Liang Huagen, Zhao Jingbo, Brouzgou Angeliki, Wang Anhu, Jing Shengyu, Kannan Palanisamy, Chen Fu, Tsiakaras Panagiotis
Jiangsu Key Laboratory of Coal-based Greenhouse Gas Control and Utilization, Carbon Neutrality Institute, China University of Mining and Technology, Xuzhou 221008, China; Laboratory of Alternative Energy Conversion Systems, Department of Mechanical Engineering, School of Engineering, University of Thessaly, Pedion Areos 38334, Greece.
Jiangsu Key Laboratory of Coal-based Greenhouse Gas Control and Utilization, Carbon Neutrality Institute, China University of Mining and Technology, Xuzhou 221008, China.
J Colloid Interface Sci. 2025 Jan;677(Pt A):1120-1133. doi: 10.1016/j.jcis.2024.07.225. Epub 2024 Jul 30.
Designing efficient dual-functional catalysts for photocatalytic oxygen reduction to produce hydrogen peroxide (HO) and photodegradation of dye pollutants is challenging. In this work, we designed and fabricated an S-scheme heterojunction (g-CN/ZnO composite photocatalyst) via one-pot calcination of a mixture of ZIF-8 and melamine in the KCl/LiCl molten salt medium. The KCN/ZnO composite produced 4.72 mM of HO within 90 min under illumination (with AM 1.5 filter), which is almost 1.3 and 7.8 times than that produced over KCN and ZnO, respectively. Simultaneously, the KCN/ZnO also showed excellent photodegradation performance for the dye pollutants (Rhodamine B, RhB), with a removal rate of 92 % within 2 h. The apparent degradation rate constant of RhB over KCN/ZnO was approximately 5-8 times that of KCN and ZnO. In the photocatalytic process, photo-generated holes and superoxide radicals are the main active species. Oxygen (O) was mainly reduced to produce HO via a two-electron (2e) pathway with superoxide radicals as intermediates and the 2e oxygen reduction reaction selectivity of KCN/ZnO was close to 69.82 %. Photo-generated holes are mainly responsible for the degradation of RhB. Compared with pure KCN and ZnO, the enhanced photocatalytic activity of the KCN/ZnO composite is mainly attributed to the following aspects: 1) larger specific surface area and pore volume is beneficial to expose more active sites; 2) stronger light harvesting ability and red-shifted absorption edge bestow the compound a stronger light utilization efficiency; 3) the construction of S-scheme heterostructure between KCN and ZnO improve the photogenerated electron-hole pairs separation ability and bestow photogenerated carriers a higher redox potential.
设计用于光催化氧还原以生产过氧化氢(HO)和光降解染料污染物的高效双功能催化剂具有挑战性。在这项工作中,我们通过在KCl/LiCl熔盐介质中对ZIF-8和三聚氰胺的混合物进行一锅煅烧,设计并制备了一种S型异质结(g-CN/ZnO复合光催化剂)。在光照(使用AM 1.5滤光片)下,KCN/ZnO复合材料在90分钟内产生了4.72 mM的HO,分别是KCN和ZnO产生量的近1.3倍和7.8倍。同时,KCN/ZnO对染料污染物(罗丹明B,RhB)也表现出优异的光降解性能,在2小时内去除率达到92%。RhB在KCN/ZnO上的表观降解速率常数约为KCN和ZnO的5-8倍。在光催化过程中,光生空穴和超氧自由基是主要的活性物种。氧气(O)主要通过以超氧自由基为中间体的双电子(2e)途径还原生成HO,KCN/ZnO的2e氧还原反应选择性接近69.82%。光生空穴主要负责RhB的降解。与纯KCN和ZnO相比,KCN/ZnO复合材料光催化活性增强主要归因于以下几个方面:1)更大的比表面积和孔体积有利于暴露更多的活性位点;2)更强的光捕获能力和红移的吸收边缘赋予该化合物更强的光利用效率;3)KCN和ZnO之间S型异质结构的构建提高了光生电子-空穴对的分离能力,并赋予光生载流子更高的氧化还原电位。