The preparation and performance of high activity Ni-Cr binary catalysts for direct borohydride fuel cells

Ni-Cr binary anode catalysts used in direct borohydride fuel cells (DBFCs) were prepared using a constant potential electrodepo- sition method. Compared with pure metal Ni catalysts, the electro-oxidation currents of borohydride ions (BH-4) more than doubled when using Ni-Cr binary catalysts under the same conditions. The enhanced activity of the Ni-Cr binary catalysts could be attributed to the change in distribution of BH-4ions on the surface of the Ni electrode. This is due to Cr electrodeposits, which allows a greater number of hydrogen atoms to catalyze from each tetrahedron BH-4 ion. The performance of Ni-Cr binary catalysts could also be improved by optimizing the electrodeposition conditions. The results show that Ni-Cr binary catalysts are optimally prepared using an electrodeposition method of 1s with a Cr3+ concentration of 0.2 mol L-1 and a potential of -0.100 V.     

Property variation of ionic liquid [Bmim][AuCl4] immobilized on carboxylated polystyrene submicrospheres with a small surface area

In order to understand the effect of surface chemical groups on the immobilized species, Au-containing imidazolium-based ionic liquid (IL) [Bmim][AuCl4] was intentionally immobilized on polystyrene (PS) submicrospheres (d～300 nm) with a very small surface area (4-10 m2/g), which possess carboxyl-moiety (COONa or COOH) on the surface. The behavior of immobilized [Bmim][AuCl4 ] on the two types of submicrospheres was investigated by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and powder X-ray diffraction (XRD). It was revealed that the melting points (Tm) of [Bmim][AuCl4 ] that had been immobilized on PS-COONa and PS-COOH submicrospheres were decreased by 2.7 and 4.1℃, respectively. The interaction mechanism between the IL and submicrosphere surface moieties was further analyzed by X-ray absorption fine structure (XAFS) analysis. The data indicated that the coordination environment of Au species changed markedly when [Bmim] [AuCl4] was immobilized on the surfaces of PS-COONa and PS-COOH submicrospheres, as illustrated by the decrease in white line peak intensity. The effect of surface COOH groups on Tm depression and the white line peak intensity of the XANES spectrum is more pronounced than that of COONa groups, most likely due to the possible hydrogen bond formation between the COOH group and [Bmim]+.     

Development of inclusions in 3104 alloy melt during heating and holding treatments

Developments in the contents of different typical inclusions in 3104 alloy melt were described during heating and holding processing. The settling process of inclusion particles was investigated by measuring the contents of inclusions in the surface, center, and bottom layers of the molten metal. In the results, main inclusions observed and determined by Prefil and PoDFA methods are MgO, Al₂O₃, spinel (MgAl₂O₄), and TiB₂ particles or thin films. It is found that some small particles of Al₂O₃ and MgO are transformed into spinel particles, and the formation rate increases as the temperature and the holding period of melt increase. The content of inclusions increases from 3.37 mm2·kg-1 to 7.54 mm2·kg-1 and then decreases to 3.08 mm2·kg-1 after holding for 90 min. This is attributed to a settling phenomenon and a significant increase in settling velocity after holding for 60 min. The content of inclusion particles decreases by means of settlement and flotation in liquid aluminum with an increase in holding time. The theoretical analysis and experiment results are in essential agreement with those from industrial production.     

混合基纳米流体在汽车散热器中的稳定性及传热特性

摘 要 使用SiO2和MWCNT纳米颗粒,在80%：20%的水/乙二醇基液中制备纳米流体,分别研究超声波振荡时间、分散剂对纳米流体稳定性的影响,结果表明：最佳振荡时间为1 h;十六烷基三甲基氯化铵（CTAC）的最佳添加量为质量分数0.05%,十二烷基苯磺酸钠（SDBS）的最佳添加量为0.1%;在最佳添加量下,CTAC的分散效果优于SDBS;在同一分散剂下,MWCNT-水/乙二醇混合基纳米流体的稳定性优于SiO2-水/乙二醇混合基纳米流体。研究不同浓度的纳米流体在不同流速、温度下的传热特性进行分析。结果表明,与基液相比,纳米流体的传热速率有了明显的提高;与纳米流体的传热速率增加相比,纳米流体浓度对压降和有效泵功的不利影响可以忽略不计。     

Silicone oil-based solar-thermal fluids dispersed with PDMS-modified Fe3O4@graphene hybrid nanoparticles

One of the most challenging problems that limit the practical application of carbon-based photothermal nanofluids is their poor dispersion stability and tendency to form aggregation. Herein, by using Fe_3O_4@graphene hybrid nanoparticles as a model system, we proposed a new method to prepare stably dispersed silicone oilbased solar-thermal nanofluids that can operate at high temperatures than water-based fluids. The introduction of Fe_3O_4 nanoparticles between graphene nanosheets not only physically increases the inter-plane distance of the graphene nanosheet but also provides numerous anchoring points for surface modification. Phosphate-terminated polydimethylsiloxane chains, which have high compatibility with the silicone oil base fluids and hightemperature stability, were synthesized and utilized to modify the Fe_3 O_4 nanoparticle surfaces. The attached chains create steric hindrance and effectively screen the strong inter-plane van der Waals attraction between graphene sheets. Dispersion stability of the nanofluids with different concentrations of surface-modified hybrid nanoparticles and heated under different temperatures was investigated. We have demonstrated that such fluids could maintain stable dispersion under a heating temperature up to 150 °C depending on the concentration of the hybrid nanoparticles. The resultant nanofluids maintained stable dispersion after repeated heating and were employed for consistent direct solar-thermal energy harvesting at 100 °C.     

Effect of exogenous lanthanum on accumulation of cadmium and its chemical form in Tomatoes

In the condition that soil is polluted by Cd(20 mg·L-1),two varieties of tomato(Lycopersicon esculintum Mill.)(plant high Cd-enriched variety(Yufen109)and plant low Cd-enriched variety(4641))treated with LaCl3 of different concentration(0,10 and 20mg·L-1)were determined for their effect on plant dry weight,anti-oxidase activity(CAT,SOD and POD),tomato fruit Cd chemical form and Cd accumulation.The results show that 10 mg?L-1LaCl3 can increase dry weight of plant at various positions and can reduce the concentration of Cd of different forms.Spraying with LaCl3(10,20 mg·L-1)can reduce Cd concentration in leaves,stems,roots and fruits of tomato plants with lowering rates of 13.7%-31.9%,9.5%-30.6%,10.8%-44.5%and 19.4%-37.0%,respectively.Suitable amount of lanthanum(10 mg·L-1 LaCl3)can increase yield of tomatoes,reduce Cd accumulation in the fruit.In the two tomato varieties,Lanthanum and Cadmium react interactively,expressing to be coexisting of both synergism and antagonistic.     

Fluorescent immunosensor based on fluorescence resonance energy transfer between CdSe/ZnS quantum dots and Au nanorods for PRRSV detection

An ultrasensitive and selective sandwich-type fluorescent immunosensor based on fluorescence resonance energy transfer (FRET) between CdSe/ZnS quantum dots (QDs) and Au nanorods (AuNRs) was developed for the rapid detection of porcine reproductive and respiratory syndrome virus (PRRSV). Modified CdSe/ZnS QDs and AuNRs were bioconjugated with primary antibodies M and GP5, respectively. When the target antigen was present, a well-known sandwich-type form CdSe/ZnS QDs-M antibody-antigen-GP5 antibody-AuNRs was produced, and thus reducing the distance between the QDs and NRs. As a result, FRET occurred and the fluorescence intensity of CdSe/ZnS QDs decreased, and this decrease was used to determine the antigen concentration. Ultrasensitive detection of PRRSV at low concentrations in swine serum was achieved with a limit of detection of 0.55 TCID₅₀/mL and a linear detection range of 10¹–3.5 ?× ?10⁴ TCID₅₀/mL. Therefore, the fluorescent immunosensor is selective and highly sensitive; specifically, it can detect PRRSV at low concentrations in swine serum over a large concentration range. This proposed detection method can facilitate the development of high-performance fluorescent immunosensors for the detection of PRRSV and other antigens.     

Interdiffusion in the Fe2O3-TiO2 system

Interdiffusion in the Fe₂O₃-TiO₂ system was investigated by the diffusion couple method in the temperature range of 1323 to 1473 K. The diffusion concentration curves of Ti⁴⁺ cations were obtained by electron probe microanalysis, according to which the Boltzmann-Matano method optimized by Broeder was used to calculate the interdiffusion coefficients. The interdiffusion coefficients almost increased linearly with the mole fraction of Ti⁴⁺ cations increasing, and they were in the range of 10^?12–10^?11cm²·s^?1. The increase of temperature could also lead to the increase of the interdiffusion coefficients at a constant concentration of Ti⁴⁺ cations. It was also found that the thickness growth of the diffusion layer obeyed the parabolic rate law.     

Highly stable N-containing polymer-based Fe/Nx/C electrocatalyst for alkaline anion exchange membrane fuel cell applications

A cost-effective electrocatalyst with high activity and stability was developed. The Fe-Nx and pyridinic-N active sites were embedded in nitrogen-doped mesoporous carbon nanomaterial by carbonization at high temperature. The electrocatalyst exhibited excellent electrochemical performance for the oxygen reduction reaction, with high onset potential and half-wave potential values (E_onset = 1.10 ?V and E_1/2 ?= ?0.944 ?V) than 20 ?wt % Pt/C catalyst (1.04 and 0.910 ?V). The mass activity of the Schiff base network (SNW) based SNW-Fe/N/C@800° electrocatalyst (0.64 ?mA ?mg^?1 @ 1 ?V) reached about half of the commercial Pt/C electrocatalyst (1.35 ?mA ?mg^?1 @ 1 ?V). The electrocatalyst followed the 4-electron transfer mechanism due to very low hydrogen peroxide yield (H₂O₂ ?< ?1.5%) was obtained. In addition, this electrocatalyst with dual active sites showed high stability during cyclic voltammetry and chronoamperometry measurements. More importantly, the electrocatalyst also demonstrated the power density of 266 ?mW ?cm^?2 in the alkaline anions exchange membrane fuel cell (AEMFC) test, indicating its prospective application for fuel cells.     

Influence of FeCl3 on radiation stability of ionic liquid BmimCl

This study investigates the effect FeCl3 on the radiation stability of the ionic liquid,1-butyl-3-methylimidazolium chloride(BmimCl) over a wide dose range of 0 to 1000 kGy under γ-ray radiation.The ionic liquid species,BmimFeCl4,was formed by adding FeCl3 into BmimCl.The results showed that the presence of FeCl4-significantly improved the radiation resistance of BmimCl,wherein the effect was more pronounced at higher FeCl4-content.Meanwhile,under irradiation,Fe(II) was generated from Fe(III),which was reduced by solvated electron.In addition,the concentration of Fe(II) increased with low level of absorbed dose,but leveled off at higher doses.Moreover,the radiation yield of the solvated electrons of BmimCl was further estimated at approximately 0.358±0.01 μmol/J in BmimCl-7 mol% FeCl3 system.     

The voltammetric behavior of concanavalin a at bare silver electrode and analytical application

The voltammetric behavior of concanavalin A at the bare silver electrode is described. Cyclic voltammograms show a pair of well-defined redox peaks for concanavalin A in the medium of phosphate buffer(pH=7.0) with electrochemical reaction rate constant ofK ₂=0.053 s^?1 and electron transfer number ofn=2. Moreover, both the oxidation currents and the reduction currents have linear relationship with concanavalin A concentrations in the range of 1.0×10^?6～2.0×10^?5 mol/L, which can be used as an analytical method for determining concanavalin A concentration.     

FTIR-ATR chamber for observation of efflorescence and deliquescence processes of NaClO4 aerosol particles on ZnSe substrate

NaClO4 aerosol particles with diameter of 5-20 microns are deposited on the ZnSe substrate. An FTIR-ATR chamber on the ZnSe substrate is set up to observe the structural changes of NaClO4 aerosol particles at crystallization relative humidity （CRH） and deliquescence relative humidity （DRH）. With the decrease of RH （relative humidity） from 96% to 24% in the efflorescence process, the absorbance of O-H stretching band of the aerosol solutions continuously decreases. A sudden decrease of the water peak is observed at RH20%, where solid particles form. Very small amount of residual interfacial water, with two weak peaks at 3602 and 3533 cm^-1, can still be resolved in the FTIR-ATR spectra of the solid particles. In the deliquescence process of the same sample, little spectral changes are observed when the value of RH varies from 5% to 29%. Before the abrupt increase of the O-H stretching band at the DRH of about RH46%, a pre-deliquescence process is observed, i.e. in the RH range between 33% and 46%, there is really a slow absorbance increase for the peak area of O-H stretching band. The O-H stretching band shows an arciform O-H en- velope, totally different from not only the FTIR-ATR spectra of ClO4^- solutions either under supersaturated state or in diluted state, but also the characteristic of the residually interfacial water discussed in the efflorescence process. Such kind of water is considered as pure water, indicating that small amount of water aggregates in the microspaces of solid aerosol particles due to the capillary cohesion effect. When the RH arrives at RH44%, two weak shoulders at 3384 and 3260 cm^-1 can be resolved, and the solid NaClO4 particles begin to be dissolved by increasing capillary cohesion water. The spectral characteristic of the v3-ClO4^- band also shows the transition from solid particles to mainly solvated ClO4^- ions.     

Synthesis and characterization of red-emitting Yb/Ho-CaSiO3 upconversion phosphors

Host material plays an important role in obtaining efficient photon upconversion and downshifting luminescence. Generally, fluoride and oxyfluoride glasses-based materials are used for high-efficiency photon upconversion. However, the poor thermal stability of fluoride glasses and the toxicity of fluorine ions limit their applications. In this report, Yb/Ho-doped CaSiO₃ wollastonite phosphors have been demonstrated as efficient red-emitting upconversion phosphors. The phosphors have been synthesized by microwave hydrothermal process followed by heat treatment at 1050 ?°C in the air environment. 2M phase of the β-wollastonite has been confirmed by X-ray diffraction and Raman spectroscopy while the existence of the Yb and Ho dopants in the CaSiO₃ lattice has been confirmed by X-ray photoelectron spectroscopy. The synthesized samples showed strong red upconversion emission centered at 662 ?nm and near-infrared downshifting emissions at 2016 ?nm upon 980 ?nm excitation. The emissions were found to depend significantly on the Ho concentration. Temporal evolution of the main emission bands was investigated to show that the energy transfer upconversion from Yb to Ho ions was responsible for the efficient upconversion and downshifting phenomenon.     

A ternary FeS_2/Fe_7S_8@nitrogen-sulfur co-doping reduced graphene oxide hybrid towards superior-performance lithium storage

Iron sulfides are promising anode materials for lithium ion batteries(LIBs) owe to their high theoretical capacity and low cost. However, unsatisfactory electronic conductivity, dissolution of polysulfides, and severe agglomeration during the cycling process limit their applications. To solve these issues, a ternary FeS_2/Fe_7S_8@nitrogensulfur co-doping reduced graphene oxide hybrid(FeS_2/Fe_7S_8@NSG) was designed and synthesized through a facile hydrolysis-sulfurization strategy, in which the FeS_2/Fe_7S_8 could be well distributed upon the NSG. The NSG was believed to buffer the volume change and augment the electronic conductivity of the electrode, and the nanodimensional FeS_2/Fe_7S_8 particles with a diameter of 50–100 nm could shorten the ion-diffusion paths during the lithiation/delithiation process. Benefiting from synergistic contributions from nano-dimensional FeS_2/Fe_7S_8 and flexible NSG, the FeS_2/Fe_7S_8@NSG hybrid displayed a high initial capacity of ～1068 m Ah g~(-1) at 200 mA g~(-1),good cycling stability(～898 mAh g~(-1) at 500 mA g~(-1) after 200 cycles) and high-rate performance. Further kinetic analysis corroborated that the introduction of NSG boosted the capacitive behavior. Above results indicate the potential applications of FeS_2/Fe_7S_8@NSG hybrid in LIBs with low-cost and high energy density.     

CO2的温室效应饱和度分析及其大气体积分数预测模型

通过精确的LBLRTM逐线积分模式建立CO_2体积分数变化模型,分析了CO_2的温室效应饱和度,并对未来地表温升的变化趋势进行了预测.结果表明,目前CO_2的持续排放只能使其在680cm~(-1)强吸收带中心达到饱和,而在未来相当长一段时间内,其仍将通过该吸收带的翼区以及1 000cm~(-1),1 350cm~(-1)与1 900cm~(-1)等弱吸收带对地表红外辐射表现出强烈的吸收,CO_2的温室效应还远未达到饱和;如果按照当前CO_22.2(mL/·m~(-3))/a的年排放速率,CO_2的大气体积分数将会持续增加,从而造成地表温度不断升高,到2056年,地表温升将会达到2K.     

Antilocalization sensing of interactions between two-dimensional electrons and surface species

We apply antilocalization measurements to experimentally study the interactions and exchange between InAs surface accumulation electrons and local magnetic moments of the rare earth ions Sm3?,Gd3?,Ho3?,and Dy3?,of the transition metal ions Ni2?,Co2?,and Fe3?,and of Fe3O4nanoparticles and Fe3?-phthalocyanine deposited on the surface.The influence of the deposited species on the surface electrons is observed through the changes in the spin–orbit scattering and magnetic spin-flip scattering rates,which carry information about magnetic interactions.Experiments indicate a temperature-dependent magnetic spin-flip scattering for Ho3?,Dy3?,Ni2?,and Co2?.Concerning the spin–orbit scattering rate,we observe an increase,except for the cases of Ni2?,Fe3?,Fe3O4nanoparticles and Fe3?-phthalocyanine.We also observe an increase in SO scattering in another system where we study the interactions of Au nanoparticles and ferromagnetic Co0.6Fe0.4nanopillars and an In0.53Ga0.47As quantum well.Experimental results are analyzed and compared to theoretical models.Our method provides a controlled way to probe the quantum properties of two-dimensional electron systems,either on the surface of InAs or in a quantum well.     

燃煤电厂锅炉PM2.5现场实测与排放特征研究

采用自设固定源PM_2.5稀释采集系统对陕西省关中地区多个燃煤电厂烟气中的颗粒物开展了现场实测与样品化学源组分分析。结果表明：4个燃煤电厂PM_2.5、PM₁₀占颗粒物比重差异较大（PM_2.5占比范围为6.92%~54.34%,PM₁₀占比范围为36.36%~73.02%）;4个燃煤电厂数浓度水平最高值（2.0×10⁴~4.0×10⁵个/cm³）差异较大,相差约1个数量级;燃煤电厂PM_2.5小粒径段颗粒物质量浓度占比大多较低,但其对PM_2.5数浓度贡献却很大（最小值>95%）,大粒径段颗粒物则相反;煤粉炉PM₁/PM_2.5较大,占比范围为35.29%~51.35%,循环流化床锅炉PM₁/PM_2.5较小,占比范围为16.62%~21.47%;SO₄^2-是燃煤电厂PM_2.5中最丰富的离子成分,各电厂SO₄^2-占总离子浓度比重范围为50.02~65.52%,Na⁺和Ca²⁺位于第2或第3位;各燃煤电厂主要检出无机元素是Si、Al、Ca、Na、Fe、Na等地壳元素;燃煤电厂PM_2.5、PM₁₀和颗粒物的排放因子范围分别为0.001~0.028 kg/t、0.002~0.086 kg/t、0.003~0.236 kg/t;除尘设施组合越复杂先进,排放因子就可能越小。     

Enhanced resistive switching properties of HfAlOx/ZrO2- based RRAM devices

Resistive Random-Access Memory (RRAM) devices are recognized as potential candidates for next-generation memory devices, due to their smallest cell size, high write/erase speed, and endurance. Particularly, the resistive switching (RS) characteristics in oxide materials have offered new opportunities for developing CMOS-compatible high-density RRAM devices. In this study, the RS behavior of HfAlO_x/ZrO₂ thin films sandwiched structure between TiN bottom electrode and Au top electrodes were investigated. It was found that Au/HfAlO_x/ZrO₂/TiN stacks were superior in terms of RS performance when compare to Au/HfAlO_x/TiN memory stacks. The devices demonstrated a good resistance ratio of high resistance state and low resistance state ～10³ for Au/HfAlO_x/TiN and ～10⁵ for Au/HfAlO_x/ZrO₂/TiN stacks, respectively. Both stacks showed good retention characteristics (>10⁴ ?s) and endurance (>10³ cycles). The experimental current-voltage characteristics fitted with different conducting mechanisms, the linear lower bias region is dominated by ohmic conductivity, whereas the non-linear higher bias region was dominated by space-charge limited current conduction mechanism.     

Fabrication and electrochemical properties of 3D nano-network LiFePO_4@multiwalled carbon nanotube composite using risedronic acid as the phosphorus source

LiFePO_4@multiwalled carbon nanotubes(LFP@MWCNTs) nanocomposite has been fabricated using risedronic acid(RDA) as a new eco-friendly phosphorus source. Microscopic, spectroscopic, and electrochemical characterization demonstrate that the MWCNTs are in the form of coiled and cross-linking nanoribbon, which wrapped and encrusted around LiFePO_4 particles to form a three-dimensional(3D) nano-network composite.This microstructure of 3D nano-network is obtained due to the reactions between RDA's special functional groups with Fe~(2+) and C-OH,-C=O or-COOH on the surface of the functionalized MWCNTs. The results also show that the particle size of the fabricated LiFePO_4@MWCNTs composite is below 300 nm with the pure crystal of olivine. This nanocomposite indicates an enhanced reversible capacity of 162.2 mAh g~(-1) at 0.2C, and high capacity retention of 76.5% even at 10C after the 800 th cycles. The electric conductivity and Li~+ diffusion coefficient(D_(Li)~+) of the LiFePO_4@MWCNTs are 3.79 × 10~(-2)S cm~(-1) and 4.46 × 10~(-11) cm~2s~(-1), respectively.These improved electrochemical parameters can be attributed to the nano-sized effect of particles, MWCNTs' wrapping effect and 3D nano-network microstructure of the LFP@MWCNTs resulted from using RDA as a new phosphorus source.     

Structure of aqueous sodium sulfate solutions derived from X-ray diffraction

A rapid liquid X-ray diffractometer was used to study the time-averaged and space-averaged structure of aqueous sodium sulfate solutions at 298 and 323 K. Difference radial distribution functions of the solutions were obtained from accurate diffraction data. The interaction distances of Na^＋-OH2 and S-H2O in solutions were found to be 0.235 and 0.385 nm, respectively, after deconvolution of superposition peaks by Gaussian multi-peak fitting program. The characteristic distance of the NaSO; contact ion pairs in higher concentration solutions was determined to be 0.345 nm, suggesting that the Na^＋ ions coordinated with SO4^2- ions in the mono-dentate form. Effects of concentration and temperature on the hydration structure of the solutions were discussed in the present paper. With a decrease in concentration, the contributions of the H2O to the diffraction pattern increase, the average coordination number of the Na^＋ ions hardly changes, while the hydration number of SO4^2- ions increases slightly. The formation of NaSO; contact ion pairs becomes easier at higher temperature. The structure of hydrogen bond in dilute solutions is broken to a considerable extent with rising temperature, and the peak at 0.290 nm splits into two peaks at 0.275 and 0.305 nm, respectively.