Dual Dynamics Engineering in COF@MOF Enabled by Laser‐Embedded Metallic Clusters for Efficient Photocatalytic Hydrogenation

Abstract Photocatalytic hydrogenation can convert solar and biomass resources into value‐added chemicals but is hindered by sluggish CO reduction and inadequate photogenerated‐carrier dynamics. Here, bulk embedding of laser‐derived metal clusters into covalent organic framework@metalorganic framework (COF@MOF) hybrids is proposed and validated to overcome these challenges, a process in which the generated active hydrogen species enable near 100% selective hydrogenation of the C─O bond. In situ laser embedding enables spatial control of clusters within the COF bulk and COF@MOF interfaces, promoting CO over CC reduction. Bulk‐embedded Pt clusters serve as sites on preformed MOF to nucleate COF growth, forming physical and carrier transfer bridges at the heterointerface via optimized band alignment. By virtue of the dual dynamics improvement, present work achieves an unprecedented yield of 100% tetrahydrofurfuryl alcohol, which is so far the highest value among all furfural hydrogenation catalysts. Further control over the loading of Pt clusters leads to hydrogen production rates up to 125.48 mmol g −1 h −1 , solidifying its status as the most active Pt‐based photocatalytic system reported to date. This dual‐dynamics strategy is general and easily adaptable to diverse metallic clusters and heterostructures, offering a versatile route to boost photocatalytic hydrogenation.