Durability of SrTiO3-TiO2 eutectic composite as a photoanode for photoelectrochemical water splitting.

The idea of employing sunlight - a virtually inexhaustible source of energy - to catalyze various chemical reactions or generate electrical current is intensively studied nowadays. Here, we describe a method for testing photoelectrochemical (PEC) stability developed using the example of photoanodes from an SrTiO3-TiO2 eutectic composite. Eutectic composite stability measurements were carried out in long-term cycles: 0.5, 1, 2, 5, 10, 20 and 50 h of constant electrode operation (total of 88.5 h). After each cycle, cyclic voltammetry, electrochemical impedance spectroscopy, reflectance, roughness, SEM/EDS microstructure analysis and the content of Sr and Ti ions in the applied electrolyte solution were examined. The initial value of the photocurrent density was 1.95 mA cm-2 at a potential of 1.5 V vs. Ag/AgCl in a pH 2 electrolyte environment and under 6 suns of illumination it increased almost four times, reaching 7.22 mA cm-2 after a total of 88.5 h of PEC stability cycles. Due to the better catalytic properties of TiO2, this phase degrades faster, causing an increase in the roughness of the electrode surface. At the same time, reflectance of the photoanode active layer dropped from around 35% to 15%. The investigated method of PEC material testing can be applied in areas beyond photoelectrochemical water splitting, such as chemistry, photovoltaics, sensing and others.

Molecular mechanism of direct electron transfer in the robust cytochrome-functionalised graphene nanosystem.

Construction of green nanodevices characterised by excellent long-term performance remains high priority in biotechnology and medicine. Tight electronic coupling of proteins to electrodes is essential for efficient direct electron transfer (DET) across the bio-organic interface. Rational modulation of this coupling depends on in-depth understanding of the intricate properties of interfacial DET. Here, we dissect the molecular mechanism of DET in a hybrid nanodevice in which a model electroactive protein, cytochrome c 553 (cyt c 553), naturally interacting with photosystem I, was interfaced with single layer graphene (SLG) via the conductive self-assembled monolayer (SAM) formed by pyrene-nitrilotriacetic acid (pyr-NTA) molecules chelated to transition metal redox centers. We demonstrate that efficient DET occurs between graphene and cyt c 553 whose kinetics and directionality depends on the metal incorporated into the bio-organic interface: Co enhances the cathodic current from SLG to haem, whereas Ni exerts the opposite effect. QM/MM simulations yield the mechanistic model of interfacial DET based on either tunnelling or hopping of electrons between graphene, pyr-NTA-M2+ SAM and cyt c 553 depending on the metal in SAM. Considerably different electronic configurations were identified for the interfacial metal redox centers: a closed-shell system for Ni and a radical system for the Co with altered occupancy of HOMO/LUMO levels. The feasibility of fine-tuning the electronic properties of the bio-molecular SAM upon incorporation of various metal centers paves the way for the rational design of the optimal molecular interface between abiotic and biotic components of the viable green hybrid devices, e.g. solar cells, optoelectronic nanosystems and solar-to-fuel assemblies.