Peer review of: A solvent-assisted ligand exchange approach enables metal-organic frameworks with diverse and (2020)

Reviewers' comments: 

Reviewer #1 (Remarks to the Author): 

The mnauscript "A Solvent-Assisted Ligand Exchange Approach Enables Metal-Organic Frameworks 
with Diverse and Complex Architectures" by Wu and coworkers is an excellent report on the formation 
of complex MOF structures. It is well-written and should be published. Nevertheless, I have some 
small comments that should be addressed. 

1. Is it possible to study the kinetics of ligand exchange/MOF transformation in more detail? Maybe by 
watching the change in time in SEM and XRD after quenching? 

2. What is the effct of initial imidazole concnetration on the process? 

3. There some reports in literature the authors should take a look at (especially the first one): 
https://doi.org/10.1002/slct.201600526 
https://pubs.acs.org/doi/abs/10.1021/jacs.7b12633 
https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201901707 
https://pubs.acs.org/doi/full/10.1021/ja403810k 
https://pubs.acs.org/doi/10.1021/acs.cgd.8b01628 

4. The authors showed some examples about concentration dependency. Nevetheless, I miss some 
summarizing discussion/rationale behind the study. 

5. Why are double shelled structures formed instead of direct growth for a thicker shell? 

6. The evaporation of Zn species during carbonization can also have an effect on porosity and should 
be discussed. 

7. Small errors in writing: "nanowires was"; "peapod-like MOF strcutures have been reported before" 
(not been reported?) 

8. The authors should add page numbers to the SI and a table of contents 



Reviewer #2 (Remarks to the Author): 

In this paper, the author reported new, facile and versatile synthesis strategies for the design of 
diverse and complex MOF architectures. By precisely adjusting the balance between the cleavage rate 
of old bonds and the formation rate of new bonds, 21 different MOF materials and 13 different types of 
MOF configurations ranging from 3D to 2D and 1D structures have been successfully prepared. In 
addition, after a carbonization treatment, MOF-derived nanoporous carbon was used for Na+ ion 
storage. Considering the overall quality of the paper, I recommend its publication after minor revision. 
1. The author mentioned that “In order to demonstrate the advantages of MOF architectures, the 
structured MOFs are subsequently carbonized to fabricate nanoporous carbon for Na+ ion storage” in 
the last paragraph of the introduction, however, it seems illogical. In view of the advantages of MOF 
architectures, why not the author uses the structured MOFs directly for Na+ ion storage? After all, no 
introduction about the advantage of carbonization was mentioned in the preamble. 
2. In line 132, is there something wrong with the “Hmim    H++mim-”. Please check it carefully. 
3. In line 322, “CV curves of all ZIF-derived porous carbon are measured at various scan rates”, it’s 
better to put the related figure into the main manuscript. 
4. Please check the captions of Fig. 2 and 3, I think it’s inappropriate to begin with “Preparation of …”. 
5. Although there are a large number of references with good quality, some important articles should 
be cited. e.g: Coordination Chemistry Reviews, 2019, 389: 119-140; Advanced Materials, 2019, 
31(6): 1804740; Coordination Chemistry Reviews, 2018, 376: 292-318; Advanced Functional 
Materials, 2018, 28(47): 1804950. 



Reviewer #3 (Remarks to the Author): 

As one of the main limitations for a broader application of MOF, controllable preparation of MOF with 
diverse and complex micro/nano-structures is still at a very early stage. In this paper, the authors 
developed a powerful synthesis strategy called “SALE” approach, and synthesized 13 different MOF 
structures including a kind of rare double-shelled nanotube. These structured MOF materials were 
carbonized to nanoporous carbon further, which exhibited excellent electrochemical property for Na+ 
storage. Overall, this work is very interesting and would add significant contribution to this filed, the 
manuscript is well-organized, and the authors have done relatively detailed investigations and 
discussions. Therefore, I strongly recommend the publication of this work in Nature Communications 
after a few clarifications. 
1. It would be better to include FTIR spectra characterization for ZIFs after the SALE process. 
2. The stability of coordination bonds for ZIF-7/ZIF-71 corresponded to pKa value of linkers, how 
about Zn-HMT/ZnCo-PPF-3 and ZnCo-BTC/ZnCo-MOF-74 ? 
3. In recent publications MOF-derived single-atom catalysts often show 3D solid particle shape, do you 
think whether or not single-atom catalysts derived from the prepared MOF nanostructures by your 
approach have an advantage over them ?