Photocatalytic properties of TiO2 sol-gel modified nanocomposite films

TiO₂ nanocomposite films with different concentrations of TiO₂ MT-150A nanoparticles were immobilized on glass substrates using a dip coating process. The crystalline structure and surface chemical state of nanocomposite film properties were examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The specific surface area and morphology of TiO₂ MT-150A nanoparticles were evaluated by the BET method and Field Emission Scanning Electron Microscopy (FE-SEM). The photocatalytic activities of films were evaluated by the methyl orange decoloring rate. XPS measurements showed that the oxygen amount (%) was related to the film composition. The composite film with 10 g/L MT-150A loading yielded the highest amount of surface oxygen (26.82%) and TiO₂ rutile showed the lowest amount of surface oxygen (13.67%) in the form of surface hydroxyl groups. The remaining oxygen was identified as lattice oxygen. In addition, the nanocomposite film with 10 g/L MT-150A loading yielded the highest photocatalytic activity.     

N-doped TiO2 nanoparticles obtained by a facile coprecipitation method at low temperature

N-doped TiO₂ nanoparticles (NPs) were synthesized using a facile synthesis route by coprecipitation method. The effect of the HNO₃ volume and calcination temperature on the structural, morphological, optical and surface properties of the N-doped TiO₂ NPs was studied. X-ray diffraction analysis showed particles of nanometric size (< 16 nm), which are consistent with HR-TEM micrographs. A slight shift of the absorption edge to higher wavelengths is observed as the HNO₃ volume and calcination temperature increases. Both X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) show the presence and stability of nitrogen in the N-doped TiO₂ structure. The photocatalytic activity of the N-doped TiO₂ NPs was assessed by testing the degradation of rhodamine B (RhB) under ultraviolet (UV) and visible light.     

Novel method for synthesis of Fe core and C shell magnetic nanoparticles

Using a newly developed method, carbon-encapsulated iron (Fe) nanoparticles were synthesized by plasma due to ultrasonication in toluene. Fe core with carbon shell nanoparticles were characterized using Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM). Fe nanoparticles of diameter 7–115 nm are encapsulated by 7–8 nm thick carbon layers. There was no iron carbide formation observed between the Fe core and the carbon shell. The Fe nanoparticles have body centered cubic (bcc) crystal structure. Synthesized nanoparticles showed a saturation magnetization of 9 A m²/kg at room temperature. After thermal treatment crystalline order of the nanoparticles improved and saturation magnetization increased to 24 A m²/kg. We foresee that the carbon-encapsulated Fe nanoparticles are biologically friendly and could have potential applications in Magnetic Resonance Imaging (MRI) and photothermal cancer therapy.     

Synthesis of nitrogen-doped carbon coated TiO2 microspheres and its application as metal support in cinnamaldehyde hydrogenation

N-doped carbon coated TiO₂ microspheres (CNx/TiO₂) were synthesized by the carbonization of the polypyrrole (PPy) coating on the surface of TiO₂ microspheres and used as support to disperse Pt and PtCo nanoparticles for investing the selective hydrogenation of cinnamaldehyde. The support and catalysts have been characterized in terms of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS). The hydrogenation results showed the conversion increased with an increase of CNx amount until the CNx coated TiO₂ microspheres completely.     

Surface structural and solar absorptance features of nitrate-based copper-cobalt oxides composite coatings: Experimental studies and molecular dynamic simulation

The copper and cobalt oxides composites coatings on aluminum substrates have been successfully synthesized via sol-gel method using nitrate-based sol precursors. The composites were characterized by X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Field Emission Scanning Electron Microscopy (FESEM), Atomic Force Microscopy (AFM), and UV–Vis–NIR spectrophotometry. The sol-gel reactions were discussed and Molecular Dynamics (MD) simulation was integrated into the study to predict molecules assembly properties. The XRD analyses revealed that the CuO and the Co₃O₄ composites were formed after the annealing process with the average difference of the calculated lattice parameters compared to ICDDs was 1.17%. The surface electronic structure was mainly consisted of tetrahedral Cu(I), octahedral Cu(II), tetrahedral Co(II), octahedral Co(III) as well as surface, sub-surface and lattice oxygen O^?. The XRD, XPS and MD simulation results showed that there was minimal (or possibly non-existing) indication of copper-cobalt mixed phase oxides formations. FESEM and AFM surveys revealed that the coating had a porous surface composed of interlinked nanoparticles in the range of ~?10 to ~?40?nm. UV–Vis–NIR reflectance spectra showed that the sol precursors concentration and the dip-drying cycle significantly influenced the absorptance value with optimum absorptance (α) of 88.7% exhibited by coating synthesized using sol concentration of 0.1?M and 10 dip-drying cycles. High absorptance value and simplicity in the synthesis process render the coatings to be very promising candidates for solar selective absorber (SSA) applications.     

Electrochemical properties of N-doped hydrogenated amorphous carbon films fabricated by plasma-enhanced chemical vapor deposition methods

Nitrogen-doped hydrogenated amorphous carbon thin films (a-C:N:H, N-doped DLC) were synthesized with microwave-assisted plasma-enhanced chemical vapor deposition widely used for DLC coating such as the inner surface of PET bottles. The electrochemical properties of N-doped DLC surfaces that can be useful in the application as an electrochemical sensor were investigated. N-doped DLC was easily fabricated using the vapor of nitrogen contained hydrocarbon as carbon and nitrogen source. A N/C ratio of resulting N-doped DLC films was 0.08 and atomic ratio of sp³/sp²-bonded carbons was 25/75. The electrical resistivity and optical gap were 0.695 Ω cm and 0.38 eV, respectively. N-doped DLC thin film was found to be an ideal polarizable electrode material with physical stability and chemical inertness. The film has a wide working potential range over 3 V, low double-layer capacitance, and high resistance to electrochemically induced corrosion in strong acid media, which were the same level as those for boron-doped diamond (BDD). The charge transfer rates for the inorganic redox species, Fe^2+/3+ and Fe(CN)₆^4−/3− at N-doped DLC were sufficiently high. The redox reaction of Ce^2+/3+ with standard potential higher than H₂O/O₂ were observed due to the wider potential window. At N-doped DLC, the change of the kinetics of Fe(CN)₆^3−/4− by surface oxidation is different from that at BDD. The rate of Fe(CN)₆^3−/4− was not varied before and after oxidative treatment on N-doped DLC includes sp² carbons, which indicates high durability of the electrochemical activity against surface oxidation.     

Microstructure and electron field emission study of diamond nanorod decorated a-SiO2 nanowires by microwave Ar–CH4/H2 plasma chemical vapor deposition with addition of N2

In our recent paper [M. K. Singh et al., Chem. Mater. 20 (2008) 1725], we reported the fabrication of Nanocrystalline diamond (NCD) fibers by template (a-SiO₂ nanowires) technique. Our present work demonstrate that the addition of nitrogen of 20% by volume in the reaction gas during synthesis induce the formation of feather-like morphology of NCD on a-SiO₂ nanowires. The feather-like morphology consists oriented diamond nanorods surrounded by an sp²-bonded carbon sheath. These have been characterized by Scanning Electron Microscopy, Transmission Electron Microscopy (high-resolution mode) and Micro-Raman spectroscopy. Electron field emission (EFE) of as-synthesized NCD fibers (with 20% N₂ addition) was observed with a threshold field of 3.5 V/µm which is quite less in comparison to previous grown NCD fibers and the current density at 10 V/µm increases around 20 times with 20% nitrogen doping in the gas source during synthesis. This may be because each diamond nanorod is enveloped in a sheath of sp²-bonded nanocarbons which provides a conducting path for electron emission.     

Single-step synthesis of N-doped TiO2 by flame aerosol method and the effect of synthesis parameters

We have established a novel route for the synthesis of N-doped TiO₂ by adopting flame aerosol (FSP) technique and investigated the effect of water content on the physico-chemical properties of the as-synthesized nanoparticles. The key characteristics of the developed method are to modify the precursor solution in order to incorporate nitrogen atoms into the TiO₂ lattice without altering the FSP set-up. The reduction of the flame enthalpy resulting in N-incorporation into the TiO₂ and the N-doping can be greatly enhanced further by the addition of secondary N-source (urea). Our XRD results reveal a shift of the (101) plane anatase diffraction peak to lower angles in our N-doped TiO₂ compared to undoped TiO_2, which suggest the distortion and strain in the crystal lattice prompted by the incorporation of the nitrogen atoms. The growth or expansion of crystal lattice can be attributed to the larger atomic radius of respective nitrogen atoms (r?=?1.7 Å) compared to oxygen (r?=?1.40 Å). Our XPS and EDX spectroscopy results elucidate that the nitrogen was effectively doped into the crystal lattice of TiO₂ in our as-synthesized N-TiO₂ catalysts predominantly in the form of interstitial nitrogen (Ti?O?N). The nitrogen atoms incorporation into the crystal lattice of titania modifies the electronic band structure of TiO₂, resulting in a new mid-gap energy state N 2p band formed above O 2p valence band. This occurrence narrows the band gap of TiO₂ (from 3.12 to ～2.51?eV) in our N-doped TiO₂ and shifts the optical absorption to the visible region.

Copyright © 2018 American Association for Aerosol Research     

Author Index to Volume 38

X-ray photoelectron spectroscopy (XPS) is a powerful technique for determining the surface chemical composition of atmospheric particles. In this article, we employed XPS to study atmospheric particles collected from Guangzhou city in typical sites and seasons. The results showed that the weight percentage of carbon, oxygen, nitrogen, and sulfur were about 70.5–87.1%, and these species dominated the surface structure of the particles independent of the collection site and season. Inorganic elements including Si, Na, Ca, Cl, Fe, K, Al, and Cu were also found on the particle surfaces. The high-resolution XPS spectra revealed: (1) High aromatic and aliphatic C-H, and other oxidized carbons were found on the surface of particles. (2) The nitrogen species were characterized by pyridinic, pyrrolic/amide, quaternary type nitrogen functionalities, and nitrate groups, indicating that inorganic and organic N species are both important components of N-containing particles. (3) Sulfate and sulfone groups were also present on the surface and were important components. The oxidized groups of C, N, and S were higher in winter samples, consistent with the monsoon weather of Guangzhou in winter, which is favorable for the formation of oxidized species. A comparison between total and surface analyses showed that the surface of particles was relatively high in organic carbon, NO₃ ^?, and SO₄ ^2?, and the interior of particles was higher in NH₄ ⁺. These results provide information on the formation of aerosols, e.g., NH₄ ⁺ may act as a very important nucleus and organic carbon, NO₃ ^?, and SO₄ ^2? coat the nuclei during particle growth.     

Low Temperature Preparation and Characterization of N-doped and N-S-codoped TiO2 by Sol–gel Route

This paper reports a new method to prepare the N-doped and N-S-codoped anatase TiO₂ photocatalysts at 100 °C. The as-prepared photocatalysts were characterized by means of XRD, Raman spectra, TEM, BET, UV–Vis diffuse reflectance spectra (DRS) and XPS. The results showed that the N-doping and N-S-codoping extended the absorbance spectra of TiO₂ into visible region with different extent. The BET surface area of the N-S-codoped TiO₂ photocatalysts was high up to 245 m²g⁻¹. The results of degradation of methyl orange (MO) solution showed that the N-doped and N-S-codoped TiO₂ photocatalysts exhibited higher photocatalytic activity than that of Degussa P-25 and the as-prepared pure TiO₂ under visible irradiation. This property can be attributed to the results of synergetic effects of absorption in the visible light region, red shift in adsorption edge, good crystallization and large surface area of the as-prepared N-doped or N-S-codoped TiO₂.     

Thermal stability and surface modifications of detonation diamond nanoparticles studied with X-ray photoelectron spectroscopy

Detonation nanodiamond (ND) particles were dispersed on silicon nitride (SiN_x) coated sc-Si substrates by spin-coating technique. Their surface density was in the 10¹⁰–10¹¹ cm^?2 range. Thermal stability and surface modifications of ND particles were studied by combined use of X-ray Photoelectron Spectroscopy (XPS) and Field Emission Gun Scanning Electron Microscopy (FEG SEM). Different oxygen-containing functional groups could be identified by XPS and their evolution versus UHV annealing temperature (400–1085 °C) could be monitored in situ. The increase of annealing temperature led to a decrease of oxygen bound to carbon. In particular, functional groups where carbon was bound to oxygen via one σ bond (C–OH, C–O–C) started decomposing first. At 970 °C carbon–oxygen components decreased further. However, the sp²/sp³ carbon ratio did not increase, thus confirming that the graphitization of ND requires higher temperatures. XPS analyses also revealed that no interaction of ND particles with the silicon nitride substrate occurred at temperatures up to about 1000 °C. However, at 1050 °C silicon nitride coated substrates started showing patch-like damaged areas attributable to interaction of silicon nitride with the underlying substrate. Nevertheless ND particles were preserved in undamaged areas, with surface densities exceeding 10¹⁰ cm^?2. These nanoparticles acted as sp³-carbon seeds in a subsequent 15 min Chemical Vapour Deposition run that allowed growing a 60–80 nm diamond film. Our previous study on Si(100) showed that detonation ND particles reacted with silicon between 800 and 900 °C and, as a consequence, no diamond film could be grown after Chemical Vapour Deposition (CVD). These findings demonstrated that the use of a thin silicon nitride buffer layer is preferable insofar as the growth of thin diamond films on silicon devices via nanoseeding is concerned.     

氮掺杂科琴黑碳材料的制备及 电催化氧还原性能研究

氮掺杂碳材料是一种有应用前景的电催化氧还原催化剂。以尿素和三聚氰胺作为氮源,在氮气气氛下高温焙烧,制得两种氮掺杂科琴黑碳材料并将其用于电催化氧还原反应。使用X射线衍射仪（XRD）、X射线光电子能谱仪（XPS）、场发射扫描电子显微镜（FESEM）、比表面物理吸附分析仪等对氮掺杂前后的科琴黑的结构和形貌进行了分析。结果表明：氮掺杂之后科琴黑仍保持石墨结构,其形貌和比表面积均无明显改变。在XPS谱图上,氮掺杂后科琴黑上存在氮元素,其中以三聚氰胺为氮源比以尿素为氮源更容易得到吡啶氮。通过循环伏安法和线性扫描伏安法研究了3个样品的电催化氧还原性能。结果表明：氮掺杂能明显提高科琴黑的电催化氧还原性能,未掺杂的 科琴黑（AC）的半波电位为0.746 V,而以尿素和三聚氰胺为氮源掺杂后的科琴黑碳材料的半波电位分别提高到了 0.756 V（尿素-N/AC）和0.786 V（三聚氰胺-N/AC）。     

Oxygen reduction activity of pyrolyzed polypyrroles studied by 15N solid-state NMR and XPS with principal component analysis

New analytical method for characterizing the nitrogen sites in N-doped carbon catalysts is proposed by employing ¹⁵N solid-state NMR. ¹⁵N labeled polypyrrole is prepared as a precursor of N-doped carbon catalysts and is pyrolyzed at several different temperatures in a nitrogen atmosphere. The oxygen reduction reaction is evaluated by rotating disk electrode experiments, and solid-state ¹⁵N NMR and XPS spectra are measured. The relationship between oxygen reduction activity and the chemical structure, combined with principal component analysis is discussed. The iron-free pyrolyzed polypyrrole samples display quite poor catalytic activity for oxygen reduction, whilst the iron-containing pyrolyzed polypyrrole samples display better oxygen reduction activity. ¹⁵N solid-state NMR spectra show that the pyrolyzed polypyrroles contain pyridinic, quaternary, pyrrolic nitrogens at edges or at defects in graphitic sheets. This is the first observation of quaternary nitrogens at edges or defects in graphitic sheets using ¹⁵N solid-state NMR. Using principal component analysis of the XPS and ¹⁵N solid-state NMR spectra, it is found that most pyridinic, quaternary, and pyrrolic nitrogen atoms are not related to oxygen reduction reaction. However, the samples which contain a larger proportion of some particular type of pyridinic nitrogen atoms show a higher activity for the oxygen reduction reaction.     

Zn2 +-assisted synthesis of concave Cu2O crystals and enhanced photocatalytic properties

The effects of Zn^2 + on the structure Cu₂O crystals and photocatalytic decoloration of methylene orange (MO) were studied. Samples were characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HRTEM), and Ultraviolet–Visible Spectroscopic (UV–VIS). The results indicated that Zn^2 + ions can transform the surface curvature of Cu₂O microcrystals from convex to concave. Tests of photodecoloration showed that the concave trisoctahedron Cu₂O microcrystals exhibited higher catalytic activity than those of octahedra Cu₂O and convex Cu₂O for MO under visible light.     

Combustion synthesis of β-SnWO4-rGO: Anode material for Li-ion battery and photocatalytic dye degradation

This article reports the synthesis β-SnWO₄–rGO nanocomposite (NC) by a simple solution combustion method followed by low temperature hydrothermal method. The β-SnWO₄–rGO NC has been characterized using various analytical tools such as X-ray diffraction (XRD), Raman spectroscopy, Scanning Electron Microscopy (SEM), High-Resolution Transmission Electron Microscopy (HR-TEM), Ultraviolet-Differential reflectance spectroscopy (UV-DRS). X-ray diffraction pattern shows the formation of cubic structured β-SnWO₄ nanoparticles (NPs) and Raman spectrum shows the presence of rGO in the composite. Transmission Electron Microscopy image shows that SnWO₄ NPs were embedded on the surface of rGO. β-SnWO₄ NPs and β-SnWO₄-rGO NC has been examined as an electrode material for Li-ion battery (LIB). β-SnWO₄ NPs and β-SnWO₄-rGO NC displays an initial discharge capacity of 1351 mAhg^?1 and 1662 mAhg^?1 which is about 23% increase in capacity. Electrochemical performance of β-SnWO₄-rGO NC at different current densities proves that it is one of the good candidates as an electrode material for LIB. β-SnWO₄-rGO NC shows enhanced photocatalytic activity against rose bengal (RB) and methylene blue (MB) compared to pure β-SnWO₄ NPs.     

Electrochemical performance of carbon gels with variable surface chemistry and physics

This study describes the electrochemical characterization of N-doped carbon xerogels in the form of microspheres and of carbon aerogels with varied porosities and surface oxygen complexes. The interfacial capacitance of N-doped carbon xerogels decreased with increased micropore surface area as determined by N₂ adsorption at ?196 °C. The interfacial capacitance showed a good correlation with the areal N_XPS concentration, and the best correlation with the areal concentration of pyrrolic or pyridonic nitrogen functionalities. The gravimetric capacitance decreased with greater xerogel microsphere diameter. The interfacial capacitance of carbon aerogels increased with higher percentage of porosity as determined from particle and true densities. The interfacial capacitance showed a linear relationship with the areal oxygen concentration and with the areal concentrations of CO- and CO₂-evolving groups.     

Cobalt oxide nanoparticles on mesoporous MCM-41 and Al-MCM-41 by supercritical CO2 deposition

CoO and Co₃O₄ nanoparticles were uniformly dispersed inside mesoporous MCM-41 and Al-MCM-41 supports using supercritical CO₂ reactive deposition. This method represents a one-pot reproducible procedure that allows the dissolution of the organocobalt precursor and supports impregnation in supercritical CO₂ at 70 °C and 110 bar, followed by the precursor thermal decomposition into cobalt species at 200 °C and 160 bar. By the relative concentration of the cobalt precursor [cobalt (II) bis (η⁵-ciclopentadienil)], the load of cobalt nanoparticles was controlled and then determined by Inductively Coupled Plasma (ICP-OES). The synthesis of CoO and Co₃O₄ species inside the MCM-41 and Al-MCM-41 substrates was confirmed by X-ray Photoelectron (XPS) and Laser Raman Spectroscopies (LRS). By N₂ adsorption and Small Angle X-ray Scattering (SAXS), it was determined that the hexagonal arrangement as well as the surface area and pore size of the substrates changed after the addition of cobalt. By means of X-ray mapping from SEM images, a homogeneous distribution of cobalt nanoparticles was observed inside the mesopores when the cobalt loading was 1 wt.%. In addition, spherical cobalt nanoparticles of average diameter close to 20 nm were detected on the outer surface of MCM-41 and Al-MCM-41 supports when the cobalt content was higher. On the other hand, by Transmission Electron Microscopy (TEM), it was possible to measure the interplanar distance of the crystalline plane of the outer nanoparticles, which was later compared with the theoretical distance values which allowed identifying the CoO and Co₃O₄ phases.     

Synthesis and characterization of monodisperse NiFe2O4 nanoparticles

Narrow size distribution nickel ferrite nanoparticles with average particle size of around 6 nm has been synthesized via rapid thermo-decomposition method in the presence of oleylamine in solution which acted as neutralizing, stabilizing and reducing agent OAm coated NiFe₂O₄ NPs. X-ray powder diffraction (XRD), Fourier Transform Infrared Spectra (FT-IR), Thermal Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM), Vibrating Simple Magnetometer (VSM) and also Mössbauer Spectroscopy were used for structural, morphological, spectroscopic and magnetic characterization of the product. The XRD analysis revealed the formation of single phase nickel ferrite with Fd-3m space group. Both FT-IR and TGA analyses confirmed the formation of desired nanocomposite. FT-IR analysis also showed characteristic IR absorption bands of the spinel nickel ferrite phase and oleylamine. TEM and SEM analysis showed that product have almost spherical structural morphology. TEM images showed that NiFe₂O₄ nanoparticles have narrow size distribution and Energy Dispersive X-ray (EDX) analysis confirmed the presence of metal ions in the required stoichiometric ratio. Superparamagnetic property of the product was confirmed by VSM. From ⁵⁷Fe Mössbauer spectroscopy data, the variation in line width, isomer shift, quadrupole splitting and hyperfine magnetic field values have been determined. The Mössbauer spectra for OAm coated NiFe₂O₄ NPs. is consisting of one paramagnetic central doublets and one magnetic Zeeman sextet. Finally, the synthetic procedure can be extended to the preparation of high quality metal or alloy nanoparticles.     

Reductant-free synthesis of magnetoplasmonic iron oxide-gold nanoparticles

Stable suspensions of spherical 10–15 nm superparamagnetic iron oxide nanoparticles (SPIONs) have been synthetized by co-precipitation, stabilized with citric acid, surface functionalized with aminopropyltriethoxysilane (APTES) and finally decorated with ultra-small gold nanoparticles (GNPs) by in situ reduction of a soluble gold salt (HAuCl₄), obtaining well dispersed SPIONs-GNPs colloids.The morphology, size and stability of the SPIONs-GNPs suspensions have been controlled by adjusting the molar ratio of the reagents (Fe/HAuCl₄ and Fe/APTES). The synthesis route differs from that typically found in literature, using tunable chelating layer modifications (such as citric acid and –NH₂ groups) of the magnetic core, depositing GNPs on the amine-functionalized iron oxide surface without the use of a specific reducing agent, and tuning the process pH and temperature. An explanation of how the different chemical species involved in the synthesis route could be responsible for the reducing action has been provided. The SPIONs-GNPs colloids have been characterized after each synthesis step by Transmission Electron Microscopy (TEM), Scanning Transmission Electron Microscopy (STEM), energy-dispersive X-ray spectroscopy (EDXS), Fourier transform infrared spectroscopy (FTIR), ζ Potential measurements, magnetic measurements with a vibrating-sample magnetometer (VSM) and UV–VIS spectroscopy. The SPIONs-GNPs colloids showed magnetoplasmonic behaviors since they maintained the plasmonic properties of GNPs and the superparamagnetic response of iron oxide NPs.     

Synthesis and photocatalytic activity of TiO2-hectorite composites

TiO₂-hectorite composites were synthesized and characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Electron Diffraction Spectrum (EDS) techniques. The course of composite formation, TiO₂ particles were intercalated into hectorite. The specific surface areas of the samples were determined by nitrogen adsorption. The composite with a Ti content 2.5% (m/m) had a higher specific surface area than other composites. Photocatalytic properties were tested in photooxidation of methylene blue (MB).