Vapor‐Assisted Mechanochemical Synthesis of Enzyme and Hydrogen‐Bonded Organic Framework Biocomposites

Abstract Hydrogen‐bonded Organic Frameworks (HOFs) emerged as a matrix for preparing highly active and stable enzyme biocomposites. Conventional biocompatible synthetic procedures in solutions, however, suffer from issues related to competition with the solvent molecules and inhomogeneous loading of the enzyme. Here, it is demonstrated that a combination of mechanochemistry and accelerated aging can be used to synthesize Hydrogen‐bonded Organic Framework (HOF) biocomposites with improved enzyme loading, activity, and protection. Advanced characterization techniques, including in situ Wide‐Angle X‐ray Scattering and Transmission Electron Microscopy, provide insights into these biocomposites' formation mechanisms and structural properties. A comparative analysis with biocomposites prepared via conventional solution synthesis reveals that vapor‐induced growth enhances protein loading, ensures a more homogeneous enzyme distribution, and improves protective properties due to distinct growth mechanisms and kinetics. This simple and green synthetic approach offers a viable alternative to innovative HOF‐based composite materials.