Hydrogen evolution reaction mechanism on Ti3C2 MXene revealed by in situ/operando Raman spectroelectrochemistry

Johnson, Denis; Lai, Hao-En; Hansen, Kyle; Balbuena, Perla B.; Djire, Abdoulaye

doi:10.1039/d2nr00222a

Cited by 29 publications

(32 citation statements)

References 41 publications

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“…The full data set for this analysis is provided in Figure S2 (supplemental information). This further elucidated the mechanism by showing that electrons were entering the Ti 3 C 2 MXene, leading to an overcharging of the lattice and termination groups [20] . This movement of electrons is what consequently leads to protons being drawn towards the surface.…”

Section: Resultsmentioning

confidence: 77%

“…This further elucidated the mechanism by showing that electrons were entering the Ti 3 C 2 MXene, leading to an overcharging of the lattice and termination groups. [20] This movement of electrons is what consequently leads to protons being drawn towards the surface. When the oxidative region of the CV was reached, the Raman spectra and electronic environment returned to initial conditions, corresponding to the excess electrons leaving the structure allowing for adsorbed protons to desorb from the structure into the bulk electrolyte.…”

Section: Chemelectrochemmentioning

confidence: 99%

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Elucidating the Charge Storage Mechanism on Ti₃C₂ MXene through In Situ Raman Spectroelectrochemistry

et al. 2022

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Current climate issues can be partially remedied through the inclusion of renewable energy sources. However, these energy sources suffer from the need for highly efficient energy storage systems. To this end, studies have been conducted on developing energy storage materials that can provide high energy and power densities. Two-dimensional (2D) carbide and nitride MXenes have the potential to provide both if their mechanism of charge storage is understood. Here, we use in situ/operando Raman spectroelectrochemistry to investigate in real time the charge storage mechanism of the benchmark Ti 3 C 2 MXene in acidic and neutral media. We found that during charge/discharge cycling in acidic media, protons are pulled towards the surface, leading to a reversible reaction with the surface termination groups leading to a switch from À OÀ to À O(OH) to À OÀ chemistry, indicative of a pseudocapacitive mechanism. In neutral media, no pseudocapacitive behavior is observed and it is found that the material exhibits an electrostatic double layer charge storage mechanism through attracting sodium ions towards the surface for transient adsorption processes. Taking into consideration the mechanism we propose, the Ti 3 C 2 MXene can exhibit a pseudocapacitance of 358 F/g within a voltage window of 1.35 V. Ultimately, these fundamental insights can be used to design electrode materials with both high energy and power densities.

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Section: Resultsmentioning

confidence: 77%

Section: Chemelectrochemmentioning

confidence: 99%

Elucidating the Charge Storage Mechanism on Ti₃C₂ MXene through In Situ Raman Spectroelectrochemistry

et al. 2022

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“…We recently showed that the active site for HER on the Mxene catalyst is the À OÀ terminated site on the basal plane. [44] For Ti-based Mxenes, open Ti and O sites are critical for achieving high HER activity. While delaminating multilayer Mxenes into few-to-single layers provide some À OÀ termination sites, the results are difficult to reproduce due to the variability in the delamination procedure.…”

Section: Resultsmentioning

confidence: 99%

“…This difference in overpotential between delaminated and multilayer Ti 3 CN is due to the difference in exposed surface area and termination groups. We recently showed that the active site for HER on the Mxene catalyst is the −O− terminated site on the basal plane [44] . For Ti‐based Mxenes, open Ti and O sites are critical for achieving high HER activity.…”

Section: Resultsmentioning

confidence: 99%

Controlling the Surface Reactivity of Hybrid Ti₃CN MXene via In‐situ Electrocatalysis

2022

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Two-dimensional (2D) carbide and nitride MXenes possess properties that are desirable for a broad range of electrocatalytic applications including the hydrogen evolution reaction (HER). These properties include high surface area, hydrophilicity, heterogeneity of redox-active transition metals, and tunable surface functionalities allowing for low HER overpotentials. In this paper, we report on the cathodic etching and À O/À OH functionalization of hybrid Ti 3 CN upon the application of an external potential for improved HER performance and show that the active sites for HER on this MXene catalyst are located primarily on the À OÀ and À OH functional groups. The overpotential for the hybrid Ti 3 CN improves by 350 mV upon in-situ À O/À OH functionalization and etching, reaching À 0.46 V vs. RHE at a current density of 10 mA cm À 2 , much lower than those reported for the benchmark Ti 3 C 2 carbide MXene. These results provide a path forward to tuning the electrocatalytic activity of MXenes and related electrocatalysts for water splitting.

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“…This high overpotential value is maybe attributed to the lack of an ideal equilibrium between Ti and O sites in this sample. 44 In the case of the chalcogen decorated Ti 3 C 2 T x MXene composite samples, it already was proven by the XPS characterization (Figures S2 and 2) that the =O content was enhanced slightly after decoration.…”

Section: Hydrogen Evolution Reactionmentioning

confidence: 87%

Chalcogen (S, Se, and Te) decorated few-layered Ti₃C₂T_x MXene hybrids: modulation of properties through covalent bonding

et al. 2023

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Hydrogen evolution reaction mechanism on Ti₃C₂ MXene revealed by in situ/operando Raman spectroelectrochemistry

Abstract: MXenes have shown great promise as electrocatalysts for the hydrogen evolution reaction (HER), but their mechanism is still poorly understood. Currently, the benchmark Ti3C2 MXene suffers from a large overpotential....

Cited by 29 publications

References 41 publications

Elucidating the Charge Storage Mechanism on Ti₃C₂ MXene through In Situ Raman Spectroelectrochemistry

Elucidating the Charge Storage Mechanism on Ti₃C₂ MXene through In Situ Raman Spectroelectrochemistry

Controlling the Surface Reactivity of Hybrid Ti₃CN MXene via In‐situ Electrocatalysis

Chalcogen (S, Se, and Te) decorated few-layered Ti₃C₂T_x MXene hybrids: modulation of properties through covalent bonding

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Hydrogen evolution reaction mechanism on Ti3C2 MXene revealed by in situ/operando Raman spectroelectrochemistry

Abstract: MXenes have shown great promise as electrocatalysts for the hydrogen evolution reaction (HER), but their mechanism is still poorly understood. Currently, the benchmark Ti3C2 MXene suffers from a large overpotential....

Cited by 29 publications

References 41 publications

Elucidating the Charge Storage Mechanism on Ti3C2 MXene through In Situ Raman Spectroelectrochemistry

Elucidating the Charge Storage Mechanism on Ti3C2 MXene through In Situ Raman Spectroelectrochemistry

Controlling the Surface Reactivity of Hybrid Ti3CN MXene via In‐situ Electrocatalysis

Chalcogen (S, Se, and Te) decorated few-layered Ti3C2Tx MXene hybrids: modulation of properties through covalent bonding

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Hydrogen evolution reaction mechanism on Ti₃C₂ MXene revealed by in situ/operando Raman spectroelectrochemistry

Elucidating the Charge Storage Mechanism on Ti₃C₂ MXene through In Situ Raman Spectroelectrochemistry

Elucidating the Charge Storage Mechanism on Ti₃C₂ MXene through In Situ Raman Spectroelectrochemistry

Controlling the Surface Reactivity of Hybrid Ti₃CN MXene via In‐situ Electrocatalysis

Chalcogen (S, Se, and Te) decorated few-layered Ti₃C₂T_x MXene hybrids: modulation of properties through covalent bonding