Mediated electrocatalysis with polyanthraquinone-functionalized monolayer-protected clusters

被引：35

作者：

Pietron, JJ ^{[1
]}

Murray, RW ^{[1
]}

机构：

[1] Univ N Carolina, Kenan Labs Chem, Chapel Hill, NC 27599 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY B | 1999年 / 103卷 / 21期

关键词：

D O I：

10.1021/jp984588w

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：

This paper describes the reduction of 1,1-dinitrocyclohexane by electrogenerated anthraquinone radical anions that are ligated to monolayer-protected gold clusters. Each cluster bears multiple (ca. 18) anthraquinone units. The clusters are prepared by place-exchange of a fraction of the cluster's original octanethiolate ligands with 1-(1,3-dithiapropyl)anthracene-9,10-dione. The electrocatalytic reduction currents are compared to those observed for anthraquinone monomer at an equivalent concentration. The electrocatalytic efficiency is larger for cluster-bound anthraquinone. The results are analyzed by digital simulation and by a discrete mathematical approach so as to determine the rate constant for electron transfer between the substrate and anthraquinone radical anion (cluster-bound and free). The rate constant is slightly larger for the free anthraquinone monomer. The enhancement in catalytic efficiency for cluster-bound anthraquinone arises from the smaller diffusion coefficient of cluster-bound anthraquinone, relative to that of the monomer, resulting in spatial compression of the reaction zone next to the electrode.

引用

页码：4440 / 4446

页数：7

共 30 条

[11] Three dimensional monolayers: Voltammetry of alkanethiolate-stabilized gold cluster molecules [J].

Green, SJ ;

Pietron, JJ ;

Stokes, JJ ;

Hostetler, MJ ;

Vu, H ;

Wuelfing, WP ;

Murray, RW .

LANGMUIR, 1998, 14 (19) :5612-5619

[12] Three-dimensional monolayers: Nanometer-sized electrodes of alkanethiolate-stabilized gold cluster molecules [J].

Green, SJ ;

Stokes, JJ ;

Hostetler, MJ ;

Pietron, J ;

Murray, RW .

JOURNAL OF PHYSICAL CHEMISTRY B, 1997, 101 (14) :2663-2668

[13] Alkanethiolate gold cluster molecules with core diameters from 1.5 to 5.2 nm: Core and monolayer properties as a function of core size [J].

Hostetler, MJ ;

Wingate, JE ;

Zhong, CJ ;

Harris, JE ;

Vachet, RW ;

Clark, MR ;

Londono, JD ;

Green, SJ ;

Stokes, JJ ;

Wignall, GD ;

Glish, GL ;

Porter, MD ;

Evans, ND ;

Murray, RW .

LANGMUIR, 1998, 14 (01) :17-30

[14] Monolayers in three dimensions: Synthesis and electrochemistry of omega-functionalized alkanethiolate-stabilized gold cluster compounds [J].

Hostetler, MJ ;

Green, SJ ;

Stokes, JJ ;

Murray, RW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (17) :4212-4213

[15] Colloids and self-assembled monolayers [J].

Hostetler, MJ ;

Murray, RW .

CURRENT OPINION IN COLLOID & INTERFACE SCIENCE, 1997, 2 (01) :42-50

[16] 28 kDa alkanethiolate-protected Au clusters give analogous solution electrochemistry and STM Coulomb staircases [J].

Ingram, RS ;

Hostetler, MJ ;

Murray, RW ;

Schaaff, TG ;

Khoury, JT ;

Whetten, RL ;

Bigioni, TP ;

Guthrie, DK ;

First, PN .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (39) :9279-9280

[17] Electroactive three-dimensional monolayers:: Anthraquinone ω-functionalized alkanethiolate-stabilized gold clusters [J].

Ingram, RS ;

Murray, RW .

LANGMUIR, 1998, 14 (15) :4115-4121

[18] Poly-hetero-omega-functionalized alkanethiolate-stabilized gold cluster compounds [J].

Ingram, RS ;

Hostetler, MJ ;

Murray, RW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (39) :9175-9178

[19] ELECTROCHEMICAL REDUCTION AND OXIDATION OF C60 FILMS [J].

JEHOULET, C ;

BARD, AJ ;

WUDL, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (14) :5456-5457

[20] A NEW GENERAL REACTION FOR PREPARING GEM DINITRO COMPOUNDS - OXIDATIVE NITRATION [J].

KAPLAN, RB ;

SHECHTER, H .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1961, 83 (16) :3535-&

← 1 2 3 →