Anderson‐Type Polyoxometalates Intercalated Cobalt–Copper Layered Double Hydroxides Heterostructures With Plum Blossom‐Like for Efficient Electroreduction of Nitrate to Ammonia

ABSTRACT Electrochemical nitrate reduction (NO 3 RR) attracts increasing attention due to its potential to promote environmental sustainability and restore the global nitrogen balance. However, the development of an electrocatalyst with excellent activity and stability remains a significant challenge. Herein, we report a heterostructured electrocatalyst {ZnMo 6 }@CuCo LDH composed of Anderson‐type polyoxometalate clusters ({ZnMo 6 }) anchored onto copper‐cobalt layered double hydroxide, which effectively addresses these limitations through a synergistic effect. The electrolyzer composed of {ZnMo 6 }@CuCo LDH achieves a Faradaic efficiency of 96.6% and an NH 3 selectivity of 91.7% at industrial‐scale current densities (>150 mA cm −2 ), with an overpotential of only −0.02 V vs. RHE. The catalyst shows almost no activity degradation over 100 h. Theoretical calculations indicate that the outstanding catalytic performance originates from the synergistic interaction between {ZnMo 6 } clusters and mixed‐valence Cu/Co sites. Incorporation of {ZnMo 6 } clusters facilitates multi‐electron transfer and * NO to * NHO conversion, lowers the free energy barrier for H 2 O dissociation, and consequently boosts * H production and NH 3 formation. Zn‐Mo‐CuCo interfacial coupling effectively promotes the electrocatalytic NO 3 RR process and inhibits the hydrogen evolution side reaction. This intercalation‐functionalized composite design, which integrates molecular clusters with 2D substrates, provides an effective strategy for developing high‐performance electrocatalysts for sustainable nitrate pollution remediation and ammonia synthesis.