Efficient electrochemical water splitting to hydrogen and oxygen is considered a promising technology to overcome our dependency on fossil fuels. Searching for novel catalytic materials for electrochemical oxygen generation is essential for improving the total efficiency of water splitting processes. We report the synthesis, structural characterization, and electrochemical performance in the oxygen evolution reaction of Fe-doped NiO nanocrystals. The facile solvothermal synthesis in tert-butanol leads to the formation of ultrasmall crystalline and highly dispersible FexNi1-xO nanoparticles with dopant concentrations of up to 20%. The increase in Fe content is accompanied by a decrease in particle size, resulting in nonagglomerated nanocrystals of 1.5-3.8 nm in size. The Fe content and composition of the nanoparticles are determined by X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy measurements, while Mössbauer and extended X-ray absorption fine structure analyses reveal a substitutional incorporation of Fe(III) into the NiO rock salt structure. The excellent dispersibility of the nanoparticles in ethanol allows for the preparation of homogeneous ca. 8 nm thin films with a smooth surface on various substrates. The turnover frequencies (TOF) of these films could be precisely calculated using a quartz crystal microbalance. Fe0.1Ni0.9O was found to have the highest electrocatalytic water oxidation activity in basic media with a TOF of 1.9 s(-1) at the overpotential of 300 mV. The current density of 10 mA cm(-2) is reached at an overpotential of 297 mV with a Tafel slope of 37 mV dec(-1). The extremely high catalytic activity, facile preparation, and low cost of the single crystalline FexNi1-xO nanoparticles make them very promising catalysts for the oxygen evolution reaction.
Light-driven water electrolysis at a semiconductor surface is a promising way to generate hydrogen from sustainable energy sources, but its efficiency is limited by the performance of available photoabsorbers. Here we report the first time investigation of covalent organic frameworks (COFs) as a new class of photoelectrodes. The presented 2D-COF structure is assembled from aromatic amine-functionalized tetraphenylethylene and thiophene-based dialdehyde building blocks to form conjugated polyimine sheets, which π-stack in the third dimension to create photoactive porous frameworks. Highly oriented COF films absorb light in the visible range to generate photoexcited electrons that diffuse to the surface and are transferred to the electrolyte, resulting in proton reduction and hydrogen evolution. The observed photoelectrochemical activity of the 2D-COF films and their photocorrosion stability in water pave the way for a novel class of photoabsorber materials with versatile optical and electronic properties that are tunable through the selection of appropriate building blocks and their three-dimensional stacking.
Ultrasmall, crystalline, and dispersible NiO nanoparticles are prepared for the first time, and it is shown that they are promising candidates as catalysts for electrochemical water oxidation. Using a solvothermal reaction in tert‐butanol, very small nickel oxide nanocrystals can be made with sizes tunable from 2.5 to 5 nm and a narrow particle size distribution. The crystals are perfectly dispersible in ethanol even after drying, giving stable transparent colloidal dispersions. The structure of the nanocrystals corresponds to phase‐pure stoichiometric nickel(ii) oxide with a partially oxidized surface exhibiting Ni(iii) states. The 3.3 nm nanoparticles demonstrate a remarkably high turn‐over frequency of 0.29 s–1 at an overpotential of g = 300 mV for electrochemical water oxidation, outperforming even expensive rare earth iridium oxide catalysts. The unique features of these NiO nanocrystals provide great potential for the preparation of novel composite materials with applications in the field of (photo)electrochemical water splitting. The dispersed colloidal solutions may also find other applications, such as the preparation of uniform hole‐conducting layers for organic solar cells.
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