RESUMO
Oxygen evolution reaction (OER) is expected to be of great importance for the future energy conversion and storage in form of hydrogen by water electrolysis. Besides the traditional noble-metal or transition metal oxide-based catalysts, carbonaceous electrocatalysts are of great interest due to their huge structural and compositional variety and unrestricted abundance. This review provides a summary of recent advances in the field of carbon-based OER catalysts ranging from "pure" or unintentionally doped carbon allotropes over heteroatom-doped carbonaceous materials and carbon/transition metal compounds to metal oxide composites where the role of carbon is mainly assigned to be a conductive support. Furthermore, the review discusses the recent developments in the field of ordered carbon framework structures (metal organic framework and covalent organic framework structures) that potentially allow a rational design of heteroatom-doped 3D porous structures with defined composition and spatial arrangement of doping atoms to deepen the understanding on the OER mechanism on carbonaceous structures in the future. Besides introducing the structural and compositional origin of electrochemical activity, the review discusses the mechanism of the catalytic activity of carbonaceous materials, their stability under OER conditions, and potential synergistic effects in combination with metal (or metal oxide) co-catalysts.
RESUMO
The efficiency of photoelectrochemical tandem cells is still limited by the availability of stable low band gap electrodes. In this work, we report a photocathode based on lithium doped copper(ii) oxide, a black p-type semiconductor. Density functional theory calculations with a Hubbard U term show that low concentrations of Li (Li0.03Cu0.97O) lead to an upward shift of the valence band maximum that crosses the Fermi level and results in a p-type semiconductor. Therefore, Li doping emerged as a suitable approach to manipulate the electronic structure of copper oxide based photocathodes. As this material class suffers from instability in water under operating conditions, the recorded photocurrents are repeatedly misinterpreted as hydrogen evolution evidence. We investigated the photocorrosion behavior of LixCu1-xO cathodes in detail and give the first mechanistic study of the fundamental physical process. The reduced copper oxide species were localized by electron energy loss spectroscopy mapping. Cu2O grows as distinct crystallites on the surface of LixCu1-xO instead of forming a dense layer. Additionally, there is no obvious Cu2O gradient inside the films, as Cu2O seems to form on all LixCu1-xO nanocrystals exposed to water. The application of a thin Ti0.8Nb0.2Ox coating by atomic layer deposition and the deposition of a platinum co-catalyst increased the stability of LixCu1-xO against decomposition. These devices showed a stable hydrogen evolution for 15 minutes.
RESUMO
We present a novel route for the preparation of supported IrO2 catalysts for the oxygen evolution reaction in proton exchange membrane electrolyzers. It uses carbon soot as a nanostructure template, which is sequentially coated with a conductive niobium-doped titanium oxide (NTO) layer and an ultrathin, highly pure IrO2 catalyst layer by atomic layer deposition (ALD). The NTO acts as an oxidation-stable conductor between the metal current distributor and the catalyst. The highly controlled film growth by ALD enables the fabrication of electrodes with a very low noble metal loading. Nonetheless, these electrodes exhibit very high catalytic activity and good stability under cyclic and constant load conditions. At an IrO2 content of less than 10 percent by mass of the oxide material and an area-based Ir content of 153 µg cm-2, the nanostructured NTO/IrO2 electrode achieves an oxygen evolution current density of 1 mA cm-2 at an overpotential of â¼250 mV, which is significantly lower than the reported values for particulate NTO/IrO2 catalysts.
