Modelling NiFe hydrogenases: nickel-based electrocatalysts for hydrogen production

Abstract

NiFe hydrogenases are unique enzymes that catalyze the H+/H2 interconversion with remarkable efficiency. The determination of the tridimensional structure of their active site (a sulfur-rich dinuclear nickel-iron cluster with diatomic cyanide and carbonyl ligands) has stimulated the synthesis of a variety of nickel-based complexes as potential electrocatalysts for hydrogen production. These catalysts may provide an adequate alternative to platinum. This paper gives an historical perspective of this biomimetic structural approach and then focusses on recently reported bio-inspired functional mimics displaying electrocatalytic activity for hydrogen production.

Splitting Water with Cobalt

“…[4] While the first two topics have been the core of artificial photosynthesis for the last two decades, and also the subject of comprehensive reviews, [13][14][15][16][17][18][19][20][21][22][23] significant achievements have been made only in the recent years as far as the design of efficient molecular catalysts for both hydrogen and oxygen evolution is concerned. These comprise FeFe, [24] NiRu, [25][26][27][28][29][30] NiMn, [31] and NiFe [25,[32][33][34] models of the active sites of hydrogenases as well as manganese [35] and ruthenium [36][37][38][39][40] catalysts as functional mimics of the PSII OEC. These systems have been reviewed recently.…”

Targeting Intermediates of [FeFe]-Hydrogenase by CO and CN Vibrational Signatures

“…In the global biological hydrogen metabolism three types of metal containing enzymes, [NiFe]-hydrogenases, [FeFe]-hydrogenases, and [Fe]-hydrogenases play a key role [1][2][3][4][5][6][7][8].…”

Solar water-splitting into H2 and O2: design principles of photosystem II and hydrogenases

“…Furthermore, some mononuclear metal complexes catalyze proton electroreduction, but turnover numbers and frequencies are rather low. 191 Recently, a promising dinuclear Ni-Ru complex has been described. 204 It meets most of the criteria for a functional model and directly reacts with and heterolytically splits dihydrogen.…”