Water electrolysis powered by renewable energies is a promising technology to produce sustainable fossil free fuels. The development and evaluation of effective catalysts are here imperative; however, due to the inclusion of elements with different redox properties and reactivity, these materials undergo dynamical changes and phase transformations during the reaction conditions. NiMoO 4 is currently investigated among other metal oxides as a promising noble metal free catalyst for the oxygen evolution reaction. Here we show that at applied bias, NiMoO 4 ·H 2 O transforms into γ-NiOOH. Time resolved operando Raman spectroscopy is utilized to follow the potential dependent phase transformation and is collaborated with elemental analysis of the electrolyte, confirming that molybdenum leaches out from the as-synthesized NiMoO 4 ·H 2 O. Molybdenum leaching increases the surface coverage of exposed nickel sites, and this in combination with the formation of γ-NiOOH enlarges the amount of active sites of the catalyst, leading to high current densities. Additionally, we discovered different NiMoO 4 nanostructures, nanoflowers, and nanorods, for which the relative ratio can be influenced by the heating ramp during the synthesis. With selective molybdenum etching we were able to assign the varying X-ray diffraction (XRD) pattern as well as Raman vibrations unambiguously to the two nanostructures, which were revealed to exhibit different stabilities in alkaline media by time-resolved in situ and operando Raman spectroscopy. We advocate that a similar approach can beneficially be applied to many other catalysts, unveiling their structural integrity, characterize the dynamic surface reformulation, and resolve any ambiguities in interpretations of the active catalyst phase.

In this work, we present the preparation and performance of screen-printed anodes for electrochemical water splitting in neutral media. With the combination of printed electrodes and molecular water oxidation catalysts, we successfully take advantage of a low-cost and up-scalable fabrication method of graphitic electrodes with the outstanding catalytic activity and stability of oligomeric ruthenium-based molecular water oxidation catalysts, offering a promising electroanode for water oxidation applications.

Herein we present non-noble metal single-atom catalysts (SACs) based on carbonized transition metal-doped zeolitic imidazolate frameworks (ZIFs) as stable and efficient electrocatalysts for the hydrogen evolution reaction in acidic media. In this work, earth-abundant metals are embedded in a porous N-rich carbon matrix by pyrolyzing metal-doped ZIF structures and characterized by spectroscopic, microscopic, and electrochemical methods. The complete synthesis of these high surface area SACs was carried out without any solvents and hence offers a promising route for a more sustainable catalyst production and industrial upscaling. As the best-performing catalyst, cobalt SAC illustrated already with a low cobalt loading of < 0.3 at.% a substantial increase in activity with an overpotential of À 322 mV for À 10 mA cm À 2 , and high stability during electrolysis at À 10 mA cm À 2 for 12 h in acidic media, with only a small decrease of 33 mV to more negative potentials after the initiation period.