Structural Modulation of TpPa-1 Covalent Organic Framework in Flow Synthesis Guided by Green Chemistry Principles

IF 9 Q2 ENGINEERING, CHEMICAL

ACS Engineering Au Pub Date : 2026-06-17 Epub Date: 2026-04-17 DOI:10.1021/acsengineeringau.5c00114

Yizhuo Xu, Nikita Rog, Catherine Mollart, Ganna Gryn’ova, Abbie Trewin, Cher Hon Lau

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Abstract

Here we present a solvent decision-making pathway for less hazardous and scalable synthesis of TpPa-1 covalent organic framework (COF) underpinned by environmental compatibility (CHEM21 framework), processability (Hansen solubility parameters), and thermodynamic suitability (free energy of solvation). Our analyses suggest that solvents with moderate solvation, such as 1,4-dioxane, propylene carbonate, and diacetin, hinder excessive reaction reversibility and promote crystallite growth. Balancing solvent greenness, compatibility, and thermodynamics, we find that diacetin is optimal for a continuous-flow synthesis. Compared with TpPa-1 COF synthesized in diacetin under batch conditions, the Brunauer–Emmett–Teller surface area of flow-derived TpPa-1 reached 418 m² g^–1, increasing CO₂ uptake by 50% at 298 K. The flow process achieved a 30-fold increase in space-time yield (STY), with excellent reproducibility and an 89% reduction in specific energy consumption. This solvent-thermodynamics-guided approach establishes a physically transparent and sustainable framework for optimizing COF synthesis under continuous-flow conditions.

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绿色化学原理指导下流动合成中TpPa‑1共价有机框架的结构调节。

在这里，我们提出了一种溶剂决策途径，以环境相容性（CHEM21框架）、可加工性（汉森溶解度参数）和热力学适应性（溶剂化自由能）为基础，用于低危害和可扩展的TpPa-1共价有机框架（COF）的合成。我们的分析表明，适度溶剂化的溶剂，如1,4-二恶烷、碳酸丙烯酯和二乙酰胆碱，阻碍了过度的反应可逆性，促进了晶体的生长。平衡溶剂绿度，相容性和热力学，我们发现二乙酰胆碱是最佳的连续流合成。与间歇条件下双乙酰胆碱合成的TpPa-1 COF相比，流动衍生的TpPa-1的brunauer - emmet - teller比表面积达到418 m2 g-1，在298 K时CO2吸收量增加了50%。流动过程的时空产率（STY）提高了30倍，具有出色的再现性，比能耗降低了89%。这种溶剂热力学导向的方法为优化连续流动条件下的COF合成建立了一个物理透明和可持续的框架。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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ACS Engineering Au 化学工程技术-

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期刊介绍：）ACS Engineering Au is an open access journal that reports significant advances in chemical engineering applied chemistry and energy covering fundamentals processes and products. The journal's broad scope includes experimental theoretical mathematical computational chemical and physical research from academic and industrial settings. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Fundamental research in such areas as thermodynamics transport phenomena (flow mixing mass & heat transfer) chemical reaction kinetics and engineering catalysis separations interfacial phenomena and materialsProcess design development and intensification (e.g. process technologies for chemicals and materials synthesis and design methods process intensification multiphase reactors scale-up systems analysis process control data correlation schemes modeling machine learning Artificial Intelligence)Product research and development involving chemical and engineering aspects (e.g. catalysts plastics elastomers fibers adhesives coatings paper membranes lubricants ceramics aerosols fluidic devices intensified process equipment)Energy and fuels (e.g. pre-treatment processing and utilization of renewable energy resources; processing and utilization of fuels; properties and structure or molecular composition of both raw fuels and refined products; fuel cells hydrogen batteries; photochemical fuel and energy production; decarbonization; electrification; microwave; cavitation)Measurement techniques computational models and data on thermo-physical thermodynamic and transport properties of materials and phase equilibrium behaviorNew methods models and tools (e.g. real-time data analytics multi-scale models physics informed machine learning models machine learning enhanced physics-based models soft sensors high-performance computing)