RESUMO
Research on graphene-related two-dimensional (2D) materials (GR2Ms) in recent years is strongly moving from academia to industrial sectors with many new developed products and devices on the market. Characterization and quality control of the GR2Ms and their properties are critical for growing industrial translation, which requires the development of appropriate and reliable analytical methods. These challenges are recognized by International Organization for Standardization (ISO 229) and International Electrotechnical Commission (IEC 113) committees to facilitate the development of these methods and standards which are currently in progress. Toward these efforts, the aim of this study was to perform an international interlaboratory comparison (ILC), conducted under Versailles Project on Advanced Materials and Standards (VAMAS) Technical Working Area (TWA) 41 "Graphene and Related 2D Materials" to evaluate the performance (reproducibility and confidence) of the thermogravimetric analysis (TGA) method as a potential new method for chemical characterization of GR2Ms. Three different types of representative and industrially manufactured GR2Ms samples, namely, pristine few-layer graphene (FLG), graphene oxide (GO), and reduced graphene oxide (rGO), were used and supplied to ILC participants to complete the study. The TGA method performance was evaluated by a series of measurements of selected parameters of the chemical and physical properties of these GR2Ms including the number of mass loss steps, thermal stability, temperature of maximum mass change rate (Tp) for each decomposition step, and the mass contents (%) of moisture, oxygen groups, carbon, and impurities (organic and non-combustible residue). TGA measurements determining these parameters were performed using the provided optimized TGA protocol on the same GR2Ms by 12 participants across academia, industry stakeholders, and national metrology institutes. This paper presents these results with corresponding statistical analysis showing low standard deviation and statistical conformity across all participants that confirm that the TGA method can be satisfactorily used for characterization of these parameters and the chemical characterization and quality control of GR2Ms. The common measurement uncertainty for each parameter, key contribution factors were identified with explanations and recommendations for their elimination and improvements toward their implementation for the development of the ISO/IEC standard for chemical characterization of GR2Ms.
RESUMO
The adsorption of the p-phenylenediamine (PPD(+)) radical cation on gold or copper nanoparticle (NP) surfaces was studied through surface-enhanced Raman scattering (SERS) spectroscopy, excited at 1064 nm. The SERS spectra were obtained from gold or copper NPs after exposure to non-oxidized p-phenylenediamine (PPD) aqueous solution, in millimolar concentration. The gold NPs were synthesized as nanoshells involving silica cores (SiO(2)@Au) and the copper NPs were obtained in aqueous medium, undergoing surface oxidation with the formation of Cu(II) oxide nanoshell (Cu@CuO). In the latter, the oxidative adsorption of PPD(+) led to the reduction of the copper oxide, present on NP surface, allowing obtaining the PPD(+) SERS spectrum. The vibrational assignments of the SERS spectra of the adsorbate were performed using the results of Density Functional Theory calculations of the Raman frequencies, which together with the SERS surface selection rules, allowed to infer the adsorption geometry of PPD(+) radical cation on both metallic surfaces. This work stress the investigation of redox processes involved in the molecular adsorption is imperative for the interpretation of the SERS results, which is even more important when copper surfaces are studied.
