An inverted rotating disc electrode (IRDE) setup was fabricated to study the hydrogen evolution reaction (HER) on a Pt electrode. Potentiodynamic polarization studies were conducted in solutions from 5 to 100 mM HClO4 on Pt at three different rotational speeds. Periodic anodic activation of the electrode yielded repeatable results. At high currents, bubble formation adversely affects current measurement in the rotating disc electrode, but not in IRDE. At large cathodic overpotentials, HER current in IRDE is limited by the mass transfer of H+ ions. Simulations show that the polarization results of HER on Pt IRDE are described well by the Volmer Heyrovsky mechanism.
Ta and Nb are group V valve metals which resist corrosion. Anodic dissolution of Ta and Nb in acidic fluoride media of varying HF concentration is investigated using potentiodynamic polarization and electrochemical impedance spectroscopy. Polarization curves showed a clear active and passive region in all the solutions employed in this study. At a given HF concentration, Nb anodic polarization currents are larger compared to those of Ta. EIS of Ta and Nb exhibited a low frequency capacitive loop in active region, and a low frequency negative differential resistance in the passive region. The surface of Ta and Nb was characterized using XPS, and it reveals the presence of both sub oxide and pentoxide. The electrochemical results could be explained by a four step mechanism involving sub-oxide and pentoxide intermediates. The analysis shows that direct dissolution of sub-oxide occurs via an electrochemical pathway and is facilitated by HF − 2 species and HF in undissociated form. On the other hand, chemical dissolution of pentoxide, which occurs in parallel, is facilitated by the HF species in undissociated form.
Dissolution rates of Ti, Zr, Nb and Ta in acidic fluoride media of different concentrations at various temperatures were measured by weight loss method, and were complemented by electrochemical measurements at room temperatures. A mathematical model to estimate the corrosion rate of these four valve metals based on the overall reaction mechanism for metal dissolution as well as H2 evolution is developed from the weight loss experiments. Valve metal dissolution process occurs through two independent pathways assisted by (HF2)− and equilibrium HF species. Except Ti, the dissolution of other valve metals studied are not significantly influenced by the H2 evolution reaction. Among the four metals evaluated, Nb offers the best corrosion resistance at high temperature and high HF concentration. The corrosion resistance of all four valve metals estimated from linear polarization, electrochemical spectroscopy and Tafel extrapolation in various concentrations of solutions match well. For Ti, dissolution rates calculated from Tafel extrapolation were lower than those based on weight loss experiments, while for Zr, Nb and Ta, they were mostly higher than those based on weight loss experiments.
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.