Kinetic analysis of catalytic reduction of 4-nitrophenol by Ag/MIL-101

doi:10.16085/j.issn.1000-6613.2016.s2.028

Abstract

Abstract: Highly dispersed and ultrafine Ag/MIL-101 was prepared by double solvent method(DSM).The size of the nanoparticles was about 1.9nm±0.6nm and the total surface area of nanoparticles could be determined precisely.The catalytic activity was investigated by photo-metrically monitoring the reduction of 4-nitrophenol(4-NP) by an excess of NaBH₄ in the presence of the nanoparticles.The kinetic data could be modelled to the Langmuir-Hinshelwood equation.The apparent reaction rate,k_app was found to be related to the total surface of the nanoparticles,to the kinetic constant,k,related to the rate-determining step,and to the adsorption constants K_4-NP and K_BH₄ for 4-NP and borohydride,respectively.The activation energy was obtained by fitting k_app obtained at different temperatures.The study also showed that the induction time,t₀,is directly related to the reaction rate constant,k,of the controlling step.

Key words: catalyst support, nanoparticles, reaction kinetics, catalytic mechanism

摘要： 采用双溶剂浸渍法制备得到了粒径为1.9nm±0.6nm高分散性的Ag/MIL-101催化剂。考察了该催化剂在过量NaBH₄存在下，还原对硝基苯酚生成对氨基苯酚反应中的催化性能。本文通过研究催化剂浓度、底物浓度和温度对催化活性的影响，获得不同条件下的表观反应速率常数k_app，采用Langmuir-Hinshelwood吸附反应模型对所得动力学数据进行拟合，获得本征反应速率常数k，底物吸附常数K_4-NP和K_BH₄，底物吸附焓、熵以及真实活化能E_A，k等热力学参数。研究表明，诱导时间t₀直接与该反应速率控制步骤的反应速率常数k有关。

关键词: 催化剂载体, 纳米粒子, 反应动力学, 催化机理

CLC Number:

TQ032.4

QIN Fengxiang, LI Pingli, HUANG Yiping, XU Yiming, LU Xiaoyong, LIU Chunjiang. Kinetic analysis of catalytic reduction of 4-nitrophenol by Ag/MIL-101[J]. Chemical Industry and Engineering Progree, 2016, 35(S2): 168-173.

秦凤祥, 李凭力, 黄益平, 徐义明, 陆晓咏, 刘春江. Ag/MIL-101催化剂还原对硝基苯酚反应动力学[J]. 化工进展, 2016, 35(S2): 168-173.

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