铋系含氧酸盐改性镁水解制氢的动/热力学研究  

Kinetic/thermodynamic study on improved hydrolysis hydrogen generation of Mg-doped bismuth series oxysalt

作　　者：林杰 刘佳溪 孙立贤[1] 徐芬[1] 罗玉梅 夏永鹏[1] 张晨晨 程日光 魏胜 黄鹏儒 李彬 张可翔 蔡丹 Jie Lin;Jiaxi Liu;Lixian Sun;Fen Xu;Yumei Luo;Yongpeng Xia;Chenchen Zhang;Riguang Cheng;Sheng Wei;Pengru Huang;Bin Li;Kexiang Zhang;Dan Cai(Guangxi Key Laboratory of Information Materials&Guangxi Collaborative Innovation Centre of Structure and Property for New Energy and Materials,School of Material Science and Engineering,Guilin University of Electronic Technology,Guilin 541004,China)

机构地区：[1]广西电子信息材料构效关系重点实验室,广西新能源材料结构与性能协同创新中心,桂林电子科技大学材料科学与工程学院,桂林541004

出　　处：《中国科学：化学》2022年第5期689-700,共12页SCIENTIA SINICA Chimica

基　　金：国家重点基础研究发展计划(编号:2018YFB1502103,2018YFB1502105);国家自然科学基金(编号:U20A20237,51863005,51462006,51102230,52101245,51871065,51971068);广西八桂学者基金;中德国际合作项目(编号:GZ1528);广西创新驱动发展专项(编号:AA19182014,AD17195073,AA17202030-1);广西信息材料重点实验室(编号:201009-Z,211017-K,211014-K,211016-K,211022-K,211023-K,201016K)资助项目。

摘　　要：Mg基制氢材料具有来源广泛、反应温和、工艺简单、安全可控、理论产氢量高等优势,是当今的研究热点.本文提出采用高能球磨方法制备Mg-Bi系含氧酸盐Bi_(x)M_(y)O_(z)(M=Ti,V,Cr,Mo,W)复合材料以改善Mg水解制氢性能.本工作研究发现,掺杂Bi_(2)Mo O_(6)的Mg基复合制氢材料具有较好的性能,Mg-7 wt%Bi_(2)Mo O_(6)在298.15 K的最大产氢速率为756.1 m L g^(-1)min(-1).通过引入多壁碳纳米管(CNTs)可以进一步改善Mg-Bi_(2)Mo O_(6)的产氢性能,Mg-7 wt%Bi_(2)Mo O_(6)/CNTs的最大产氢速率达2172.4 m L g^(-1)min(-1),产氢活化能下降至23.6 k J mol^(-1).X光电子能谱(XPS)分析表明Bi_(2)Mo O_(6)/CNTs与Mg在球磨过程中发生固相反应生成Bi单质.密度泛函理论(DFT)计算揭示Bi原子掺杂可改变Mg的局域电荷分布,增强Mg对H_(2)O的吸附能,并降低H_(2)O解离后H原子的吸附能,促进水解反应进行.Study of high efficiency hydrogen production materials has attracted many researchers’attention.Mg-based hydrogen production material has the advantages of wide sources,mild reaction,simple process,safety control,and high hydrogen production capacity.In this article,Mg was doped with bismuth series oxysalt Bi_(x)M_(y)O_(z)(M=Ti,V,Cr,Mo,W)by high energy ball milling method to improve the performance of hydrolytic hydrogen generation for the first time.It was found that Bi_(2)Mo O_(6)/CNTs enhanced the hydrogen generation performance of Mg and increased the initial hydrogen generation rate.The optimal hydrogen generation rate increased to 2172.4 m L g^(-1)min(-1),and the related activation energy decreased to 23.6 k J mol^(-1).Density functional theory(DFT)calculation found that doped Bi atom enhanced the adsorption of H_(2)O on Mg and reduced the adsorption of H atom by changing the local charge distribution,thus promoting the hydrolysis reaction.

关 键 词：水解制氢 Mg 铋系含氧酸盐 动力学 热力学 

分 类 号：TQ116.2[化学工程—无机化工]