Molecular+Simulation+Group
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Algorithm Identifies Optimal Pairs for Composing Metal-Organic Frameworks
The integration of metal-organic frameworks (MOFs) and other metal nanoparticles has increasingly led to the creation of new multifunctional materials. Many researchers have integrated MOFs with other classes of materials to produce new structures with synergetic properties.
Despite there being over 70,000 collections of synthesized MOFs that can be used as building blocks, the precise nature of the interaction and the bonding at the interface between the two materials still remains unknown. The question is how to sort out the right matching pairs out of 70,000 MOFs.
An algorithmic study published in Nature Communications by a KAIST research team presents a clue for finding the perfect pairs. The team, led by Professor Ji-Han Kim from the Department of Chemical and Biomolecular Engineering, developed a joint computational and experimental approach to rationally design MOF@MOFs, a composite of MOFs where an MOF is grown on a different MOF.
Professor Kim’s team, in collaboration with UNIST, noted that the metal node of one MOF can coordinately bond with the linker of a different MOF and the precisely matched interface configurations at atomic and molecular levels can enhance the likelihood of synthesizing MOF@MOFs.
They screened thousands of MOFs and identified optimal MOF pairs that can seamlessly connect to one another by taking advantage of the fact that the metal node of one MOF can form coordination bonds with the linkers of the second MOF. Six pairs predicted from the computational algorithm successfully grew into single crystals.
This computational workflow can readily extend into other classes of materials and can lead to the rapid exploration of the composite MOFs arena for accelerated materials development. Even more, the workflow can enhance the likelihood of synthesizing MOF@MOFs in the form of large single crystals, and thereby demonstrated the utility of rationally designing the MOF@MOFs.
This study is the first algorithm for predicting the synthesis of composite MOFs, to the best of their knowledge. Professor Kim said, “The number of predicted pairs can increase even more with the more general 2D lattice matching, and it is worth investigating in the future.”
This study was supported by Samsung Research Funding & Incubation Center of Samsung Electronics.
(Figure: An example of a rationally synthesized MOF@MOFs (cubic HKUST-1@MOF-5 ))
2019.08.30 View 15059 -
Expanding Gas Storage Capacity of Nanoporous Materials
A KAIST research team led by Professor Jihan Kim of the Department of Chemical and Biomolecular Engineering has successfully proposed a rational defect engineering methodology that can greatly enhance the gas storage capacity of nanoporous materials. The team conducted a high-throughput computational screening of a large experimental metal-organic framework database to identify 13 candidate materials that could experience significant methane uptake enhancement with only a small proportion of linker vacancy defects.
This research was published online on November 16 in Nature Communications, with M.S. candidate Sanggyu Chong from KAIST as the first author and post-doctorate researcher Günther Thiele from the Department of Chemistry at UC Berkeley as a contributing author.
Metal-organic frameworks, hereinafter MOF, are crystalline nanoporous materials that are comprised of metal clusters and organic linkers continuously bound together by coordination bonds. Due to their ultrahigh surface areas and pore volumes, they have been widely studied for various energy and environment applications.
Similar to other crystalline materials, MOFs are never perfectly crystalline and are likely to contain several different types of defects within their crystalline structures. Among these defects, linker vacancy defects, or the random absence of linker vacancies in their designated bonding positions, are known to be controllable by practicing careful control over the synthesis conditions.
The research team combined the concepts of rational defect engineering over the linker vacancy defects and the potential presence of inaccessible pores within MOFs to propose a methodology where controlled the introduction of linker vacancy defects could lead to a dramatic enhancement in gas adsorption and storage capacities.
The study utilized a Graphic Processing Unit (GPU) code developed by Professor Kim in a high-throughput computational screening of 12,000 experimentally synthesized MOFs to identify the structures with significant amounts of pores that were inaccessible for methane. In determining the presence of inaccessible pores, a flood-fill algorithm was performed over the energy-low regions of the structure, which is the same algorithm used for filling an area with color in Microsoft Paint.
For the MOFs with significant amounts of inaccessible pores, as determined from the screening, the research team emulated linker vacancy defects in their crystalline structures so that the previously inaccessible pores would be newly merged into the main adsorption channel with the introduction of defects for additional surface area and pore volume available for adsorption. The research team successfully identified 13 structures that would experience up to a 55.56% increase in their methane uptake with less than 8.33% of the linker vacancy defects.
The research team believes that this rational defect engineering scheme can be further utilized for many other applications in areas such as selective adsorption of an adsorbate from a gas mixture and the semi-permanent capture of gas molecules.
This research was conducted with the support of the Mid-career Research Program of the National Research Foundation of Korea.
Figure1. A diagram for flood fill algorithm and example of identification of inaccessible regions within the MOFs, using the flood fill algorithm
Figure2. Methane energy contours before and after detect introduction
2017.12.04 View 7147 -
Analysis of Gas Adsorption Properties for Amorphous Porous Materials
Professor Jihan Kim from the Department of Chemical and Biomolecular Engineering at KAIST has developed a method to predict gas adsorption properties of amorphous porous materials.
Metal-organic frameworks (MOFs) have large surface area and high density of pores, making them appropriate for various energy and environmental-related applications. And although most MOFs are crystalline, these structures can deform during synthesis and/or industrial processes, leading to loss in long-range order. Unfortunately, without the structural information, existing computer simulation techniques cannot be used to model these materials.
In this research, Professor Kim’s research team demonstrated that one can replace the material properties of structurally deformed MOFs with those of crystalline MOFs to indirectly analyze/model the material properties of amorphous materials. First, the team conducted simulations on methane gas adsorption properties for over 12,000 crystalline MOFs to obtain a large training set data, and created a resulting structure-property map. Upon mapping the experimental data of amorphous MOFs onto the structure-property map, results showed that regardless of crystallinity, the gas adsorption properties of MOFs showed congruence and consistency amongst one another.
Based on these findings, selected crystalline MOFs with the most similar gas adsorption properties as the collapsed structure from the 12,000 candidates. Then, the team verified that the adsorption properties of these similar MOFs can be successfully transferred to the deformed MOFs across different temperatures and even to different gas molecules (e.g. hydrogen), demonstrating transferability of properties.
These findings allow material property prediction in porous materials such as MOFs without structural information, and the techniques here can be used to better predict and understand optimal materials for various applications including, carbon dioxide capture, gas storage and separations.
This research was conducted in collaboration with Professor Dae-Woon Lim at Kyoto University, Professor Myunghyun Paik at Seoul National University, Professor Minyoung Yoon at Gachon University, and Aadesh Harale at Saudi Arabian Oil Company. The research was published in the Proceedings of the National Academy of Sciences (PNAS) online on 10 July and the co-first authors were Ph. D. candidate WooSeok Jeong and Professor Dae-Woon Lim.
This research was funded by the Saudi Aramco-KAIST CO2 Management Center.
(Figure 1. Trends in structure - material property map and in collapsed structures)
(Figure 2. Transferability between the experimental results of collapsed MOFs and the simulation results of crystalline MOFs)
2017.07.26 View 8544