Influence of hydroxyapatite on maghemite-to-hematite phase transfer of FeO x -hydroxyapatite composite

FeO _x -hydroxyapatite (FeO _x -HAP) composites with different FeO _x contents were prepared, and compared with pure FeO_x, the FeO _x -HAP composites exhibit strongly magnetic behavior in an external magnetic field even after 600 °C calcination. The combination of ⁵⁷Fe Mössbauer and Fe K-edge XAFS indicates that HAP can stabilize the size and crystal phase of γ-Fe₂O₃ during heat treatment. Even after 600 °C calcination, the interaction imposed by HAP could produce large amounts of distorted octahedral coordination Fe sites in the interior lattice and then result in strong magnetism. The thermally stable γ-Fe₂O₃-HAP composites may provide a new opportunity for developing efficient supported crystal-dependent catalysts.     

Synthesis and characterization of LiMn1-x Fe x PO4/carbon nanotubes composites as cathodes for Li-ion batteries

Carbon nanotubes (CNT) coated with LiMn_1-x Fe _x PO₄ (0.2?≤?x?≤?0.8), as possible cathode materials, was synthesized by using a sol–gel process (Polyol method), after annealing under flowing nitrogen. X-ray diffraction (XRD) patterns of the composites confirmed the formation of the olivine structured LiMn_1-x Fe _x PO₄ phase and no secondary phases were detected. The morphological investigation revealed the formation of agglomerates with particles size ranging between 300 and 700 nm. XRD investigation of composites shows difference of the morphology by doping CNT and carbon black in the composites. Transmission electron microscopy shows the growth of nano-sized particles on CNT (20–70 nm) and the agglomeration of primary particles to form secondary particles. The X-ray photoelectron spectroscopy showed that the Fe and Mn ions are in divalent states in the LiMn_1-x Fe _x PO₄ composites. The cyclic voltamograms showed the oxidation peaks of iron and manganese ions at 3.53–3.63 and 4.05–4.33 V, respectively, while the reduction peaks were found at 3.21–3.42 V (iron reduction) and 3.85–3.93 V (manganese reduction) depending on the iron content in the composition. The LiMn_0.6Fe_0.4PO₄/CNT composite (x?=?0.4) (with 20 %?wt CNT) delivered a specific capacity of 120 mAhg^?1 (at a discharge rate of C/20 and RT).     

Effects of CeO2-ZrO2 present in Pd/Al2O3 catalysts on the redox behavior of PdOx and their combustion activity

The ceria-zirconium-modified alumina-supported palladium catalysts are prepared using impregnation method with H₂PdCl₄ as Pd source, hydrazine hydrate as reducing agent. The physicochemical properties of these catalysts are characterized by BET surface area (BET), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), temperature programmed reduction (H₂-TPR) and temperature programmed oxidation (O₂-TPO) techniques, and their catalytic activities for the combustion of methane are examined. The results show that the palladium mainly exist in a highly dispersed PdO species on Ce-Zr-rich grains as well as Al₂O₃-rich grains surfaces, and a stable PdO species due to the strong interaction between PdO and CeO₂-ZrO₂ on the Ce-Zr/Al₂O₃ surfaces. The catalytic activity is strongly related to the redox behavior of PdO species highly dispersed on Ce-Zr-rich grains and Al₂O₃-rich grains surfaces, and the higher the reducibility of the PdO species, the higher the catalytic activity. The presence of Ce-Zr in Pd/Al₂O₃ catalyst would inhibit the site growth of PdO_x particles and decomposition of PdO to Pd⁰, and the reoxidation property of Pd⁰ to PdO_x is significantly improved, which obviously increases thermal stability and catalytic activity of Pd/Ce-Zr/Al₂O₃ catalyst for the methane combustion.     

Characterisation of Sonochemically Produced PdO Nanoparticles by X‐ray Absorption Near Edge Structure Spectroscopy

Brij‐35 [polyoxyethylene(23) lauryl ether] stabilised palladium nanoparticles, obtained on attempted sonochemical reduction of PdCl₂ by sodium sulfite in water under Argon, instantaneously oxidized to PdO. The particles obtained were stable and have narrow size distribution with an average size of 10 nm diameter. PdO nanoparticles were reduced to Pd nanoparticles in an autoclave by treatment with 50 bar hydrogen at 140 °C. The catalytic behaviour of Pd nanoparticles, thus obtained, is unusual in comparison with conventional Pd catalysts. The nanoparticles were characterized by UV‐Vis spectroscopy, TEM and their X‐ray Absorption Near Edge Structure (XANES) at the Pd‐L‐III edge.     

Dielectric study on Zn1−x Mg x O ceramic materials prepared by the solid-state route

The present work investigates the structural and dielectric properties of Zn_1?x Mg _x O composites prepared by the standard sintering method at 1200 °C during 24 h and doped with different weight percentages of MgO (x = 0–40 %). For this purpose, the scanning electron microscopy (SEM) was used to study the effect of the magnesium’s proportion on the morphology and crystallinity of the obtained samples. The SEM observations have shown rougher surfaces of the samples covered by grains having prismatic shapes and different sizes. The dielectric properties of the ceramics were investigated by spectroscopic impedance at different temperatures and frequencies, thus showing a frequency-dependent dispersion of the permittivity constants and dielectric losses. From these measurements, the relaxation processes were identified and their activation energies extracted. Dielectric responses were correlated with the microstructure and chemical composition of the ZnMgO composites. The mechanisms of ac conductivity are controlled by the polaron hopping and the electron tunneling models. Concerning the tunneling model, two types corresponding to the overlapping large polaron tunneling model for the composites Zn_0.9Mg_0.1O and Zn_0.8Mg_0.2O and the small polaron tunneling model for the composites Zn_0.64Mg_0.36O (in the frequency range 1.7 × 10⁴ Hz–1 MHz) and Zn_0.6Mg_0.4O were observed. Besides, one type of hopping model corresponding to the correlated barrier hopping for the composites ZnO and Zn_0.64Mg_0.36O (in the frequency range 6 × 10²–1.7 × 10⁴ Hz) was noted.     

Electroreduction of oxygen on Pd catalysts supported on Ti-modified carbon

Carbon supports modified with well dispersed anatase TiO₂ (C–Ti-X; X (0.25, 0.5, 0.75, and 1.0) represents mass ratio of Ti precursor to carbon) were synthesized with various Ti loadings and used to support Pd catalysts for oxygen reduction. The anatase nanoparticles increased in size with increasing Ti loading. Pd dispersion improved with increasing Ti loading up to the C–Ti-0.75, which resulted in the best catalytic activity. Although the Pd dispersion was lowest on the C–Ti-1.0, it showed better catalytic performance than the catalysts supported on C–Ti-0.25 and C–Ti-0.5. At 0.8 V (vs. RHE), the best catalytic activity achieved was respectively 2.7 and 2.7 times the mass and specific activities of Pd supported on un-modified carbon. The interaction between Pd and highly dispersed TiO₂ is believed to improve the catalytic activity of Pd supported on TiO₂-modified carbons.     

Study of Au/SnO x –Al2O3 catalysts used in CO oxidation by in situ Mössbauer spectroscopy

The active catalytic components in tin oxide containing alumina-supported gold catalyst were examined by comparing and analysing the in situ Mössbauer spectra of the SnO _x –Al₂O₃ support and the 3 wt.% Au/SnO _x –Al₂O₃ catalyst (1.1 wt.% Sn, Au/Sn = 3:2 atomic ratio). Samples were prepared by using organometallic precursor of ¹¹⁹SnMe₄ (enriched). First tin was grafted to the alumina surface from the organometallic precursor compound. In the next step the grafted complexes were decomposed in flowing oxygen. Gold was deposited onto the SnO _x –Al₂O₃ support in the subsequent step. Analysis of in situ spectra shows that in Au/SnO _x –Al₂O₃ catalyst after activation in hydrogen at 620 K tin may occur in three different oxidation states [Sn (IV), Sn(II) and Sn(0)] simultaneously. The metallic tin is a component of the bimetallic AuSn alloy phase. Data presented provide the first evidence for the formation of alloy-type supported Sn–Au catalyst on alumina. Furthermore, from the spectra recorded at different temperatures, values of the Debye temperatures and recoilless fractions were also determined for the various species. The results show that in catalytic oxidation of carbon monoxide at room temperature the dominant part of Sn(II) and the AuSn alloy is oxidized.     

Oxidation of benzene on a vanadium-molybdenum catalyst in the presence of thiophene

The catalytic oxidation of benzene by air oxygen on a vanadium-molybdenum mixed oxide (1 ? x)V₂O₅ · xMoO₃ (x = 0.25) over a temperature range of 200–320°C is studied. It is shown that the introduction of small amounts of thiophene into benzene inhibits the oxidation to maleic anhydride in this temperature range. It is established that the operation of the catalyst is accompanied by significant changes in its phase composition and morphology, with a few first operation cycles being characterized by a high conversion of benzene. A possible mechanism of the process is proposed.     

Synthesis,characterization, and electrochemical performance of nitrogen-modified Pt–Fe alloy nanoparticles supported on ordered mesoporous carbons

A method has been demonstrated to synthesize nitrogen-modified Pt–Fe alloyed nanoparticles (9.2–11.3 nm) supported on ordered mesoporous carbon (Pt _x Fe_100?x N/OMC), which is fabricated by a conventional wet chemical synthesis of Pt–Fe alloyed nanoparticles and followed by carbonization of the nanoparticles with tetraethylenepentamine as nitrogen chelating agent. Among these electrocatalysts, the Pt₃₀Fe₇₀N/OMC has highly catalytic activity for the oxygen reduction reaction (ORR) with significantly enhanced methanol tolerance as well. Combining the results from X-ray diffraction and X-ray absorption spectroscopy, it can be observed that Pt metal in the Pt₃₀Fe₇₀N/OMC is present in the outer shell of Pt–Fe alloys with face-centered cubic crystalline structure. By X-ray photoelectron spectroscopy, the nitrogen-modified Pt surface of Pt₃₀Fe₇₀N/OMC exhibits significant selectivity toward the ORR in the presence of methanol. This enhancement of methanol tolerance could be attributed to the inhibition of methanol adsorption resulting from the modification of the Pt surface with nitrogen.     

Surface properties of palladium catalysts supported on ternary ZrO2–Al2O3–WOx oxides prepared by the sol–gel method: Study of the chemical state of the support

The surface properties of Pd and Pd–Pt catalysts supported on binary ZrO₂–WOx and ternary ZrO₂–Al₂O₃–WOx oxides prepared by the sol–gel method were studied. Special attention was paid to the study of the texture of the catalysts as well as the chemical state of tungstated zirconia and tungstated zirconia promoted with alumina in the palladium catalysts. The catalysts were tested in the isomerization of n-hexane and were characterized by N₂ physisorption, XRD, TPR, Raman spectroscopy, XPS and FT-IR of adsorbed pyridine. The catalysts had bimodal pore size distributions with mesopores in the range 55–70 Å and macropores of 1000 Å in diameter. The catalysts had a surface WOx coverage (4.4–6.0 W nm^?2) lower than that of the theoretical monolayer (7.0 W nm^?2). A lower acidity of the ternary ZrO₂–Al₂O₃–WOx oxide as compared to the binary ZrO₂–WOx oxide was found. Higher activity in the isomerisation of n-hexane was obtained in the Pd–Pt catalysts supported on ternary ZrAlW oxides prepared by sol–gel that is correlated with the coexistence on the surface of W⁴⁺ (WO₂) or W⁰ and W⁶⁺ (Al₂(WO₄)₃) species, ZrO₂ in the tetragonal phase and a high amount of ZrOx suboxides species in a low oxidation state (Zr³⁺ and Zr²⁺).     

In situ,facile synthesis of La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript>/nitrogen-doped graphene: a high-performance catalyst for rechargeable Li-O<Subscript>2</Subscript> batteries

We have successfully devised a simple method to synthesize La_0.8Sr_0.2MnO₃ with nitrogen-doped graphene composites (LSM/NrGO) and investigated their catalytic performance in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Interestingly, the LSM/NrGO composites demonstrate outstanding catalytic performance in ORR, including high limiting current density and superior onset potential, compared to bare LSM nanocrystals or nitrogen-doped graphene, showing a performance close to that of commercial Pt/C. Moreover, Li-O₂ batteries assembled based on the LSM/NrGO catalysts exhibited brilliant performance, especially during long-term cycling, where the terminal discharge voltage still exceeded 2.31 V after 360 cycles. The excellent catalytic performance is mainly attributed to the large specific surface area (152.24 m² g^?1) of the materials, which provides many catalytic active sites, and the mesoporous structure (2 to 50 nm), which can facilitate the penetration of oxygen molecules into the surface of the nanoparticles and mass transfer.     

Ion beam shaping of embedded metal nanoparticles by Si+ ion irradiation

Fine Co and Pt nanoparticles are nucleated when a silica sample is implanted with 400 keV Co⁺ and 1370 keV Pt⁺ ions. At the implanted range, Co and Pt react to form small Co _x Pt_(1?x) nanoparticles during Si⁺ ion irradiation at 300 °C. Thermal annealing of the pre-implanted silica substrate at 1000 °C results in the formation of spherical nanoparticles of various sizes. When irradiated with Si⁺ ions at 300 °C, particles in the size range of 5–17 nm undergo rod-like shape transformation with an elongation in the direction of the incident ion beam, while those particles in the size range of 17–26 nm turn into elliptical shape. Moreover, it is suspected that very big nanoparticles (size >26 nm) decrease in size, while small nanoparticles (size <5 nm) do not undergo any transformation. During Si⁺ ion irradiation, the crystalline nature of the nanoparticles is preserved. The results are discussed in the light of the thermal spike model.     

Dielectric relaxation in NBT–ST ceramic composite materials

Lead-free piezoelectric ceramic composites (1-x) Na_0.5Bi_0.5TiO₃-xSrTiO₃, where x?=?0.05, 0.10, 0.15 and 0.2, are prepared by mixing independently-prepared individual phases through sol–gel method. X-ray diffraction revealed the coexistence of rhombohedral and cubic phases. Surface morphology of the composites is observed using SEM, and both the phases are observed in the samples. Spectroscopic studies of the composites are characterized based on Fourier transform infrared, and vibration bands are analyzed at room temperature in the wave number region 500–3,000 cm^?1. Dielectric properties of these composites are measured from room temperature to 400 °C in the frequency range 1–10 kHz, and these studies indicate the presence of defect clusters within the composite materials. P–E hysteresis loops of these samples were measured as a function of temperature and observed large anomalies in the behavior compared to pure sodium bismuth titanate (NBT) (the host material). Unlike NBT, all the composites exhibited excellent P–E loops. In addition, decrease in remanence polarization is observed, with increase of SrTiO₃ at room temperature. Piezoelectric parameter d₃₃ is measured on poled composites.     

Magnetic M<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>@N-C as heterogeneous catalysts for the catalytic oxidation of aniline solution with sulfate radicals

Metal nanoparticles have been combined with magnet metal–organic frameworks (MOFs) to afford new materials that demonstrate an efficient catalytic degradation, high stability, and excellent reusability in areas of catalysis because of their exceptionally high surface areas and structural diversity. Magnetic M _x O _y @N-C (M = Fe, Co, Mn) nanocrystals were formed on nitrogen-doped carbon surface by using 8-hydroxyquinoline as a C/N precursor. The Co@N-C, MnO@N-C, and Fe/Fe₂O₃@N-C catalysts were characterized by X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), N₂ adsorption/desorption, and X-ray photoelectron spectroscopy (XPS). The catalytic performances of catalysts were thoroughly investigated in the oxidation of aniline solution based on sulfate radicals (SO₄ ^?.) toward Fenton-like reaction. Magnetic M _x O _y @N-C exhibits an unexpectedly high catalytic activity in the degradation of aniline in water. A high magnetic M _x O _y @N-C catalytic activity was observed after the evaluation by aniline degradation in water. Aniline degradation was found to follow the first-order kinetics, and as a result, various metals significantly affected the structures and performances of the catalysts, and their catalytic activity followed the order of Co > Mn > Fe. The nanoparticles displayed good magnetic separation under the magnetic field.

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Graphical Abstract ?

     

Optical and structural properties of Zn1−x Mg x O ceramic materials

This paper reports structural, optical and cathodoluminescence characterizations of sintered Zn_1?x Mg _x O composite materials. The effects of MgO composition on these film properties have been analyzed. X-ray diffraction (XRD) confirms that all composites are polycrystalline with prominent hexagonal wurtzite structure along two preferred orientations (002) and (101) for the crystallite growth. Above doping content x = 10 %, the formation of the hexagonal ZnMgO alloy phase and the segregation of the cubic MgO phase start. From reflectance and absorption measurements, we determined the band gap energy which tends to increase from 3.287 to 3.827 eV as the doping content increases. This widening of the optical band gap is explained by the Burstein–Moss effect which causes a significant increase of electron concentration (2.89 × 10¹⁸?5.19 × 10²⁰ cm^?3). The luminescent properties of the Zn_1?x Mg _x O pellets are studied by cathodoluminescence (CL) at room and liquid nitrogen temperatures under different electron beam excitations. At room temperature, the CL spectra of the Zn_1?x Mg _x O composites exhibit a dominant broad yellow-green light band at 2.38 eV and two ultraviolet emission peaks at 3.24 and 3.45 eV corresponding to the luminescence of the hexagonal ZnO and ZnMgO structures, respectively. For the doped ZnO samples, it reveals also new red peaks at 1.72 and 1.77 eV assigned to impurities’ emissions. However, the CL spectra recorded at 77 K show the presence of excitonic emission peaks related to recombination of free exciton (X _A), neutral donor-bound excitons (D⁰X) and their phonon replicas. The CL intensity and energy position of the green, red and ultraviolet emission peaks are found to depend strongly on the MgO doping content. The CL intensity of the UV and red emissions is more enhanced than the green light when the MgO content increases. CL imaging analysis shows that the repartition of the emitting centers in Zn_1?x Mg _x O composites is intimately connected to the film composition and surface morphology.     

Structure and optical properties of Cd-substituted ZnO (Zn1−x Cd x O) thin films synthesized by the dc reactive magnetron sputtering

The ternary Zn_1?x Cd _x O (x = 0, 0.2) thin films with wurtzite structure and highly (002)-preferred orientations were deposited on glass substrates by the direct current (dc) reactive magnetron sputtering method. The X-ray diffraction, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), optical absorption spectra and photoluminescence (PL) were employed to investigate the structural and the optical properties in detail. The results indicated that as x varied from x = 0–0.2, the diffraction angle of the (002) peaks decreased from ~34.36° to ~33.38° and the lattice spacing increased from 0.260 to 0.268 nm. Moreover, the optical band-gap of the Zn_1?x Cd _x O thin films with the wurtzite structure decreased from 3.20 eV at x = 0–2.70 eV at x = 0.2. Correspondingly, the near-band-edge PL was tuned in a wide visible region from ~393 to 467 nm. The chemical bonding states of Cd in Zn_1?x Cd _x O alloy thin films were examined by XPS analysis.     

Effect of Co substitution for Fe in Sr2FeMoO6 on electrocatalytic properties for oxygen reduction in alkaline medium

Double perovskites Sr₂Fe_1???x Co _x MoO₆ (x?=?0, 0.25, 0.5, 0.75 and 1) have been investigated as cathode material for oxygen reduction reaction (ORR) in 0.5 M NaOH at 25 °C using the rotating disk electrode. The electrocatalytic powders were prepared by a solid-state process and characterised by X-Ray powder diffraction, scanning electron microscopy and infrared spectroscopy. The electrochemical techniques considered are linear voltammetry, steady-state polarization and impedance spectroscopy. The electrocatalysts Sr₂Fe_1???x Co _x MoO₆/C consisting of the double perovskite oxides and carbon (Vulcan XC-72) were mixed and spread out into a thin layer on a glassy carbon substrate. The electrocatalytic activity was strongly influenced by the Co substitution at room temperature. The relation between catalytic performance and the degree of Co content was examined. The Co-containing catalysts exhibited lower activity attributed to their high resistivity, and the highest activity toward oxygen reduction was observed for Sr₂CoMoO₆.     

Metal oxide-embedded porous carbon nanoparticles as high-performance anode materials for lithium ion batteries

Conjugated microporous polymer (CMP) was used as a precursor to fabricate porous carbon nanoparticles (PCNs) embedded with different metal oxides (NiO_x, CoO_x, and MnO_x). Rate performance tests indicate that 10% MnO_x embedded PCNs (MnO_x10-PCN) show superior rate performance over PCN. MnO_x10-PCN and PCN were further investigated by XRD, XPS, TG, SEM, TEM, FT-IR, BET, cyclic voltammetry, and galvanostatic discharge–charge test. XRD and XPS results reveal that MnO and MnO₂ phase co-exist in the MnO_x10-PCN. SEM results indicate that both MnO_x10-PCN and PCN are spherical particles with a size ranging from 20 to 50 nm. TEM results imply that MnO_x nanoparticles are incorporated inside some porous carbon nanoparticles. FT-IR results indicate some residuary benzene rings remain in the MnO_x10-PCN and PCN. BET analysis reveals that pore properties of MnO_x10-PCN are very near to that of CMP. These unique features ensure MnO_x10-PCN possesses high reversible capacity, excellent rate performance, and long cycling life. MnO_x10-PCN delivers an initial reversible capacity of 986 mAh g^?1 at 0.2 C. In addition, the capacity cycled at 2 C for 700 cycles is even higher than its original capacity.     

Ferrimagnetic nanoparticles for self-controlled magnetic hyperthermia

Based on the Heisenberg model including single-site uniaxial anisotropy and using aGreen’s function technique we studied the influence of size and composition effects on theCurie temperature T _C , saturationmagnetization M _S and coercivityH _C of spherical nanoparticles with astructural formulaM e _1?x Zn _x Fe₂O₄,Me = Ni, Cu, Co, Mn. It is shown that for x = 0.4–0.5and d = 10–20 nm these nanoparticles have aT _C  = 315 K and are suitable for aself-controlled magnetic hyperthermia.     

The local electronic structure of PdO crystal and PdO catalyst supported on SiO2 and γ-Al2O3 from L3 and L1 x-ray absorption Pd edge in XANES spectra

We have studied the local electronic structure of PdO catalysts supported on characteristic inert and quasi-inert substrate from experiment on X-ray absorption near edge structure XANES using Synchrotron radiation. From the joint analysis of L₃ absorption edge and XPS core data in Pd and PdO we find that the white line in PdO XANES is an excitonic state with 0.8 eV binding energy. From the joint analysis of L₃ and L₁ edges the p-like and the d-like local unoccupied electronic states have been determined. The local structure of PdO catalysts is different from that of PdO crystal. Evidence for structural disorder in PdO catalysts and PdO-substrate interaction is reported.