Liu Huiyu, Du Chenyu, Sheng Jianping, Zhong Fengyi, He Ye, Zhang Fengying, Zhou Ying, Sun Yanjuan, Dong Fan
School of Resources and Environment, University of Electronic Science and Technology of China, Chengdu 611731, China.
Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 611731, China.
ACS Nano. 2024 Sep 3;18(35):24558-24568. doi: 10.1021/acsnano.4c09197. Epub 2024 Aug 19.
Perovskite nanocrystals (PCNs) exhibit a significant quantum confinement effect that enhances multiexciton generation, making them promising for photocatalytic CO reduction. However, their conversion efficiency is hindered by poor exciton dissociation. To address this, we synthesized ferrocene-methanol-functionalized CsPbBr (CPB/FcMeOH) using a ligand engineering approach. By manipulating the electronic coupling between ligands and the PCN surface, facilitated by the increased dipole moment from hydrogen bonding in FcMeOH molecules, we effectively controlled exciton dissociation and interfacial charge transfer. Under 5 h of irradiation, the CO yield of CPB/FcMeOH reached 772.79 μmol g, 4.95 times higher than pristine CPB. This high activity is due to the formation of hydrogen-bonded FcMeOH clusters on the CPB surface. The nonpolar disruption and strong dipole moment of FcMeOH molecules enhance electronic coupling between the FcMeOH ligands and the CPB surface, reducing the surface barrier energy. Consequently, exciton dissociation and interfacial charge transfer are promoted, efficiently utilizing multiple excitons in quantum-confined domains. Transient absorption spectroscopy confirms that CPB/FcMeOH exhibits optimized exciton behavior with fast internal relaxation, trapping, and a short recombination time, allowing photogenerated charges to more rapidly participate in CO reduction.
钙钛矿纳米晶体（PCNs）表现出显著的量子限制效应，这种效应增强了多激子的产生，使其在光催化CO还原方面具有潜力。然而，激子解离效率低下阻碍了它们的转化效率。为了解决这个问题，我们采用配体工程方法合成了二茂铁 - 甲醇功能化的CsPbBr（CPB/FcMeOH）。通过操纵配体与PCN表面之间的电子耦合，由于FcMeOH分子中氢键增加了偶极矩，我们有效地控制了激子解离和界面电荷转移。在5小时的光照下，CPB/FcMeOH的CO产量达到772.79 μmol g，比原始CPB高4.95倍。这种高活性归因于CPB表面形成了氢键连接的FcMeOH簇。FcMeOH分子的非极性破坏和强偶极矩增强了FcMeOH配体与CPB表面之间的电子耦合，降低了表面势垒能。因此，促进了激子解离和界面电荷转移，有效地利用了量子限制域中的多个激子。瞬态吸收光谱证实，CPB/FcMeOH表现出优化的激子行为，具有快速的内部弛豫、俘获和短复合时间，使光生电荷能够更迅速地参与CO还原。
