分子偶极子和空间位阻工程调节 PTCDA/PTA 的电子结构以实现高效光催化析氢和抗生素降解,Advanced Functional Materials

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分子偶极子和空间位阻工程调节 PTCDA/PTA 的电子结构以实现高效光催化析氢和抗生素降解
Advanced Functional Materials ( IF 18.5 ) Pub Date : 2023-12-22 , DOI: 10.1002/adfm.202314894
Weili Yu ₁ , Ningjie Fang ₁ , Ruobing Wang ₁ , Zhaobing Liu ₁ , Yinghao Chu ₁ , Chenxi Huang ₁

Affiliation

电荷分离不足和激子传输缓慢严重限制了基于苝平面的有机光催化剂的利用。在此，通过π - π相互作用使PTA在PTCDA表面原位结晶，首次成功制备了新型PTCDA/PTA（苝-3,4,9,10-四甲酸二酐/苝四甲酸）。负载8%PTCDA的PTCDA/PTA表现出最佳的光催化性能。光催化H ₂析出速率达到45.06 mmol g ^-1 h ^-1，分别是纯PTA和PTCDA的1.93倍和4506.00倍。同时，它还表现出优异的抗生素光降解活性，其中盐酸四环素（TC-HCl）和氧氟沙星（OFL）在30 min内去除效率均超过90%。通过调节苝平面的结构，可以精确调节空间位阻和内部偶极矩。这些导致堆积模式的改变，促进π - π堆积程度和强内电场的形成，同时提高了光催化活性。激发态密度泛函理论 (DFT) 计算揭示了电子-空穴对的重新分布，其遵循 II 型机制。所提出的光催化机制通过液相色谱-质谱法（LC-MS）确定。此外，还评估了降解产物的毒性。这项工作为水修复和能源生产的高性能和多功能光催化剂的设计提供了有用的策略。

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Molecule Dipole and Steric Hindrance Engineering to Modulate Electronic Structure of PTCDA/PTA for Highly Efficient Photocatalytic Hydrogen Evolution and Antibiotics Degradation

Insufficient charge separation and slow exciton transport severely limit the utilization of perylene-plane-based organic photocatalysts. Herein, a novel PTCDA/PTA (perylene-3,4,9,10-tetracarboxylic dianhydride/perylenetetracarboxylic acid) is successfully prepared for the first time by the in situ crystallization of PTA on the surface of PTCDA through π–π interaction. The PTCDA/PTA loading with 8%PTCDA showed the optimum photocatalytic performance. The photocatalytic H₂ evolution rate reached 45.06 mmol g⁻¹ h⁻¹, which is 1.93-fold and 4506.00-fold higher than that of pure PTA and PTCDA. Meanwhile, it also exhibited excellent antibiotics photodegradation activities, in which both the removal efficiency of tetracycline hydrochloride (TC-HCl) and ofloxacin (OFL) are more over 90% within 30 min. By modulating the structures of perylene plane, the steric hindrance and internal dipole moments can be precisely tuned. These lead to the change of stacking mode, promoting the degree of π–π stacking and formation of strong internal electric field, while improved the photocatalytic activity. Excited state density functional theory (DFT) calculations unveil the redistribution of electron-hole pairs, which obeys a type II mechanism. The proposed photocatalytic mechanism is determined by liquid chromatography-mass spectrometry (LC-MS). Besides, the toxicities of the degradation products are also evaluated. The work provides useful strategy for the design of high-performance and multifunctional photocatalysts toward water remediation and energy production.

更新日期：2023-12-22

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