Abstract Chemical‐looping gasification (CLG) offers a promising route for renewable biomass valorization, yet conventional oxygen carrier regeneration with O₂/H₂O is energy‐intensive and often produces low‐quality syngas. Here, we develop an inverse ZrO 2 /Co 3 O 4 oxygen carrier that enables selective biochar oxidation and efficient lattice‐oxygen transfer for improved CLG performance. Under optimized conditions, the inverse CoZr‐75 achieves a gas yield of 21.96 mmol g biomass −1 with an H 2 /CO‐rich syngas and a lower heating value of 9.95 MJ m −3 , outperforming conventional counterparts and enhancing H₂ productivity by 242%. During regeneration, CO predominantly is generated via selective oxidation of residual carbon, indicating suppressed deep oxidation. Structural and operando analyses reveal a uniform Zr–O–Co interfacial architecture with enhanced reducibility and reversible redox cycling (Co 3 O 4 ⇌ CoO ⇌ Co 0 ), accounting for its stability and reactivity. These results demonstrate that inverse interfacial engineering provides an effective strategy for designing high‐performance oxygen carriers and advancing efficient, selective biomass‐to‐syngas conversion.
Gao et al. (2026) studied this question.