TiO2/Bi12O17Cl2异质结的光催化失活机制与再生

Photocatalytic deactivation mechanism and regeneration for TiO2/Bi12O17Cl2 heterojunctions

  • 摘要: 光催化剂稳定性是当前制约半导体光催化技术工业化广泛应用的关键技术瓶颈。光催化失活与活性回复是决定光催化剂稳定性的重要因素。研究者虽然在提高半导体光催化剂活性和选择性方面取得了突破性进展,但是对光催化剂的失活与再生少有关注。本文针对具有可见光响应的高活性TiO2/Bi12O17Cl2异质结在污水净化领域的应用,研究了固-液多相光催化体系中TiO2/Bi12O17Cl2异质结的光催化失活机理,进而提出使其活性回复的再生策略。结果表明,TiO2/Bi12O17Cl2异质结初始失活是因为催化剂表面吸附了不完全降解中间相,这阻碍了光生载流子的有效转移与分离。随着光催化时间延长,TiO2/Bi12O17Cl2异质结界面解离,促使TiO2纳米球团聚,Bi12O17Cl2纳米片取向再结晶,光催化剂表面的O空位浓度减少,进而使活性物质 \bullet \mathrmO_2^- 产率降低,光生 \mathrme^- 、 \mathrmh^+ 的有效分离率降低,这是导致TiO2/Bi12O17Cl2异质结持续快速失活的主要原因。在此基础上,以 \mathrmC\mathrml^- 为媒介,采用溶剂热合成法修复失活样品的微观结构,获得再生TiO2/BixOyClz异质结。与失活样品对比,再生TiO2/BixOyClz异质结的光催化活性回复率达到100%。

     

    Abstract: The stability of photocatalysts is currently a crucial technical bottleneck that restricts its widespread industrial application. Photocatalytic deactivation and activity recovery are the essential indicators of photocatalytic stability. Researchers have made remarkable progress in improving photocatalytic activity and selectivity,however, little attention has been paid on the deactivation and regeneration of photocatalysts. Herein, we focus on the TiO2/Bi12O17Cl2 heterojunction with excellent visible-light response photocatalytic activity, aiming to purify wastewater in a solid-liquid multiphase photocatalytic system. The deactivation mechanism of TiO2/Bi12O17Cl2 heterojunction was investigated, and an effective regeneration strategy was proposed to restore its activity subsequently. The initial deactivation of TiO2/Bi12O17Cl2 heterojunction occurs due to the surface adsorption of intermediate phase resulting from incomplete degradation, which hinders the transfer and separation of photo-generated charge carriers. With the extension of irradiation time, the interface of TiO2/Bi12O17Cl2 heterojunction dissociates, leading to the agglomeration of TiO2 nanospheres and the preferential recrystallization of Bi12O17Cl2 nanosheets. As a result, the concentration of oxygen vacancies on the photocatalyst surface decreases. This reduction lowers the yield rate of \bullet \mathrmO_2^- , and diminishes the separation efficiency of photogenerated \mathrme^- and \mathrmh^+ pairs. These are the primary reasons for the persistantand rapid deactivation of TiO2/Bi12O17Cl2 heterojunction. Based on the results, \mathrmC\mathrml^- was employed as a medium to repair the microstructure of deactivated samples using solvothermal method. The regenerated TiO2/BixOyClz heterojunction achieved a 100% recovery rate of photocatalytic activity compared to the deactivated samples.

     

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