Microemulsion synthesis of ms/tz-BiVO4 composites: The effect of pH on crystal structure and photocatalytic performance

In this work, BiVO₄ composites, containing the tetragonal zircon phase (tz-BiVO₄), and monoclinic scheelite phase (ms-BiVO₄), were synthesized using the microemulsion method. The effect of pH on phase composition and photocatalytic activity were investigated. Based on X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), a ms/tz-BiVO₄ composite forms at pH = 1.0 and pure ms-BiVO₄ is obtained in the pH range 4.0–10.0. The three primary steps in preparing BiVO₄ were monitored by optical microscopy and the role played by the microemulsion on the phase composition of BiVO₄ is explained. Photoluminescence spectroscopy (PL), UV–visible diffuse reflectance spectroscopy (UV-DRS), Brunauer-Emmett-Teller (BET), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) were employed to characterize the physical and chemical properties of BiVO₄ composites. The composite formed at pH = 1 exhibited the lowest hole-electron (h⁺-e^-) recombination rate, resulting in the highest photocatalytic activity towards microcystin-LR (MC-LR), with near 100% removal of MC-LR in 5 h. ESR and trapping experiments indicated that MC-LR degradation was mediated primarily by hydroxyl radicals (•OH), superoxide radicals (O₂^•−) and photogenerated holes (h⁺).     

水热法制备Sr_2FeNiO_6催化剂及其催化性能研究

采用水热法制备双钙钛矿催化剂Sr_2FeNiO_6,考察不同浓度KOH溶液(4 mol·L~(-1)、6 mol·L~(-1)、8 mol·L~(-1)、10 mol·L~(-1)、12 mol·L~(-1)、14 mol·L~(-1))对催化剂性能的影响,利用X射线衍射、比表面积测定、程序升温还原和扫描电镜等对样品进行性能表征,并以催化甲烷燃烧为目标,考察催化剂催化性能。结果表明,矿化剂KOH浓度对样品性能影响较大,当浓度为10 mol·L~(-1)时,起燃温度最低,T_(10%)为430℃;浓度为8 mol·L~(-1)时,样品比表面积最大,为19.0 m~2·g~(-1),完全燃烧温度最低,T_(90%)为610℃。     

Techno-economic feasibility of methanol synthesis using dual fuel system in a parallel process design configuration with control on green house gas emissions

Recently, the methanol production has received a lot of attraction in the process industries due to its wide applications in the synthesis of many commercial chemicals and fuels. Most of the coal to methanol processes suffers from higher water consumption, greenhouse gas (GHG) emissions and lower yields. The aim of this study is to develop a novel energy efficient and economic viable process that may not only increase the methanol production capacity but also offers the less energy requirements with improved process economics. In this study, coal gasification process is sequentially integrated in the parallel design configuration with the natural gas reforming technology to enhance the heating value of the resulting syngas for methanol production. To achieve this aim, two case studies have been developed and compared in terms of overall process performance and economics. Case 1 represents the conventional coal to methanol process, whereas, case 2 represents the conceptual design of integrating the gasification and reforming technologies for enhanced methanol production. The process efficiencies calculated for case 1 and case 2 is 63.2% and 70.0%, respectively. It has been seen from results that the methanol production energy for case 1 and case 2 is 0.69 kg/W and 0.76 kg/W, respectively. In terms of process economics, the methanol production cost for case 1 and case 2 has been estimated as 250 €/tonne and 234 €/tonne, respectively. The comparative analysis showed that the case 2 design not only offers higher process performance but also enhances the process feasibility compared to the conventional coal based processes.     

Pore structure of reactively synthesized nanolaminate Ti3SiC2 alloyed with Al

Ti₃SiC₂ has the unique properties integrating the advantages of metals and ceramics, and good open pore structure when alloyed with Al. In this work, porous Ti₃SiC₂ compounds with different Al/Si atom ratios were prepared through the reactive synthesis of elemental powders at 1300 °C. The results indicate that the phase compositions are determined by Al element mole number, and that the pore structure can be controlled through varying Ti particle size. The MAX phase transits from Ti₃SiC₂ with Al element mole number no more than 0.6 to Ti₃AlC₂ with Al element mole number in the range of 0.8–1.2. When Al element mole number is 0.6, the porous compound has a single MAX phase of Ti₃SiC₂ with uniform microporous structure and high bending strength. Porous Ti₃SiC₂ alloyed with 0.6Al has a slow linear increase rate of 0.0083%/μm in open porosity with increasing Ti particle size, and a strict linear relationship between the maximum aperture and Ti particle size with the increase rate of 0.0342 μm/μm. The pore structure formed by the phase transition mechanism for porous MAX phase has the smallest tortuosity factor compared with that formed by the clearance mechanism and the Kirkendall effect.     

Liquid-phase flash sintering 8YSZ with alkali halide sintering aids

The properties of ZrO₂: 8 mol% Y₂O₃ (8YSZ) ceramics with LiF and KCl sintering aids for liquid phase formation during electric field-assisted sintering were studied. Sintering experiments were carried out at 650 °C under 200 V cm⁻¹ AC electric field by varying current density, current application time, as well as LiF and KCl contents. Pellets sintered with KCl addition had cavities, cracks and fractures. Pellets sintered with 15 wt.% LiF, on the other hand, were homogeneous after thermal removal of LiF upon Joule heating. Low electric current densities coupled with longer application times produced homogeneous specimens. Three different stages were identified during sintering experiments: (i) LiF melting with the electric field applied at furnace temperatures lower than its melting point, (ii) shrinkage due to liquid phase formation and LiF removal, (iii) final densification due to grain growth and pore elimination. The electrical behavior and an estimate of the porosity were carried out by electrochemical impedance spectroscopy measurements.     

Rapid fabrication of Al4SiC4 using a self-propagating high-temperature synthesis method

As a promising high-temperature ceramic, aluminum silicon carbide (Al₄SiC₄) has attracted much attention. Al₄SiC₄ is usually synthesized at high temperatures with a long reaction time in an electric furnace. Self-propagating high-temperature synthesis (SHS) is a promising technique for rapid synthesis. In this study, Al₄SiC₄ was prepared by the SHS method from a mixture of silicon, aluminum and carbon black with the addition of poly(tetrafluoroethylene) (PTFE) as an exothermic promoter. The experimental results showed that the use of a high-pressure Ar atmosphere could retain the gaseous materials in the pellet mixture, and the PTFE additive promoted the formation of silicon carbide. In addition, the oxide layer present on the surface of silicon particles inhibited the reaction between silicon and carbon. As a result, high-purity Al₄SiC₄ could be synthesized from aluminum, silicon, and carbon black with 15 wt% PTFE under 1.0 MPa Ar atmosphere in several seconds by the SHS method.     

The optical spectra characterization of Cr2+:ZnSe polycrystalline synthesized by direct reaction of Zn–Cr alloy and element Se

Cr²⁺:ZnSe materials have attracted much attention as candidates for mid-infrared laser source either in the form of polycrystalline powders, or bulk ceramics, single crystals and nano-materials. In this work, a novel method for synthesizing Cr²⁺:ZnSe polycrystalline by direct reaction of Zn–Cr alloy and element Se (DRAE) was proposed. The zinc alloy containing 0.1 at% Cr was prepared by dissolving Cr in zinc liquid in a closed quartz ampoule. X-ray diffraction (XRD) results showed that the synthesized Cr²⁺:ZnSe polycrystalline was with a Zinc-blend structure. X-ray photoelectron spectroscopy (XPS) spectra showed that there was no un-reacted element of Zn, or Se. Cr²⁺ ions successfully and uniformly doped into ZnSe crystal lattice, which is confirmed by the diffuse reflectance spectrum, Raman spectrum and mid-infrared photoluminescence spectra. Furthermore, the sample showed excellent mid-infrared properties without luminescence quenching in the region 1800–3000 nm, and the decay-time was about 5 μs. The as-synthesized Cr²⁺:ZnSe polycrystalline meets the requirement for the preparation of mid-infrared ceramic or single crystals. These results indicate that the novel strategy of DRAE is valid for the synthesis of other transition metal doped ZnSe materials.     

New titanium (III) phosphite structure and its application as anode for lithium ion batteries

A new titanium (III) phosphite Ti₂(HPO₃)₃, has been synthesized under hydrothermal conditions. The solid-state structure of this material was solved using single-crystal X-ray diffraction. The anionic inorganic skeleton has a three-dimensional structure, which is built up by TiO₆ octahedral units linked together via bridging HPO₃ pseudo pyramids, giving rise to tunnels along the three crystallographic axes. This new compound displays a high thermal stability limit of 625 °C. IR and Raman spectroscopies show the vibrational modes of the (HPO₃)²⁻oxoanions. Electrochemical activity of this phase toward reversible insertion of Li ion was studied for the first time by galvanostatic charge-discharge measurements, an insertion host for reversible accommodation of Li⁺ was observed.     

Introducing four different branch structures in PET by reactive processing––A rheological investigation

Chain extension/branching by reactive processing is a well-known method to enhance the rheological properties of polymers. In this study, pyromellitic dianhydride, poly(glycolic acid), triglycidyl isocyanurate, and bisphenol A diglycidyl ether were used as chain extender/branching agents to produce branched Polyethylene terephthalate (PETs) with four different molecular structures. According to the linear rheological characterizations, the storage modulus and complex viscosity of modified PET samples enhanced significantly after branching. The shear viscosities of modified PET show a pronounced shear-thinning behavior and a remarkable increase at low frequencies, which can be an indication of the existence of long-chain branches (LCBs) in the molecular structure of polymer and broadening the molecular weight distribution. Fourier transform infrared (FTIR) and differential scanning calorimetry (DSC) analysis were used to investigate the effect of branching agents on the chemical structure and thermal properties of PET, respectively. DSC results show that higher amounts of LCBs lead to lower melting and crystallization temperatures.