Liquid phase oxidation of alkanes using Cu/Co-perchlorophthalocyanine immobilized MCM-41 under mild reaction conditions

被引:35
作者
Karandikar, P [1 ]
Chandwadkar, AJ [1 ]
Agashe, M [1 ]
Ramgir, NS [1 ]
Sivasanker, S [1 ]
机构
[1] Natl Chem Lab, Catalysis Div, Pune 411008, Maharashtra, India
关键词
MCM-41; immobilization; dispersion; Cu/Co-AM(PS); alkane oxidation; axo-metal species;
D O I
10.1016/j.apcata.2005.09.012
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Amino-functionalized MCM-41 (NH2-MCM-41) was used to immobilize CU/CO-Cl16PC complex, i.e. Cu/Co-AM(PS) for liquid phase oxidation of alkanes under mild reaction conditions. Higher rates of reaction and better catalytic activity values were obtained for Cu/Co-AM(PS) as compared to Cu/Co-Cl16PC grafted on (i) amino-functionalized SiO2 [Cu/Co-ASiO(2)] and (ii) non-functionalized MCM-41 [Cu/Co-M(l)] catalysts along with neat metal complex under identical conditions. The catalysts were evaluated by comparing two different oxidants: (i) TBHP and (ii) O-2/aldehyde. The rate of conversion and percent selectivity differ for the above two oxidants due to differences in stability of radical species and in their homolytic/heterolytic pathways. The homolytic dissociation of oxygen favors a higher rate of conversion in the case of TBHP, whereas the heterolytic mechanism favors a higher selectivity for cyclohexanone in the case Of O-2/aldehyde. The catalysts were characterized by XRD, MAS NMR, N-2-adsorption, microanalysis, UV-vis, FTIR and cyclic voltammetry. The UV-vis spectra reveal a blue shift for the metal phthalocyanine-immobilized samples, indicating unimolecular dispersion of metal complex within the channels of MCM-41. Cyclic voltammetry results suggest some coordinative interaction of the amino group of NH2-MCM-41 with the metal on grafting with the complex. (c) 2005 Elsevier B.V. All rights reserved.
引用
收藏
页码:220 / 230
页数:11
相关论文
共 24 条
[1]   Cu2+-phthalocyanine and Co2+-perfluorophthalocyanine incorporated inside Y faujasite and mesoporous MCM-41 as heterogeneous catalysts for the oxidation of cyclohexane [J].
Armengol, E ;
Corma, A ;
Fornés, V ;
García, H ;
Primo, J .
APPLIED CATALYSIS A-GENERAL, 1999, 181 (02) :305-312
[2]   ZEOLITE ENCAPSULATED COBALT(II) AND COPPER(II) PERFLUOROPHTHALOCYANINES - SYNTHESIS AND CHARACTERIZATION [J].
BALKUS, KJ ;
GABRIELOV, AG ;
BELL, SL ;
BEDIOUI, F ;
ROUE, L ;
DEVYNCK, J .
INORGANIC CHEMISTRY, 1994, 33 (01) :67-72
[3]   A NEW FAMILY OF MESOPOROUS MOLECULAR-SIEVES PREPARED WITH LIQUID-CRYSTAL TEMPLATES [J].
BECK, JS ;
VARTULI, JC ;
ROTH, WJ ;
LEONOWICZ, ME ;
KRESGE, CT ;
SCHMITT, KD ;
CHU, CTW ;
OLSON, DH ;
SHEPPARD, EW ;
MCCULLEN, SB ;
HIGGINS, JB ;
SCHLENKER, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (27) :10834-10843
[4]   Synthesis, characterization, and catalytic properties of mesoporous tin-containing analogs of MCM-41 [J].
Chaudhari, K ;
Das, TK ;
Rajmohanan, PR ;
Lazar, K ;
Sivasanker, S ;
Chandwadkar, AJ .
JOURNAL OF CATALYSIS, 1999, 183 (02) :281-291
[5]   Synthesis, properties, and structure of a stable cobalt(III) alkyl peroxide complex and its role in the oxidation of cyclohexane [J].
Chavez, FA ;
Nguyen, CV ;
Olmstead, MM ;
Mascharak, PK .
INORGANIC CHEMISTRY, 1996, 35 (21) :6282-6291
[6]   HYDROXYLATION AND EPOXIDATION REACTIONS CATALYZED BY SYNTHETIC METALLOPORPHYRINATES - MODELS RELATED TO THE ACTIVE OXYGEN SPECIES OF CYTOCHROME-P-450 [J].
GROVES, JT ;
KRUPER, WJ ;
NEMO, TE ;
MYERS, RS .
JOURNAL OF MOLECULAR CATALYSIS, 1980, 7 (02) :169-177
[7]   Effective catalysis of simple metalloporphyrins for cyclohexane oxidation with air in the absence of additives and solvents [J].
Guo, CC ;
Chu, MF ;
Liu, Q ;
Liu, Y ;
Guo, DC ;
Liu, XQ .
APPLIED CATALYSIS A-GENERAL, 2003, 246 (02) :303-309
[8]  
KARANDIKAR P, 2004, APPL CATAL A-GEN, V257, P33143
[9]   Synthesis and crystal structure determination of some asymmetrical and symmetrical CR-type macrocyclic schiff base complexes, with a single pendant coordinating 2-aminoethyl arm [J].
Keypour, H ;
Salehzadeh, S ;
Pritchard, RG ;
Parish, RV .
INORGANIC CHEMISTRY, 2000, 39 (25) :5787-5790
[10]   Aerobic oxidation of alkanes and alkenes in the presence of aldehydes catalyzed by copper salts and copper-crown ether [J].
Komiya, N ;
Naota, T ;
Oda, Y ;
Murahashi, SI .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1997, 117 (1-3) :21-37