Surface Heterogeneity in Amorphous Silica Nanoparticles Evidenced from Tapping AFM–IR Nanospectroscopy

• Published in: Analytical chemistry (Washington) Vol. 95; no. 2; pp. 1505 - 1512
• Main Authors: Benedis, Denys V., Dazzi, Alexandre, Rivallan, Mickaël, Pirngruber, Gerhard D.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 17.01.2023
• Subjects: Amorphous materials; Analytical chemistry; Atomic force microscopy; Chemical Sciences; Chemistry; Fourier transforms; Heterogeneity; Infrared radiation; Infrared spectra; Infrared spectroscopy; Inorganic materials; Nanoparticles; Polymers; Polymethyl methacrylate; Sample preparation; Silica; Silicon dioxide; Spectrum analysis; Stability analysis; Surface layers; Nanoparticles; Fourier transform infrared spectroscopy; Infrared light; Silica; Organic compounds
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/acs.analchem.2c04533

In this work, we propose to evaluate and validate an emerging spectroscopic space-resolved technique: atomic force microscopy coupled with infrared spectroscopy (AFM–IR) for inorganic materials in tapping mode at the nanoscale. For this aim, a preliminary investigation of sample preparation techniques was done and the stability of tapping AFM–IR spectra was evaluated on reference samples [poly­(methyl methacrylate) and silica]. It was concluded that for a homogeneous polymer, it is possible to compare AFM–IR spectra with conventional Fourier-transform infrared (FTIR) spectra obtained in transmission. When an inorganic solid is considered, AFM–IR spectra are different from the global FTIR spectrum which indicates that the AFM–IR technique probes a volume which is not representative of global composition, that is, the external surface layer. Moreover, local infrared spectra recorded in the tapping mode of the external surface are significantly different depending on the analyzed regions of the same particle and between particles of the amorphous silica, implying surface heterogeneity. The AFM–IR technique allows surface description of amorphous inorganic materials at the nanoscale and opens new frontiers in the characterization of functional nanoscale and crystalline materials.