧化工艺策略有望作为一种通用的环保化学手段应用于其他有机合成工艺。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Highly selective epoxidation of styrene over mesoporous carbon support with titanium dioxide under ambient photocatalytic condition
The main purpose of this paper was to design a novel structure mesoporous carbon composite materials and develop economic and green photocatalytic oxidation process for common chemical reaction intermediates of styrene oxide under ambient condition based on the basic principle of environmentally friendly chemistry. Order mesoporous silica was prepared by conventional hydrothermal method using triblock copolymer as template agent, and then order mesoporous carbon materials were synthesized via a simple template method by adding sucrose to the sulfuric-acid-treated mesoporous silica and followed by carbonization and removal template of mesoporous silica on account of inverse replica effects. The composite mesoporous carbon materials assembled in situ anatase TiO2 of different contents were obtained through impregnation and sintering at 700℃ for 2h in nitrogen atmosphere for both removal of unhydrolyzed tetrabutyl titanate and crystallization of titanium dioxide. All the composite catalysts had been unambiguously characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscoscopy, scanning electron microscopy, and high-resolution transmission electron microscopy, etc. Structural and morphological of prepared carbon materials showed that the typical ordered mesoporous structure was maintained after TiO2 insertion and active component of TiO2 was uniformly distributed in mesoporous carbon channels. A variety of reaction parameters such as molar ration of H2O2 to the styrene, reaction time, solvent, the amount of catalyst and so on were optimized at length for epoxidation of styrene with H2O2 as the oxidant over prepared composite catalysts under photo-irradiation. The results indicated that reaction conversion reached over 30% with 90% selectivity under the photocatalytic condition for room temperature, 0.50g of styrene, 2.00g of H2O2(30%wt%), 0.200g of catalyst and 3h reaction time. This process strategy for green photocatalytic oxidation under ambient condition was expected to be applied to other organic synthesis processes as a general environmentally benign chemical means.
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