Boosting exciton dissociation and charge transfer in CsPbBr3 QDs via ferrocene derivative ligation for CO2 photoreduction

• 成果类型: Article
• 署名作者: Du, Chenyu; Sheng, Jianping; Zhong, Fengyi; He, Ye; Liu, Huiyu; Sun, Yanjuan; Dong, Fan
• 署名单位: University of Electronic Science & Technology of China; University of Electronic Science & Technology of China
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-13728
• DOI: 10.1073/pnas.2315956121
• 发表日期: 2024-02-27
• 关键词: ultrafast electron-transfer; dot-organic complexes; cdse quantum dots; perovskite nanocrystals; binding; reduction; DYNAMICS; carriers; cspbx3; br

摘要

Photo- catalytic CO2 reduction with perovskite quantum dots (QDs) shows potential for solar energy storage, but it encounters challenges due to the intricate multi- electron photoreduction processes and thermodynamic and kinetic obstacles associated with them. This study aimed to improve photo- catalytic performance by addressing surface barriers and utilizing multiple- exciton generation in perovskite QDs. A facile surface engineering method was employed, involving the grafting of ferrocene carboxylic acid (FCA) onto CsPbBr3 (CPB) QDs, to overcome limitations arising from restricted multiple- exciton dissociation and inefficient charge transfer dynamics. Kelvin Probe Force Microscopy and XPS spectral confirmed successfully creating an FCA- modulated microelectric field through the Cs active site, thus facilitating electron transfer, disrupting surface barrier energy, and promoting multi- exciton dissociations. Transient absorption spectroscopy showed enhanced charge transfer and reduced energybarriers, resulting in an impressive CO2-to-CO conversion rate of 132.8 mu mol g -1 h -1 with 96.5% selectivity. The CPB-FCA catalyst exhibited four- cycle reusability and 72 h of long- term stability, marking a significant nine- fold improvement compared to pristine CPB (14.4 mu mol g -1 h-1). These results provide insights into the influential role of FCA in regulating intramolecular charge transfer, enhancing multi- exciton dissociation, and improving CO2 photoreduction on CPB QDs. Furthermore, these findings offer valuable knowledge for controlling quantum- confined exciton dissociation to enhance CO2 photocatalysis.