Rafael Gregorio Mendes, Ph.D

Exploring 2D Materials Atom-by-Atom Using TEM

Electron beam / 2D nanomaterials interactions


Abstract:  Since the advent of monolayered 2D transition metal carbide and nitrides (MXenes) in 2011, the number of different monolayer systems and the study thereof have been on the rise. Mo2Ti2C3 is one of the least studied MXenes and new insights to this material are of value to the field. Here, the stability of Mo2Ti2C3 under electron irradiation is investigated. A transmission electron microscope (TEM) is used to study the structural and elemental changes in situ. It is found that Mo2Ti2C3 is reasonably stable for the first 2 min of irradiation. However, structural changes occur thereafter, which trigger increasingly rapid and significant rearrangement. This results in the formation of pores and two new nanomaterials, namely, N-doped graphene membranes and Mo nanoribbons. The study provides insight into the stability of Mo2Ti2C3 monolayers against electron irradiation, which will allow for reliable future study of the material using TEM. Furthermore, these findings will facilitate further research in the rapidly growing field of electron beam driven chemistry and engineering of nanomaterials. 
Abstract: Two-dimensional polymeric graphitic carbon nitride (g-C3N4) is a low-cost material with versatile properties that can be enhanced by the introduction of dopant atoms and by changing the degree of polymerization/stoichiometry, which offers significant benefits for numerous applications. Herein, we investigate the stability of g-C3N4 under electron beam irradiation inside a transmission electron microscope operating at different electron acceleration voltages. Our findings indicate that the degradation of g-C3N4 occurs with N species preferentially removed over C species. However, the precise nitrogen group from which N is removed from g-C3N4 (C–N–C, =NH or –NH2) is unclear. Moreover, the rate of degradation increases with decreasing electron acceleration voltage, suggesting that inelastic scattering events (radiolysis) dominate over elastic events (knock-on damage). The rate of degradation by removing N atoms is also sensitive to the current density. Hence, we demonstrate that both the electron acceleration voltage and the current density are parameters with which one can use to control the stoichiometry. Moreover, as N species were preferentially removed, the d-spacing of the carbon nitride structure increased. These findings provide a deeper understanding of g-C3N4. 

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