Selective conversion of CO into ethanol on Cu(511) surface reconstructed from Cu(pc): Operando studies by electrochemical scanning tunneling microscopy, mass spectrometry, quartz crystal nanobalance, and infrared spectroscopy

Baricuatro, Jack H.; Kim, Youn-Geun; Tsang, Chu F.; Javier, Alnald; Cummins, Kyle D.; Hemminger, John C.

doi:10.1016/j.jelechem.2019.113704

Cited by 11 publications

(15 citation statements)

References 23 publications

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“…Adsorbed species play key roles in critical steps that control the reaction rate and product specificity. The surface science approach is particularly suitable for non-noble electrodes like Cu whose surface is not only susceptible to air oxidation at ambient conditions , but is also structurally dynamic. , The protocol entails the scrutiny of surfaces with well-defined structure and composition before, during, and after the reaction of interest so that unambiguous correlations can be drawn. , We have used a suite of operando methods, electrochemical scanning tunneling microscopy (ECSTM), , differential electrochemical mass spectrometry (DEMS), , electrochemical quartz-crystal nanobalance (ECQCN), , and polarization-modulation infrared spectroscopy (PMIRS), − to uncover unprecedented atomic-level details of the behavior of polycrystalline ,, and single-crystal Cu electrodes ,,,, during CO 2 RR. We are interested in the surface interaction of CO because it is the first isolable intermediate of CO 2 reduction and serves as an analytical surrogate for CO 2 , especially in alkaline solution.…”

Section: Introductionmentioning

confidence: 99%

Operando Electrochemical Spectroscopy for CO on Cu(100) at pH 1 to 13: Validation of Grand Canonical Potential Predictions

et al. 2021

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Electrochemical reduction of CO2 to value-added products is an attractive strategy to address issues of increasing atmospheric CO2 concentration. Cu is the only pure metal catalyst known to electrochemically convert CO2 to appreciable amounts of oxygenates and hydrocarbons such as C2H5OH, CH4, and C2H4, but the Faraday efficiencies are too low and the onset potentials are too high. To discover electrocatalytic systems better than Cu, we use in silico strategies based on new grand canonical potential (GCP) methods, but the complexity of the electrode–electrolyte interface makes it difficult to validate the accuracy of GCP. Operando electrochemical polarization-modulation infrared spectroscopy (PMIRS) provides a performance benchmark for theoretical tools that account for the vibrational stretching frequencies of surface-bound CO, νCO, as a function of pH and applied potential U. We show here that GCP calculations of the surface coverages of H*, OH*, and CO* on Cu(100) as a function of U lead to excellent predictions of the potential-dependent νCO and its shift with pH from 1 to 13. This validation justifies the use of GCP for predicting the performance of catalyst designs.

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Section: Introductionmentioning

confidence: 99%

Operando Electrochemical Spectroscopy for CO on Cu(100) at pH 1 to 13: Validation of Grand Canonical Potential Predictions

et al. 2021

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“…A reconstructed Cu structure is consistent with previous studies demonstrating that the electrochemical oxidative-reductive process generates selective active sites for C-C coupling. 43,51 While we cannot rule out a small fraction of oxidized Cu below the error range of our LCF analysis, these post-mortem measurements suggest that control over the morphological transformation during catalysis may be a key parameter for achieving high catalytic activities in a practical CO electrolyzer.…”

Section: ■ Results and Discussionmentioning

confidence: 79%

Correlating Oxidation State and Surface Area to Activity from Operando Studies of Copper CO Electroreduction Catalysts in a Gas-Fed Device

et al. 2020

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The rational design of high-performance electrocatalysts requires a detailed understanding of dynamic changes in catalyst properties, including oxidation states, surface area, and morphology under realistic working conditions. Oxide-derived Cu catalysts exhibit a remarkable selectivity towards multi-carbon products for the electrochemical CO reduction reaction (CORR), but the exact role of oxide remains elusive for explaining the performance enhancements. Here, we used operando X-ray absorption spectroscopy (XAS) coupled with simultaneous measurements of catalyst activity and selectivity by gas chromatography (GC) to study the relationship between oxidation states of Cu-based catalysts and activity for ethylene (C 2 H 4 ) production in a CO gas-fed cell. By utilizing a custom-built XAS cell, oxidation states of Cu catalysts can be probed in device-relevant settings and under high current densities (>80 mA/cm -2 ) for CORR. By employing an electrochemical oxidation process, we found that the Cu oxidation states and specific ion species do not correlate with C 2 H 4 production. The difference in CORR activity is also investigated in relation to the electrochemical surface area (ECSA) changes. While hydrogen evolution reaction (HER) activity is positively correlated to the ECSA changes, the increased C 2 H 4 activity is not proportional to ECSA. Ex-situ characterization from microscopic techniques suggests that the changes in C 2 H 4 activity and selectivity may arise from a morphological transformation that evolves into a more active structure. These comprehensive results give rise to the development of a cell regeneration method that can restore the performance of Cu catalyst without cell disassembly. Our study establishes a basis for the rational design of highly active electrocatalysts for broad-range reactions in a gas-fed device.

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“…Kim et al have reported significant work using operando EC-STM to study Cu electrocatalyst surface restructuring and intermediate species adsorption for electrochemical CO 2 reduction. [205][206][207][208][209] During CO 2 reduction on Cu, the extent of hydrocarbon and alcohol formation depends on the crystal orientation of the electrocatalyst. It had previously been observed that polycrystalline Cu unexpectedly behaves like crystalline Cu(100) and generates ethylene as a major product.…”

Section: Ec-stmmentioning

confidence: 99%

In Situ Analytical Techniques for the Investigation of Material Stability and Interface Dynamics in Electrocatalytic and Photoelectrochemical Applications

et al. 2021

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Selective conversion of CO into ethanol on Cu(511) surface reconstructed from Cu(pc): Operando studies by electrochemical scanning tunneling microscopy, mass spectrometry, quartz crystal nanobalance, and infrared spectroscopy

Cited by 11 publications

References 23 publications

Operando Electrochemical Spectroscopy for CO on Cu(100) at pH 1 to 13: Validation of Grand Canonical Potential Predictions

Operando Electrochemical Spectroscopy for CO on Cu(100) at pH 1 to 13: Validation of Grand Canonical Potential Predictions

Correlating Oxidation State and Surface Area to Activity from Operando Studies of Copper CO Electroreduction Catalysts in a Gas-Fed Device

In Situ Analytical Techniques for the Investigation of Material Stability and Interface Dynamics in Electrocatalytic and Photoelectrochemical Applications

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