Computational Insights into Interactions between Ca Species and α-Fe_2O_3(001)

CaCl2 can be sprayed onto sinter surface,which can improve the low temperature reduction degradation index(RDI+3.15)of sinter.This has been recognized;however,there are various opinions on the inhibition mechanism of it.At the same time,the corrosion of Cl element on equipment is very serious.First-principle calculations based on density functional theory were performed to investigate the binding mechanisms of calcium species on a α-Fe2O3(0 0 1) surface.This is crucial in demonstrating the role of the CaCl2 on improving the low temperature reduction degradation index.It has been determined that Cl could greatly increase the adsorption of the vacuum layer for the Ca/Fe2O3 system and the relaxation produced by adsorption made bond length decrease,bond energies increase and structure compact.Those are the main reasons that inhibiting the reduction disintegration of sinter.     

Influence of Rinse on Self-Activated Luminescence in ZnS Nanocrystallite

The self-activated (SA) luminescence in ZnS nanoparticles was studied by comparing the UV-light irradiation induced spectral change, Raman spectra, and EPR spectra of the un-rinsed and rinsed samples. The results show that the SA centers prefer to occupy the sites near the surface and that the donor of SA emission may be related to organic functional groups such as - OH, - CH3, and - CO0. The EPR signals are enhanced remarkably in the rinsed nanoparticles comparing with that in the un-rinsed ones. It is believed that organic functional groups physically combine with the surface dangling bonds of ZnS nanoparticles, leading the nonradiauve transition channels to decrease, and thus the SA emission to increase     

Effects of Support on Catalytic Behavior of Combustion Catalyst La0.8Sr0. 2CoO3／γ-Al2O3

Combustion catalyst La0.8Sr0.2CoO3 (LSC) is expected to possess relatively high activity for the oxidation of carbon monoxide and many hydrocarbons. If γ-Al2O3 is used as its support, cobalt ions can easily react with γ-Al2O3 at not very high temperature to form spinel CoAl2O4 or spinel-like, which decreases the activity of the combustion catalyst. In this paper, MgAl2O4 and CaAl2O4 were pre-eoated on γ-Al2O3 by impregnation respectively, which formed compound support for LSC. It is shown that, when MgAl2O4 layer is covered on the surface of MgAl2O4 by impregnation, the entering of cobalt ions into γ-Al2O3 lattice is restrained, then LSC formed on the surface of MgAl2O4, which leads to a good catalytic activity of xylene complete oxidation. But the layer of MgAl2O4 should be thick enough to reach 30% (mass fraction) MgO in the support due to large size particle of MgAl2O4 crystalline. If polyvinyl alcohol (PVA) is added into the impregnation solution adequately, MgAl2O4 particles formed on the surface of γ-Al2O3 are getting smaller, and less amount of MgAl2O4 is needed to cover up the surface of γ-Al2O3. If CaAl2O4 layer substituted for MgAl2O4, more closed cover is obtained in virtue of fine particles of CaAl2O4. The activity examination shows that smaller particles of MgAl2O4 or CaAl2O4 Call be more effective to hinder cobalt ions entering the lattice of γ-Al2O3, and better activities will be obtained.     

Efficient removal of phosphate from aqueous solution using novel magnetic nanocomposites with Fe_3O_4@SiO_2 core and mesoporous CeO_2 shell

Fe_3O_4@SiO_2 magnetic nanoparticles functionalized with mesoporous cerium oxide(Fe_3O_4@SiO_2@mCeO_2) was fabricated as a novel adsorbent to remove phosphate from water. The prepared adsorbent was characterized by X-ray diffractometry(XRD), transmission electron microscopy(TEM), nitrogen adsorption-desorption and vibrating sample magnetometry(VSM), and its phosphate removal performance was investigated through the batch adsorption studies. Characterization results confirmed that mesoporous cerium oxide was successfully assembled on the surface of Fe_3O_4@SiO_2 nanoparticles, and the synthesized adsorbent possessed a typical core-shell structure with a BET surface area of 195 m~2/g, accessible mesopores of 2.6 nm, and the saturation magnetization of 21.11 emu/g. The newly developed adsorbent had an excellent performance in adsorbing phosphate, and its maximum adsorption capacity calculated from the Langmuir model was 64.07 mg/g. The adsorption was fast, and the kinetic data could be best fitted with the pseudo-second-order kinetic model. The phosphate removal decreased with the increase of solution pH(2 to 10), while the higher ionic strength slightly promoted the phosphate adsorption. The presence of Cl~– and SO~(2–)_4 could enhance the adsorption of phosphate whereas HCO~–_ 3 had interfering effect on the phosphate adsorption. The adsorption mechanism was studied by analyzing Zeta potential and FTIR spectroscopy, and the results indicated that the replacement of the surface hydroxyl groups by phosphate ions with the formation of inner-sphere complex played a key role in the phosphate adsorption. The spent adsorbent could be quickly separated from aqueous solution with the assistance of the external magnetic field, and the adsorbed phosphate could be effectively desorbed using a 1 mol/L NaOH solution.     

Effect of rare earths surface treatment on tribological properties of carbon fibers reinforced PTFE composite under oil-lubricated condition

The effect of rare earths （RE） surface treatment of carbon fibers （CF） on tribological properties of CF reinforced polytetrafluoroethylene （PTFE） composites under oil-lubricated condition was investigated. Experimental results revealed that RE treated CF reinforced PTFE （CF/PTFE） composite had the lowest friction coefficient and wear under various applied loads and sliding speeds compared with untreated and air-oxidated composites. X-ray photoelectron spectroscopy （XPS） study of carbon fiber surface showed that, after RE treatment, oxygen concentration increased obviously, and the amount of oxygen-containing groups on CF surfaces were largely increased. The increase in the amount of oxygen-containing groups enhanced interfacial adhesion between CF and PTFE matrix. With strong interfacial adhesion of the composite, stress could be effectively transmitted to carbon fibers; carbon fibers were strongly bonded with VITE matrix, and large scale rubbing-off of PTFE be prevented, therefore, tribological properties of the composite was improved.     

Surface Characteristics of Rare Earth Treated Carbon Fibers and Interfacial Properties of Composites

Effect of rare earth treatment on surface physicochemical properties of carbon fibers and interfacial properties of carbon fiber/epoxy composites was investigated, and the interfacial adhesion mechanism of treated carbon fiber/epoxy composite was analyzed. It was found that rare earth treatment led to an increase of fiber surface roughness, improvement of oxygeaa-containing groups, and introduction of rare earth element on the carbon fiber surface. As a result, coordination linkages between fibers and rare earth, and between rare earth and resin matrix were formed separately, thereby the interlaminar shear strength （ILSS） of composites increased, which indicated the improvement of the interfacial adhesion between fibers and matrix resin resulting from the increase of carboxyl and carbonyl.     

Effects of Support on Catalytic Behavior of Combustion Catalyst La0.8Sr0.2CoO3/γ-Al2O3

Combustion catalyst La0.8Sr0.2CoO3 (LSC) is expected to possess relatively high activity for the oxidation of carbon monoxide and many hydrocarbons. If γ-Al2O3 is used as its support, cobalt ions can easily react with γ-Al2O3 at not very high temperature to form spinel CoAl2O4 or spinel-like, which decreases the activity of the combustion catalyst. In this paper, MgAl2O4 and CaAl2O4 were pre-coated on γ-Al2O3 by impregnation respectively, which formed compound support for LSC. It is shown that, when MgAl2O4 layer is covered on the surface of MgAl2O4 by impregnation, the entering of cobalt ions into γ-Al2O3 lattice is restrained, then LSC formed on the surface of MgAl2O4, which leads to a good catalytic activity of xylene complete oxidation. But the layer of MgAl2O4 should be thick enough to reach 30% (mass fraction) MgO in the support due to large size particle of MgAl2O4 crystalline. If polyvinyl alcohol (PVA) is added into the impregnation solution adequately, MgAl2O4 particles formed on the surface of γ-Al2O3 are getting smaller, and less amount of MgAl2O4 is needed to cover up the surface of γ-Al2O3. If CaAl2O4 layer substituted for MgAl2O4, more closed cover is obtained in virtue of fine particles of CaAl2O4. The activity examination shows that smaller particles of MgAl2O4 or CaAl2O4 can be more effective to hinder cobalt ions entering the lattice of γ-Al2O3, and better activities will be obtained.     

Mechanisms of Enhancement of Photocatalytic Properties and Activity of Nd^3＋ -Doped TiO2 for Methyl Orange Degradation

Nd^3 -doped TiO2 powders were prepared by the sol-gel method. Their crystal pattern and parameter, the specific surface area, the surface chemical state of Ti and the ratio of O/Ti were characterized. The results show that Nd impurity hinders the crystal transformation, and decreases the relative intensity of (101) peak. The crystallite sizes of Nd^3 -doped TiO2 powders decrease while their specific surface area increase owing to the Nd^3 doping. The XPS measurement shows that the content of Ti (Ⅲ) and ratio of O/Ti on their surfaces increase significantly with the increase of Nd^3 dosage. The adsorption and photodegradation experiments show that the optimum molar content of Nd^3 is 1.2%.     

Enhancement of potassium resistance of Ce-Ti oxide catalyst for NH3-SCR reaction by modification with holmium

Alkali metal K in exhaust gas has a deactivation effect on NH₃-SCR catalysts.In this work,it is discovered that the addition of Ho on CeTi catalyst can remarkably strengthen its K tolerance.The conclusions of Brunauer-Emmett-Teller(BET),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),NH₃ temperature programmed desorption(NH₃-TPD)and H₂temperature programmed reduction(H₂-TPR)analyses demonstrate that the enhancement of K resistance mainly originates from its stronger surface acidity and redox capability,the higher concentration of Ce³⁺species and surface chemisorbed oxygen.In situ DRIFT analysis reveals that the introduction of Ho on CeTi can remarkably improve the adsorption of NH₃ and NO_x species on catalyst surface,accompanied by the intensified reactivity of ad-NH₃ species,which should also administer to improve the K resistance.     

Mechanism of Effect of Microwave Modification on Pulverized Coal Combustion Properties

The mechanism of microwave modification on facilitating the combustion properties of pulverized coal(PC)was investigated.Experimental researches on granularity and functional group as well as combustion properties of PC before and after modification were carried out.Micromorphology observation indicated that the size of PC particles was relatively small,which was in accordance with the results of granularity analysis of PC.FT-IR(Fourier-transform infrared)spectra of two PCs indicated that the proportion of the functional groups with high activity increased after microwave irradiation.Furthermore,no valid effect of microwave was found on carbon matrix except small variations in PC particle size,which only led to subtle improvement in combustion of residual coke.Activation energies of Yungang and Yangquan PCs in temperature zone between 450-650℃ were reduced by 12.00%and 10.13%,respectively,which meant that microwave modification might effectively facilitate the combustion properties of PC.Nevertheless,decrease in activation energies of residual cokes was 3.56%and 3.67%respectively,which was subtle and can be regarded as the result of smaller particle size produced by microwave irradiation.     

Glycine functionalized activated carbon derived from navel orange peel for enhancement recovery of Gd(Ⅲ)

Glycine functionalized activated carbon adsorption material (NOPAC-GLY-X) was successfully prepared by one-step thermal decomposition using agricultural waste navel orange peel as a precursor. Through batch adsorption experiments, it is found that the adsorption performance of Gd(III) on activated carbon can be significantly enhanced by glycine modification. The adsorption isotherms of the NOPACs conform to the Langmuir isotherm model, and the maximum adsorption capacity of the activated carbon sample NOPAC-Gly-60 is approximately 48.5 mg/g. The Gd(III) adsorption capacity of navel orange peel activated carbon can be doubled after glycine modification, and the adsorption efficiency of gadolinium can reach 99% at pH = 7. The physicochemical properties of the prepared adsorbents were characterized by Brunauer-Emmett-Teller (BET), Fourier transform infrared spectroscopy (FTIR), elemental analysis (EA), and X-ray photoelectron spectroscopy (XPS). The characterization test shows that the specific surface area of the sample increases from 1121 to 1523 m²/g, and the ratio of (N + O)/C increases from 10.8% to 30.0% by the glycine modification. After five cycles of adsorption–desorption, the adsorption capacity can still be maintained at 88% of the initial capacity. NOPAC-GLY-60 has excellent adsorption selectivity for Gd(III). With the obvious advantages of simple synthesis steps and low cost, the activated carbon modification method adopted in this study has great application value in the field of rare earth adsorption and recovery.     

Combined influence of Ce(Ⅲ) and iodide ions for corrosion protection of AA 2024-T3 in acidic to neutral chloride-rich environments:Electrochemical and surface characterization studies

It has been reported that trivalent cerium salts are effective inhibitors for corrosion of AA2024-T3 in neutral to alkaline co rrosive enviro nments,but poor in acidic environments.In this study,work was done for extending corrosion resistance provided by Ce(NO₃)₃ to acidic pHs as low as 2.5 through the addition of iodide ions.To this end,potentiodynamic polarization was used to ascertain the optimum Ce(Ⅲ)concentration for the inhibition of AA2024-T3 corrosion in 3.5%NaCl s...     

Synthesis of two lanthanide clusters LnIII4 (Gd4 and Dy4) with [2 × 2] square grid shape: Magnetocaloric effect and slow magnetic relaxation behaviors

Two isostructural tetranuclear lanthanide clusters named [Ln₄(L)₄(CH₃O)₄]·CH₃OH (Ln = Gd(III) for 1, Dy(III) for 2, H₂L = N′-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl) picolinohydrazide) were successfully isolated by using a polydentate Schiff based ligand and Ln(III) nitrate salts. The structures of 1 and 2 were characterized by X-ray structural analyses, they are held by four double deprotonated ligands L²⁻. In them all the lanthanide ions are eight-coordinated and distributed over four vertices of a parallelogram, presenting a Ln₄ cluster with a strict [2 × 2] square grid pattern. The details of magnetic analysis show that 1 displays weak anti-ferromagnetic exchange between neighboring Gd(III) ions through carboxylate oxygen and methanol oxygen ligand atoms. Furthermore, 1 exhibits significant magnetocaloric effect with the maximum entropy change –ΔS_m value of 28.5 J/(kg·K) for ΔH = 7.0 T at 2.0 K. For compound 2, remarkable slow magnetic relaxation behaviors are observed in the presence of zero magnetic field with τ₀ = 1.02 × 10⁻⁶ s and energy barrier ΔE/k_B = 43.24 K.     

Optical,thermal and luminescence properties of La2O3–Ga2O3–ZrO2 glasses co-doped with Tm3+/Yb3+ prepared by containerless technique

Bulk La₂O₃–Ga₂O₃–ZrO₂ (LGZ) glass and Tm³⁺/Yb³⁺ co-doped LGZ glasses were synthesized successfully using containerless technique. Raman spectra result reveals that the matrix sample possesses the low maximum phonon energy of ～642 cm^?1. The glasses show good compatibility between large Abbe numbers (>31) and high refractive indices (n_d > 1.93). Moreover, transmittance measurements reflect that the glasses have high infrared transmittance of ～81.9%, small OH^– absorption coefficient and long mid-infrared cut-off wavelengths (～7.5 μm). The surface morphology of host glass was characterized by scanning electron microscopy (SEM) micrograph and energy dispersive spectroscopy (EDS) tests reflect that the doped compositions are distributed into the matrix glass homogeneously. The results of thermal analysis show that the glasses have good thermal properties (T_g > 769 °C). Excited by 980 nm laser, an intense 1810 nm fluorescence is obtained originating from the transition: ³F₄ → ³H₆ of Tm³⁺ ion, accompanied by upconversion emission. It can be observed that 1810 nm fluorescence has the highest intensity at 1 mol% Yb₂O₃ and owns broad full width at half-maximum (>245 nm), the luminescence intensity of ³F₄ → ³H₆ transition increases with rising temperature from 300 to 550 K. Furthermore, the value of energy transfer efficiency shows that Yb³⁺ can transfer energy to Tm³⁺ effectively. By fitting the attenuation curves, the lifetimes of 1810 and 474 nm emission can be acquired.     

Adsorption behavior of rare earth elements using polyethyleneglycol (phosphomolybdate and tungstate) heteropolyacid sorbents in nitric solution

A new type of crystalline sorbent was prepared by the reaction of polyethyleneglycol (PEG) with phosphomolybdic (PMo) and phosphotungstic (PW) heteropolyacids. The morphology of the obtained sorbents was studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It has been shown that a complexing reaction occurs between PEG and the heteropolyacids. By using these sorbents, the adsorption behaviors of rare earth elements in nitric solution were studied. The effects of temperature, contact time, nitric acid and initial metal ion concentration on the adsorption were investigated. In 0.1–5.0 mol L^− 1HNO₃, the adsorption percentage decreases with the increase of acid concentration. H,PEG400,PW and H,PEG400,PMo exhibited a different selectivity for rare earth metals, with H,PEG400,PW adsorbing in the order of La³⁺ > Y³⁺ > Pr³⁺ > Gd³⁺ > Sm³⁺, and H,PEG400,PMo in the order of Y³⁺ > La³⁺ > Pr³⁺ > Gd³⁺ > Sm³⁺. The experimental maximum adsorption capacities of the sorbents are in the range of 90–225 mg g^− 1 for Y³⁺, La³⁺, Pr³⁺, Sm³⁺ and Gd³⁺. In all cases, the maximum adsorption capacities of H,PEG400,PW are near to those of H,PEG400,PMo. The equilibrium data were evaluated according to the Freundlich and Langmuir isotherms and the Langmuir equation gave a better fit and modeled the adsorption well.     

Design of luminescence in(Sr,Gd)Li(Al,Mg)3N4:Eu2+ deep red phosphors via crystal field engineering for full-spectrum WLEDs

Red phosphor,with longer wavelength,is highly desirable for full-spectrum WLEDs.Targeted deep red phosphors(Sr,Gd)Li(AI,Mg)₃N₄:Eu²⁺ were designed from the initial model of SrLiAl₃N₄:Eu²⁺ by structural modification.The correlations among structural evolution,crystal-field environment,and luminescence properties were elucidated.Replacing Sr²⁺ with Gd³⁺in(Sr,Gd)LiAl₃N₄:Eu²⁺ leads...     

Sorption behaviour and mechanism of ytterbium(III) on imino-diacetic acid resin

The sorption behaviour and mechanism of a novel chelate resin, imino-diacetic acid resin (IDAAR), for Yb(III) has been investigated in HAc–NaAc medium. The sorption of Yb(III) obeys the Freundlich isotherm. Optimum sorption for Yb(III) on IDAAR is at pH 5.13 and the statically saturated sorption capacity is 187 mg/g resin at 298 K. Yb(III) can be eluted using 1~2 mol L^− 1 HCl and the resin can be regenerated and reused without apparent decrease of sorption capacity. The apparent sorption rate constant is k₂₉₈ = 1.57 × 10^− 5 s^− 1; the apparent activation energy is 13.8 kJ mol^− 1 and the enthalpy change ΔH of IDAAR for Yb(III) is 29.8 kJ mol^− 1. The sorption mechanism of IDAAR for Yb(III) was examined by using chemical methods and IR spectrometry. The molar coordination ratio of the functional group of IDAAR to Yb(III) is 3:1 with the coordination compound formed between oxygen atoms in the functional group of IDAAR and Yb(III).     

Effect of doped strontium on catalytic properties of La1‒xSrxMnO3 for rhodamine B degradation

A series of La_1‒xSr_xMnO₃ samples were prepared by sol–gel method and used to degrade rhodamine B (RhB) in water. All samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N₂ adsorption–desorption, temperature-programmed reduction of H₂ (H₂-TPR) and temperature-programmed desorption of O₂ (O₂-TPD). The results show that the degradation of RhB is highly dependent on the initial pH value of solution. Sr doping enhances the degradation ability of LaMnO₃ for RhB in the time range of 0–40 min under a strong acidic environment, but all samples exhibit similar degradation rate from 40 to 60 min. In La_0.7Sr_0.3MnO₃–RhB reaction system, there are two different degradation pathways, including N-de-ethylation, chromophore cleavage, ring-opening and mineralization. La_1‒xSr_xMnO₃ (x ≤ 0.3) has the perovskite structure of La–Mn oxides, while La_0.6Sr_0.4MnO₃ exhibits a Sr_0.4MnLa_0.6O_2.98 perovskite phase. Sr doping leads to distortion of rhombohedral crystal structure and increases the relative content of Mn⁴⁺. The perovskite structure is stable in strong acidic environment during RhB degradation, but the relative content of Mn⁴⁺ and Mn³⁺ on the material surface changes. Sr doped LaMnO₃ achieves specific surface area of 58.8 m²/g and total pore volume of 0.152 cm³/g. Furthermore, Sr²⁺ doping improves redox properties of La–Mn oxides, and the presence of defects makes oxygen diffusion easier compared with the undoped samples.     

Cr3+/Y3+ co-doped persistent luminescence nanoparticles with biological window activation for in vivo repeatable imaging

The near-infrared (NIR) persistent luminescence materials (PLMs) can remain long-lasting luminescence after removal of the excitation light, which permits bioimaging with high sensitivity owing to the absence of background fluorescence interference from in situ excitation. Recently, the NIR PLMs have aroused intensive research interest in bioimaging. However, the optimal excitation wavelength of current NIR PLMs is located in the ultraviolet region with shallow tissue penetration, making it difficult to activate effectively in vivo, and seriously hindering their further application in bioimaging. Herein, we report a novel kind of Cr³⁺ ions and Y³⁺ ions co-doped NIR PLM, Zn_1.3Ga_1.4Sn_0.3O₄:Cr³⁺,Y³⁺ (ZGSCY), which emits NIR persistent luminescence at 696 nm. Compared with Zn_1.3Ga_1.4Sn_0.3O₄:Cr³⁺ (ZGSC) excited by the light with a wavelength in the biological window (>650 nm), after being co-doped with Y³⁺ ions, the NIR persistent luminescence performance of ZGSCY is significantly improved because of the increase of trap concentration in the matrix. In addition, we synthesized ZGSCY nanoparticles (NPs) by the combustion method, which exhibit excellent optical properties after being excited by the light with a wavelength in the biological window. After surface modification with PEG, the ZGSCY NPs present low cytotoxicity. Notably, due to the co-doping of Y³⁺ ions, the signal-to-noise ratio (SNR) of ZGSCY NPs in vivo imaging is about 1.8 times higher than that of the ZGSC NPs. Furthermore, the rechargeable in vivo imaging and passive tumor-targeted imaging are successfully achieved by activating with a light-emitting diode (LED, 659 nm) after intravenous injection of ZGSCY. Thus, this kind of NIR PLM with high excitation efficiency performance in the biological window is expected to promote its biomedical application in deep tissues.