Wang Yilin, Zhao Zhenlong, Sun Rui, Bian Ji, Zhang Ziqing, Jing Liqiang
Key Laboratory of Functional Inorganic Materials Chemistry (Ministry of Education), School of Chemistry and Materials Science, International Joint Research Center for Catalytic Technology, Heilongjiang University, Harbin 150080, P. R. China.
Key Lab of Groundwater Resources and Environment of Ministry of Education, Key Lab of Water Resources and Aquatic Environment of Jilin Province, College of New Energy and Environment, Jilin University, Changchun 130012, P. R. China.
Nanoscale. 2022 Jun 9;14(22):8041-8049. doi: 10.1039/d2nr01753a.
Developing efficient Z-scheme heterojunctions with wide visible-light responsive perylene diimide (PDI) is highly desired for CO conversion, while the effective charge transfer and separation are crucial. Herein, TiO-modulated tetra(4-carboxyphenyl)porphyrin/perylene diimide (T-TP/PDI) organic nano-heterojunctions have been fabricated for CO reduction, in which TP and PDI are first assembled π-π interactions between their similar 2D conjugate structures, and then the TiO nanoparticles ( 10 nm) are anchored as an energy platform through the carboxyl groups on TP. The optimal one exhibits a ∼10-fold enhancement in photocatalytic activity compared with the pristine PDI. Based on the time-resolved surface photovoltage responses, electron paramagnetic resonance signals, diffuse reflectance infrared Fourier transform spectra and the amount evaluation of HO as the water-oxidation intermediate, it is suggested that the exceptional photoactivity be ascribed to the accelerated charge transfer and separation resulting from the constructed Z-scheme nano-heterojunctions with intimate interfacial interactions and the introduced energy platform TiO oriented towards largely inhibiting the type-II charge transfer pathway. This work diversifies the strategies for constructing efficient organic Z-scheme heterojunctions, and provides insight into interface correlation among components.
开发具有宽可见光响应性苝二酰亚胺（PDI）的高效Z型异质结对于CO转化非常有必要，而有效的电荷转移和分离至关重要。在此，制备了TiO调制的四（4-羧基苯基）卟啉/苝二酰亚胺（T-TP/PDI）有机纳米异质结用于CO还原，其中TP和PDI首先通过其相似二维共轭结构之间的π-π相互作用组装，然后10nm的TiO纳米颗粒通过TP上的羧基作为能量平台锚定。与原始PDI相比，最佳的一个光催化活性提高了约10倍。基于时间分辨表面光电压响应、电子顺磁共振信号、漫反射红外傅里叶变换光谱以及作为水氧化中间体的HO的量评估，表明优异的光活性归因于由具有紧密界面相互作用的构建的Z型纳米异质结和引入的能量平台TiO导致的加速电荷转移和分离，这在很大程度上抑制了II型电荷转移途径。这项工作使构建高效有机Z型异质结的策略多样化，并深入了解了各组分之间的界面相关性。
