Intracrystalline diffusion in Metal Organic Framework during heterogeneous catalysis: Influence of particle size on the activity of MIL-100 (Fe) for oxidation reactions

被引：75
作者：
Dhakshinamoorthy, Amarajothi [1 ,2 ]
Alvaro, Mercedes [1 ,2 ]
Hwang, Young Kyu [3 ]
Seo, You-Kyong [3 ]
Corma, Avelino [1 ,2 ]
Garcia, Hermenegildo [1 ,2 ]
机构：
[1] Univ Politecn Valencia, Inst Univ Tecnol Quim CSIC UPV, Valencia 46022, Spain
[2] Univ Politecn Valencia, Dept Quim, Valencia 46022, Spain
[3] Korea Res Inst Chem Technol, Res Grp Nanocatalyst, Biorefinery Res Ctr, Taejon 305600, South Korea
来源：
DALTON TRANSACTIONS | 2011年 / 40卷 / 40期
关键词：
AEROBIC OXIDATION; MICROWAVE SYNTHESIS; ZEOLITES; MEMBRANES; SORPTION; AMINES; MOFS; CU;
D O I：
10.1039/c1dt10826c
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Three MIL-100 (Fe) samples differing in average crystal size (from 60-70 to >400 nm) have been synthesized by microwave heating using three HF/Fe(3+) ratios. Oxidation of diphenylmethane with tert-butylhydroperoxide (TBHP) and thiophenol with oxygen are catalyzed by three MIL-100 (Fe) samples with similar reaction rates regardless of its average particle size. In contrast, the activity of the three MIL-100 (Fe) samples for the oxidation of bulky triphenylmethane by TBHP largely depends on the average crystal size of the sample: the smaller the average particle size, the larger the initial reaction rate of triphenylmethane oxidation. These results show that diffusion limitation takes place on MOF catalysis depending on the substrate size and provides indirect evidence that these reactions take place inside the intracrystalline space of the porous catalysts.
引用
收藏
页码：10719 / 10724
页数：6
相关论文
共 31 条
[1]   Probing the Lewis acidity and catalytic activity of the metal-organic framework [Cu3(btc)2] (BTC = benzene-1,3,5-tricarboxylate) [J].
Alaerts, Luc ;
Seguin, Etienne ;
Poelman, Hilde ;
Thibault-Starzyk, Frederic ;
Jacobs, Pierre A. ;
De Vos, Dirk E. .
CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (28) :7353-7363
[2]   Zeolite membranes -: state of their development and perspective [J].
Caro, J ;
Noack, M ;
Kölsch, P ;
Schäfer, R .
MICROPOROUS AND MESOPOROUS MATERIALS, 2000, 38 (01) :3-24
[3]   Supramolecular self-assembled molecules as organic directing agent for synthesis of zeolites [J].
Corma, A ;
Rey, F ;
Rius, J ;
Sabater, MJ ;
Valencia, S .
NATURE, 2004, 431 (7006) :287-290
[4]   A large-cavity zeolite with wide pore windows and potential as an oil refining catalyst [J].
Corma, A ;
Díaz-Cabañas, M ;
Martínez-Triguero, J ;
Rey, F ;
Rius, J .
NATURE, 2002, 418 (6897) :514-517
[5]   Engineering Metal Organic Frameworks for Heterogeneous Catalysis [J].
Corma, A. ;
Garcia, H. ;
Llabres i Xamena, F. X. L. I. .
CHEMICAL REVIEWS, 2010, 110 (08) :4606-4655
[6]   Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer-Villiger oxidations [J].
Corma, A ;
Nemeth, LT ;
Renz, M ;
Valencia, S .
NATURE, 2001, 412 (6845) :423-425
[7]   High-throughput synthesis and catalytic properties of a molecular sieve with 18-and 10-member rings [J].
Corma, Avelino ;
Diaz-Cabanas, Maria J. ;
Luis Jorda, Jose ;
Martinez, Cristina ;
Moliner, Manuel .
NATURE, 2006, 443 (7113) :842-845
[8]   Cu and Au Metal-Organic Frameworks Bridge the Gap between Homogeneous and Heterogeneous Catalysts for Alkene Cyclopropanation Reactions [J].
Corma, Avelino ;
Iglesias, Marta ;
Llabres i Xamena, Francese X. ;
Sanchez, Felix .
CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (32) :9789-9795
[9]   Delineating similarities and dissimilarities in the use of metal organic frameworks and zeolites as heterogeneous catalysts for organic reactions [J].
Dhakshinamoorthy, Amarajothi ;
Alvaro, Mercedes ;
Corma, Avelino ;
Garcia, Hermenegildo .
DALTON TRANSACTIONS, 2011, 40 (24) :6344-6360
[10]   Atmospheric-Pressure, Liquid-Phase, Selective Aerobic Oxidation of Alkanes Catalysed by Metal-Organic Frameworks [J].
Dhakshinamoorthy, Amarajothi ;
Alvaro, Mercedes ;
Garcia, Hermenegildo .
CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (22) :6256-6262
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