CNR ExploRA

Articolo in rivista, 2023, ENG, 10.1021/acsanm.3c01645

Synthetic Control over the Surface Chemistry of Blue-Emitting Perovskite Nanocrystals for Photocatalysis

Grisorio, Roberto; Dibenedetto, Carlo Nazareno; Matuhina, Anastasia; Grandhi, Gopal Krishnamurthy; Vivo, Paola; Fanizza, Elisabetta; Striccoli, Marinella; Suranna, Gian Paolo

Politecnico di Bari; Università degli studi di Bari Aldo Moro; Consiglio Nazionale delle Ricerche; Tampere University; CNR NANOTEC-Istituto di Nanotecnologia

Lead halide perovskite nanocrystals (NCs) are particularly suitable for light-emitting and photocatalysis applications, where their potential can be maximized by controlling the surface composition of their organic shell. In this study, the preparation of CsPbClBr NCs at room temperature in toluene is described. Three differently structured surfactants are utilized for the synthesis, each with a specific function, namely, the solubilization of the lead precursor (n-HeptNBr), the surface passivation with halide modification (dimethyldioctadecylammonium chloride), and the protection of the surface-active sites (octanoic acid) for photocatalysis. Under these conditions, nearly monodispersed blue-emitting nanocubes are selectively obtained in a one-pot synthesis by combining specific amounts of the perovskite precursors. As supported by thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR) spectroscopy investigations, the organic shell of the obtained NCs is composed of electrostatically bound dimethyldioctadecylammonium ions, granting robustness to the corresponding NCs, and octanoic acid molecules, interacting with the nanoparticle surface through weaker secondary bonds. The obtained NCs exhibit a high photoluminescence quantum yield (PLQY = 72 ± 3%) notwithstanding multiexponential recombination dynamics of the excited state, resulting from the different passivation modes at the NC surface. Moreover, the NCs show a remarkable optical stability after exposure to high temperatures and to water contact due to the high surface density of the multifunctional organic ligands. The introduction of 4-tert-butylphenyl thiol promotes a charge transfer process at the NC/thiol interface formed upon removal of the labile ligands (octanoic acid) at the NC surface. In these conditions, the NCs are prone to the photoinduced conversion of the aromatic thiol into the corresponding disulfide without varying the optical properties of the perovskite photocatalyst upon the substrate conversion. Therefore, the obtained results cast light on the versatility of the surface engineering of lead halide perovskite NCs for efficient blue emission and photocatalysis with improved stability.

ACS applied nano materials 6 (9), pp. 8082–8092