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1.
J Am Chem Soc ; 2020 Dec 31.
Artigo em Inglês | MEDLINE | ID: mdl-33382947

RESUMO

The electrochemical CO2 reduction reaction (CO2RR) using Cu-based catalysts holds great potential for producing valuable multi-carbon products from renewable energy. However, the chemical and structural state of Cu catalyst surfaces during the CO2RR remains a matter of debate. Here, we show the structural evolution of the near-surface region of polycrystalline Cu electrodes under in situ conditions through a combination of grazing incidence X-ray absorption spectroscopy (GIXAS) and X-ray diffraction (GIXRD). The in situ GIXAS reveals that the surface oxide layer is fully reduced to metallic Cu before the onset potential for CO2RR, and the catalyst maintains the metallic state across the potentials relevant to the CO2RR. We also find a preferential surface reconstruction of the polycrystalline Cu surface toward (100) facets in the presence of CO2. Quantitative analysis of the reconstruction profiles reveals that the degree of reconstruction increases with increasingly negative applied potentials, and it persists when the applied potential returns to more positive values. These findings show that the surface of Cu electrocatalysts is dynamic during the CO2RR, and emphasize the importance of in situ characterization to understand the surface structure and its role in electrocatalysis.

2.
Phys Chem Chem Phys ; 21(10): 5402-5408, 2019 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-30785434

RESUMO

The rational improvement of current and developing electrochemical technologies requires atomistic understanding of electrode-electrolyte interfaces. However, examining these interfaces under operando conditions, where performance is typically evaluated and benchmarked, remains challenging, as it necessitates incorporating an operando probe during full electrochemical operation. In this study, we describe a custom electrochemical flow cell that enables near-surface-sensitive operando investigation of planar thin-film catalysts at significant hydrogen evolution reaction (HER) rates (in excess of -100 mA cm-2) using grazing incidence X-ray methods. Grazing-incidence X-ray spectroscopy and diffraction were implemented on the same sample under identical HER conditions, demonstrating how the combined measurements track changing redox chemistry and structure of Cu thin-film catalyst surfaces as a function of electrochemical conditions. The coupling of these methods with improved mass transport and hydrodynamic control establishes a new paradigm for operando measurement design, enabling unique insights into the key fundamental processes occurring at the catalyst-electrolyte interface.

3.
Langmuir ; 33(37): 9464-9471, 2017 09 19.
Artigo em Inglês | MEDLINE | ID: mdl-28691827

RESUMO

We have studied the influence of low concentrations (0.1 M) of the ionic liquid 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl) on suppressing the hydrogen evolution reaction (HER) using polycrystalline Ag, Cu, and Fe electrodes in aqueous acidic and basic media. HER suppression is generally desired when aiming to catalyze other reactions of interests, e.g., CO2 electro-reduction. Cyclic voltammetry and chronoamperometry measurements were performed at potentials between -0.2 and -0.8 V versus the reversible hydrogen electrode (RHE) to investigate HER activity in a simulated CO2 electrolysis environment without the CO2. In an acidic electrolyte, a decrease in HER activity was observed for all three electrodes with the largest effect being that of Fe, where the HER activity was suppressed by 75% at -0.5 V versus RHE. In contrast to the effect of [EMIM]Cl in an acidic electrolyte, no HER suppression was observed in basic media. Using 1H nuclear magnetic resonance spectroscopy on the electrolyte before and after electrolysis, it was determined that [EMIM]Cl breaks down at both the working and counter electrodes under reaction conditions under both acidic and basic conditions. These results underscore the challenges in employing ionic liquids for electrochemical reactions such as CO2 reduction.

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