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The magnetic and neutron diffraction studies of La{sub 1−x}Sr{sub x}MnO{sub 3} nanoparticles prepared via molten salt synthesis

Series of single-phase La{sub 1−x}Sr{sub x}MnO{sub 3} nanoparticles (x=0.25−0.47) with the size of about 50 nm was prepared in molten NaNO{sub 2}. TEM evidenced well dispersed particles that are not interconnected by sintering bridges in contrast to traditional products. Interestingly, some reduction of the perovskite cell volume, particularly at higher Sr-contents, was detected by XRD. Moreover, reduced magnetization and decreased Curie temperature in comparison to sol–gel samples were observed. Neutron diffraction analysis of the as-prepared nanoparticles and several comparative samples with x=0.37 indicated that the anomalous behavior of studied particles probably originate in the overdoped outer shell. The overdoping might result from both the surface oxygen chemisorption and from an increased Sr concentration in the shell. By all means, the overdoping would lead to compressive surface stress, driving the x=0.37 ground state toward a mixture of FM and A-type AFM ordering as observed by neutron diffraction. - Graphical abstract: La{sub 1−x}Sr{sub x}MnO{sub 3} nanoparticles with the size of about 50 nm were prepared by newly established method in molten NaNO{sub 2}. TEM proved the formation of well-separated particles without sintering bridges, the major advantage over traditional preparation methods. - Highlights: • Series of La{sub 1−x}Sr{sub x}MnO{sub 3} nanoparticles was prepared by novel method in NaNO{sub 2} melt. • Lower magnetization and Curie temperature in comparison to sol–gel nanoparticles was observed. • Overdoping of outer shell was indicated by neutron diffraction and cerimetric titration. • Overdoping shifts La{sub 0.37}Sr{sub 0.63}MnO{sub 3} ground state to a mixture of FM and A-type AFM ordering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of lanthanide on the microstructure and structure of LnMn{sub 0.5}Fe{sub 0.5}O{sub 3} nanoparticles with Ln=La, Pr, Nd, Sm and Gd prepared by the polymer precursor method

The synthesis of LnMn{sub 0.5}Fe{sub 0.5}O{sub 3} perovskite nanoparticles by the polymer precursor method showed a strong intrinsic dependence with different lanthanides (Ln=La, Pr, Nd, Sm and Gd). The polymerization level reached in the polymer precursor was proportional to the atomic number of lanthanide with exception of samarium, which showed the formation of a different precursor based in a citrate chelate with ethyleneglycol bonded as adduct. The increasing level of polymerization of the polymer precursors showed the formation of large-size perovskite nanoparticles after its calcination. SAXS and TEM analyses suggested that nanoparticles obtained, using this method, have a squared-like microstructure in connection with the polymer precursor microstructure. Structural analysis showed an orthorhombic structure with a slight decline in the Jahn–Teller distortion when the atomic number of lanthanide increases. Mössbauer spectroscopy showed the presence of a majority site in agreement with the Pbnm orthorhombic structure best fitted with Rietveld refinements and in some cases, a more distorted site attributed to local inhomogeneities and oxygen vacancies. - Highlights: • Precursor polymerization level is lower in the presence of lighter lanthanides. • Lighter lanthanide perovskite nanoparticles after calcination are lower-sized. • Nanoparticles obtained by this method have lamellae microstructure. • Jahn–Teller distortion declines for heavier lanthanide perovskites. • Oxygen vacancy phase was observed in lighter lanthanide perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Irreversible phase transitions due to laser-based T-jump heating of precursor Eu:ZrO{sub 2}/Tb:Y{sub 2}O{sub 3} core/shell nanoparticles

Amorphous precursors of Eu-doped-ZrO{sub 2}/Tb-doped-Y{sub 2}O{sub 3} (p-Eu:ZrO{sub 2}/p-Tb:Y{sub 2}O{sub 3}) core/shell nanoparticles are rapidly heated to temperatures between 200 °C and 950 °C for periods between 2 s and 60 s using a CO{sub 2} laser. During this heating process the nanoparticles undergo irreversible phase changes. The fluorescence spectra due to Eu{sup 3+} dopants in the core and Tb{sup 3+} dopants in the shell are used to identify distinct phases within the material and to generate time/temperature phase diagrams. Such phase diagrams can potentially help to determine unknown time/temperature histories in thermosensor applications. - Graphical abstract: A CO{sub 2} laser is used for rapid heating of p-Eu:ZrO{sub 2}/p-Tb:Y{sub 2}O{sub 3} core/shell nanoparticles. Optical spectra are used to identify distinct phases and to determine its thermal history. - Highlights: • Synthesized oxide precursors of lanthanide doped core/shell nanoparticles. • Heated core/shell nanoparticles via laser-based T-jump technique. • Observed time- and temperature-dependent irreversible phase transition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid synthesis of Co, Ni co-doped ZnO nanoparticles: Optical and electrochemical properties

We report for the first time a rapid preparation of Zn{sub 1−2x}Co{sub x}Ni{sub x}O nanoparticles via a versatile and environmentally friendly route, microwave-assisted hydrothermal (MAH) method. The Co, Ni co-doped ZnO nanoparticles present an effect on photoluminescence and electrochemical properties, exhibiting excellent electrocatalytic performance compared to undoped ZnO sample. Photoluminescence spectroscopy measurements indicated the reduction of the green–orange–red visible emission region after adding Co and Ni ions, revealing the formation of alternative pathways for the generated recombination. The presence of these metallic ions into ZnO creates different defects, contributing to a local structural disorder, as revealed by Raman spectra. Electrochemical experiments revealed that the electrocatalytic oxidation of dopamine on ZnO attached to multi-walled carbon nanotubes improved significantly in the Co, Ni co-doped ZnO samples when compared to pure ZnO. - Graphical abstract: Rapid synthesis of Co, Ni co-doped ZnO nanoparticles: optical and electrochemical properties. Co, Ni co-doped ZnO hexagonal nanoparticles with optical and electrocatalytic properties were successfully prepared for the first time using a microwave hydrothermal method at mild conditions. - Highlights: • Co{sup 2+} and Ni{sup 2+} into ZnO lattice obtained a mild and environmentally friendly process. • The heating method strongly influences in the growth and shape of the particles. • Short-range defects generated by the ions insertion affects the photoluminescence. • Doped ZnO nanoparticles improve the electrocatalytic properties of pure oxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ag@ZnO core-shell nanoparticles study by first principle: The structural, magnetic and optical properties

Ag@ZnO core-shell nanoparticles of around 72 atoms have been investigated by the density functional theory, revealing proving for the first time that the core-shell structure exhibits a shrinkage phenomenon from outer shell in agreement with the other studies in literatures. Our calculations predict that the Ag@ZnO core-shell structure is a ferromagnetic spin polarized state, and the magnetism mainly stems from the spin splitting of 2p electrons of O atoms. In addition, the total and partial DOS of Ag@ZnO indicate that the nanostructure is a half-metallic nanoparticle and has the characters of the p-type semiconductor. Furthermore, the optical properties calculations show that the absorption edge of Ag@ZnO have a red shift and good photocatalysis compare to that of the bulk ZnO. These results of the Ag@ZnO core-shell structure obtain a well agreement with the experimental measurement. - Graphical abstract: Geometric structure of (a) Ag@ZnO core-shell nanostructure; (b) the core of Ag; (c) the shell of ZnO The core-shell nanoparticle Ag@ZnO contains Ag inner core of radius of 4 Å and ZnO outer shell with thickness of 2 Å. Ag@ZnO core-shell nanoparticles of around 72 atoms have been proved for the first time that the core-shell structure exhibit a shrinkage phenomenon from outer shell. Our calculations predict that the Ag@ZnO core-shell structure is a half-metallic nanoparticle and has the characters of the p-type semiconductor. The absorption edge of Ag@ZnO have a red shift and get good photo-catalysis compare to that of the bulk ZnO.

36 MATERIALS SCIENCE↗

J-aggregation in porphyrin nanoparticles induced by diphenylalanine

In this report, L-diphenylalanine-decorated tetraphenylporphyrin (TPPtFF{sub C}) was synthesized and self-assembled into regular nano-architechtures. The morphology of the assemblies varied with the concentration of TPPtFF{sub C}. The absorption spectra of the nanoparticles show the Soret band merges with the Q bands and redistributes with great red-shift, indicative of the formation of J-aggregates of the porphyrin molecules. The fluorescence emission of the nanoparticles is merged and red-shifted to near-infrared region. Studies of absorption and fluorescence spectra reveal an indispensible role of diphenylalanine group in the formation of J-aggregates. The Raman spectra disclose that diprotonation of the porphyrin core contributes to delocalized coherent excited states in the nanoparticles. The positive cotton effect in circular dichroism spectra corresponding to the Soret band of TPPtFF{sub C} in solution confirms the formation of J-aggregates with right-handed chirality of the dipole moment. This report will shed light on the rational design of porphyrin-peptide conjugates to mimic naturally light-harvesting complexes. - Graphical abstract: TPPtFF{sub C} was synthesized and self-assembled into regular nano-architectures. Photophysical property studies of the nanoparticles indicate the porphyrin molecules form typical J-aggregates. The diprotonation of the porphyrin core and the FF group play an indispensible role in the formation of J-aggregates. - Highlights: • Porphyrin-peptide conjugates were self-assembled into regular nanostructures. • The photophysical properties of the nanoparicles indicate formation of typical J-aggregates. • The Raman spectra confirm that diprotonation of the porphyrin core contributes to exciton coherence in the nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancement of photoluminescence of different quantum dots by Ag@SiO{sub 2} core–shell nanoparticles

Highlights: ► Enhancement effects of CdS/ZnS, Cd{sub 0.3}Pb{sub 0.7}S and ZnS QDs linked to Ag@SiO{sub 2} nanoparticles were studied. ► There existed an optimal thickness of SiO{sub 2} shell on the enhancement. ► The enhancement factor was in the range of 2.5–3 for CdS/ZnS and Cd{sub 0.3}Pb{sub 0.7}S QDs. ► The PL intensity of ZnS QD was totally quenched due to absorption by silver particles. - Abstract: The enhancement of photoluminescence of several quantum dots, namely CdS/ZnS, Cd{sub 0.3}Pb{sub 0.7}S and pure ZnS, by Ag@SiO{sub 2} core–shell nanoparticles is studied and reported in this work. 3-Aminopropyltriethoxysilane (APS) was used to link QDs to the core–shell nanoparticles. For CdS/ZnS, the Ag@SiO{sub 2} nanoparticles showed a maximum enhancement of about 2.5 due to surface plasmon resonance of silver particles when the shell thickness was 16 nm. When the shell thickness increased to 30 nm, the enhancement effect became negligible. Conversely, when the thickness decreased to 6 nm, the effect was also smaller due to possible capture of excited electrons by silver particles. For Cd{sub 0.3}Pb{sub 0.7}S, a similar enhancement effect was observed. However when pure ZnS was the QD, the photoluminescence went zero after the QD was linked to Ag@SiO{sub 2} nanoparticles. This was caused by the fact that for ZnS QDs, the emission wavelength was 415 nm, which also corresponds to the absorbance peak of silver particles.

36 MATERIALS SCIENCE↗

Characterization and antibacterial properties of stable silver substituted hydroxyapatite nanoparticles synthesized through surfactant assisted microwave process

Highlights: • Stable nano sized silver substitute hydroxyapatite is prepared under surfactant assisted microwave process at 600 W power for 7 min. • The nanoparticles are in the size range of 58–72 nm and exert uniform elongated spheroid morphology. • Increase in silver concentration resulted in better dielectric properties. • Good antibacterial activity and silver release. - Abstract: The present study reports a relatively simple method for the synthesis of stable silver substituted hydroxyapatite nanoparticles with controlled morphology and particle size. In order to achieve this, CTAB is included as a surfactant in the microwave refluxing process (600 W for 7 min). The nanoparticles produced with different silver ion concentrations (0.05, 0.1 and 0.2 wt%) were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX) and Brunauer–Emmett–Teller (BET) analysis. XRD and FTIR analyses reveal that the Ag-HA nanoparticles were phase pure at 1000 °C. FESEM images showed that the produced nanoparticles are in the size range of 58–72 nm and exert uniform elongated spheroid morphology. The dielectric properties suggest that the increase in dielectric constant (ε′) and dissipation factor (D) values with increasing Ag concentrations. Antibacterial performance of the Ag-HA samples elucidated using disk diffusion technique (DDT) and minimum inhibitory concentration (MIC) demonstrates anti-bacterial activity against Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa and Escherichia coli. This effect was dose dependent and was more pronounced against Gram-negative bacteria than Gram-positive organisms.

36 MATERIALS SCIENCE↗

Innovative methodology for the synthesis of Ba-M hexaferrite BaFe{sub 12}O{sub 19} nanoparticles

Graphical abstract: Transmission electron microscope images for the BaFe12O19. - Highlights: • BaFe{sub 12}O{sub 19}nanoparticles were prepared in single-phase from organometallic precursors. • BaFe{sub 12}O{sub 19} possesses small size 65 nm, H{sub C} = 3695 Oe and M{sub s} = 58 emu/g. • This method of preparation could be extended in the synthesis of other metal oxide nanoparticles. - Abstract: In this piece of work, high quality and homogeneity, barium hexaferrite (BaM) BaFe{sub 12}O{sub 19} nanoparticles were prepared from organometallic precursors for the 1st time. This method is based on the formation of supramolecular crystal structure of Ba[Fe(H{sub 3}NCH{sub 2}CH{sub 2}NH{sub 3})]Cl{sub 7}·8H{sub 2}O. The crystal structure, morphology and magnetic properties of BaFe{sub 12}O{sub 19} at two different annealing temperatures namely 1000 °C and 1200 °C were investigated using X-ray diffraction, transmission electron microscope TEM and vibrating sample magnetometry (VSM). The results show that monophasic nanoparticles of hexaferrites were obtained. Nanoparticles of crystallite size 40–50 nm distinguished by narrow distribution and excellent homogeneity were obtained with superior magnetic properties which suggested single-domain particles of Ba-M hexaferrite.

36 MATERIALS SCIENCE↗

Synthesis and characterization of WO{sub 3} spherical nanoparticles and nanorods

Graphical abstract: Two different morphology WO{sub 3} nanoparticles are synthesized by a simple and new wet chemical route through control over pH, temperature and structure directing agents. Reaction mechanism has been proposed for the formation of different morphologies. Nanorod WO{sub 3} has better crystallinity with less specific surface area compared to the spherical nanoparticles. Comparable band gaps are obtained for both the nanoparticles. - Highlights: • Spherical WO{sub 3} nanoparticle and nanorod synthesis mechanisms proposed. • Thermal analysis and spectroscopy confirms the intermediate reactions. • Both of the morphology has pure and monoclinic phase with identical band gap energy. - Abstract: Simple and new wet chemical routes are adopted for the synthesis of tungsten trioxide (WO{sub 3}) nanopowders having two different morphologies such as spherical and rod-like. Acid catalyzed exothermic reaction and a structure directing reagent have been used to control the formation of spherical and rod shaped nanoparticles, respectively. Thermal analysis and FTIR spectral data have been used to confirm the formation of the intermediate and the ultimate reaction products. X-ray and Raman spectroscopic data indicate the monoclinic structure of both forms of the particles. Rod shaped WO{sub 3} particles exhibit better crystallinity and low specific surface area compared to those exhibited by spherical particles. Band gaps are found to be nearly identical irrespective of the morphology.

36 MATERIALS SCIENCE↗

Europium doped lanthanum zirconate nanoparticles with high concentration quenching

Graphical abstract: - Highlights: • Eu:La{sub 2}Zr{sub 2}O{sub 7} nanoparticles were prepared facilely by a kinetically modified molten salt method. • High color purity and concentration quenching were achieved in these La{sub 2}Zr{sub 2}O{sub 7}:Eu nanoparticles. • Concentration quenching mechanism was discussed for Eu{sup 3+} in these Eu:La{sub 2}Zr{sub 2}O{sub 7} nanoparticles. - Abstract: A series of Eu{sup 3+} doped lanthanum zirconate (La{sub 2}Zr{sub 2}O{sub 7}) nanoparticles (NPs, 20 ± 5 nm in diameter) with cubic fluorite structure were facilely synthesized by a kinetically modified molten salt synthetic (MSS) process and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and photoluminescence spectra (PL). Under the excitation of 405 nm, intense red emission with high color purity can be observed in the Eu{sup 3+} doped La{sub 2}Zr{sub 2}O{sub 7} NPs. Moreover, the as-prepared Eu:La{sub 2}Zr{sub 2}O{sub 7} NPs possess high concentration quenching, which is as high as ∼32.5 mol% of europium dopants in the La{sub 2}Zr{sub 2}O{sub 7} host. The corresponding concentration quenching mechanism was discussed as well. Our results confirm that the kinetically modified MSS process is a promising approach for preparing rare earth (RE) ions doped A{sub 2}B{sub 2}O{sub 7} nanoparticles with uniform RE doping and high concentration quenching.

36 MATERIALS SCIENCE↗

The effect of Ni addition on the structure of Pt–Sn/C nanoparticles by electron microscopy

Highlights: • A typical Pt/SnO{sub 2} core–shell structure is present in Pt–Sn. • The most of SnO{sub 2} species are likely clustered in Pt–Sn. • SnO{sub 2} nanoparticles prefer to locate close to Pt–Sn–Ni nanoclusters. • Main crystallographic structures are either cubic Pt or PtSn{sub 2}. - Abstract: Carbon supported bimetallic Pt–Sn and trimetallic Pt–Sn–Ni nanoparticles were synthesized by Bönnemann's colloidal precursor method and characterized by high-resolution transmission electron microscopy (HR-TEM) and energy dispersive X-ray analysis (EDX) techniques. HR-TEM and EDX results demonstrated that SnO{sub 2} nanoparticles tend to form clusters in Pt–Sn/C; however, the presence of Ni in the Pt–Sn/C gives rise to an induced interaction between SnO{sub 2} and Pt nanoparticles. Electron diffraction patterns of Pt–Sn–Ni/C showed that either cubic Pt or PtSn{sub 2} structures are present. From the selected area EDX analysis, it was found that both of these structures contain Sn. This suggests that Pt–Sn–Ni/C nanoparticles may be partially covered by Sn-richer PtSn{sub 2} alloyed structure.

36 MATERIALS SCIENCE↗

Electronic structure, magnetic and structural properties of Ni doped ZnO nanoparticles

Highlights: • XRD, and HR-TEM results show the single phase nature of Ni doped ZnO nanoparticles. • dc magnetization results indicate the RT-FM in Ni doped ZnO nanoparticles. • Ni L{sub 3,2} edge NEXAFS spectra infer that Ni ions are in +2 valence state. • O K edge NEXAFS spectra show that O vacancy increases with Ni doping in ZnO. - Abstract: We report structural, magnetic and electronic structural properties of Ni doped ZnO nanoparticles prepared by auto-combustion method. The prepared nanoparticles were characterized by using X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, and dc magnetization measurements. The XRD and HR-TEM results indicate that Ni doped ZnO nanoparticles have single phase nature with wurtzite lattice and exclude the presence of secondary phase. NEXAFS measurements performed at Ni L{sub 3,2}-edges indicates that Ni ions are in +2 valence state and exclude the presence of Ni metal clusters. O K-edge NEXAFS spectra indicate an increase in oxygen vacancies with Ni-doping, while Zn L{sub 3,2}-edge show the absence of Zn-vacancies. The magnetization measurements performed at room temperature shows that pure and Ni doped ZnO exhibits ferromagnetic behavior.

36 MATERIALS SCIENCE↗

Carbon nanotubes-dispersed TiO{sub 2} nanoparticles with their enhanced photocatalytic activity

Graphical abstract: Carbon nanotubes-dispersed TiO{sub 2} nanoparticles with their enhanced photocatalytic activity. - Abstract: A novel carbon nanotubes (CNTs)-dispersed route is used to prepare high-activity titanium dioxide nanoparticles (TiO{sub 2}). Field-emission scanning electron microscopy and transmission electron microscopy reveals that the irregular TiO{sub 2} nanoparticles with diameters of 10–20 nm are highly dispersed. X-ray diffraction and specific surface area measurement show that high-activity anatase crystal is formed and the specific surface area of TiO{sub 2} nanoparticles is 147.36 m{sup 2}/g. The photoactivity of TiO{sub 2} was tested by photodegradation of Rhodamine B. The result shows that the photocatalytic activity of TiO{sub 2} nanoparticles prepared by the CNTs-dispersed route is three times higher than that by conventional hydrothermal treatment.

36 MATERIALS SCIENCE↗

Palladium nanoparticles anchored on graphene nanosheets: Methanol, ethanol oxidation reactions and their kinetic studies

Highlights: • Palladium nanoparticles decorated graphene is synthesized in a single step. • Electro-catalytic activity of Gra/Pd toward alcohol oxidation is evaluated. • 1:1 Gra/Pd exhibits good electro-catalytic activity and efficient electron transfer. - Abstract: Palladium nanoparticles decorated graphene (Gra/Pd nanocomposite) was synthesized by simultaneous chemical reduction of graphene oxide and palladium salt in a single step. The negatively charged graphene oxide (GO) facilitates uniform distribution of Pd{sup 2+} ions onto its surface. The subsequent reduction by hydrazine hydrate provides well dispersed Pd nanoparticles decorated graphene. Different amount of Pd nanoparticles on graphene was synthesized by changing the volume to weight ratio of GO to PdCl{sub 2}. X-ray diffraction studies showed FCC lattice of Pd with predominant (1 1 1) plane. SEM and TEM studies revealed that thin graphene nanosheets are decorated by Pd nanoparticles. Raman spectroscopic studies revealed the presence of graphene nanosheets. The electro-catalytic activity of Gra/Pd nanocomposites toward methanol and ethanol oxidation in alkaline medium was evaluated by cyclic voltammetric studies. 1:1 Gra/Pd nanocomposite exhibited good electro-catalytic activity and efficient electron transfer. The kinetics of electron transfer was studied using chronoamperometry. Improved electro-catalytic activity of 1:1 Gra/Pd nanocomposite toward alcohol oxidation makes it as a potential anode for the alcohol fuel cells.

36 MATERIALS SCIENCE↗

Photocatalytic characteristics of single phase Fe-doped anatase TiO{sub 2} nanoparticles sensitized with vitamin B{sub 12}

Highlights: • Anatase TiO{sub 2}/B{sub 12} hybrid nanostructured catalyst was successfully synthesized by sol–gel technique. • The nanoparticle catalyst was doped with iron at several concentrations. • Nanoparticles were characterized in detail by XRD, Raman, TEM, EDS, and spectroscopy techniques. • The formation mechanism and role of point defects on photocatalytic properties were discussed. • A structure-property-processing correlation was established. - Abstract: We report a processing-structure-property correlation in B{sub 12}-anatase titania hybrid catalysts doped with several concentrations of iron. Our results clearly show that low-level iron doping alters structure, defect content, and photocatalytic characteristics of TiO{sub 2}. XRD and Raman studies revealed formation of a single-phase anatase TiO{sub 2} where no iron based segregation in particular iron oxide, was detected. FT-IR spectra clearly confirmed sensitization of TiO{sub 2} nanoparticles with vitamin B{sub 12}. TEM micrographs and diffraction patterns confirmed crystallization of anatase nanoparticles with a radius of 15–20 nm. Both XRD and Raman signals showed a peak shift and a peak broadening which are surmised to originate from creation of point defects, namely oxygen vacancy and titanium interstitial. The doped samples revealed a narrower band gap as compared to undoped samples. Photocatalytic activity of the samples was assessed through measuring the decomposition rate of rhodamine B. It was found that sensitization with vitamin B{sub 12} and Fe-doping significantly enhances the photocatalytic efficiency of the anatase nanoparticles. We also showed that there is an optimum Fe-doping level where the maximum photocatalytic activity is achieved. The boost of photocatalytic activity was qualitatively understood to originate from a more effective use of the light photons, formation of point defects, which enhance the charge separation, higher carrier mobility.

36 MATERIALS SCIENCE↗

Synthesis of monodisperse MFe{sub 2}O{sub 4} (M = Fe and Zn) nanoparticles for polydiethylsiloxane-based ferrofluid with a solvothermal method

Highlights: • MFe{sub 2}O{sub 4} nanoparticles were synthesized through a facile solvothermal method. • The relationship between viscosity and temperature of the polydiethylsiloxane-based ferrofluid is discussed. • Fe{sub 3}O{sub 4} nanoparticles have a saturation magnetization of 73.06 emu/g at room temperature. - Abstract: Monodisperse MFe{sub 2}O{sub 4} (M = Fe, Zn) nanoparticles were successfully synthesized for the application of polydiethylsiloxane-based (PDES) ferrofluids (FFs) via a novel solvothermal method, with which 1-octanol and 1-octanamine act as binary solvent, oleic acid (OA) as the surfactant and metal acetylacetonate [M(acac){sub 3}](M = Fe and Zn) as the metal source. X-ray diffractometer confirms that the resultant nanoparticles are pure MFe{sub 2}O{sub 4} with a spinel structure. Infrared spectroscopy indicates that oleic acid is bound to the surface of MFe{sub 2}O{sub 4} through a covalent bond between carboxylate (COO{sup −}) and metal cations. The ratio of 1-octanol and 1-octanamine plays a key role in the formation of the sphere-shaped morphology. Transmission electron microscopy (TEM) images confirm that the Fe{sub 3}O{sub 4} particles are of 4–11 nm with good monodispersity and a narrow size distribution. The saturation magnetization of Fe{sub 3}O{sub 4} nanoparticles with sizes of 7 nm can reach up to 73.06 emu/g. Polydiethylsiloxane-based (PDES) FFs show relatively smaller changes of the viscosity with low temperatures (from −7 to 20 °C) than the polydimethylsiloxane-based (PDMS) FFs. For FFs applications, the relationship between viscosity and temperature is also discussed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses: Preparation and their effects on photoluminescence of lanthanide complexes

Highlights: • Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses were prepared via the Stöber process. • Sm and Dy complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. • The complex-doped Ag@SiO{sub 2} composites show stronger luminescent intensities than pure complexes. • The luminescent intensities of the composites strongly depend on the SiO{sub 2} shell thickness. - Abstract: Three kinds of almost spherical core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses (10, 25 and 80 nm) were prepared via the Stöber process. The Ag core nanoparticles were prepared by reducing silver nitrate with sodium citrate. The size, morphology and structure of core–shell Ag@SiO{sub 2} nanoparticles were characterized by transmission electron microscopy. Subsequently, eight kinds of lanthanide complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. The composition of the lanthanide complexes was characterized by elemental analysis, IR and UV spectra. Finally, lanthanide complexes were attached to the surface of Ag@SiO{sub 2} nanoparticles to form lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites. The results show that the complex-doped Ag@SiO{sub 2} nanocomposites display much stronger luminescence intensities than the lanthanide complexes. Furthermore, the luminescence intensities of the lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites with SiO{sub 2} shell thickness of 25 nm are stronger than those of the nanocomposites with SiO{sub 2} shell thickness of 10 and 80 nm.

77 NANOSCIENCE AND NANOTECHNOLOGY↗