中孔载体上组装Ti催化活性中心的研究Ⅰ—钛配合物在中孔HMS载体上的组装 |
Assembly of Titanium Catalytic Active Center over Mesoporous SilicasⅠ— Assembly of Titanium Complexes over HMS |
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摘要: 利用六角中孔硅载体(记为HMS)上丰富的表面羟基与钛酸异丙酯、四氯化钛的交换反应,实现了钛配合物在载体上的组装。FT-IR表征表明载体与钛化合物的键合作用会使样品出现一个新的960cm-1带,该带可归属于与钛化合物键合的Si-OH振动带;交换温度会明显影响钛化合物与载体羟基的交换反应模式;酒石酸二乙酯(DET)被键合后其C=O带没有明显位移证明DET是以其OH与键合在载体上的钛化合物发生键合作用。在催化苯乙烯环氧化反应中,键合于载体上的钛配合物比其均相配合物的催化活性要高得多,钛源、配体和交换温度对催化氧化活性和环氧化选择性均有较大影响。 |
关键词: 中孔分子筛 HMS 钛配合物 组装 催化氧化 苯乙烯环氧化 |
基金项目: 国家自然科学基金(No.29773013) |
Abstract: The assembled methods for anchoring titanium complexes over hexagonal mesoporous silicas (HMS) were studied by bonding interaction of the surface's OH groups on HMS with Ti(OiPr)4 or TiCl4. The characterized results indicate that the stronger binding of Ti compounds with HMS leads to the appearance of 960cm-1 band which is attributed to the vibration of Si-OH connected with Ti compound. The shift of the carbonyl band of diethyl tartate (DET) anchored on HMS-Ti compound is smaller than that of DET mixed with Ti(O iPr)4 in toluene at room temperature, this indicates that DET is anchored on the carrier through the bonding of the OH groups of DET with Ti compounds. Ti complex bound on HMS is more active than the free Ti complex for the epoxidation of styrene with tertbutyl hydroperoxide (TBHP). Ti source, ligand and exchanged temperature have significant influences on the oxidative activity and the selectivity to epoxide of assembled catalysts. |
Keywords: mesoporous molecular sieves HMS bond assembly catalytic oxidation epoxidation of styrene |
投稿时间:1999-12-21 修订日期:2000-02-25 |
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伏再辉,尹笃林,赵伟,毛丽秋,张鲁西,银董红,张友玉.中孔载体上组装Ti催化活性中心的研究Ⅰ—钛配合物在中孔HMS载体上的组装[J].无机化学学报,2000,16(4):624-630. |
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