清华大学朱永法团队报道了超分子光催化剂中，一步双电子氧还原非对称质子化驱动的高效H₂O₂光合作用。相关研究成果发表在2024年11月27日出版的《德国应用化学》。

光催化过氧化氢（H₂O₂）生产已成为传统蒽醌工艺的一种有吸引力的替代品。然而，其性能往往受到氧还原反应（ORR）的低选择性和缓慢动力学的阻碍。

该文报道了一种基于蒽唑啉的超分子光催化剂SA-SADF-H⁺，其具有不对称的质子化结构，用于水和空气中H₂O₂的光合作用。非对称质子化的引入破坏了SADF的初始镜像对称性，显著增强了分子偶极，促进了有效的电荷分离和电子转移。

此外，这种改性增加了SA-SADF-H⁺的亲水性，使水和溶解氧能够与催化位点相互作用。改变的电子密度分布为Yeager型O₂吸附创造了许多双活性位点，通过直接的一步双电子途径促进了对H₂O₂的有效ORR。

值得注意的是，SA-SADF-H⁺以4667μmol L^-1 h^-1的速率实现了出色的光催化H₂O₂生产，太阳能到化学转化率（SCC）达到1.35%，超过了大多数有机光催化系统。此外，SA-SADF-H⁺具有显著的光催化抗菌活性，在60分钟内对金黄色葡萄球菌达到100%的抗菌效率。

附：英文原文

Title: Unsymmetric Protonation Driven Highly Efficient H2O2 Photosynthesis in Supramolecular Photocatalysts via One-Step Two-Electron Oxygen Reduction

Author: Wenting Li, Bing Han, Yuhan Liu, Jingyi Xu, Huarui He, Gege Wang, Junshan Li, Yaxin Zhai, Xiaolin Zhu, Yongfa Zhu

Issue&Volume: 2024-11-27

Abstract: Photocatalytic hydrogen peroxide (H2O2) production has emerged as an attractive alternative to the traditional anthraquinone process. However, its performance is often hindered by low selectivity and sluggish kinetics of oxygen reduction reaction (ORR). Herein, we report an anthrazoline-based supramolecular photocatalyst, SA-SADF-H+, featuring an unsymmetric protonation structure for H2O2 photosynthesis from water and air. The introduction of unsymmetric protonation disrupts the initial mirror symmetry of SADF, significantly enhancing the molecular dipole and facilitating efficient charge separation and electron transfer. Additionally, this modification increases the hydrophilicity of SA-SADF-H+, enabling the interaction of water and dissolved oxygen with the catalytic sites. The altered electron density distribution creates numerous dual active sites for Yeager-type O2 adsorption, facilitating an efficient ORR towards H2O2 via a direct one-step two-electron pathway. Notably, SA-SADF-H+ achieves an outstanding photocatalytic H2O2 production at a rate of 4667 μmol L-1 h-1, with a remarkable solar-to-chemical conversion (SCC) of 1.35%, surpassing most organic photocatalytic systems. Furthermore, SA-SADF-H+ demonstrates remarkable photocatalytic antibacterial activity, achieving 100% antibacterial efficiency against Staphylococcus aureus within 60 min.

DOI: 10.1002/anie.202421356

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202421356