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  Bimetal-organic complex self-assembly engineered dual-functional NiP/PNC catalysts.
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  Electronegativity-driven Ni–L–Zn motifs controllably generated atomic-scale defects.
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  Atomic P simultaneously modulates NiP active centers and P, N-co-doped carbon layer.
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  NiP/PNC catalyst obtained 90.56 % sorbitol yield at 200 °C and excellent stability.
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  NiP-catalyzed H2 heterolysis coupled with PNC-mediated H2O dissociation drives cascade efficiency.

The catalytic valorization of cellulose into sorbitol offers a sustainable pathway for biomass resource utilization, yet its efficiency remains constrained by suboptimal synergy between hydrolysis and hydrogenation processes. Herein, an innovative strategy was proposed for constructing a phosphorus/nitrogen co-doped carbon layer supported nickel phosphide catalyst (NiP/PNC) via coordination-driven self-assembly. The engineered P/N co-doped carbon layer creates an electron-rich microenvironment, significantly enhancing H+ generation through efficient H2O adsorption and polarization. Meanwhile, frustrated Lewis pairs (FPLs) formed at the NiP-OH interface drive heterolytic H2 dissociation, yielding highly reactive Hδ+/Hδ− species that synergistically promote cellulose hydrolysis and hydrogenation. Under optimized conditions (200 °C, 5 h, 4 MPa H2), the NiP/PNC catalyst achieved a remarkable sorbitol yield exceeding 90 % in water and demonstrated satisfactory cyclic stability. Experimental characterizations and DFT calculations reveal that the bifunctional active sites coordinate a cascade reaction pathway: the electron-deficient P/N-doped carbon facilitates H2O activation, while FLPs-mediated H2 heterolysis substantially reduces the energy barrier for hydrogen dissociation. This work pioneers a catalysis modulation strategy through rational electronic and structural modulation, providing fundamental insights into the design of multifunctional catalysts for sustainable biomass conversion.