Functionalization and passivation of ultrathin alumina films of defined sub-nanometer thickness with self-assembled monolayers.

Instability of ultrathin surface oxides on alloys under environmental conditions can limit the opportunities for applications of these systems when the thickness control of the insulating oxide film is crucial for device performance. A procedure is developed to directly deposit self-assembled monolayers (SAM) from solvent onto substrates prepared under ultra-high vacuum conditions without exposure to air. As an example, rhenium photosensitizers functionalized with carboxyl linker groups are attached to ultrathin alumina grown on NiAl(1 1 0). The thickness change of the oxide layer during the SAM deposition is quantified by x-ray photoelectron spectroscopy and can be drastically reduced to one atomic layer. The SAM acts as a capping layer, stabilizing the oxide thin film under environmental conditions. Ultraviolet photoelectron spectroscopy elucidates the band alignment in the resulting heterostructure. The method for molecule attachment presented in this manuscript can be extended to a broad class of molecules vulnerable to pyrolysis upon evaporation and presents an elegant method for attaching molecular layers on solid substrates that are sensitive to air.

Atomically dispersed hybrid nickel-iridium sites for photoelectrocatalysis.

Atomically dispersed supported catalysts can maximize atom efficiency and minimize cost. In spite of much progress in gas-phase catalysis, applying such catalysts in the field of renewable energy coupled with electrochemistry remains a challenge due to their limited durability in electrolyte. Here, we report a robust and atomically dispersed hybrid catalyst formed in situ on a hematite semiconductor support during photoelectrochemical oxygen evolution by electrostatic adsorption of soluble monomeric [Ir(OH)6]2- coupled to positively charged NiOx sites. The alkali-stable [Ir(OH)6]2- features synergistically enhanced activity toward water oxidation through NiOx that acts as a "movable bridge" of charge transfer from the hematite surface to the single iridium center. This hybrid catalyst sustains high performance and stability in alkaline electrolyte for >80 h of operation. Our findings provide a promising path for soluble catalysts that are weakly and reversibly bound to semiconductor-supported hole-accumulation inorganic materials under catalytic reaction conditions as hybrid active sites for photoelectrocatalysis.

The impact of metalation on adsorption geometry, electronic level alignment and UV-stability of organic macrocycles on TiO2(110).

Metal complexes of the tetradentate bipyridine based macrocycle pyrphyrin (Pyr) have recently shown promise as water reduction catalysts in homogeneous photochemical water splitting reactions. In this study, the adsorption and metalation of pyrphyrin on stoichiometric TiO2(110) is investigated in ultrahigh vacuum by means of scanning tunneling microscopy, photoelectron spectroscopy, low-energy electron diffraction, and density functional theory. In a joint experimental and computational effort, the local adsorption geometry at low coverage, the long-range molecular ordering at higher coverage and the electronic structure have been determined for both the bare ligand and the cobalt-metalated Pyr molecule on TiO2. The energy level alignment of CoPyr/TiO2 supports electron injection into TiO2 upon photoexcitation of the CoPyr complex and thus renders it a potential sensitizer dye. Importantly, Co-incorporation is found to stabilize the Pyr molecule against photo-induced degradation, while the bare ligand is decomposed rapidly under continuous UV-irradiation. This interesting phenomenon is discussed in terms of additional de-excitation channels for electronically highly excited molecular states.