Improved Hydrophobicity in Zr‐MOFs for Capture of Volatile Organic Compounds in Biomedical Applications

ABSTRACT Breath analysis reveals a wealth of information through the presence of hundreds of volatile organic compounds (VOCs) produced by metabolic processes. Particular combinations of VOCs can serve as chemical signatures for disease diagnosis. However, the inherent humidity in exhaled breath poses significant challenges for effective VOC capture using adsorbent materials. In this study, we present a groundbreaking approach that combines advanced modeling methods with experimental validation to enhance VOC recovery via post‐synthetic modification of a well‐studied metal‐organic framework, MOF‐808. Through the incorporation of fluorinated functional groups, we effectively modified the pore environment to exhibit hydrophobic properties, thereby enhancing its capacity for the selective capture of VOCs. The best performing derivative, MOF‐808‐F5, outperforms the parent MOF‐808, achieving recovery rates of 92% for propanal, 67% for octane, and 79% for toluene at 95% relative humidity. Density functional theory revealed that the most significant enhancements in binding enthalpy occur at the weakest adsorption sites of the parent MOF‐808. The strategy described herein not only enhances VOC selectivity but also dramatically increases the overall performance of the MOF, underscoring the power of integrating modeling and experimental validation in the development of advanced materials for breath analysis.