title: A TiO₂ nanoparticle system for sacrificial solar H₂ production prepared by rational combination of a hydrogenase with a ruthenium photosensitizer.
abstract: A hybrid system comprising a hydrogenase and a photosensitizer co-attached to a nanoparticle serves as a rational model for fast dihydrogen (H(2)) production using visible light. This chapter describes a stepwise procedure for preparing TiO(2) nanoparticles functionalized with a hydrogenase from Desulfomicrobium baculatum (Db [NiFeSe]-H) and a tris(bipyridyl)ruthenium photosensitizer (RuP). Upon irradiation with visible light, these particles produce H(2) from neutral water at room temperature in the presence of a sacrificial electron donor - a test-system for the cathodic half reaction of water splitting. In particular, we describe how a hydrogenase and a photosensitizer with desired properties, including strong adsorption on TiO(2), can be selected by electrochemical methods. The catalyst Db [NiFeSe]-H is selected for its high H(2) production activity even when H(2) and traces of O(2) are present. Adsorption of Db [NiFeSe]-H and RuP on TiO(2) electrodes results in high electrochemical and photocatalytic activities that translate into nanoparticles exhibiting efficient light harvesting, charge separation, and sacrificial H(2) generation.
authors.affiliation: Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
authors.forename: Erwin
authors.initials: E
authors.lastname: Reisner
authors.forename: Fraser A
authors.initials: FA
authors.lastname: Armstrong
mesh_terms: D000327:Adsorption; D055162:Biocatalysis; D020564:Deltaproteobacteria / Q000737:chemistry; D055664:Electrochemical Techniques; D004566:Electrodes; D006859:Hydrogen / Q000378:metabolism; D006864:Hydrogenase / Q000737:chemistry / Q000302:isolation & purification / Q000378:metabolism*; D008839:Microelectrodes; D053758:Nanoparticles / Q000737:chemistry; D055668:Photochemical Processes; D017319:Photosensitizing Agents / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013057:Spectrum Analysis; D013472:Sunlight; D014025:Titanium / Q000737:chemistry*; D014867:Water
chemical_list: D017319:Photosensitizing Agents; D011725:Pyridines; D014867:Water; C009495:titanium dioxide; D012428:Ruthenium; D006859:Hydrogen; D014025:Titanium; D006864:Hydrogenase