Anodic molecular hydrogen formation on Ru and Cu electrodes

Scott, Søren B.; Engstfeld, Albert K.; Jusys, Z.; Hochfilzer, Degenhart; Knøsgaard, Nikolaj Rørbæk; Trimarco, Daniel Bøndergaard; Vesborg, Peter Christian Kjærgaard; Behm, R. Jürgen; Chorkendorff, Ib

doi:10.1039/d0cy01213k

Cited by 21 publications

(27 citation statements)

References 121 publications

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“…Electrochemistry–mass spectrometry (EC–MS) was pioneered by Bruckenstein and Gadde and has, since its further development in the 1980s, matured into a highly versatile and reliable tool to study electrochemical reactions, ranging from CO/CO 2 reduction, , water splitting, − hydrocarbon oxidation, , and metal dissolution to nonaqueous chemistries such as electrolyte and cathode decomposition reactions relevant for Li-ion batteries. − Recent iterations of EC–MS are able to reach an impressive temporal resolution, − which makes it possible to study the dynamic behavior of electrochemical reactions. This ability is particularly important for studying deactivation mechanisms or the effect of load variations, both relevant for practical applications, as well as for more fundamental aspects such as mechanism discrimination or transient activity measurements.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Interfacial Reaction Rates from Electrochemistry–Mass Spectrometry

et al. 2021

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Electrochemistry−mass spectrometry is a versatile and reliable tool to study the interfacial reaction rates of Faradaic processes with high temporal resolutions. However, the measured mass spectrometric signals typically do not directly correspond to the partial current density toward the analyte due to mass transport effects. Here, we introduce a mathematical framework, grounded on a mass transport model, to obtain a quantitative and truly dynamic partial current density from a measured mass spectrometer signal by means of deconvolution. Furthermore, it is shown that the time resolution of electrochemistry−mass spectrometry is limited by entropy-driven processes during mass transport to the mass spectrometer. The methodology is validated by comparing the measured impulse responses of hydrogen and oxygen evolution to the model predictions and subsequently applied to uncover dynamic phenomena during hydrogen and oxygen evolution in an acidic electrolyte.

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Section: Introductionmentioning

confidence: 99%

Dynamic Interfacial Reaction Rates from Electrochemistry–Mass Spectrometry

et al. 2021

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“…A recent advance in electrochemical mass spectrometry (EC-MS) provides submonolayer sensitivity for gas-generating reactions with time resolution on the order of 1 s. 25,26 The method was recently used to study H 2 evolution from polycrystalline Cu in alkaline media. 27 Surprisingly, some H 2 was generated at potentials positive of the reversible hydrogen electrode. The unanticipated phenomenon was attributed to a hydroxide displacement reaction where adsorbed hydrogen atoms combine and desorb as molecular H 2 as opposed to oxidative desorption as H 3 O + .…”

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confidence: 99%

“…The unanticipated phenomenon was attributed to a hydroxide displacement reaction where adsorbed hydrogen atoms combine and desorb as molecular H 2 as opposed to oxidative desorption as H 3 O + . 27 In the present work, EC-MS was applied to examine competitive adsorption and desorption of H and various anions on the three primary low-index surfaces of Cu. In parallel with the mass spectrometry study, vibrational spectroscopy using shell isolated nanoparticle enhanced Raman spectroscopy (SHINERS) was used to examine Cu(111) under near identical conditions, revealing previously unresolved features that are central to understanding the role of H in Cu surface chemistry.…”

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confidence: 99%

Surface Hydride Formation on Cu(111) and Its Decomposition to Form H₂ in Acid Electrolytes

Tackett

Raciti

Walker

et al. 2021

J. Phys. Chem. Lett.

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Mass spectrometry and Raman vibrational spectroscopy were used to follow competitive dynamics between adsorption and desorption of H and anions during potential cycling of three low-index Cu surfaces in acid electrolytes. Unique to Cu(111) is a redox wave for surface hydride formation coincident with anion desorption, while the reverse reaction of hydride decomposition with anion adsorption yields H 2 by recombination rather than oxidation to H 3 O + . Charge imbalance between the reactions accounts for the asymmetric voltammetry in SO 4 2− , ClO 4 − , PO 4 3− , and Cl − electrolytes with pH 0.68−4.5. Two-dimensional hydride formation is evidenced by the reduction wave prior to H 2 evolution and vibrational bands between 995 and 1130 cm −1 . In contrast to Cu(111), no distinct voltammetric signature of surface hydride formation is observed on Cu(110) and Cu(100). The Cu(111) hydride surface phase may serve to catalyze hydrofunctionalization reactions such as CO 2 reduction to CH 4 and should be broadly useful in electro-organic synthesis.

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“…The electrochemical experiments were performed in an electrochemical mass spectrometry setup with second-scale time resolution and sub monolayer sensitivity for gaseous electrochemical products. 22 This high sensitivity enables activity measurements to be performed at very low catalyst loadings where the intrinsic activity of nanoparticles can be studied by minimizing particle−particle interactions and masstransport limitations. The setup is based on a silicon membrane chip that forms the interface between the electrochemical cell and the mass spectrometer.…”

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confidence: 99%

The Importance of Potential Control for Accurate Studies of Electrochemical CO Reduction

et al. 2021

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CO reduction studies over nanostructured copper catalysts are hindered by copper's instability in alkaline conditions, which results in dissolution during immersion into the electrolyte, leading to ill-defined catalyst morphologies and loadings. Immersing catalysts under potential control can alleviate this problem, but an experimental approach for cells generally used for CO reduction experiments is lacking. We demonstrate that by using an auxiliary electrochemical cell, electrodes can be introduced under potential control in these kinds of reactors. We investigated CO reduction over mass-selected copper nanoparticles using electrochemistry−mass spectrometry and show that the CO reduction activity increases by 4 orders of magnitude compared to experiments without potential control. This is attributed to the inhibition of Cu dissolution during immersion into the electrolyte as demonstrated by subsequent copper-stripping experiments. Thus, this study stresses the need for the application of such procedures in order to determine the intrinsic activity of nanostructured copper catalysts.

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Anodic molecular hydrogen formation on Ru and Cu electrodes

Abstract: Electrochemical hydrogen adsorption and desorption, and the state of adsorbed hydrogen (*H) on metal surfaces are of fundamental interest as well as practical importance for the hydrogen evolution reaction (HER)...

Cited by 21 publications

References 121 publications

Dynamic Interfacial Reaction Rates from Electrochemistry–Mass Spectrometry

Dynamic Interfacial Reaction Rates from Electrochemistry–Mass Spectrometry

Surface Hydride Formation on Cu(111) and Its Decomposition to Form H₂ in Acid Electrolytes

The Importance of Potential Control for Accurate Studies of Electrochemical CO Reduction

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Anodic molecular hydrogen formation on Ru and Cu electrodes

Abstract: Electrochemical hydrogen adsorption and desorption, and the state of adsorbed hydrogen (*H) on metal surfaces are of fundamental interest as well as practical importance for the hydrogen evolution reaction (HER)...

Cited by 21 publications

References 121 publications

Dynamic Interfacial Reaction Rates from Electrochemistry–Mass Spectrometry

Dynamic Interfacial Reaction Rates from Electrochemistry–Mass Spectrometry

Surface Hydride Formation on Cu(111) and Its Decomposition to Form H2 in Acid Electrolytes

The Importance of Potential Control for Accurate Studies of Electrochemical CO Reduction

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Product

Resources

About

Surface Hydride Formation on Cu(111) and Its Decomposition to Form H₂ in Acid Electrolytes