膨润土负载钌催化剂制备及其催化氨硼烷水解产氢研究

doi:10.19964/j.issn.1006-4990.2020-0421

摘要/Abstract

摘要：

采用浸渍-化学还原法制备了钌/膨润土（Ru/Ben）催化剂,考察了钌含量、还原剂硼氢化钠用量、还原温度以及反应条件等对Ru/Ben催化氨硼烷（NH₃BH₃）水解产氢的影响。结果表明,在钌负载量为0.3%（质量分数）、钌与还原剂硼氢化钠物质的量比为1∶2.5、还原温度为303 K条件下,制备的Ru/Ben中Ru微晶尺寸为3.8 nm,Ru/Ben催化NH₃BH₃水解产氢的转化频率（TOF）为145 mol/（mol·min）;搅拌转速为450 r/min时,外扩散限制消除,产氢速率最大;产氢速率与Ru/Ben浓度成正比,催化剂界面反应是氨硼烷水解产氢反应的控速步骤,Ru/Ben催化NH₃BH₃水解产氢反应对催化剂浓度的反应级数为0.7;反应温度越高,氨硼烷向催化剂表面的传质速率越高、产物氢气及副产物偏硼酸钠从催化剂表面越易脱附,产氢速率越大。动力学计算表明,Ru/Ben催化NH₃BH₃水解产氢反应的产氢速率与氨硼烷浓度无关,活化能为15 kJ/mol。

关键词: 钌, 膨润土, 氨硼烷, 产氢

Abstract:

Ruthenium/bentonite（Ru/Ben） catalysts were prepared via an impregnation-reduction method using NaBH₄ as the reducing agent.The effects of ruthenium content,amount of reducing agent of sodium borohydride,reduction temperature and reaction conditions on the hydrolysis of ammonia borane（NH₃BH₃） catalyzed by Ru/Ben were investigated.The results showed that under the conditions of Ru loading of 0.3%（mass fraction）,the molar ratio of Ru to NaBH₄ was 1∶2.5,and the reduction temperature was 303 K,the size of Ru microcrystalline in Ru/Ben was 3.8 nm,and the conversion frequency（TOF） of Ru/Ben catalyzed hydrolysis of NH₃BH₃ was 145 mol/（mol·min）.When the stirring speed reached 450 r/min,external diffusion could be neglected,resulting in the highest reaction rate towards hydrogen generation.The rate of hydrogen production was directly proportional to the concentration of Ru/Ben.The interfacial reaction of catalyst was the decisive step in the hydrolysis of NH₃BH₃ to generate hydrogen.The order of Ru/Ben catalyzed hydrolysis of NH₃BH₃ to generate hydrogen was 0.7.The higher the reaction temperature,the higher the mass transfer rate of ammonia borane to the catalyst surface,the easier desorption of hydrogen and sodium metaborate from the catalyst surface,and the higher the hydrogen generation rate.The kinetic calculation showed that the hydrogen production rate of NH₃BH₃ hydrolysis catalyzed by Ru/Ben was independent of the concentration of aminoborane,and the activation energy was 15 kJ/mol.

Key words: Ru, bentonite, ammonia borane, hydrogen generation

中图分类号:

O643.36

陈凌霞,王琪,孙海杰,陈志浩,刘冉冉. 膨润土负载钌催化剂制备及其催化氨硼烷水解产氢研究[J]. 无机盐工业, 2021, 53(6): 199-204.

Chen Lingxia,Wang Qi,Sun Haijie,Chen Zhihao,Liu Ranran. Study on preparation of bentonite supported Ru catalysts and their performance for hydrogen generation from catalytic hydrolysis of ammonia borane[J]. Inorganic Chemicals Industry, 2021, 53(6): 199-204.

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催化剂	表观活化能/ （kJ·mol^-1）	催化剂	表观活化能/ （kJ·mol^-1）
Ru/g-C₃N₄^[23]	37	Ru/MIL-96^[27]	48
Ru/C^[24]	35	Ru/MIL-101^[28]	51
Ru/Graphene^[14]	12	Ru/micro HAP^[18]	58
Ru/Carbon^[15]	76	Ru/TiO₂^[29]	87
Ru/γ-Al₂O₃^[16]	67	Ru/Ce（OH）CO₃^[30]	60
Ru/Al₂O₃^[17]	48	Ru/HAP^[31]	44
Ru/MIL-41^[25]	42	Ru/Ben（本研究）	15
Ru/MIL-53^[26]	29

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