Covalent Organic Framework Synthesis via Reversible Polycondensation

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Solution Overview

Problem

Traditional methods for preparing covalent organic framework (COF) materials result in products with low crystallinity, irregular morphology, and limited specific surface area, restricting their application due to narrow application range and complex processes.

Innovation Solution

A reversible polycondensation-termination method using control agents AP and BP is introduced, which involves dissolving monomers in solvents with added control agents and catalysts, followed by mixing and reacting to produce COF materials with high crystallinity and specific surface area, and a reversible degradation-recombination method to repair defects in existing COF materials.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If traditional methods are used to prepare COF materials, then the preparation process is simple, but the crystallinity and morphology of the products are poor

Engineering Contradiction:
ImprovecrystallinityVSAvoidprocess complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent introduces a template agent as an intermediary substance during the COF preparation process. This template agent guides the self-assembly of monomers into ordered structures, thereby improving crystallinity without requiring complex post-processing steps. The template agent acts as a mediator that facilitates the formation of high-quality COF structures during the synthesis process itself.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Area of stationary object

If traditional methods are used to prepare COF materials, then the preparation process is simple, but the specific surface area is reduced

Engineering Contradiction:
Improvespecific surface areaVSAvoidprocess complexity
Core Design Contradiction:
Area of stationary objectVSDevice complexity

Solution Approach 1:

The template agent serves as a mediator that directs the formation of COF structures with optimized pore configurations. By controlling the assembly process through this intermediary, the method achieves higher specific surface area while maintaining process simplicity, as the template agent enables direct formation of high-surface-area structures during synthesis rather than requiring subsequent modification steps.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent employs parameter changes by adjusting the type and concentration of template agents, solvent conditions, and reaction parameters to optimize COF structure formation. These parameter adjustments enable control over the final COF morphology and surface area, achieving high specific surface area products through optimized synthesis conditions rather than complex post-processing.

Inventive Principle:
Principle #35Parameter changes

3Shape

If traditional methods are used to prepare COF materials, then the process is simple, but the morphology controllability is poor

Engineering Contradiction:
Improvemorphology controllabilityVSAvoidprocess complexity
Core Design Contradiction:
ShapeVSDevice complexity

Solution Approach 1:

The template agent acts as a morphology-controlling intermediary that directs the self-assembly process to produce COF materials with desired shapes and sizes. By selecting appropriate template agents, the method achieves good morphology controllability while keeping the synthesis process relatively simple, as the template agent guides structure formation during synthesis rather than requiring complex post-synthesis shaping operations.

Inventive Principle:
Principle #24Intermediary (Mediator)

4Manufacturing precision

If existing COF materials have defects, then repair methods are needed, but the repair process increases complexity

Engineering Contradiction:
ImprovecrystallinityVSAvoidrepair process complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent applies the discarding and recovering principle by introducing a repair agent that selectively binds to and removes defect sites from COF materials. The repair agent temporarily associates with defects, facilitates their removal or correction, and then dissociates, allowing the COF structure to be recovered in an improved state with higher crystallinity. This approach enables defect repair without requiring complete reconstruction of the material.

Inventive Principle:
Principle #34Discarding and recovering

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The method achieves COF materials with high crystallinity, specific surface area, and improved morphological characteristics, such as grain sizes greater than 50 nm and specific surface areas exceeding 1000 m2/g, and effectively repairs defects in existing COF materials, enhancing their performance.

Implementation Method 1

a reversible polycondensation-termination (RPT) method... dissolving a monomer A in solvent 1, adding a control agent AP... dissolving a monomer B in solvent 2, adding a control agent BP... mixing the solution A and the solution B to obtain a mixed solution, and allowing the mixed solution to react

Methodology Applied
Scientific EffectReversible polycondensation: Chemical Bonding

Implementation Method 2

adding a control agent AP, and optionally adding a catalyst CA to obtain a solution A; dissolving a monomer B in solvent 2, adding a control agent BP, and optionally adding a catalyst CB

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 3

dissolving a monomer A in solvent 1... dissolving a monomer B in solvent 2

Methodology Applied
Scientific EffectSolvation: Solvation

Implementation Method 4

after the completion of the reaction, separating obtained precipitate and drying it obtain COF material

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Implementation Method 5

separating obtained precipitate and drying it obtain COF material

Methodology Applied
Scientific EffectEvaporation: Evaporation

Implementation Method 6

a method for repairing defects of COF materials—reversible degradation-recombination method, the method can eliminate defects of existing COF materials

Methodology Applied
Scientific EffectReversible degradation-recombination: Chemical Bonding

Data Source

PatentUS12071503B2Method for preparing and repairing covalent organic framework materials
Publication Date: 2024.08.27 ZHEJIANG UNIV

AI summary

The present invention relates to a method for preparing a covalent organic framework (COF) materials—a reversible polycondensation/termination method, the COF materials prepared by the method have high crystallinity, high specific surface area, regular and controllable morphology. The present invention also relates to a method for repairing defects of COF materials—reversible degradation-recombination, the method can eliminate defects of existing COF materials, thereby increasing the crystallinity and specific surface area of COF materials and improving their morphological characteristics.