CO Binding Energy is an Incomplete Descriptor of Cu-Based Catalysts for the Electrochemical CO2 Reduction Reaction.

CO binding energy has been employed as a descriptor in the catalyst design for the electrochemical CO2 reduction reactions (CO2 RR). The reliability of the descriptor has yet been experimentally verified due to the lack of suitable methods to determine CO binding energies. In this work, we determined the standard CO adsorption enthalpies ( Δ H C O ∘ ${\Delta {H}_{CO}^{^\circ{}}}$ ) of undoped and doped oxide-derived Cu (OD-Cu) samples, and for the first time established the correlation of Δ H C O ∘ ${\Delta {H}_{CO}^{^\circ{}}}$ with the Faradaic efficiencies (FE) for C2+ products. A clear volcano shaped dependence of the FE for C2+ products on Δ H C O ∘ ${\Delta {H}_{CO}^{^\circ{}}}$ is observed on OD-Cu catalysts prepared with the same hydrothermal durations, however, the trend becomes less clear when all catalysts investigated are taken into account. The relative abundance of Cu sites active for the CO2 -to-CO conversion and the further reduction of CO is identified as another key descriptor.

Correlating the Experimentally Determined CO Adsorption Enthalpy with the Electrochemical CO Reduction Performance on Cu Surfaces.

CO binding energy has been widely employed as a descriptor for effective catalysts in the electrochemical CO2 and CO reduction reactions (CO(2) RR), however, it has yet to be determined experimentally at electrochemical interfaces due to the lack of suitable techniques. In this work, we developed a method to determine the standard adsorption enthalpy of CO on Cu surfaces with quantitative surface enhanced infrared absorption spectroscopy. On dendritic Cu at -0.75 V vs. SHE, the standard adsorption enthalpy, entropy and Gibbs free energy were determined to 1.5±0.5 kJ mol-1 , ≈37.9±13.4 J/(mol K), and ≈-9.8±4.0 kJ mol-1 , respectively. Comparison of the standard adsorption enthalpy of oxide-derived Cu and dendritic Cu, as well as their CORR activities, suggests the presence of stronger binding sites on OD Cu, which could favor multicarbon products. The method developed in this work will help establish the correlation between the CO binding energy and the CO(2) RR activity.

C-C Coupling Is Unlikely to Be the Rate-Determining Step in the Formation of C2+ Products in the Copper-Catalyzed Electrochemical Reduction of CO.

The identity of the rate-determining step (RDS) in the electrochemical CO reduction reaction (CORR) on Cu catalysts remains unresolved because: 1) the presence of mass transport limitation of CO; and 2) the absence of quantitative correlation between CO partial pressure (pCO ) and surface CO coverage. In this work, we determined CO adsorption isotherms on Cu in a broad pH range of 7.2-12.9. Together with electrokinetic data, we demonstrate that the reaction orders of adsorbed CO at pCO <0.4 and >0.6 atm are 1st and 0th , respectively, for multi-carbon (C2+ ) products on three Cu catalysts. These results indicate that the C-C coupling is unlikely to be the RDS in the formation of C2+ products in the CORR. We propose that the hydrogenation of CO with adsorbed water is the RDS, and the site competition between CO and water leads to the observed transition of the CO reaction order.

Mechanistic Implications of Low CO Coverage on Cu in the Electrochemical CO and CO2 Reduction Reactions.

Electrochemical CO or CO2 reduction reactions (CO(2)RR), powered by renewable energy, represent one of the promising strategies for upgrading CO2 to valuable products. To design efficient and selective catalysts for the CO(2)RR, a comprehensive mechanistic understanding is necessary, including a comprehensive understanding of the reaction network and the identity of kinetically relevant steps. Surface-adsorbed CO (COad) is the most commonly reported reaction intermediate in the CO(2)RR, and its surface coverage (θCO) and binding energy are proposed to be key to the catalytic performance. Recent experimental evidence sugguests that θCO on Cu electrode at electrochemical conditions is quite low (∼0.05 monolayer), while relatively high θCO is often assumed in literature mechanistic discussion. This Perspective briefly summarizes existing efforts in determining θCO on Cu surfaces, analyzes mechanistic impacts of low θCO on the reaction pathway and catalytic performance, and discusses potential fruitful future directions in advancing our understanding of the Cu-catalyzed CO(2)RR.

Benchmarking of commercial Cu catalysts in CO2 electro-reduction using a gas-diffusion type microfluidic flow electrolyzer.

In this work, three commercial Cu catalysts were benchmarked in the CO2RR using a gas-diffusion type microfluidic flow electrolyzer. We showed that commercial Cu could deliver a high FE of near 80% for C2+ product formations at 300 mA cm-2. By tuning the catalyst loading, a high reaction rate of near 1 A cm-2 with a C2+ product FE over 70% was achieved. Our results demonstrated that commercial Cu could achieve similar or better performances compared to many current catalysts by design in the CO2RR using similar electrolyzers. In addition, we showed that high CO reduction reaction (CORR) performance could also be achieved on commercial Cu, and disparities between CO and CO2 electrolysis were discussed.

Weak CO binding sites induced by Cu-Ag interfaces promote CO electroreduction to multi-carbon liquid products.

Electrochemical reduction of carbon monoxide to high-value multi-carbon (C2+) products offers an appealing route to store sustainable energy and make use of the chief greenhouse gas leading to climate change, i.e., CO2. Among potential products, C2+ liquid products such as ethanol are of particular interest owing to their high energy density and industrial relevance. In this work, we demonstrate that Ag-modified oxide-derive Cu catalysts prepared via high-energy ball milling exhibit near 80% Faradaic efficiencies for C2+ liquid products at commercially relevant current densities (>100 mA cm-2) in the CO electroreduction in a microfluidic flow cell. Such performance is retained in an over 100-hour electrolysis in a 100 cm2 membrane electrode assembly (MEA) electrolyzer. A method based on surface-enhanced infrared absorption spectroscopy is developed to characterize the CO binding strength on the catalyst surface. The lower C and O affinities of the Cu-Ag interfacial sites in the prepared catalysts are proposed to be responsible for the enhanced selectivity for C2+ oxygenates, which is the experimental verification of recent computational predictions.

Action at a distance: organic cation induced long range organization of interfacial water enhances hydrogen evolution and oxidation kinetics.

Engineering efficient electrode-electrolyte interfaces for the hydrogen evolution and oxidation reactions (HOR/HER) is central to the growing hydrogen economy. Existing descriptors for HOR/HER catalysts focused on species that could directly impact the immediate micro-environment of surface-mediated reactions, such as the binding energies of adsorbates. In this work, we demonstrate that bulky organic cations, such as tetrapropyl ammonium, are able to induce a long-range structure of interfacial water molecules and enhance the HOR/HER kinetics even though they are located outside the outer Helmholtz plane. Through a combination of electrokinetic analysis, molecular dynamics and in situ spectroscopic investigations, we propose that the structure-making ability of bulky hydrophobic cations promotes the formation of hydrogen-bonded water chains connecting the electrode surface to the bulk electrolyte. In alkaline electrolytes, the HOR/HER involve the activation of interfacial water by donating or abstracting protons. The structural diffusion mechanism of protons in aqueous electrolytes enables water molecules and cations located at a distance from the electrode to influence surface-mediated reactions. The findings reported in this work highlight the prospect of leveraging the nonlocal mechanism to enhance electrocatalytic performance.