Harnessing Natural Wood Architecture: A Self‐Supporting, Hierarchically Porous <scp>NiFe</scp> @Carbon Capacitive Anode Enhances Electricity Generation and Storage in Microbial Fuel Cells

We report a mild “Zn(NO 3 ) 2 interlayer‐expansion” strategy that converts micron‐thick wood cell walls into porous nanosheets, yielding a porous carbon (PC) that preserves the native low‐tortuosity channel architecture of wood. Electrodeposition of Ni–Fe layered double hydroxide onto PC produced a self‐supporting capacitive anode (NiFe@PC). The resulting hierarchical pore network, together with high specific surface area (1111.94 m 2 g −1 ), markedly accelerated ion and mass transfer rate (charge transfer resistance decreased by 87.54%) and produced a high areal capacitance of 154.91 mF cm −2 . When employed as microbial fuel cell anode, NiFe@PC achieved an accumulated total charge of 0.64 C cm −2 and a maximum power density of 3.67 W m −2 , significantly exceeding conventional carbon cloth anode (0.17 C cm −2 and 1.99 W m −2 ). The low‐tortuosity channels of PC expanded available space for microbial growth. Total microbial adhesion was increased by 4.1‐fold and thereby directly enhanced the secretion of electron mediators. Ni–Fe sites on PC selectively enriched Geobacter (87.40%), and the Ni 2+ /Ni 3+ and Fe 2+ /Fe 3+ redox couples facilitated extracellular electron transfer and storage. These findings highlight the unique potential of natural wood architecture for constructing efficient, self‐supporting capacitive anodes and motivate the application of structure‐guided PC materials in energy conversion and storage applications.