Titanium nitride is a hard and inert conducting material that has yet not been widely used as electrode material for electroanalytical applications although there are highly developed protocols available to produce well adherent micro and nanostructured electrodes. In this paper the possibilities of using titanium nitride thin films for electroanalytical applications is investigated. Scanning electrochemical microscope (SECM) was used for analysis of the redox kinetics of a selected fast redox couple at thin films of titanium nitride (TiN) in different thicknesses. The investigation was carried out by approaching an amperometric ultramicroelectrode (UME) to the TiN film while the soluble redox couple (ferrocenemethanol/ferrociniummethanol) served as mediator in a SECM configuration. The substrate was biased at a potential so that it rereduces the species being produced at the UME, thus controlling the feedback effect. Normalized current -distance curves were fitted to the theoretical model in order to find the apparent heterogeneous standard rate constant (k8) at the sample. The data are further supported by structural investigation of the TiN films using scanning force microscopy and X-ray photoelectron spectroscopy. It was found that the kinetics are little influenced by prolonged storage in air. The heterogeneous standard rate constants in 2 mM ferrocenemethanol were (0.73 AE 0.05) Â 10 À3 cm s À1 for 20 nm TiN thin layer, (1.5 AE 0.2) Â 10 À3 cm s À1 for 100 nm TiN thin layer and (1.3 AE 0.2) Â 10 À3 cm s À1 for 300 nm TiN thin layer after prolonged storage in air. Oxidative surface treatment (in order to remove organic adsorbates) decreased the kinetics in agreement with a thicker oxide layer on the material. The results suggest that their direct use for amperometric detection of reversible redox systems in particular at miniaturized configurations may be advantageous.
Biphasic titanium alloys are preferred materials for load‐bearing metallic implants such as artificial joints. A comprehensive understanding of the electron‐transfer behavior of the native oxide layer on these materials is of great significance for improving the biocompatibility of such alloys. The combined use of different scanning probe techniques shows different electronic conductivities and electron‐transfer properties of passive layers formed on α and β phases (see figure).
Current collectors called bipolar plates (BPP) are important elements within the conversion unit of the vanadium redox flow battery (VRFB). They are in direct contact with acidic electrolytes, containing vanadium species in different oxidation states. The influence of the state of charge (SOC) on the calendar aging of BPPs was examined. Graphite-polypropylene BPPs were immersed in positive and negative vanadium electrolytes at 0%, 20%, 80% and 100% SOC for 30, 90 and 190 days. H 2 gas evolution was observed as side reaction on the surface of the BPPs in the negative electrolyte. After electroless aging, scanning electron (SEM) and confocal microscopy measurements showed no significant changes in the surface morphology. The electrical conductivities of the BPPs were not affected significantly. However, contact angle (θ) measurements revealed that the positive electrolyte influenced the wettability of the BPPs. X-ray photoelectron (XP) spectroscopy showed progressing oxidation of the BPP surfaces in the positive electrolyte and adsorption or entrapment of vanadium ions in the pores at high SOC. Cyclic voltammograms (CV) provided evidence that the graphite was oxidized combined with an increase in effective surface area. ATR-FTIR measurements showed slight oxidation of pure polypropylene granulate in the positive electrolyte with 100% SOC. The increasing energy power supply from intermittent renewable energy sources requires a rapid introduction of efficient energy storages. One promising technology is the vanadium redox flow battery (VRFB), as it enables to scale the power and the storage capacity independently according to specific requirements.1,2 In addition the VRFB is characterized by a fast response time and long electrolyte cycle life.3 Each reaction unit in a VRFB stack is composed of two half-cells separated by a membrane consisting of an electrode in contact with a current collector called bipolar plate (BPP).2 In a battery stack the BPPs are "non-active" components that conduct current from one cell to the other. They physically separate adjacent cells from each other while staying in contact with acidic half-cell electrolytes containing vanadium species in different oxidation states on each side. 4 For brevity we call the V 2+ /V 3+ solution "negative electrolyte" and the VO 2+ /VO 2 + solution "positive electrolyte". While vanadium redox reactions mainly occur on the surfaces of the porous electrodes, they could also occur unintentionally on the surfaces of the BPPs. [5][6][7] Therefore, a good BPP should be characterized by a high chemical and mechanical stability, high electrical conductivity and impermeability to preclude leakage. 8 Metallic BPPs are usually not used in VRFB as they corrode in acidic environments and would need a protective layer.5,9,10 Therefore, graphite based BPPs are commonly used as they possess a good electrical conductivity and a better chemical stability. 4 However, pure graphite plates are not favored as BPPs due to their high weight and cost as well as low mechanical stre...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.