[1]孙海杰,刘欣改,陈志浩*,等.羟基磷灰石负载Ru催化氨硼烷产氢性能研究[J].江西师范大学学报(自然科学版),2020,(04):424-428.[doi:10.16357/j.cnki.issn1000-5862.2020.04.15]
　SUN Haijie,LIU Xingai,CHEN Zhihao*,et al.The Performance of Ru/HAP Catalysts for Hydrogen Generation from Catalytic Hydrolysis of Ammonia Borane[J].Journal of Jiangxi Normal University:Natural Science Edition,2020,(04):424-428.[doi:10.16357/j.cnki.issn1000-5862.2020.04.15]
点击复制

羟基磷灰石负载Ru催化氨硼烷产氢性能研究()
分享到：

《江西师范大学学报》（自然科学版）[ISSN:1006-6977/CN:61-1281/TN]

卷:
期数:
2020年04期
页码:
424-428
栏目:
新能源材料研究
出版日期:
2020-08-10

文章信息/Info

Title:
The Performance of Ru/HAP Catalysts for Hydrogen Generation from Catalytic Hydrolysis of Ammonia Borane
文章编号:
1000-5862(2020)04-0424-05
作者:
孙海杰1; 刘欣改1; 陈志浩2*; 陈凌霞1*; 刘冉冉1; 梅洋洋1
1.郑州师范学院化学化工学院,河南 郑州 450044; 2.中国烟草研究院郑州烟草研究院,河南 郑州 450001
Author(s):
SUN Haijie1; LIU Xingai1; CHEN Zhihao2*; CHEN Lingxia1*; LIU Ranran1; MEI Yangyang1
1.School of Chemistry and Chemical Engineering,Zhengzhou University,Zhengzhou Henan 450044,China; 2.Zhengzhou Tobacco Research Institute,China Tobacco,Zhengzhou Henan 450001,China
关键词:
Ru;  羟基磷灰石;  氨硼烷;  产氢
Keywords:
Ru;  hydroxyapatite;  ammonia borane;  hydrogen generation
分类号:
TQ 127.2
DOI:
10.16357/j.cnki.issn1000-5862.2020.04.15
文献标志码:
A
摘要:
采用浸渍-还原法制备了Ru/羟基磷灰石(HAP)催化剂,并考察了Ru负载量、还原剂硼氢化钠的用量、还原温度以及反应条件对催化剂Ru/HAP催化BH3NH3水解产氢的影响.结果表明:当Ru的负载质量分数为0.3%、Ru与还原剂硼氢化钠的物质的量比为1.0:2.2、还原温度为303 K时,Ru/HAP催化剂催化BH3NH3水解产氢的转化频率TOF为125 mol H2·mol-1Ru·min-1.当搅拌转速为450 r·min-1时,外扩散限制消除,产氢速率最大.产氢速率与催化剂浓度成正比,氨硼烷水解产氢反应由催化剂界面反应控制,Ru/HAP催化剂催化BH3NH3水解产氢反应对催化剂浓度反应级数为0.8.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,产氢速率逐渐增大.反应动力学计算表明Ru/HAP催化剂催化BH3NH3水解产氢反应对氨硼烷浓度为0级反应,活化能为44 kJ·mol-1.
Abstract:
Hydroxyapatite(HAP)supported Ru catalysts are synthesized with an impregnation-reduction method using NaBH4 as the reducing agent.The prepared catalysts are evaluated for the hydrogen generation via catalytic hydrolysis of BH3NH3.Effect of catalytic activity is investigated by varying the impregnated Ru loading,amount of reducing agent,reduction temperature as well as the reaction conditions.It is found that the TOF of 125 mol H2·mol-1Ru·min-1 is achieved by adjusting Ru loading to be 0.3% at 303 K of reaction temperature,while the molar ratio of Ru:NaBH4 is 1.0:2.2.Moreover,when the stirring speed is enhanced to be 450 r·min-1,external diffusion can be eliminated,leading to the highest reaction rate towards hydrogen generation.In addition,catalytic activity increases with enhancing the amount of used catalyst,indicating that catalytic hydrolysis of BH3NH3 towards hydrogen production is controlled by the interfacial reaction over the catalyst surface.And the reaction order of catalytic hydrolysis of BH3NH3 to the concentration of applied catalyst is calculated to be 0.8.Furthermore,with increasing the reaction temperature,it gets more suitable for the desorption of NaBO2,the side product of hydrolysis of BH3NH3,from the catalyst surface.This leads to the enhancement of the reaction rate towards hydrogen formation.According to the kinetic calculation,it suggests that the hydrolysis of BH3NH3 towards hydrogen generation over Ru/HAP is a zero order reaction in responding to the concentration of BH3NH3.The activation energy is 44 kJ·mol-1.

参考文献/References:

[1] 孙海杰,陈凌霞,张玉凤,等.钴-硼/二氧化锆催化剂催化硼氢化钠水解制氢研究[J].无机盐工业,2019,51(3):72-76.
[2] 孙海杰,陈凌霞,黄振旭,等.第四周期过渡金属催化硼氢化钠水解制氢研究[J].无机盐工业,2017,49(5):14-17.
[3] 孙海杰,黄振旭,王雅苹,等.非晶态合金Ru-B/ZrO2催化剂催化硼氢化钠水解制氢性能的研究[J].化工新型材料,2018,46(1):102-105.
[4] 张磊,涂倩,陈学年,等.氨硼烷释氢纳米金属催化剂研究[J].化学进展,2014,26(5):750-756.
[5] 李燕,邓雨真,俞晶灵,等.氨硼烷分解制氢及其再生的研究进展[J].化工进展,2019,38(12):5330-5338.
[6] 杨晓婧,尚伟,李兰兰,等.金属催化氨硼烷研究进展[J].电源技术,2014,38(7):1387-1389.
[7] 张帅,王斯瑶,姜召,等.静电纺丝技术在氨硼烷水解脱氢催化剂制备中的应用[J].化工进展,2019,38(7):3194-3206.
[8] 杨兰,罗威,程功臻.氨硼烷水解制氢的研究进展[J].大学化学,2014,26(6):1-10.
[9] 陈健民,卢章辉,熊丽华.Ru/Ce(OH)CO3纳米复合材料催化氨硼烷水解产氢[J].无机化学学报,2016,32(10):1816-1824.
[10] 桑婉璐,李兰兰,高若源,等.氨硼烷水解制氢催化剂载体的研究进展[J].材料导报,2017,31(9):27-33.
[11] Zhang Peng,Wu Tianbin,Jiang Tao,et al.Ru-Zn supported on hydroxyapatite as an effective catalyst for partial hydrogenation of benzene[J].Green Chem,2013,15:152-159.
[12] 孙海杰,陈凌霞,黄振旭,等.还原介质和还原温度对Ru-Zn催化苯选择加氢制环己烯性能的影响[J].化工进展,2017,36(8):2962-2970.
[13] Cao Nan,Luo Wei,Cheng Gongzhen,et al.One-step synthesis of grapheme supported Ru nanoparticles as efficient catalysts for hydrolytic dehydrogenation of ammnonia borane[J].Int J Hydrogen Energy,2013,38(27):11964-11972.
[14] Basua S,Brockmana A,Gagare P,et al.Chemical kinetics of Ru-catalyzed ammonia borane hydrolysis[J].J Power Sources,2009,188(1):238-243.
[15] Hu Sungcheng,Chen Yuwen.Partial Hydrogenation of benzene to cyclohexene on ruthenium catalysts supported on La2O3-ZnO binary oxides[J].Ind Eng Chem Res,1997,36(12):5153-5159.
[16] 朱玉玲,郑修成,刘蒲.磁性花生壳负载钯催化剂的制备及催化氨硼烷释氢性能[J].信阳师范学院学报:自然科学版,2019,32(2):276-280.
[17] Dong Hua,Yang Hanxi,Ai Xinping,et al.Hydrogen production from catalytic hydrolysis of sodium borohydride solution using nickel boride catalyst[J].Int J Hydrogen Energy,2003,28(10):1095-1100.
[18] Giovanni P R,Umit B D,Philippe M,et al.Faicile synthesis by polyol method of a ruthenium catalyst supported on γ-Al2O3 for hydrolytic dehydrogenation of ammonia borane[J].Catal Today,2011,170(1):85-92.
[19] Can H,Metin Ö.A facile synthesis of early monodisperse ruthenium nanoparticles and their catalysis in the hydrolytic dehydrogenation of ammonia borane for chemical hydrogen storage[J].Appl Catal B:Environmental,2012,125(3):304-310.
[20] Kohsuke M,Kohei M,Hiromi Y,et al.Ru and Ru-Ni nanoparticles on TiO2 support as extremely active catalysts for hydrogen production from ammonia-borane[J].ACS Catal,2016,6(5):3128-3135.

备注/Memo

备注/Memo:
收稿日期:2020-02-05
基金项目:国家自然科学基金(21908203),国家级大学生创新创业训练计划(201912949002),河南省科技攻关课题(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课题(18A150018)和郑州师范学院环境催化科研创新团队基金(702010)资助项目.
作者简介:孙海杰(1982-),男,河南长葛人,副教授,博士,主要从事物理化学和催化化学研究.E-mail:sunhaijie406
更新日期/Last Update: 2020-08-10