近日，江南大学朱永法团队报道了揭示激发态偶极矩的作用：控制卟啉光催化剂上非牺牲H₂O₂的产生。这一研究成果发表在2025年10月8日出版的《德国应用化学》杂志上。

在有机光催化剂上同时进行氧还原反应（ORR）和水氧化反应（WOR）生产H₂O₂，理论上实现了100%的原子经济性。然而，人们对这种有机体系中的电荷分离和转移机制仍然知之甚少，特别是基于基态偶极矩（μg）的有机分子设计往往无法预测光催化行为。

研究组合成了一系列羧基修饰的四苯基卟啉超分子光催化剂（TPP-(COOH)_n，其中n = 1~ 4,8），考察了其构效关系。H₂O₂生成活性遵循TPP-(COOH)₂ < TPP-(COOH) < TPP-(COOH)₃ < TPP-(COOH)₈ < TPP-(COOH)₄的顺序，随着激发态偶极矩（μe）而增加，而不是传统认为的μg或-COOH基团的数量。μe受羧基取代引起的O - 2p带中心位移的影响，通过内部电场控制电荷的分离和转移。

此外，激子解离研究表明，低介电TPP-(COOH)_n表现出显著延长的激子寿命。5 ns)，使得μe成为关键的活性决定因素。基于这一发现，研究组设计了一种高μe酞菁超分子光催化剂（H₂Pc(COOH)₈），在420 nm处实现了前所未有的58 mM·h^-1·g^-1，量子效率（QE）为18.7%。该研究建立了μe作为有机光催化剂上H₂O₂生成的预测参数。

附：英文原文

Title: Unveiling the Role of Excited-State Dipole Moment: Governing Non-Sacrificial H2O2 Generation on Porphyrin Photocatalysts

Author: Yaning Zhang, Jiawei Zhang, Shuai Dou, Hengjun Shang, Jing Xu, Yuming Dong, Ying Zhang, Yang Lou, Chengsi Pan, Yongfa Zhu

Issue&Volume: 2025-10-08

Abstract: H2O2 production via the simultaneous oxygen reduction reaction (ORR) and water oxidation reaction (WOR) on organic photocatalysts theoretically achieves 100% atom economy. However, the charge separation and transfer mechanism in such organic systems remains poorly understood, especially as organic molecular designs based on ground-state dipole moments (μg) often fail to predict photocatalytic behavior. Here, we synthesize a series of carboxyl-modified tetraphenylporphyrin supramolecular photocatalysts (TPP-(COOH)n, where n = 1～4, 8) to investigate the structure-activity relationship. The H2O2 generation activity follows the order TPP-(COOH)2 < TPP-(COOH) < TPP-(COOH)3 < TPP-(COOH)8 < TPP-(COOH)4, increasing with the excited-state dipole moment (μe) rather than the traditionally considered μg or number of -COOH groups. The μe, influenced by O 2p-band center shifts from carboxyl substitution, is demonstrated to govern the charge separation and transfer via an internal electric field. Moreover, exciton dissociation studies indicated that low-dielectric TPP-(COOH)n exhibits notably prolonged excitonic lifetimes (ca. 5 ns), making μe the key activity determinant. Based on this insight, we designed a high-μe phthalocyanine supramolecular photocatalyst (H2Pc(COOH)8), achieving an unprecedented H2O2 production rate of 58 mM·h1·g1 and a quantum efficiency (QE) of 18.7% at 420 nm. This study establishes μe as a predictive parameter for H2O2 generation on organic photocatalysts.

DOI: 10.1002/anie.202512844

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202512844