Vapor-Assisted Catalysis Enables Precise Construction of MOF-Derived Hierarchical Carbon Nanoarrays for...

The synthesis of MOF-derived carbons with high surface area and conductivity is challenged by a fundamental trade-off between architectural preservation and catalytic graphitization. Here, we introduce a spatially decoupled, vapor-assisted pyrolysis strategy where a Co-MOF precursor array is physically separated from a vapor-generating Zn-MOF auxiliary. During pyrolysis, a remote Zn vapor flux simultaneously preserves the precursor's nanosheet morphology by suppressing Co nanoparticle aggregation and catalytically grows dense carbon nanotube (CNT) arrays. This process yields an integrated 0D-1D-2D hierarchical carbon architecture with high surface area and graphitization. As a self-supporting supercapacitor electrode, the optimized material delivers a specific capacitance of 360 F g^-1, excellent rate capability (53% retention at 50 A g^-1), and robust cycling stability. Mechanistic studies and density functional theory calculations confirm the pivotal role of Zn vapor in modulating Co catalysis for morphology control and reveal a synergy between heteroatoms and cobalt that optimizes K⁺ storage kinetics. This remote-regulation strategy establishes a generalizable platform for designing hierarchical carbon materials for advanced energy storage.