Improved Surface-Enhanced Raman Scattering Performance of 2D Ti3C2Tx MXene Embedded in PVDF Film Enabled by Photoinduction and Electric Field Modulation.

In this study, we introduce a synergistic approach to enhance the surface-enhanced Raman scattering (SERS) signal in two-dimensional (2D) MXene through photo-irradiation and electric field modulation. Our methodology involves the integration of 2D Ti3C2Tx MXene with piezoelectric polyvinylidene fluoride (PVDF) polymer, resulting in the creation of a free-standing, flexible composite film. On this composite film, a thin layer of Au was deposited. Our flexible substrate was able to sense methylene blue (MB), crystal violet (CV), 4-aminothiophenol (ATP), and melamine. The SERS substrate exhibits low detection limit of 10-8 M MB with a 6.7 × 106 enhancement factor (EF). The SERS substrate enables picomolar (pM) detection sensitivity for CV molecules with an EF of 9.2 × 109. Furthermore, the introduction of photo-irradiation leads to an additional ∼3.5-fold enhancement in the SERS signal, which is attributed to the altered work function and defects. The application of mechanical force to the piezoelectric PVDF/Ti3C2Tx film results in a ∼4.5-fold boost in SERS signal due to mechanical force-induced electrical energy. The fabrication strategy employed here for producing a flexible piezoelectric PVDF/Ti3C2Tx film holds significant promise for expanding the potential application of 2D MXene in rapid, on-site sensing scenarios.

Functionalization and patterning of nanocellulose films by surface-bound nanoparticles of hydrolyzable tannins and multivalent metal ions.

Inspired by the Bogolanfini dyeing technique, we report how flexible nanofibrillated cellulose (CNF) films can be functionalized and patterned by surface-bound nanoparticles of hydrolyzable tannins and multivalent metal ions with tunable colors. Molecular dynamics simulations show that gallic acid (GA) and ellagic acid (EA) rapidly adsorb and assemble on the CNF surface, and atomic force microscopy confirms that nanosized GA assemblies cover the surface of the CNF. CNF films were patterned with tannin-metal ion nanoparticles by an in-fibre reaction between the pre-impregnated tannin and the metal ions in the printing ink. Spectroscopic studies show that the FeIII/II ions interact with GA and form surface-bound, stable GA-FeIII/II nanoparticles. The functionalization and patterning of CNF films with metal ion-hydrolyzable tannin nanoparticles is a versatile route to functionalize films based on renewable materials and of interest for biomedical and environmental applications.

Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets.

Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped silicon using synchrotron-based techniques.

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S(2-) (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S(2-) species, but significantly increases the concentration of larger S clusters [polysulfides (Sn(2-), n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metal transition in S-hyperdoped Si samples. Based on the experimental results and the calculations by density functional theory, the chemical state of the S species and the formation of the S-dopant states in the band gap of Si are critical in determining the sub-band gap absorptance of hyperdoped Si samples.

Observation of the origin of d0 magnetism in ZnO nanostructures using X-ray-based microscopic and spectroscopic techniques.

Efforts have been made to elucidate the origin of d(0) magnetism in ZnO nanocactuses (NCs) and nanowires (NWs) using X-ray-based microscopic and spectroscopic techniques. The photoluminescence and O K-edge and Zn L3,2-edge X-ray-excited optical luminescence spectra showed that ZnO NCs contain more defects than NWs do and that in ZnO NCs, more defects are present at the O sites than at the Zn sites. Specifically, the results of O K-edge scanning transmission X-ray microscopy (STXM) and the corresponding X-ray-absorption near-edge structure (XANES) spectroscopy demonstrated that the impurity (non-stoichiometric) region in ZnO NCs contains a greater defect population than the thick region. The intensity of O K-edge STXM-XANES in the impurity region is more predominant in ZnO NCs than in NWs. The increase in the unoccupied (occupied) density of states at/above (at/below) the conduction-band minimum (valence-band maximum) or the Fermi level is related to the population of defects at the O sites, as revealed by comparing the ZnO NCs to the NWs. The results of O K-edge and Zn L3,2-edge X-ray magnetic circular dichroism demonstrated that the origin of magnetization is attributable to the O 2p orbitals rather than the Zn d orbitals. Further, the local density approximation (LDA) + U verified that vacancies in the form of dangling or unpaired 2p states (due to Zn vacancies) induced a significant local spin moment in the nearest-neighboring O atoms to the defect center, which was determined from the uneven local spin density by analyzing the partial density of states of O 2p in ZnO.

High coercivity of oleic acid capped CoFe2O4 nanoparticles at room temperature.

High coercivity (9.47 kOe) has been obtained for oleic acid capped chemically synthesized CoFe(2)O(4) nanoparticles of crystallite size approximately 20 nm. X-ray diffraction analysis confirms the formation of spinel phase in these nanoparticles. Thermal annealing at various temperatures increases the particle size and ultimately shows bulk like properties at particle size approximately 56 nm. The nature of bonding of oleic acid with CoFe(2)O(4) nanoparticles and amount of oleic acid in the sample is determined by Fourier transform infrared spectroscopy and thermogrvimetric analysis, respectively. The Raman analysis suggests that the samples are under strain due to capping molecules. Cation distribution in the sample is studied using Mossbauer spectroscopy. Oleic acid concentration dependent studies show that the amount of capping molecules plays an important role in achieving such a high coercivity. On the basis of above observations, it has been proposed that very high coercivity (9.47 kOe) is the result of the magnetic anisotropy, strain, and disorder of the surface spins developed by covalently bonded oleic acid to the surface of CoFe(2)O(4) nanoparticles.

A facile and fast approach for the synthesis of doped nanoparticles using a microfluidic device.

The microfluidic approach emerges as a new and promising technology for the synthesis of nanomaterials. A microreactor allows a variety of reaction conditions to be quickly scanned without consuming large amounts of raw material. In this study, we investigated the synthesis of water soluble 1-thioglycerol-capped Mn-doped ZnS nanocrystalline semiconductor nanoparticles (TG-capped ZnS:Mn) via a microfluidic approach. This is the first report for the successful doping of Mn in a ZnS semiconductor at room temperature as well as at 80 °C using a microreactor. Transmission electron microscopy and x-ray diffraction analysis show that the average particle size of Mn-doped ZnS nanoparticles is ∼3.0 nm with a zinc-blende structure. Photoluminescence, x-ray photoelectron spectroscopy, atomic absorption spectroscopy and electron paramagnetic resonance studies were carried out to confirm that the Mn(2+) dopants are present in the ZnS nanoparticles.

Template-free ZnS nanorod synthesis by microwave irradiation.

We report template-free, microwave-irradiation-assisted growth of ZnS nanorods. Using this facile and high yield technique we could grow nanostructures of approximately 50-100 nm diameter and more than 1 µm in length. Effects of microwave power and irradiation time on the growth process were investigated. It was revealed that the time of refluxing plays a vital role in determining the thickness of the rods. This simple technique using a multimode microwave source may prove to be a potential tool for growing similar nanostructures of other oxide-, sulfide- and selenide-based compound semiconductors.