A Molecular Approach to Self‐Supported Cobalt‐Substituted ZnO Materials as Remarkably Stable Electrocatalysts for Water Oxidation

In regard to earth‐abundant cobalt water oxidation catalysts, very recent findings show the reorganization of the materials to amorphous active phases under catalytic conditions. To further understand this concept, a unique cobalt‐substituted crystalline zinc oxide (Co:ZnO) precatalyst has been synthesized by low‐temperature solvolysis of molecular heterobimetallic Co_4?xZn_xO₄ (x=1–3) precursors in benzylamine. Its electrophoretic deposition onto fluorinated tin oxide electrodes leads after oxidative conditioning to an amorphous self‐supported water‐oxidation electrocatalyst, which was observed by HR‐TEM on FIB lamellas of the EPD layers. The Co‐rich hydroxide‐oxidic electrocatalyst performs at very low overpotentials (512 mV at pH 7; 330 mV at pH 12), while chronoamperometry shows a stable catalytic current over several hours.     

3D amorphous carbon and graphene co-modified LiFePO4 composite derived from polyol process as electrode for high power lithium-ion batteries

Amorphous carbon and graphene co-modified LiFePO_4 nanocomposite has been synthesized via a facile polyol process in connection with a following thermal treatment.Various characterization techniques,including XRD.Mossbauer spectra,Raman spectra,SEM,TEM,BET,O_2-TPO,galvano charge-discharge,CV and EIS were applied to investigate the phase composition,carbon content,morphological structure and electrochemical performance of the synthesized samples.The effect of introducing way of carbon sources on the properties and performance of LiFePO_4/C/graphene composite was paid special attention.Under optimized synthetic conditions,highly crystalized olivine-type LiFePO_4was successfully obtained with electron conductive Fe_2P and FeP as the main impurity phases.SEM and TEM analyses demonstrated the graphene sheets were randomly distributed inside the sample to create an open structured LiFePO_4 with respect to graphene,while the glucosederived carbon mainly coated over LiFeP04 particles which effectively connected the graphene sheets and LiFePO_4 particles to result in a more efficient charge transfer process.As a result,favorable electrochemical performance was achieved.The performance of the amorphous carbon-graphene co-modified LiFePO_4 was further progressively improved upon cycling in the first 200 cycles to reach a reversible specificcapacity as high as 97 mAh·g~(-1) at 10 C rate.     

诺贝尔奖宠儿——碳元素的前世今生

碳元素历史悠久,与现代人类社会联系紧密,对人类未来意义重大,多次斩获诺贝尔奖。在揭开碳元素的发现史之后,介绍了活性炭、碳纤维、玻璃碳等无定形碳以及热解炭等过渡碳的重要作用。此外,晶形碳的经典同素异形体--C60富勒烯、碳纳米管、石墨烯的独特结构造就了其在纳米材料领域的非凡用途;新型同素异形体的合成、发现与应用更是碳元素研究领域的热点。     

Accurate Control of VS2 Nanosheets for Coexisting High Photoluminescence and Photothermal Conversion Efficiency

In two‐dimensional (2D) amorphous nanosheets, the electron–phonon coupling triggered by localization of the electronic state as well as multiple‐scattering feature make it exhibit excellent performance in optical science. VS₂ nanosheets, especially single‐layer nanosheets with controllable electronic structure and intrinsic optical properties, have rarely been reported owing to the limited preparation methods. Now, a controllable and feasible switching method is used to fabricate 2D amorphous VS₂ and partial crystallized 2D VO₂(D) nanosheets by altering the pressure and temperature of supercritical CO₂ precisely. Thanks to the strong carrier localization and the quantum confinement, the unique 2D amorphous structures exhibit full band absorption, strong photoluminescence, and outstanding photothermal conversion efficiency.     

SERS Activity of Semiconductors: Crystalline and Amorphous Nanomaterials

Surface‐enhanced Raman scattering (SERS) spectroscopy on semiconductors has attracted increasing attention due to its high spectral reproducibility and unique selectively to target molecules. Recently, endeavors have been made in fabricating novel SERS‐active semiconductor substrates and exploring new enhancement mechanisms to improve the sensitivity of semiconductor substrates. This Minireview explains the enhancement mechanism of the semiconductor SERS effect in a brief tutorial and summarize recent developments of novel semiconductor substrates, in particular with regard to the remarkable SERS activity of amorphous semiconductor nanomaterials. Potential applications of semiconductor SERS are also a key issue of concern. We discuss a variety of promising applications of semiconductor SERS in the fields of in situ analytical chemistry, spectroelectrochemical analysis, biological sensing, and trace detection.     

新鲜苹果汁可溶性固形物含量的傅里叶变换近红外光谱检测

用傅里叶变换近红外(FTNIR)光谱透射方式对新鲜苹果汁溶性固形物含量(SSC)进行了快速定量分析。实验共测定了60个果汁样品的SSC,并采集了样品的近红外光谱数据。42个样品用来建模,剩下的18个用来验证模型的性能。对实验室测得的SSC与FTNIR光谱数据进行相关性分析,以TQ 6.2.1定量分析软件中集成的主成分回归法(PCR)和偏最小二乘回归法(PLS)建立了检测模型。该研究对比了不同光谱范围内建立的检测模型的性能。根据预测平方根误差(RMSEP)和相关系数(r2)进行不同模型的预测性能,最好的新鲜苹果汁SSC预测模型的RMSEP＝0.603 0Brix,r2＝0.997。结果表明FT-NIR可以作为一种可靠、准确、快速的无损检测方法来评价新鲜果汁的可溶性固形物含量。     

Isobaric thermal expansivities of polyethylenes with various crystallinities over the pressure range from 0.1 to 300 MPa and over the temperature range from 303 to 393 K

A pressure-controlled scanning calorimeter (PCSC) has been applied for measuring the isobaric volume thermal expansivities (α_p) of crystalline polymers as a function of pressure up to 300 MPa at various temperatures. The measurements have been performed for several well-defined polyethylenes with various degrees of crystallinity at 302.6, 333.0, 362.6, and 393.0 K. The results are reported as values of coefficients in a correlation equation, which facilitates the use of reported data over large ranges of temperature and pressure. The general pressure-temperature behavior of α_p for all polyethylenes under study is such that α_p increases with temperature and decreases with pressure. The increase with temperature is smaller at high pressures and the isotherms of α_p have a tendency to converge at high pressures; α_p decreases linearly with the crystallinity of the polyethylene over the whole range of pressure and temperature under investigation. From the linear approximation of experimental data for polyethylenes with various crystallinities the estimated α_p for both crystal and amorphous phases of polyethylenes have been determined as a function of pressure up to 300 MPa at 302.6, 333.0, and 362.5 K. The obtained results have been compared with available literature crystallographic data and with the values derived from the Pastine theoretical equation of state for both crystalline and amorphous phases. © 1996 John Wiley & Sons, Inc.     

A relationship between macroradical decay kinetics and α-segmental dynamics in glassy amorphous polymers

For a series of five amorphous polymers with a broad range of T_g values the kinetics of macroradical decay was measured by ESR technique and evaluated by the second-order kinetic model. It was found that the temperature T_tr of the transition between two regions of different reactivity in free radical decay reaction agrees quite well with the temperature parameter T₀ of the Vogel-Fulcher-Tamman-Hesse (VFTH) equation for α-segmental dynamics. This parameter represents the onset of α-segmental mobility in glassy state below T_g. A nontraditional way of the estimation of T₀ values for α-segmental dynamics through study of the macroradical decay in glassy state of amorphous polymers has been suggested. © 1996 John Wiley & Sons, Inc.     

Novel poly(aryl ether phthalazinium) ionomers and their properties

The synthesis of N-phenyl phthalazinium salts by condensation of a 1,2-diaroylbenzene with phenylhydrazine is described. This reaction was utilized to prepare novel poly(aryl ether phthalazinium) ionomers by the direct condensation of poly(aryl ether ketone)s with phenylhydrazine. The preparation of poly(aryl ether phthalazinium) ionomers by methylation of poly(aryl ether phthalazine)s is also described. Most of the ionomers are amorphous, thermally stable, and soluble in organic solvents. They can be cast into flexible and strong films. The glass transition temperature of the ionomers ranges from 297 to 363°C, an increase of 12 to 100°C over the corresponding neutral polymers. © 1996 John Wiley & Sons, Inc.     

Ni-B非晶态合金催化苯丙酮酸加氢合成苯丙氨酸

通过化学还原法制备了纳米非晶态Ni-B合金催化剂,考察了其对苯丙酮酸胺化加氢合成苯丙氨酸的催化性能.结果表明,相对于传统雷尼镍和漆原镍催化剂,非晶态合金催化剂表现出更为优异的活性和选择性,并且当非晶态Ni-B合金负载在SiO2载体上时,其活性和选择性均得到较大提高(高达97.67%).非晶态合金催化剂对苯丙氨酸合成反应表现出较好活性和选择性的原因主要是硼提供部分电子给镍的效应以及非晶态合金颗粒的纳米尺寸效应.