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Heterostructures with a rich phase boundary are attractive for surface-mediated microwave absorption (MA) materials. However, understanding the MA mechanisms behind the heterogeneous interface remains a challenge. Herein, a phosphine (PH3) vapor-assisted phase and structure engineering strategy was proposed to construct three-dimensional (3D) porous Ni12P5/Ni2P heterostructures as microwave absorbers and explore the role of the heterointerface in MA performance. The results indicated that the heterogeneous interface between Ni12P5 and N