MCM-41限域的Ni基催化剂N-乙基咔唑催化储氢研究

N-乙基咔唑（NEC）类含氮有机液体储氢量高、储放氢可逆且温度低，被认为是最具潜力的氢载体之一。开发高活性、高12H-NEC选择性、廉价Ni催化剂是NEC推广应用的关键。由于NEC的部分加氢产物4H-NEC和8H-NEC与Ni催化剂作用较弱，导致12H-NEC选择性较低。针对这一难题，申请人提出以下思路（1）利用MCM-41分子筛的限域作用增加中间产物浓度使反应向正向移动；（2）在MCM-41中引入酸中心增强分子筛与Ni相互作用、引入电负性较强的P元素形成NixP使Ni金属纳米粒子形成缺电子结构，增强其与中间产物的作用，提高催化剂加氢活性与12H-NEC选择性。本项目拟在前期工作基础上，系统研究分子筛酸中心与Ni/P比对Ni催化剂结构与加氢性能的影响，开发具有较高活性与12H-NEC选择性的催化剂；通过原位表征与动力学研究，揭示NEC加氢反应机理，为NEC储氢技术提供理论依据与技术支撑。

Nitrogenous liquid organic compounds such as N-ethycarboze (NEC) have high hydrogen storage capacity, reversible hydrogen storage and release at moderate temperature, making it one of the most promising hydrogen carriers. Construction of unexpensive Ni catalysts with high activity and selectivity of 12H-NEC is the key to the application of NEC. The weak interaction between Ni particles and the NEC hydrogenation intermediates, e.g. 4H-NEC and 8H-NEC, leads to the low selectivity of 12H-NEC. To solve this problem, the applicant propose the following two strategies to increase the hydrogenation activity and 12H-NEC selectivity of the Ni catalyst. The first one is to increase the concentration of intermediate products on the catalyst active site by using the confined effect of MCM-41 mesoporous molecular sieve, which will push the hydrogenation reaction moving forward; The second one is to enhance the interaction between Ni particles and intermediates by introducing the acid site to MCM-41 and forming electro-deficient structure of Ni by doping the electronegative P element in Ni to generate NixP. Based on the previous work, the influence of acid site and Ni/P ratio on the structure of Ni catalysts and its hydrogenation performance will be systematically investigated, and the hydrogen storage catalyst with high activity and 12H-NEC selectivity will be developed in this project. The hydrogenation reaction mechanism of NEC will be revealed by the in-situ characterization and kinetic study. The above results will provide theoretical basis and technical support for the NEC hydrogen storage technology.