Nanoscale morphological evolution of monocrystalline Pt surfaces during cathodic corrosion.

This paper studies the cathodic corrosion of a spherical single crystal of platinum in an aqueous alkaline electrolyte, to map out the detailed facet dependence of the corrosion structures forming during this still largely unexplored electrochemical phenomenon. We find that anisotropic corrosion of the platinum electrode takes place in different stages. Initially, corrosion etch pits are formed, which reflect the local symmetry of the surface: square pits on (100) facets, triangular pits on (111) facets, and rectangular pits on (110) facets. We hypothesize that these etch pits are formed through a ternary metal hydride corrosion intermediate. In contrast to anodic corrosion, the (111) facet corrodes the fastest, and the (110) facet corrodes the slowest. For cathodic corrosion on the (100) facet and on higher-index surfaces close to the (100) plane, the etch pit destabilizes in a second growth stage, by etching faster in the (111) direction, leading to arms in the etch pit, yielding a concave octagon-shaped pit. In a third growth stage, these arms develop side arms, leading to a structure that strongly resembles a self-similar diffusion-limited growth pattern, with strongly preferred growth directions.

Interfacial Water Tuning by Intermolecular Spacing for Stable CO2 Electroreduction to C2+ Products.

Electroreduction of CO2 to multi-carbon (C2+ ) products is a promising approach for utilization of renewable energy, in which the interfacial water quantity is critical for both the C2+ product selectivity and the stability of Cu-based electrocatalytic sites. Functionalization of long-chain alkyl molecules on a catalyst surface can help to increase its stability, while it also tends to block the transport of water, thus inhibiting the C2+ product formation. Herein, we demonstrate the fine tuning of interfacial water by surface assembly of toluene on Cu nanosheets, allowing for sustained and enriched CO2 supply but retarded water transfer to catalytic surface. Compared to bare Cu with fast cathodic corrosion and long-chain alkyl-modified Cu with main CO product, the toluene assembly on Cu nanosheet surface enabled a high Faradaic efficiency of 78 % for C2+ and a partial current density of 1.81 A cm-2 . The toluene-modified Cu catalyst further exhibited highly stable CO2 -to-C2 H4 conversion of 400 h in a membrane-electrode-assembly electrolyzer, suggesting the attractive feature for both efficient C2+ selectivity and excellent stability.

Self-Standing Metal Foam Catalysts for Cathodic Electro-Organic Synthesis.

Although electro-organic synthesis is currently receiving renewed interest because of its potential to enable sustainability in chemical processes to value-added products, challenges in process development persist: For reductive transformations performed in protic media, an inherent issue is the limited choice of metallic cathode materials that can effectively suppress the parasitic hydrogen evolution reaction (HER) while maintaining a high activity toward the targeted electro-organic reaction. Current development trends are aimed at avoiding the previously used HER-suppressing elements (Cd, Hg, and Pb) because of their toxicity. Here, this work reports the rational design of highly porous foam-type binary and ternary electrocatalysts with reduced Pb content. Optimized cathodes are tested in electro-organic reductions using an oxime to nitrile transformation as a model reaction relevant for the synthesis of fine chemicals. Their electrocatalytic performance is compared with that of the model CuSn7Pb15 bronze alloy that has recently been endorsed as the best cathode replacement for bare Pb electrodes. All developed metal foam catalysts outperform both bare Pb and the CuSn7Pb15 benchmark in terms of chemical yield and energetic efficiency. Moreover, post-electrolysis analysis of the crude electrolyte mixture and the cathode's surfaces through inductively coupled plasma mass spectrometry (ICP-MS) and scanning electron microscopy (SEM), respectively, reveal the foam catalysts' elevated resistance to cathodic corrosion.

Morphological Stability of Copper Surfaces under Reducing Conditions.

Though copper is a capable electrocatalyst for the CO2 reduction reaction (CO2RR), it rapidly deactivates to produce mostly hydrogen. A current hypothesis as to why this occurs is that potential-induced morphological restructuring takes place, leading to a redistribution of the facets at the interface resulting in a shift in the catalytic activity to favor the hydrogen evolution reaction over CO2RR. Here, we investigate the veracity of this hypothesis by studying the changes in the voltammetry of various copper surfaces, specifically the three principal orientations and a polycrystalline surface, after being subjected to strongly cathodic conditions. The basal planes were chosen as model catalysts, while polycrystalline copper was included as a means of investigating the overall behavior of defect-rich facets with many low coordination steps and kink sites. We found that all surfaces exhibited (perhaps surprisingly) high stability when subjected to strongly cathodic potentials in a concentrated alkaline electrolyte (10 M NaOH). Proof for morphological stability under CO2RR-representative conditions (60 min at -0.75 V in 0.5 M KHCO3) was obtained from identical location scanning electron microscopy, where the mesoscopic morphology for a nanoparticle-covered copper surface was found unchanged to within the instrument accuracy. Observed changes in voltammetry under such conditions, we found, were not indicative of a redistribution of surface sites but of electrode fouling. Besides impurities, we show that (brief) exposure to oxygen or oxidizing conditions (i.e., 1 min) leads to copper exhibiting changing morphology upon cathodic treatment which, we posit, is ultimately the reason why many groups report the evolution of copper morphology during CO2RR: accidental oxidation/reduction cycles.

Top-Down Synthesis of Nanostructured Platinum-Lanthanide Alloy Oxygen Reduction Reaction Catalysts: Pt xPr/C as an Example.

The oxygen reduction reaction (ORR) is of great interest for future sustainable energy conversion and storage, especially concerning fuel cell applications. The preparation of active, affordable, and scalable electrocatalysts and their application in fuel cell engines of hydrogen cars is a prominent step toward the reduction of air pollution, especially in urban areas. Alloying nanostructured Pt with lanthanides is a promising approach to enhance its catalytic ORR activity, whereby the development of a simple synthetic route turned out to be a nontrivial endeavor. Herein, for the first time, we present a successful single-step, scalable top-down synthetic route for Pt-lanthanide alloy nanoparticles, as witnessed by the example of Pr-alloyed Pt nanoparticles. The catalyst was characterized by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and photoelectron spectroscopy, and its electrocatalytic oxygen reduction activity was investigated using a rotating disk electrode technique. Pt xPr/C showed ∼3.5 times higher [1.96 mA/cm2Pt, 0.9 V vs reversible hydrogen electrode (RHE)] specific activity and ∼1.7 times higher (0.7 A/mgPt, 0.9 V vs RHE) mass activity compared to commercial Pt/C catalysts. On the basis of previous findings and characterization of the Pt xPr/C catalyst, the activity improvement over commercial Pt/C originates from a lattice strain introduced by the alloying process.

Cathodic Corrosion of a Bulk Wire to Nonaggregated Functional Nanocrystals and Nanoalloys.

A key enabling step in leveraging the properties of nanoparticles (NPs) is to explore new, simple, controllable, and scalable nanotechnologies for their syntheses. Among "wet" methods, cathodic corrosion has been used to synthesize catalytic aggregates with some control over their size and preferential faceting. Here, we report on a modification of the cathodic corrosion method for producing a range of nonaggregated nanocrystals (Pt, Pd, Au, Ag, Cu, Rh, Ir, and Ni) and nanoalloys (Pt50Au50, Pd50Au50, and Ag xAu100- x) with potential for scaling up the production rate. The method employs poly(vinylpyrrolidone) (PVP) as a stabilizer in an electrolyte solution containing nonreducible cations (Na+, Ca2+), and cathodic corrosion of the corresponding wires takes place in the electrolyte under ultrasonication. The ultrasonication not only promotes particle-PVP interactions (enhancing NP dispersion and diluting locally high NP concentration) but also increases the production rate by a factor of ca. 5. Further increase in the production rate can be achieved through parallelization of electrodes to construct comb electrodes. With respect to applications, carbon-supported Pt NPs prepared by the new method exhibit catalytic activity and durability for methanol oxidation comparable or better than the commercial benchmark catalyst. A variety of Ag xAu100- x nanoalloys are characterized by ultraviolet-visible absorption spectroscopy and high-resolution transmission electron microscopy. The protocol for NP synthesis by cathodic corrosion should be a step toward its further use in academic research as well as in its practical upscaling.

Alkali Metal Cation Effects in Structuring Pt, Rh, and Au Surfaces through Cathodic Corrosion.

Cathodic corrosion is an electrochemical etching process that alters metallic surfaces by creating nanoparticles and a variety of etching features. Because these features typically have a preferential orientation, cathodic corrosion can be applied to modify and nanostructure electrode surfaces. However, this application of cathodic corrosion is currently limited by an insufficient chemical understanding of its underlying mechanism. This includes the role of alkali metal cations, which are thought to be crucial in both enabling cathodic corrosion and controlling its final facet preference. This work addresses this knowledge gap by exploring the cathodic corrosion of Pt, Rh, and Au in LiOH, NaOH, and KOH through both experimental and theoretical methods. These methods demonstrate that cations are adsorbed during cathodic corrosion and play a major role in controlling the onset potential and final surface morphology in cathodic corrosion. Interestingly, an equally significant role appears to be played by adsorbed hydrogen, based on calculations using literature density functional theory data. Considering the significance of both hydrogen and electrolyte cations, it is hypothesized that cathodic corrosion might proceed via an intermediate ternary metal hydride. This fundamental insight leads to both metal-specific recommendations and more general guidelines for applying cathodic corrosion to structure metallic surfaces.