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Approaching efficient H2O2 electrosynthesis on ZnO nanorod via a combined strategy of crystal facet-engineering and
Haoying Cheng1, Yaoxin Li2, Zhanyang Wang2
1State Key Laboratory of Structural Chemistry, Fujian Key Laboratory of Nanomaterials, and CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China; College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian 350007, China; Fujian College, University of Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Abstract:
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.
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