纳米碳材料液相催化反应及原位电喷雾解吸质谱跟踪

Carbon-based nanomaterials including carbon nanotube and graphene show great promise for potential applications in heterogeneous catalysis due to high specific surface area, good chemical stability, remarkable electrical and thermal properties, and controllable chemical surface. However, so far the synthesized carbocatalysts exhibit complex structure including defects, dopants and various functional groups. In addition, the lack of in situ characterization methodologies for reactive intermediates makes it challenging to unravel the mechanistic picture of carbon catalysts in most reactions. In this project carbon-based nanomaterials including carbon nanotube and graphene are modified using reductive alkylation reaction, in which the carbon skeleton of carbon nanotube and graphene are intact without the introduction of structural defects, dopants and various oxygen-containing functional groups. The catalytic performances of these carbon-based nanomaterials in various liquid-phase reactions are evaluated. By means of in situ desorption electrospray ionization-mass spectrometry (DESI-MS) technique, the reactive intermediates in liquid-phase reaction could be captured and analyzed in real time, unraveling the heterogeneous interface processes.

以碳纳米管和石墨烯为代表的纳米碳材料由于具有高的比表面积、良好的化学稳定性、优异的传输电子和传热特性、可调控的化学表面等优良特性在催化领域具有广泛的应用前景。然而，由于现有合成方法制备得到的纳米碳材料表面化学性质往往复杂多样，再加上原位表征技术的相对滞后，人们对纳米碳材料在催化反应中的非均相本质作用认识还非常不足。本项目以各种功能化纳米碳材料为催化剂，构建液相反应条件下反应物种在催化剂表面吸附和活化的化学环境，以原位电喷雾解吸质谱（DESI-MS）技术监测催化剂表面活性中间体的生成，获得反应条件下物种形成和转化的分子细节，研究反应机理，为高催化性能纳米碳材料的设计、优化合成提供实验基础和理论依据。

现有合成方法制备得到的纳米碳材料表面化学性质复杂多样，再加上原位表征技术的相对滞后，人们对纳米碳材料在催化反应中的非均相本质作用认识非常不足。本项目以各种功能化纳米碳材料为催化剂，设计和构建液相反应条件下反应物种在催化剂表面吸附和活化的化学环境，以原位电喷雾解吸质谱（DESI-MS）技术监测催化剂表面活性中间体的生成，获得了反应条件下物种形成和转化的分子细节，研究反应机理，为高催化性能纳米碳材料的设计、优化合成提供了实验基础。我们还将纳米碳材料可控功能化方法推广至其它二维材料，制备得到包括g-C3N4和WO3纳米片在内的多种二维材料，研究了它们的光催化和电化学储能等领域的应用。本项目关于石墨电弧放电法和燃烧法合成新型富勒烯的研究，首次合成得到了含有双七元环的对称内凹型C70的非IPR异构体衍生物C70Cl6和第一个含有双七元环的非经典富勒烯C66的氢化物C66H4，激发了人们对非经典富勒烯的进一步探索。