In Situ Observation of Hot Carrier Transfer at Plasmonic Au/Metal‐Organic Frameworks (MOFs) Interfaces

• Published in: Chemistry : a European journal 2022-09, Vol.28 (50), p.e202200919-n/a
• Main Authors: Wang, Shuobo, Wu, Lei, Li, Jikun, Deng, Chaoyuan, Xue, Jing, Tang, Daojian, Ji, Hongwei, Chen, Chuncheng, Zhang, Yuchao, Zhao, Jincai
• Format: Article
• Language: English
• Subjects: Benzyl alcohol; Catalytic activity; Charge transfer; Chemistry; Chromium; Electrochemistry; Electron paramagnetic resonance; Electron spin resonance; EPR spectroscopy; Gold; Heterostructures; Hot electrons; Interfaces; Metal-organic frameworks; Oxidation; Photocatalysis; Photocatalysts; Plasmonics; Spectroscopy; surface plasmon resonance
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202200919

Constructing heterostructures have been demonstrated as an ideal strategy for boosting charge separation on plasmonic photocatalysts, but the detailed interface charge transfer mechanism remains elusive. Herein, that authors fabricate plasmonic Au and metal‐organic frameworks (MOFs, NH2−MIL‐125 and MIL‐125 used in this work) heterostructures and explore the interface charge transfer mechanism by in situ electron paramagnetic resonance (EPR) spectroscopy and electrochemical measurements. The plasmon‐excited hot electrons on Au can transfer across the Au/MOF interface and be captured by the coordinatively unsaturated sites of secondary building units (Ti8O8(OH)4 cluster) of the MOF structure, and the plasmon‐excited hot holes on Au tend to transfer to and be trapped at the functionalized organic ligand (1,4‐benzenedicarboxylate−NH2). The spatially separated hot electrons and holes exhibit boosted the photocatalytic activity for chromium (VI) reduction and selective benzyl alcohol oxidation. This work illustrates the advantage of the versatile functionalization of MOF structures enabling molecular‐level manipulation of interface charge transfer on plasmonic photocatalysts. MOF structures possess the advantage of molecular‐level tunability via functionalization of both secondary building units (SBUs) and organic ligands, which manipulate interface charge transfer and separation on plasmonic photocatalysts. It is observed that hot electrons on Au can be captured by the coordinatively unsaturated sites of SBUs in MOF structures, while hot holes on Au tend to transfer to and be trapped at the functionalized organic ligand.