PONE-D-20-00322

Valorization of biomass into amine- functionalized bio graphene for efficient Ciprofloxacin removal, modeling and optimization study

PLOS ONE

Dear Dr Mohammadi,

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Kind regards,

Mohammad Al-Ghouti

Academic Editor

PLOS ONE

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1. In your Methods section, please provide additional information on the origin of the corn stover samples. If these were obtained from markets or stores, please provide the geographic coordinates and names of the purchase locations (e.g., stores, markets), if available, as well as any further details about the purchased items (e.g., lot number, source origin, description of appearance) to ensure reproducibility of the analyses.

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Reviewers' comments:

Reviewer's Responses to Questions

Comments to the Author

1. Is the manuscript technically sound, and do the data support the conclusions?

The manuscript must describe a technically sound piece of scientific research with data that supports the conclusions. Experiments must have been conducted rigorously, with appropriate controls, replication, and sample sizes. The conclusions must be drawn appropriately based on the data presented.

Reviewer #1: Yes

Reviewer #2: Partly

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2. Has the statistical analysis been performed appropriately and rigorously?

Reviewer #1: Yes

Reviewer #2: N/A

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3. Have the authors made all data underlying the findings in their manuscript fully available?

The PLOS Data policy requires authors to make all data underlying the findings described in their manuscript fully available without restriction, with rare exception (please refer to the Data Availability Statement in the manuscript PDF file). The data should be provided as part of the manuscript or its supporting information, or deposited to a public repository. For example, in addition to summary statistics, the data points behind means, medians and variance measures should be available. If there are restrictions on publicly sharing data—e.g. participant privacy or use of data from a third party—those must be specified.

Reviewer #1: Yes

Reviewer #2: Yes

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4. Is the manuscript presented in an intelligible fashion and written in standard English?

PLOS ONE does not copyedit accepted manuscripts, so the language in submitted articles must be clear, correct, and unambiguous. Any typographical or grammatical errors should be corrected at revision, so please note any specific errors here.

Reviewer #1: No

Reviewer #2: Yes

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5. Review Comments to the Author

Please use the space provided to explain your answers to the questions above. You may also include additional comments for the author, including concerns about dual publication, research ethics, or publication ethics. (Please upload your review as an attachment if it exceeds 20,000 characters)

Reviewer #1: The manuscript describes the preparation and utilization of an aminated bio-graphene as adsorbent for removal of ciprofloxacin in water. Results indicate a good performance of the material and a favorable adsorption process.

I believe this work is provides enough data to corroborate conclusions of the authors and has a sufficient degree of novelty, therefore it is worthy of publication. However, a major issue affects the manuscript: it does not deepen and explain the scientific phenomena underlying the adsorption process. The authors should clarify that the amino groups, in particular under acidic conditions, can easily bind acid contaminants (i.e., containing a carboxyl group), like ciprofloxacin. The results obtained by RSM should be elucidated under this point of view, citing suitable literature on aminated adsorbents (e.g., DOI: 10.1016/j.ijbiomac.2020.01.171, 10.1016/j.reactfunctpolym.2019.104354, 10.3390/polym11101701).

In addition to this major issue, others require revision as well:

- The title should explicitly mention that the paper deals with adsorption, hence it might be revised as “Valorization of biomass into amine-functionalized bio-graphene for efficient Ciprofloxacin adsorption in water- modeling and optimization study”.

- English should be carefully revised. Just few examples in the abstract:

* the first two sentences might be revised as: ”A green synthesis approach was adopted to prepare amine-functionalized bio-graphene (AFBG) as an efficient and low cost adsorbent that can be obtained from abundant agricultural wastes. In this study, it was successfully employed to remove Ciprofloxacin (CIP) from water.”

* ln. 32, add “, respectively,” after the numbers

* ln 36, replace the sentence between parentheses with “(<delta>Go<0, <delta>Ho>0, and <delta>So>0)”

- ln 57, DOI: 10.1016/j.watres.2018.04.056 might be a suitable citation here.

- ln 78, DOI: 10.3390/polym11101701 might be a suitable citation here.

- ln 91 revise measure unit to “kHz” (i.e., k in lower case).

- ln 113 and ln 127, the authors affirm that the method was previously reported but no reference is provided.

- ln 162-164, characterization methods should be moved in the ‘Materials and methods’ section.

- ln 325 Kelvin measure unit must be written with capital letter

Reviewer #2: The manuscript titled "Valorization of biomass into amine- functionalized bio graphene for efficient Ciprofloxacin removal, modeling and optimization study" represents some good results but the writing should be revised. The following questions should be addressed before acceptance.

1. English usage and grammar should be carefully checked throughout the manuscript.

2. Please add the schematic diagram of synthesis route that it can show reaction step in details.

3. Fig. 1 in Page 8: 'Fig 1. The XRD images of (a) raw corn stover (b) combusted corn stover at 275°C (CCS) and (c) bio graphene. But the expression at the bottom is ' It can be seen in Fig. 1. (b) that by combustion of corn stover at 270°C'. Please confirm the temperature is 275°C or 270°C.

4. Fig. 2 in Page 9, the SEM image of (a) bio graphene obtained from corn stover using thermo-chemical process and (b) functionalized bio grapheme using grafting amine groups method should be compared at the same image scale.

5. In Page 9, it is claimed that structure of nano-bio graphene synthesized by thermo-chemical reduction method was observed by TEM images. In my opinion, the TEM image of functionalized bio grapheme using grafting amine groups method is recommended.

6. The discussion of the regeneration ability of amine-functionalized bio-Graphene for ciprofloxacin removal is strongly recommended.

7. Some relevant literatures may be cited to support the research significance of this wok, such as:

(1) Chemical Engineering Research and Design, 2020, 154, 192-202;

(2) Industrial and Engineering Chemistry Research, 2019, 58, 17075-17087;

(3) Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2020, 588: 124393.

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Reviewer #1: No

Reviewer #2: No

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Valorization of biomass into amine- functionalized bio graphene for efficient Ciprofloxacin adsorptionin water-modeling and optimization study

PONE-D-20-00322R1

Dear Dr. Mohammadi,

We are pleased to inform you that your manuscript has been judged scientifically suitable for publication and will be formally accepted for publication once it complies with all outstanding technical requirements.

Within one week, you will receive an e-mail containing information on the amendments required prior to publication. When all required modifications have been addressed, you will receive a formal acceptance letter and your manuscript will proceed to our production department and be scheduled for publication.

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With kind regards,

Mohammad Al-Ghouti

Academic Editor

PLOS ONE

Additional Editor Comments (optional):

Reviewers' comments:

Reviewer's Responses to Questions

Comments to the Author

1. If the authors have adequately addressed your comments raised in a previous round of review and you feel that this manuscript is now acceptable for publication, you may indicate that here to bypass the “Comments to the Author” section, enter your conflict of interest statement in the “Confidential to Editor” section, and submit your "Accept" recommendation.

Reviewer #1: All comments have been addressed

Reviewer #2: All comments have been addressed

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2. Is the manuscript technically sound, and do the data support the conclusions?

The manuscript must describe a technically sound piece of scientific research with data that supports the conclusions. Experiments must have been conducted rigorously, with appropriate controls, replication, and sample sizes. The conclusions must be drawn appropriately based on the data presented.

Reviewer #1: Yes

Reviewer #2: Yes

**********

3. Has the statistical analysis been performed appropriately and rigorously?

Reviewer #1: Yes

Reviewer #2: Yes

**********

4. Have the authors made all data underlying the findings in their manuscript fully available?

The PLOS Data policy requires authors to make all data underlying the findings described in their manuscript fully available without restriction, with rare exception (please refer to the Data Availability Statement in the manuscript PDF file). The data should be provided as part of the manuscript or its supporting information, or deposited to a public repository. For example, in addition to summary statistics, the data points behind means, medians and variance measures should be available. If there are restrictions on publicly sharing data—e.g. participant privacy or use of data from a third party—those must be specified.

Reviewer #1: Yes

Reviewer #2: Yes

**********

5. Is the manuscript presented in an intelligible fashion and written in standard English?

PLOS ONE does not copyedit accepted manuscripts, so the language in submitted articles must be clear, correct, and unambiguous. Any typographical or grammatical errors should be corrected at revision, so please note any specific errors here.

Reviewer #1: Yes

Reviewer #2: Yes

**********

6. Review Comments to the Author

Please use the space provided to explain your answers to the questions above. You may also include additional comments for the author, including concerns about dual publication, research ethics, or publication ethics. (Please upload your review as an attachment if it exceeds 20,000 characters)

Reviewer #1: The authors revised all the issues I raised in my previous comments, therefore I suggest acceptance of the manuscript in its present form.

Reviewer #2: (No Response)

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7. PLOS authors have the option to publish the peer review history of their article (what does this mean?). If published, this will include your full peer review and any attached files.

If you choose “no”, your identity will remain anonymous but your review may still be made public.

Do you want your identity to be public for this peer review? For information about this choice, including consent withdrawal, please see our Privacy Policy.

Reviewer #1: No

Reviewer #2: No