Kirkendall Effect‐Driven Interface Engineering Facilitates Water Dissociation for Dual‐Site H2O2 Electrosynthesis Simultaneously at the Anode and Cathode

The direct integration of renewable energy into H2O2 electrosynthesis systems offers a promising strategy to minimize energy losses and costs. Due to the intermittency of renewable energy, the dual-site catalysts must efficiently enable both the two-electron oxygen reduction reaction (2e- ORR) and water oxidation reaction (2e- WOR). The Kirkendall effect was employed to engineer interfaces and construct a NiZnOx─C catalyst with exposed (100) facets. The hetero-cluster NiOx induces oxygen vacancies and built-in electric fields, which facilitate water activation and subsequent formation of hydrogen and hydroxyl radicals, thereby enabling a single catalyst to rapidly electrosynthesize H2O2 at both the anode and cathode. Notably, 2e- ORR on the cathode enabled rapid synthesis of high-concentration H2O2 (33987 mg L-1, 33.18 mol gcatalyst -1 h-1). NiZnOx─C achieves stable 2e- ORR/WOR coupling in a continuous-flow reactor, operating reliably for 4 h under simulated alternating current (AC) and peaking at a total Faradaic efficiency of 150.9% under amperage-level direct currents. This work provides insights into interface engineering based on the Kirkendall effect, demonstrating the feasibility of directly integrating intermittent renewable energy into H2O2 electrosynthesis systems.