Issue 24, 2023

Molecular-level degradation pathways of black phosphorus revealed by mass spectrometry fingerprinting

Abstract

Understanding the molecular mechanism of material transformation raises a great challenge for material characterization techniques. As a promising 2D material, the application potential of black phosphorus (BP) is seriously compromised by its environmental instability. However, until now, the degradation mechanism of BP remains ambiguous. Here we show that by using laser desorption ionization mass spectrometry (LDI-MS) fingerprinting it is possible to unravel the degradation pathways of BP at the molecular level without any chemical labeling. We found that BP-based materials can generate intrinsic phosphorus cluster (Pn+ or Pn) fingerprint peaks in LDI-MS in both positive-ion and negative-ion modes, which allows the degradation processes of BP materials to be monitored by providing abundant mass information about intermediates and products with the sample-to-sample RSDs in the range of 1.0–28.4%. The stability of BP or cerium-encapsulated BP was monitored under ambient and increased temperature conditions for up to 20 or 180 days. Notably, by using LDI-MS fingerprinting, we reveal an unreported BP degradation pathway, i.e., nitrogen (N2)-addition oxidation, in addition to the direct oxidation pathway. Our results not only enable an in-depth understanding of the chemical instability of BP, but also, importantly, demonstrate a new powerful platform for monitoring and characterization of material transformation.

Graphical abstract: Molecular-level degradation pathways of black phosphorus revealed by mass spectrometry fingerprinting

Supplementary files

Article information

Article type
Edge Article
Submitted
15 nov 2022
Accepted
24 maj 2023
First published
25 maj 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 6669-6678

Molecular-level degradation pathways of black phosphorus revealed by mass spectrometry fingerprinting

X. Huang, Y. Li, G. Qu, X. Yu, D. Cao, Q. Liu and G. Jiang, Chem. Sci., 2023, 14, 6669 DOI: 10.1039/D2SC06297F

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