Fe-Ni-based alloys as highly active and low-cost oxygen evolution reaction catalyst in alkaline media.

NiFe-based oxo-hydroxides are highly active for the oxygen evolution reaction but require complex synthesis and are poorly durable when deposited on foreign supports. Herein we demonstrate that easily processable, Earth-abundant and cheap Fe-Ni alloys spontaneously develop a highly active NiFe oxo-hydroxide surface, exsolved upon electrochemical activation. While the manufacturing process and the initial surface state of the alloys do not impact the oxygen evolution reaction performance, the growth/composition of the NiFe oxo-hydroxide surface layer depends on the alloying elements and initial atomic Fe/Ni ratio, hence driving oxygen evolution reaction activity. Whatever the initial Fe/Ni ratio of the Fe-Ni alloy (varying between 0.004 and 7.4), the best oxygen evolution reaction performance (beyond that of commercial IrO2) and durability was obtained for a surface Fe/Ni ratio between 0.2 and 0.4 and includes numerous active sites (high NiIII/NiII capacitive response) and high efficiency (high Fe/Ni ratio). This knowledge paves the way to active and durable Fe-Ni alloy oxygen-evolving electrodes for alkaline water electrolysers.

Water electrolysis: from textbook knowledge to the latest scientific strategies and industrial developments.

Replacing fossil fuels with energy sources and carriers that are sustainable, environmentally benign, and affordable is amongst the most pressing challenges for future socio-economic development. To that goal, hydrogen is presumed to be the most promising energy carrier. Electrocatalytic water splitting, if driven by green electricity, would provide hydrogen with minimal CO2 footprint. The viability of water electrolysis still hinges on the availability of durable earth-abundant electrocatalyst materials and the overall process efficiency. This review spans from the fundamentals of electrocatalytically initiated water splitting to the very latest scientific findings from university and institutional research, also covering specifications and special features of the current industrial processes and those processes currently being tested in large-scale applications. Recently developed strategies are described for the optimisation and discovery of active and durable materials for electrodes that ever-increasingly harness first-principles calculations and machine learning. In addition, a technoeconomic analysis of water electrolysis is included that allows an assessment of the extent to which a large-scale implementation of water splitting can help to combat climate change. This review article is intended to cross-pollinate and strengthen efforts from fundamental understanding to technical implementation and to improve the 'junctions' between the field's physical chemists, materials scientists and engineers, as well as stimulate much-needed exchange among these groups on challenges encountered in the different domains.

Electrochemical Strain Dynamics in Noble Metal Nanocatalysts.

The theoretical design of effective metal electrocatalysts for energy conversion and storage devices relies greatly on supposed unilateral effects of catalysts structure on electrocatalyzed reactions. Here, by using high-energy X-ray diffraction from the new Extremely Brilliant Source of the European Synchrotron Radiation Facility (ESRF-EBS) on device-relevant Pd and Pt nanocatalysts during cyclic voltammetry experiments in liquid electrolytes, we reveal the near ubiquitous feedback from various electrochemical processes on nanocatalyst strain. Beyond challenging and extending the current understanding of practical nanocatalysts behavior in electrochemical environment, the reported electrochemical strain provides experimental access to nanocatalysts absorption and adsorption trends (i.e., reactivity and stability descriptors) operando. The ease and power in monitoring such key catalyst properties at new and future beamlines is foreseen to provide a discovery platform toward the study of nanocatalysts encompassing a large variety of applications, from model environments to the device level.

From Bad Electrochemical Practices to an Environmental and Waste Reducing Approach for the Generation of Active Hydrogen Evolving Electrodes.

The electrodeposition of noble metals using corresponding dissolved metal salts represents an interesting process for the improvement of the electrocatalytic hydrogen evolution reaction (HER) properties of less active substrate materials. The fact that only a small fraction of the dissolved noble metals reaches the substrate represents a serious obstacle to this common procedure. We therefore chose a different path. It was found that the HER activity of Ni42 alloy drastically increased (η=140 mV at j=10 mA cm-2 ; pH 1) when a platinum counter electrode was used during polarization experiments in acid. This improvement was caused by a platinum transfer from the platinum anode to the steel cathode, a process which occurred simultaneously to the hydrogen evolution. The negligible accumulation of Pt (26 µg) in the electrolyte turns this straight-forward transfer procedure into a highly cost-effective, environmentally friendly, and waste reducing approach for the generation of cheap, stable and effective HER electrodes.

The influence of mass-transport conditions on the ethanol oxidation reaction (EOR) mechanism of Pt/C electrocatalysts.

This study aims to provide further understanding of the influence of different parameters that control mass-transport (the revolution rate of the rotating disk electrode and the potential scan rate) on the ethanol oxidation reaction (EOR). The experiments were conducted on a home-made carbon-supported 20 wt% Pt/C electrocatalyst, synthesized using a modified polyol method, and characterized in terms of physicochemical properties by thermogravimetric analysis (TGA), powder X-ray diffraction (XRD) and transmission electron microscopy (TEM). The EOR at the thin active layer of this electrocatalyst was characterized using both differential electrochemical mass spectrometry (DEMS) in a flow cell configuration and the rotating disc electrode (RDE). The results demonstrate that operating under stationary conditions (low scan rate and high RDE speed) hinders complete ethanol electrooxidation into CO2 and favors the poisoning of the electrocatalyst surface by hydroxide and strong ethanol adsorbates. As such, the EOR appears to be more efficient and faster under dynamic conditions than in near steady-state.

Influence of H- and OH-adsorbates on the ethanol oxidation reaction--a DEMS study.

The ethanol oxidation reaction (EOR) was investigated by potentiodynamic techniques on Pt/C, Rh/C, Pt-Rh/C, Pt-SnO2/C and Pt-Rh-SnO2/C by differential electrochemical mass spectrometry (DEMS) in a flow cell system. Prior to the cyclic voltammetries, adsorption of H- and OH-species was carried out by chronoamperometry at Ead = 0.05 and 1 V vs. RHE, respectively, in order to examine their influence on the EOR on the different electrocatalysts. For the sake of comparison, another adsorption potential was chosen at Ead = 0.3 V vs. RHE, in the double layer region (i.e. in the absence of such adsorbates). For this study, 20 wt% electrocatalysts were synthesized using a modified polyol method and were physically characterized by inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray diffraction (XRD) and transmission electron microscopy (TEM). When comparing the first and second cycles of the cyclic voltammograms (CVs) on Pt/C and Pt-SnO2/C, the presence of Had on the electrocatalyst surface seems to hinder the initiation of the ethanol electrooxidation, whereas the reaction onset potential is shifted negatively with the presence of OH-adsorbates. In contrast to them, the EOR on Rh/C is enhanced when the electrocatalyst surface is covered with Had and is inhibited after adsorption at Ead = 0.3 and 1 V vs. RHE. Finally, on Pt-Rh/C and Pt-Rh-SnO2/C, neither the H- nor OH-adsorbates do impact the EOR initiation. The lowest EOR onset was recorded on Pt-SnO2/C and Pt-Rh-SnO2/C electrocatalysts. The CO2 currency efficiency (CCE) was also determined for each electrocatalyst and demonstrated higher values on Pt-Rh-SnO2/C.

Reversibility of Pt-Skin and Pt-Skeleton Nanostructures in Acidic Media.

Following a well-defined series of acid and heat treatments on a benchmark Pt3Co/C sample, three different nanostructures of interest for the electrocatalysis of the oxygen reduction reaction were tailored. These nanostructures could be sorted into the "Pt-skin" structure, made of one pure Pt overlayer, and the "Pt-skeleton" structure, made of 2-3 Pt overlayers surrounding the Pt-Co alloy core. Using a unique combination of high-resolution aberration-corrected STEM-EELS, XRD, EXAFS, and XANES measurements, we provide atomically resolved pictures of these different nanostructures, including measurement of the Pt-shell thickness forming in acidic media and the resulting changes of the bulk and core chemical composition. It is shown that the Pt-skin is reverted toward the Pt-skeleton upon contact with acid electrolyte. This change in structure causes strong variations of the chemical composition.

Impact of metal cations on the electrocatalytic properties of Pt/C nanoparticles at multiple phase interfaces.

Proton-exchange membrane fuel cells (PEMFCs) use carbon-supported nanoparticles based on platinum and its alloys to accelerate the rate of the sluggish oxygen-reduction reaction (ORR). The most common metals alloyed to Pt include Co, Ni and Cu, and are thermodynamically unstable in the PEMFC environment. Their dissolution yields the formation and redistribution of metal cations (M(y+)) within the membrane electrode assembly (MEA). Metal cations can also contaminate the MEA when metallic bipolar plates are used as current collectors. In each case, the electrical performance of the PEMFC severely decreases, an effect that is commonly attributed to the poisoning of the sulfonic acid groups of the perfluorosulfonated membrane (PEM) and the resulting decrease of the proton transport properties. However, the impact of metal cations on the kinetics of electrochemical reactions involving adsorption/desorption and bond-breaking processes remains poorly understood. In this paper, we use model electrodes to highlight the effect of metal cations on Pt/C nanoparticles coated or not with a perfluorosulfonated ionomer for the CO electrooxidation reaction and the oxygen reduction reaction. We show that metal cations negatively impact the ORR kinetics and the mass-transport resistance of molecular oxygen. However, the specific adsorption of sulfonate groups of the Nafion® ionomer locally modifies the double layer structure and increases the tolerance to metal cations, even in the presence of sulphate ions in the electrolyte. The survey is extended by using an ultramicroelectrode with cavity and a solid state cell (SSC) specifically developed for this study.

The role of the support in CO(ads) monolayer electrooxidation on Pt nanoparticles: Pt/WO(x)vs. Pt/C.

The electrocatalytic properties of home-made Pt nanoparticles supported onto WO(x) were determined for the electrooxidation of a CO(ads) monolayer and compared with that of a commercial Pt/C having the same Pt particle size. By combining electrochemical and spectroscopic techniques, we found that Pt/WO(x) nanoparticles exhibit a very high tolerance to CO at low electrode potentials (E = 0.1 V vs. RHE), which was never reported in the literature before. CO adsorption at E = 0.1 V vs. RHE on Pt/WO(x) yields CO(2) production as observed by Fourier-transform infrared spectroscopy (FTIR). When the gas bubbling in solution changes from CO to Ar, the current attenuates and the CO(2) production vanishes. This points towards a limited number of "active sites" and a slow step in the electrocatalytic process. When H(2) is used to purge the electrolyte from CO, a steep and continuous increase of the H(2) electrooxidation current is observed pointing towards continuous liberation of the Pt catalytic sites. The high tolerance to CO of Pt/WO(x) is discussed in terms of strong metal-support interaction (SMSI), which involves formation of a metal-oxide film partially covering the Pt nanoparticles (encapsulation) and creation of W-OH groups upon H(+) insertion at low electrode potentials.