Oxygen dissociation by concerted action of di-iron centers in metal-organic coordination networks at surfaces: modeling non-heme iron enzymes.
The high chemical reactivity of unsaturated metal sites is a key factor for the development of novel devices with applications in sensor engineering and catalysis. It is also central in the research for sustainable energy concepts, e.g., the efficient production and conversion of chemical fuels. Here, we study the process of oxygen dissociation by a surface-supported metal-organic network that displays close structural and functional analogies with the cofactors of non-heme enzymes. We synthesize a two-dimensional array of chemically active di-iron sites on a Cu(001) surface where molecular oxygen readily dissociates at room temperature. We provide an atomic-level structural and electronic characterization before and after reaction by combining scanning tunneling microscopy, X-ray absorption spectroscopy, and density functional theory. The latter identifies a novel mechanism for O2 dissociation controlled by the cooperative catalytic action of two Fe2+ ions. The high structural flexibility of the organic ligands, the mobility of the metal centers, and the hydrogen bonding formation are shown to be essential for the functionality of these active centers allowing to mimick biologically relevant reactions in a confined environment.
CNR-IOM DEMOCRITOS, Theory@Elettra Group, Istituto Officina dei Materiali, c/o Sincrotrone Trieste-SS14, Km 163, 5 Basovizza, I-34012 Trieste, Italy. fabris@democritos.it
Stefano
S
Fabris
Sebastian
S
Stepanow
Nian
N
Lin
Pietro
P
Gambardella
Alexandre
A
Dmitriev
Jan
J
Honolka
Stefano
S
Baroni
Klaus
K
Kern
D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008667:Metalloproteins / Q000737:chemistry*; D008954:Models, Biological; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory; D013499:Surface Properties; D056928:X-Ray Absorption Spectroscopy
D056831:Coordination Complexes; D008667:Metalloproteins; D003300:Copper; D007501:Iron; D010100:Oxygen