摘要
该文探究了原位还原第四周期过渡金属盐(FeCl_(2)、CoCl_(2)、NiCl_(2)、CuCl_(2)和ZnCl_(2))催化氨硼烷水解产氢性能,发现它们催化氨硼烷水解产氢活性由高至低依次为CuCl_(2)>CoCl_(2)>NiCl_(2)>FeCl_(2)>ZnCl_(2),这些盐催化氨硼烷水解产氢速率与它们及其相应金属组成电对的标准还原电极电势呈近似线性关系,这说明标准还原电势越高,相应金属盐越易被还原为金属,对应金属催化剂催化氨硼烷水解产氢的活性越高.在原位还原CuCl_(2)、CoCl_(2)和NiCl_(2)催化剂中分别存在金属Cu、Co和Ni物相,催化氨硼烷水解产氢速率较快.原位还原CoCl_(2)、NiCl_(2)和CuCl_(2)催化氨硼烷水解产氢的最佳搅拌速率分别为210、480和210 r·min^(-1),最佳用量分别为0.0010、0.0005和0.0020 mol,转化频率(TOF)分别为104.9 mol H_(2)·mol^(-1)Co·min^(-1)、21.6 mol H_(2)·mol^(-1)Ni·min^(-1)和217.2 mol H_(2)·mol^(-1)Cu·min^(-1).动力学计算结果表明原位还原CoCl_(2)、NiCl_(2)和CuCl_(2)催化氨硼烷水解产氢的活化能分别为35、65和6 kJ·mol^(-1).原位还原CoCl_(2)催化剂具有磁性,易与反应液分离,且团聚不明显,循环使用性能显著优于原位还原的CuCl_(2).
The fourth period transition metal catalysts are synthesized by in-situ reduction of FeCl_(2),CoCl_(2),NiCl_(2),CuCl_(2)and ZnCl_(2).And the prepared catalysts are evaluated for hydrolysis of BH3NH3 towards hydrogen production.It is found that the catalytic activity over the tested transition metal catalysts is ranked as CuCl_(2)>CoCl_(2)>NiCl_(2)>FeCl_(2)>ZnCl_(2),which depends linearly on their corresponding standard electric potential and indicates that higher standard electric potential leads to the easier reduction of the corresponding metal salt.This further improves the catalytic activity of hydrolysis of BH3NH3 towards hydrogen production.When 0.0010 mol CoCl_(2),0.0005 mol NiCl_(2)and 0.0020 mol CuCl_(2)are in-situ reduced and applied for the catalytic experiments,the optimum stirring rate is 210,480 and 210 rpm,respectively.And the TOF obtained over Co,Ni and Cu catalysts is 104.9 mol H_(2)·mol^(-1)Co·min^(-1),21.6 mol H_(2)·mol^(-1)Ni·min^(-1)and 217.2 mol H_(2)·mol^(-1) Cu·min^(-1),respectively.According to the kinetic calculation,the Ea over the in-situ reduced CoCl_(2),NiCl_(2) and CuCl_(2) is 35,65 and 6 kJ·mol^(-1),respectively.Furthermore,magnetic properties are detected over the in-situ reduced CoCl_(2) catalyst,which is easily separated from reaction environments.And no obvious aggregation is observed.More importantly,the reusability of Co catalyst is clearly superior to that observed over in-situ reduced CuCl_(2) catalyst.
作者
孙海杰
王琪
陈志浩
陈凌霞
秦皓
彭智昆
SUN Haijie;WANG Qi;CHEN Zhihao;CHEN Lingxia;QIN Hao;PENG Zhikun(School of Chemistry and Chemical Engineering,Zhengzhou Normal University,Zhengzhou Henan 450044,China;Zhengzhou Tobacco Research Institute,China National Tobacco Corporation,Zhengzhou Henan 450001,China;Henan Institutes of Advanced Technology,Zhengzhou University,Zhengzhou Henan 450003,China)
出处
《江西师范大学学报（自然科学版）》
CAS
北大核心
2021年第3期226-232,共7页
Journal of Jiangxi Normal University(Natural Science Edition)
基金
国家自然科学基金(201908203)
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)
河南省大学生创新创业训练计划(S202012949001)
河南省高等学校重点科研课题(18A150018)
郑州师范学院环境催化科研创新团队基金(702010)资助项目.
关键词
氨硼烷
氢气
过渡金属
钴
镍
铜
BH_(3)NH_(3)
hydrogen generation
transition metals
Co
Ni
Cu
作者简介
孙海杰(1982—),男,河南郑州人,副教授,博士,主要从事物理化学、催化化学研究.E-mail:sunhaijie406@163.com;通讯作者:陈志浩(1986—),男,河南郑州人,高级工程师,博士,主要从事物理化学、多相催化及化学工艺方面的研究.E-mail:chenzh@ztir.com.cn;通讯作者:彭智昆(1988—),男,河南安阳人,讲师,博士,主要从事物理化学及多相催化研究.E-mail:pengzhikun@zzu.edu.cn。
