【作者】 陈娜；

【导师】 许宪祝；

【作者基本信息】 哈尔滨工业大学 ， 无机化学， 2014， 硕士

【摘要】 有序介孔材料M41S系列，例如MCM-41，MCM-48，MCM-50等的成功发现和合成将孔材料的孔直径，由微孔领域延伸到介孔范围。在催化应用中掺杂金属基团后的MCM-41材料往往具有更好的催化活性，因此科研工作者关注较多的是掺杂其他原子或原子团的纯硅的MCM-41介孔材料。以期在保持介孔材料的特性及孔道结构优势的同时还获取金属离子所持有的催化功能。本篇论文在是室温条件下，以氢氧化钠为碱源，以阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)为模版剂，采用一步原位合成法和后合成法快速制备了不同锡含量和碱源含量的介孔Sn-MCM-41纳米粒子。通过以下分析手段，对制备的样品的结构进行了细致的表征，表征方法包括SEM，N2吸附-脱附，FT-IR，TEM，XRD，UV-vis等。实验还探究了掺杂金属锡的含量，碱源氢氧化钠加入量对Sn-MCM-41纳米粒子结构的影响。实验及表征结果表明，在室温条件下，采用原位合成法和后合成法制备的碱源NaOH加入量为3.5ml的介孔Sn-MCM-41纳米粒子都具有良好的有序度；而当氢氧化钠溶液的加入量增加为7ml时，合成的样品粒子尺寸明显增加，且有序度降低。将原位合成法和后合成法合成的介孔材料Sn-MCM-41纳米粒子作为催化剂，以环境友好的过氧化氢H2O2作氧化剂，以1,4-二氧六环为溶剂，催化底物金刚烷酮的Baeyer-Villiger催化氧化反应。研究结果表明，在金刚烷酮的Baeyer-Villiger催化氧化反应中，以制备的Sn-MCM-41纳米粒子为催化剂时，样品显露出较高的催化活性。在反应体系中，反应开始后金刚烷酮的转换率随反应的进行不断提高，到达一定时间后，金刚烷酮的转换率不再具有明显变化。反应结束时，底物金刚烷酮的转化率最高达到98%以上。原位合成法合成制备的Sn-MCM-41纳米粒子在催化反应后，经过洗涤及再次培烧后，样品重复利用四次后活性也没有明显改变。更多还原

【Abstract】 The successful discovery and synthesis of ordered mesoporous molecularsieve,M41S (MCM-41, MCM-48, MCM-50) series silicon oxide,extended the porediameter of molecular sieve from micropore to the field of mesoporous. Themesoporous materials MCM-41mixed with other metal atoms were the key point ofresearch because of whose the catalytic activity better then pure silicon. Due to thepresence of metal ions on the skeleton or metal elements loaded outside of the surface,MCM-41was given acid centers and redox sites, which owed structural features andproperties of porous in the mesoporous materials, at the same time, it owed thecatalytic properties of the metal ions.In this paper, ordered Sn-MCM-41nanoparticles synthesised by in-suit methodand post-synthesis method were successfully prepared under room-temperature usingdifferent tin and base contents, in which NaOH and CTAB were used as base sourceand surfactant. The samples were characterized by TEM, XRD, SEM, N2adsorption-desorption isotherms measurement, FT-IR and UV-vis spectroscopy.Besides, effects of the content of NaOH and tin source on the mesoporous structureswere investigated. Additionally, ordered Sn-MCM-41nanoparticles were obtained bythe post-synthesis method. Both in room-temperature and post-synthesis method,experiments and characterization results show the mesoporous Sn-MCM-41nanoparticles have good degree of order when the source of base amount is3.5ml;however when the addition amount of the sodium hydroxide solution is7ml, thedegree of order decreased obviously.The samples prepared by the two synthetic methods were used as catalysts inadamantanone Baeyer-Villiger hydroxylation with H2O2as oxidant. Experimentsresults show that Sn-MCM-41nanoparticles showed higher catalytic activity in theadamantane Baeyer-Villiger catalytic oxidation reaction. In the reaction system, therate of adamantane conversion enhances unceasingly. After a certain time, the rate ofadamantane conversion is no longer change. In the end of the reaction, the adamantanereaction rate up to98%. Sn-MCM-41nanoparticles reusing activity did not reduceafter four times in room temperature synthesis method.更多还原