Enzymatic versus Inorganic Oxygen Reduction Catalysts: Comparison of the Energy Levels in a Free-Energy Scheme

被引:69
作者
Kjaergaard, Christian H. [1 ]
Rossmeisl, Jan [1 ]
Norskov, Jens K. [1 ]
机构
[1] Nano DTU Tech Univ Denmark, Ctr Atom Scale Mat Design CAMD, Dept Phys, DK-2800 Lyngby, Denmark
关键词
CYTOCHROME-C-OXIDASE; ACTIVE-SITE; LACCASE; O-2; MECHANISM; DIOXYGEN; WATER; HEME; ELECTROCATALYSTS; SPECTROSCOPY;
D O I
10.1021/ic900798q
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
In this paper, we present a method to directly compare the energy levels of intermediates in enzymatic and inorganic oxygen reduction catalysts. We initially describe how the energy levels of a Pt(111) catalyst, operating at pH = 0, are obtained. By a simple procedure, we then convert the energy levels of cytochrome c oxidase (CcO) models obtained at physiological pH = 7 to the energy levels at pH = 0, which allows for comparison. Furthermore, we illustrate how different bias voltages will affect the free-energy landscapes of the catalysts. This allows us to determine the so-called theoretical overpotential of each system, which is shown to be significantly lower for the enzymatic catalysts compared to the inorganic Pt(111) catalyst. Finally, we construct theoretical polarization curves for the CcO models, in order to illustrate the effect of the low overpotentials on turnover rates per site.
引用
收藏
页码:3567 / 3572
页数:6
相关论文
共 36 条
[1]   Scaling properties of adsorption energies for hydrogen-containing molecules on transition-metal surfaces [J].
Abild-Pedersen, F. ;
Greeley, J. ;
Studt, F. ;
Rossmeisl, J. ;
Munter, T. R. ;
Moses, P. G. ;
Skulason, E. ;
Bligaard, T. ;
Norskov, J. K. .
PHYSICAL REVIEW LETTERS, 2007, 99 (01)
[2]  
[Anonymous], 1999, CATTECH
[3]   Quantum chemistry applied to the mechanisms of transition metal containing enzymes -: Cytochrome c oxidase, a particularly challenging case [J].
Blomberg, Margareta R. A. ;
Siegbahn, Per E. M. .
JOURNAL OF COMPUTATIONAL CHEMISTRY, 2006, 27 (12) :1373-1384
[4]   Kinetic studies on the reaction between Trametes villosa laccase and dioxygen [J].
Bukh, Christian ;
Lund, Martin ;
Bjerrum, Morten J. .
JOURNAL OF INORGANIC BIOCHEMISTRY, 2006, 100 (09) :1547-1557
[5]   REACTIVITY OF THE LACCASE TRINUCLEAR COPPER ACTIVE-SITE WITH DIOXYGEN - AN X-RAY ABSORPTION-EDGE STUDY [J].
COLE, JL ;
TAN, GO ;
YANG, EK ;
HODGSON, KO ;
SOLOMON, EI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (06) :2243-2249
[6]   Heme/copper terminal oxidases [J].
FergusonMiller, S ;
Babcock, GT .
CHEMICAL REVIEWS, 1996, 96 (07) :2889-2907
[7]   Just a Dream-or Future Reality? [J].
Gasteiger, Hubert A. ;
Markovic, Nenad M. .
SCIENCE, 2009, 324 (5923) :48-49
[8]   Calculated reaction cycle of cytochrome c oxidase [J].
Kaukonen, Markus .
JOURNAL OF PHYSICAL CHEMISTRY B, 2007, 111 (43) :12543-12550
[9]  
Kitagawa T, 1997, PROG INORG CHEM, V45, P431
[10]   Nature of the intermediate formed in the reduction of O2 to H2O at the trinuclear copper cluster active site in native laccase [J].
Lee, SK ;
George, SD ;
Antholine, WE ;
Hedman, B ;
Hodgson, KO ;
Solomon, EI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (21) :6180-6193