Chen Xinfeng, Peng Chengdong, Dan Wenyan, Yu Long, Wu Yinan, Fei Honghan
School of Chemical Science and Engineering, Shanghai Key Laboratory of Chemical Assessment and Sustainability, Tongji University, Shanghai, 200092, PR China.
College of Environmental Science and Engineering, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai, 200092, PR China.
Nat Commun. 2022 Aug 6;13(1):4592. doi: 10.1038/s41467-022-32367-0.
Organolead halide hybrids have many promising attributes for photocatalysis, e.g. tunable bandgaps and excellent carrier transport, but their instability constraints render them vulnerable to polar molecules and limit their photocatalysis in moisture. Herein, we report the construction of metal-organic frameworks based on [PbX] (X = Br-/I-) chains as secondary building units and 2-amino-terephthalate as organic linkers, and extend their applications in photocatalytic CO reduction with water vapor as the reductant. Hall effect measurement and ultrafast transient absorption spectroscopy demonstrate the bromo/iodo-bridged frameworks have substantially enhanced photocarrier transport, which results in photocatalytic performances superior to conventional metal-oxo metal-organic frameworks. Moreover, in contrast to lead perovskites, the [PbX]-based frameworks have accessible porosity and high moisture stability for gas-phase photocatalytic reaction between CO and HO. This work significantly advances the excellent carrier transport of lead perovskites into the field of metal-organic frameworks.
有机铅卤化物杂化物在光催化方面具有许多有前景的特性，例如可调节的带隙和出色的载流子传输，但它们的不稳定性限制使其易受极性分子影响，并限制了它们在潮湿环境中的光催化作用。在此，我们报道了基于[PbX]（X = Br-/I-）链作为二级构建单元和2-氨基对苯二甲酸作为有机连接体构建金属有机框架，并将其应用扩展到以水蒸气作为还原剂的光催化CO还原反应中。霍尔效应测量和超快瞬态吸收光谱表明，溴/碘桥联框架的光载流子传输得到了显著增强，这导致其光催化性能优于传统的金属氧基金属有机框架。此外，与铅基钙钛矿相比，基于[PbX]的框架具有可及的孔隙率和高湿度稳定性，适用于CO与H₂O之间的气相光催化反应。这项工作显著地将铅基钙钛矿出色的载流子传输特性引入到金属有机框架领域。
