NMR studies of the thermal evolution of the Ga-In-Sn and Ga-In liquid alloys embedded into opal matrices were carried out. Temperature dependences of the gallium lineshape, shift of the resonance frequency (Knight shift), and intensity were obtained upon cooling down to the alloy freezing and subsequent warming. A second highfrequency 71 Ga NMR signal emerged for both alloys upon cooling, the NMR line intensity transferring gradually into this additional signal. The Knight shifts of the signals differed noticeably. The transformations of the gallium line upon warming were continuous and not affected by changes in the alloy compositions induced by melting. 115 In NMR measurements were conducted to monitor the alloy compositions at freezing and melting. The findings suggest the occurrence of the liquid-liquid phase transition in the strongly supercooled alloys under nanoconfinement.
Engineering the physics and chemistry of 2D materials is a key to unlock the potential of the advanced e‐nose technologies limited by the current semiconductor technologies. Herein, the adjustment of the graphene's morphology, physics, and gas sensing properties upon its carboxylation via the developed photochemical method is demonstrated. Formation of matrices of nanoscale holes yet with the retention of the lamellar structure of the graphene layer is signified upon the introduction of up to 9.5 at% of carboxyl groups. The impact of the applied carboxylation on the conduction mechanism and electronic structure is demonstrated. The appearance of a set of the localized states in the valence band is revealed, originating from the molecular orbitals of carboxyls as is signified by the proposed approach for the identification of electronic states in graphene chemical derivatives. Given holey structure, predominance of highly affine carboxyls, and lateral inhomogeneity, the enhanced detection and discrimination of various alcohols, acetone, and ammonia vapors at room temperature is demonstrated. The opposite chemiresistive response toward ammonia in the humid air is also experimentally revealed and justified by the performed density functional theory modeling on the effect of ammonia, water, and their mix on electronic structure, and resistivity of the carboxylated graphene.
The derivatization of graphene to engineer its band structure is a subject of significant attention nowadays, extending the frames of graphene material applications in the fields of catalysis, sensing, and energy harvesting. Yet, the accurate identification of a certain group and its effect on graphene’s electronic structure is an intricate question. Herein, we propose the advanced fingerprinting of the epoxide and hydroxyl groups on the graphene layers via core-level methods and reveal the modification of their valence band (VB) upon the introduction of these oxygen functionalities. The distinctive contribution of epoxide and hydroxyl groups to the C 1s X-ray photoelectron spectra was indicated experimentally, allowing the quantitative characterization of each group, not just their sum. The appearance of a set of localized states in graphene’s VB related to the molecular orbitals of the introduced functionalities was signified both experimentally and theoretically. Applying the density functional theory calculations, the impact of the localized states corresponding to the molecular orbitals of the hydroxyl and epoxide groups was decomposed. Altogether, these findings unveiled the particular contribution of the epoxide and hydroxyl groups to the core-level spectra and band structure of graphene derivatives, advancing graphene functionalization as a tool to engineer its physical properties.
(23)Na NMR studies of sodium nanoparticles confined to porous glass with the 3.5 nm mean pore size were carried out. The emergence of the second component of the NMR line was observed below 240 K that evidences the occurrence of another modification of metallic sodium. The phase transition temperature is much higher than the martensite transformation temperature in bulk sodium.
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