The iridium complex [Cp*Ir(H 2 O) 3 ](SO 4 ) was used as an organometallic source for the electrodeposition of iridium oxide onto Fe 2 O 3 . The new iridium-containing electrode allowed us to study the coupling between the photocatalytic properties of hematite and the electrocatalytic properties of the iridium-based material. A cathodic shift of the photocurrent for water oxidation upon electrodeposition of the iridium complex was observed, which increased with increasing surface concentration of IrO x on Fe 2 O 3 . The shift for the highest surface concentration of iridium tested amounts to 300 mV at 200 μA·cm −2 current density. The catalytic mechanism of the IrO x layer was unveiled by impedance spectroscopy measurements fitted to a physical model and can be explained on the basis of a highly capacitive layer, which enhances charge separation and stores photogenerated holes at Fe 2 O 3 , subsequently oxidizing water. These findings improve our understanding of the mechanism of water oxidation by heterogeneous Ir-based catalysts coupled to semiconductor electrodes.

Hydrogen generation by using quantum dot based heterostructures has emerged as a promising strategy to develop artificial photosynthesis devices. In the present study, we sensitize mesoporous TiO 2 electrodes with in-situ deposited PbS/CdS quantum dots (QDs), aiming at harvesting light in both the visible and the near infrared for hydrogen generation. This heterostructure exhibits a remarkable photocurrent of 6 mA·cm -2 leading to 60 ml·cm -2 ·day -1 hydrogen generation. Most importantly, confirmation of the contribution of infrared photons to H 2 generation was provided by the incident-photon-to-current-efficiency (IPCE), and the integrated current was in excellent agreement with that obtained through cyclic voltammetry.The main electronic processes (accumulation, transport and recombination) were identified by impedance spectroscopy, which appears as a simple and reliable methodology to evaluate the limiting factors of these photoelectrodes. Based on this TiO 2 /PbS/CdS heterostructrure, a "quasiartificial leaf" has been developed, which has proven to produce hydrogen under simulated solar illumination at (4.30 ± 0.25) ml·cm -2 ·day -1 .

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No abstract

Hydrogen gas is an attractive alternative electron donor since it is produced in large quantities as a side product in the metallurgical industry. Aim of this study was to demonstrate that microbial anodic hydrogen oxidation on a non-catalyzed graphite electrode can be coupled with cathodic copper reduction in a BES to simultaneously recover copper and produce power. The strategy was first to grow an anodic biofilm on acetate, then replace the acetate with hydrogen as electron donor, and finally combine hydrogen oxidation with copper reduction in the cathode. The maximum current density was 1.8 A/m2 at-250 mV anode potential vs Ag/AgCl. When coupled with Cu2+ reduction, the maximum power density was 0.25 W/m2 at a current density of 0.48 A/m2. Anode overpotentials were higher compared to acetate oxidation, probably a result of limited hydrogen solubility and transfer.