Vapor‐Assisted Catalysis Enables Precise Construction of MOF‐Derived Hierarchical Carbon Nanoarrays for High‐Performance Supercapacitors

A remote‐control strategy for catalyst design is unveiled for advanced carbon materials. During pyrolysis, zinc vapor from a physically separate source guides cobalt catalysts to construct a hierarchical carbon nanoarray. This approach prevents structural collapse while directing the dense growth of carbon nanotubes, yielding a material with exceptional performance for supercapacitors. ABSTRACT 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. A remote-control strategy for catalyst design is unveiled for advanced carbon materials. During pyrolysis, zinc vapor from a physically separate source guides cobalt catalysts to construct a hierarchical carbon nanoarray. This approach prevents structural collapse while directing the dense growth of carbon nanotubes, yielding a material with exceptional performance for supercapacitors. ABSTRACT 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. Advanced Science, EarlyView.