Nanoscale assembly of BiVO4/CdS/CoOx core-shell heterojunction for enhanced photoelectrochemical water splitting

Porous BiVO4 electrodes were conformally decorated with CdS via a chemical bath deposition process. The highest photocurrent at 1.1 V vs. RHE was achieved for a BiVO4/CdS composite (4.54 mA cm(-2)), compared with CdS (1.19 mA cm(-2)) and bare BiVO4 (2.1 mA cm(-2)), under AM 1.5G illumination. This improvement in the photoefficiency can be ascribed to both the enhanced optical absorption properties and the charge separation due to the heterojunction formation between BiVO4 and CdS. Furthermore, the BiVO4/CdS photoanode was protected with a CoOx layer to substantially increase the photostability of the material. The new BiVO4/CdS/CoOx nanostructure exhibited a highly stable photocurrent density of similar to 5 mA cm(-2). The capability to produce O-2 was locally investigated by scanning photoelectrochemical microscope, which showed a good agreement between photocurrent and O-2 reduction current maps. This work develops an efficient route to improve the photo-electrochemical performance of BiVO4 and its long-term stability.Web of Science116art. no. 68

Electrocatalytic methanol oxidation with nanoporous gold: microstructure and selectivity

The properties of Nanoporous Gold (NPG) obtained by the selective dissolution of Ag from an Au–Ag alloy can be tuned by the details of its fabrication, and specifically the residual Ag content is correlated to the ligament size of the material. We link this correlation to methanol electro-oxidation. Specifically, two different NPG types (obtained by potentiostatic dealloying) are compared with one obtained by free corrosion. They show remarkable differences in activity. Quantitative product analysis reveals that NPG shows nearly selective oxidation of CH3OH to HCOO− when NPG is used as an active electrode in contrast to planar Au. This trend can further be enhanced when applying finer nanoporous structures that are linked to a higher Ag content. X-ray photoelectron spectroscopy (XPS) reveals changes in the nature of residual Ag from which we conclude that Ag is not a passive component in the methanol oxidation process.Deutsche Forschungsgemeinschaft (DFG

Crystal Structure, Spectroscopic Investigations, and Physical Properties of the Ternary Intermetallic REPt2Al3 (RE = Y, Dy–Tm) and RE2Pt3Al4 Representatives (RE = Tm, Lu)

The REPt2Al3 compounds of the late rare-earth metals (RE = Y, Dy–Tm) were found to crystallize isostructural. Single-crystal X-ray investigations of YPt2Al3 revealed an orthorhombic unit cell (a = 1080.73(6), b = 1871.96(9), c = 413.04(2) pm, wR2 = 0.0780, 942 F2 values, 46 variables) with space group Cmmm (oC48; q2pji2hedb). A comparison with the Pearson database indicated that YPt2Al3 forms a new structure type, in which the Pt and Al atoms form a [Pt2Al3]δ− polyanion and the Y atoms reside in the cavities within the framework. Via a group-subgroup scheme, the relationship between the PrNi2Al3-type structure and the new YPt2Al3-type structure was illustrated. The compounds with RE = Dy–Tm were characterized by powder X-ray diffraction experiments. While YPt2Al3 is a Pauli-paramagnet, the other REPt2Al3 (RE = Dy–Tm) compounds exhibit paramagnetic behavior, which is in line with the rare-earth atoms being in the trivalent oxidation state. DyPt2Al3 and TmPt2Al3 exhibit ferromagnetic ordering at TC = 10.8(1) and 4.7(1) K and HoPt2Al3 antiferromagnetic ordering at TN = 5.5(1) K, respectively. Attempts to synthesize the isostructural lutetium compound resulted in the formation of Lu2Pt3Al4 (Ce2Ir3Sb4-type, Pnma, a = 1343.4(2), b = 416.41(8), c = 1141.1(2) pm), which could also be realized with thulium. The structure was refined from single-crystal data (wR2 = 0.0940, 1605 F2 values, 56 variables). Again, a polyanion with bonding Pt–Al interactions was found, and the two distinct Lu atoms were residing in the cavities of the [Pt3Al4]δ– framework. X-ray photoelectron spectroscopy (XPS) measurements were conducted to examine the electron transfer from the rare-earth atoms onto the polyanionic framework