非晶态Ni-B合金柱撑的石墨烯层柱状多孔材料的组装、结构特征及其催化加氢性能

Due to its unique structure and properties, graphene provides a novel load type catalyst carrier, and also a new way to assemble highly efficient catalysts. This subject plans to assemble a graphene layer porous catalyst pillared with Ni-B amorphous alloy by controlled oxidization and reduction. Then selective catalytic hydrogenation of nitrobenzene to aniline as a probe reaction will be proposed to study effect of the unique structure and properties of graphene on its catalytic properties. Assembly process of the catalysts and characteristics of the pillared porous structure will be studied by a series of measurements such as AFM, HRTEM, SEM, Raman spectra, XPS, XRD, TG-DTA, etc. By in situ FTIR, temperature-programmed desorption and adsorption as well as surface pulse response, catalytic reaction mechanism will be discussed, in order to reveal the effect of grapheme on molecular activation, species migration and surface reaction, and also to propose an assembly rule of the pillared graphene layer catalyst. The subject will provide relevant theory and technology for the development of novel and highly efficient load type catalyst carrier, and also provide efficient catalysts for the development of novel environmental friendly synthesis technology of aniline. Therefore, this subject has important theory value and broad application prospects.

石墨烯特有的结构与性能为负载型催化剂提供一种新的载体，为组装高效催化剂提供一种新方法。本项目拟采用可控氧化和可控还原，组装非晶态Ni-B合金为柱撑的石墨烯夹层多孔催化剂，并以硝基苯选择加氢制苯胺为探针反应，研究石墨烯独特的空间结构和理化性能对其催化性能的影响。通过AFM、HRTEM、SEM、Raman、XPS，XRD、TG-DTA等系列表征，研究催化剂的组装过程和柱撑孔道特征，并通过原位红外光谱、吸附-程序升温脱附和表面脉冲反应研究催化反应机理，揭示石墨烯在分子活化，物种迁移和表面反应中的作用，提出无机柱撑石墨烯层状催化剂的组装规律，为研发新型高效负载型催化剂载体提供相关理论和技术，为开发环境友好的苯胺合成新技术提供高效催化剂，所以本项目具有重要的理论价值和广阔的应用前景。

石墨烯特有的结构与性能为催化剂和贮能包覆材料的组装提供了一种新的方法。本项目围绕非晶态合金催化剂的改进，研制出由膨胀石墨改性的Ni-Mo-P-EG非晶态合金催化剂；由六钛酸钾负载的Ni-B/K2Ti6O13催化剂；通过可控水解-化学还原法制备具有网状结构特征的非晶态合金Ni-B/SiO2催化剂；通过引入助剂，研制出Ni-Cu-B非晶态合金催化剂，考察了催化剂对硝基苯加氢制苯胺、糠醛选择性加氢制备环戊酮的催化性能，其中硝基苯在100℃、氢气压力 1.8 MPa 下，非晶态合金Ni-B/SiO2催化剂上反应 120 min时，硝基苯的转化率达99.9%，苯胺的选择性达99.8%，连续反应5次，未观察到催化剂失活现象。糠醛在160 ℃、氢气分压0.8 MPa ，Ni-Cu-B非晶态合金催化剂上选择性加氢反应的糠醛转化率为100%，环戊酮的选择性为52.9%，连续反应5次，未观察到催化剂失活现象。基于石墨烯具有良好的包覆性能，通过自组装，合成具有壳-核结构的石墨烯/脂肪酸复合相变贮能复合微胶囊，当石墨烯含量为2 wt%和5 wt%时，复合材料的导热系数分别增加到0.497 W•m-1•K-1和0.562 W•m-1•K-1。通过现代分析手段，对催化剂和复合贮能相变材料的结构进行表征，得到了材料的微观结构特征，关联催化剂的活性数据和贮能材料的性能数据，揭示非晶态合金催化剂的调变规律和石墨烯包覆的贮能相变材料的结构本质，为研发高性能的非晶态合金催化剂和开发新型相变贮能材料提供基础数据和关键技术。