负载型Ru/CN催化剂的制备及其催化氨硼烷水解制氢研究

Study on preparation of supported Ru/CN catalysts and their performance for hydrogen generation from catalytic hydrolysis of ammonia borane

  • 摘要: 以三聚氰胺、三聚氰酸以及柠檬酸为原料高温焙烧合成氮化碳载体(CN),再采用浸渍-还原法制备得到Ru/CN负载型单原子催化剂。利用各种表征手段来探究催化剂的结构组成及微观形貌,进而考察不同因素对氨硼烷(NH3BH3,AB)水解制氢反应速率的影响。结果表明:催化剂的晶格条纹间距为0.211 nm,对应于Ru的(002)晶面,证明Ru纳米粒子成功负载于CN载体表面。Ru负载量为0.05 mmol的Ru/CN催化剂TOF值为446.4 min-1,Ru/CN催化AB水解制氢反应相对于催化剂用量可以近似看作一级反应;升温可以增大反应物分子之间的有效碰撞频率,促使制氢反应更易进行;且经计算分析表明,AB浓度对于Ru/CN催化AB水解制氢反应具有正向影响,活化能为53.6 kJ/mol,Ru/CN催化剂在经过5次循环使用后,仍能催化AB完全水解制氢。

     

    Abstract: Carbon nitride support (CN) was synthesized by high-temperature calcination using melamine, cyanuric acid, and citric acid as raw materials, and then Ru/CN supported single atom catalyst was prepared by impregnation reduction method. Utilize various characterization methods to investigate the structural composition and microstructure of catalysts, and then investigate the influence of different factors on the rate of hydrogen production by hydrolysis of ammonia borane (NH3BH3, AB). The results showed that the lattice stripe spacing of the catalyst was 0.211 nm, corresponding to the (002) crystal plane of Ru, indicating that Ru nanoparticles were successfully loaded on the surface of the CN carrier. The TOF value of Ru/CN catalyst with a Ru loading of 0.05 mmol is 446.4 min-1. The Ru/CN catalyzed AB hydrolysis hydrogen production reaction can be approximately regarded as a first-order reaction relative to the amount of catalyst used; heating up can increase the effective collision frequency between reactant molecules, promoting easier hydrogen production reactions; and through calculation and analysis, it is shown that the concentration of AB has a positive effect on the Ru/CN catalyzed AB hydrolysis hydrogen production reaction, with an activation energy of 53.6 kJ/mol. After 5 cycles of use, the Ru/CN catalyst can still catalyze AB complete hydrolysis hydrogen production.

     

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