High piezo/photocatalytic efficiency of Ag/Bi_(5)O_(7)I nanocomposite using mechanical and solar energy for N2 fixation and methyl orange degradation

In this work,Ag/Bi_(5)O_(7)I nanocomposite was prepared and firstly applied in piezo/photocatalytic reduction of N2 to NH3 and methyl orange(MO)degradation.Bi_(5)O_(7)I was synthesized via a hydrothermal-calcination method and shows nanorods morphology.Ag nanoparticles(NPs)were photo deposited on the Bi_(5)O_(7)I nanorods as electron trappers to improve the spatial separation of charge carriers,which was confirmed via XPS,TEM,and electronic chemical analyses.The catalytic test indicates that Bi_(5)O_(7)I presents the piezoelectric-like behavior,while the loading of Ag NPs can strengthen the character.Under ultrasonic vibration,the optimal Ag/Bi_(5)O_(7)I presents high efficiency in MO degradation.The degradation rate is determined to be 0.033 min
1,which is 4.7 folds faster than that of Bi_(5)O_(7)I.The Ag/Bi_(5)O_(7)I also presents a high performance in piezocatalytic N2 fixation.The piezocatalytic NH3 generation rate reaches 65.4 μmol L^(-1)g^(-1)h^(-1)with water as a hole scavenger.The addition of methanol can hasten the piezoelectric catalytic reaction.Interestingly,when ultrasonic vibration and light irradiation simultaneously act on the Ag/Bi_(5)O_(7)I catalyst,higher performance in NH3 generation and MO degradation is observed.However,due to the weak adhesion of Ag NPs,some Ag NPs would fall off from the Bi_(5)O_(7)I surface under long-term ultrasonic vibration,which would greatly reduce the piezoelectric catalytic performance.This result indicates that a strong binding force is required when preparing the piezoelectric composite catalyst.The current work provides new insights for the development of highly efficient catalysts that can use multiple energies.

Protective and water-repellent properties of alkylcarboxylic and alkylphosphonic acid films on technically pure magnesium

The formation of superhydrophobic coatings using low-toxicity corrosion inhibitors is a promising method for corrosion protection of metals and alloys. In this study, the effects of surface roughness and the of the adsorbed substance structure on wettability and corrosion resistance of commercially pure magnesium were investigated. Surface roughness was created by three different methods: paper grinding,etching in nitric acid solution and laser treatment. Oleic, stearic and octadecylphosphonic acids were investigated as potential surface modifiers for the formation of corrosion resistant superhydrophobic coatings. It has been shown that the protective and hydrophobic properties of acid films on magnesium, as well as their stability, are determined by both the initial surface morphology and the nature of the inhibitors.Experimentally, the laser treatment was found to be preferable to mechanical and chemical surface preparation and the best hydrophobic agent among the studied acids is phosphonic acid. The most stable films with excellent superhydrophobic and protective properties in atmospheres of high humidity and salt spray clamber are formed in a solution of 0.001 M octadecylphosphonic acid on the surface of magnesium with high roughness. In addition, the effect of vinyltrimethoxysilane on the protective and hydrophobic properties of stearic acid and octadecylphosphonic acid films was investigated. The results of direct corrosion tests and wetting contact angle degradation kinetics studies showed that the protective and hydrophobic properties of stearic acid can be enhanced by its layer-by-layer adsorption with silane.They practically reach the parameters of octadecylphosphonic acid.

Facile preparation of Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3) heterojunction for enhanced performance in catalytic nitrogen fixation via photocatalysis and piezo-photocatalysis

In this work, a novel heterojunction composite Ag_(2)S/KTa_(x)Nb_(1-x)O_(3)was designed and synthesized through a combination of hydrothermal and precipitation procedures. The Ta/Nb ratio of the KTa_(x)Nb_(1-x)O_(3)and the Ag_(2)S content were optimized. The best 0.5% Ag_(2)S/KTa_(0.5)Nb_(0.5)O_(3)(KTN) sample presents an enhanced photocatalytic performance in ammonia synthesis than KTN and Ag_(2)S. Under simulated sunlight, the NH_(3)generation rate of 0.5% Ag_(2)S/KTN reaches 2.0 times that of pure KTN. Under visible light, the reaction rate ratio of the two catalysts is 6.0.XRD, XPS, and TEM analysis revealed that Ag2S was intimately decorated on the KTN nanocubes surface, which promoted the electron transfer between the two semiconductors. The band structure investigation indicated that the Ag_(2)S/KTN heterojunction established a type-Ⅱ band alignment with intimate contact, thus realizing the effective transfer and separation of photogenerated carriers. The change in charge separation was considered as the main reason for the enhanced photocatalytic performance. Interestingly, the Ag_(2)S/KTN composite exhibited higher NH3generation performance under the combined action of ultrasonic vibration and simulated sunlight. The enhanced piezo-photocatalytic performance can be ascribed that the piezoelectric effect of KTN improved the bulk separation of charge carriers in KTN. This study not only provides a potential catalyst for photocatalytic nitrogen fixation but also shows new ideas for the design of highly efficient catalysts via semiconductor modification and external field coupling.

In-depth analysis of the influence of bio-silica filler(Didymosphenia geminata frustules)on the properties of Mg matrix composites

A novel metal matrix composites(MMC)with Mg matrix reinforced with natural filler in the form of Didymosphenia geminata frustules(algae with distinctive siliceous shells)are presented in this work.Pulse plasma sintering(PPS)was used to manufacture Mg-based composites with 1,5 and 10 vol.%ceramic filler.As a reference,pure Mg was sintered.The results show that the addition of 1 vol.%Didymosphenia geminata frustules to the Mg matrix increases its corrosion resistance by supporting passivation reactions,and do not affect the morphology of L929 fibroblasts.Addition of 5 vol.%the filler does not cause cytotoxic effects,but it supports microgalvanic reactions leading to the greater corrosion rate.Higher content than 5 vol.%the filler causes significant microgalvanic corrosion,as well as increases cytotoxicity due to the greater micro-galvanic effect of the composites containing 10 and 15 vol.%diatoms.The results of contact angle measurements show the hydrophilic character of the investigated materials,with slightly increase in numerical values with addition of amount of ceramic reinforcement.The addition of Didymosphenia geminata frustules causes changes in a thermo-elastic properties such as mean apparent value of coefficient of thermal expansion(CTE)and thermal conductivity(λ).The addition of siliceous reinforcement resulted in a linear decrease of CTE and reduction in thermal conductivity over the entire temperature range.With the increasing addition of Didymosphenia geminata frustules,an increase in strength with a decrease in compressive strain is observed.In all composites an increase in microhardness was attained.The results clearly indicate that filler in the form of Didymosphenia geminata frustules may significantly change the most important properties of pure Mg,indicating its wide potential in the application of Mg-based composites with a special focus on biomedical use.

Qualitative Considerations on the Influence of the Gases Water Vapor and Carbon Dioxide on the Global Environmental Temperature from the Point of View of Textbook Knowledge

The solar radiation that hits the Earth conditions the dynamic equilibrium that prevails on our planet. Consideration of basic physical-chemical knowledge shows that this equilibrium can be changed only by additional energy input or prolongation of the interaction time solar radiation—Earth matter. The contribution of H2O(g) and CO2 to the protection of the earth against excessive warming is experimentally and by basic laws of nature secured. For a greenhouse effect, a part of the earth radiation must be radiated back to the earth and then into space. If one understands the earth radiation as radiation of a black body with the average global environmental temperature, from all vibrations normal modes of the gases H2O(g) and CO2 only the bending mode of CO2 with 4% of the solar constant can contribute beside the rotational modes of the water to the greenhouse effect. The contributions of the normal modes of H2O(g) and CO2 to the heat capacity of the atmosphere are negligible. Therefore, in agreement with studies by K. Ångström, CO2 contributes only to the stabilization of the global environmental temperature. Whether the use of renewable energies can actually at least mitigate the increase of the environmental temperature is by no means certain but must be examined for each individual case. With certainty, this goal can only be achieved by reducing the energy consumption of mankind.

Structural Analysis and Magnetic Properties of Gd-Doped Li-Ni Ferrites Prepared Using Rheological Phase Reaction Method

A series of Gd-doped Li-Ni ferrites with the formula of LiNi0.5GdxFe2-xO4 where x = 0.00 - 0.08 in steps of 0.02, were prepared by thermolysis of oxalate precursors obtained by rheological phase reaction. The structure, morphology, and the magnetic properties of the samples were characterized by powder X-ray diffraction （XRD）, atomic force microscopy （AFM） and a vibrating sample magnetometer （VSM）. A single spinel phase was obtained in the range of x = 0.00 - 0.04. The lattice parameters of the Gd-doped samples were larger than that of pure Li-Ni ferrite, and increased in the range of 0.00 ≤ x ≤ 0.04, then decreased up to x = 0.08, because of the formation of the secondary phase （Gd- FeO3）. All samples were spheric particles with an average size of about 100 nm, but agglomerated to some extent. The hysteresis loops indicated that the saturation magnetization decreased gradually with increasing Gd content, while the variation of coercivity was related to the microstructure of the Gd-doped samples.

A comparative study of formaldehyde and carbon monoxide complete oxidation on MnO_x-CeO_2 catalysts

MnOx-CeO2 composite catalysts were prepared by a coprecipitation method and tested for formaldehyde （HCHO） and carbon monoxide （CO） oxidation. X-ray photon spectroscopy （XPS） results indicated that the average oxidation state of surface Mn species in CeMn composite catalyst was higher compared to the pure MnOx. The enhancement of reactivity for HCHO oxidation was due to the activation of the lattice oxygen species in MnOx by the addition of CeO2, which was confirmed by the H2 temperature programmed reduction （HE-TPR） results. The remarkable enhancement of reactivity for CO oxidation by the addition of CeO2 was due to the active oxygen species generated on the CeO2 surface which directly participated in the reaction.

Preparation of High-Surface Area Nano-CeO_2 by Template-Assisted Precipitation Method

The high-surface area nano-CeO2 was prepared by Ce（NO3）3 by precipitation method, with surfactant cetyhrimethyl ammonium bromide （CTAB） as templating agent. The effects of the precipitating agents, reaction temperature, ageing time, and calcination temperature on the surface area, as well as the pore structure and the mean crystallite size of nano-CeO2 were studied. It was found that the reaction of Ce（NO3）3 with NaOH in the presence of CTAB at 90℃ for 12 h yieldsed a cerium oxide/surfaetant mixture, which after calcination at 400℃ resulted in high-surface area nano-CeO2. The mean crystallite size of CeO2 was approximately 6 nm, surface area was in excess of 200 m^2· g ^- 1, pore size was approximately 9 nm, and the pore distribution was concentrative. Moreover, the surface area can still reach 147 m^2·g^- 1 after calcination at 700 ℃, which showed the good thermal stability of the CeO2. The number of oxygen vacancies in the structure of CeO2 corresponded with the surface area of CeO2, and the high surface area was propitious to the formalion of oxygen vacancies.

Catalytic combustion of toluene over Pd-based monolithic catalysts with a novel washcoat Ce_(0.8)Zr_(0.15)La_(0.05)O_δ

Two novel washcoats Ce0.8Zr0.15La0.05Oδ and Ce0.8Zr0.2O2 was prepared by an impregnation method, which acted as a host for the active Pd component to prepare Pd/Ce0.8Zr0.15La0.05Oδ/substrate and Pd/Ce0.8Zr0.2O2/substrate monolithic catalysts for toluene combustion. The washcoats was characterized by X-ray diffraction (XRD), Raman spectroscopy, Brunauner-Emmett-Teller (BET), and H2-temperature-programmed reduction (H2-TPR). The result indicated that both the washcoats had strong vibration-shock resistance according to ultrasonic test. Doping La3+ into CeO2-ZrO2 solid solution could generate more oxygen vacancies, and could inhibit the sinter of CeO2-ZrO2 solid solution when calcined at high temperatures (800, 900 and 1000 °C). The washcoat Ce0.8Zr0.15La0.05Oδ had much better redox properties. The reductive temperature of Ce4+ species shifted to low temperature by 60 °C when the washcoats calcined at high temperatures (800, 900 and 1000 °C). The Pd/Ce0.8Zr0.15La0.05Oδ/substrate monolithic catalyst calcination at 500 °C had the best catalytic activity and the 95% toluene conversion at a temperature as low as 190 °C. When calcined at low temperature (500 and 700 °C), the catalytic activity has little improvement, however, when calcined at high temperature, the catalytic activity of Pd/Ce0.8Zr0.15La0.05Oδ/substrate monolithic catalysts had significant improvement. As catalyst washcoat, the Ce0.8Zr0.15La0.05Oδ had better thermal stability than the washcoat Ce0.8Zr0.2O2, the developed Pd/Ce0.8Zr0.15La0.05Oδ/ substrate monolithic catalyst in this work was promising for eliminating Volatile organic compounds.

Characterization of CuO Species and Thermal Solid-Solid Interaction in CuO/CeO_2-Al_2O_3 Catalyst by In-Situ XRD, Raman Spectroscopy and TPR

Transference of CuO species and thermal solid-solid interaction in CuO/CeO2-Al2O3 catalyst prepared by an impregnation method were characterized by in-situ XRD, Raman spectroscopy and H2-TPR techniques. For the catalyst calcined at 300℃, two kinds of CuO species coexist on the surface, that is, highly dispersed and bulk CuO crystalline phase. Four kinds of CuO species are present for the catalyst calcined at 600 ℃, ： （1） highly dispersed CuO, （2） bulk CuO on the surface, （3） bulk CuO in the internal layer of CeO2, and （4） CuAl2O4 formed from CuO-Al2O3 interaction. For the catalyst calcined at 800 ℃,C, besides very little highly dispersed and bulk CuO on the surface, most of the CuO has transferred into the internal layer of CeO2 and the mass of CuAl2O4 are increased. At 900 ℃,, all of CuO has diffused into the internal layer of CeO2 and formed CuAl2O4. The results show that the distribution of CuO species in the catalysts depends on the calcination temperature; the different CuO species can be effectively confirmed by in-situ XRD, Raman spectroscopy and H2-TPR techniques.

Photoluminescent properties of Sr_2SiO_4:Eu^(3+) and Sr_2SiO_4:Eu^(2+) phosphors prepared by solid-state reaction method

Eu2＋ and （or） Eu3＋ doped Sr2SiO4 phosphors particles were synthesized by a conventional solid-state reaction technique, and their structural and optical properties were investigated. The X-ray diffraction （XRD） results showed that the obtained phosphors were composed of orthorhombic α′-Sr2SiO4 and monoclinic β-Sr2SiO4 phase. When excited under 256 nm, Sr2SiO4：Eu3＋ phosphors showed intense emission in the red region. Sr2SiO4：Eu3＋ phosphors exhibited white emissions （x=0.30, y=0.40, Tc=6500 K） ranging from 425 to 650 nm when it was excited by near-ultraviolet （near-UV） light, indicating that Sr2SiOn：Eu2＋ was a good light-conversion phosphor candidate for near-UV chip.

Spectroscopy Study on Crystal Structure of Ce(NO_3)_3(phen)_2 and Interactions of Ce(NO_3)_3(phen)_2 with DNA

The absorption, fluorescence and Raman spectra of Ce(NO3)(3)(phen)(2) complex were assigned and the crystal structure of the complex was studied. Meanwhile the interactions between Cc (NO3)(3) (phen)(2) and DNA were studied by spectrum methods. As DNA was added, it is found that both the UV absorption bands of Ce(NO3)(3)(phen)(2) and the SERS bands of Ce(NO3)(3)(phen)(2) weaken evidently, while the fluorescence intensity of Ce(NO3)(3)(phen)(2) enhance dramatically. The complex compete against EB on the reaction with DNA. It is indicated by this spectrum methods that there are strong interactions between Ce(NO3)(3)(phen)(2) and DNA, and the bond mode is intercalation. The bond constant of the complex with DNA is determined to be 1.7 x 10(5).

Upconversion properties of Y_2O_3:Er films prepared by sol-gel method

Y2O3：Er^3＋ films were prepared by a simple sol-gel process. The structural properties of Y2O3：Er^3＋ films were characterized with X-ray diffraction, Fourier transform infrared spectroscopy and field emission scanning electron microscopy. The results indicated that the Y2O3：Er^3＋ films might have high upconversion efficiency because of their low vibrational energy. Under 785 and 980 nm laser excitation, the samples showed green （^2H11/2→^4I15/2, ^4S3/2→^4I15/2） and red （^4F9/2→^4I15/2） upconversion emissions. The upconversion mechanisms were studied in detail through laser power dependence. Excited state absorption and energy transfer process were discussed as possible upconversion mechanisms. The cross relaxation process in Er^3＋ was also investigated.

Explosive limits of mixed gases containing CH_4,CO and C_2H_4 in the goaf area

The explosive gases CO and C2H4, released mainly flammable gases during the process of coal self-ignition, are of the most important ingredients of the multi-component gases in goaf areas, along with CH4. We have determined some of the parameters of explosive properties of the one-component gases CH4, CO and C2H4 using an explosive trial device of polybasic explosive gas mixtures and emphasized particularly the effect on the limits of explosive concentration of the binary explosive mixed gases CH4+CO, CH4+C2H4, as a function of the amount of CO, C2H4 and inert flame resisting gases (N2, CO2). The experimental results show that the effect of inert gases on the explosive limits of mixed gases, given the property of explosive gas, is obvious: the inert gases (N2, CO2) possess some inhibitory effects on the explosion of the multi-component explosive gas mixtures. The results will provide some experimental support to suppress the occurrence of the gas explosions in goaf areas and provide some directions for designing explosion-proof electric equipment and fire arresters.

Synthesis,optimization and characterization of biochar based catalyst from sawdust for simultaneous esterification and transesterification

The development of a benign environmental catalyst for the generation of biodiesel is an area of importance to reduce the overall usage of fossil fuels. In the current work, biochar was produced by slow pyrolysis of Irul wood sawdust. The optimization for biochar generation was carried out for different reaction temperatures and heating durations. The biochar was used to prepare solid acid catalysts by sulfonation process. The characterization of biochar and the sulfonated catalyst were carried out using Elemental analysis, Fourier Transform Infrared spectroscopy(FTIR), Powder X-ray Diffraction(XRD), Thermo Gravimetric Analysis(TGA), Scanning Electron Microscopy(SEM) and Surface area analyzer(BET). The characterization results showed that sulfonation of biochar resulted in biochar based solid acid catalyst containing various functional acidic groups like weak acidic\\OH groups, strong acidic\\COOH and SO3 H groups. The total acid density and sulfonic acid group density of catalyst were estimated and showed excellent acidic sites concentration which gives a good catalytic activity for biodiesel production through simultaneous esterification and transesterification. The enhanced catalytic activity is due to the high acid density of SO3 H groups and the reactant accessibility towards acidic sites as well as the strong affinity between the hydrophilic reactants and the neutral OH groups which are bonded with the polycyclic aromatic carbon rings. The performance of biochar catalyst for the production of biodiesel was evaluated by comparing the yield obtained. The FTIR and Gas Chromatography–Mass Spectroscopy(GC–MS) were also carried out for the analysis of biodiesel produced.

Carbon dioxide reforming of methane on monolithic Ni/Al_2O_3-based catalysts

Nickel-alumina catalysts supported on cordierite monoliths of honeycomb structure surpass essentially the conventional granulated ones with respect to the output in carbon dioxide reforming of methane. Adjusting the surface acid-base properties of catalysts by introduction of alkali metal （Na, K） oxides inhibits the carbonization and as a result, improves the operational stability of these catalysts. An effect of promotion of nickel-alumina based composite doped by lanthanum oxide is found. This effect, caused by an additional route for the CO2 activation on Ni-La2O3/Al2O3/cordierite catalyst, is displayed in increase of methane conversion under conditions of an oxidant excess.

Luminescence intensification of lanthanide complexes by silver nanoparticles incorporated in sol-gel matrix

We present how the luminescence of europium RR-2-P-oxides complexes can be increased by interaction of electronic levels of the complex with the radiation field of silver nanoparticles （NPs）. The procedure by which silver NPs are formed in a sol-gel polyurethane matrix precursor was elaborated. The formed Ag NPs were combined with Eu complex incorporated in ormocer matrix. The emission spectra of the complexes without silver NPs were compared with spectra of the same complexes with addition of silver NPs. As the result of the interaction of the electronic levels of lanthaaide ligands with silver plasmons, dramatic increase of luminescence was observed.

Syntheses, Characterizations, Crystal Structures and Antibacterial Activities of Two Zinc(II) Complexes with a Schiff Base Derived from o-Vanillin and p-Toluidine

Two new zinc（Ⅱ） complexes, [Zn2L2Ch].2[ZnL（CH3OH）Cl2] 1 and [ZnL2（NO3）2] 2, were synthesized by reacting ZnX2.nH2O （X = Cl^-, NO3^-） and a Schiff base ligand 2-[（4-methylphenylimino）methyl]-6-methoxyphenol （C15HIsNO2, L） which was obtained by the condensation of o-vanillin （2-hydroxy-3-methoxybenzaldehyde） with p-toluidine. Both 1 and 2 were characterized by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, IH-NMR spectra and thermogravimetrie analysis. The Schiff base ligand and its zinc（Ⅱ） complexes have been tested in vitro to evaluate their antibacterial activity against bacteria, viz., Escherichia Coli, Staphylococcus aureus and Bacillus Subtilis. The results show that these complexes have higher activity than the corresponding free Schiff base ligand against the same bacteria.

A Series of Lanthanide-organic Frameworks Constructed by Ln_4(OH)_4 Clusters and Mixed Ligands

Three new lanthanide-organic compounds, namely, [Ln_2(OH)_2(oba)(2-pc)_2]n(Ln =Er(1), Ho(2), and Dy(3))(oba = 4,4?-oxybis(benzoate), 2-pc = 2-pyrazinecarboxylic acid) have been obtained under hydrothermal conditions. These compounds are isostructural and exhibit 2 D layered structures by incorporating [Ln_4(μ_3-OH)_4]^(8+) clusters and the mixed linkers of oba and 2-pc. It is interesting that decarboxylation occurred in the ortho position and 2,3-pyrazinedicarboxylic acid was partially transformed into 2-pc under hydrothermal conditions. Compound 3 emits a typical Dy^(3+) emission spectrum. Furthermore, the PXRD, TGA and IR spectra were also studied.