Ag/MIL-101催化剂还原对硝基苯酚反应动力学

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

化工进展 ›› 2016, Vol. 35 ›› Issue (S2): 168-173.DOI: 10.16085/j.issn.1000-6613.2016.s2.028

Ag/MIL-101催化剂还原对硝基苯酚反应动力学

秦凤祥¹, 李凭力¹, 黄益平², 徐义明², 陆晓咏², 刘春江¹

1. 天津大学化工学院, 天津 300072;
2. 中建安装工程有限公司, 江苏南京 210023

收稿日期:2016-04-21 修回日期:2016-06-21 出版日期:2016-12-31 发布日期:2016-12-22
通讯作者: 秦凤祥(1987-),男,博士,工程师。E-mail:qinfeng137@163.com。

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

QIN Fengxiang¹, LI Pingli¹, HUANG Yiping², XU Yiming², LU Xiaoyong², LIU Chunjiang¹

1. School of Chemical Engineering, Tianjin University, Tianjin 300072, China;
2. China Construction Installation Engineering Co., Ltd., Nanjing 210023, Jiangsu, China

Received:2016-04-21 Revised:2016-06-21 Online:2016-12-31 Published:2016-12-22

摘要/Abstract

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

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

中图分类号:

TQ032.4

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.

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.

参考文献

[1] VALVEKENS P,VERMOORTELE F,DE VOS D.Metal-organic frameworks as catalysts:the role of metal active sites[J].Catal.Sci.& Tech.,2013,3(1):1435-1445.
[2] AIJAZ A,XU Qiang. Catalysis with metal nanoparticles immobilized within the pores of metal-organic frameworks[J]. J. Phys. Chem.Lett.,2014,5(8):1400-1411.
[3] ZENG Jie,ZHANG Qiang,CHEN Jingyi,et al.A comparison study of the catalytic properties of Au-based nanocages,nanoboxes,and nanoparticles[J].Nano.Lett.,2010,10(1):30-35.
[4] ESUMI K,ISONO R,YOSHIMURA T.Preparation of PAMAM-and PPI-metal(silver,platinum,and palladium)nanocomposites and their catalytic activities for reduction of 4-nitrophenol[J].Langmuir,2004,20(1):237-243.
[5] WUNDER S,LU Yan,ALBRECHT M,et al.Catalytic activity of faceted gold nanoparticles studied by a model reaction:evidence for substrate-induced surface restructuring[J].ACS Catalysis,2011,1(8):908-916.
[6] LASZLO K,PODKOSCIELNY P,DABROWSKI A. Heterogeneity of polymer-based active carbons in adsorption of aqueous solutions of phenol and 2,3,4-trichlorophenol[J]. Langmuir,2003,19(13):5287-5294.
[7] WUNDER S,POLZER F,Lu Yan,et al.Kinetic analysis of catalytic reduction of 4-nitrophenol by metallic nanoparticles immobilized in spherical polyelectrolyte brushes[J].J.Phys.Chem.C,2010,114(19):8814-8820.
[8] ANTONELS N C,MEIJBOOM R.Preparation of well-defined dendrimer encapsulated ruthenium nanoparticles and their evaluation in the reduction of 4-nitrophenol according to the Langmuir-Hinshelwood approach[J].Langmuir,2013,29(44):13433-13442.
[9] GUELLA G,PATTON B,MIOTELLO A.Kinetic features of the platinum catalyzed hydrolysis of sodium borohydride from 11B NMR measurements[J].J.Phys.Chem.C,2007,111(50):18744-18750.
[10] LIU B H,LI Z P.A review:hydrogen generation from borohydride hydrolysis reaction[J].Journal of Power Sources,2009,187(2):527-534.

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Ag/MIL-101催化剂还原对硝基苯酚反应动力学

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

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