Template‐Free Synthesis of Porous Fe3O4/SiOC(H) Nanocomposites with Enhanced Catalytic Activity

We present a template‐free synthesis of Fe₃O₄/SiOC(H) nanocomposites with in situ formed Fe₃O₄ nanoparticles with a size of about 50 nm embedded in a nanoporous SiOC(H) matrix obtained via a polymer‐derived ceramic route. Firstly, a single‐source precursor (SSP) was synthesized by the reaction of allylhydridopolycarbosilane (AHPCS) with Fe‐acetylacetonate [Fe(acac)₃] at 140°C. The SSP was heat‐treated at 170°C to generate Fe₃O₄ nanocrystals in the cross‐linked polymeric matrix. Subsequently, the SSP was pyrolyzed at 600°C–700°C in argon atmosphere to yield porous Fe₃O₄/SiOC(H) nanocomposites with the high BET surface area up to 390 m²/g, a high micropore surface area of 301 m²/g, and a high micropore volume of 0.142 cm³/g. The Fe‐free SiOC(H) ceramic matrix derived from original AHPCS is nonporous. The in situ formation of Fe₃O₄ nanoparticles embedded homogeneously within a nanoporous SiOC(H) matrix shows significantly enhanced catalytic degradation of xylene orange in aqueous solution with H₂O₂ as oxidant as compared with pure commercial Fe₃O₄ nanoparticles.     

Synthesis and Characterization of NiO Nano‐Spheres by Templating on Chitosan as a Green Precursor

In this study, nickel oxide was prepared through the calcination of extrusion dripped chitosan/nickel nitrate beads. The morphology and structural properties of the products were studied using various characterization techniques. Uniformly distributed nickel oxide was formed as observed from the studies of surface morphology where the processing parameters play a huge role on the resulting morphology. TEM results have shown that nickel oxide with crystallite sizes of 10–30 nm was obtained. The Fourier‐transform infrared spectra studies show an intense peak at 525 cm^?1, which is attributed to the vibration of Ni–O bond. Furthermore, the XRD results show NiO diffraction peaks correspond to (111), (200), (220), (311), and (222) which indicates that a bunsenite structure with a face‐centered cubic phase was produced in this study. The usage of 500°C as the lower limit in this study is justified due to the complete removal of the templating material as seen in the thermalgravimetric analysis studies. Furthermore, it was obtained that the largest surface area of nickel oxide synthesized using this technique is 48.024 m²/g with pore sizes of 19.843 nm. The usage of chitosan as a green template for the synthesis of nanoparticles has shown promising results which allows a more economical and sustainable approach for the fabrication of nanomaterials.     

Direct Ink Writing of a Preceramic Polymer and Fillers to Produce Hardystonite (Ca2ZnSi2O7) Bioceramic Scaffolds

The direct ink writing of an ink composed of a preceramic polymer and fillers was used to produce hardystonite (Ca₂ZnSi₂O₇) bioceramic scaffolds. Suitable formulations were developed for the extrusion of fine filaments (350 μm diameter) through a nozzle. The preceramic polymer was employed with the double purpose of contributing to the rheology of the ink by increasing its viscosity and of forming the hardystonite phase upon heat treatment by reacting with the fillers. A control of the rheology is essential when spanning features have to be produced, and therefore the main rheological characteristics of the inks were measured (flow curves, dynamic oscillation tests, viscosity recovery tests) and compared to models reported in the literature. Highly porous scaffolds (up to 80% total porosity) were produced and heat treated in air or in nitrogen atmosphere. The influence of the heat‐treatment atmosphere on the morphology, crystalline phase assemblage, and compressive strength of the scaffolds was investigated.     

超临界甲醇中前驱物对制备超细镍粉体的影响

本文以不同的镍基前驱物（氧化镍、乙酸镍、硝酸镍）在超临界甲醇条件下制备超细镍粉体,考察了体系温度、压力、反应时间以及前驱物种类对制备超细镍粉体的影响。通过SEM和XRD对制备产物的形貌和物相进行表征分析。结果表明,超临界甲醇的还原性随着温度和压力的升高而显著增强,在反应体系中,甲醇既起到溶剂作用又起到还原剂的作用。此外,通过考察前驱物种类对制备过程的影响可知,前驱物的种类对制备超细镍有显著的影响,乙酸镍在超临界甲醇250 ℃,9 MPa条件下即能够得到纯的超细镍,硝酸镍则需要更高的温度和压力（280 ℃,14.0 MPa）,而以氧化镍为前驱物时即使在300 ℃,20 MPa的条件下也只得到镍和氧化镍的混合物。     

Time‐resolved investigation of Cu(In,Ga)Se2 growth and Ga gradient formation during fast selenisation of metallic precursors

Ga segregation at the backside of Cu(In,Ga)Se₂ solar cell absorbers is a commonly observed phenomenon for a large variety of sequential fabrication processes. Here, we investigate the correlation between Se incorporation, phase formation and Ga segregation during fast selenisation of Cu–In–Ga precursor films in elemental selenium vapour. Se incorporation and phase formation are analysed by real‐time synchrotron‐based X‐ray diffraction and fluorescence analysis. Correlations between phase formation and depth distributions are gained by interrupting the process at several points and by subsequent ex situ cross‐sectional electron microscopy and Raman spectroscopy. The presented results reveal that the main share of Se incorporation takes place within a few seconds during formation of In–Se at the top part of the film, accompanied by outdiffusion of In out of a ternary Cu–In–Ga phase. Surprisingly, CuInSe₂ starts to form at the surface on top of the In–Se layer, leading to an intermediate double graded Cu depth distribution. The remaining Ga‐rich metal phase at the back is finally selenised by indiffusion of Se. On the basis of a proposed growth model, we discuss possible strategies and limitations for the avoidance of Ga segregation during fast selenisation of metallic precursors. Solar cells made from samples selenised with a total annealing time of 6.5 min reached conversion efficiencies of up to 14.2 % (total area, without anti‐reflective coating). The evolution of the Cu(In,Ga)Se₂ diffraction signals reveals that the minimum process time for high‐quality Cu(In,Ga)Se₂ absorbers is limited by cation ordering rather than Se incorporation. Copyright © 2014 John Wiley & Sons, Ltd.     

Functional mesoporous poly(ionic liquid)-based copolymer monoliths: From synthesis to catalysis and microporous carbon production

Ionic liquid-functionalized mesoporous polymeric networks with specific surface area up to 935 m²/g have been successfully synthesized one pot by solvothermal copolymerization of divinylbenzene and monomeric ionic liquids. The as-obtained polymers exhibit a monolithic structure featuring large pore volumes, an abundant mesoporosity and an adjustable content of ionic liquids. The effect of the reaction conditions on the pore structure has been studied in detail. These poly(ionic liquid)-based porous networks (PILPNs) have then been employed as precursors in two distinct applications, namely organocatalysis and production of microporous carbon monoliths. Selected organocatalyzed reactions, including carbonatation of propylene oxide by cycloaddition with carbon dioxide, benzoin condensation, and cyanosilylation of benzaldehyde have been readily triggered by PILPNs acting as crosslinked polymer-supported (pre)catalysts. The two latter reactions required the prior deprotonation of the imidazolium salt units with a strong base to successfully generate polymer-supported N-heterocyclic carbenes, referred to as poly(NHC)s. Facile recycling and reuse of polymer-supported (pre)catalysts was achieved by simple filtration owing to the heterogeneous reaction conditions. Furthermore, PILPNs could be easily converted into microporous carbon monoliths via CO₂ activation.     

水洗条件对聚丙烯腈碳纤维及其原丝性能的影响

对二甲基亚砜法(DMSO)生产聚丙烯腈(PAN)碳纤维原丝的水洗温度、时间、方式等进行探讨,进而对水洗工艺进行优化和改善。实验结果表明,控制单束12k PAN原丝水洗水用量在400~500 L/h,水洗温度在45℃,水洗时间在30~40 min,通过在水洗槽中增加拍打辊及V型隔板,可以实现丝束内DMSO残留质量分数≤0.07%。     

From Isonitriles to Unsaturated NHC Complexes of Gold,Palladium and Platinum

In a modular template synthesis, unsaturated NHC complexes of gold, palladium and platinum were synthesized from simple metal salts, isonitriles and amines with acetal or ketal groups. Upon the addition of amines with tethered acetal or ketal moieties to the metal‐activated isonitrile, first nitrogen acyclic carbene (NAC) complexes are formed. These undergo ring closure and elimination to the unsaturated NHC complexes upon addition of acid. This simple strategy opens an attractive and fast approach to NHC complexes of gold, palladium and platinum. The modular approach allows a fast modification and is well‐suited for the synthesis of unsymetrically and symmetrically substituted unsaturated NHC complexes.

     

先驱体法制备氮化硼纤维的研究

以三聚氰胺和硼酸为原料,用有机化学法合成先驱体,制备氮化硼纤维。采用中和滴定法、红外吸收光谱、X射线衍射及扫描电镜进行氮化硼纤维的氮含量的测定及结构分析。结果表明:合成的先驱体是结晶体,晶体发育良好;制得的氮化硼纤维具有B-N键、B-N六元环的特征吸收;随着氮化处理温度的提高, 氮化硼纤维的氮含量增加;用扫描电镜观察1 700℃制得的氮化硼纤维的直径为2-5μm,长径比为20- 100,氮含量为53．46％。     

Laser direct writing of β-Co/Ga and Mn/Ga alloy microstructures from organometallic single-source precursors

β-Co/Ga and Mn/Ga alloys have been deposited on various substrates by laser direct write chemical vapour deposition (LCVD) from novel single-source precursors. The preformed alloy stoichiometry of 1:1 defined by the metal ratio of the precursors, (CO)₄Co-GaEt₂(NMe₃) (1) and (CO)₅Mn-GaEt₂(NMe₃) (2), is retained within the deposited structures. The depositions were up to 1.5 μm thick and the lateral dimension (4 μm) was determined by the diameter of the laser focus. The deposited structures were contaminated with ∼10 at. % C and O (by AES).