石墨烯/银纳米颗粒复合材料的制备及其对双氧水的电化学检测

以氧化石墨烯(GO)和硝酸银为原材料,聚乙烯吡咯烷酮(PVP)为还原剂和稳定剂,通过水热法制备出还原氧化石墨烯/银纳米颗粒(rGO/AgNPs)复合材料。采用透射电子显微镜(TEM)、X射线衍射(XRD)及紫外-可见分光光度计(UV-Vis)对rGO/AgNPs复合材料的形貌、组成和结构进行表征。同时,将rGO/AgNPs复合材料修饰到玻碳电极表面制备出过氧化氢(H_2O_2)电化学传感器,通过循环伏安法(CV)和计时安培响应法(i-t)对传感器进行电化学性能测试。实验结果表明:制备的rGO/AgNPs传感器具有较好的电化学性能,其对H_2O_2检测的灵敏度为340.6μA·(mmol/L)~(-1)·cm~(-2),响应时间为3s,最低检测极限为7.5μmol/L(S/N=3),线性检测范围为20~4950μmol/L(线性相关系数为R=0.9973)。     

MoS2/g-C3N4复合催化剂的制备及CdSe量子点敏化产氢性能研究

太阳能光催化分解水制氢被认为是从根本上解决能源与环境问题较为理想的途径之一。在以尿素为原料制得石墨相氮化碳(g-C_3N_4)的基础之上,采用简单的低温溶液反应法将二硫化钼(MoS_2)与石墨相氮化碳(g-C_3N_4)复合得到复合催化剂MoS_2/g-C_3N_4,并利用透射电子显微镜(TEM)、X射线衍射(XRD)、紫外-可见漫反射(DRS)、傅里叶变换红外光谱(FT-IR)和荧光光谱等对该复合光催化剂的组成、形貌和光物理性能进行了表征;进而以CdSe量子点为光敏剂,三乙醇胺(TEOA)为牺牲剂,构建了不含贵金属的三组分光催化产氢体系,并对体系pH值、CdSe量子点浓度等对产氢性能的影响进行了研究。结果表明:将MoS_2纳米颗粒负载到g-C_3N_4上可使g-C_3N_4的光催化产氢性能得到显著提高。当MoS_2负载量为7%(质量比)时,在最佳的条件下(pH=9.0,CdSe量子点的体积为25mL),最大产氢速率达到了141.74μmol·h-1,6h的产氢总量达到了212.61μmol。最后,结合荧光猝灭实验,推测了该体系的产氢机理。     

Polyethylene Glycol–CaCl2 Coordination Compounds as a Novel Form‐Stable Phase Change Material with Excellent Thermophysical Properties

Polyethylene glycols (PEGs) have been extensively studied as phase change materials (PCMs). To overcome the problem of liquid leakage, the authors firstly report a novel form‐stable phase change material (FSPCM) using coordination compound. The structure, morphology, thermal property, and thermal stability of the self‐prepared samples are determined. The obtained results confirm the existence of coordination bonds between PEG and Ca²⁺ species, and no liquid leakage is observed for the synthesized PEG–CaCl₂ composites at temperatures as high as 120 °C. The PEG8000–CaCl₂ (1:2) FSPCM exhibits a relatively large latent heat of 147.7 J g^?1, corresponding to 87.8% of that of pure PEG. From the dynamical viewpoint, the activation energy of crystallization process is increased by only 5.2% for the PEG8000–CaCl₂ composite due to the formation of coordination bonds; however, the activation energy is reduced by 18.3% during melting process. After adding 3 wt% conductive carbon black, the heat storage performance of the PEG phase change material can be optimized. The PEG‐CaCl₂ composite would be a promising material for thermal energy storage applications and can be used in various engineering fields.

     

Selective Nanoscale Fabrication with Roughness Reduction of Polycrystalline Silicon by Physically Induced Fluorine Bonds Using Atomic Force Microscope

Polycrystalline silicon (poly-Si) is widely used as a gate layer in integrated circuits, transistors, and channels through nanofabrication. Nanoremoval and roughness control are required for nanomanufacturing of various electronic devices. Herein, a nanoscale removal method is developed to overcome the limitations of microcracks, complex procedures, and time-consuming conventional fabrication and lithography methods. The method is implemented with a mechanically induced poly-Si phase transition using atomic force microscope (AFM). Mechanical force induces the covalent bonds between silicon and fluorine atoms which cause the phase transition of poly-Si. Then, the bond structure of the Si molecules is weakened and selectively removed by nano-Newton-scale force using AFM. A selective nanoscale removal with roughness control is implemented in 0.5 mM TBAF solution after mechanical force (43.58–58.21 nN) is applied. By the magnitude of nano-Newton force, the removal depth of poly-Si is controlled from 2.66 to 21.52 nm. Finally, the nanoscale fabrication on poly-Si wafer is achieved. The proposed nanoremoval mechanism is a simple fabrication method that provides selective, nanoscale, and highly efficient removal with roughness control.     

Thermodynamic studies on the complete phase diagram of aqueous two phase system containing polyethylene glycol dimethyl ether 2000 and di-potassium hydrogen phosphate at different temperatures

The liquid-liquid equilibrium of polyethylene glycol dimethyl ether 2000 (PEGDME₂₀₀₀)+K₂HPO₄+H₂O system has been determined experimentally at T=(298.15,303.15,308.15 and 318.15) K. The liquid-solid and complete phase diagram of this system was also obtained at T=(298.15 and 308.15) K. A nonlinear temperature dependent equation was successfully used for the correlation of the experimental binodal data. Furthermore, a temperature dependent Setschenow-type equation was successfully used for the correlation of the tie-lines of the studied system. Moreover, the effect of temperature on the binodal curves and the tie-lines for the investigated aqueous two-phase system have been studied. Also, the free energies of cloud points for this system and some previously studied systems containing PEGDME₂₀₀₀ were calculated from which it was concluded that the increase of the entropy is the driving force for formation of aqueous two-phase systems. Additionally, the calculated free energies for phase separation of the studied systems were used to investigate the salting-out ability of the salts having different anions. Furthermore, the complete phase diagram of the investigated system was compared with the corresponding phase diagrams of previously studied systems, in which the PEGDME₂₀₀₀ has been used, in order to obtain some information regarding the phase behavior of these PEGDME₂₀₀₀+salt+water systems.     

A new dynamic hydrogen reference electrode for applications in thin-film sensor systems

The realization and applicability of a new dynamic hydrogen reference electrode (DHRE) within an electrochemical microcell for sensor applications is reported. The electrodes are fabricated in thin-film technology and fixed within a flow-through device. An experimental setup for accurate electrochemical potential measurements is described. Smooth platinum, platinized platinum and pHEMA coated electrodes are investigated with regard to their initialization behavior, stability, reproducibility and interference with electrolytes. It is found that platinized platinum DHREs show excellent stability and reproducibility. For uncoated electrodes, the electrochemical potential is established within seconds. The potential is independent of the pH value within the range of pH 4–10. Interference with sulfate and phosphate is observed. Thus, the platinized platinum DHRE is well suited for bioanalytical sensor applications, where the pH value is buffered and the concentrations of the disturbing anions are constant or very low.     

Application of the independent molecule model to elucidate the dynamics of structure I methane hydrate: a second report

Two model systems of methane hydrate are constructed. One has a small cage surrounded by 12 large cages. The other has a large cage surrounded by four small cages and ten large cages. Three different H-bonding network patterns between waters are formed, and three random configurations of methane in each cage are chosen. A new method called the surface water fixed model is presented in which the energy minimum conformations for both model systems are preserved close to the X-ray crystallized structure. With normal mode analysis, we calculated frequencies of 2916.6 cm⁻¹ for a small cage at a centre, 2915.9 cm⁻¹ not at a centre, and 2911.7 cm⁻¹ for a large cage at a centre, and 2911.3 cm⁻¹ not at a centre. These frequencies are in moderate agreement with the corresponding Raman spectra, though not adequate. With our new method, however, it should be possible to improve agreement with the Raman spectra, if a model system vastly larger than the present model systems were constructed.     

共价键长的变化规律及计算

研究了共坐键长的变化规律,提出了两个影响键长的参数,即配位体的半径与中心原子半径之比Rraio和由中心原子组成的基团拓扑指数F2,用BP神经网络法,逼近了50个、预测了11个简单无机分子中非含氢原子键的键长,其计算误差基本上在2pm以内。     

Ion-cyclotron resonance study of elementary stages of the catalytic oxidation of CO by N2O in the presence of VIA-group metal ions

Gas phase reactions of Mo⁺ and W⁺ ions with the molecules of various oxidants (NO, O₂, N₂O, CH₂O, C₂H₄O) were studied using ion cyclotron resonance. In oxidation with N₂O the mono-, di- and trioxide metal cations are formed consecutively. The trioxide MO₃ ⁺ ions of both metals react with CO to form CO₂ and MO₂ ⁺ ions. In this way, catalytic reaction N₂O + CO N₂ + CO₂ occurs in the gas phase with MoO₃ ⁺ /MoO₂ ⁺ and WO₃ ⁺/WO₂ ⁺ couples as catalysts. The rate constants have been measured for both stages of the catalytic cycle as well as for the stages of the catalyst preparation. Metal-oxygen bond energies were estimated for MoO_x ⁺ and WO_x ⁺ species with various x. The mechanism of CO oxidation with MoO_x ⁺ and WO_x ⁺ cations as catalysts in the gas phase is discussed in comparison with that for the oxidation over classical solid oxide catalysts.