物理化学学报 >> 2014, Vol. 30 >> Issue (6): 1180-1186.doi: 10.3866/PKU.WHXB201404141

催化和表面科学 上一篇    下一篇

原位合成钴/还原氧化石墨烯纳米粒子催化氨硼烷制氢

杨宇雯1, 冯刚2, 卢章辉1, 胡娜1, 张飞1, 陈祥树1   

  1. 1 江西师范大学化学化工学院, 南昌330022;
    2 中国石化上海石油化工研究院, 上海201208
  • 收稿日期:2014-01-09 修回日期:2014-04-14 发布日期:2014-05-26
  • 通讯作者: 卢章辉,陈祥树 E-mail:luzh@jxnu.edu.cn;cxs66cn@jxnu.edu.cn
  • 基金资助:

    国家自然科学基金(21103074),江西省自然科学基金(20114BAB203010,20132BAB203014),江西省对外合作计划(20111BDH80023),江西省教育厅科技重点项目(GJJ14230),江西省研究生创新基金(YC2013-S105),江西师范大学青年英才培育计划资助项目,江西省青年科学家培养对象(20133BCB23011)及江西省赣鄱英才555 工程资助

In situ Synthesis of Reduced Graphene Oxide Supported Co Nanoparticles as Efficient Catalysts for Hydrogen Generation from NH3BH3

YANG Yu-Wen1, FENG Gang2, LU Zhang-Hui1, HU Na1, ZHANG Fei1, CHEN Xiang-Shu1   

  1. 1 College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, P. R. China;
    2 Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai 201208, P. R. China
  • Received:2014-01-09 Revised:2014-04-14 Published:2014-05-26
  • Contact: LU Zhang-Hui, CHEN Xiang-Shu E-mail:luzh@jxnu.edu.cn;cxs66cn@jxnu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21103074), Natural Science Foundation of Jiangxi Province, China (20114BAB203010, 20132BAB203014), Jiangxi Provincial Department of Science and Technology, China (20111BDH80023), Jiangxi Provincial Education Department, China (GJJ14230), Scientific Research Foundation of Graduate School of Jiangxi Province, China (YC2013-S105), Sponsored Program for Cultivating Youths of Outstanding Ability in Jiangxi Normal University, China, Young Scientist Foundation of Jiangxi Province, China (20133BCB23011), and "Gan-po talent 555" Project of Jiangxi Province, China.

摘要:

采用简单的原位还原合成方法,利用具有温和还原性能的氨硼烷作为还原剂,在室温下一步还原氧化石墨烯和氯化钴混合溶液制备了还原氧化石墨烯负载钴纳米复合材料催化剂. 利用所制备的钴/还原氧化石墨烯催化剂催化氨硼烷水解制氢,发现钴/还原氧化石墨烯具有优异的催化性能. 相对于没有负载的钴纳米粒子以及采用硼氢化钠作为还原剂制备的钴/还原氧化石墨烯催化剂,采用氨硼烷还原制备的钴/还原氧化石墨烯催化剂表现出更加优越的催化性能. 动力学测试表明,钴/还原氧化石墨烯催化氨硼烷水解反应为零级反应,同时钴/还原氧化石墨烯催化剂催化氨硼烷水解反应的活化能为27.10 kJ·mol-1,低于大部分已报道的其它催化剂,甚至一些贵金属催化剂的活化能. 钴/还原氧化石墨烯催化剂有着稳定的循环使用性,特别是其具有的磁性使得它能够直接从溶液中通过磁力回收,极具应用前景. 这种简单有效的合成方法有望推广到其它的金属-还原氧化石墨烯纳米复合材料体系.

关键词: 储能材料, 还原氧化石墨烯, 钴纳米粒子, 氨硼烷, 制氢

Abstract:

Cobalt nanoparticles (NPs) supported on reduced graphene oxide (RGO) were synthesized by a one-step in situ co-reduction of an aqueous solution of cobalt(Ⅱ) chloride and graphene oxide (GO) using ammonia borane (AB) as the sole reductant under ambient conditions. The as-synthesized Co/RGO catalysts exhibited high catalytic activity for the hydrolytic dehydrogenation of AB at room temperature. The assynthesized Co/RGO nanocatalysts exhibited much higher catalytic activity than the RGO-free Co counterpart. Compared with the nanocatalysts reduced by NaBH4, the Co/RGO nanocatalysts generated by the milder reductant AB exhibited superior catalytic activity. Moreover, kinetic studies indicate that the catalytic hydrolysis of AB by Co/RGO has zero order kinetics with respect to the substrate concentration. The hydrolysis activation energy is estimated to be about 27.10 kJ·mol-1, which is lower than most reported data for the same reaction conusing non-noble metal catalysts and some noble metal containing catalysts. Furthermore, the RGO-supported Co NPs show good recyclability and magnetic reusability for hydrogen generation from an aqueous solution of AB, which enables the practical reuse of the catalysts. Hence, this general method indicates that AB can be used as both a potential hydrogen storage material and an efficient reducing agent, and can be easily extended to the facile preparation of other RGO-based metallic systems.

Key words: Energy storage material, Reduced graphene oxide, Co nanoparticle, Ammonia borane, Hydrogen generation

MSC2000: 

  • O643