Opportunities from Metal Organic Frameworks to Develop Porous Carbons Catalysts Involved in Fine Chemical Synthesis
Round 1
Reviewer 1 Report
This manuscript by Prof. Perez-Mayoral, Prof. Matos et al. is a review article covering the recent progress of carbon-based porous materials derived from metal-organic frameworks (MOFs), and the applications of the title materials toward organic synthesis reactions. The author has gone through the brief fundamental information of MOFs, and their final fate upon thermolysis. A wide range of organic synthesis reactions are discussed. This line of the work has rapidly grown from the infant stage over years. Most of the important results have been covered in the review article. This Reviewer enthusiastically recommends the acceptance of the manuscript to the Journal.
There is one issue this Reviewer would like to raise to the author. It would enrich the manuscript if the corresponding reactions from conventional catalytic systems are compared with those by the MOF-derived catalytic materials. From the relevant comparison, it would give readers a large scope to envision the high potentials of the MOF-derived materials toward catalytic reactions. It can offer benchmark information for people who are interested in the specific research.
Author Response
Response: Thanks a lot for the positive comments of the reviewer.
Concerning the last comment, it is very difficult due to the great variability of the used reaction conditions. In order to include some comparisons, we added some details when reported in the same paper.
Based on that, the following paragraphs has been included or revised according to the reviewer suggestion:
Line 307: “Note that PZS-900-2h catalyst obtained from PZS polymer by thermal treatment promoted the reaction with notably lower conversion (12% after 6 h) and selectivity (66%).”
Line 335: “These results contrast with those obtained in the presence of traditional Pd/C catalyst in which selectivity is changed leading to cyclohexanol/cyclohexanone as reaction products in 18% of conversion and 95 of selectivity.”
Line 384: “…as demonstrated from the calculated TOF values (TOF = 1570, and 29 min-1 when using MDNM(75Zn25Mn) or MnO/activated carbon catalysts, respectively, for benzyl alcohol oxidation).“
Line 447: “Taken into account that Cu/AC-N2 sample barely catalyzed the reaction (1% of conversion vs 17% for Cu@C-N2), it was possible to conclude that Cu0 and Cu2O phases are the truly catalytic active species. Similar enhancement of conversion values was observed for Cu/AC-H2 (14%) and Cu@C-H2 (27%) samples, demonstrating then the superior catalytic performance of MOF-derived porous carbons.”
Line 505: “Pd/MPC as mesoporous carbon material exhibiting high surface area resulted on high catalytic activity (up to 90% of yield after 60 min) and reusability in the green hydrodechlorination of 4-chlorophenol to phenol in water, at 25 °C, in the presence of NaOH as neutralizing agent of released HCl, compared to other reported catalytic systems, such as Pd–Al pillared clays, prepared by either impregnation method or by ion-exchange and even a novel fibrous nano-silica (KCC-1) based nanocatalyst (Ni@Pd/KCC-1).”
Author Response File: 
Author Response.pdf
Reviewer 2 Report
This is an interesting review that covers the literature on the development of porous carbon catalysts using metal-organic frameworks. It is a rapidly developing field, hence this review fills an important literature gap. Overall, the paper is well-organized and covers the topic well. The tables are very useful and provide easily accessible information. Based on the above, I am happy to recommend publication of this review in Catalysts, after carefully editing typos, etc.
Author Response
Response: Thanks a lot for the positive comments of the reviewer. The manuscript has been revised and typos have been corrected.
Reviewer 3 Report
This review briefly summarizes synthetic strategies to prepare MOFs and MOF-derived The whole manuscript is smooth and the result is of interest. I recommend the publication of this article after minor revisions mentioned below.
1. The MS discussed some synthetic methods to prepare MOFs. The author should explain the advantages and disadvantages of these methods.
2. Some related literature should be cited as follows:
Zhao Su-Qin, Gu Jin-Zhong, Syntheses, Structures and Catalytic Activity in Knoevenagle Condensation Reaction of of Two Diphenyl Ether Tetracarboxylic Acid-Co(II) Coordination Polymers, Chinese J. Inorg. Chem., 2022, 38(1), 161-170.
Author Response
Response: Authors are grateful to the reviewer for this comment.
According with your suggestion, the following paragraph has been included in the text:
Line 132: “There are advantages and disadvantages for the different synthetic approaches. The solvothermal method and more traditional one has the advantage of being a one pot method allowing single crystal at moderate temperatures, however it has the disadvantages of high reaction times, the use of solvents and easy formation of byproducts. Mecanochemical Method on the other hand is a solvent free method, performed at ambient temperature thus less hazardous, however it can have problems of pore volume. Microwave assisted method allows short reaction time and results in high purity products with good control over the crystal size, however some problems of reproducibility have been reported due to the use of different equipment, and the industrial scale of this methodology can be limited. The electrochemical method is an alternative that avoids the use of more hazardous solutions, can be operated in a continuous mode allowing for higher production rates and facilitating possible industrial application, however it requires specific conditions to work. The use of sonication for the synthesis has the advantageous of being a fast and energy-efficient method, allowing the obtention of nano size crystals, nevertheless there is no control over the local temperature of reaction. [1, 22] These and other aspect should be considered when of the selection of the most adequate synthetic method for a specific application.”
- Some related literature should be cited as follows:
Zhao Su-Qin, Gu Jin-Zhong, Syntheses, Structures and Catalytic Activity in Knoevenagle Condensation Reaction of of Two Diphenyl Ether Tetracarboxylic Acid-Co(II) Coordination Polymers, Chinese J. Inorg. Chem., 2022, 38(1), 161-170.
Response: Thank a lot for your suggestion but authors think that this cite has not been included in this manuscript. Our contribution is focused onto the application of MOF-derived porous carbons catalysts in fine chemical synthesis.
