RESUMO
TiO2 has been extensively studied in many fields including photocatalysis, electrochemistry, optics, etc. Understanding the mechanism of the anatase-rutile phase transition (ART) process is critical for the design of TiO2-based high-activity photocatalysts and tuning its properties for other applications. In this work, the ART process using individual anatase micro-particles with a large percentage of (001) facets was monitored and studied. Phase concentration evolution obtained via Raman microscopy was correlated with the morphological evolution observed in scanning electron microscope (SEM) images. The ART of anatase microcrystals is dominated by surface nucleation and growth, but the ART processes of individual anatase particles are distinctive and depend on the various rutile nucleation sites. Two types of transformation pathways are observed. In one type of ART pathway, the rutile phase nucleated at a corner of an anatase microcrystal and grew in one direction along the edge of the crystal firstly followed by propagation over the rest of the microcrystal in the orthogonal direction on the surface and to the bulk of the crystal. The kinetics of the ART follows the first-order model with two distinct rate constants. The fast reaction rate is from the surface nucleation and growth, and the slow rate is from the bulk nucleation and growth. In the other type of ART pathway, multiple rutile nucleation sites formed simultaneously on different edges and corners of the microcrystal. The rutile phase spread over the whole crystal from these nucleation sites with a small contribution of bulk nucleation. Our study on the ART of individual micro-sized crystals bridges the material gap between bulk crystals and nano-sized TiO2 particles. The anatase/rutile co-existing particle will provide a perfect platform to study the synergistic effect between the anatase phase and the rutile phase in their catalytic performances.
RESUMO
Surface-enhanced Raman scattering (SERS) spectroscopy is a popular technique for detecting chemicals in small quantities. Rough metallic surfaces with nanofeatures are some of the most widespread and commercially successful substrates for efficient SERS measurements. A rough metallic surface creates a high-density random distribution of so-called "hot spots" with local optical field enhancement causing Raman signal to increase. In this Letter, we revisit the classic SERS experiment [Surf. Sci.158, 229 (1985)SUSCAS0039-602810.1016/0039-6028(85)90297-3] with rough metallic surfaces covered by a thin layer of copper phthalocyanine molecules. As a modification to the classic configuration, we apply an adaptive wavefront correction of a laser beam profile. As a result, we demonstrate an increase in brightness of local SERS hot spots and redistribution of Raman signal over the substrate area. We hypothesize that the improvement is due to optimal coupling of the shaped laser beam to the random plasmonic nanoantenna configurations. We show that the proposed adaptive-SERS modification is independent of the exact structure of the surface roughness and topography, works with many rough surfaces, and gives brighter Raman hot spots in comparison with conventional SERS measurements. We prove that the adaptive SERS is a powerful instrument for improving SERS sensitivity.
RESUMO
Studies of optical properties of doped nanocrystals of tungsten trioxide can elucidate new information about the material. A novel molecule-enhanced photoluminescence (PL) of potassium-doped tungsten trioxide (K x WO) was explored in the presence of different gases to understand charge transfer between molecules and K x WO on the properties of the material. We performed Raman spectroscopy and PL experiments in the presence of gaseous acetone or ethanol mixed with other gases (N2 and O2). PL at 630 nm from K x WO was observed and further enhanced when the sample was continuously irradiated with a 532 nm CW laser in acetone. A mechanism of strong emission of the PL induced by the charge transfer between the acetone and the K x WO is proposed.