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.

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.

Palladium Electrodeposition onto Pt(100): Two-Layer Underpotential Deposition.

Electrodeposition of the first Pd layers onto Pt(100) was investigated using cyclic voltammetry at a low scan rate (0.1 mV·s-1). Ultrathin films were characterized by cyclic voltammetry in 0.1 M H2SO4 solution and with ex situ AFM (atomic force microscopy). For the first time, we evidenced the underpotential character of the deposition of the first two Pd layers, characterized by a two-step mechanism, each step corresponding to the deposition of a complete Pd atomic layer. For thicker deposits, especially above 10 monolayers as equivalent thickness, the electrochemical characterization displays a strong irreversibility and a broadening of the adsorption/desorption peaks, associated with a reduction of long-range ordered flat areas. Ex situ AFM images are in agreement with this description. They show rough thick deposits and the growth of (100)-oriented rectangular shaped islands with their sides aligned with the two [011] and [0-11] perpendicular directions of the (100) Pt surface.

Growth mechanisms of Pd nanofilms electrodeposited onto Au(111): an in situ grazing incidence X-ray diffraction study.

Electrochemical deposition of ultra-thin Pd films onto Au(111) single crystals in a solution containing chloride was studied with in situ surface X-ray diffraction measurements. We report a detailed description of the growth mode, as well as film morphology and lattice parameters as a function of thickness, from 2 up to 10 monolayers (ML) as equivalent thickness. An almost ideal layer-by-layer pseudomorphic growth is observed up to two deposited ML. For higher thicknesses, it is followed by the growth of large 3D Pd bulk-like islands. They are about 20 ± 5 ML high and ∼220 Å in diameter for the Pd4ML film and occupy only about 20% of the surface. Their height increases faster than their size with the Pd deposited amount. We could clearly show that chlorides do not play any role in inhibiting the three-dimensional growth of Pd/Au(111) films. We could also unequivocally correlate the features observed by electrochemical surface characterisation in an acidic medium with the detailed structure obtained by diffraction.

Evidence of the substrate effect in hydrogen electroinsertion into palladium atomic layers by means of in situ surface X-ray diffraction.

In this work, we report an in situ surface X-ray diffraction study of the hydrogen electroinsertion in a two-monolayer equivalent palladium electrodeposit on Pt(111). The role of chloride in the deposition solution in favoring layer-by-layer film growth is evidenced. Three Pd layers are necessary to describe the deposit structure correctly, but the third-layer occupancy is quite low, equal to about 0.22. As a major result, resistance to hydriding of the two atomic Pd layers closest to the Pt interface is observed, which is linked to a strong effect of the Pt(111) substrate. As a consequence, we observe the lowering of the total hydride stoichiometry compared to bulk Pd. Our measurements also reveal good reversibility of the deposit structure, at least toward one hydrogen insertion-desorption cycle.

Characterization and methanol electrooxidation studies of Pt(111)/Os surfaces prepared by spontaneous deposition.

Catalytic activity of the Pt(111)/Os surface toward methanol electrooxidation was optimized by exploring a wide range of Os coverage. Various methods of surface analyses were used, including electroanalytical, STM, and XPS methods. The Pt(111) surface was decorated with nanosized Os islands by spontaneous deposition, and the Os coverage was controlled by changing the exposure time to the Os-containing electrolyte. The structure of Os deposits on Pt(111) was characterized and quantified by in situ STM and stripping voltammetry. We found that the optimal Os surface coverage of Pt(111) for methanol electrooxidation was 0.7 +/- 0.1 ML, close to 1.0 +/- 0.1 Os packing density. Apparently, the high osmium coverage Pt(111)/Os surface provides more of the necessary oxygen-containing species (e.g., Os-OH) for effective methanol electrooxidation than the Pt(111)/Os surfaces with lower Os coverage (vs e.g., Ru-OH). Supporting evidence for this conjecture comes from the CO electrooxidation data, which show that the onset potential for CO stripping is lowered from 0.53 to 0.45 V when the Os coverage is increased from 0.2 to 0.7 ML. However, the activity of Pt(111)/Os for methanol electrooxidation decreases when the Os coverage is higher than 0.7 +/- 0.1 ML, indicating that Pt sites uncovered by Os are necessary for sustaining significant methanol oxidation rates. Furthermore, osmium is inactive for methanol electrooxidation when the platinum substrate is absent: Os deposits on Au(111), a bulk Os ingot, and thick films of electrodeposited Os on Pt(111), all compare poorly to Pt(111)/Os. We conclude that a bifunctional mechanism applies to the methanol electrooxidation similarly to Pt(111)/Ru, although with fewer available Pt sites. Finally, the potential window for methanol electrooxidation on Pt(111)/Os was observed to shift positively versus Pt(111)/Ru. Because of the difference in the Os and Ru oxophilicity under electrochemical conditions, the Os deposit provides fewer oxygen-containing species, at least below 0.5 V vs RHE. Both higher coverage of Os than Ru and the higher potentials are required to provide a sufficient number of active oxygen-containing species for the effective removal of the site-blocking CO from the catalyst surface when the methanol electrooxidation process occurs.