High-performance photocatalysts for the selective oxidation of alcohols to carbonyl compounds

With an increase in awareness about the need for green chemistry, there is a shift in focus towards identifying eco-compatible technologies that can improve product yield and eliminate the use or generation of hazardous compounds. An immediate practical example of such an approach is the development of sustainable methods for alcohol oxidation as alternatives to the current processes that are energy intensive and rely on ecotoxic chemicals. In this regard, heterogeneous photocatalysis has been identified as a robust technique to catalyze reactions under benign conditions, which would otherwise require harsh synthesis routes. With the advent of materials sciences and nanotechnology, there has been a tremendous increase in the scope of applicability of photocatalysis in fine chemicals synthesis. Though an attractive choice, much of the fundamental information pertaining to catalyst activity, selectivity and reaction conditions for optimum conversion are still to be investigated for most of these systems. To this end, this review will encompass recent achievements in the selective photocatalytic oxidation of alcohols by harnessing solar radiation as a viable source of energy. The discussion will be arranged based on common types of photocatalysts reported in literature, namely metal oxides (eg, TiO₂ and ZnO, Nb₂O₅), sulphides (eg, CdS, CuS, and Bi₂S₃), and carbonaceous photocatalysts (eg, g-C₃N₄). Several such candidates for photocatalysts will be discussed critically with the aim of providing useful insight into developing selective photocatalysts that can oxidize alcohols via eco-friendly pathways along with high yields.     

絮体表面形态对膜污染预测的影响

现有对混凝-膜过滤过程中膜污染的预测分析，一般采用XDLVO理论对光滑界面的作用能进行计算，但混凝絮体表面形态会对预测结果产生较大的影响。利用正弦波球体模型对粗糙腐殖酸(HA)絮体表面进行模拟，并通过表面元素积分法(SEI)结合XDLVO理论与复合辛普森规则，对不同粗糙程度的混凝絮体与聚偏氟乙烯(PVDF)膜的界面作用能进行量化模拟；并将结果与传统XDLVO理论模拟的光滑界面作用能进行了比较。实验结果表明，该模型适用于混凝-膜过滤体系中絮体界面作用能的模拟，同时在模拟过程中，由于粗糙度的不同会导致界面作用能在数值上存在1~2个数量级的差异；并且粗糙的絮体较完全光滑的絮体与膜污染趋势的拟合程度更高，即引入絮体表面形态对利用絮体与膜界面间相互作用能表征膜污染趋势的置信度更高。     

海面油膜的偏振反射特性仿真实验

为了给海面溢油污染识别检测提供理论基础,根据菲涅尔反射公式的偏振反射系数,结合偏振双向反射率因子和粗糙海面的概率密度分布函数,建立了完善的pBRDF模型,仿真在不同太阳入射角度、不同探测器观测角度以及不同海面风速风向等条件下海水和油膜的偏振反射分布函数。结果表明:海水和油膜太阳天顶角为53°和56°时P偏振反射率分别为1.0×10^-5和2.5×10^-5,S偏振反射率随着太阳天顶角的增加而增加;海面风速越大偏振反射率峰值越小;海面风向只改变pBRDF的空间位置;海水和油膜线偏振度空间分布有明显差异。搭建实验平台相机以40°拍摄时,得出海水和油膜的线偏振度分别在0.2~0.4, 0.5~0.7之间,同时表明利用偏振探测获取目标场景的偏振度和偏振角图可提高图像质量。     

核聚变堆用钨表面超精密抛光的研究现状与趋势

钨作为未来核聚变堆中最有前景的面向等离子体材料,在反应堆工况下将承受高能粒子的辐照冲击。表面质量的好坏会直接影响材料的氢/氦滞留行为和辐照损伤程度,进而影响聚变堆的安全性和可靠性。现阶段,针对钨的抗辐照改性研究主要着眼于材料的成分、结构和组织设计,关于机械加工对材料表面抗辐照改性的研究甚少。文章聚焦前沿科学问题,从机械加工角度分析核材料领域科学问题,结合国内外相关研究成果及核聚变堆用钨(PFM-W)的机械加工现状,阐述了PFM-W表面超精密抛光的必要性。通过对比不同抛光方法,提出了磁流变抛光和力流变抛光是较为适合PFM-W表面超精密加工的观点,并对未来PFM-W表面超精密抛光研究趋势进行了分析,重点在抛光方法的探索以及抛光后材料表面质量对抗辐照性能影响的研究。     

金刚石涂层微铣刀的铣削加工试验

为了掌握金刚石涂层对其铣削性能的影响，针对直径为50 μm级的硬质合金微铣刀，进行了金刚石涂层与未涂层硬质合金微铣刀具微槽铣削试验。通过使用线电极电火花磨削技术制备出直径为50 μm级的D形微铣刀,采用金刚石涂层和未涂层刀具在纯铜工件上开展微槽铣削工艺试验；使用白光干涉仪、超景深显微镜等仪器来观测微槽表面形貌、粗糙度等随铣削距离变化的规律，分析金刚石涂层对硬质合金微铣刀铣削加工质量的影响。结果表明：采用金刚石涂层刀具加工的微槽具有较少的毛刺，表面粗糙度值约为未涂层刀具铣削的粗糙度值的1/2，并且能够在一定距离内保持稳定的槽宽、粗糙度值和侧面形貌。     

基于UG的正交车铣加工回转体表面微观残留仿真

正交车铣加工的回转体表面由铣刀与工件的复合相对运动形成,其形成机理独特,多个参数影响其表面微观形貌。为研究切削参数对正交车铣回转体表面微观残留的影响,基于UG建立了正交车铣回转体表面的仿真加工方法,并通过Vericut构建了虚拟五轴车铣加工环境,由此仿真研究了周向每齿进给量对正交车铣回转体表面微观残留的影响,发现已加工表面微观残留高度随周向每齿进给量增加显著增大。     

香兰素基非离子表面活性剂的动态表面张力与气/液界面吸附行为

通过最大气泡压力法测定香兰素基聚氧乙烯醚(VAEO)的动态表面张力,利用Word-Tordai方程研究其在气/液界面的吸附行为。结果表明,质量浓度低于临界胶束浓度(cmc)时,VAEO在吸附前期为扩散控制吸附,在吸附后期为混合动力控制吸附;质量浓度大于cmc时,为混合动力控制吸附,胶束不影响吸附行为。VAEO_(10)和VAEO_(20)的扩散系数D的数量级为10~(-11)m~2/s,比文献报道的壬基酚聚氧乙烯醚(NPEO_9)低一个数量级。     

Microwave dielectric ceramics in (Mg1/3Sb2/3)O2-ZrO2-TiO2 system with near zero τf and low loss in a very wide range

A series of (ZrTi)_1-x(Mg_1/3Sb_2/3)_2xO₄ (0.04?≤?x?≤?0.36) ceramics were successfully synthesized through the conventional solid-state processing. Appropriate content of CuO was added as sintering aids to promote the density of ceramics. The XRD analysis revealed that the main crystalline phase of ceramics sintered at optimal temperature belonged to α-PbO₂-type structure. Raman spectroscopy and far infrared reflectivity (FIR) spectra were employed to study the phonon modes of ceramics, which explained the relationship between microwave dielectric properties and structure. It is interesting that the τ_f are near-zero (+6.6 ~ ?4.6?ppm/°C) and meanwhile the Q×f are relatively high (29,000–41,800?GHz) for samples with x in a very wide range of 0.10–0.36. In this range, their dielectric constants (ε_r) can be adjustable from 35.4 to 24.4. The results demonstrated this ceramic system is a potential candidate for microwave dielectric applications requiring an adjustable dielectric constants and near zero τ_f.     

MOCVD-derived GdYBCO tapes with smooth surface and low Rs based on a new self-heating technology

The metal organic chemical vapor deposition (MOCVD) method was used to prepare GdYBCO films on LaMnO₃/ homo epitaxial-MgO/ ion-beam-assisted-deposition-MgO/ solution-deposition-planarization-Y₂O₃ buffered Hastelloy tapes. By adopting a simple self-heating technique, the substrates were heated by the joule effect after applying a heating current (I_h) through Hastelloy metal tapes. The effects of substrate temperature and (Gd, Y)/Ba ratio (r_c) in the precursor on the biaxial texture, surface morphology and superconducting performance of GdYBCO films were systematically investigated by varying the values of I_h and r_c. Needle-like outgrowths formed on the substrate surface were characterized using a scanning electron microscope, energy dispersive spectrometer and X-ray diffraction system. The results show that a high I_h or r_c leads to the formation of needle-like outgrowths. Therefore, I_h and r_c are crucial process parameters that control the growth of needle-like outgrowths on the surface of GdYBCO films. Three hundred nanometer thick GdYBCO films were prepared at different I_h and r_c by the MOCVD process. At an I_h of 27.0?A and an r_c of 0.6, the surface of the GdYBCO film was very smooth and dense, which can provide a good template for multiple depositions of GdYBCO films. The critical current density of the deposited 300?nm-thick GdYBCO film was 4.4 MA/cm² (77?K, 0?T), which is attributed to good biaxial texture and appropriate film composition. Furthermore, the microwave surface resistance (77?K, 10?GHz) of the GdYBCO film was merely 0.581?mΩ.     

Surface sedimentation and adherence of Nano‐SiO2 to improve thermal stability and flame resistance of melamine‐formaldehyde foam via sol‐gel method

Melamine‐formaldehyde foam possesses intrinsic flame retardance; however, relative poor thermal stability and a certain amount of heat release rate restrict its applications in heated environment to a degree. In the present research, sol‐gel method has been adopted to precipitate nano‐SiO₂ particles on the surface of the melamine‐formaldehyde foam's fibers to construct a protective inorganic gel layer. Taking advantages of the shielding effects of the gel layer, the thermal‐oxygen degradation of the foam can be greatly retarded during heating; hence, the thermal stability is remarkably improved, and the flame retardance is further enhanced. In addition, introducing a small amount of membrane‐forming agent in the sol‐gel system can make the depositional nano‐SiO₂ particles well adhered to avoid dusting.