Run(n=2～7)金属团簇与氧反应的DFT研究

采用密度泛函理论的广义梯度近似(DFT／GGA)，对Run簇(n=2～7)与氧相互作用的几何结构与电子结构及吸附能之间的关系进行讨论。对氧原子及氧分子在Run金属簇上的吸附研究表明：电荷主要是从Ru的5s、4d轨道向O的2p轨道迁移，并使得金属．金属之间的键减弱。比较特殊的是当氧分子在桥位吸附时，Ru与吸附的O2会发生化学反应，并且由于Ru金属轨道的电子向O2的反键πg轨道转移，导致Ru-O之间的键的生成以及O-O之间的键发生断裂。同时，作者也观察到Ru．Ru之间的化学键发生断裂，形成具有原子活性的自由Ru原子，这可以部分解释一旦氧化物种形成，经过一诱导期后，氧化反应会加速进行的实验事实。     

Electrocatalysis of oxygen reduction on a carbon supported platinum-vanadium alloy in polymer electrolyte fuel cells

The electrocatalysis of the oxygen reduction reaction (ORR) on carbon supported Pt:V 1:1 catalyst in polymer electrolyte fuel cells (PEFC) was investigated. At an oxygen pressure of 1 atm results indicate a lower electrocatalytic activity for the ORR in the presence of vanadium. However, at an O₂ pressure ≥2 atm an enhanced electrocatalytic property of PtV/C compared with Pt/C is revealed. This result indicates the occurrence of a different electrocatalytic mechanism for the ORR on Pt/C and PtV/C. An increase of mass transport overpotentials is observed for the PtV/C catalyst, and this was related to the presence of vanadium oxide. Indeed, XRD analysis revealed that only about 30% of V present in the catalyst is alloyed with Pt, forming a face centred cubic (fcc) Pt₃V solid solution. A thermal treatment at 850 °C under reducing atmosphere leads to the formation of an ordered fcc Pt₂V phase. After this, the ORR activity of PtV/C at O₂ pressure 1 atm is higher than that of Pt/C.     

Influence of current density on oxygen transfer in an electroflotation cell

The objective of this work is to study the transfer of oxygen from gas to liquid phase in an electroflotation cell. The measurements were performed in a laboratory scale cell using insoluble electrodes, titanium coated with ruthenium oxide as anode and stainless steel as cathode. The volumetric mass transfer coefficient K _L a, was characterized for clean tap water as liquid phase for different values of current density (J). The global coefficient of mass transfer based on the liquid film, K _L , and the specific interfacial area, a, were characterized. A model which relates K _L a to current density was established. Different evaluation criteria of oxygen transfer in electroflotation process were determined and compared with other aeration process.     

Tetragonal structure, anionic vacancies and catalytic activity of SO4-ZrO2 catalysts for n-butane isomerization

An assessment of the influence of the crystal structure, surface hydroxylation state and previous oxidation/reduction pretreatments on the activity of sulfate-zirconia catalysts for isomerization of n-butane was performed using crystalline and amorphous zirconia supports. Different sulfation methods were used for the preparation of bulk and supported SO₄²⁻-ZrO₂ with monoclinic, tetragonal and tetragonal+monoclinic structures. Activity was important only for the samples that contained tetragonal crystals. The catalysts prepared from pure monoclinic zirconia showed negligible activity. SO₄²⁻-ZrO₂ catalysts prepared by sulfation of crystalline zirconia displayed sites with lower acidity and cracking activity than those sulfated in the amorphous state. Prereduction of the zirconia samples with H₂ was found to greatly increase the catalytic activity, and a maximum rate was found at a reduction temperature of 550–600 °C, coinciding with a TPR peak supposedly associated with the removal of lattice oxygen and the creation of lattice defects. A weaker dependence of catalytic activity on the density or type of surface OH groups on zirconia (before sulfation) was found in this work.

A model of active site generation was constructed in order to stress the dependence on the crystal structure and crystal defects. Current and previous results suggest that tetragonal structure in active SO₄²⁻-ZrO₂ is a consequence of the stabilization of anionic vacancies in zirconia. Anionic vacancies are in turn supposed to be related to the catalytic activity for n-butane isomerization through the stabilization of electrons from ionized intermediates.     

杀菌型双吸剂的制备与性质研究

用可以同时吸氧气与二氧化碳的双吸剂和挥发性抑菌剂富马酸单甲酯(MMF)复合成新型食品保鲜剂,能抑制30多种常见的霉菌等生物的生长,以可抗氧化变质和二氧化碳的影响。可用于粮食、蔬菜水果、干果、药物等的保质储存,改善了单纯双吸剂的保鲜性能,延长了食品的保鲜期。     

Structure, thermal-stability and reducibility of Si-doped Ce–Zr–O solid solution

The Si-doped Ce–Zr–O solid solutions have been prepared by the reverse microemulsion method. The effects of Si and its content on the structure characters, thermal-stability and reducibility of the Ce–Zr–O solid solution have been studied by N₂ adsorption, XRD, laser Raman (LR), TPR, FT-IR, NMR and XPS methods. The results indicate that, there are the bonds of Si–O–M (Ce or Zr) in the Ce–Zr–Si–O solid solutions, and the presence of Si can increase obviously the surface area, thermal-stability, crystal lattice distortion rate, and reducibility of the solid solution. The surface area of the sample with 20 wt.% Si reaches 153 m² g⁻¹ after being calcined at 900 °C for 6 h. The Ce–Zr–O solid solution with 5.2–10 wt.% Si shows excellent thermal-stability and reducibility.     

Synthesis and characterization of new flame‐retardant poly(amide‐imide)s containing phosphine oxide and hydantoin moieties in the main chain

Six new flame‐retardant poly(amide‐imide)s (PAIs) 9a–f with high inherent viscosities containing phosphine oxide and hydantoin moieties in main chain were synthesized from the polycondensation reaction of N,N′‐(3,3′‐diphenylphenylphosphine oxide) bistrimellitimide diacid chloride 7 with six hydantoin derivatives 8a–f by two different methods such as solution and microwave assisted polycondensation. Results showed that the microwave assisted polycondensation, by using a domestic microwave oven, proceeded rapidly, compared with solution polycondensation, and was completed in about 7–9 min. All of the obtained polymers were fully characterized by means of elemental analysis, viscosity measurements, solubility test, and FTIR spectroscopy. Thermal properties and flame retardant behavior of the PAIs 9a–f were investigated using thermal gravimetric analysis (TGA and DTG) and limited Oxygen index (LOI). Data obtained by thermal analysis (TGA and DTG) revealed that these polymers showed good thermal stability. Furthermore, high char yields in TGA and good LOI values indicated that these polymers are capable of exhibiting good flame retardant properties. These polymers can be potentially utilized in flame retardant thermoplastic materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5062–5071, 2006     

Oxygen reduction on platinum electrodes in base: Theoretical study

Electrode-potential-dependent activation energies for electron transfer have been calculated using a local reaction center model and constrained variation theory for the oxygen reduction reaction on platinum in base. Results for four one-electron transfer steps are presented. For the first, O₂(ads) is predicted to be reduced to adsorbed superoxide, O₂⁻(ads), which dissociates with a low activation barrier to O(ads) + O⁻(ads). Then a proton transfer form H₂O(ads) to O⁻(ads) takes place, forming OH(ads) + OH⁻(aq). The second electron transfer reacts O(ads) with H₂O(aq) to form a second OH(ads) + OH⁻(aq). The third and fourth electron transfers react the two OH(ads) with two H₂O(aq) to form two H₂O(ads) + two OH⁻(aq). All three different surface reduction reactions are predicted to have reversible potentials in the −0.24 V(SHE) to −0.29 V(SHE) range for 0.1 M base and activation energies for the superoxide formation step are close to the experimentally observed range in 0.1 M base for the overall four-electron to water over the three low index (1 1 0) (1 0 0) and (1 1 1) surfaces: 0.38-0.49 eV at 0.35 eV respectively at 0.88 V(RHE). Predicted reversible potentials for forming O₂⁻(ads) are compared with estimates from the experimental literature. The difference between the acid mechanism, where the peroxyl radical, OOH(ads) is the first reduction intermediate, and the base mechanism, where superoxide, O₂⁻(ads) is the first reduction intermediate, is discussed.     

Estimating oxygen consumption from heart rate using adaptive neuro-fuzzy inference system and analytical approaches

In new approaches based on adaptive neuro-fuzzy systems (ANFIS) and analytical method, heart rate (HR) measurements were used to estimate oxygen consumption (VO₂). Thirty-five participants performed Meyer and Flenghi's step-test (eight of which performed regeneration release work), during which heart rate and oxygen consumption were measured. Two individualized models and a General ANFIS model that does not require individual calibration were developed. Results indicated the superior precision achieved with individualized ANFIS modelling (RMSE = 1.0 and 2.8 ml/kg min in laboratory and field, respectively). The analytical model outperformed the traditional linear calibration and Flex-HR methods with field data. The General ANFIS model's estimates of VO₂ were not significantly different from actual field VO₂ measurements (RMSE = 3.5 ml/kg min). With its ease of use and low implementation cost, the General ANFIS model shows potential to replace any of the traditional individualized methods for VO₂ estimation from HR data collected in the field.     

NO emission of oxygen-enriched CH4/O2/N2 premixed flames under electric field

This work investigates the electric field effect on nitrogen oxide (NO) pollutant formation and emission composition of premixed flames in order to provide better insight on the mechanism of controlling the combustion process by electro-physical means. The present study aims to investigate experimentally the effect of radial DC electric field on premixed laminar methane flame. The electric field effect on flame shape, emission composition and NO emission index of flame is investigated experimentally under the action of direct-current electric field under varying equivalence ratio and level of oxygen enrichment. The results show that ionic wind effects cause the distortion in flame shape. The ionic wind effects diminish with increasing flow rate and level of oxygen enrichment. Minimal effects on NO are measured for flames under the influence of electric field and vanished as the level of oxygen enrichment is increased. This was well supported by the temperature profile measurement in the post flame gas showing no field-induced modification also. It seemed that the action of an electric field on a flame with a geometry that remains practically undeformed produces very minimal effect on pollutant emission.