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• The property of AMRs biochar has been improved by H 3 PO 4 -modification. • The using of PBC as carrier to load nZVI improved the agglomeration of Fe particles. • PBC and nZVI/PBC enhanced biogas yield by more than 20% in AD of corn straw. • The nZVI/PBC exhibited higher ability in maintaining the stability of AD system. Antibiotic mycelial residues (AMRs), as recyclable hazardous waste, can realize efficient utilization by reasonable treatment. To solve the problems of undeveloped pore structure and low specific surface area existed in AMR biochar, this study first modified biochar by phosphoric acid (H 3 PO 4) to prepare PBC (H 3 PO 4 -modified biochar). Then, PBC was used as carrier to load nano zero-valent iron (nZVI) for preparation of nZVI/PBC. Finally, the biochar materials were used to promote anaerobic digestion (AD) of corn straw. The results showed that H 3 PO 4 -modification can effectively improve the specific surface area, pore structure, and electron donating capacity of AMRs biochar. The using of PBC as carrier to load nZVI attenuated the agglomeration of nZVI particles. Both PBC and nZVI/PBC improved the AD process, with biogas yield enhanced by 29.63% and 29.26%, respectively. The nZVI/PBC exhibited higher ability in maintaining the stability of AD system and promotion of fiber degradation than PBC. [ABSTRACT FROM AUTHOR]