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The development of efficient and stable earth-abundant water oxidation catalysts is vital for economically feasible water-splitting systems. Cobalt phosphate (CoPi)-based catalysts belong to the relevant class of nonprecious electrocatalysts studied for the oxygen evolution reaction (OER). In this work, an in-depth investigation of the electrochemical activation of CoPi-based electrocatalysts by cyclic voltammetry (CV) is presented. Atomic layer deposition (ALD) is adopted because it enables the synthesis of CoPi films with cobalt-to-phosphorous ratios between 1.4 and 1.9. It is shown that the pristine chemical composition of the CoPi film strongly influences its OER activity in the early stages of the activation process as well as after prolonged exposure to the electrolyte. The best performing CoPi catalyst, displaying a current density of 3.9 mA cm –2 at 1.8 V versus reversible hydrogen electrode and a Tafel slope of 155 mV/dec at pH 8.0, is selected for an in-depth study of the evolution of its electrochemical properties, chemical composition, and electrochemical active surface area (ECSA) during the activation process. Upon the increase of the number of CV cycles, the OER performance increases, in parallel with the development of a noncatalytic wave in the CV scan, which points out to the reversible oxidation of Co 2+ species to Co 3+ species. X-ray photoelectron spectroscopy and Rutherford backscattering measurements indicate that phosphorous progressively leaches out the CoPi film bulk upon prolonged exposure to the electrolyte. In parallel, the ECSA of the films increases by up to a factor of 40, depending on the initial stoichiometry. The ECSA of the activated CoPi films shows a universal linear correlation with the OER activity for the whole range of CoPi chemical composition. It can be concluded that the adoption of ALD in CoPi-based electrocatalysis enables, next to the well-established control over film growth and properties, to disclose the mechanisms behind the CoPi electrocatalyst activation.

Solar hydrogen is a promising sustainable energy vector, and steady progress has been made in the development of photoelectrochemical (PEC) cells. Most research in this field has focused on using acidic or alkaline liquid electrolytes for ionic transfer. However, the performance is limited by (i) scattering of light and blocking of catalytic sites by gas bubbles and (ii) mass transport limitations. An attractive alternative to a liquid water feedstock is to use the water vapor present as humidity in ambient air, which has been demonstrated to mitigate the above problems and can expand the geographical range where these devices can be utilized. Here, we show how the functionalization of porous TiO 2 and WO 3 photoanodes with solid electrolytesproton conducting Aquivion and Nafion ionomersenables the capture of water from ambient air and allows subsequent PEC hydrogen production. The optimization strategy of photoanode functionalization was examined through testing the effect of ionomer loading and the ionomer composition. Optimized functionalized photoanodes operating at 60% relative humidity (RH) and T cell = 30−70 °C were able to recover up to 90% of the performance obtained at 1.23 V versus reverse hydrogen electrode (RHE) when water is introduced in the liquid phase (i.e., conventional PEC operation). Full performance recovery is achieved at a higher applied potential. In addition, long-term experiments have shown remarkable stability at 60% RH for 64 h of cycling (8 h continuous illumination−8 h dark), demonstrating that the concept can be applicable outdoors.

Carbon dioxide and steam solid oxide co-electrolysis is a key technology for exploiting renewable electricity to generate syngas feedstock for the Fischer-Tropsch synthesis. The integration of this process with methane partial oxidation in a single cell can eliminate or even reverse the electrical power demands of co-electrolysis, while simultaneously producing syngas at industrially attractive H2/CO ratios. Nevertheless, this system is rather complex, and requires catalytically active and coke tolerant electrodes. Here, we report on a low-substitution rhodium-titanate perovskite (La0.43Ca0.37Rh0.06Ti0.94O3) electrode for the process, capable of exsolving high Rh nanoparticle populations, and assembled in a symmetrical solid oxide cell configuration. By introducing dry methane to the anode compartment, the electricity demands are impressively decreased, even allowing syngas and electricity cogeneration. To provide further insight on Rh nanoparticles role on methane-to-syngas conversion, we adjusted their size and population by altering the reduction temperature of the perovskite. Our results exemplify how the exsolution concept can be employed to efficiently exploit noble metals for activating low-reactivity greenhouse gases in challenging energy related applications.

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