Bidentate Lewis Base Ligand-Mediated Surface Stabilization and Modulation of the Electronic Structure of CsPbBr3 Perovskite Nanocrystals

Hassan, Md. Samim; Basera, Pooja; Khan, Bilawal; Portniagin, Arsenii S.; Vighnesh, Kunnathodi; Wu, Ye; Rusanov, Daniil A.; Babak, Maria; He, Jr-Hau; Bajdich, Michal; Rogach, Andrey L.

doi:10.1021/jacs.4c13724

Bidentate Lewis Base Ligand-Mediated Surface Stabilization and Modulation of the Electronic Structure of CsPbBr₃ Perovskite Nanocrystals

Journal Article · Thu Dec 19 23:00:00 EST 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c13724· OSTI ID:2574848

Hassan, Md. Samim ^[1]; Basera, Pooja ^[2]; ^[1]; Portniagin, Arsenii S. ^[1]; ^[1]; Wu, Ye ^[1]; Rusanov, Daniil A. ^[1]; ^[1]; ^[1]; ^[3]; ^[1]

City University of Hong Kong (China)
Stanford University, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

The desorption of conventional ligands from the surface of halide perovskite nanocrystals (NCs) often causes their structural instability and the deterioration of the optoelectronic properties. To address this challenge, we present an approach of using a bidentate Lewis base ligand, namely, 1,4-bis(diphenylphosphino)butane (DBPP), for the synthesis of CsPbBr₃ NCs. The phosphine group of DBPP has a strong interaction with PbBr₂ precursor, forming a highly crystalline intermediate complex during the reaction. In the presence of oleic acid, the uncoordinated phosphine group of DBPP is converted into the phosphonium cation, which strongly binds with the surface bromide of the formed CsPbBr₃ NCs through hydrogen bonding. Density functional theory calculations suggest that DBPP can strongly bind to the undercoordinated lead and surface bromide ions of CsPbBr₃ NCs through its unprotonated and protonated phosphine groups, respectively. The robust binding of DBPP with the surface of perovskite NCs helps to preserve their structural integrity under various environmental stresses. Moreover, the electron density and energy levels are regulated in DBPP-capped CsPbBr₃ NCs via the efficient transfer of electrons from the ligands to the NCs, resulting in their improved photocatalytic CO₂ reduction performance. Furthermore, our study highlights the potential of using bidentate ligands to stabilize the surface of perovskite NCs and modulate their optical and electronic properties.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Energy Research Scientific Computing Center (NERSC)

Grant/Contract Number:: AC02-05CH11231; SC0021266

OSTI ID:: 2574848

Alternate ID(s):: OSTI ID: 2575242

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 1 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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