College of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Eastern Hualan Avenue, Xinxiang 453003, China.
College of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Eastern Hualan Avenue, Xinxiang 453003, China.
J Hazard Mater. 2017 Oct 5;339:43-53. doi: 10.1016/j.jhazmat.2017.06.011. Epub 2017 Jun 8.
Photocatalytic degradation by semiconductors is an ideal way to solve the environmental problem. Here, the porous Mn doped g-CN photocatalyst was synthesized by the calcination-refluxing method. The as-prepared g-CN exhibits the high activity of photocatalytic degradation under visible light irradiation ( > 400nm) in the mixed system of Cr(VI) and organic pollutants. Especially, the photocatalytic activity of Cr(VI) reduction was increased from 9.5% to 76.5%, while that of Rhodamine B(RhB) degradation was enhanced from 15.3% to 88.9% after 60min irradiation. The porous Mn doped g-CN still keeps the high degradation efficiency of mixed pollutants in the 7th running. Based on the computational modeling, the Mn doping and carboxyl modification affect the atomic arrangement and molecular orbital distribution of the g-CN semiconductor, leading to the enhancement of photo-induced carrier separation. Additionally, the active oxygen species and intermediates in the photoreaction process were discovered by ESR measurement and UV-vis test. The RhB degradation in synergistic photocatalysis not only inhibits the reverse reaction of Cr(VI) reduction, but also validly supply the photogenerated electrons by the photosensitization effect. This work may be useful for rationally designing photocatalysts and providing illuminating insights into the photocatalytic mechanism.
半导体的光催化降解是解决环境问题的理想方法。在这里,通过煅烧回流法合成了多孔 Mn 掺杂 g-CN 光催化剂。所制备的 g-CN 在 Cr(VI)和有机污染物的混合体系中在可见光照射(>400nm)下表现出高的光催化降解活性。特别是,在 60min 照射后,Cr(VI)还原的光催化活性从 9.5%提高到 76.5%,而 Rhodamine B(RhB)降解的光催化活性从 15.3%提高到 88.9%。多孔 Mn 掺杂 g-CN 在第 7 次运行中仍然保持混合污染物的高降解效率。基于计算建模,Mn 掺杂和羧基改性影响 g-CN 半导体的原子排列和分子轨道分布,导致光致载流子分离增强。此外,通过 ESR 测量和 UV-vis 测试发现了光反应过程中的活性氧物种和中间体。协同光催化中 RhB 的降解不仅抑制了 Cr(VI)还原的逆反应,而且还通过敏化作用有效地提供了光生电子。这项工作可能有助于合理设计光催化剂,并为光催化机制提供启示。