Semiconducting two dimensional black phosphorus (2D BP) has recently attracted a lot of interest thanks to its peculiar properties, which render it suitable for applications in materials science.1 In particular, the surface functionalization of 2D BP and the formation of heterostructures is particularly promising for electrical, optoelectronic and photocatalytic applications. In addition, being 2D BP a potential good ligand for metals, its application in the field of catalysis is also possible. Herein, we bring two examples of easy non-covalent functionalization of 2D BP. In a first study, we investigate the chemical-physics and the nature of the interactions involved in the formation of heterostructures of 2D BP with organoboron derivatives of a conjugated fluorescent molecule (pyrene). NMR experiments in suspension and DFT simulations confirm that only non-covalent interactions are involved. The energetic gain in the formation of the heterostructures arises from the interaction of P atoms with both C atoms of the pyrene core and with B atom of the boronic functionality. We demonstrate through Raman spectroscopy an increased stability towards oxidation in air of 2D BP (more than three months), accompanied by a band-gap lowering by around 0.10 eV, while time-resolved fluorescence spectroscopy shows a stabilization effect also of the organic moieties, in the heterostructures. The second study focuses on 2D BP functionalized in situ with Au nanoclusters through a deposition-precipitation solid-liquid heterogeneous reaction. This reaction leads to the desired 2D support/metal intimacy of contact and also the desired Au nano-morphology. Spectroscopic and morphological characterization, supported by DFT calculations, prove the effective functionalization of 2D BP with Au nanoclusters with nanometric size and non-full metallic character, and the total preservation of 2D BP structure and functionality. In particular, XPS analysis on these systems gives experimental evidence of the soft-pairing/coordination of surface P atoms with the Au(I) atoms on the surface of the nanoclusters. The photonic properties of the 2D BP/Au system are investigated through Surface Plasmon Enhanced (SPR) Raman studies. The authors thank the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (Grant Agreement No. 670173) for funding the project PHOSFUN by an ERC Advanced Grant to MP. References [1]M. Peruzzini, R. Bini, M. Bolognesi, M. Caporali, M. Ceppatelli, F. Cicogna, S. Coiai, S. Heun, A. Ienco, I. Iglesias Benito, A. Kumar, G. Manca, E. Passaglia, D. Scelta, M. Serrano-Ruiz, F. Telesio, S. Toffanin, M. Vanni, Eur. J. Inorg. Chem. 2019, 2019, 1476-1494.
Investigation of the modulation of the non-covalent interaction between 2D BP and fluorescent pyrene derivatives endowed with different functional substituents
Salvatore Moschetto;Margherita Bolognesi;Mariachiara Trapani;Federico Prescimone;Claudia Ferroni;Gabriele Manca;Andrea Ienco;Lucia Calucci;Silvia Borsacchi;Maria Caporali;Michele Muccini;Maurizio Peruzzini;Stefano Toffanin
2018
Abstract
Semiconducting two dimensional black phosphorus (2D BP) has recently attracted a lot of interest thanks to its peculiar properties, which render it suitable for applications in materials science.1 In particular, the surface functionalization of 2D BP and the formation of heterostructures is particularly promising for electrical, optoelectronic and photocatalytic applications. In addition, being 2D BP a potential good ligand for metals, its application in the field of catalysis is also possible. Herein, we bring two examples of easy non-covalent functionalization of 2D BP. In a first study, we investigate the chemical-physics and the nature of the interactions involved in the formation of heterostructures of 2D BP with organoboron derivatives of a conjugated fluorescent molecule (pyrene). NMR experiments in suspension and DFT simulations confirm that only non-covalent interactions are involved. The energetic gain in the formation of the heterostructures arises from the interaction of P atoms with both C atoms of the pyrene core and with B atom of the boronic functionality. We demonstrate through Raman spectroscopy an increased stability towards oxidation in air of 2D BP (more than three months), accompanied by a band-gap lowering by around 0.10 eV, while time-resolved fluorescence spectroscopy shows a stabilization effect also of the organic moieties, in the heterostructures. The second study focuses on 2D BP functionalized in situ with Au nanoclusters through a deposition-precipitation solid-liquid heterogeneous reaction. This reaction leads to the desired 2D support/metal intimacy of contact and also the desired Au nano-morphology. Spectroscopic and morphological characterization, supported by DFT calculations, prove the effective functionalization of 2D BP with Au nanoclusters with nanometric size and non-full metallic character, and the total preservation of 2D BP structure and functionality. In particular, XPS analysis on these systems gives experimental evidence of the soft-pairing/coordination of surface P atoms with the Au(I) atoms on the surface of the nanoclusters. The photonic properties of the 2D BP/Au system are investigated through Surface Plasmon Enhanced (SPR) Raman studies. The authors thank the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (Grant Agreement No. 670173) for funding the project PHOSFUN by an ERC Advanced Grant to MP. References [1]M. Peruzzini, R. Bini, M. Bolognesi, M. Caporali, M. Ceppatelli, F. Cicogna, S. Coiai, S. Heun, A. Ienco, I. Iglesias Benito, A. Kumar, G. Manca, E. Passaglia, D. Scelta, M. Serrano-Ruiz, F. Telesio, S. Toffanin, M. Vanni, Eur. J. Inorg. Chem. 2019, 2019, 1476-1494.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
