Titanium Oxycarbide as Platinum-Free Electrocatalyst for Ethanol Oxidation.

The compound material titanium oxycarbide (TiOC) is found to be an effective electrocatalyst for the electrochemical oxidation of ethanol to CO2. The complete course of this reaction is one of the main challenges in direct ethanol fuel cells (DEFCs). While TiOC has previously been investigated as catalyst support material only, in this study we show that TiOC alone is able to oxidize ethanol to acetaldehyde without the need of expensive noble metal catalysts like Pt. It is suggested that this behavior is attributed to the presence of both undercoordinated sites, which allow ethanol to adsorb, and oxygenated sites, which facilitate the activation of water. This is a milestone in DEFC research and development and opens up innovative possibilities for the design of catalyst materials for intermediate temperature fuel cells.

True Nature of the Transition-Metal Carbide/Liquid Interface Determines Its Reactivity.

Compound materials, such as transition-metal (TM) carbides, are anticipated to be effective electrocatalysts for the carbon dioxide reduction reaction (CO2RR) to useful chemicals. This expectation is nurtured by density functional theory (DFT) predictions of a break of key adsorption energy scaling relations that limit CO2RR at parent TMs. Here, we evaluate these prospects for hexagonal Mo2C in aqueous electrolytes in a multimethod experiment and theory approach. We find that surface oxide formation completely suppresses the CO2 activation. The oxides are stable down to potentials as low as -1.9 V versus the standard hydrogen electrode, and solely the hydrogen evolution reaction (HER) is found to be active. This generally points to the absolute imperative of recognizing the true interface establishing under operando conditions in computational screening of catalyst materials. When protected from ambient air and used in nonaqueous electrolyte, Mo2C indeed shows CO2RR activity.

Zirconium Oxycarbide: A Highly Stable Catalyst Material for Electrochemical Energy Conversion.

Metal carbides and oxycarbides have recently gained considerable interest due to their (electro)catalytic properties that differ from those of transition metals and that have potential to outperform them as well. The stability of zirconium oxycarbide nanopowders (ZrO0.31 C0.69 ), synthesized via a hybrid solid-liquid route, is investigated in different gas atmospheres from room temperature to 800 °C by using in-situ X-ray diffraction and in-situ electrical impedance spectroscopy. To feature the properties of a structurally stable Zr oxycarbide with high oxygen content, a stoichiometry of ZrO0.31 C0.69 has been selected. ZrO0.31 C0.69 is stable in reducing gases with only minor amounts of tetragonal ZrO2 being formed at high temperatures, whereas it decomposes in CO2 and O2 gas atmosphere. From online differential electrochemical mass spectrometry measurements, the hydrogen evolution reaction (HER) onset potential is determined at -0.4 VRHE . CO2 formation is detected at potentials as positive as 1.9 VRHE as ZrO0.31 C0.69 decomposition product, and oxygen is anodically formed at 2.5 VRHE , which shows the high electrochemical stability of this material in acidic electrolyte. This peopwery makes the material suited for electrocatalytic reactions at anodic potentials, such as CO and alcohol oxidation reactions, in general.