羟基磷灰石负载Ni催化剂中Ni含量对催化甲烷二氧化碳重整制合成气性能的影响

以低温沉淀方法制备的羟基磷灰石(HAp)为载体,采用浸渍法制备了一系列不同Ni含量的Ni/HAp催化剂,并采用BET、H2-TPR、XRD、SEM、FT-IR、TEM和TG-DTA技术对催化剂进行了表征。结果表明,NiO含量为13%的催化剂表现出最好的催化甲烷二氧化碳重整制合成气活性,在850℃、空速3.6×104mL/(h·gcat)的反应条件下,甲烷和二氧化碳的转化率在10 h内分别稳定在72%和83%。这主要归因于催化剂中金属和载体之间的强相互作用。虽然反应后的催化剂表面有少量的积炭,但这些积炭多以丝状炭存在,并不会影响催化剂的活性和稳定性。     

Multi‐walled carbon nanotube modified dummy‐template magnetic molecularly imprinted microspheres as solid‐phase extraction material for the determination of polychlorinated biphenyls in fish

Novel multi‐walled carbon nanotube modified dummy‐template molecularly imprinted microspheres (MWCNTs@DMMIPs) were successfully synthesized as adsorbents for six kinds of polychlorinated biphenyls (PCBs). MWCNTs@DMMIPs were prepared by a surface molecular imprinting technique. Core–shell Fe₃O₄@SiO₂ nanoparticles were employed as magnetic support. 3,4‐Dichlorobenzene acetic acid was used as a dummy template instead of PCBs, methacrylic acid was used as functional monomer and ethylene glycol dimethacrylate was used as the cross‐linker. The resulting absorbent was characterized by various methods. The adsorbent was employed for extracting PCBs and exhibited good selectivity and high adsorption efficiency. Furthermore, it was reusable and capable of magnetic separation. Adsorption kinetics fit well with a pseudo‐second‐order kinetic equation and also exhibited a three‐stage intra‐particle diffusion model. The Freundlich model was used to describe the adsorption isotherms. The materials were successfully applied to the magnetic dispersive solid‐phase extraction of six kinds of PCBs followed by gas chromatography with mass spectrometry determination in fish samples, the limit of detection of six kinds of PCBs were 0.0028–0.0068 μg/L and spiked recoveries ranged between 73.41 and 114.21%. The prepared adsorbent was expected to be a new material for the removal and recovery of PCBs from contaminated foods.     

Graphene‐sensitized microporous membrane/solvent microextraction for the preconcentration of cinnamic acid derivatives in Rhizoma Typhonii

A novel graphene‐sensitized microporous membrane/solvent microextraction method named microporous membrane/graphene/solvent synergistic microextraction, coupled with high‐performance liquid chromatography and UV detection, was developed and introduced for the extraction and determination of three cinnamic acid derivatives in Rhizoma Typhonii. Several factors affecting performance were investigated and optimized, including the types of graphene and extraction solvent, concentration of graphene dispersed in octanol, sample phase pH, ionic strength, stirring rate, extraction time, extraction temperature, and sample volume. Under optimized conditions, the enrichment factors of cinnamic acid derivatives ranged from 75 to 269. Good linearities were obtained from 0.01 to 10 μg/mL for all analytes with regression coefficients between 0.9927 and 0.9994. The limits of quantification were <1 ng/mL, and satisfactory recoveries (99–104%) and precision (1.1–10.8%) were also achieved. The synergistic microextraction mechanism based on graphene sensitization was analyzed and described. The experimental results showed that the method was simple, sensitive, practical, and effective for the preconcentration and determination of cinnamic acid derivatives in Rhizoma Typhonii.     

Extraction of methocarbamol from human plasma with a polypyrrole/multiwalled carbon nanotubes composite decorated with magnetic nanoparticles as an adsorbent followed by electrospray ionization ion mobility spectrometry detection†

In this work, a polypyrrole/multiwalled carbon nanotubes composite decorated with Fe₃O₄ nanoparticles was chemically synthesized and applied as a novel adsorbent for the extraction of methocarbamol from human plasma. Electrospray ionization ion mobility spectrometry was used for the determination of the analyte. The properties of the magnetic‐modified adsorbent were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform IR spectroscopy, and X‐ray diffraction. The effects of experimental parameters on the extraction efficiency of the sorbent were investigated. Under the optimized conditions, the linear dynamic range was found to be 2–150 ng/mL with the detection limit of 0.9 ng/mL. The relative standard deviation was 5.3% for three replicate measurements of methocarbamol in plasma sample. The extraction efficiency of the sorbent for the determination of different drugs with various polarities was also compared to that of Fe₃O₄‐polypyrrole and Fe₃O₄‐multiwalled carbon nanotubes sorbents. Finally, the method was used for the determination of methocarbamol in blood samples.     

ZnO纳米线基MWNTs/PVDF复合热电材料的制备及特性研究

将不同比例的多壁碳管(MWNTs)与聚偏二氟乙烯(PVDF)聚合物混合后,喷涂于n型ZnO半导体纳米线阵列上,制备了一种新型ZnO纳米线基MWNTs/PVDF热电复合材料.与以往采用价格昂贵的p型与n型单壁碳纳米管(SWNTs)与聚合物混合制备的复合热电材料特性相比,这种新型热电复合材料在降低制造成本的同时,利用分散于聚合物中MWNTs的一维电子传输特性及形成的大量界面势垒,加上ZnO半导体纳米线具有的较高载流子密度与迁移率,提高了复合热电材料中电子的输运特性,增加了材料对声子的散射强度.测试发现,在一定的温度梯度下,随着MWNTs添加质量百分比的增加,热电材料的温差电动势和电导率也随之增加,但其Seebeck系数变化量不大.研究表明,这种热电材料有望替代采用p型与n型SWNTs构建的SWNTs/PVDF复合热电材料.研究结果对开发超轻、无毒、廉价、可应用于各种微纳电子领域的新型电源具有重要的参考价值.     

Electrochemical Properties of Hollow‐Structured MnS–Carbon Nanocomposite Powders Prepared by a One‐Pot Spray Pyrolysis Process

Spherical, hollow MnS? C composite powders were prepared from a solution of manganese salt, thiourea, and sucrose by one‐pot spray pyrolysis. The MnS? C composite powders were generated by direct sulfidation of MnO with hydrogen sulfide gas generated in situ by decomposition of thiourea during spray pyrolysis. Sucrose, which is used as a carbon source material, plays a key role in the formation of the MnS? C composite powders by improving the reducing atmosphere around the powders. Dot‐mapping images of the composite powders demonstrated uniform distribution of the manganese, sulfur, and carbon components within the MnS? C composite powder. Fine crystals of MnS were uniformly mixed with carbon derived from polymerization and carbonization of sucrose. The carbon content of the MnS? C composite powders was 26 wt %. The discharge capacities of the MnS? C composite powders in the 2nd and 200th cycles were 863 and 967 mA h g^?1, respectively, at a current density of 1000 mA g^?1. The spherical and hollow morphology of the MnS? C composite powders was completely retained, even after 200 cycles. The enhanced cycling and rate performance of the MnS? C composite powders is ascribed to the structural stability of the composite powders.     

Carbon‐Coated LiTi2(PO4)3: An Ideal Insertion Host for Lithium‐Ion and Sodium‐Ion Batteries

We report the extraordinary performance of carbon‐coated sodium super ion conductor (NASICON)‐type LiTi₂(PO₄)₃ as an ideal host matrix for reversible insertion of both Li and Na ions. The NASICON‐type compound was prepared by means of a Pechini‐type polymerizable complex method and was subsequently carbon coated. Several characterization techniques such as XRD, thermogravimetric analysis (TGA), field‐emission (FE) SEM, TEM, and Raman analysis were used to study the physicochemical properties. Both guest species underwent a two‐phase insertion mechanism during the charge/discharge process that was clearly evidenced from galvanostatic and cyclic voltammetric studies. Unlike that of Li (≈1.5 moles of Li), Na insertion exhibits better reversibility (≈1.59 moles of Na) while experiencing a slightly higher capacity fade (≈8 % higher than Li) and polarization (780 mV) than Li. However, excellent rate capability profiles were noted for Na insertion relative to its counterpart Li. Overall, the Na insertion properties were found to be superior relative to Li insertion, which makes carbon‐coated NASICON‐type LiTi₂(PO₄)₃ hosts attractive for the development of next‐generation batteries.     

Integration of [(Co(bpy)3]2+ Electron Mediator with Heterogeneous Photocatalysts for CO2 Conversion

An efficient chemical system for electron generation and transfer is constructed by the integration of an electron mediator ([Co(bpy)₃]²⁺; bpy=2,2′‐bipyridine) with semiconductor photocatalysts. The introduction of [Co(bpy)₃]²⁺ remarkably enhances the photocatalytic activity of pristine semiconductor photocatalysts for heterogeneous CO₂ conversion; this is attributable to the acceleration of charge separation. Of particular interest is that the excellent photocatalytic activity of heterogeneous catalysts can be developed as a universal photocatalytic CO₂ reduction system. The present findings clearly demonstrate that the integration of an electron mediator with semiconductors is a feasible process for the design and development of efficient photochemical systems for CO₂ conversion.     

Investigation of Coenzyme Q10 by Voltammetry

A simple, accurate and rapid voltammetric method has been developed for the quantitative determination of coenzyme Q₁₀. Studies with direct current voltammetry were carried out using a glassy carbon electrode (GCE) in a phosphate buffer solution (pH 6.86). A well-defined oxidation peak of CoQ₁₀ was obtained at -0.600 V vs Ag/AgCl. The magnitude of the oxidation peak current has been found to be related to the concentration of the coenzyme over the range of (2.010^-5 to 2.010^-4 M) (r = 0,991). Antioxidant activity of CoQ₁₀ was investigated.     

Utilization of Environmentally Benign Dicyandiamide as a Precursor for the Synthesis of Ordered Mesoporous Carbon Nitride and its Application in Base‐Catalyzed Reactions

Assisted by a new dissolution procedure, dicyandiamide (DCDA), an environmentally benign and cheap precursor, has been employed for the synthesis of mesoporous carbon nitride (CN) materials through a nanocasting approach. The synthesized mesoporous materials possessed high specific surface areas (269–715 m² g^?1) with narrow pore‐size distributions (about 5 nm) and faithfully replicated the mesostructures of the SBA‐15 and FDU‐12 templates. Several characterization techniques, including XRD, SAXS, TEM, Raman and FTIR spectroscopy, XPS, and CO₂‐TPD, were used to analyze the physicochemical properties of these materials and the results showed that the mesoporous CND materials had graphitic‐like structures and consisted of CN heterocycles, as well as amino groups. In a series of Knoevenagel condensation reactions, as exemplified by the reaction of various aldehydes and nitriles, these mesoporous CND materials demonstrated high and stable catalytic activities, owing to an abundance of basic sites.