The rate-determining term of electrocatalytic reactions with first-order kinetics

Huang, Jun; Zhu, Xinwei; Eikerling, Michael

doi:10.1016/j.electacta.2021.139019

Cited by 32 publications

(57 citation statements)

References 56 publications

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“…In the context of a serial resistor network, the notion of a ratedetermining term (RDT) becomes meaningful. 33,42 As shown in Figure 3b deviation: the surface charging effects and lateral adsorbate− adsorbate interactions. φ OHP is negative due to negative σ M (Figure 3d), and decreases with overpotential following the surface charging relation, as presented in Figure S9.…”

Section: Reaction Environmentmentioning

confidence: 98%

“…Therefore, the activity of CO 2 RR to CO can be represented as a series of resistances. In the context of a serial resistor network, the notion of a rate-determining term (RDT) becomes meaningful. , …”

Section: Revealing the Impact Of The Local Reaction Environmentmentioning

confidence: 99%

“…When φ M < −0.4 V, is the RDT, and . A more general analysis of the Tafel slope of multielectron reactions can be found in ref .…”

Section: Revealing the Impact Of The Local Reaction Environmentmentioning

confidence: 99%

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Electrochemical CO₂ Reduction at Silver from a Local Perspective

2021

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The electrochemical reduction of CO2 to chemical fuels and value-added chemicals is a viable pathway to store renewably generated electrical energy and to mitigate the negative impact of anthropogenic CO2 production. Herein, we study how the local reaction environment dictates the mechanism and kinetics of CO2 reduction to CO at an Ag electrode. The local reaction environment is determined using a hierarchical model that accounts for multistep reaction kinetics, specific surface charging state at a given electrode potential, and mass transport phenomena. The model reveals vital mechanistic insights into the reaction behavior. The increasing Tafel slope with overpotential is seen to be influenced by the surface charging relation and mass transport effects. In addition, the decrease of the CO current density at high overpotentials is found to be caused not only by the decrease in CO2 concentration due to mass transport, surface charge effects, and pH increase but also by lateral interactions between HCOOad, COOHad, and Had. Moreover, we explore how the electrolyte properties, including bicarbonate concentration, solvated cation size, and CO2 partial pressure, tune the local reaction environment.

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Section: Reaction Environmentmentioning

confidence: 98%

Section: Revealing the Impact Of The Local Reaction Environmentmentioning

confidence: 99%

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Electrochemical CO₂ Reduction at Silver from a Local Perspective

2021

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“…Typically, the potential‐determining steps for OER can either be the formation of *O from *OH (Equation (15)) or the transformation of *O to *OOH (Equations (17)–(21)) in OER as determined through DFT. [ 78,79 ] Partanen et al. studied the kinetic barriers of the OER on singly and doubly N‐doped single‐walled carbon nanotubes, denoted as NCNTs and N2CNTs, respectively.…”

Section: Fundamentals Of Oxygen Electrocatalysis On N‐doped Carbon Ma...mentioning

confidence: 99%

“…Typically, the potential-determining steps for OER can either be the formation of *O from *OH (Equation ( 15)) or the transformation of *O to *OOH (Equations ( 17)-( 21)) in OER as determined through DFT. [78,79] Partanen et al studied the kinetic barriers of the OER on singly and doubly N-doped single-walled carbon nanotubes, denoted as NCNTs and N2CNTs, respectively. [80] A four-step OER process was considered and the formation of *OOH was found to be the rate-determining step on both structures, while the kinetic barrier over NCNTs is 0.4 eV lower than that over N2CNTs.…”

Section: Oer: Reaction Pathway and Mechanismsmentioning

confidence: 99%

Nitrogen‐Rich Carbonaceous Materials for Advanced Oxygen Electrocatalysis: Synthesis, Characterization, and Activity of Nitrogen Sites

Meng

Morales

et al. 2022

Adv Funct Materials

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Nitrogen‐doped carbons are among the fastest‐growing class of materials used for oxygen electrocatalysis, namely, the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), thanks to their low cost, environmental friendliness, excellent electrical conductivity, and scalable synthesis. The perspective of replacing precious metal‐based electrocatalysts with nitrogen‐doped carbon is highly desirable for reducing costs in energy conversion and storage systems. In this review, the role of nitrogen and N‐induced structural defects on the enhanced performance of N‐doped carbon electrocatalysts toward the OER and the ORR as well as their applications for energy conversion and storage technologies is summarized. The synthesis of N‐doped carbon electrocatalysts and the characterization of their nitrogen functional groups and active sites for the conversion of oxygen are also reviewed. The electrocatalytic performance of the main types of N‐doped carbon materials for OER/ORR electrocatalysis are then discussed. Finally, major challenges and future opportunities of N‐doped carbons as advanced oxygen electrocatalysts are highlighted.

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(B, N)‐Rich B−C−N Nanosheet‐assembled Microwires as Effective Electrocatalysts for Oxygen Reduction Reaction

Cao,

Yang,

et al. 2023

ChemNanoMat

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Developing highly active and stable nanocarbon electrocatalysts for the oxygen reduction reaction (ORR) in alkaline medium has attracted much attention due to their potential as an alternative to traditional metal‐based or noble metal catalysts. Herein, a unique micro‐nano structure of (B, N)‐rich B−C−N nanosheet‐assembled microwires (BCNNAM) were synthesized and driven electrochemical oxide reduction reaction. The diameter of the microwires about 1 μm, while the nanosheets have an average thickness of less than 20 nm. The compact nanosheets are mostly separated with a bending, curling and crumpling morphology. All those constitutes a ternary system with large surface area and abundant activity sites facilitate fast mass/electron transport for ORR catalytic activity. Thus, the B, N‐rich B−C−N nanosheet‐assembled microwires show significantly improved electrocatalytic activity with an onset potential of 0.95 V and half‐wave potential of 0.83 V compared to BNNAM, nitride‐doped carbon, porous carbon and a commercial Pt/C electrocatalyst. Such high catalytic performance of B, N‐rich B−C−N micro‐nano structures is due to the enhanced activity by the coexistence of B, C and N and the mass transfer promoted by the unique hierarchical porous structure.

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The rate-determining term of electrocatalytic reactions with first-order kinetics

Cited by 32 publications

References 56 publications

Electrochemical CO₂ Reduction at Silver from a Local Perspective

Electrochemical CO₂ Reduction at Silver from a Local Perspective

Nitrogen‐Rich Carbonaceous Materials for Advanced Oxygen Electrocatalysis: Synthesis, Characterization, and Activity of Nitrogen Sites

(B, N)‐Rich B−C−N Nanosheet‐assembled Microwires as Effective Electrocatalysts for Oxygen Reduction Reaction

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The rate-determining term of electrocatalytic reactions with first-order kinetics

Cited by 32 publications

References 56 publications

Electrochemical CO2 Reduction at Silver from a Local Perspective

Electrochemical CO2 Reduction at Silver from a Local Perspective

Nitrogen‐Rich Carbonaceous Materials for Advanced Oxygen Electrocatalysis: Synthesis, Characterization, and Activity of Nitrogen Sites

(B, N)‐Rich B−C−N Nanosheet‐assembled Microwires as Effective Electrocatalysts for Oxygen Reduction Reaction

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Electrochemical CO₂ Reduction at Silver from a Local Perspective

Electrochemical CO₂ Reduction at Silver from a Local Perspective