Research Progress of Carbon Deposition on Ni-Based Catalyst for CO₂-CH₄ Reforming

Round 1

Reviewer 1 Report

The authors reported a review of the carbon deposition on Ni-based catalysts. This work investigates the thermodynamics, kinetics, and reaction mechanism of CO₂-CH₄ reforming. However, some revisions are required before it can be considered for publication.

1.       Please rewrite the abstract that shows the strong points of your article. These abstracts are so general and can't display the key points of your manuscript.

2.       There are much more attractive reviews on this topic. Why did the authors choose this topic?  Please explain it briefly at the end of the introduction section.

3.       Because the review is long, it is better to have a picture of each quote to make it interesting for the reader. Pictures convey the content clearly and better. You have not put appropriate figures, so this is boring for readers. please add the related figures for each quote.

 

4.       There are some grammar and punctuation mistakes. Please check the entire manuscript and correct them. 

Author Response

Dear Dr. 

We are very grateful for your letter and the reviewers’ comments on our manuscript catalysts-2269319. According to the comments, we carefully revised the manuscript, and all the revisions were marked in yellow color in the revised manuscript. In this detailed response, we would like to answer the reviewer’s comments point by point.

Author Response File: Author Response.pdf

Reviewer 2 Report

It is mentioned in the introduction that Fischer and Tropsch first discovered this reaction. I would suggest referring to the original paper (Fischer, F.; Tropsch, H. Conversion of methane into hydrogen and carbon monoxide. Brennst. Chem. 1928, 3, 29), but the possibility of a reaction between methane and carbon dioxide was already mentioned by Lang (Lang, J. Experimentelle Beiträge zur Kenntnis der Vorgänge bei der Wasser-und Heizgasbereitung. Z. Phys. Chem. 1888, 2, 161–183.) in the late 19th century,  It is correctly written that a attention is paid to the investigation of the reaction all over the world, however, one of the references given is about the hydrogenation of CO₂ [1] and does not mention the review of well-known researchers such as [18]. 

The second chapter presents the thermodynamics of CO₂ + CH₄ reaction. I would emphasize that equations 1-5 are equilibrium processes and the equilibrium is strongly influenced by the temperature. In addition to describing the changes, I would recommend to show the changes in equilibrium conversion and equilibrium product distribution as a function of temperature on a figure.

When describing the mechanism of the reaction, there is no mention of hydrogen-assisted CO₂ dissociation.

It is correctly mentioned in several places that surface carbon can be formed from the decomposition of CH₄ and from the disproportionation of CO, and that CO₂ can dissociate on the surface. However, I did not find any results on the adsorption or on the interaction of CH₄, CO₂ and CO with Ni.

In a separate chapter is written about the carbon formation and the types of surface carbon.  This section is too general. It does not discuss how the surface carbon forms can be distinguished (except by SEM). It is mentioned that amorphous carbon reacts with oxygen around 200 °C, while graphitized carbon reacts at a significantly higher temperature, but no other specific data or method are provided. Only one reference is given, although quite a few paper have dealt with the reactivity of surface carbon.

The amount of carbon produced during the reaction is not mentioned anywhere, this would be especially important when the effect of additives on the formation of carbon is discussed.

There is also no specific data in the chapter on bimetallic catalysts and on the effect of the support. I would recommend summarizing in tables the formation rates, conversions, and the amount of deposited carbon obtained on different supported Ni and on different bimetallic catalysts.

Unfortunately, mixed reformation is only discussed in one paragraph, while it would be a good possibility to reduce carbon deposition.

Author Response

Dear Dr. 

We are very grateful for your letter and the reviewers’ comments on our manuscript catalysts-2269319. According to the comments, we carefully revised the manuscript, and all the revisions were marked in yellow color in the revised manuscript. In this detailed response, we would like to answer the reviewer’s comments point by point.

Author Response File: Author Response.pdf

Reviewer 3 Report

This review reports many papers and focuses on specific performance and optimization results. However, this work fails to have a deeper understanding of the mechanism and insight into the DRM reaction and carbon deposition growth.   

1, As a review paper with "research progress", the literature is not up-to-date enough. This work randomly has literature from 2010. It is known that DRM has a lot of papers published every year. More up-to-date works should be reported.

Besides, only 3 figures are shown and 2 of 3 are morphology. This is not acceptable for a review work covering 129 kinds of literature. More representative figures should be shown to demonstrate the insight of DRM for readers.

Some work is recommended as below:

Y. Song, E. Ozdemir, S. Ramesh, A. Adishev, S. Subramanian, A. Harale, M. Albuali, B.A. Fadhel, A. Jamal, D. Moon, Dry reforming of methane by stable Ni–Mo nanocatalysts on single-crystalline MgO, Science, 367 (2020) 777-781.

M. Zhang, J. Zhang, Y. Wu, J. Pan, Q. Zhang, Y. Tan, Y. Han, Insight into the effects of the oxygen species over Ni/ZrO2 catalyst surface on methane reforming with carbon dioxide, Applied Catalysis B: Environmental, 244 (2019) 427-437.

X. Yan, T. Hu, P. Liu, S. Li, B. Zhao, Q. Zhang, W. Jiao, S. Chen, P. Wang, J. Lu, Highly efficient and stable Ni/CeO2-SiO2 catalyst for dry reforming of methane: Effect of interfacial structure of Ni/CeO2 on SiO2, Applied Catalysis B: Environmental, 246 (2019) 221-231.

Jin, Baitang, et al. "Engineering metal-oxide interface by depositing ZrO2 overcoating on Ni/Al2O3 for dry reforming of methane." Chemical Engineering Journal 436 (2022): 135195.

Vogt, Charlotte, et al. "Structure sensitivity in steam and dry methane reforming over nickel: activity and carbon formation." ACS Catalysis 10.2 (2019): 1428-1438.

Luisetto, Igor, et al. "Dry reforming of methane over Ni supported on doped CeO2: New insight on the role of dopants for CO2 activation." Journal of CO2 Utilization 30 (2019): 63-78.

Jin, Baitang, Shiguang Li, and Xinhua Liang. "Enhanced activity and stability of MgO-promoted Ni/Al2O3 catalyst for dry reforming of methane: Role of MgO." Fuel 284 (2021): 119082.

Ewbank, Jessica L., et al. "Effect of metal–support interactions in Ni/Al2O3 catalysts with low metal loading for methane dry reforming." Applied Catalysis A: General 494 (2015): 57-67.

Wang, Yaning, Rongjun Zhang, and Binhang Yan. "Ni/Ce0. 9Eu0. 1O1. 95 with enhanced coke resistance for dry reforming of methane." Journal of Catalysis 407 (2022): 77-89.

 

2. The language needs to be improved. Besides, there are many typos such as “strong interaction 459 between the support and the mental”.

It is hard to understand “From the point of thermodynamics, the △H value of CRM is high of 247 kJ/mol, indicating that the reverse reaction of CRM can theoretically release energy of 247 kJ/mol.”

3. The reaction CH4+CO2 is usually named dry reforming of methane. And this name is suggested to be used or at least mentioned for this review.

4. The author mentions "In traditional CRM process, high temperature (>1000 K) and low pressure (~1 atm) are usually required to obtain efficient conversion of methane and carbon dioxide to syngas." But the CRM (or DRM) has not been widely used in the industry. This condition is mainly for research purposes. Please check and beware of the claim.

5. The author claimed "Support is a very important part of catalyst. In CO2-CH4 reforming reaction, commonly used supports are Al2O3, MgO, CeO2, TiO2, SiO2, etc. Although the support itself 425 has no activity in the reaction, it can change the overall performance of the catalyst." It has been reported that support plays an important role in CO2 activation. This is not true. For instance, some work reported different activity of the acid surface and the basic surface of the support. (Das, Subhasis, et al. "A study of the synergy between support surface properties and catalyst deactivation for CO2 reforming over supported Ni nanoparticles." Applied Catalysis A: General 545 (2017): 113-126.)

6. The author reported the TEM in Fig 3 in 4.2.2. This is not related to elimination. It is suggested to move to 4.1.

7. There are many types of carbon. If this paper focuses on carbon deposition, the types of carbon should be discussed (NI3C, Cα, Cβ, Cγ) and relative results from the literature should be given, such as TEM, TPO, Raman.

8. In CRM (or DRM), CO₂ activation is very important for carbon deposition but this review ignored the importance. For instance, the literature [53] mainly talks about this but the author put this in the “Inhibition of carbon deposition from the stability of Ni component;” This is not reasonable. It is recommended to have a series of enhanced CO₂-activation catalysts and discussion should be made about the different CO2 activation on oxide.  

 

 

 

 

Author Response

Dear Dr. 

We are very grateful for your letter and the reviewers’ comments on our manuscript catalysts-2269319. According to the comments, we carefully revised the manuscript, and all the revisions were marked in yellow color in the revised manuscript. In this detailed response, we would like to answer the reviewer’s comments point by point.

Author Response File: Author Response.pdf

Round 2

Reviewer 1 Report

 Accept in present form

Reviewer 2 Report

The authors modified the manuscript according to the referee's suggestions.

Reviewer 3 Report

This work has been improved and can be published now.