SGM 8

Phosphorene, a new two dimensional platform for advanced materials

2D nanomaterials are very promising in nanodevice applications due to their surprising properties such as high electric mobility, outstanding structural properties, and large specific surface area. Recently, phosphorene, the all-P counterpart of graphene, has been prepared starting from black phosphorus (BP). Small amounts of single and few layers sheets of the new material have been obtained by either micromechanical cleavage (Scotch tape method) or liquid exfoliation.

We have performed a detailed study of the influence of water in the exfoliation of black phosphorus in dimethylsulfoxide, by examining the role played by the amount of water. Three different ranges of molar ratio between black phosphorus and water were considered. Atomic force microscopy, scanning electron microscopy, and transmission electron microscopy gave information on the morphology of black phosphorus nanosheets and their lateral dimension and thickness. X-ray powder diffraction proved the crystalline nature of the samples and also the chemical composition of the material in each condition tested. Comparing the data, an evident and dramatic influence of the concentration of water on the quality of the BP atomic layers is observed and highlights the best working conditions to be adopted in the exfoliation process in order to get good quality phosphorene flakes.

Fig5
Fig 1: Left: AFM image obtained from drop-cast BP flakes of a sample having P/H2O molar ratio equal to 2, scale bar = 600 nm. Right: height profile map.

In a second step, nickel nanoparticles were dispersed on the surface of exfoliated black phosphorus (see Fig. 2) and the resulting nanohybrid Ni/2D bP showed an improved stability with respect to pristine 2D bP when kept under ambient conditions in the dark. Ni/2D bP was applied as a catalyst in the semihydrogenation of phenylacetylene and exhibited high conversion and selectivity towards styrene. These features were preserved after recycling tests revealing the high stability of the nanohybrid.


Fig 2: HAADF-STEM of Ni/2D bP with the inset showing atomic resolution for 2D BP.

Publications:

  1. Manuel Serrano-Ruiz, Maria Caporali, Andrea Ienco, Vincenzo Piazza, Stefan Heun, and Maurizio Peruzzini: The Role of Water in the Preparation and Stabilization of High-Quality Phosphorene Flakes, arXiv:1511.04330 [cond-mat.mes-hall].
  2. Manuel Serrano-Ruiz, Maria Caporali, Andrea Ienco, Vincenzo Piazza, Stefan Heun, and Maurizio Peruzzini: The Role of Water in the Preparation and Stabilization of High-Quality Phosphorene Flakes, Adv. Mater. Interfaces 2016, 3, 1500441.
  3. M. Caporali, M. Serrano-Ruiz, F. Telesio, S. Heun, G. Nicotra, C. Spinella, and M. Peruzzini: Decoration of exfoliated black phosphorus with nickel nanoparticles and its applications in catalysis, arXiv:1609.05010 [cond-mat.mes-hall].
  4. M. Caporali, M. Serrano-Ruiz, F. Telesio, S. Heun, G. Nicotra, C. Spinella, and M. Peruzzini: Decoration of exfoliated black phosphorus with nickel nanoparticles and its applications in catalysis, Chem. Commun. 53 (2017) 10946 – 10949.
  5. Matteo Vanni, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Martina Banchelli, Paolo Matteini, Antonio Massilimiliano Mio, Giuseppe Nicotra, Corrado Spinella, Stefano Caporali, Andrea Giaccherini, Francesco d’Acapito, Maria Caporali, and Maurizio Peruzzini: Black Phosphorus/Palladium Nanohybrid: Unraveling the Nature of P-Pd Interaction and Application in Selective Hydrogenation, arXiv:1903.02363 [physics.chem-ph].
  6. M. Vanni, M. Serrano-Ruiz, F. Telesio, S. Heun, M. Banchelli, P. Matteini, A. M. Mio, G. Nicotra, C. Spinella, S. Caporali, A. Giaccherini, F. d’Acapito, M. Caporali, and M. Peruzzini: Black Phosphorus/Palladium nanohybrid: unraveling the nature of Pd-P interaction and application in selective hydrogenation, Chem. Mater. 31 (2019) 5075 – 5080.
  7. M. Peruzzini, R. Bini, M. Bolgnesi, M. Caporali, M. Ceppatelli, F. Cicogna, S. Coiai, S. Heun, A. Ienco, I. I. Benito, A. Kumar, G. Manca, E. Passaglia, D. Scelta, M. Serrano-Ruiz, F. Telesio, S. Toffanin, and M. Vanni: A perspective on recent advances in phosphorene functionalization and its applications in devices, arXiv:1903.11904 [cond-mat.mes-hall].
  8. M. Peruzzini, R. Bini, M. Bolgnesi, M. Caporali, M. Ceppatelli, F. Cicogna, S. Coiai, S. Heun, A. Ienco, I. I. Benito, A. Kumar, G. Manca, E. Passaglia, D. Scelta, M. Serrano-Ruiz, F. Telesio, S. Toffanin, and M. Vanni: A perspective on recent advances in phosphorene functionalization and its applications in devices, Eur. J. Inorg. Chem. (2019) 1476 – 1494.
  9. Maria Caporali, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Alberto Verdini, Albano Cossaro, Matteo Dalmiglio, Andrea Goldoni, and Maurizio Peruzzini: Enhanced ambient stability of exfoliated black phosphorus by passivation with nickel nanoparticles, arXiv:1908.00237 [physics.chem-ph].
  10. Maria Caporali, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Alberto Verdini, Albano Cossaro, Matteo Dalmiglio, Andrea Goldoni, and Maurizio Peruzzini: Enhanced ambient stability of exfoliated black phosphorus by passivation with nickel nanoparticles, Nanotechnology 31 (2020) 275708.
  11. M.Vanni, M.Serrano-Ruiz, F.Telesio, S.Heun, M.Banchelli, P.Matteini, A.M.Mio, G.Nicotra, C.Spinella, S. Caporali, A.Giaccherini, F. d’Acapito, M.Caporali, and M.Peruzzini: Black Phosphorus/Palladium Nanohybrid: Unraveling the Nature of P–Pd Interaction and Application in Selective Hydrogenation, IT CRG AT ESRF Activity Report 2019.

Presented at:

  1. Manuel Serrano-Ruiz, Maria Caporali, Andrea Ienco, Stefan Heun, Maurizio Peruzzini: Preparation of exfoliated black phosphorus and its gas adsorption properties, Workshop “Metals, Water, and Sun” 2015, Almeria, Spain, 21 – 22 May 2015. [Abstract] [Poster]
  2. Manuel Serrano-Ruiz, Maria Caporali, Andrea Ienco, Vincenzo Piazza, Stefan Heun, Maurizio Peruzzini: Water influence in the preparation and stabilization of high quality phosphorene flakes, ISOC 2015, Camerino, Italy, 5 – 9 September 2015. [Abstract] [Poster]
  3. Maria Caporali, Manuel Serrano-Ruiz, Andrea Ienco, Stefan Heun, and Maurizio Peruzzini: Phosphorene: the P-analogue of graphene, XXXIV Congresso Interregionale delle Sezioni Toscana, Umbria, Marche e Abruzzo della Società Chimica Italiana – TUMA 34, Perugia, Italy, 23 – 25 September 2015 (invited). [Abstract] [Talk]
  4. Andrea Ienco, Manuel Serrano-Ruiz, Maria Caporali, Stefan Heun, Maurizio Peruzzini: Phosphorene, a new two dimensional platform for advanced materials, FISMAT 2015, Palermo, Italy, September 28 – October 2, 2015 (oral). [Abstract] [Talk]
  5. Salvatore Interlandi, Maria Caporali, Manuel Serrano Ruiz, Andrea Ienco, Stefan Heun, Maurizio Peruzzini: Few-layer black phosphorus functionalized with metal nanoparticles: full characterization and catalytic activity on hydrogenation reactions, 13th European Workshop on Phosphorus Chemistry, EWPC-13, Berlin, Germany, 7 – 9 March 2016 (oral). [Abstract] [Talk]
  6. Maria Caporali, Manuel Serrano-Ruiz, Salvatore Interlandi, Andrea Ienco, Stefan Heun, Maurizio Peruzzini: Few-layer black phosphorus as novel support for metal nanoparticles, E-MRS 2016 Spring Meeting, Lille, France, May 2 to 6, 2016 (oral). [Abstract] [Talk]
  7. Maria Caporali, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Giuseppe Nicotra, Corrado Spinella, Stefano Caporali, Maurizio Peruzzini: Noncovalent functionalization of few-layer black phosphorus with metal nanoparticles and its application in catalysis, Nano Innovation 2016, Rome, Italy, 20 – 23 September 2016 (oral). [Abstract] [Talk]
  8. S. Heun: Novel 2D materials to study interactions between light and matter, Workshop “Fundamental Metrology”, Torino, Italy, 2 December 2016 (oral). [Talk]
  9. Maria Caporali, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Giuseppe Nicotra, Corrado Spinella, and Maurizio Peruzzini: Decorating few-layer black phosphorous with Nickel nanoparticles and application of the nanohybrid in catalysis, Ceramics for Energy (CEn 2017), Faenza, Italy, 7 – 9 June 2017 (oral). [Abstract] [Talk]
  10. Maria Caporali: Phosphorene: a new member of the 2D family with multifaceted applications in materials science, 11th International School on Hybrid and Organic Photovoltaics (ISOPHOS) and 4th School on Advanced Materials for Photonics, Electronics and Biolectronics (MAPHEBIO), Arbatax (Sardinia – Italy), 3 – 7 September 2017 (invited). [Talk]
  11. Maria Caporali, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Giuseppe Nicotra, Corrado Spinella, Maurizio Peruzzini: Functionalization of exfoliated black phosphorus with metal nanoparticles and application of the nanohybrid in catalysis, DSCTM Conferenza di Dipartimento 2017, Alghero, Italy, 19 – 20 October 2017 (poster). [Abstract] [Poster]
  12. Matteo Vanni, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Maria Caporali, Maurizio Peruzzini: 2D black phosphorus decorated with palladium nanoparticles. Synthesis, characterization and catalytic applications, 15th European Workshop in Phosphorus Chemistry (EWPC-15), Uppsala University, Sweden, 14-16 March 2018 (oral). [Abstract] [Talk]
  13. Maria Caporali, Manuel Serrano-Ruiz, Matteo Vanni, Francesca Telesio, Stefan Heun, Giuseppe Nicotra, Corrado Spinella, Maurizio Peruzzini: When 2D black phosphorus meets transition metal nanoparticles: synthesis, characterization and application, XXVIII International Conference on Organometallic Chemistry, Florence, Italy, 15-20 July 2018 (oral). [Abstract] [Talk]
  14. Matteo Vanni, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Maria Caporali, Maurizio Peruzzini: Palladium Nanoparticles Immobilized on Exfoliated Black Phosphorus, XXVIII International Conference on Organometallic Chemistry, Florence, Italy, 15-20 July 2018 (poster). [Abstract] [Poster]
  15. Maria Caporali, Matteo Vanni, Manuel Serrano Ruiz, Francesca Telesio, Stefan Heun, Martina Banchelli, Paolo Matteini, Alberto Verdini, Maurizio Peruzzini: Surface functionalization of exfoliated black phosphorus with transition metal nanoparticles: enhancement of ambient stability and selectivity in chemical processes, Materials.it 2018, Bologna, Italy, 22-26 October 2018 (invited). [Abstract] [Talk]
  16. Matteo Vanni, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Maria Caporali, Maurizio Peruzzini: Immobilization of Palladium Nanoparticles on Exfiliated Black Phosphorus, PhD Day, Università degli Studi di Siena, Italy, 14 November 2018 (Best Poster Prize). [Poster]
  17. Matteo Vanni, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Martina Banchelli, Paolo Matteini, Antonio Massimiliano Mio, Giuseppe Nicotra, Corrado Spinella, Stefano Caporali, Andrea Giaccherini, Francesco d’Acapito, Maria Caporali, Maurizio Peruzzini: Palladium/black phosphorus nanohybrid: what surface techniques tell us about the Pd-P interaction, 16th European Workshop on Phosphorus Chemistry, School of Chemistry, University of Bristol, Bristol, UK, Wednesday 24 April – Friday 26 April 2019. [Abstract] [Poster]
  18. Matteo Vanni, Manuel Serrano-Ruiz, Andrea Giaccherini, Francesco d’Acapito, Antonio Massimiliano Mio, Giuseppe Nicotra, Francesca Telesio, Stefan Heun, Martina Banchelli, Paolo Matteini, Maria Caporali, Maurizio Peruzzini: Palladium/Black Phosphorus Nanohybrid: Unraveling the Nature of Pd-P Interaction and Application in Catalysis, E-MRS Spring Meeting 2019, Nice, France, 27 – 31 May 2019 (oral). [Abstract] [Talk]
  19. Maria Caporali, Matteo Vanni, Manuel Serrano-Ruiz, Francesca Telesio, Stefan Heun, Martina Banchelli, Paolo Matteini, Antonio Massilimiliano Mio, Giuseppe Nicotra, Corrado Spinella, Stefano Caporali, Andrea Giaccherini, Francesco d’Acapito, Maurizio Peruzzini: Phosphorene: a rising star in the 2D world, Chemistry of graphene and applications in catalysis and polymer composites, Milan, Italy, 13 June 2019 (oral). [Abstract] [Talk]