Review on the Energy Transformation Application of Black Phosphorus and Its Composites

Round 1

Reviewer 1 Report

The presented paper is a review on the application of black phosphorus (including composite materials) in energy storage, photocatalysis and electrocatalysis. While the first application is somewhat out of the scope of the journal, the other two fit well. The topic is actual and interesting and increasing efforts are made in recent years in it. Therefore, the review is topical. However, I think it should be significantly improved before publishing.

 

Some general remarks:

1. A missing part of the review is the comparison with other materials (not based on BP) that have shown a good performance in the discussed processes.

 2. The paper covers a lot of recent literature. However, I think some key papers were not considered. For instance: 

https://pubs.rsc.org/en/content/articlelanding/2019/nr/c9nr04348a

https://www.pnas.org/doi/pdf/10.1073/pnas.1416581112

https://www.mdpi.com/2079-4991/6/11/194

https://pubs.acs.org/doi/abs/10.1021/jacs.7b08416

https://www.sciencedirect.com/science/article/pii/S1385894719334126

 3. Line 98: “advanced oxidation technologies such as photocatalysis” – not all photocatalytic reactions are oxidation technologies.

 4. Line 183: “Carbon dioxide (CO₂) emission reduction is also of great significance to the conversion of carbon dioxide into carbon monoxide products.” Conversion of CO₂ to CO is only one of the many routes for reduction of the CO₂ emissions. Please rewrite.

 5. Line 184: “The use of electrocatalytic technology to promote carbon dioxide emission reduction can … develop new energy sources.” The sentence is confusing. To produce an energy source from CO₂ one should lose more energy than will be gained.

 6. Line 190: “However, due to the limitations of the traditional synthesis methods of catalytic materials and their higher surface energy, most of these catalytic materials are massive or granular in shape, and therefore have fewer active centers.” This is not true (examples – zeolites, MOFs). 

 There are too many technical mistakes that hinder reading:

Line 29: proved à proven

Line 48: will be discussed in the paper à will be discussed.

Line 52: Mg(NO₃)2 à Mg(NO₃)₂

Line 80: g(-1) à g^-1.

Line 101: degradation technology have  à  degradation technology to have.

Line 114: (center dot O-2(-)) à  please replace by chemical formulae.

Line 115: H2 – H₂.

Line 155: Layered black phosphorus is a unique …  à  This sentence should be moved somewhere at the beginning of the paper.

Line 205: Pumera once et al.  à  Pumera et al. 

References. Some of the paper titles are capitalized (e.g. Ref. 3), some not.

References. Please, use sub- and superscripts where necessary (for instance Bi2WO6 in ref. 1)

Reference 48: Materials Today: Proceedings (capitalize)

Reference 51: Correct the authors’ names.

Reference 109: List the authors in the journal style.

The whole text: Please, leave a space before “[“ and, when applicable, after “]”.

The whole text: Please, ese etc. instead et. al. when no people are listed.

 

Author Response

Manuscript ID: catalysts-1972400

TITLE: Review on the energy transformation application of black phosphorus and its composites

CATALYSTS

   

Dear Prof. Abigail Zhao

 

Thank you very much for sending us the reviewer’s reports on our manuscript (Paper Ref.: No.: catalysts-1972400). We also thank reviewers for reading our manuscript and providing valuable comments. According to reviewers’ suggestions, we have made extensive modification to the original manuscript. Here, we attached the revised manuscript in work format for your approval. The changes are highlighted in the annotated COPY. The point-to-point responses to the referees’ comments are listed below. The list of changes is provided in the last part of this letter.

 

We look forward to receiving your decision soon.

 

With best regards,

Shancheng Yan

School of Geography and Biological Information,

Nanjing University of Posts and Telecommunications,

Nanjing 210023, China

E-mail: [email protected]

Phone: +86 25-85866634

Fax: +86 25-85866634

 

 

 

 

 

 

 

 

The point-to-point responses to the referees’ comments

(For clarity, the referees’ comments are cited in italics)

 

Reviewer #1:

The presented paper is a review on the application of black phosphorus (including composite materials) in energy storage, photocatalysis and electrocatalysis. While the first application is somewhat out of the scope of the journal, the other two fit well. The topic is actual and interesting and increasing efforts are made in recent years in it. Therefore, the review is topical. However, I think it should be significantly improved before publishing.

1. A missing part of the review is the comparison with other materials (not based on BP) that have shown a good performance in the discussed processes.

Reply: Thanks for pointing this out. We have made a comparison with other materials (not based on BP) and the results are shown in Figure 4. In addition to this, a brief summary of the black phosphorus-based materials presented in the article has been made and the results are shown in Table 1. Based on comparative results，it can be illustrated that black phosphorus is well suited for use as a photocatalyst.

Figure 4. H₂ evolution rate of several groups of black phosphorus-based materials with and without black phosphorus.

 

Table 1. Comparison on hydrogen production rates of a number of black phosphorus-based materials.

Catalyst	apparent quantum yield (%)	H2 evolution rate(umolg-1h-1)	Wavelength range(λ)	Ref.
BP/g-C3N4	3 1.25	427 101	>420nm >780nm	[92]
BP/CN	/	786	>420nm	[94]
BP/MoS2	1.2	1286 341	>420nm >550nm	[96]
BP/TiO2	/	112	>420nm	[103]
Co2P/BP	2.42	1191	>420nm	[104]
BP/ Cs2AgBiBr6	/	104.6	>420nm	[105]
Pt/BP	4	447	>420nm	[106]

 

2. The paper covers a lot of recent literature. However, I think some key papers were not considered. For instance: 

https://pubs.rsc.org/en/content/articlelanding/2019/nr/c9nr04348a

https://www.pnas.org/doi/pdf/10.1073/pnas.1416581112

https://www.mdpi.com/2079-4991/6/11/194

https://pubs.acs.org/doi/abs/10.1021/jacs.7b08416

https://www.sciencedirect.com/science/article/pii/S1385894719334126

Reply: Thanks for your suggestion. We have read these articles and they have inspired us so much that we have added them to the Ref. [18], Ref. [26], Ref. [27], Ref. [46], Ref. [92], and introduced them. The specific modification part shall be filled in the list of changes.

3. Line 98: “advanced oxidation technologies such as photocatalysis” – not all photocatalytic reactions are oxidation technologies.

Reply: Thanks for pointing this out. We have modified the relevant statements “Among various physical, chemical and biological technologies for pollution control, advanced oxidation technologies such as photochemical oxidation, ozone oxidation and so on.”

4. Line 183: “Carbon dioxide (CO₂) emission reduction is also of great significance to the conversion of carbon dioxide into carbon monoxide products.” Conversion of CO₂to CO is only one of the many routes for reduction of the CO₂emissions. Please rewrite.

Reply: Thanks for pointing this out. To make the presentation of the article more rigorous, we have rewritten this sentence as “At present, the conversion of carbon dioxide to carbon monoxide products is one of the more promising of the many methods of carbon dioxide emission reduction.”

5. Line 184: “The use of electrocatalytic technology to promote carbon dioxide emission reduction can … develop new energy sources.” The sentence is confusing. To produce an energy source from CO₂one should lose more energy than will be gained.

Reply: Thanks for pointing this out. We would replace this sentence with “The use of electrocatalysis technology to promote carbon dioxide emission reduction offers advantages over other CO₂ recovery strategies because of its relatively simple operating conditions (it can be carried out at ambient temperature and pressure) and its ability to convert CO2 into usable fuel using clean renewable energy sources, which is a multiple benefit.” Although this method is more energy intensive, it can be carried out using clean renewable energy and is environmentally friendly.

6. Line 190: “However, due to the limitations of the traditional synthesis methods of catalytic materials and their higher surface energy, most of these catalytic materials are massive or granular in shape, and therefore have fewer active centers.” This is not true (examples – zeolites, MOFs). 

Reply: Thanks for pointing this out. After your reminder, we realize this mistake and have rewritten this sentence as “However, these alloys have certain limitations, such as higher surface energy and lower surface activity.” These alloy materials refer specifically to the copper, gold and silver mentioned earlier.

 

Thank you very much for taking the responsibility of pointing out our technical errors. We are sorry that we have made so many technical mistakes and we have corrected all the errors you have mentioned. Thank you once again.

 

 

 

 

 

 

 

 

 

 

The list of changes

NO	In the original manuscript	In the revised manuscript	Note
In the main text:
1	None	Line 134-136, Page 4 Line 171-174, Page 5 Line 181-190, Page 5-6 Figure 4 Table 1	Added In response to Reviewer # 1’s Comment 1
2	None	Ref. [18], Ref. [26], Ref. [27], Ref. [46], Ref. [92], Line 118-136, Page 4; Figure 3	Added In response to Reviewer # 1’s Comment 2
3	Line 98, Page 3	Line 100-101, Page 3 Replaced ‘photocatalysis’ with ‘photochemical oxidation’	Modified In response to Reviewer # 1’s Comment 3
4	Line 183, Page 4	Line 233-234, Page 7 Rewrite this sentence	Modified In response to Reviewer # 1’s Comment 4
5	Line 184, Page 4	Line 235-239, Page 7 Revise and explain the sentence	Modified In response to Reviewer # 1’s Comment 5
6	Line 190, Page 5	Line 242-243, Page 7 Revise and explain the sentence	Modified In response to Reviewer # 1’s Comment 6

 

 

Author Response File: Author Response.pdf

Reviewer 2 Report

Dear editor,

The manuscript concerns the review about the black phosphorus and its applications in different fields. However, I do not think the manuscript is well organized. The manuscript concerns many literature, but the authors did not focus on any of them, and they should discuss some of the literature that are important carefully. Unfortunately, they just listed simply all the reported results, I think it cannot be accepted in its current status. 

Author Response

Manuscript ID: catalysts-1972400

TITLE: Review on the energy transformation application of black phosphorus and its composites

CATALYSTS

  Dear Prof. Abigail Zhao

Thank you very much for sending us the reviewer’s reports on our manuscript (Paper Ref.: No.: catalysts-1972400). We also thank reviewers for reading our manuscript and providing valuable comments. According to reviewers’ suggestions, we have made extensive modification to the original manuscript. Here, we attached the revised manuscript in work format for your approval. The changes are highlighted in the annotated COPY. The point-to-point responses to the referees’ comments are listed below. The list of changes is provided in the last part of this letter.

We look forward to receiving your decision soon.

With best regards,

Shancheng Yan

School of Geography and Biological Information,

Nanjing University of Posts and Telecommunications,

Nanjing 210023, China

E-mail: [email protected]

Phone: +86 25-85866634

Fax: +86 25-85866634

 

The point-to-point responses to the referees’ comments

(For clarity, the referees’ comments are cited in italics)

 

Reviewer #2:

The manuscript concerns the review about the black phosphorus and its applications in different fields. However, I do not think the manuscript is well organized. The manuscript concerns many literature, but the authors did not focus on any of them, and they should discuss some of the literature that are important carefully. Unfortunately, they just listed simply all the reported results, I think it cannot be accepted in its current status. 

 

Reply: Thank you very much for your valuable suggestions, on the basis of which we have carefully revised the article. We have discussed in detail some valuable articles on photocatalysis and electrocatalysis, for example Line 122-136, Figure 3, Line 194-206, Figure 5 and so on. To enhance the organisation of the manuscript, we have also added comparative figures and summary tables to the article. Thank you again for your valuable comments on our manuscript!

 

Line 122-136:

One representative work is the first design of a binary nanohybrid (BP/CN) of two dimensional (2D) black phosphorus (BP) and graphitic carbon nitride (CN) by Zhu et al. [92]. They used methanol as a sacrificial electron donor to burst holes generated by band gap excitation for photocatalytic hydrogen precipitation on BP/CN. Proposed schematic diagram for the visible and NIR light activated photocatalytic H2 evolution using BP/CN in the presence of methanol is shown in Figure 3. They also found that the best hydrogen precipitation rate of 427 umolg-1h-1 was achieved at a BP:CN ratio of 1:4, while the hydrogen production rate was 101 umolg-1h-1 under 780 nm light irradia-tion. Compared to relatively conventional catalysts, Pt/CN at the hydrogen production rate under 780 nm light irradiation was almost zero, so it is said that BP/CN showed stronger catalytic activity in the visible near infrared region. When BP/CN is irradiated with >780 nm light, the excited electrons in the CB band of BP are trapped by interfacial P-N defects, thereby enhancing the photocatalytic performance. The hydrogen pro-duction rate of pure graphitic carbon nitride is approximately 168 umolg-1h-1, compared to which BP/CN has a better catalytic performance.

 

Figure 3. Proposed schematic diagram for the visible and NIR light activated photo-

catalytic H2 evolution using BP/CN in the presence of methanol. (reproduced with permission from Ref. [92], © American Chemical Society 2017).

 

Line 194-206

One representative work is the 2D Heterostructure of Amorphous CoFeB Coating Black Phosphorus Nanosheets to improve the efficiency of electrocatalytic water oxida-tion done by Chen et al. [110]. Exfoliated black phosphorus (EBP) nanosheets have high carrier mobility due to their two-dimensional (2D) layered structure, but are limited by an excess of oxygen-containing intermediate adsorption and rapid deterioration in air. To address this issue, they prepared nanohybrids of amorphous CoFeB nanosheets on BP nanosheets. Through electronic interactions and oxygen affinity differences be-tween EBP and CoFeB nanosheets, the heterostructure is able to balance the uptake of oxygen-containing intermediates to achieve the optimum state for facilitating the OER process. In addition，the EBP (crystalline) and CoFeB (amorphous) hybrid displays the superiorities of quick charge carrier transfer and abundant reactive sites, respectively. Schematic diagram of the typical processes for OER and MOR is shown in Figure 5.

 

 

 

Figure 5. Schematic diagram of the typical processes for OER and MOR. (repro-duced with permission from Ref. [110] , © American Chemical Society 2021).

Author Response File: Author Response.pdf

Round 2

Reviewer 1 Report

The authors have taken into account all of the remarks and they significantly improved the manuscript. There are few things left to be corrected, mainly in the new text. For instance, the chemical formulae of superoxide is not correct. In line 58 "ese etc." should be changed to "etc.". The Caption of Fig. 4 should be improved, to e.g. "H2 evolution rate of several groups of materials with and without black phosphorus".

Reviewer 2 Report

Dear editor,

         Sorry for the late because of the new round of Covid-19 in my city.

         I read the revised manuscript and think it can be accepted now.

Yours sincerely,

Xiao-Bing Cui