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
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
[11]   Aerobic Oxidation of Benzylic Alcohols Catalyzed by Metal-Organic Frameworks Assisted by TEMPO [J].
Dhakshinamoorthy, Amarajothi ;
Alvaro, Mercedes ;
Garcia, Hermenegildo .
ACS CATALYSIS, 2011, 1 (01) :48-53
[12]   Metal Organic Frameworks as Solid Acid Catalysts for Acetalization of Aldehydes with Methanol [J].
Dhakshinamoorthy, Amarajothi ;
Alvaro, Mercedes ;
Garcia, Hermenegildo .
ADVANCED SYNTHESIS & CATALYSIS, 2010, 352 (17) :3022-3030
[13]   Aerobic Oxidation of Benzyl Amines to Benzyl Imines Catalyzed by Metal-Organic Framework Solids [J].
Dhakshinamoorthy, Amarajothi ;
Alvaro, Mercedes ;
Garcia, Hermenegildo .
CHEMCATCHEM, 2010, 2 (11) :1438-1443
[14]   Aerobic oxidation of thiols to disulfides using iron metal-organic frameworks as solid redox catalysts [J].
Dhakshinamoorthy, Amarajothi ;
Alvaro, Mercedes ;
Garcia, Hermenegildo .
CHEMICAL COMMUNICATIONS, 2010, 46 (35) :6476-6478
[15]   Metal organic frameworks as heterogeneous catalysts for the selective N-methylation of aromatic primary amines with dimethyl carbonate [J].
Dhakshinamoorthy, Amarajothi ;
Alvaro, Mercedes ;
Garcia, Hermenegildo .
APPLIED CATALYSIS A-GENERAL, 2010, 378 (01) :19-25
[16]   Claisen-Schmidt Condensation Catalyzed by Metal-Organic Frameworks [J].
Dhakshinamoorthy, Amarajothi ;
Alvaro, Mercedes ;
Garcia, Hermenegildo .
ADVANCED SYNTHESIS & CATALYSIS, 2010, 352 (04) :711-717
[17]   Metal organic frameworks as efficient heterogeneous catalysts for the oxidation of benzylic compounds with t-butylhydroperoxide [J].
Dhakshinamoorthy, Amarajothi ;
Alvaro, Mercedes ;
Garcia, Hermenegildo .
JOURNAL OF CATALYSIS, 2009, 267 (01) :1-4
[18]   Metal-Organic Frameworks: Opportunities for Catalysis [J].
Farrusseng, David ;
Aguado, Sonia ;
Pinel, Catherine .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (41) :7502-7513
[19]   SYNTHESIS AND CHARACTERIZATION OF ZEOLITE (MFI) MEMBRANES ON POROUS CERAMIC SUPPORTS [J].
GEUS, ER ;
DENEXTER, MJ ;
VANBEKKUM, H .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1992, 88 (20) :3101-3109
[20]   Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate with large pores [J].
Horcajada, Patricia ;
Surble, Suzy ;
Serre, Christian ;
Hong, Do-Young ;
Seo, You-Kyong ;
Chang, Jong-San ;
Greneche, Jean-Marc ;
Margiolaki, Irene ;
Ferey, Gerard .
CHEMICAL COMMUNICATIONS, 2007, (27) :2820-2822