Evolution of electrical conductivity and semiconductor to metal transition of iron oxides at extreme conditions

Iron oxides are widely found as ores in Earth's crust and are also important constituents of its interiors. Their polymorphism, composition changes, and electronic structures play essential roles in controlling the structure and geodynamic properties of the solid Earth. While all-natural occurring iron oxides are semiconductors or insulators at ambient pressure, they start to metalize under pressure. Here in this work, we review the electronic conductivity and metallization of iron oxides under high-pressure conditions found in Earth's lower mantle. We summarize that the metallization of iron oxides is generally controlled by the pressure-induced bandgap closure near the Fermi level. After metallization, they possess much higher electrical and thermal conductivity, which will facilitate the thermal convection, support a more stable and thicker D^{$\prime\prime$} layer, and formulate Earth's magnetic field, all of which will constrain the large-scale dynamos of the mantle and core.     

水热法制备二氧化锡/钨酸铋复合光催化材料及其催化活性研究

本文用水热法制备了正交晶系的纳米球状结构的二氧化锡和正交晶系的由片状聚集成球状结构的钨酸铋,并且对二者进行了复合,制备出了二氧化锡/钨酸铋复合光催化材料。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、比表面积测试仪(BET)、紫外可见分光光度计等技术对复合样品的结构、形貌、比表面积、孔容孔径和光学性质进行了表征。用碘钨灯模拟太阳光,分别以二氧化锡、钨酸铋和二氧化锡/钨酸铋复合材料为催化剂降解罗丹明B(RhB),研究所制备的二氧化锡/钨酸铋复合材料的光催化活性。光催化90 min时二氧化锡、钨酸铋和二氧化锡/钨酸铋对罗丹明B的降解率分别是9%、22%和30%。实验结果表明,在可见光下,二氧化锡/钨酸铋复合材料的光催化活性要高于单一的二氧化锡和钨酸铋。     

Domain-based local pair natural orbital methods within the correlation consistent composite approach

Ab initio composite approaches have been utilized to model and predict main group thermochemistry within 1 kcal mol⁻¹, on average, from well-established reliable experiments, primarily for molecules with less than 30 atoms. For molecules of increasing size and complexity, such as biomolecular complexes, composite methodologies have been limited in their application. Therefore, the domain-based local pair natural orbital (DLPNO) methods have been implemented within the correlation consistent composite approach (ccCA) framework, namely DLPNO-ccCA, to reduce the computational cost (disk space, CPU (central processing unit) time, memory) and predict energetic properties such as enthalpies of formation, noncovalent interactions, and conformation energies for organic biomolecular complexes including one of the largest molecules examined via composite strategies, within 1 kcal mol⁻¹, after calibration with 119 molecules and a set of linear alkanes. © 2019 Wiley Periodicals, Inc.     

Nickel(II) Schiff base complex supported on nano‐titanium dioxide: A novel straightforward route for preparation of supported Schiff base complexes applying 2,4‐toluenediisocyanate

For the first time, a novel, straightforward and inexpensive route for immobilization of metals in Schiff base complex form is reported applying 2,4‐toluenediisocyanate as a precursor of primary amine group. A nickel(II) Schiff base complex supported on nano‐TiO₂ was designed and synthesized as an effective heterogeneous nanocatalyst for organic reactions, and well characterized using various techniques such as Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, energy‐dispersive X‐ray analysis and thermogravimetric analysis. The catalytic efficiency of the complex was evaluated in selective oxidation of sulfide to sulfoxide by hydrogen peroxide as an oxidant under solvent‐free conditions at room temperature, which successfully resulted in high yield and high conversion of products. Effective factors including solvent type, oxidant and catalyst amount were also optimized. The catalyst shows outstanding reusability and could be impressively recovered for six consecutive cycles without significant change of its catalytic efficiency.     

Structural and phase characteristics of the diamond/matrix interfacial zone in high-resistant diamond composites

The structural-phase state of the contact zone and the factors that influence on the strength of diamond retention in the diamond carbide composites were determined. Composites were obtained by the new hybrid technology that eliminates the reheating of the metalized coating. The elaborated technology combines the thermal diffusion metallization of a diamond and the sintering by the scheme of self-dosed impregnation in a one-stage technological cycle. By the methods of electron microscopy, X-ray diffraction analysis, and Raman spectroscopy the structural and phase characteristics of the interphase boundary were investigated. The improvement of chemical and mechanical adhesion between the diamond and carbide matrix was obtained. It was shown that the specific productivity of the samples with a metalized diamond component is 39% higher than those without metallization.     

原位合成Bi3O4Br/Bi12O17Br2光催化剂及其对磺胺甲噁唑降解性能

Bi_xO_yBr_z光催化剂在有机药物废水处理领域有着非常广阔的潜在应用价值,但因光生电子和空穴的快速复合而表现出较低的光催化效率,进而限制了其应用范围。通过简易的水解-焙烧法原位制得一种新型的Bi₃O₄Br/Bi₁₂O₁₇Br₂复合光催化剂,并以磺胺甲噁唑(SMX)为模拟药物污染物进行了光催化性能测试,对所制催化剂进行了X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)、电化学阻抗(EIS)、光致发光光谱(PL)等表征。结果表明所制备的Bi₃O₄Br/Bi₁₂O₁₇Br₂复合光催化剂具有较强的光生载流子分离率、较低的界面电荷转移电阻,进而展示出优异的光催化降解SMX性能,在模拟太阳光下照射30 min,SMX降解率达到87%,相较于纯的Bi₃O₄Br和Bi₁₂O₁₇Br₂催化剂,降解率分别提升了30%和24%。最后基于自由基捕获实验和催化剂能带结构分析了所制催化剂的降解机理。     

Liquid-Repellent Metal Oxide Photocatalysts

Metal oxide photocatalysts (MOPCs) decompose organic molecules under illumination. However, the application of MOPCs in industry and research is currently limited by their intrinsic hydrophilicity because MOPCs can be wetted by most liquids. To achieve liquid repellency, the surface needs to possess a low surface energy, but most organic molecules with low surface energy are degraded by photocatalytic activity. Herein, current methods to achieve liquid repellency on MOPCs, while preventing degradation of hydrophobic coatings, are reviewed. Classically, composite materials containing MOPCs and hydrophobic organic compounds possess good liquid repellency. However, composites normally form irregular coatings and are hard to prepare on surfaces such as those that are mesoporous or nanostructured. In addition, the adhesion of composites to substrates is often weak, resulting in delamination. Recent studies have shown that the direct grafting reaction of polydimethylsiloxane (PDMS) from silicone oil (methyl-terminated PDMS) under illumination results in a stable polymer brush. This easy and simple grafting method allows us to create stable liquid-repellent surfaces on MOPCs of various types, structures, and sizes. In particular, super-liquid-repellent drops with an underlying air layer can be created on PDMS-grafted nano-/microstructured MOPCs. Potential applications of surfaces combining liquid repellency and photocatalytic activity are also discussed; thus offering new ways of using MOPCs in a wider range of applications.     

Self‐assembled polyurea macromer nanodispersion and resulting hybrid polyurea‐acrylic emulsions and films

A polyurea macromer (PUM) was synthesized and dispersed in basic conditions to form self‐assembled nanoparticles (<20 nm dispersions, up to 30 wt % aq. soln.). These nanoparticles enabled surfactant‐free emulsion polymerization to form hybrid polyurea‐acrylic particles despite the absence of a measureable water‐soluble fraction. The T_g of the starting PUM material was a strong function of the PUM's extent of neutralization and hydration (varying between 100 °C and >175 °C) due to changes in hydrogen and ionic bonding. Two separate hybrid polyurea‐acrylic emulsion systems were prepared: one by direct polymerization of (meth)acrylic monomers in the presence of the nanodispersion and a second by a physical blend of PUM nanodispersion with an acrylic latex control. The direct polymerization method resulted in a hybrid emulsion particle size that developed by a mechanism resembling conventional emulsion polymerization and was unlike that described for seeded polyurethane dispersion systems. Film hardness was shown to increase with increasing coating thickness for the hybrid film prepared by direct polymerization. The resulting mechanical properties could be explained by applying mechanical models for a composite foam structure. These results were unprecedented for normal elastomer films. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1373–1388     

4D Printing based piezoelectric composite for medical applications

Additive manufacturing (AM), otherwise known as three‐dimensional (3D) printing, is driving major innovations in many areas, such as engineering, manufacturing, art, education, and medicine. Although a considerable amount of progress has been made in this field, additional research work is required to overcome various remaining challenges. Recently, one of the actively researched areas lies in the AM of smart materials and structures. Electroactive materials incorporated in 3D printing have given birth to 4D printing, where 3D printed structures can perform as actuating and/or sensing systems, making it possible to deliver electrical signals under external mechanical stimuli and vice versa. In this paper, we present a lightweight, low cost piezoelectric material based on the dispersion of inorganic ferroelectric submicron particles in a polymer matrix. We report on how the proposed material is compatible with the AM process. Finally, we discuss its potential applications for healthcare, especially in smart implants prostheses. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 109–115