Structural Characterization and Physical Properties of Double Perovskite La2FeReO6+δ Powders

The structural, optical, dielectric, and magnetic properties of double perovskite La2FeReO6+δ (LFRO) powders synthesized by solid-state reaction method under CO reduced atmosphere are reported on in this paper. Reitveld refinements on the XRD data revealed that the LFRO powders crystallized in an orthogonal structure (Pbnm space group) with column-like morphology. The molar ratios of La, Fe, and Re elements were close to 2:1:1. XPS spectra verified the mixed chemical states of Fe and Re ions, and two oxygen species in the LFRO powders. The LFRO ceramics exhibited a relaxor-like dielectric behavior, and the associated activation energy was 0.05 eV. Possible origins of the dielectric relaxation behavior are discussed based on the hopping of electrons among the hetero-valence ions at B-site, oxygen ion hopping through the vacant oxygen sites, and the jumping of electrons trapped in the shallower level created by oxygen vacancy. The LFRO powders display room temperature ferromagnetism with Curie temperature of 746 K. A Griffiths-like phase was observed in the LFRO powders with a Griffiths temperature of 758 K. The direct optical band gap of the LFRO powders was 2.30 eV, deduced from their absorption spectra, as confirmed by their green photoluminescence spectra with a strong peak around 556 nm.

Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy

The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220–250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.

Rapid Functionalization of Polytetrafluorethylene (PTFE) Surfaces with Nitrogen Functional Groups

The biocompatibility of body implants made from polytetrafluoroethylene (PTFE) is inadequate; therefore, the surface should be grafted with biocompatible molecules. Because PTFE is an inert polymer, the adhesion of the biocompatible film may not be appropriate. Therefore, the PFTE surface should be modified to enable better adhesion, preferably by functionalization with amino groups. A two-step process for functionalization of PTFE surface is described. The first step employs inductively coupled hydrogen plasma in the H-mode and the second ammonia plasma. The evolution of functional groups upon treatment with ammonia plasma in different modes is presented. The surface is saturated with nitrogen groups within a second if ammonia plasma is sustained in the H-mode at the pressure of 35 Pa and forward power of 200 W. The nitrogen-rich surface film persists for several seconds, while prolonged treatment causes etching. The etching is suppressed but not eliminated using pulsed ammonia plasma at 35 Pa and 200 W. Ammonia plasma in the E-mode at the same pressure, but forward power of 25 W, causes more gradual functionalization and etching was not observed even at prolonged treatments up to 100 s. Detailed investigation of the XPS spectra enabled revealing the surface kinetics for all three cases.

Improved Photocatalytic Water Splitting Activity of Highly Porous WO3 Photoanodes by Electrochemical H+ Intercalation

WO3 photoanodes are widely used in photoelectrochemical catalysis, but typically the as-synthesized material is annealed before application. It is therefore desirable to explore less energy-intensive treatments. In this study, WO3 films of up to 3.9 μm thickness were obtained by galvanostatic anodization of tungsten foil in a neutral-pH Na2SO4 and NaF electrolyte, also containing a NaH2PO2 additive (to suppress O2 accumulation on the pore walls). Additionally, the WO3 photoanodes were modified by applying a cathodic reduction (H+ intercalation) and anodic activation treatment in-situ. XPS spectra revealed that intercalation modifies WO3 films; the amount of W5+-O and O-vacancy bonds was increased. Furthermore, subsequent activation leads to a decrease of the W5+ signal, but the amount of O-vacancy bonds remains elevated. The as-prepared and reduced (intercalated & activated) films were tested as OER photoanodes in acidic 0.1 M Na2SO4 media, under illumination with a 365 nm wavelength LED. It was observed that thinner films generated larger photocurrents. The peculiarities detected by XPS for reduced films correlate well with their improved photocatalytic activity. Photo-electrochemical impedance and intensity modulated photocurrent spectroscopies were combined with steady-state measurements in order to elucidate the effects of H+ intercalation on photoelectrochemical performance. The reduction results in films with enhanced photoexcited charge carrier generation/separation, improved conductivity, and possibly even suppressed bulk recombination. Thus, the intercalation & activation adopted in this study can be reliably used to improve the overall activity of as-synthesized WO3 photoanodes, and particularly of those that are initially poorly photoactive.

Facile fabrication of Fe-TiO2 thin film and its photocatalytic activity

Fe3+-TiO2 (Fe-TiO2) thin films were successfully prepared using a “sandwich” approach. TiO2 NPs were doped with different Fe3+ content (0.05%, 0.1%, 0.2% molar ratio), and the modified TiO2 NPs were deposited on glass flat support by dip coating.Structural, morphological, optical, and photocatalytic properties of Fe-TiO2 thin films were studied. XPS spectra confirm the presence of Ti, Fe, O, and defective –OH groups at the material surface. The Fe 2p spectrum demonstrates the existence of Fe3+. SEM images indicate that the incorporation of Fe3+ deforms in some degree the homogeneity of the TiO2 system. Additionally, incorporation of Fe3+ ions to the network creates an impurity band near the VB due to the oxygen vacancies, resulting in the reduction of the effective optical band gap. Photocatalytic activity of fabricated thin films in the elimination of sulfamethoxazole (SMT) follows pseudo first-order kinetics. The highest SMT removal yields were achieved using the sample with 0.05%Fe. Additionally, the use of greater thicknesses improves the removal performance. However, material detachment limits the maximum usable value around 6 µm.Finally, stability and reusability of catalysts were confirmed studying the photocatalytic activity over three cycles and evaluating that no Fe3+ leaching occurred. Graphical abstract

Evaluating Effect of Metallic Ions On Aggregation Behavior of Amyloid Aβ42 By AFM Imaging and SERS

Background: Excessive aggregation of β-amyloid peptides (Aβ) is regarded as the hallmark of Alzheimer’s disease. Exploring the underlying mechanism regulating Aβ aggregation remains challenging and investigating aggregation events of Aβ in the presence and absence of metal ions at molecular level would be meaningful in elucidating the role of metal cations on interactions between Aβ molecules. In this study, chemical self-assembled monolayer (SAM) method was employed to fabricate monolayer of β-amyloid peptides Aβ42 on gold substrate with a bolaamphiphile named 16-Mercaptohexadecanoic acid (MHA). Firstly, the samples of gold substrate (blank control), the MHA-modified substrate and the Aβ42-modified substrate were detected by X-ray photoelectron spectroscopy (XPS) to track the self-assembly process. Aggregation behaviors of Aβ42 before and after metallic ions (Zn2+、Ca2+、Al3+) treated were monitored by atomic force microscopy (AFM) and the interaction between Aβ42 and metallic ions (Zn2+、Ca2+、Al3+) was investigated by surface-enhanced Raman Scattering (SERS), respectively.Results: The XPS spectra of binding energy of gold substrate (blank control), the MHA-modified substrate and the Aβ42-modified substrate are well fitted with the corresponding monolayer’s composition, which indicates that Aβ42 monolayer is well formed. The recorded surface morphology of different experimental groups obtained by AFM showed markedly different nanostructures, indicating occurrence of aggregation events between Aβ42 molecules after adding metal ions to the solution. Compared to the control group, the presence of metal ions resulted in the increased size of surface structures on the observed 3D topography. Further study by SERS showed that the Raman strength of Aβ42 changes significantly after the metal cation treatment. A considerable part of the amide bonds interacts with metal cations, leading to a structural change, which is characterized by the weakened β-fold Raman peak.Conclusion: The AFM imaging results suggest that aggregation events occurred between Aβ42 molecules with the addition of metal cations. Furthermore, the effect of metallic cations on the conformational change of Aβ42 studied by SERS supported the results obtained by AFM imaging. Taken together, the results showed that the presence of substoichiometric metal cations promotes aggregation behavior between Aβ42 molecules on the substrate at pH 7.4.

Enhancing electrical properties of carbon nanotubes thin films by silicon incorporation

Silicon incorporated carbon nanotube (Si-CNTs) thin films was prepared by radio frequency plasma enhanced chemical vapor deposition technique. Tetraethyl orthosilicate solution was used for incorporation of silicon in CNTs thin films. Energy dispersive X-ray analysis shows that the silicon atomic percentage was varied from 0 % to 6.1 %. The chemical binding energies of carbon and silicon were analyzed from X-ray photoelectron spectroscopy data. The various peaks at ~531 eV, ~ 285 eV, ~155 eV and ~104 eV was observed in the XPS spectra due to the oxygen, carbon and silicon respectively. Surface morphologies of Si-CNTs thin films have been analyzed by field emission scanning electron microscopy, which revels that the length of the silicon incorporated carbon nanotubes ~500 nm and corresponding diameter ~80 nm. The room temperature electrical conductivity was increased whereas the activation energy was decreased with the increase of atomic percentage of silicon in Si-CNTs thin films. The room temperature electrical conductivity was increased from 4.3 × 103 to 7.1 × 104 S cm−1 as the silicon atomic percentage in Si-CNTs thin films increases from 0 to 6.1 % respectively.

The Electrochemical Behaviour of Quaternary Amine-Based Room-Temperature Ionic Liquid N4111(TFSI)

In this study, we used the in situ X-ray photoelectron spectroscopy (XPS), in situ mass spectroscopy, cyclic voltammetry and electrochemical impedance spectroscopy methods, for the first time, in a detailed exploration of the electrochemical behaviour of a quaternary amine cation-based room-temperature ionic liquid, butyl-trimethyl-ammonium bis(trifluoromethylsulfonyl)imide (N4111(TFSI)), at the negatively and positively polarised molybdenum carbide-derived micro-mesoporous carbon (mmp-C(Mo2C)) electrodes that can be used as high surface area supporting material for electrocatalysts. The shapes of the C 1s, N 1s, O 1s, F 1s and S 2p XPS spectra were stable for N4111(TFSI) within a very wide potential range. The XPS data indicated the non-specific adsorption character of the cations and anions in the potential range from −2.00 V to 0.00 V. Thus, this region can be used for the detailed analysis of catalytic reaction mechanisms. We observed strong adsorption from 0.00 V to 1.80 V, and at E > 1.80 V, very strong adsorption of the N4111(TFSI) at the mmp-C(Mo2C) took place. At more negative potentials than −2.00 V, the formation of a surface layer containing both N4111+ cations and TFSI− anions was established with the formation of various gaseous compounds. Collected data indicated the electrochemical instability of the N4111+ cation at E < −2.00 V.

Removal of Cd2+ from Water Containing Ca2+, Mg2+ using Titanate Nanotubes Modified by Carbon

Ca2+ and Mg2+ usually exist in natural water. When Cd2+ is removed from water by adsorption, it will be inhibited by these two ions. Titanate nanotubes (TNTs) have an effective adsorption capacity for Cd2+ due to extraordinary ion-exchange property. However, TNTs also adsorb Ca2+ and Mg2+ in water. In this study, carbon-modified TNT (TNT/C or TNT/HC) was synthesized by hydrothermal synthesis. The transmission electron microscope (TEM) images show that TNT/C or TNT/HC still keep nanotube morphology. The experimental results show the order of adsorption amount to Cd2+ is TNT > TNT/C > TNT/HC when there is no Ca2+ or Mg2+. But when there is Ca2+ or Mg2+ in the water, the order of Cd2+ adsorption capacity becomes TNT/HC > TNT/C > TNT. It indicates that the surface carbon-modification can alleviate the hindrance of Ca2+ or Mg2+ to Cd2+ removal. This is because the carbon on the surface of TNT captured part of Ca2+ or Mg2+, it made more Cd2+ be successfully absorbed by TNT through ion exchange. This mechanism was confirmed by XPS spectra analysis. The results of this paper can provide ideas for the adsorption and removal of Cd2+ in water in the presence of Ca2+ or Mg2+.