Charge Transfer Rates Controlled by Frequency Dispersion of Double-Layer Capacitances

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

Comments and Suggestions for Authors

This manuscript presents a relevant and timely investigation into charge transfer kinetics and negative capacitance in electrochemical systems. The topic is interesting, and the experimental approach, particularly the use of impedance analysis, is appropriate. However, a few areas would benefit from clarification or revision to improve the manuscript's clarity and overall presentation. Please consider the following suggestions:

1. Reviewer Comment (Abstract):

The abstract covers a valuable and timely topic, but the writing needs improvement for better clarity and impact.

Some sentences are too long or complex, making key ideas hard to follow.

Certain terms or phrases (e.g., ranged too widely dispersed, power of the time, as if it were kinetics) are unclear or confusing.

2. Reviewer Comment (Introduction, lines 30–33):

The list of steps describing the observed rates of electrode reactions is generally reasonable, but some parts could be clearer. In particular, the terms “neutralization of local charge with salts” and “complication by double layers” are not typically described as separate kinetic steps in standard electrochemistry. Instead, these are usually considered modifying or influencing factors that affect the charge transfer and mass transfer steps, rather than independent processes.

Comments on the Quality of English Language

The manuscript would benefit from careful language editing to improve clarity, sentence structure, and terminology. While the overall meaning is understandable, several sections contain awkward phrasing, overly long sentences, and nonstandard expressions that may hinder comprehension. A thorough revision by a proficient English speaker or a professional editing service is recommended to enhance readability and ensure precise scientific communication.

Author Response

Our response in written in the attachment

Author Response File: Author Response.pdf

Reviewer 2 Report

Comments and Suggestions for Authors

Charge Transfer Rates Controlled by Frequency Dispersion of Double Layer Capacitances

Koichi Jeremiah Aoki and Jingyuan Chen

The authors report on a correction method to calculating rate constants of charge transfer reactions. The authors have taken into account the time-variation of the DLC, which affects the heterogeneous electrode kinetics. The authors have considered the correction for the solvation delay and examined this phenomenon by electrochemical impedance spectroscopy to conclude the delay from diffusion-control was attributed to the negative capacitance rather than the charge transfer.

Although the paper has value in understanding charge transfer rates at DLC, it needs to be more coherent. This manuscript can be accepted after addressing the specific comments listed below:

1. It would be helpful to the readers if the authors improve a little bit on the theory sections, particularly by separating the equations from sentences. It will take a bit more space but easy for the readers to follow.

2. From the Kinetic Rate equation it seems that authors have assumed first order rate equations only. Are dipole interactions always first order? 

3. Please explain the fig. 2 equivalent electrical circuit model properly, with all the associated terms used in the figure.

4. The authors have used Z_k1 and Z₁ as well as Z_k2 and Z₂ synonymously. Please use only one in plots and equations.

5. Does the working electrode influence the results? Has the authors performed or considered to perform experiments with other working electrodes, other than Pt, to validate their model? 

6. The impedance is plotted across 0.5 Hz to 5 kHz frequency range. Is there value in running cyclic voltammetry at multiple scan rates (faster and slower) to bring out electrochemical features to better interpret this model?

Author Response

Our reply is written in the attachment.

Author Response File: Author Response.pdf

Reviewer 3 Report

Comments and Suggestions for Authors

The manuscript titled “Charge Transfer Rates Controlled by Frequency Dispersion of Double Layer Capacitances” presented theoretical and experimental study on the effects of frequency dispersion in double layer capacitance (DLC) on the kinetics of charge transfer (CT) reactions. This work proposes a modified kinetic model, which incorporates negative capacitance (NC) into the interpretation of impedance, and validates it with a ferrocenyl derivative by ac impedance methods.

The manuscript was well written and organized, and adequate theory was given as well. In addition, the experimental results were clearly presented. Therefore, I recommend accepting this manuscript after minor revisions, here are my comments:

1. The original Nyquist posts need to be provided.
2. The fitting parameters of Nyquist plots should also be given.
3. In line 227 and 228, the formate of citations (41 and 42) needs to be consistent.
4. In the reference section, please correct reference 1-8.

Author Response

Our response and revision are in the attachment together with a revised file.

Author Response File: Author Response.pdf