Interfacial Water at a CO-Predosed Platinum Electrode: A Surface Enhanced Infrared Study with Strong Hydrogen Evolution Reaction Control

Yan, Yan-Gang; Peng, Bin; Yang, Yao‐Yue; Cai, Wen‐Bin; Bund, Andreas; Stimming, Ulrich

doi:10.1021/jp104180n

Cited by 24 publications

(31 citation statements)

References 69 publications

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“…Interaction of adsorbed CO with the interfacial water also contributed to the broadening of the CO peak from 10 in UHHV to 23 cm –1 in an electrolyte solution where the CO dipole vibration is coupled with that of interfacial water . A strong (a sort of chemical) bonding between the interfacial free water with CO ad has been suggested by Yan and co-workers . Our findings now demonstrate that CO ad interacting with interfacial water are CO L molecules.…”

supporting

confidence: 79%

“…The broad peak at 3462 cm −1 in Figure 1a is assigned to the νO−H oscillators of bulk-like water molecules possessing an extended hydrogen bonding network. Yan et al 30 further deconvoluted this band into three subpeaks at 3550, 3450, and 3250 cm −1 for the water with partially broken hydrogen bonding, the liquid-like water, and the icelike water, respectively. The two overlapping peaks at 3617 and 3659 cm −1 are assigned to the interfacial water molecules between CO ad and bulk-like water molecules.…”

mentioning

confidence: 99%

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Titrating Pt Surface with CO Molecules

Ren

Gobrogge

Lundgren

2019

J. Phys. Chem. Lett.

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Identification and quantification of the surface sites on Pt nanoparticles are essential for developing more active electrocatalysts for many practical devices such as fuel cells and electrochemical fuel generators. In this work, we studied CO adsorption from dissolved CO in an H 2 SO 4 electrolyte solution on a polycrystalline Pt film electrode held at a constant potential in the underpotential hydrogen deposition region using in situ attenuated total reflectance-surface-enhanced IR absorption spectroscopy (ATR-SEIRAS). Slowing down the adsorption rate by limiting the CO addition rate to the solution allows the individual CO molecules arriving at the Pt surface to rearrange, move to, and occupy their most energetically favorable sites. By using ATR-SEIRAS spectroscopy to follow the stepwise CO adsorption process, one can identify and quantify the Pt surface sites along with uncovering the CO adsorption energetic sequence. This method of slow CO adsorption on the Pt surface is analogous to the chemical titrations used for quantitative chemical analyses.

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confidence: 79%

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confidence: 99%

Titrating Pt Surface with CO Molecules

Ren

Gobrogge

Lundgren

2019

J. Phys. Chem. Lett.

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“…On the basis of this observation, the interaction of water with CO ads is often considered to be weak (78,119) compared with the hydrogen bonding in bulk water. However, it was shown that this interaction affects the electronic structure of the metal−CO bond (120), and it was suggested that the CO ads −H2O interaction may be stronger than previously assumed (121). Irrespective of this debate, our observations suggest that the two larger cations disrupt the CO ads −H2O interaction.…”

Section: Dependence Of the Co Ads −H 2 O Interaction On Cation Identitymentioning

confidence: 46%

“…Prior reports established that this band arises from interfacial waters that directly interact with CO ads (78,92,(117)(118)(119)(120)(121). These waters, which are not directly adsorbed on the electrode surface, have their O−D bonds pointed toward the terminal oxygen of CO ads (78,119).…”

Section: Dependence Of the Co Ads −H 2 O Interaction On Cation Identitymentioning

confidence: 95%

Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction

Gunathunge

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

138

160

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The product selectivity of many heterogeneous electrocatalytic processes is profoundly affected by the liquid side of the electrocatalytic interface. The electrocatalytic reduction of CO to hydrocarbons on Cu electrodes is a prototypical example of such a process. However, probing the interactions of surface-bound intermediates with their liquid reaction environment poses a formidable experimental challenge. As a result, the molecular origins of the dependence of the product selectivity on the characteristics of the electrolyte are still poorly understood. Herein, we examined the chemical and electrostatic interactions of surfaceadsorbed CO with its liquid reaction environment. Using a series of quaternary alkyl ammonium cations (methyl 4 N + , ethyl 4 N + , propyl 4 N + , and butyl 4 N + ), we systematically tuned the properties of this environment. With differential electrochemical mass spectrometry (DEMS), we show that ethylene is produced in the presence of methyl 4 N + and ethyl 4 N + cations, whereas this product is not synthesized in propyl 4 N + -and butyl 4 N + -containing electrolytes. Surface-enhanced infrared absorption spectroscopy (SEIRAS) reveals that the cations do not block CO adsorption sites and that the cation-dependent interfacial electric field is too small to account for the observed changes in selectivity. However, SEIRAS shows that an intermolecular interaction between surface-adsorbed CO and interfacial water is disrupted in the presence of the two larger cations. This observation suggests that this interaction promotes the hydrogenation of surface-bound CO to ethylene. Our study provides a critical molecular-level insight into how interactions of surface species with the liquid reaction environment control the selectivity of this complex electrocatalytic process.hydrogen bonding | cation effects | electrocatalysis | carbon dioxide reduction | catalytic selectivity T he reaction environment profoundly impacts the kinetics of many chemical processes. Examples include the influence of the solvating environment on the rates of electron transfer (1), isomerization (2), peptide folding (3), and organic reactions (4), as well as the sensitivity of enzymatic catalysis to changes in the molecular structure of the active site (5). For a chemical process that can lead to multiple reaction products, solvent effects can impact the relative rates of product formation and therefore the product selectivity (6, 7). These effects, which can have complex energetic and/or dynamical origins (1,8,9), are fundamentally rooted in intermolecular interactions between the reactants and their environment. In the context of heterogeneous electrocatalysis, the reaction environment is asymmetric; i.e., reactants at the electrochemical interface are interacting with the solid electrode and the liquid electrolyte. Understanding the interactions of intermediates with their interfacial environment is essential for controlling the reaction paths of electrocatalytic processes that exhibit poor product selectivity.The reduc...

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“…In general electrochemical routines, nickel alloy catalysts present high activity for the HER in alkaline electrolytes, while they are often degraded in acidic solutions. Pt has very small over potential for HER and exhibits excellent electrocatalytic activity, but the scarcity and high prices of these kinds of noble metals prohibit their widespread applications 10 . Therefore, exploring an economical, highly active, chemically stable and abundant materials as HER catalyst to replace the above noble metal and nickel alloy catalysts is of great importance and has attracted a great deal of attention in recent years.…”

mentioning

confidence: 99%

Charge-Transfer Induced High Efficient Hydrogen Evolution of MoS2/graphene Cocatalyst

et al. 2015

Sci Rep

111

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The MoS 2 and reduced graphite oxide (rGO) composite has attracted intensive attention due to its favorable performance as hydrogen evolution reaction (HER) catalyst, but still lacking is the theoretical understanding from a dynamic perspective regarding to the influence of electron transfer, as well as the connection between conductivity and the promoted HER performance. Based on the first-principles calculations, we here clearly reveal how an excess of negative charge density affects the variation of Gibbs free energy (ΔG) and the corresponding HER behavior. It is demonstrated that the electron plays a crucial role in the HER routine. To verify the theoretical analyses, the MoS 2 and reduced graphite oxide (rGO) composite with well defined 3-dimensional configuration was synthesized via a facile one-step approach for the first time. The experimental data show that the HER performance have a direct link to the conductivity. These findings pave the way for a further developing of 2-dimension based composites for HER applications.In recent years, the demands for the renewable and clean energy resources gradually become urgent for the growing problems of environmental pollution. Hydrogen, as a clean and efficient fuel source, has been vigorously pursued as a promising candidate for future energy carrier. The traditional way to produce hydrogen involving CO 2 release and the high temperature reaction condition will be phased out gradually for the related disadvantages 1 , therefore, developing techniques to produce hydrogen from economic and renewable resources can be beneficial to a significant reduction in consumption of fossil fuel and a lower CO 2 emissions. Recently, massive efforts have been devoted to producing hydrogen by electrochemical or photoelectrocatalytic processes from water splitting [2][3][4] . So far, many kinds of materials including nickel alloy, carbides, polymeric carbon nitride and transition metal chalcogenides have been attempted to serve as the HER catalysts [5][6][7] . Among these, the most common catalysts used for HER are noble metals, such as ruthenium, iridium and platinum 8,9 . In general electrochemical routines, nickel alloy catalysts present high activity for the HER in alkaline electrolytes, while they are often degraded in acidic solutions. Pt has very small over potential for HER and exhibits excellent electrocatalytic activity, but the scarcity and high prices of these kinds of noble metals prohibit their widespread applications 10

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Interfacial Water at a CO-Predosed Platinum Electrode: A Surface Enhanced Infrared Study with Strong Hydrogen Evolution Reaction Control

Cited by 24 publications

References 69 publications

Titrating Pt Surface with CO Molecules

Titrating Pt Surface with CO Molecules

Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction

Charge-Transfer Induced High Efficient Hydrogen Evolution of MoS2/graphene Cocatalyst

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