Non‐Covalent Host–Guest Extraction of Methanol Enables Enhanced Syngas‐to‐Methanol Conversion Over Hybrid Oxide–Porous Framework Catalysis

ABSTRACT Product formation is commonly regarded as the endpoint of heterogeneous catalysis, yet the subsequent fate of products near active surfaces critically affects catalytic turnover. For syngas‐to‐methanol conversion over Cu/Zn/Al (CZA) catalysts, product retention and re‐adsorption represent an underappreciated limitation governing both activity and selectivity. Methanol generated at metal–oxide interfaces tends to remain near active sites, where interactions with surface hydroxyls trigger secondary reactions such as the water–gas shift. By physically mixing commercial CZA with hydrogen‐bond‐rich porous frameworks, we introduce a non‐covalent host–guest extraction pathway that captures methanol from the interfacial region and facilitates its release into the gas phase. This extraction shifts the local adsorption–desorption equilibrium, suppresses methanol re‐adsorption, and boosts methanol space–time yield by 1.12–1.43 times relative to pristine CZA, while retaining > 92.3% selectivity. In situ spectroscopy, transient kinetics, and simulations confirm the porous framework acts as a molecular sink, regulating methanol residence time and transport without direct catalytic participation. This effect is general across distinct metal–organic and covalent organic frameworks, establishing non‐covalent extraction as a transferable strategy. This work demonstrates that non‐covalent control of product desorption and transport serves as a complementary design principle for heterogeneous catalysis beyond conventional active‐site engineering.