Keeping sight of copper in single-atom catalysts for electrochemical carbon dioxide reduction

Creissen, Charles E.; Fontecave, Marc

doi:10.1038/s41467-022-30027-x

Cited by 74 publications

(61 citation statements)

References 30 publications

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“…17 In addition, a more interesting structural transformation occurred on Cu SACs during CO 2 reduction. Fontecave et al 18,19 reported that single-atom Cu 2+ dispersed in the N-doped carbon material, under a certain range of negative electrode potential, could be transformed into Cu 0 small clusters. In turn, it can be restored to Cu 2+ in the initial atomic dispersion state after releasing the applied potential or switching to a positive potential.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Stability of Copper Single-Atom Catalysts under Working Conditions

et al. 2022

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The long-term stability of single-atom catalysts is a major factor affecting their large-scale commercial application. How to evaluate the dynamic stability of single-atom catalysts under working conditions is still lacking. Here, taking a single copper atom embedded in N-doped graphene as an example, the "constant-potential hybrid-solvation dynamic model" is used to evaluate the reversible transformation between copper single atoms and clusters under realistic reaction conditions. It is revealed that the adsorption of H is a vital driving force for the leaching of the Cu single atom from the catalyst surface. The more negative the electrode potential, the stronger the adsorption of H. As a result, the competitive hydrogen evolution reaction is inhibited, and Cu−N bonds are weakened, resulting in some Cu atoms being tethered on the catalyst surface and some being dissolved in the aqueous solution. The collision of the Cu atoms in the two states forms a transient Cu cluster structure as a true catalytic active site to promote CO 2 reduction to ethanol. As the applied potential is released or switched to a positive value, hydroxyl radicals (OH • ) play a dominant role in the oxidation process of the Cu cluster, and then Cu returns to the initial atomic dispersion state by redeposition, completing the reconstruction cycle of the copper catalyst. Our work provides a fundamental understanding of the dynamic stability of Cu single-atom catalysts under working conditions at the atomic level and calls for a reassessment of the stability of currently reported single-atom catalysts considering realistic reaction conditions.

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Section: Introductionmentioning

confidence: 99%

Dynamic Stability of Copper Single-Atom Catalysts under Working Conditions

et al. 2022

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“…Hence, these Cu clusters have been proposed to be responsible for the activity of the catalyst towards the CO 2 RR. 6,11 It is important to note that this process is reversible, namely that CuN 4 sites are regenerated upon reoxidation. This seems to be a quite general behaviour of single Cu sites since such a reversible rearrangement of Cu species (the interconversion of single site and clusters), has also been observed with Cu phthalocyanine as well as with O-ligated single Cu atoms anchored in oxygenated carbon, 12,13 as clearly established by operando XAS.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical CO₂ reduction on Cu single atom catalyst and Cu nanoclusters: an ab initio approach

Cruz

Fontecave

2022

Phys. Chem. Chem. Phys.

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“…However, previously reported catalysts suffered from the easy desorption of *CO intermediate and the aggregation into copper clusters in the electrocatalysis process. [10] Compared with inorganic catalysts, crystalline metal complexes have the advantages of clear catalytic sites and structural designability. [11] As crystalline porous materials, a number of two-dimensional (2D) conductive covalent-organic frame-works (COFs), [12] compared to metal-organic frameworks, are constructed through covalent bonds, endowing them with impressive stability for device application.…”

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confidence: 99%

A Stable and Conductive Covalent Organic Framework with Isolated Active Sites for Highly Selective Electroreduction of Carbon Dioxide to Acetate

et al. 2022

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Electroreduction of CO2 to acetate provides a promising strategy to reduce CO2 emissions and store renewable energy, but acetate is usually a by‐product. Here, we show a stable and conductive two‐dimensional phthalocyanine‐based covalent‐organic framework (COF) as an electrocatalyst for reduction of CO2 to acetate with a single‐product Faradaic efficiency (FE) of 90.3(2)% at −0.8 V (vs. RHE) and a current density of 12.5 mA cm−2 in 0.1 M KHCO3 solution. No obvious degradation was observed over 80 hours of continuous operation. Combined with the comparison of the properties of other catalysts with isolated metal active sites, theoretical calculations and in situ infrared spectroscopy revealed that the isolated copper‐phthalocyanine active site with high electron density is conducive to the key step of C−C coupling of *CH3 with CO2 to produce acetate, and can avoid the coupling of *CO with *CO or *CHO to produce ethylene and ethanol.

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Keeping sight of copper in single-atom catalysts for electrochemical carbon dioxide reduction

Cited by 74 publications

References 30 publications

Dynamic Stability of Copper Single-Atom Catalysts under Working Conditions

Dynamic Stability of Copper Single-Atom Catalysts under Working Conditions

Electrochemical CO₂ reduction on Cu single atom catalyst and Cu nanoclusters: an ab initio approach

A Stable and Conductive Covalent Organic Framework with Isolated Active Sites for Highly Selective Electroreduction of Carbon Dioxide to Acetate

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Keeping sight of copper in single-atom catalysts for electrochemical carbon dioxide reduction

Cited by 74 publications

References 30 publications

Dynamic Stability of Copper Single-Atom Catalysts under Working Conditions

Dynamic Stability of Copper Single-Atom Catalysts under Working Conditions

Electrochemical CO2 reduction on Cu single atom catalyst and Cu nanoclusters: an ab initio approach

A Stable and Conductive Covalent Organic Framework with Isolated Active Sites for Highly Selective Electroreduction of Carbon Dioxide to Acetate

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Electrochemical CO₂ reduction on Cu single atom catalyst and Cu nanoclusters: an ab initio approach