Emergence of Potential-Controlled Cu-Nanocuboids and Graphene-Covered Cu-Nanocuboids under Operando CO2 Electroreduction.

The electroreduction of CO2 (CO2RR) is a promising strategy toward sustainable fuels. Cu is the only Earth-abundant and pure metal capable of catalyzing CO2-to-hydrocarbons conversion with significant Faradaic efficiencies; yet, its dynamic structure under operando CO2RR conditions remains unknown. Here, we track the Cu structure operando by electrochemical scanning tunneling microscopy and Raman spectroscopy. Surprisingly, polycrystalline Cu surfaces reconstruct forming Cu nanocuboids whose size can be controlled by the polarization potential and the time employed in their in situ synthesis, without the assistance of organic surfactants and/or halide anions. If the Cu surface is covered by a graphene monolayer, smaller features with enhanced catalytic activity for CO2RR can be prepared. The graphene-protecting layer softens the 3D morphological changes that Cu-based catalysts suffer when exposed to aggressive electrochemical environments and allows us to track the kinetic roughening process. This novel strategy is promising for improving Cu long-term stability, and consequently, it could be used as a platform to ultimately control product selectivity.

High-Pressure CO Electroreduction at Silver Produces Ethanol and Propanol.

Reducing CO2 to long-chain carbon products is attractive considering such products are typically more valuable than shorter ones. However, the best electrocatalyst for making such products from CO2 , copper, lacks selectivity. By studying alternate C2+ producing catalysts we can increase our mechanistic understanding, which is beneficial for improving catalyst performance. Therefore, we investigate CO reduction on silver, as density functional theory (DFT) results predict it to be good at forming ethanol. To address the current disagreement between DFT and experimental results (ethanol vs. no ethanol), we investigated CO reduction at higher surface coverage (by increasing pressure) to ascertain if desorption effects can explain the discrepancy. In terms of product trends, our results agree with the DFT-proposed acetaldehyde-like intermediate, yielding ethanol and propanol as C2+ products-making the CO2 electrochemistry of silver very similar to that of copper at sufficiently high coverage.

The reactivity of platinum microelectrodes.

Despite the widespread application of ultramicroelectrodes (UMEs), the customary method of their electrochemical characterization via outer sphere redox probing has serious limitations. In this study we provide additional insights into this subject by measuring not only outer sphere redox couples, but also blank voltammetries and the reactivity towards various catalytic reactions of Pt UMEs. The data for the UMEs are compared to those for macroscale Pt electrodes that can be flame-annealed. Although the reactivity is similar for reactions that are rather insensitive to the surface structure (and/or composition), UMEs perform much worse for more surface sensitive catalytic reactions. This effect can be explained by the UMEs being contaminated much faster, though it remains to be established if the origin of this contamination lies in the preparation method or in the impurities in the (high-purity grade) chemicals used. Our study recommends that catalytic reactivity measurements on ultramicroelectrodes should always be accompanied by blank voltammetries and the results have to be interpreted extremely carefully.

Rational design of nanoscale stabilized oxide catalysts for OER with OC22.

The efficiency of H2 production via water electrolysis is limited by the sluggish oxygen evolution reaction (OER). As such, significant emphasis has been placed upon improving the rate of OER through the anode catalyst. More recently, the Open Catalyst 2022 (OC22) framework has provided a large dataset of density functional theory (DFT) calculations for OER intermediates on the surfaces of oxides. When coupled with state-of-the-art graph neural network models, total energy predictions can be achieved with a mean absolute error as low as 0.22 eV. In this work, we interpolated a database of the total energy predictions for all slabs and OER surface intermediates for 4119 oxide materials in the original OC22 dataset using pre-trained models from the OC22 framework. This database includes all terminations of all facets up to a maximum Miller index of 1. To demonstrate the full utility of this database, we constructed a flexible screening framework to identify viable candidate anode catalysts for OER under varying reaction conditions for bulk, surface, and nanoscale Pourbaix stability as well as material cost, overpotential, and metastability. From our assessment, we were able to identify 122 and 68 viable candidates for OER under the bulk and nanoscale regime, respectively.

Enhanced Electrochemical CO2 Reduction to Formate on Poly(4-vinylpyridine)-Modified Copper and Gold Electrodes.

Developing active and selective catalysts that convert CO2 into valuable products remains a critical challenge for further application of the electrochemical CO2 reduction reaction (CO2RR). Catalytic tuning with organic additives/films has emerged as a promising strategy to tune CO2RR activity and selectivity. Herein, we report a facile method to significantly change CO2RR selectivity and activity of copper and gold electrodes. We found improved selectivity toward HCOOH at low overpotentials on both polycrystalline Cu and Au electrodes after chemical modification with a poly(4-vinylpyridine) (P4VP) layer. In situ attenuated total reflection surface-enhanced infrared reflection-adsorption spectroscopy and contact angle measurements indicate that the hydrophobic nature of the P4VP layer limits mass transport of HCO3- and H2O, whereas it has little influence on CO2 mass transport. Moreover, the early onset of HCOOH formation and the enhanced formation of HCOOH over CO suggest that P4VP modification promotes a surface hydride mechanism for HCOOH formation on both electrodes.

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.