Effects of doping in 25-atom bimetallic nanocluster catalysts for carbon–carbon coupling reaction of iodoanisole and phenylacetylene

We here report the catalytic effects of foreign atoms (Cu, Ag, and Pt) doped into well-defined 25-gold-atom nanoclusters. Using the carbon-carbon coupling reaction of p-iodoanisole and phenylacetylene as a model reaction, the gold-based bimetallic MxAu25?x(SR)18 (–SR=–SCH2CH2Ph) nanoclusters (supported on titania) were found to exhibit distinct effects on the conversion of p-iodoanisole as well as the selectivity for the Sonogashira cross-coupling product, 1-methoxy-4-(2-phenylethynyl)benzene). Compared to Au25(SR)18, the centrally doped Pt1Au24(SR)18 causes a drop in catalytic activity but with the selectivity retained, while the AgxAu25?x(SR)18 nanoclusters gave an overall performance comparable to Au25(SR)18. Interestingly, CuxAu25?x(SR)18 nanoclusters prefer the Ullmann homo-coupling pathway and give rise to product 4,4′-dimethoxy-1,1′-biphenyl, which is in opposite to the other three nanocluster catalysts. Our overall conclusion is that the conversion of p-iodoanisole is largely affected by the electronic effect in the bimetallic nanoclusters’ 13-atom core (i.e., Pt1Au12, CuxAu13?x, and Au13, with the exception of Ag doping), and that the selectivity is primarily determined by the type of atoms on the MxAu12?x shell (M=Ag, Cu, and Au) in the nanocluster catalysts.     

Efficient Degradation 4-Nitrophenol by Photocatalysis from Modified TiO2 Doped Copper

In the present study,a film consisting of TiO_2 doped with copper was prepared for efficiently decomposing 4-nitrophenol(4-NP) by photocatalysis.The preparing process of TiO_2 doped with copper includes two procedures:preparing Ti(OH)_4 doped with copper and synthesizing anatase and rutile TiO_2 doped with copper.Ti(OH)_4 doped with copper could be achieved by hydrolyzing TiCl_4in the mixed solution containing deionized water and copper oxalate.The Ti(OH)_4 doped with copper can be gained successfully by the following procedures:rinsing,drying and vacuum drying.The Ti(OH)_4 doped with copper could be converted into anatase TiO_2 doped with copper and rutile TiO_2 doped with copper by incineration for 4.5 h at 723 and 1 073 K,respectively.Characterizations of anatase TiO_2 doped with copper and rutile TiO_2 doped with copper were determined by X-ray diffraction(XRD) and energy dispersion of X-ray(EDX).Anatase and rutile TiO_2 doped with copper were dissolved in a mixed solution containing isopropanol and diethylamine.Stainless electrode was submerged into with the solutions,the film of TiO_2 was formed by drying the thin layer at a ramp rate of 3℃/min until 373 K,and this temperature was held for 1 h.The temperature of the oven was subsequently increased to a final temperature of 823 K at a ramp rate of 3℃/min,and was held at this value for 1 h.The stainless steel covered with modified TiO_2 film was utilized as the anode.The stainless steel mesh was used as the cathode.The cathode and anode were connected with the source and immersed into the solution with 100 mg/L 4-NP.The whole reaction on photocatalysis was perfectly carried out after ultraviolet radiation and aerator were run.The experimental results showed that:cracking ratio of 4-NP ring,the removal ratio of chemical oxygen demand(COD) and total organic carbon(TOC) were respectively more than 90%,80% and 80% within 2 h.Degradation of 4-NP implied its potential application in associated wastewater.     

Induced modi fi cations in the properties of Sr doped BiFeO3 multiferr oics

Multiferroics exhibit unique combination of ferroic properties,simultaneously.For instance,in BiFeO3,magnetic and electric properties co-exist.In this work,BiFeO3 and Sr-doped BiFeO3 samples with general formula,Bi1-x Srx FeO3(x=0.00,0.05,0.10,0.20,and 0.30) were synthesized by sol-gel auto-combustion technique,in order to investigate these ferroic properties.The samples were confrmed to have perovskite type rhombohedral structure,characteristic of BiFeO3.A dilute phase of Bi2Fe4O9was also found in all the Sr-doped samples.The micrographs of the palletized samples revealed that minutely doped Sr might not have any effect on the morphology of the samples.Frequency dependent dielectric measurements were carried out at room temperature for all the samples from 100 Hz to 1 MHz.The dielectric constant of un-doped sample at low frequency was 52 which decreased with increasing Sr doping.An enhancement of magnetic properties was observed with increasing the Sr contents.Pure BiFeO3 material was observed to have the least value of remanent magnetization.As the Sr2+ tions were doped in BiFeO3,its magnetization and remanence were increased to 0.867 emu/g and 0.175 emu/g,respectively,at x=0.30.     

Fabrication of SrFe_(12-x)Ni_xO_(19) nanoparticles and investigation on their structural,magnetic and dielectric properties

Sr Fe12-xNixO19 nanoparticles(x = 0–1) were synthesized by a combustion sol–gel method. Their structure, dielectric and magnetic properties were investigated by X-ray diffraction(XRD), scanning electron microscopy(SEM), an LCR metry, and vibrating sample magnetometry(VSM).The results reveal that all samples of Ni doped compounds(Sr Fe12-xNixO19) with x 0.2 are single phase. It appears that the Fe3+ ions are substituted by Ni2+ ions on the crystallographic sites of the Sr Fe12O19 structure; however, for x ≥ 0.2, the secondary Ni phase ferrite(Ni Fe2O3) appears, which reduces the saturation magnetization and coercivity. In addition, Ni doping reduces the dielectric constant, dielectric loss, and alternating current(ac) electrical conductivity of the samples. The variation in ac conductivity(σac) with frequency shows that the electrical conductivity in these ferrites is mainly attributed to the electron hopping mechanism.Therefore; all the single-phase Ni doped samples are suitable for use in magnetic recording media and microwave devices.     

Catalytic combustion properties of nanocomplex oxide for natural gas

The catalysts of copper oxide supported on cerium dioxide were prepared by different methods for methane catalytic combustion. The effects of copper content in the catalysts and calcination temperatures of the catalysts on the catalytic activity are investigated. Results show that the complex oxide catalyst exhibits high catalytic activity for methane combustion due to the synergistic effect of CuO and CeO₂. The catalyst prepared by impregnation is more active than that prepared by controlled coprecipitation even if CuO content is the same. When W(CuO)<13%, the light-off temperature and full conversion temperature for the CH₄ reaction decrease with the increasing of CuO content in the catalysts. However, when the copper content is above 13%, the excess CuO has a negative effect on the catalytic activity owing to the formation of bulk CuO particles. A proper calcinations temperature of 650 ℃ can lead to a high dispersion of CuO and accordingly can enhance the catalytic activity of the composites.     

Electrical anisotropy of oriented trans-polyacetylene undoped and doped with SO3

We use extended Hückel methods of molecular orbitds and crystal orbitals (EHMO/CO) to calculate the two-dimensional band structures of highly oriented trans-polyacetylene (PA) undoped and doped with SO3. According to the energy band theory of solids, we explain the changes of band gap (Eg) and bandwidth (BW) from undoped PA to SO3-doped PA, and discuss the electrical anisotropy of oriented trans-polyacetylene doped with SO3. The calculated results show that the conductivity anisotropy ratio (σ∥/σ┴) is determined by Eg and BW in the directions both parallel (σ∥) and perpendicular (σ┴) to the PA chains, respectively. The conductivity anisotropy ratio σ∥/σ┴ decreases when PA is doped with SO3, because the dopant plays a conjugated bridge role between the interchains of PA, and makes the dopant itself and PA chains show a strong interchain coupling. The theoretical results for undoped and doped PA are in good agreement with experimental ones.     

Electrical anisotropy of orientedtrans-polyacetylene undoped and doped with SO3

We use extended Huckel methods of molecular orbitds and crystal orbitals (EHMO/CO) to calculate the two-dimensional band structures of highly oriented trans-polyacetylene (PA) undoped and doped with SO3. According to the energy band theory of solids, we explain the changes of band gap (Eg) and bandwidth (BW) from undoped PA to SO3-doped PA, and discuss the electrical anisotropy of oriented trans-polyacetylene doped with SO3. The calculated results show that the conductivity anisotropy ratio (σ///σ⊥) is determined by Eg and BW in the directions both parallel (σ//) and perpendicular (σ⊥) to the PA chains, respectively. The conductivity anisotropy ratio σ///σ⊥ decreases when PA is doped with SO3, because the dopant plays a conjugated bridge role between the interchains of PA, and makes the dopant itself and PA chains show a strong interchain coupling. The theoretical results for undoped and doped PA are in good agreement with experimental ones.     

Effect of annealing on properties of Mg doped Zn-ferrite nanoparticles

A comparison of structural and magnetic properties of as-prepared and annealed(900 1C) Mg doped Zn ferrite nanoparticles(Zn1 xMgxFe2O4,with x=0, 0.1, 0.2, 0.3, 0.4 and 0.5) is presented. X-ray diffraction(XRD) studies confirmed the cubic spinel structure for both the as-prepared and annealed nanoparticles. The average crystallite size and lattice parameter were increased by annealing. Scanning electron microscopy(SEM)images also showed that the average particle size increased after annealing. Fourier transform infrared spectroscopy(FTIR) also confirmed the spinel structure for both series of nanoparticles. For both annealed and as-prepared nanoparticles, the O–Mtet.–O vibrational band shifts towards higher wave numbers with increased Mg concentration due to cationic rearrangement on the lattice sites. Magnetization studies revealed an anomalous decreasing magnetization for the annealed nanoparticles which is also ascribed to cationic rearrangement on the lattice sites after annealing. The measurement of coercivity showed a decreasing trend by annealing due to the increased nanoparticle size and better crystallinity.     

Enhancement of figure of merit (ZT) by doping Bi in Mg2Si for energy harvesting applications

Magnesium Silicide is one of the interesting thermoelectric materials known for relative abundance of its constituents, thermal stability, non-toxicity and environmental friendly nature. In this paper we have theoretically studied Bi doped Mg_2Si. The electronic structure calculations predict non-existence of the energy gap for Mg_2Si_(1-x)Bi_x with(0.125≤ x≤0.5). It has been found that the system with x=0.125 exhibits highest Seebeck coefficient and electrical conductivity. Due to low thermal conductivity at x=0.125, Mg_2Si_(0.875)Bi_(0.125) attained maximum value of dimensionless figure of merit 0.67 at 1200 K. With increase in concentration of Bi,the value of figure of merit decreases.     

Doping inorganic ions to regulate bioactivity of Ca –P coating on bioabsorbable high purity magnesium

Performance of biomaterials was strongly affected by their surface properties and could be designed artificially to meet specific biomedical requirements. In this study, F(F), Si O2 4(Si), or HCO 3(C)-doped Ca–P coatings were fabricated by biomimetic deposition on the surface of biodegradable high-purity magnesium(HP Mg). The crystalline phases, morphologies and compositions of Ca–P coatings had been characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and energy-dispersive spectroscopy(EDS). The biomineralization and corrosion resistance of doped Ca–P coatings had also been investigated. The results showed that the Ca–P coating with or without doped elements mainly contained the plate-like dicalcium phosphate dehydrate(DCPD) phase. The doped F, Si, or C changed the surface morphology of Ca–P coatings after mineralization. Doped F enhanced the mineralization of Ca–P coating, and doped Si retarded the mineralization of Ca–P coating.However, H2 evolution of HP Mg discs with different Ca–P coatings was close to 0.4–0.7 ml/cm2 after two-week immersion. That meant that the corrosion resistance of the Ca–P coatings with different or without doped elements did not change significantly.     

White organic light-emitting devices using Zn（BTZ）2 doped with Rubrene as emitting layer

Zn(BTZ)2 was synthesized from the complex reaction between zinc acetate dihydrate and 2-(2-hydroxyphenyl) benzothiazolate. Then Zn(BTZ)2 was used as main light-emitting material doped with different amounts of fluorescent dye Rubrene and fabricated a series of white organic light emitting devices. The configurations were as follows: ITO/PVK:TPD/Zn(BTZ)2:Rubrene/Al. The doping concentration of Rubrene in Zn(BTZ)2 was 1.2%, 0.12%, 0.08% and 0.05%, respectively. According to the EL spectra and CIE coordinates of the above devices, the optimum doping concentration (0.05%, weight percent) had been determined. The steady and bright white light emitting of the device with 0.05% doping concentration had been obtained, and the white emission covered a wide range of driving voltage (10--22.5 V). The CIE coordinates were (x=0.341, y=0.334) at the driving voltage of 20 V, which was very close to the equi-energy point (x=0.333, y=0.333), and the corresponding luminance and external quantum efficiency were 4048 Cd/m^2 and 0.63% (4.05 Cd/A), respectively. Lastly, we also discussed the emitting mechanisms of the material and the devices.     

Near-infrared to visible up-conversion emissions of Er^3＋ doped Al2O3 powders derived from the sol-gel method

The Er3 doped Al2O3 powders were prepared by the sol-gel method using the aluminium isopropoxide [Al(OC3H7)3]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)3.5H2O]. The different phase structure, including three crystalline types of (Al,Er)2O3 phases, γ, θ, α, and two Er-Al-O phases, ErAlO3 and Al10Er6O24, was obtained with the 1 mol% Er3 doped Al2O3 powders at the different sintering temperatures of 600―1200℃. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the 2H11/2, 4S3/2→4I15/2 and 4F9/2→4I15/2 transitions of Er3 , were detected by a 978 nm semiconductor laser diodes excitation. The phase structure and OH content had evident influence on the up-conversion emissions intensity. The maximum intensities of both the green and red emissions were obtained respectively for the Er3 doped Al2O3 powders sintered at 1200 ℃, which was composed mainly of α-(Al,Er)2O3, less of ErAlO3 and Al10Er6O24 phases, and with the least OH content. The two-photon absorption up-conversion process was involved in the green and red up-conversion emissions of the Er3 doped Al2O3 powders.     

Improved photocatalytic activity of nano CuO-incorporated TiO2 granules prepared by spray drying

4 wt% CuO–96 wt% TiO2 granules were prepared by a spray drying process. The microstructure and optical property of CuO–TiO2 granules were studied. The results indicate that copper existed in the form of CuO. The spray dried granules possess spherical geometry and smooth surface with grain size in the range of 40–80 μm. CuO–TiO2 has a relatively smaller E g value(2.85 eV) than Ti O2(3.17 eV). The photocatalytic property of CuO–TiO2 granules was investigated by degradation of a model pollutant(the azo dye methyl orange) under the irradiation of the xenon lamp equipped with a band pass fi lter of 365 nm. The CuO–TiO2spray-dried granules degrade about 10% more MO than TiO2spray-dried granules under UV irradiation within the same time. The XPS spectra suggested that Cu2 tand reduced copper species were coexistent in reacted CuO–TiO2 photocatalyst. The improvement of photocatalytic activity for CuO–TiO2 was mainly attributed to effective separation of photogenerated electron–hole pairs in the presence of CuO.     

Microstructural features of flower like Fe brushite

The iron doped brushite(Fe-DCPD) nano particles were synthesized via co-precipitation method with Fe concentrations(0 ≤x≤ 1) in steps 0.2. The influence of iron concentration on the crystallinity, particle shape,morphology, optical, magnetic and electrical properties was investigated. The results showed that iron doping content is the crucial factor in the variation of physical properties. The particle shape changed from spheres at x=0.2 to be fiber network at x = 0.8. The saturation magnetization(Ms) increased from 0.4(emu/g) at x = 0.2 to 1.6(emu/g) at x = 0.8 which is considered more than four times with a considerable decrease of coercive field.     

Fabrication and superconducting properties of nano-SiC doped MgB2 tapes

Nano-SiC doped MgB2 tapes were prepared by the in situ powder-in-tube method. Heat treatment was performed at 650℃ for 1 h. XRD data indicate that SiC particles had reacted with the MgB2 during sintering process. MgB2 core seemed to be denser after SiC doping, and the critical temperature was slightly depressed. The critical current density Jc of the SiC doped tapes was significantly enhanced in magnetic fields up to 14 T compared to the undoped ones. For the 5% SiC doped samples, Jc was in- creased by a factor of 32 at 4.2 K, 10 T. The enhancement of Jc-B properties in SiC doped MgB2 tapes is considered to be due to the enhancement of grain linkages and the introduction of effective flux pining centers. The substitution of B by C in MgB2 grains is thought to be the main reason for the improve- ment of the flux pinning ability in SiC doped MgB2 tapes.     

Fabrication of SrFe12-xNixO19 nanoparticles and investigation on their structural,magnetic and dielectric properties

SrFe12?xNixO19 nanoparticles (x = 0–1) were synthesized by a combustion sol–gel method. Their structure, dielectric and magnetic properties were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), an LCR metry, and vibrating sample mag-netometry (VSM).The results reveal that all samples of Ni doped compounds (SrFe12?xNixO19) withx < 0.2 are single phase. It appears that the Fe3+ions are substituted by Ni2+ ions on the crystallographic sites of the SrFe12O19 structure; however, forx≥ 0.2, the secondary Ni phase ferrite (NiFe2O3) appears, which reduces the saturation magnetization and coercivity. In addition, Ni doping reduces the dielectric con-stant, dielectric loss, and alternating current (ac) electrical conductivity of the samples. The variation in ac conductivity (σac) with frequency shows that the electrical conductivity in these ferrites is mainly attributed to the electron hopping mechanism.Therefore; all the single-phase Ni doped samples are suitable for use in magnetic recording media and microwave devices.     

Structure and transport studies on nanometer YBCO/PBCGO multilayers

We have fabricated M doped （M = Al, Co, Fe, Ga, Ni and Zn） PrBa2Cu3O7（PBCO）, i.e. PrBa2（CU1-xMx）3O7. The doping levels x are 0.05, 0.10, 0.15, and 0.20. X-ray data indicated no significant second phase for substituting Cu by Al, Co, Fe and Ga up to 20%. However impurity phases were detected for Ni and Zn substituted samples with doping levels equal to and higher than 15%. At 77 K the electrical resistivity of these compounds is orders in magnitude higher than that of PBCO. We also found that although the lattice parameters in the doped samples differ from PBCO, all samples remain orthorhombic. The lattice parameters of the doped sample are very close to those of YBa2CU3O7-δ （YBCO） and PBCO. For this reason these compounds are better materials to be used as the I-layer for YBCO SIS junctions. Results of structural and transport studies on 2000 A thick PrBa2[Cu0.80G0.2]3O7 （PBCGO） and YBCO/PBCGO multilayers are presented in this paper.     

Improvements of dielectric properties of Cu doped LaTiO_(3+δ)

The ceramic composites of Cu-doped La_(1-x )Cu_x TiO_(3+δ)(x=0.05, 0.15, 0.3, 0.5) were synthesized by conventional solid-state reaction. The complex dielectric properties of the composites were investigated as a function of temperature(77 K ≤T≤ 320 K) and frequency(100 Hz ≤ f ≤1 MHz) separately. In all composites, the dielectric constants increase monotonously and the dielectric loss undulates with temperature. And it is clearly observed that extraordinarily high low-frequency dielectric constant(～10~4)appear at room temperature in La_0.5Cu_0.5TiO_(3+δ), which is 100 times larger than that of La_0.95Cu_0.05 TiO_(3+δ). Interestingly, the dielectric constants increase remarkably with the doped Cu contents, meanwhile the dielectric loss for all samples is ideal lower than 1 at room temperature in the measured frequency range. By means of complex impedance analysis, the improvements of dielectric properties are attributed to both bulk contribution and grain boundary effect, in which the bulk polaronic relaxation and the Maxwell–Wagner relaxation due to grain boundary response are heightened remarkably with the high doped Cu contents.     

Synthesis of ZnWO4−x nanorods with oxygen vacancy for efficient photocatalytic degradation of tetracycline

Persistent organic pollutants (POPs) especially tetracycline pose a great threat to human health, and the photocatalytic degradation of tetracycline by ZnWO4 nanomaterials has drawn much attention. To improve the photo-response range and photoactivity, we prepared ZnWO4?x sample with oxygen vacancies by solvothermally treating Zn(NO3)3 and Na2WO4 in water/ethanol/PEG-400 mixture where ethanol could act as a reducing agent to selectively remove some oxygen atoms from ZnWO4. ZnWO4?x sample is composed of nanorods with length of ~50 nm and diameter of ~20 nm. Furthermore, ZnWO4?x nanorods are brown and exhibit the obviously broadened photoabsorption from ultraviolet (UV) to near infrared (NIR) region, compared with the tradition white ZnWO4 nanorod without oxygen vacancies and with UV absorption edge of 365 nm. Under the irradiation of UV or ultraviolet-visible-near infrared (UV–Vis–NIR) light, ZnWO4?x nanorods can photocatalytically degrade 91% or 78% tetracycline, higher than those (67% or 71%) by ZnWO4 nanorods. The enhanced photocatalytic efficiency can be attributed to the introduction of oxygen vacancies which have been found to reduce photogenerated electron-hole pair recombination and narrow band gap.     

Influence of Te doping on the dielectric and optical properties of InBi crystals grown by directional freezing

Stoichiometric pure and tellurium (Te) doped indium bismuthide (InBi) were grown using the directional freezing technique in a fabricated furnace. The X-ray diffraction profiles identified the crystallinity and phase composition. The surface topographical features were observed by scanning electron microscopy and atomic force microscopy. The energy dispersive analysis by X-rays was performed to identify the atomic proportion of elements. Studies on the temperature dependence of dielectric constant (?), loss tangent (tanδ), and AC conductivity (σ_ac) reveal the existence of a ferroelectric phase transition in the doped material at 403 K. When InBi is doped with tellurium (4.04 at%), a band gap of 0.20 eV can be achieved, and this is confirmed using Fourier transform infrared studies. The results thus show the conversion of semimetallic InBi to a semiconductor with the optical properties suitable for use in infrared detectors.