Combinatorial Vibration-Mode Assignment for the FTIR Spectrum of Crystalline Melamine: A Strategic Approach toward Theoretical IR Vibrational Calculations of Triazine-Based Compounds

Although polymeric graphitic carbon nitride (g-C₃N₄) has been widely studied as metal-free photocatalyst, the description of its structure still remains a great challenge. Fourier transform infrared (FTIR) spectroscopy can provide complementary structural information. In this paper, we reconsider the representative crystalline melamine and develop a strategic approach to theoretically calculate the IR vibrations of this triazine-based nitrogen-rich system. IR calculations were based on three different models: a single molecule, a 4-molecule unit cell, and a 32-molecule cluster, respectively. By this comparative study the contribution of the intermolecular weak interactions were elucidated in detail. An accurate and visualized description on the experimental FTIR spectrum has been further presented by a combinatorial vibration-mode assignment based on the calculated potential energy distribution of the 32-molecule cluster. The theoretical approach reported in this study opens the way to the facile and accurate assignment for IR vibrational modes of other complex triazine-based compounds, such as g-C₃N₄

Functionalization of Single-Wall Carbon Nanotubes with Chromophores of Opposite Internal Dipole Orientation

We report the functionalization of carbon nanotubes with two azobenzene-based chromophores with large internal dipole moments and opposite dipole orientations. The molecules are attached to the nanotubes noncovalently via a pyrene tether. A combination of characterization techniques shows uniform molecular coverage on the nanotubes, with minimal aggregation of excess chromophores on the substrate. The large on/off ratios and the subthreshold swings of the nanotube-based field-effect transistors (FETs) are preserved after functionalization, and different shifts in threshold voltage are observed for each chromophore. Ab initio calculations verify the properties of the synthesized chromophores and indicate very small charge transfer, confirming a strong, noncovalent functionalization

Tuning the Photocatalytic Activity of Graphitic Carbon Nitride by Plasma-Based Surface Modification

In this study, we demonstrate that plasma treatment can be a facile and environmentally friendly approach to perform surface modification of graphitic carbon nitride (g-CN), leading to a remarkable modulation on its photocatalytic activity. The bulk properties of g-CN, including the particle size, structure, composition, and electronic band structures, have no changes after being treated by oxygen or nitrogen plasma; however, its surface composition and specific surface area exhibit remarkable differences corresponding to an oxygen functionalization induced by the plasma post-treatment. The introduced oxygen functional groups play a key role in reducing the recombination rate of the photoexcited charge carries. As a consequence, the oxygen-plasma-treated sample shows a much superior photocatalytic activity, which is about 4.2 times higher than that of the pristine g-CN for the degradation of rhodamine B (RhB) under visible light irradiation, while the activity of nitrogen-plasma-treated sample exhibits a slight decrease. Furthermore, both of the plasma-treated samples are found to possess impressive photocatalytic stabilities. Our results suggest that plasma treatment could be a conventional strategy to perform surface modification of g-CN in forms of both powders and thin films, which holds broad interest not only for developing g-CN-based high-performance photocatalysts but also for constructing photoelectrochemical cells and photoelectronic devices with improved energy conversion efficiencies

Low-Temperature, Directly Depositing Individual Single-Walled Carbon Nanotubes for Fabrication of Suspended Nanotube Devices

Single-walled carbon nanotubes (SWNTs) grown by chemical vapor deposition (CVD) are widely used for fabrication of high-performance nanotube devices. However, the high-temperature growth is incompatible with the current complementary metal-oxide semiconductor (CMOS) technology. We demonstrate a low-temperature and direct deposition of the CVD-grown SWNTs. The nanotubes are synthesized by floating catalytic CVD technique and further carried by the flowing gas directly to the low-temperature area. Individual SWNTs have been successfully deposited on Si/SiO₂ substrates covered with a polymethylmethacrylate layer, which results in a suspended geometry of the nanotube in the fabricated devices. We subsequently investigate the electrical-transport properties of a representative small band gap nanotube, which exhibits an ambipolar feature with <i>p</i>-channel mobility up to 1410 cm² V^–1 S^–1 at room temperature. Furthermore, low-temperature measurements down to 4 K reveal different transport characteristics with the gate voltage biased near zero or at a large negative value, respectively