Partial Reactions of Copper Dissolution under Cathodic Polarization in Acidic Media

Kreizer, I. V.; Маршаков, И. К.; Tutukina, N. M.; Зарцын, И. Д.

doi:10.1023/b:prom.0000013107.65745.b0

Cited by 12 publications

(5 citation statements)

References 3 publications

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“…The beneficial effect of the latter was assigned to the reduction of ZnO to Zn. Oxygen also has detrimental effects on cathodes in acidic media at low negative potentials and, for example, cathodes such as Ag 201 and Cu 202 − 204 can corrode to some extent. With Cu cathodes, the initial rate of dissolution was high, but later the produced metal cations started to electrodeposit back onto the cathode and the corrosion reached a steady state.…”

Section: Cathodic Corrosion Processesmentioning

confidence: 99%

“…With Cu cathodes, the initial rate of dissolution was high, but later the produced metal cations started to electrodeposit back onto the cathode and the corrosion reached a steady state. 202,204 However, this type of corrosion could have important consequences when these cathode materials are used in flow cells and the solution is not deareated. There, the electrodeposition could be effectively inhibited, and, in addition, this type of corrosion-redeposit process could affect the Faradaic efficiency as well.…”

Section: Formation Of Organometallicsmentioning

confidence: 99%

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Cathodic Corrosion of Metal Electrodes—How to Prevent It in Electroorganic Synthesis

et al. 2021

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The critical aspects of the corrosion of metal electrodes in cathodic reductions are covered. We discuss the involved mechanisms including alloying with alkali metals, cathodic etching in aqueous and aprotic media, and formation of metal hydrides and organometallics. Successful approaches that have been implemented to suppress cathodic corrosion are reviewed. We present several examples from electroorganic synthesis where the clever use of alloys instead of soft neat heavy metals and the application of protective cationic additives have allowed to successfully exploit these materials as cathodes. Because of the high overpotential for the hydrogen evolution reaction, such cathodes can contribute toward more sustainable green synthetic processes. The reported strategies expand the applications of organic electrosynthesis because a more negative regime is accessible within protic media and common metal poisons, e.g., sulfur-containing substrates, are compatible with these cathodes. The strongly diminished hydrogen evolution side reaction paves the way for more efficient reductive electroorganic conversions.

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Section: Cathodic Corrosion Processesmentioning

confidence: 99%

Section: Formation Of Organometallicsmentioning

confidence: 99%

Cathodic Corrosion of Metal Electrodes—How to Prevent It in Electroorganic Synthesis

et al. 2021

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“…38,39 Anomalous dissolution of Cu in acidic media under cathodic polarization was previously connected to the oxygen reduction reaction (ORR). [40][41][42] In addition to reaction intermediates, the cathodic bias itself contributes to the evolution of surface morphology. For instance, a joint experimental-theoretical study on graphene-covered polycrystalline copper showed that at negative potentials (< -1.0 V vs SHE), closed packed facets such as Cu(111) and Cu(100) reconstruct to more stable undercoordinated sites.…”

Section: Operating Parameters Influence Cu Dissolution Ratementioning

confidence: 99%

Cu+ transient species mediate Cu catalyst reconstruction during CO2 electroreduction

Vávra

Dattila²,

Kormányos

et al. 2022

Preprint

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Understanding metal surface reconstruction during operation is of the uttermost importance in heterogeneous catalysis as it directly affects the available active sites. However, surface reconstruction is notoriously difficult to study because of the dynamic nature of the phenomena behind it. Here, we report on the mechanism and the intermediates, which drive the rearrangement of copper catalysts during the electrochemical CO2 reduction reaction. In-situ methods, including mass spectrometry and fluorescence spectroscopy, evidence a dissolution – redeposition process mediated by transient species containing copper in +1 oxidation state. Theory identifies copper-adsorbate complexes which form in solution under operating conditions. Copper carbonyls and oxalates emerge as the major reaction-specific species driving copper reconstruction. This work motivates future studies to specifically target these compounds to improve the catalyst operational stability in the electrochemical CO2 reduction reaction.

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“…S13a and S12b, respectively, which are consistent with the CV observations. It's important to emphasize that in our experiments, the electrolyte was thoroughly de-aerated to eliminate oxygen, which, if present, could lead to further dissolution of Cu, as reported in previous studies 54 . To experimentally demonstrate this, we intentionally reintroduced oxygen into the H 2 SO 4 electrolyte by blowing air (Table S1, entry 9), which then resulted in significant copper dissolution observable through both IL-TEM and CV methods (Figs.…”

Section: A Hitherto Unexplored Yet Critical Reconstruction Pathway Fo...mentioning

confidence: 88%

Alkali cation-induced cathodic corrosion in Cu electrocatalysts

Liu,

Li,

Wang

et al. 2024

Nat Commun

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The reconstruction of Cu catalysts during electrochemical reduction of CO2 is a widely known but poorly understood phenomenon. Herein, we examine the structural evolution of Cu nanocubes under CO2 reduction reaction and its relevant reaction conditions using identical location transmission electron microscopy, cyclic voltammetry, in situ X-ray absorption fine structure spectroscopy and ab initio molecular dynamics simulation. Our results suggest that Cu catalysts reconstruct via a hitherto unexplored yet critical pathway - alkali cation-induced cathodic corrosion, when the electrode potential is more negative than an onset value (e.g., −0.4 VRHE when using 0.1 M KHCO3). Having alkali cations in the electrolyte is critical for such a process. Consequently, Cu catalysts will inevitably undergo surface reconstructions during a typical process of CO2 reduction reaction, resulting in dynamic catalyst morphologies. While having these reconstructions does not necessarily preclude stable electrocatalytic reactions, they will indeed prohibit long-term selectivity and activity enhancement by controlling the morphology of Cu pre-catalysts. Alternatively, by operating Cu catalysts at less negative potentials in the CO electrochemical reduction, we show that Cu nanocubes can provide a much more stable selectivity advantage over spherical Cu nanoparticles.

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Partial Reactions of Copper Dissolution under Cathodic Polarization in Acidic Media

Cited by 12 publications

References 3 publications

Cathodic Corrosion of Metal Electrodes—How to Prevent It in Electroorganic Synthesis

Cathodic Corrosion of Metal Electrodes—How to Prevent It in Electroorganic Synthesis

Cu+ transient species mediate Cu catalyst reconstruction during CO2 electroreduction

Alkali cation-induced cathodic corrosion in Cu electrocatalysts

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