Interlayer Reaction of Thiosulfate in a Confined Region of Layered Double Hydroxides
Interlayer Reaction of Thiosulfate in a Confined Region of Layered Double Hydroxides
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DOI：
10.3866/pku.whxb201111243
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发表时间：
2012
影响因子：
10.9
通讯作者：
Wang Li-geng;Y. Ting;Li Yuan;Shi Wei;N. Zhe-ming
中科院分区：
文献类型：
--
作者：
Wang Li-geng;Y. Ting;Li Yuan;Shi Wei;N. Zhe-ming
将硫代硫酸盐阴离子（S2O2-3）插入到ZnAl层状双氢氧化物（LDH）中，讨论了其与六氰高铁酸盐（III）（Fe(CN)3-6）在LDH层间的封闭区域内的氧化反应。利用x射线衍射（XRD）和傅里叶变换红外光谱（FTIR）对中间态和最终产物进行了测量，氧化产物四硫酸盐（S4O2-6）溶解在溶液中，而还原产物六氰高铁酸盐（II）存在于LDH的中间层中。此外，在间歇模式下研究了该反应的动力学。研究了初始Fe(CN)3-6浓度、ZnAl-S2O3 LDH用量和反应温度对氧化反应的影响。反应遵循以Crank-Ginstling和Brounstein模型为代表的扩散控制过程，表观活化能为24.6 kJ。mol-1，大约是13.7 kJ。Mol-1比相同条件下的溶液反应少。采用分子动力学方法模拟了含水率对层间距的影响。仿真结果表明，该微反应器的尺寸在溶液环境中可以按一定的方向进行调节。根据实验结果和理论计算，提出了层间反应的机理。这种层状材料可以作为一种新型的纳米反应器来调节化学反应的速率。
The thiosulfate anion(S2O2-3) was intercalated into a ZnAl layered double hydroxide(LDH),and its oxidation reaction with hexacyanoferrate(III)(Fe(CN)3-6) in the confined region between the layers of LDH has been discussed.Based measurements of the intermediate state and final product using X-ray diffraction(XRD) and Fourier transform infrared(FTIR) spectroscopy,the oxidation product tetrathionate(S4O2-6) dissolved in solution,while the reduction product hexacyanoferrate(II) existed in the interlayer of the LDH.Furthermore,the kinetics of this reaction were investigated in batch mode.The influences of the initial Fe(CN)3-6 concentration,ZnAl-S2O3 LDH quantity,and reaction temperature on the oxidation reaction were studied.The reaction follows a diffusion-controlled process represented by Crank-Ginstling and Brounstein model with the apparent activation energy of 24.6 kJ.mol-1,which was about 13.7 kJ.mol-1 less than that of the solution reaction under the same conditions.The influence of water content on interlayer spacing was simulated by molecular dynamics.The simulation result shows that the size of this microreactor can be regulated in a certain orientation in the solution environment.From the experimental results and theoretical calculation,we propose a mechanism for the interlayer reaction.This layered material can be used as a novel nano-reactor to regulate the rate of chemical reactions.