From the journal Environmental Science: Atmospheres Peer review history

01-Sep-2021

Dear Dr Xue:

Manuscript ID: EA-ART-07-2021-000060
TITLE: Enhanced adsorption performance for aromatic sulfur compounds over hierarchical structure AgX zeolite

Thank you for your submission to Environmental Science: Atmospheres, published by the Royal Society of Chemistry. I sent your manuscript to reviewers and I have now received their reports which are copied below.

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Dr Nønne Prisle
Associate Editor, Environmental Sciences: Atmospheres

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Reviewer 1

1. "Environmental Significance Statement“: From this statement, we cannot find any information related to the zeolite catalysts used in this work although the release of sulfur is harmful to the atmospheres. This statement should be revised.
2. Fig 3b: I can not undestand why the BT loadings at high temperature are much more than that at low temperature. If the same trends were found for the TP and 4,6-DMDBT? The according experimental result aslo should be provided.
3. The recyclability of catalysts of AgX-CA(3.0)： In such experiment, how to treat the adsorbed TP, BT and 4,6-DMDBT inside the zeolite cages?
4. How to comapre the adsorbed laodings for TP, BP and 4,6-DMDBT in the unit of mmol/g and not mg/g? On ths basis of Fig. 3, it seemed that both of the saturated adsorption capacity and adsorptive desulfurization performance of 4,6-DMDBT were much larger than the other small molecule. This result cannot be well explained.

Reviewer 2

The paper discusses the synthesis of hierarchical AgX zeolites fo adsorption of aromatic sulphur compounds. The paper can potentially be published but it needs a major revision mostly on the English and lack of more specific literature review as well as quantitative comparison with the state-of-the-art materials for similar applications. Below my comments:

- The English needs an extensive revision, there are my incorrect forms and misspelling. To give some examples, in the abstract words such as "compoundds", sentences like "we synthesis" (synthesis is not a verb), and many other mistakes in the whole document. The current form in not up to standard for an RSC journal. I would suggest a revision from someone proficient in Academic English

- Caption of Scheme 1 is ambiguous and not clear, I do not follow clearly what is going on there, what is the link between b) and c) if any?

- Fig 1b, each peak is deconvoluted into two peaks but the main peak could be fitted with a single peak without deconvolution, can the authors comment on that?

- The authors are missing a very recent development in hierarchical zeolites, the work of Fan et al., Angew.Chem.2020,132,19646–19654.

- The discussion should contain more quantitative information, for example when it says "On the basis of the experiment above, the as-synthesized AgX-CA(3.0) exhibits higher adsorption desulfurization performance and durability than those of AgX, AgX CA(1.5), and AgX-CA(2.0). The superb adsorption desulfurization" the authors need to state numbers on adsorption capacity and compare those with literature. They could perhaps be summarised in a table.

- The methodology section on adsorption experiments need references as these are well-know model. The authors could refer to Zhu et. al., Chemical Engineering Journal 306 (2016) 67–76.

Dear Editor,
Thank you very much for your kind help. We have revised the manuscript (EA-ART-07-2021-000060), according to the editor and reviewers. We have also responded point by point to the comments as listed below. We hope that the revised manuscript is acceptable for publication in Environmental Science: Atmospheres.
Best Regards,

Yours sincerely,


Replies to Reviews:
Referee: 1
Comments to the Author
Question 1: “Environmental Significance Statement”: From this statement, we cannot find any information related to the zeolite catalysts used in this work although the release of sulfur is harmful to the atmospheres. This statement should be revised.
Response: Thanks for the Reviewer’s kind suggestion. Zeolites are crystalline aluminosilicate minerals with porous structure, and also be effective H2S adsorbents. The above statement has been modified to “Zeolites can be effectively absorbed and removed on H2S toxic substance, and then they owned excellent regenerability and stable structure during catalysis process.” [1-2] Besides, we have optimized the “Environmental Significance Statement” in the revised manuscript.

Question 2: Fig 3b: I can not understand why the BT loadings at high temperature are much more than that at low temperature. If the same trends were found for the TP and 4,6-DMDBT? The according experimental result also should be provided.
Response: The adsorption rate of sulfur compounds on AgX-CA(3.0) becomes faster with temperature increasing, which is attributed to the activation energy of substances that can be decreased and thus enable the fast diffusion of sulfur compounds on the absorbent surface. Ishaq et al. [3] investigated the effect of temperature on adsorption of BT on bentonite over the temperature range of 20 to 60oC, the adsorption capacity was increased with the increased temperature. Furthermore, due to that the enthalpy change of adsorption process (ΔH) was positive, the adsorption of BT on bentonite was endothermic. Therefore, higher the temperature is, better the absorption performance becomes. Besides, as the increase of temperature, the adsorption performance of TP and 4, 6-DMDBT also exhibits a similar trend as well as BT.

Question 3: The recyclability of catalysts of AgX-CA(3.0): In such experiment, how to treat the adsorbed TP, BT and 4,6-DMDBT inside the zeolite cages?
Response: The stability test of our adsorbent followed same reaction conditions for firstly absorption test. After each reaction, the adsorbent was separated by centrifugation and washed with water and ethanol for several times to remove impurities. Afterwards, the adsorbent was calcined at 723 K for 2 h, and recorded its weight and reused in the next cycle. We have made relative change in experiment section for this manuscript.

Question 4: How to compare the adsorbed loadings for TP, BT and 4,6-DMDBT in the unit of mmol/g and not mg/g? On the basis of Fig. 3, it seemed that both of the saturated adsorption capacity and adsorptive desulfurization performance of 4, 6-DMDBT were much larger than the other small molecule. This result cannot be well explained.
Response: Thanks for reviewer’s kind suggestion. Several authors have reported the adsorbed loadings for sulfur in the unit of mg/g [5]. The Ag metal ion supported on Zeolites causes π-complex between metal ions and sulfur compounds due to the existence of π-bond of TP. Velu et al. We have reported that the removal of aromatic sulfur compounds in model jet fuel is in the order 1-BTP > TP, which is consistent with the decrease in the electron density of S atoms in TP [6]. The two methyl groups of 4, 6-DMDBT increase the electron density of benzene ring, which is benefit to the formation of feedback π bond and further enhance the adsorption desulfurization [7]”. We also have made change in this manuscript.




Referee: 2
Comments to the Author
The paper discusses the synthesis of hierarchical AgX zeolites for adsorption of aromatic sulphur compounds. The paper can potentially be published but it needs a major revision mostly on the English and lack of more specific literature review as well as quantitative comparison with the state-of-the-art materials for similar applications. Below my comments:
Question 1: The English needs an extensive revision, there are my incorrect forms and misspelling. To give some examples, in the abstract words such as "compoundds", sentences like "we synthesis" (synthesis is not a verb), and many other mistakes in the whole document. The current form in not up to standard for an RSC journal. I would suggest a revision from someone proficient in Academic English
Response: We are sorry that our manuscript exists some grammatical errors and sentence structure issues. We modify the above problems in the revised manuscript.

Question 2: Caption of Scheme 1 is ambiguous and not clear, I do not follow clearly what is going on there, what is the link between b) and c) if any?
Response: We have revised the above description for scheme 1. Scheme 1 (b) shows the silver supported on original NaX; (c) shows the silver supported on hierarchical NaX after sequential acid-alkali treatments.

Question 3: Fig 1b, each peak is deconvoluted into two peaks but the main peak could be fitted with a single peak without deconvolution, can the authors comment on that?
Response: According to previous reports [8], Ag species can exist in the valence states of metallic Ag0 and ionic Ag+. The peaks around and 368.6 eV can be ascribed to metallic Ag0, while other peaks around and 367.8 eV are ascribed to Ag+. Therefore, we have deconvoluted them into two peaks which are corresponding to the Ag 3d spectra.

Question 4: The authors are missing a very recent development in hierarchical zeolites, the work of Fan et al., Angew. Chem. 2020, 132, 19646–19654.
Response: We have cited these recent works in Reference 31 of our manuscrip.

Question 5: The discussion should contain more quantitative information, for example when it says "On the basis of the experiment above, the as-synthesized AgX-CA(3.0) exhibits higher adsorption desulfurization performance and durability than those of AgX, AgX CA(1.5), and AgX-CA(2.0). The superb adsorption desulfurization" the authors need to state numbers on adsorption capacity and compare those with literature. They could perhaps be summarised in a table.
Response: We have compared adsorption desulfurization performance of AgX-CA(3.0) with those of recently reported, representative Zeolite-based absorbents (Table S6 in SI). The comparison reveals that AgX-CA(3.0) is among the best of zeolite-based absorbents toward adsorption desulfurization both in terms of activity and stability. The detailed data was listed in Table S5 of supporting information. Besides, we have added the related discussion in our manuscript.

Question 6: The methodology section on adsorption experiments need references as these are well-know model. The authors could refer to Zhu et. al., Chemical Engineering Journal 306 (2016) 67–76.
Response: Thanks for the Reviewer’s kind suggestion. The related work has been cited in reference 33 of our manuscript.












Reference
1. M. Ozekmekci, G. Salkic, M. F. Fellah, Fuel. Process. Technol., 2015, 139, 49–60.
2. L. Oliveira, J. G. Meneguin, M. V. Pereira, Micropor. Mesopor. Mat., 2019, 284, 247–257.
3. I. Muhammad, S. Siraj, A. Imtiaz, U. Hameed, Y. Muhammad, A. Alia, J Saudi Chem Soc., 2017, 21, 143–151.
4. N. Bekta, B. A. Aim, S. Kara, J. Hazard. Mater., 2004, 112, 115–122.
5. F. Tian, Q. Shen, Z. Fu, Y. Wu and C. Jia, Fuel Process. Technol., 2014, 128, 176–182.
6. S. Velu, X. Ma, C. Song, Ind. Eng. Chem. Res., 2003, 42, 5293.
7. R.T. Yang, A. Takahashi, F. H. Yang, Ind. Eng. Chem. Res., 2001, 40, 6236.
8. K. X. Lee and J. A. Valla, Appl. Catal B., 2017, 201, 359–369.

12-Oct-2021

Dear Dr Xue:

Manuscript ID: EA-ART-07-2021-000060.R1
TITLE: Enhanced adsorption performance for aromatic sulfur compounds over hierarchical structure AgX zeolite

Thank you for submitting your revised manuscript to Environmental Science: Atmospheres. After considering the changes you have made, I am pleased to accept your manuscript for publication in its current form. I have copied any final comments from the reviewer(s) below.

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Dr Nønne Prisle
Associate Editor, Environmental Sciences: Atmospheres

Reviewer 1

Accept