Enhanced Sonophotocatalytic Degradation of Acid Red 14 Using Fe3O4@SiO2/PAEDTC@MIL-101 (Fe) Based on Metal-Organic Framework
, Andrés Alexis RamÃrez-Coronel 4, Firas Rahi Alhachami 5, Nezamaddin Mengelizadeh 6 and Davoud Balarak 7,*
Round 1
Reviewer 1 Report
Catalysts: Enhanced Sonophotocatalytic Degradation of Acid Red 14 using Fe3O4/SiO2/PAEDTC @MIL-101 (Fe) Based on Metal-Organic Framework
1. How much concentration of HCl was used in synthesis method for the modification? In addition, the synthesis method of Fe3O4 SiO2/PAEDTC should be described in detail.
2. In TEM image, the Fe3O4 SiO2/PAEDTC@MIL- 101 (Fe) composite image looks different from bare materials why? The scale bar is missing in Fig.3c.
3. The authors discussed BET. But there is no Figures for BET analysis.
4. What is the main difference between sonolysis and sonocatalytic experiment in Fig 5a.
5. Why didn’t the authors evaluate the different catalysts for AR-14 degradation? It should be provided for comparison in this work.
6. The novelty of the work should be established.
7. The following references may be included in the manuscript for the sonocatalytic mechanism, Journal of Molecular Liquids 344 (2021) 117740, Composites Part B: Engineering 215 (2021) 108780.
Author Response
Dear Editor and Reviewers
Thank you for your constructive and valuable comments. All comments are considered, and the corrections are highlighted in the text by using red color for reviewer 1 and yellow for reviewer 2.
Hopefully, we have succeeded to make necessary revisions, and our paper would be acceptable for publication. I hope our explanations would be convincing. However, if there is ambiguity or omission in the description, please tell us to be checked.
Best regards
Reviewer 1:
Q1. How much concentration of HCl was used in synthesis method for the modification? In addition, the synthesis method of Fe3O4 SiO2/PAEDTC should be described in detail.
Response: The materials and methods were thoroughly reviewed and revised.
Q2. In TEM image, the Fe3O4 SiO2/PAEDTC@MIL- 101 (Fe) composite image looks different from bare materials why? The scale bar is missing in Fig.3c.
Response: We, the authors, thank the reviewers for their suggestions to improve the article. In the TEM figure, we have loaded the wrong figure. In our work process, the TEM characteristics of the Fe3O4 SiO2/PAEDTC catalyst were not determined due to the lack of enough financial resource for conducting our research. Therefore, the TEM figure was modified by the decision of the authors.
Q3. The authors discussed BET. But there is no Figures for BET analysis.
Response: Added in Figure 4 as suggested by the referee.
Q4. What is the main difference between sonolysis and sonocatalytic experiment in Fig 5a.
Response: Sonolysis is the process of utilization of ultrasonic irradiation without the presence of Fe3O4 SiO2/PAEDTC@MIL-101 (Fe), to produce HO• in aqueous media. Meanwhile, in the sonocatalytic process, particles such as Fe3O4 SiO2/PAEDTC@MIL-101 (Fe) are used to improve efficiency by transferring electrons to a higher surface and increasing the number of cavitation bubbles. In our study, when Fe3O4 SiO2/PAEDTC@MIL- 101 (Fe) nanoparticles are added to the sonolysis solution, the removal efficiency of AR14 during the 60 min reaction time increased from 42.9% to 70.9%. Similarly, the kinetic rate in sonocatalytic (0.0185 min-1) process was higher than that of sonolysis (0.008 min-1) alone.
Q5. Why didn’t the authors evaluate the different catalysts for AR-14 degradation? It should be provided for comparison in this work.
Response: The comparison was done completely in the text and summarized in the table 2.
Q6. The novelty of the work should be established.
Response: the authors of the study innovation reported on page 3 line 80-82 However, the following content can justify the innovation of our work
In recent years, semiconducting catalysts have attracted more attention in energy storage and environmental improvement. Choosing the type of catalyst for practical applications depends on stability, effective cost, high photocatalytic potential, and maximum adsorption of solar energy for pollutant degradation. Among the proposed semiconductor materials, TiO2 is considered more stable due to its excellent catalytic activity, non-toxicity, and stability. However, during use, it has low absorption in the visible region of the solar spectrum. For this purpose, MIL-101(Fe) was used as an active photocatalyst in this study. Also, to improve the photocatalytic efficiency, reduce the e-/h+ recombination rate, and easily separate the particles after use, the MIL-101(Fe) surface was coated with Fe3O4@SiO2. The results of diagnostic analyses (SEM, TEM, and XRD) showed good loading of Fe3O4@SiO2 on the MIL-101(Fe) surface. In addition to choosing the type of catalyst, checking the mineralization rate of the target pollutant as well as the degradability of the treatment products are important parameters in proposing the present process for practical applications. In the present study, the rate of mineralization was investigated by TOC and COD, and the present results showed that the dye can be mineralized with a high percentage. Also, the BOD5/COD rate showed that the dye can be converted into biodegradable products at a low reaction time.
Determining the energy consumption of degradation systems is one of the important parameters affecting the proposal of the present process for the practical application of treatment. Therefore, the energy consumption was calculated. The range of energy consumed for different dye concentrations was between 19.33-48.62 kWh/m3, which is lower than the energy consumption reported by Abdelhaleem et al. for the degradation of Carbofuran by N doped-TiO2/H2O2 (138 kWh/m3) and Li et al. for the degradation of diclofenac by Bi2S3/BiOBr/BC (674/74 kWh/m3). The low energy consumption required in the present study can be due to the appropriate pairing of particles for pollutant adsorption, reduction of electron-hole recombination, and higher production of reactive species. The recyclability of the sonophotocatalyst for dye degradation in the consecutive reaction cycle showed that the catalyst can be used up to 8 times with a minimum efficiency reduction of 10%, which indicates the excellent recyclability of the sonophotocatalyst compared to previous studies. According to the results, the Fe3O4/SiO2/PAEDTC@MIL-101 (Fe)/UV/US process is a promising and effective system for the treatment of dye solution due to the excellent stability of the sonophotocatalyst, energy saving, complete degradation, and high pollutant mineralization.
Q7. The following references may be included in the manuscript for the sonocatalytic mechanism, Journal of Molecular Liquids 344 (2021) 117740, Composites Part B: Engineering 215 (2021) 108780.
Response: Thanks for the suggested useful references, added in the text of the article.
Dear Reviewer, thank you for the time you have spent reviewing our manuscript and for your positive consideration. The required correction was done.
Reviewer 2 Report
Reviewer Comments: The manuscript presents a study on the "Enhanced Sonophotocatalytic Degradation of Acid Red 14 using Fe3O4/SiO2/PAEDTC@MIL-101(Fe) Based on Metal-Organic Framework". I found the work more interesting and some important results are also reported in detail. The topic of the manuscript is more interesting. The design of the study is well; however, after carefully reading the text, revisions were needed prior to a possible publication in this journal:
(1) The N2 adsorption-desorption isotherm was performed, but the isotherm and pore size distribution graph is missing. The author should provide it.
(2) To explain the transfer of the electrons between metal and semiconductors, the work function (or Fermi level) of the prepared samples should be measured.
(3) In the introduction, the following references may be read and cited during the revision to improve the quality and to extend the readership.
· https://doi.org/10.1016/j.jssc.2022.123565
· https://doi.org/10.1016/j.enmm.2022.100711
· https://doi.org/10.1016/j.molstruc.2021.131397
(4) To understand the interaction of light and catalysts, Band Gap energy evaluation/optical analysis of the catalysts should be performed.
(5) To understand the structure, the recycled catalysts should be investigated thru XRD, SEM, or TEM.
(6) Comparative study should be included and compare the sonophotocatalytic activity of the current catalysts with some recently reported catalysts
(7) Some Future prospects should be included in the conclusion part.
Author Response
Dear Editor and Reviewers
Thank you for your constructive and valuable comments. All comments are considered, and the corrections are highlighted in the text by using red color for reviewer 1 and yellow for reviewer 2.
Hopefully, we have succeeded to make necessary revisions, and our paper would be acceptable for publication. I hope our explanations would be convincing. However, if there is ambiguity or omission in the description, please tell us to be checked.
Best regards
Reviewer 2
Q1. The N2 adsorption-desorption isotherm was performed, but the isotherm and pore size distribution graph is missing. The author should provide it.
Response: Added in Figure 4 as suggested by the referee.
Q2. In the introduction, the following references may be read and cited during the revision to improve the quality and to extend the readership. https://doi.org/10.1016/j.jssc.2022.123565 https://doi.org/10.1016/j.enmm.2022.100711 https://doi.org/10.1016/j.molstruc.2021.131397
Response: Thanks for the suggested useful references, added in the text of the article.
Q3. To understand the interaction of light and catalysts, Band Gap energy evaluation/optical analysis of the catalysts should be performed.
Response: Added in Figure 4e as suggested by the referee.
Q4. To understand the structure, the recycled catalysts should be investigated thru XRD, SEM, or TEM.
Response: Added in Figure 6e (Initial XRD (1) and after eight recovery times (2) as suggested by the referee.
Q5. Comparative study should be included and compare the sonophotocatalytic activity of the current catalysts with some recently reported catalysts
Response: According to the reviewer's suggestion, the comparison between different sonophotocatalysts in the degradation of dyes was reported in Table 2. Regarding the comparison of different catalysts in our study, we performed different removal systems (absorption, US, UV, US/catalyst, UV/catalyst and US/UV/catalyst) in color removal for a better understanding of the present system. In the next study, we authors will examine all the materials present in the catalyst in dye removal.
Q6. To explain the transfer of the electrons between metal and semiconductors, the work function (or Fermi level) of the prepared samples should be measured.
Response: we appreciate the reviewer for the good suggestion. Since their low financial support has been considered for our research, we were only able to analyze the characteristics of the catalyst, materials and measure operational parameters. Nevertheless, your suggestion for improving the article will definitely be considered in future studies.
Q7. Some Future prospects should be included in the conclusion part.
Response: conclusion was revised and Future prospects added.
Dear Reviewer, thank you for the time you have spent reviewing our manuscript and for your positive consideration. The required correction was done.
Round 2
Reviewer 1 Report
The current version of the manuscript can be ready for publication.
Reviewer 2 Report
The authors revised the manuscript carefully and improved the quality of the manuscript. I agree to accept the manuscript in its current form.
