RESUMEN
Screening new electrocatalysts is key to the development of new materials for next-generation energy devices such as fuel cells and electrolyzers. The counter electrodes used in such tests are often made from materials such as Pt and Au, which can dissolve during testing and deposit onto test electrocatalysts, resulting in inaccurate results. The most common strategy for preventing this effect is to separate the counter electrode from the test material using an ion-transporting Nafion membrane. Here, we use X-ray photoelectron spectroscopy, energy-dispersive X-ray analysis, mass spectrometry, and voltammetry to demonstrate the limitations of this approach during constant-current, extended stability testing of electrocatalysts for H2 evolution. We show that Nafion membranes cannot prevent contamination of carbon electrocatalysts by Pt and Au counter electrodes, leading to an apparent increase in the electrocatalytic activity of the carbon. We then demonstrate that carbon counter electrodes in undivided cells can contaminate and deactivate Pt and Au electrocatalysts for H2 evolution. We show that use of a setup composed of a glass frit separating a carbon counter electrode from the test electrocatalyst can prevent these effects. Finally, we discuss these phenomena using H2 evolution at MoS2 and at a K6[P2W18O62](H2O)14/carbon nanotube composite as test reactions.
RESUMEN
Protic ionic liquids (PILs) are ionic liquids that are formed by transferring protons from Brønsted acids to Brønsted bases. While they nominally consist entirely of ions, PILs can often behave as though they contain a significant amount of neutral species (either molecules or ion clusters), and there is currently a lot of interest in determining the degree of "ionicity" of PILs. In this contribution, we describe a simple electroanalytical method for detecting and quantifying residual excess acids in a series of ammonium-based PILs (diethylmethylammonium triflate [dema][TfO], dimethylethylammonium triflate [dmea][TfO], triethylammonium trifluoroacetate [tea][TfAc], and dimethylbutylammonium triflate [dmba][TfO]). Ultra-microelectrode voltammetry reveals that some of the accepted methods for synthesizing PILs can readily result in the formation of nonstoichiometric PILs containing up to 230 mM excess acid. In addition, vacuum purification of PILs is of limited use in cases where nonstoichiometric PILs are formed. Although excess bases can be readily removed from PILs under ambient conditions, excess acids cannot be removed, even under high vacuum. The effects of excess acid on the electrocatalytic oxygen reduction reaction (ORR) in PILs have been studied, and the onset potential of the ORR in [dema][TfO] increases by 0.8 V upon addition of acid to PIL. On the basis of the results of our analyses, we provide some recommendations for the synthesis of highly ionic PILs.
RESUMEN
Electrolytic water splitting could potentially provide clean H2 for a future "hydrogen economy". However, as H2 and O2 are produced in close proximity to each other in water electrolyzers, mixing of the gases can occur during electrolysis, with potentially dangerous consequences. Herein, we describe an electrochemical water-splitting cell, in which mixing of the electrogenerated gases is impossible. In our cell, separate H2- and O2-evolving cells are connected electrically by a bipolar electrode in contact with an inexpensive dissolved redox couple (K3Fe(CN)6/K4Fe(CN)6). Electrolytic water splitting occurs in tandem with oxidation/reduction of the K3Fe(CN)6/K4Fe(CN) redox couples in the separate compartments, affording completely spatially separated H2 and O2 evolution. We demonstrate operation of our prototype cell using conventional Pt electrodes for each gas-evolving reaction, as well as using earth-abundant Ni2P electrocatalysts for H2 evolution. Furthermore, we show that our cell can be run in reverse and operate as a H2 fuel cell, releasing the energy stored in the electrogenerated H2 and O2. We also describe how the absence of an ionically conducting electrolyte bridging the H2- and O2-electrode compartments makes it possible to develop H2 fuel cells in which the anode and cathode are at different pH values, thereby increasing the voltage above that of conventional fuel cells. The use of our cell design in electrolyzers could result in dramatically improved safety during operation and the generation of higher-purity H2 than available from conventional electrolysis systems. Our cell could also be readily modified for the electrosynthesis of other chemicals, where mixing of the electrochemical products is undesirable.
RESUMEN
Imperforate anus is an uncommon congenital anomaly. Colon atresia is even more infrequent. This report describes a newborn with the simultaneous occurrence of these 2 anomalies, a condition that is exceedingly rare.
