Approaching efficient H2O2 electrosynthesis on ZnO nanorod via a combined strategy of crystal facet-engineering and surface amorphization.

Two-electron oxygen reduction reaction (2e- ORR) offers a sustainable pathway for hydrogen peroxide production, yet its efficiency relies on cost-effective electrocatalysts with tailored active sites. Herein, a hybrid ZnO@ZnO2-x nanorod with tunable oxygen vacancies (Ov) in the outer-skin peroxidate thin film was developed as a neutral electrocatalyst for hydrogen peroxide production through cation-terminated facet-engineering and surface amorphous peroxidation. The optimized ZnO@ZnO2-x (named am-ZNR-180-24) electrocatalyst with a moderate oxygen vacancy concentration (∼17.9 at.% from XPS) on {0001} polar-facets demonstrates a nearly 100 % selectivity for H2O2 generation, achieving a high production rate of 11.63 mol·gcat.-1·h-1, with ultrahigh and stable Faradaic efficiency (>90 %) in a flow-cell system, which ranks among the highest levels of reported metal compounds electrocatalysts. Characterizations and theoretical results unveil that Ov on the polar (002) plane modulate the Zn 3d-band center, optimizing the adsorption of *OOH intermediates to favor 2e- ORR.