广西师范大学学报（自然科学版） ›› 2021, Vol. 39 ›› Issue (3): 92-101.doi: 10.16088/j.issn.1001-6600.2020030904

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Ru/ZrO2催化剂催化氨硼烷水解产氢研究

孙海杰1, 刘欣改1, 陈志浩2*, 陈凌霞1*, 张路1, 梅洋洋1   

  1. 1.郑州师范学院 化学化工学院, 河南 郑州 450044;
    2.中国烟草总公司郑州烟草研究院, 河南 郑州 450001
  • 收稿日期:2020-03-09 修回日期:2020-07-23 发布日期:2021-05-13
  • 通讯作者: 陈凌霞(1968—),女,河南郑州人,郑州师范学院教授,博士。E-mail: clingxia@vip.163.com。 陈志浩(1986—),男,河南郑州人,中国烟草总公司郑州烟草研究院工程师,博士。E-mail: chenzh@ztir.com.cn
  • 基金资助:
    国家自然科学基金(21908203); 国家级大学生创新创业训练计划项目(201912949002); 河南省科技攻关项目(192102210139); 河南省高等学校青年骨干教师培养计划(2019GGJS252); 河南省高等学校重点科研项目(18A150018); 郑州师范学院环境催化科研创新团队项目(702010)

Performance of Ru/ZrO2 Catalysts for Hydrogen Generation from Catalytic Hydrolysis of Ammonia Borane

SUN Haijie1, LIU Xingai1, CHEN Zhihao2*, CHEN Lingxia1*, ZHANG Lu1, MEI Yangyang1   

  1. 1. School of Chemistry and Chemical Engineering, Zhengzhou Normal University, Zhengzhou Henan 450044, China;
    2. Zhengzhou Tobacco Research Institute, China National Tobacco Corporation, Zhengzhou Henan 450001, China
  • Received:2020-03-09 Revised:2020-07-23 Published:2021-05-13

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摘要： 采用浸渍-化学还原法制备了Ru/ZrO2催化剂,并考察了钌负载量、硼氢化钠的用量、还原温度以及反应条件对催化剂Ru/ZrO2催化BH3NH3水解产氢的影响。结果表明,在钌的负载量为0.4%,钌与还原剂硼氢化钠的物质的量比为1∶1.6,还原温度为303 K时,Ru微晶尺寸为3.2 nm,Ru/ZrO2催化剂催化BH3NH3水解产氢的转化频率TOF(turn over frequency)为38.4 mol/mol(Ru)·min。搅拌转速为450 r/min时,外扩散限制消除,产氢速率最大;产氢速率与催化剂用量成正比,氨硼烷水解产氢反应由催化剂界面反应控制;随着反应温度的升高,氨硼烷产氢速率系数增大,副产物偏硼酸钠越易从催化剂表面脱附,产氢速率越大。反应动力学计算表明Ru/ZrO2催化剂催化BH3NH3水解产氢速率与氨硼烷浓度无关,活化能为66 kJ/mol。

关键词: 钌, 二氧化锆, 催化剂, 氨硼烷, 产氢

Abstract: ZrO2 supported Ru catalysts were synthesized with an impregnation-chemical reduction method using NaBH4 as the reducing agent. The prepared catalysts were evaluated for the hydrogen generation via catalytic hydrolysis of BH3NH3. Effect of catalytic activity was investigated by varying the impregnated Ru loading, amount of reducing agent, reduction temperature as well as the reaction conditions. It was found that the TOF (Turnover Frequency) of 38.4 mol/mol(Ru)·min was achieved by adjusting Ru loading to 0.4 at 303 K of reaction temperature, while the molar ratio of Ru to NaBH4 was 1:1.6. The Ru particle size of 3.2 nm was observed. Moreover, when the stirring speed was 450 r/min, external diffusion could be eliminated, leading to the highest reaction rate towards hydrogen generation. In addition, catalytic activity increased with enhancing the amount of used catalyst, indicating that catalytic hydrolysis of BH3NH3 towards hydrogen production was controlled by the interfacial reaction over the catalyst surface. Furthermore, with the reaction temperature increasing, it gets more suitable for the desorption of NaBO2, the side product of hydrolysis of BH3NH3, from the catalyst surface. This results in the enhancement of the reaction rate towards hydrogen formation. According to the kinetic calculation, it suggests that the reaction rate of hydrolysis of BH3NH3 towards hydrogen generation over Ru/ZrO2 is irrelevant to the concentration of BH3NH3. The activation energy is 66 kJ/mol.

Key words: Ru, ZrO2, catalyst, ammonia borane, hydrogen generation

中图分类号: 

  • TQ116
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