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Published on: September 20, 2012
Interfacial Oxophilicity Engineering Modulates Surface Hydroxyl Chemistry for Enhanced Electrocatalytic
Jun Wang1, Wenrui Jin1, Junyue Yin1
1State Key Laboratory of Organic-Inorganic Composites, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, People's Republic of China.
Abstract:
Electrocatalytic nitrogen oxidation offers an ambient route to nitrate, but the competition between oxygenated intermediates and N2 adsorption limits efficient nitrate formation. Here, we construct a La2O3-Co3O4 heterojunction to regulate the interfacial oxygen/hydroxyl environment through differential oxophilicity. At 2.01 V vs. the reversible hydrogen electrode (RHE), La2O3-Co3O4 delivers a nitrate yield rate of 47.38 µg h-1 mgcat -1 with Faradaic efficiency(NO3 -) of 18.77%, outperforming the individual oxides and the corresponding physical-mixture control. Potential-dependent O 1sX-ray photoelectron spectroscopy (XPS), quasi-in situ Co 2p XPS, in situ vibrational spectroscopy, and density functional theory (DFT) reveal a distinct interfacial oxygen/hydroxyl response and preferential thermodynamic stabilization of La-associated hydroxyl configurations under anodic conditions. These results link the enhanced nitrate formation to interfacial hydroxyl regulation and identify oxophilicity engineering as a useful strategy for electrocatalytic nitrogen oxidation.
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