For aqueous solutions with freezable bound water, vitrification and recrystallization are mingled, which brings difficulty to application and misleads the interpretation of relevant experiments. Here, we report a quantification scheme for the freezable bound water based on the water-content dependence of glass transition temperature, by which also the concentration range for the solutions that may undergo recrystallization finds a clear definition. Furthermore, we find that depending on the amount of the freezable bound water, different temperature protocols should be devised to achieve a complete recrystallization. Our results may be helpful for understanding the dynamics of supercooled aqueous solutions and for improving their manipulation in various industries.
Thin films of ternary compounds CuxlnyN and CuxTiyN were grown by magnetron sputtering to improve the thermal stability of Cu3N, a material that decomposes below 300 ℃, and thus promises many interesting applications in directwriting. The effect of In or Ti incorporation in altering the structure and physical properties of copper nitride was evaluated by characterizing the film structure, surface morphology, and temperature dependence of electrical resistivity. More Ti than In can be accommodated by copper nitride without completely deteriorating the Cu3N lattice. A small amount of In or Ti can improve the crystallinity, and consequently the surface morphology. While the decomposition temperature is rarely influenced by In, the Ti-doped sample, Cu59.31Ti2.64N38.05, shows an X-ray diffraction pattern dominated by characteristic Cu3N peaks, even after annealing at 500 ℃. Both In and Ti reduce the bandgap of the original Cu3N phase, resulting in a smaller electrical resistivity at room temperature. The samples with more Ti content manifest metal-semiconductor transition when cooled from room temperature down to 50 K. These results can be useful in improving the applicability of copper-nitride-based thin films.
Nitrogen-doped single-walled carbon nanotubes （CNx-SWNTs） with tunable dopant concentrations were synthesized by chemical vapor deposition （CVD）, and their structure and elemental composition were characterized by using transmission electron microscopy （TEM） in combination with electron energy loss spectroscopy （EELS）. By comparing the Raman spectra of pristine and doped nanotubes, we observed the doping-induced Raman G band phonon stiffening and 2D band phonon softening, both of which reflect doping-induced renormalization of the electron and phonon energies in the nan- otubes and behave as expected in accord with the n-type doping effect. On the basis of first principles calculations of the distribution of delocalized carrier density in both the pristine and doped nanotubes, we show how the n-type doping occurs when nitrogen heteroatoms are substitutionally incorporated into the honeycomb tube-shell carbon lattice.
The cobalt phosphate-/cobalt borate-based oxygen-evolving catalysts （OECs） are the important class of earth-abundant electrocatalysts that can operate with high activity for water splitting under benign conditions. This article reports the integration of cobalt phosphate （Co- Pi） and cobalt borate （Co-Bi） OECs with three-dimensional （3D） graphene foam （GF） for the electrocatalytic water oxidation reaction. The GF showed a unique advantage to serve as a highly conductive 3D support with large capacity for anchoring and loading Co-OECs, thereby facilitating mass and charge transfer due to the large amount of active sites provided by the 3D graphene scaffold. As a result, this integrated system of GF and Co-OECs exhibits synergistically enhanced catalytic activity. The overpotential （η） of Co-Pi and Co-Bi/graphene catalysts is about 0.390 and 0.315 V in neutral solutions, respectively. Besides, the integrated Co-OECs/graphene catalysts have also exhibited improved and stable oxygen evolution catalytic ability in alkaline solution.
Min ZengHao WangChong ZhaoJiake WeiWenlong WangXuedong Bai
The recent development of synthesis processes to assemble graphene sheets into porous three-dimensional （3D）macroscopic structures are reviewed, including our efforts on 3D graphene structures. Mechanisms for building 3D graphene architectures and their composite materials are also summarized. The functional systems based on 3D graphene architectures provide a significant enhancement in the efficacy due to their unique structures and properties.
Hydration water can even decide the physicochemical properties of hydrated organic molecules. However, by far the most important hydration number for organic molecules, in particular polyethylene glycol which we are concerned with here, usually suffers from a large discrepancy. Here, we provide a scheme for accurate and unambiguous quantification of the hydration number based on the universal water-content dependence of glass transition temperature for aqueous solutions, testified by experimental results for polyethylene glycol molecules of a molar weight ranging from 200 to 20000.Moreover, we also clarify the fundamental misunderstanding lying in the definition and quantification of hydration water for PEG molecules in the literature, therein the hydration number for PEG in water-rich solutions has been determined at a critical concentration, across which the properties of the solution display obviously distinct water-content dependence.
Phase transition in two dimensional molybdenum disulfide (MoS_2) can be induced by several methods and has been investigated for decades. Alkali metal insertion of MoS_2 had been proved an effective method to cause phase transition early in 1970s, and has been gaining renewed interest recently, due to the possible application of MoS_2 in energy storage. The alkali metal intercalation of MoS_2 has been studied by various techniques, among which in-situ transmission electron microscopy (TEM) provides unique capability of real time resolving the structural evolution of the materials at high spatial resolutions. Here by in-situ TEM technique we investigated the structural evolution of MoS_2 upon lithium and sodium intercalation, along with transformation of the nanosheet and variation of the electron diffraction patterns. The intercalation process is accompanied by emergence of superstructures, which exist in several forms. The ion intercalation results in phase transition of MoS_2 from 2H to 1T, and the driving mechanism of the phase transition are discussed. The work provides a more comprehensive understanding of ion intercalation induced phase transition of MoS_2.
Qianming HuangLifen WangZhi XuWenlong WangXuedong Bai
