Pencil graphite as electrode platform for free chlorine sensors and energy storage devices

Jahidul Islam; Han Shao; Md. Mizanur Rahman Badal; Kafil M. Razeeb; Mamun Jamal

doi:10.1371/journal.pone.0248142

Peer Review History

Original SubmissionOctober 24, 2020
15 Dec 2020 Decision Letter - Zafar Ghouri, Editor PONE-D-20-33482 Pencil graphite as electrode platform for free chlorine sensors and energy storage devices PLOS ONE Dear Dr. Jamal, Thank you for submitting your manuscript to PLOS ONE. After careful consideration, we feel that it has merit but does not fully meet PLOS ONE’s publication criteria as it currently stands. Therefore, we invite you to submit a revised version of the manuscript that addresses the points raised during the review process. Please submit your revised manuscript by Jan 29 2021 11:59PM. If you will need more time than this to complete your revisions, please reply to this message or contact the journal office at plosone@plos.org. When you're ready to submit your revision, log on to https://www.editorialmanager.com/pone/ and select the 'Submissions Needing Revision' folder to locate your manuscript file. 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Protocols.io assigns your protocol its own identifier (DOI) so that it can be cited independently in the future. For instructions see: http://journals.plos.org/plosone/s/submission-guidelines#loc-laboratory-protocols We look forward to receiving your revised manuscript. Kind regards, Zafar Khan Ghouri Academic Editor PLOS ONE Journal Requirements: Journal requirements: When submitting your revision, we need you to address these additional requirements. 1. Please ensure that your manuscript meets PLOS ONE's style requirements, including those for file naming. The PLOS ONE style templates can be found at https://journals.plos.org/plosone/s/file?id=wjVg/PLOSOne_formatting_sample_main_body.pdf and https://journals.plos.org/plosone/s/file?id=ba62/PLOSOne_formatting_sample_title_authors_affiliations.pdf 2. Please ensure that vendor details for all materials and equipment used are provided. We note that these may be missing for the cellulose paper and pencil graphite. 3. Please include captions for your Supporting Information files at the end of your manuscript, and update any in-text citations to match accordingly. Please see our Supporting Information guidelines for more information: http://journals.plos.org/plosone/s/supporting-information. [Note: HTML markup is below. Please do not edit.] 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 ******** 2. Has the statistical analysis been performed appropriately and rigorously? Reviewer #1: Yes Reviewer #2: Yes ****** 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 ****** 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: Yes Reviewer #2: No ****** 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: This paper reports the use of pencil graphite as an electrode for dual applications that include the detection of free residual chlorine using electro-oxidation process and as an electrochemical energy storage cathode. The pencil graphite is then transferred to cellulose paper by drawing ten times and applied for the detection of free residual chlorine, which shows a sensitivity of 27 µA mM-1 cm-2 with a limit of detection of 88.9 µM and linearity up to 7 mM the work is performed systematically and it is presented nicely in the manuscript. Pencil graphite can be used for both sensor and energy-storage applications Reviewer #2: The authors have studied and reported the use of Pencil Graphite as Electrode Platform for Free Chlorine Sensors and Energy Storage Devices. While I greatly appreciate the authors for the effort taken, I feel the manuscript needs major revision to be accepted for publication. 1. Incorrect sentence formation is present at various parts of the manuscript that makes the readability of manuscript difficult. The authors need to seriously look into it. 2. The cyclic stability test was carried out only for 100 cycles and it shows a retention of 95.8%. This shows the poor efficiency of the material. The authors are recommended to carry out the test for higher number of cycles (>5000 at least). 3. In the introduction, various literatures are written (ex: Mariad, Maria et al. Aditya et al.) However, the citations to the same are not present. 4. In the materials section, it is advised to mention the name of the compounds and then write their chemical formula, instead of writing only the formula. 5. The authors claim that synthesized pencil graphite is a green material. The authors have to justify this statement. 6. The full form of PDPE to be abbreviated initially. Correct all such mistakes. 7. ‘Every day the electrode was tested for two weeks.’ No meaning and connection to the previous statement. 8. Caption of Fig. 2 appears in the middle of a paragraph, which breaks the continuity. 9. The authors could quantify FRC using UV spectroscopy and other analytical techniques for better comparison. ****** 6. 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Revision 1
23 Jan 2021 Author Response PONE-D-20-33482 Pencil graphite as electrode platform for free chlorine sensors and energy storage devices The authors would like to thank the reviewers for their valuable comments and suggestions to improve the manuscript. The response to the reviewers are as follows: Reviewer #1: This paper reports the use of pencil graphite as an electrode for dual applications that include the detection of free residual chlorine using electro-oxidation process and as an electrochemical energy storage cathode. The pencil graphite is then transferred to cellulose paper by drawing ten times and applied for the detection of free residual chlorine, which shows a sensitivity of 27 µA mM-1 cm-2 with a limit of detection of 88.9 µM and linearity up to 7 mM the work is performed systematically and it is presented nicely in the manuscript. Pencil graphite can be used for both sensor and energy-storage applications. Responses: Thanks to the reviewer for appreciating our work. Reviewer #2: The authors have studied and reported the use of Pencil Graphite as Electrode Platform for Free Chlorine Sensors and Energy Storage Devices. While I greatly appreciate the authors for the effort taken, I feel the manuscript needs major revision to be accepted for publication. Responses: We would like to thank the reviewer for the critical analysis of our manuscript. Revisions have been made in the updated version of the manuscript. 1. Incorrect sentence formation is present at various parts of the manuscript that makes the readability of manuscript difficult. The authors need to seriously look into it. Responses: English has been corrected throughout the manuscript. A copy of the manuscript with track changes has been enclosed with the submission. 2. The cyclic stability test was carried out only for 100 cycles and it shows a retention of 95.8%. This shows the poor efficiency of the material. The authors are recommended to carry out the test for higher number of cycles (>5000 at least). Responses: In this work, we have showed Zn as anode, graphene coated PGE as cathode and a mixture of aluminum chloride (AlCl3) and zinc acetate (Zn(CH3COO)2) as electrolyte. In terms of safety, simplicity and cost, the proposed aqueous battery possess a huge potential as a cost effective energy storage device. However, we have only studied the cyclic stability test up to 100 cycles, which shows almost no efficiency loss. Currently, work is in progress to improve the cyclability of this battery. As these experiments are on-going, the outcome of these studies will be reported in a separate article. It is also worth mentioning that Angell et al. [1] fabricated a graphite powder based cathode material based aqueous battery with Al3+ as electrolyte, and reported the cyclability up to 180 cycles. Similar graphitic materials based aqueous energy storage devices have been reported by many other authors [2-6] with similar cycle life. References 1. Angell, M.; Pan, C.-J.; Rong, Y.; Yuan, C.; Lin, M.-C.; Hwang, B.-J.; Dai, H., High Coulombic efficiency aluminum-ion battery using an AlCl3-urea ionic liquid analog electrolyte. Proceedings of the National Academy of Sciences 2017, 114 (5), 834-839. 2. Kravchyk, K. V.; Wang, S.; Piveteau, L.; Kovalenko, M. V., Efficient Aluminum Chloride–Natural Graphite Battery. Chemistry of Materials 2017, 29 (10), 4484-4492. 3. Sun, H.; Wang, W.; Yu, Z.; Yuan, Y.; Wang, S.; Jiao, S., A new aluminium-ion battery with high voltage, high safety and low cost. Chemical Communications 2015, 51 (59), 11892-11895. 4. Wang, W.; Jiang, B.; Xiong, W.; Sun, H.; Lin, Z.; Hu, L.; Tu, J.; Hou, J.; Zhu, H.; Jiao, S., A new cathode material for super-valent battery based on aluminium ion intercalation and deintercalation. Scientific Reports 2013, 3 (1), 3383. 5. Lin, M.-C.; Gong, M.; Lu, B.; Wu, Y.; Wang, D.-Y.; Guan, M.; Angell, M.; Chen, C.; Yang, J.; Hwang, B.-J.; Dai, H., An ultrafast rechargeable aluminium-ion battery. Nature 2015, 520 (7547), 324-328. 6. Zhang, X.; Tang, Y.; Zhang, F.; Lee, C.-S., A Novel Aluminum–Graphite Dual-Ion Battery. Advanced Energy Materials 2016, 6 (11), 1502588. 3. In the introduction, various literatures are written (ex: Mariad, Maria et al. Aditya et al.) However, the citations to the same are not present. Responses: It is fixed in the manuscript. 4. In the materials section, it is advised to mention the name of the compounds and then write their chemical formula, instead of writing only the formula. Responses: It is fixed in the manuscript. 5. The authors claim that synthesized pencil graphite is a green material. The authors have to justify this statement. Responses: In both the abstract and introduction section, we have claimed about the green materials as follows: Abstract “Therefore, pencil graphite due to its excellent electro-oxidation and conducting properties, can be successfully implemented as a low cost, disposable and green material for both sensor and energy-storage applications.” Introduction “So, these extremely simple, green, and low-cost pencil graphite-derived electrodes can be implemented in the future IOT sensor and energy storage applications.” Please find below the justification of PGE as green material: Green material involves eliminating and avoiding the use of toxic and hazardous reagents and solvents in the manufacturing and applications process [1, 2]. Pencil graphite is a biodegradable material and also recyclable. These commercial pencil graphite does not use any hazardous chemicals. In addition, using pencil drawn on to paper make the fabrication more environment friendly. In our case, we used the pencil graphite without any further modification as free residual chlorine sensor, and with a simple one-step cyclic voltammetry, it has been used as cathode in aqueous battery application. Thereby, it was termed as a green material. Reference 1. Srinivasulu Kanaparthi and Sushmee Badhulika, Solvent-free fabrication of a biodegradable all-carbon paper based field effect transistor for human motion detection through strain sensing, Green Chem., 2016,18, 3640-3646. 2. https://en.wikipedia.org/wiki/Green_chemistry. 6. The full form of PDPE to be abbreviated initially. Correct all such mistakes. Responses: These type of issues have been fixed in the manuscript. 7. ‘Every day the electrode was tested for two weeks.’ No meaning and connection to the previous statement. Responses: Following lines are included now in the manuscript to make the connections with the statements. “The electrode stability was tested using amperometry at an applied potential of 1.5 V vs. Ag/AgCl, with 1 mM of NaOCl added. Electrodes were tested daily over the course of two weeks; and stored at room temperature within a closed glass vial in between the measurements. Between subsequent measurements, the electrodes were cleaned in DI water and dried using nitrogen gas.” 8. Caption of Fig. 2 appears in the middle of a paragraph, which breaks the continuity. Responses: It is fixed in the manuscript. 9. The authors could quantify FRC using UV spectroscopy and other analytical techniques for better comparison. Responses: Currently we are working on inter laboratory and intra laboratory validation of FRC sensor, along with substrate improvement. We are hoping to publish these work in a separate paper, as currently it is in progress. As this work is the first of its kind, we have studied the behavior of PGE and PDPE as FRC sensor, as well as showed its feasibility as energy storage materials with small modification. Currently, work is in progress to improve the nature of the substrate so that these electrodes can be used in any real samples. Attachments Attachment Submitted filename: Responses to reviewer comments.docx https://doi.org/10.1371/journal.pone.0248142.r002
22 Feb 2021 Decision Letter - Zafar Ghouri, Editor Pencil graphite as electrode platform for free chlorine sensors and energy storage devices PONE-D-20-33482R1 Dear Dr. Jamal, We’re pleased to inform you that your manuscript has been judged scientifically suitable for publication and will be formally accepted for publication once it meets all outstanding technical requirements. Within one week, you’ll receive an e-mail detailing the required amendments. When these have been addressed, you’ll receive a formal acceptance letter and your manuscript will be scheduled for publication. An invoice for payment will follow shortly after the formal acceptance. To ensure an efficient process, please log into Editorial Manager at http://www.editorialmanager.com/pone/, click the 'Update My Information' link at the top of the page, and double check that your user information is up-to-date. If you have any billing related questions, please contact our Author Billing department directly at authorbilling@plos.org. If your institution or institutions have a press office, please notify them about your upcoming paper to help maximize its impact. If they’ll be preparing press materials, please inform our press team as soon as possible -- no later than 48 hours after receiving the formal acceptance. Your manuscript will remain under strict press embargo until 2 pm Eastern Time on the date of publication. For more information, please contact onepress@plos.org. Kind regards, Zafar Khan Ghouri Academic Editor PLOS ONE Additional Editor Comments (optional): It's my pleasure to inform you that, after the peer review, your paper, Pencil graphite as electrode platform for free chlorine sensors and energy storage devices has been accepted. Reviewers' comments: https://doi.org/10.1371/journal.pone.0248142.r003
Formally Accepted
25 Feb 2021 Acceptance Letter - Zafar Ghouri, Editor PONE-D-20-33482R1 Pencil graphite as electrode platform for free chlorine sensors and energy storage devices Dear Dr. Jamal: I'm pleased to inform you that your manuscript has been deemed suitable for publication in PLOS ONE. Congratulations! Your manuscript is now with our production department. If your institution or institutions have a press office, please let them know about your upcoming paper now to help maximize its impact. If they'll be preparing press materials, please inform our press team within the next 48 hours. Your manuscript will remain under strict press embargo until 2 pm Eastern Time on the date of publication. For more information please contact onepress@plos.org. If we can help with anything else, please email us at plosone@plos.org. Thank you for submitting your work to PLOS ONE and supporting open access. Kind regards, PLOS ONE Editorial Office Staff on behalf of Dr. Zafar Ghouri Academic Editor PLOS ONE https://doi.org/10.1371/journal.pone.0248142.r004

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