期刊
ACS CATALYSIS
卷 12, 期 16, 页码 10004-10017出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c02326
关键词
photocatalysis; surface-interface; surface defects; NO removal; carrier separation
资金
- National Natural Science Foundation of China [21902161, 22076193]
- National Key R&D Program of China [2020YFA0710303]
- Postdoctoral Science Foundation of China [2019T120137, 2018M641484]
- Alexander von Humboldt Foundation
Semiconductor-based photocatalysis is a promising method for air purification by removing nitrogen oxide (NO) pollutants. However, the efficiency of photocatalytic treatment is hampered by sluggish carrier separation, catalyst deactivation, and incomplete oxidation. In this study, various ZnO structures with deliberate surface defect constructions were fabricated to address these issues. The results showed that ZnO rich in oxygen vacancies exhibited significantly enhanced NO removal efficiency and fewer toxic byproducts compared to pristine and vacancy-poor ZnO. Furthermore, the surface defects promoted not only carrier separation but also molecular oxygen activation, resulting in the generation of strong oxidant superoxide radicals and improved efficiency. Density functional theory calculations confirmed the successful adsorption and activation of NO and molecular oxygen on the defective surface, further contributing to the enhanced NO conversions.
Semiconductor-based photocatalysis is an ideal method for air purification by eliminating nitrogen oxide (NO). However, sluggish carrier separation, photocatalysts deactivation and incomplete oxidation are significant bottlenecks for photocatalytic treatment of indoor pollutant NO. Herein, ZnO with assorted structures is fabricated and undergoes further modification for deliberate surface defect constructions. Utilized flux agents during the synthesis provide a more feasible reducing atmosphere, under which spontaneous generations of the surface vacancies become easier, and gradient concentrations are precisely controlled. Photocatalyst characterizations affirm the successful creation of surface defects, which are further evaluated by solar-light-driven NO (ppb level) removal investigations. Results showed that ZnO rich in oxygen vacancies (V-O-rich ZnO) exhibited 5.43 and 1.63 times enhanced NO removal with fewer toxic product NO2 formations than its counterparts pristine and Vo-poor ZnO, respectively. Importantly, with higher V-O on the unusual nonpolar facets, V-O-rich ZnO does not only display enhanced NO conversion, but also shows the unselective NO removal process by producing NO3-. The plausible reaction mechanisms of promoted NO conversions are further investigated based on the surface V-O, well-positioned band structures, and enhanced carrier separations. Results showed that the surface V-O with gradient concentrations are not only promoted carrier separation, but also facilitate molecular oxygen activation, leading to the generations of strong oxidant superoxide radicals (center dot O-2(-)), and contributing to the enhanced improved efficiency. Adsorption of small molecules (O-2, H2O and NO) on the defective surface was further investigated by density functional theory (DFT) calculations, which validated the successful adsorption/activation of NO and O-2, further contributed to the improved NO conversions.
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