Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts
Authors
Mitrović, Aleksandra D.
Wild, Stefan
Lloret, Vicent
Fickert, Michael
Assebban, Mhamed

Márkus, Bence Gábor
Simon, Ferenc
Hauke, Frank

Abellán, Gonzalo

Hirsch, Andreas
Article (Published version)
Metadata
Show full item recordAbstract
Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, 31P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well a...s electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.
Source:
European Chemical Societies, 2021, 27, 3361-3366Publisher:
- Wiley-VCH Verlag
Funding / projects:
- European Research Council (ERC Advanced Grant 742145 B-PhosphoChem to A.H.)
- European Research Council (ERC Starting Grant 2D-PnictoChem 804110 to G.A.)
- European Union Seventh Framework Programme (agreement No. 604391) Graphene Flagship
- Generalitat Valenciana (CIDEGENT/2018/001and iDiFEDER/2018/061 co-financed by FEDER)
- Spanish MICINN (PID2019-111742GA-I00 and Excellence Unit María de Maeztu (CEX2019-000919-M))
- Deutsche Forschungsgemeinschaft (DFG, FLAG-ERA AB694/2-1)
- Innovation Office of Hungary (NKFIH) Grant Nos. K119442 and 2017-1.2.1-NKP-2017-00001
DOI: 10.1002/chem.202003584
ISSN: 0947-6539
WoS: 000609283600001
Scopus: 2-s2.0-85100218473
Collections
Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Mitrović, Aleksandra D. AU - Wild, Stefan AU - Lloret, Vicent AU - Fickert, Michael AU - Assebban, Mhamed AU - Márkus, Bence Gábor AU - Simon, Ferenc AU - Hauke, Frank AU - Abellán, Gonzalo AU - Hirsch, Andreas PY - 2021 UR - https://cherry.chem.bg.ac.rs/handle/123456789/4501 AB - Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, 31P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction. PB - Wiley-VCH Verlag T2 - European Chemical Societies T1 - Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts VL - 27 SP - 3361 EP - 3366 DO - 10.1002/chem.202003584 ER -
@article{ author = "Mitrović, Aleksandra D. and Wild, Stefan and Lloret, Vicent and Fickert, Michael and Assebban, Mhamed and Márkus, Bence Gábor and Simon, Ferenc and Hauke, Frank and Abellán, Gonzalo and Hirsch, Andreas", year = "2021", abstract = "Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, 31P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.", publisher = "Wiley-VCH Verlag", journal = "European Chemical Societies", title = "Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts", volume = "27", pages = "3361-3366", doi = "10.1002/chem.202003584" }
Mitrović, A. D., Wild, S., Lloret, V., Fickert, M., Assebban, M., Márkus, B. G., Simon, F., Hauke, F., Abellán, G.,& Hirsch, A.. (2021). Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts. in European Chemical Societies Wiley-VCH Verlag., 27, 3361-3366. https://doi.org/10.1002/chem.202003584
Mitrović AD, Wild S, Lloret V, Fickert M, Assebban M, Márkus BG, Simon F, Hauke F, Abellán G, Hirsch A. Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts. in European Chemical Societies. 2021;27:3361-3366. doi:10.1002/chem.202003584 .
Mitrović, Aleksandra D., Wild, Stefan, Lloret, Vicent, Fickert, Michael, Assebban, Mhamed, Márkus, Bence Gábor, Simon, Ferenc, Hauke, Frank, Abellán, Gonzalo, Hirsch, Andreas, "Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts" in European Chemical Societies, 27 (2021):3361-3366, https://doi.org/10.1002/chem.202003584 . .