福州大学王心晨研究团队报道了可见光催化中B-N路易斯对对官能化共轭聚合物激子效应的调控。相关研究成果于2024年10月28日发表于国际一流学术期刊《德国应用化学》。

强激子效应在有机共轭聚合物半导体中很常见，严重阻碍了用于进行光催化的自由电荷载流子的产生。因此，探索调节聚合物中激子解离的新途径对促进光催化具有深远意义。

研究人员开发了一系列B-N路易斯对官能化共轭聚合物，通过调节电荷转移途径来最小化激子效应。理论研究表明，引入B-N-Lewis对可以显著增加电荷转移距离（D指数）和电子转移量，降低库仑吸引能（EC），这有助于打破激子和电荷载流子共存的平衡。

进一步的实验结果表明，在光激发下，单线态激子有效地解离成更多的自由电荷载流子，参与表面反应。优化的聚合物PyPBM在可见光照射下，光催化氢气和过氧化氢生产性能呈指数级增长。

附：英文原文

Title: Regulation of Exciton Effects in Functionalized Conjugated Polymers by B-N Lewis Pairs for Visible-Light Photocatalysis

Author: Chenglong Ru, Xiaoyu Nie, Zhi-An Lan, Zhiming Pan, Wandong Xing, Sibo Wang, Jimmy C. Yu, Yidong Hou, Xinchen Wang

Issue&Volume: 2024-10-28

Abstract: Strong excitonic effects are common in organic conjugated polymer semiconductors, severely hindering the generation of free charge carriers for conducting photocatalysis. Therefore, exploring new channels to modulate exciton dissociation in polymers is far-reaching in facilitating photocatalysis. A series of B-N Lewis pair functionalized conjugated polymers have been developed to minimize exciton effects by modulating charge transfer pathways. Theoretical studies have shown that introducing B-N Lewis pairs can dramatically increase the distance of charge transfer (D index) and the amount of electron transfer and reduce the Coulomb attraction energy (EC), which contributes to breaking the equilibrium of the coexistence of excitons and charge carriers. Further experimental results show that the singlet excitons are efficiently dissociated into more free-charge carriers under photoexcitation to participate in surface reactions. The optimized polymer PyPBM shows an exponential increase in photocatalytic hydrogen and hydrogen peroxide production performance by visible light illumination.

DOI: 10.1002/anie.202417712

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202417712