【摘要】 柴油车尾气排放的碳烟颗粒对人类的生存环境和身体健康带来了严重危害.催化燃烧是消除碳烟颗粒污染的有效途径.碳烟颗粒催化燃烧是固-固-气相反应,因此催化剂本身具有活泼的氧中心且其能与碳烟颗粒有效接触是提高反应效率的关键因素.为改善碳烟颗粒与催化剂的接触,设计制备三维有序大孔（3DOM）催化剂,使碳烟颗粒可以进入催化剂孔道内部,增加其与催化剂的有效接触,是提高反应活性的有效途径.此外,在催化剂晶格中掺杂其它金属离子形成固溶体结构,可提高其氧化还原性能,也可有效提高其碳烟燃烧活性.SnO₂富含活泼的表面缺位氧和可还原的晶格氧,且其熔点高达1630℃,具有良好的热稳定性,被广泛用于制备气体传感、电化学和催化等材料.在过去的6年中,本课题组在SnO₂催化化学领域做了大量系统的工作,将SnO₂基催化材料用于多种环保和能源反应.发现通过其它阳离子Fe³⁺,Cr³⁺,Ta⁵⁺,Ce⁴⁺和Nb⁵⁺等的掺杂,替换晶格中部分Sn⁴⁺形成金红石型SnO₂固溶体结构,可显著提高催化剂氧物种的流动性、活性和本身的热稳定性.本文采用胶体晶体模板法制备出了Ce⁴⁺,Mn³⁺和Cu²⁺离子掺杂的SnO₂三维有序大孔固溶体催化剂用于松散接触条件下的碳烟催化燃烧.采用SEM,TEM,XRD,STEM-mapping,O₂-TPD和XPS等手段对催化剂进行表征,研究其碳烟催化燃烧性能.SEM和TEM结果表明已成功合成三维有序大孔结构样品.XRD,Raman和STEM-mapping结果表明,Ce⁴⁺,Mn³⁺和Cu²⁺离子均进入四方金红石型SnO₂晶格形成固溶体结构.另外,Raman,H₂-TPR,XPS和O₂-TPD等结果发现上述离子掺杂三维大孔SnO₂后,催化剂表面形成了更活泼、丰富的氧物种,有利于碳烟颗粒燃烧.其中3DOM-Cu₁Sn₉催化剂具有最丰富的活泼氧中心,因此表现出最高的活性.更多还原

【Abstract】 A series of three-dimensionally ordered macroporous（3 DOM） SnO₂-based catalysts modified by the cations Ce⁴⁺, Mn³⁺, and Cu²⁺ have been prepared by using a colloidal crystal templating method and tested for soot combustion under loose contact condition. XRD and STEM mapping results confirm that all the secondary metal cations have entered the lattice matrix of tetragonal rutile SnO₂ to form non-continuous solid solutions, thus impeding crystallization and improving the surface areas and pore volumes of the modified catalysts. In comparison with regular SnO₂ nanoparticles, the 3 DOM SnO₂ displays evidently improved activity, testifying that the formation of the 3 DOM structure can anchor the soot particulates in the macro-pores, which ensures that the contact of the soot particles with the active sites on the 3 DOM skeleton is more easily formed, thus benefiting the target reaction. With the incorporation of the secondary metal cations, the activity of the catalyst can be further improved due to the formation of more abundant mobile oxygen species. In summary, these effects are believed to be the major factors responsible for the activity of the catalyst.更多还原