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To recover valuable products from biomass, bifunctional catalysts (N-Fe/BC) capable of microwave absorption and oriented production of phenolics were prepared by a one-pot method involving the microwave-induced K2FeO4. Its catalytic performances were evaluated, and the catalytic mechanism was explored using a model compound and DFT calculations. The cycle performance and deactivation mechanism were investigated. N-Fe/BC possessed a large S BET value (265.21 m2 g–1), good pore distribution, and abundant Fe and N species, resulting in good dielectric and catalytic properties. After catalysis, the heating rates reached 63.78–107.84 °C min–1, and the selectivity and yield of phenol-enriched bio-oil improved significantly, reaching maximum values of 80.28% and 38.09 wt % at 550 °C with 20 wt % N-Fe/BC, respectively. Model compound experiments and DFT calculations showed that N-Fe/BC directionally generated phenolics by changing the reaction path and forming “hot spots” that stimulated the catalytic reforming of oxygen-containing compounds. The catalytic performance decreased slightly after five cycles, due to active site loss, carbon deposition, and pore collapse.

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