期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 27, 期 10, 页码 3361-3366出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202003584
关键词
amorphization; Balz-Schiemann product; black phosphorus; red phosphorus; sacrificial catalysts
资金
- European Research Council (ERC) [742145 B-PhosphoChem]
- ERC Starting Grant [2D-PnictoChem 804110]
- European Union [604391]
- Generalitat Valenciana [CIDEGENT/2018/001, iDiFEDER/2018/061]
- FEDER
- Spanish MICINN [PID2019-111742GAI00]
- Deutsche Forschungsgemeinschaft (DFG) [FLAG-ERA AB694/2-1, SFB 953]
- Alexander von Humboldt (AvH) Foundation for a postdoctoral fellowship
- National Research, Development, and Innovation Office of Hungary (NKFIH) [K119442, 2017-1.2.1-NKP-2017-00001]
- Excellence Unit Mara de Maeztu [CEX2019-000919-M]
- Projekt DEAL
In this study, the structural evolution of 2D black phosphorus upon the addition of electrophilic diazonium salts was investigated, revealing the absence of covalent functionalization in both neutral and reductive routes, with an unexpected interface conversion of BP to red phosphorus observed in the latter case. The potential radical mechanism underlying this reaction was explored using various analytical techniques.
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.
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