The effects of calcination temperature and dispersants on the catalytic performance of Co0.8Cu0.2/CNC for the hydrolysis of ammonia borane to hydrogen were investigated
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摘要: 氨硼烷(NH3BH3,AB)被认为是一种便携式制氢的理想储氢材料。本工作在常温下搅拌反应物得到Co0.8Cu0.2-ZIF前驱体,并高温焙烧此前驱体制备了一种双金属碳立方体(Co0.8Cu0.2/CNC)催化剂。此外,采用多种表征方法对催化剂的微观结构以及组成成分进行了研究。通过单一变量法探究了催化剂的变化规律。结果表明,少量Cu的加入会对Co0.8Cu0.2/CNC催化剂的立方体形貌有一定的稳固作用。当分散剂为CTAB且焙烧温度为873 K时,其催化AB水解制氢的活化能(Ea)为50.79 kJ/mol,转化频率(TOF)值高达23.37 min−1。此外,该催化剂经过25次循环后仍然可以催化AB完全水解制氢,表明该催化剂的稳定性能良好。Abstract: Ammonia borane (NH3BH3, AB) is considered as an ideal hydrogen storage material for portable hydrogen production. In this paper, Co0.8Cu0.2-ZIF precursor was obtained by stirring the reactants at room temperature, and a bimetallic carbon cube (Co0.8Cu0.2/CNC) catalyst was prepared by roasting this precursor at high temperature. In addition, the microstructure as well as the composition of the catalyst was investigated using various characterization methods. The change rule of the catalyst was explored by the single-variable method. The results showed that the addition of a small amount of Cu had a stabilizing effect on the cubic morphology of the Co0.8Cu0.2/CNC catalyst. When the dispersant was CTAB and the roasting temperature was 873 K, the activation energy (Ea) for catalyzing the hydrolysis of AB to hydrogen was 50.79 kJ/mol, and the transition frequency (TOF) value was as high as 23.37 min−1. In addition, the catalyst could still catalyze the complete hydrolysis of AB to hydrogen after 25 cycles, which indicated that the catalyst had good stability performance.
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Key words:
- Bimetallic carbon cube /
- ammonia borane /
- hydrogen hydrolysis
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图 3 (a)−(c)Co0.8Cu0.2/CNC不同放大倍率的TEM图像;(d)晶格条纹计算;(e)粒径分布;(f)Co0.8Cu0.2/CNC中Cu、C和Co的相应元素映射
Figure 3 (a)−(c) TEM image of Co0.8Cu0.2/CNC with different magnification; (d) calculation image of lattice fringe; (e) particle size distribution of Co0.8Cu0.2/CNC; (f) the corresponding elemental mapping of Cu, C and Co
表 1 Co/CNC、Co0.8Cu0.2/CNC和Cu/C催化剂的ICP-AES测试
Table 1 ICP-AES results of Co/CNC、Co0.8Cu0.2/CNC and Cu/C catalysts
Catalyst Co w/% Cu w/% Co-Cu initaial composition
(molor ratio)Cu-Co final composition
(molor ratio)Final metals/catalyst
(mmol·100 mg−1)Co/CNC 20.90 — — — 0.354 Co0.8Cu0.2/CNC 18.50 4.36 80∶20 82∶18 0.382 Cu/C 49.73 — — — 0.782 -
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