Transient Kinetic Directing: A Removable Metal‑Ion‑Mediated Pathway to Structurally Refined MOFs for High‑Performance Hydrogen Storage

ABSTRACT The synthesis of high‐capacity hydrogen storage MOF adsorbents at ambient temperature demands strong sorption sites, yet achieving this goal without sacrificing framework stability remains a fundamental challenge. Here, we propose a novel “transient kinetic directing” strategy that bypasses this trade‑off by structurally elevating the MOF framework to unlock its intrinsic hydrogen sorption potential, without external metal ion incorporation. Using fully removable Ni (II) ions to modulate a kinetically delayed crystallization reaction, we precisely control MOF‐808 crystallization through a transient Ni‑involved gel, which can effectively suppress crystal defects, thereby yielding intrinsic MOF‐808 crystals (named MOF‐808‐int) with accessible open metal sites (OMSs). Notably, MOF‐808‐int achieves both volumetric H 2 storage capacity of 14.2 g L − 1 at 298 K and 100 bar and deliverable volumetric H 2 storage capacity of 52.5 g L −1 (77 K, 100 bar → 160 K, 5 bar) among the top records for all MOF‐based hydrogen storage materials. Grand canonical Monte Carlo (GCMC) simulation results suggest that accessible OMSs account for initial hydrogen sorption at low pressures, followed by micropore filling at high pressures. This work thus establishes “transient kinetic directing” as a paradigm for unlocking the latent potential of stable MOF adsorbents through kinetic pathway control.