Catalysis

Engineering

Mechanochemistry

Materials science

Molecule

Chemical engineering

Ball mill

Matrix (chemical analysis)

Nanotechnology

Organic chemistry

Reticular connective tissue

Composite material

Rational design

Mechanosynthesis

Medicine

Chemistry

Hydrogen bond

Pathology

Angewandte Chemie International Edition

Rational synthesis of hydrogen-bonded organic frameworks (HOFs) with predicted structure has been a long-term challenge. Herein, by using the efficient, simple, low-cost, and scalable mechanosynthesis, we demonstrate that reticular chemistry is applicable to HOF assemblies based on building blocks with different geometry, connectivity, and functionality. The obtained crystalline HOFs show uniform nano-sized morphology, which is challenging or unachievable for conventional solution-based methods. Furthermore, the one-pot mechanosynthesis generated a series of Pd@HOF composites with noticeably different CO oxidation activities. In situ DRIFTS studies indicate that the most efficient composite, counterintuitively, shows the weakest CO affinity to Pd sites while the strongest CO affinity to HOF matrix, revealing the vital role of porous matrix to the catalytic performance. This work paves a new avenue for rational synthesis of HOF and HOF-based composites for broad application potential.

Reticular Synthesis of Hydrogen‐Bonded Organic Frameworks and Their Derivatives via Mechanochemistry