Al‐Induced Local Coordination Engineering of Ni: Steering the Two‐Electron Oxygen Reduction Process

Abstract Synthesis of hydrogen peroxide (H 2 O 2 ) via two‐electron oxygen reduction (2e⁻ ORR) is a promising alternative to the traditional anthraquinone process. However, the adsorption strength of catalyst active centers toward the * OOH intermediate directly restricts the activity of the 2e⁻ ORR. In this study, a coordination engineering strategy is innovatively proposed. High selectivity and stability in H 2 O 2 synthesis are achieved by tuning Ni's coordination environment and intermediate adsorption, and the structure‐activity mechanism is systematically revealed. Synchrotron radiation and density functional theory showed Al introduction altered the coordination number of Ni, modified the hybridization of p‐d orbitals, and accurately regulate the adsorption of * OOH, establishing a volcanic correlation among the coordination number, orbital characteristics, and catalytic performance. The H 2 O 2 selectivity of NiAl‐LDH 0.66:0.33 catalyst reaches 94.23 ± 0.78% at 0.4 V versus RHE, and there is no obvious attenuation after 20 000 cycles and 96.30% average Faradaic efficiency in a 120‐hour test. Moreover, the catalyst exhibits excellent H 2 O 2 synthesis and in situ Rhodamine B degradation in the solid electrolyte system. The coordination engineering strategy and the revealed structure‐performance mechanism in this study offer crucial theoretical support and practical solutions for developing green H 2 O 2 synthesis technology.