Multivariate ZIF Synthesis via Linker Coding
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Solution Overview
Problem
The challenge lies in synthesizing specific and exceptional zeolitic imidazolate frameworks (ZIFs) from the vast number of predicted structures, as only a small subset has been made, and existing methods fail to efficiently access the predicted structures with hexagonal prism or cube secondary building units (SBUs) that are of high industrial interest.
Innovation Solution
A general strategy is developed using multivariate imidazolate linkers with different functionalities, particularly at the 2-positions, to 'code' hexagonal prism or cube SBUs in ZIF structures, allowing for the synthesis of specific ZIFs like ZIF-128, -412, -413, -414, -418, -585, -636, -640, -723, -725, -726, -740, and -813, which exhibit exceptional properties such as large pore openings and high CO2 uptake.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Adaptability or versatility
If conventional synthesis methods are used, then only a small subset of predicted zeolite structures can be made, but the vast number of predicted structures including those with hexagonal prism and cube SBUs remain inaccessible
Solution Approach 1:
The patent changes the chemical parameters of the imidazolate linkers by introducing different functionalities at the 2-position (2R-Im vs 2H-Im). This parameter change enables access to different ZIF structures including those with hexagonal prism and cube SBUs that were previously inaccessible through conventional synthesis methods
Solution Approach 2:
The patent segments the imidazolate linker into different functional variants (2R-Im and 2H-Im) that can be independently selected to code for specific SBU types. This segmentation allows systematic exploration of different ZIF structures by combining different linker functionalities
2Manufacturing precision
If multivariate imidazolate linkers with different functionalities are used to code hexagonal prism or cube SBUs, then specific ZIF structures can be synthesized, but the synthesis process becomes more complex
Solution Approach 1:
The patent uses parameter changes in the imidazolate linker functionality (2R-Im vs 2H-Im) to precisely control the formation of specific SBU structures. This allows manufacturing precision in achieving target ZIF structures while managing synthesis complexity through systematic parameter selection
3Quantity of substance
If larger unit cells with larger pore openings are created, then gas storage capacity and separation performance improve, but the crystal structure becomes more complex
Solution Approach 1:
The patent applies local quality by creating specific SBU structures (hexagonal prism and cube) at local positions within the crystal lattice. These localized structural features combine to form larger unit cells with enhanced gas storage capacity while maintaining overall structural order
Solution Approach 2:
The patent creates composite ZIF structures by combining different imidazolate linker types (2R-Im and 2H-Im) with metal nodes to form hybrid frameworks. This composite approach enables larger unit cells with improved gas storage properties while managing structural complexity through systematic design
Data Source
AI summary
The disclosure provides for multivariant zeolitic imidazolate frameworks (ZIFs), methods of making thereof, and methods of use therefrom.