Catalyst parameters determining activity and selectivity of supported gold nanoparticles for the aerobic oxidation of alcohols:: The molecular reaction mechanism

被引：379

作者：

Abad, Alberto ^{[1
]}

Corma, Avelino ^{[1
]}

Garcia, Hermenegildo ^{[1
]}

机构：

[1] Univ Politecn Valencia, Inst Tecnol Quim, CSIC, Valencia 46022, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2008年 / 14卷 / 01期

关键词：

alcohols; gold; heterogeneous catalysis; nanoparticles; oxidation;

D O I：

10.1002/chem.200701263

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

As previously reported for for solventless reactions, gold nanoparticles supported on ceria are also excellent general heterogeneous catalysts for the aerobic oxidations of alcohols in organic solvents. Among organic solvents it was found that toluene is a convenient one. A systematic study on the influence of the particle size and gold content on the support has established that the activity correlates linearly with the total number of external gold atoms, and with the surface coverage of the support. Amongst catalysts with different supports, but similar gold particle size and content, gold on ceria exhibits the highest activity. By means of a kinetic study (influence of sigma(+) parameter, kinetic isotopic effect, temperature, alcohol concentration and oxygen pressure) a mechanistic proposal consisting of the formation of metal-alcoholate, beta-hydride shift from carbon to metal and M-H oxidation has been proposed that explains all experimental results.

引用

页码：212 / 222

页数：11

共 54 条

[1] A collaborative effect between gold and a support induces the selective oxidation of alcohols [J].

Abad, A ;

Concepción, P ;

Corma, A ;

García, H .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (26) :4066-4069

[2]

ABAD A, 2006, CHEM COMMUN, V3178

[3] Efficient chemoselective alcohol oxidation using oxygen as oxidant.: Superior performance of gold over palladium catalysts [J].

Abad, Alberto ;

Almela, Carles ;

Corma, Avelino ;

Garcia, Hermenegildo .

TETRAHEDRON, 2006, 62 (28) :6666-6672

[4] Nanoparticles as recyclable catalysts: The frontier between homogeneous and heterogeneous catalysis [J].

Astruc, D ;

Lu, F ;

Aranzaes, JR .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (48) :7852-7872

[5] Promotion by sulfur of gold catalysts for crotyl alcohol formation from crotonaldehyde hydrogenation [J].

Bailie, JE ;

Hutchings, GJ .

CHEMICAL COMMUNICATIONS, 1999, (21) :2151-2152

[6] MEAN COORDINATION NUMBERS AND THE NONMETAL METAL TRANSITION IN CLUSTERS [J].

BENFIELD, RE .

JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1992, 88 (08) :1107-1110

[7]

BON GC, 1973, J CHEM SOC CHEM COMM, V13, pB444

[8] Gold-catalysed oxidation of carbon monoxide [J].

Bond, GC ;

Thompson, DT .

GOLD BULLETIN, 2000, 33 (02) :41-51

[9] Catalysis by gold [J].

Bond, GC ;

Thompson, DT .

CATALYSIS REVIEWS-SCIENCE AND ENGINEERING, 1999, 41 (3-4) :319-388

[10] Selective oxidation of glycerol to glyceric acid using a gold catalyst in aqueous sodium hydroxide [J].

Carrettin, S ;

McMorn, P ;

Johnston, P ;

Griffin, K ;

Hutchings, GJ .

CHEMICAL COMMUNICATIONS, 2002, (07) :696-697

← 1 2 3 4 5 6 →