Fast Screening for Copper‐Based Bimetallic Electrocatalysts: Efficient Electrocatalytic Reduction of CO<sub>2</sub>to C<sub>2+</sub>Products on Magnesium‐Modified Copper

Xie, Mingcan; Shen, Yan; Ma, Wenchao; Wei, Di‐Ye; Zhang, Biao; Wang, Zihan; Wang, Yihan; Zhang, Qinghong; Xie, Shunji; Wang, Cheng; Wang, Ye

doi:10.1002/ange.202213423

Cited by 6 publications

(3 citation statements)

References 32 publications

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“…Thus, a strategy involving sequential electrochemical testing and online product quantification of well-controlled reaction conditions within geometrically well-defined reactors would be ideal for automating kinetic analysis. This automation strategy has been used to screen catalysts for the (photo)electrochemical CO 2 reduction reaction. − We demonstrate that a similar automation concept can be tailored to automate electrochemical kinetic analysis workflows.…”

Section: Introductionmentioning

confidence: 99%

Nonidealities in CO₂ Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis

Zeng,

Padia,

Chen

et al. 2024

ACS Cent. Sci.

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In electrocatalysis, mechanistic analysis of reaction rate data often relies on the linearization of relatively simple rate equations; this is the basis for typical Tafel and reactant order dependence analyses. However, for more complex reaction phenomena, such as surface coverage effects or mixed control, these common linearization strategies will yield incomplete or uninterpretable results. Cohesive kinetic analysis, which is often used in thermocatalysis and involves quantitative model fitting for data collected over a wide range of reaction conditions, requires more data but also provides a more robust strategy for interrogating reaction mechanisms. In this work, we report a robotic system that improves the experimental workflow for collecting electrochemical rate data by automating sequential testing of up to 10 electrochemical cells, where each cell can have a different electrode, electrolyte, gas-phase reactant composition, and applied voltage. We used this system to investigate the mechanism of carbon dioxide electroreduction to carbon monoxide at several immobilized metal tetrapyrroles. Specifically, at cobalt phthalocyanine (CoPc), cobalt tetraphenylporphyrin (CoTPP), and iron phthalocyanine (FePc), we see signatures of complex reaction mechanisms, where observed bicarbonate and CO 2 order dependences change with applied potential. We illustrate how phenomena such as electrolyte poisoning and potential-dependent degrees of rate control can explain the observed kinetic behaviors. Our mechanistic analysis suggests that CoPc and CoTPP share a similar reaction mechanism, akin to one previously proposed, whereas the mechanism for FePc likely involves a species later in the catalytic cycle as the most abundant reactive intermediate. Our study illustrates that complex reaction mechanisms that are not amenable to common Tafel and order dependence analyses may be quite prevalent across this class of immobilized metal tetrapyrrole electrocatalysts.

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Section: Introductionmentioning

confidence: 99%

Nonidealities in CO₂ Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis

Zeng,

Padia,

Chen

et al. 2024

ACS Cent. Sci.

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“…It also induces the rearrangement of the metal electronic structure, optimizes the adsorption of the key intermediates, and thus affects the intrinsic catalytic activity. 29,30 For instance, the doping of oxophilic transition metal Cr enables the modulation of the binding abilities of hydrogen and hydroxyl ions on the Ni surfaces. 31 The isolated Cu(I) ions strongly conjugated with NCN 2 − exhibit highly delocalized electrons, reducing the Cu−O interaction of the adsorbed CH 3 O* intermediate and thus switching the reaction paths.…”

Section: Introductionmentioning

confidence: 99%

Oxophilicity-Controlled CO₂ Electroreduction to C₂₊ Alcohols over Lewis Acid Metal-Doped Cu^δ+ Catalysts

Zhang,

Feng,

et al. 2023

J. Am. Chem. Soc.

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Cu-based electrocatalysts have great potential for facilitating CO 2 reduction to produce energy-intensive fuels and chemicals. However, it remains challenging to obtain high product selectivity due to the inevitable strong competition among various pathways. Here, we propose a strategy to regulate the adsorption of oxygen-associated active species on Cu by introducing an oxophilic metal, which can effectively improve the selectivity of C 2+ alcohols. Theoretical calculations manifested that doping of Lewis acid metal Al into Cu can affect the C−O bond and Cu−C bond breaking toward the selectively determining intermediate (shared by ethanol and ethylene), thus prioritizing the ethanol pathway. Experimentally, the Al-doped Cu catalyst exhibited an outstanding C 2+ Faradaic efficiency (FE) of 84.5% with remarkable stability. In particular, the C 2+ alcohol FE could reach 55.2% with a partial current density of 354.2 mA cm −2 and a formation rate of 1066.8 μmol cm −2 h −1 . A detailed experimental study revealed that Al doping improved the adsorption strength of active oxygen species on the Cu surface and stabilized the key intermediate *OC 2 H 5 , leading to high selectivity toward ethanol. Further investigation showed that this strategy could also be extended to other Lewis acid metals.

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“…This automation strategy has been used to screen catalysts for the (photo)electrochemical CO2 reduction reaction (CO2RR). [26][27][28][29] We demonstrate that a similar automation concept can be tailored to automate electrochemical kinetic analysis workflows. In this work, we introduce a robotic platform designed to automate electrochemical reaction rate data collection.…”

Section: Introductionmentioning

confidence: 99%

Non-idealities in CO2 electroreduction mechanisms revealed by automation-assisted kinetic analysis

Zeng,

Padia,

Maalouf

et al. 2023

Preprint

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In electrocatalysis, mechanistic analysis of reaction rate data often relies on linearization of relatively simple rate equations; this is the basis for typical Tafel and reactant order dependence analyses. However, for more complex reaction phenomena, such as surface coverage effects or mixed control, these common linearization strategies will yield incomplete or uninterpretable results. Cohesive kinetic analysis, which is often used in thermocatalysis and involves quantitative model fitting for data collected over a wide range of reaction conditions, requires more data but also provides a more robust strategy for interrogating reaction mechanisms. In this work, we report a robotic system that improves the experimental workflow for collecting electrochemical rate data by automating sequential testing of up to ten electrochemical cells that can each have a different electrode, electrolyte, gas-phase reactant composition, and applied voltage. We use this system to investigate the mechanism of carbon dioxide electroreduction to carbon monoxide at several immobilized metal tetrapyrroles. Specifically, at cobalt phthalocyanine (CoPc), cobalt tetraphenylporphyrin (CoTPP), and iron phthalocyanine (FePc), we see signatures of complex reaction mechanisms, where observed bicarbonate and CO2 order dependences change with applied potential. We illustrate how phenomena such as electrolyte poisoning and potential-dependent degrees of rate control can explain the observed kinetic behaviors. Our mechanistic analysis suggests that CoPc and CoTPP share a similar reaction mechanism, akin to one that has been previously proposed, whereas the mechanism for FePc likely involves a species later in the catalytic cycle as the most abundant reactive intermediate. Our study illustrates that complex reaction mechanisms which are not amenable to common Tafel and order dependence analyses may be quite prevalent across this class of immobilized metal tetrapyrrole electrocatalysts.

show abstract

Fast Screening for Copper‐Based Bimetallic Electrocatalysts: Efficient Electrocatalytic Reduction of CO₂to C₂₊Products on Magnesium‐Modified Copper

Cited by 6 publications

References 32 publications

Nonidealities in CO₂ Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis

Nonidealities in CO₂ Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis

Oxophilicity-Controlled CO₂ Electroreduction to C₂₊ Alcohols over Lewis Acid Metal-Doped Cu^δ+ Catalysts

Non-idealities in CO2 electroreduction mechanisms revealed by automation-assisted kinetic analysis

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Fast Screening for Copper‐Based Bimetallic Electrocatalysts: Efficient Electrocatalytic Reduction of CO2to C2+Products on Magnesium‐Modified Copper

Cited by 6 publications

References 32 publications

Nonidealities in CO2 Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis

Nonidealities in CO2 Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis

Oxophilicity-Controlled CO2 Electroreduction to C2+ Alcohols over Lewis Acid Metal-Doped Cuδ+ Catalysts

Non-idealities in CO2 electroreduction mechanisms revealed by automation-assisted kinetic analysis

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Resources

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Fast Screening for Copper‐Based Bimetallic Electrocatalysts: Efficient Electrocatalytic Reduction of CO₂to C₂₊Products on Magnesium‐Modified Copper

Nonidealities in CO₂ Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis

Nonidealities in CO₂ Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis

Oxophilicity-Controlled CO₂ Electroreduction to C₂₊ Alcohols over Lewis Acid Metal-Doped Cu^δ+ Catalysts