超细钴纳米粒子催化1-己烯低压氢甲酰化反应的原位红外光谱研究

利用原位透射红外光谱研究了2.8 nm超细钴纳米粒子在2~3 MPa合成气(CO:H₂ = 1:1)和100 ^oC条件下催化的1-己烯氢甲酰化反应. 结果表明, 在反应中出现与Co₂(CO)₈类似的红外吸收峰(2071, 2041和2022 cm^-1), 被证明是不同Co位点端式吸附CO. 首次观测到了位于2054 cm^-1处吸收峰处的物种, 可能归属为RCH₂CH₂COCo. 通过此中间物种,产物醛可以在钴催化剂表面经由结合一个氢原子脱除反应而获得.     

In situ introduction of dispersed metallic Ag nanoparticles into the channels of mesoporous carbon CMK-3

An in situ reduction method has been developed to fabricate metallic Ag nanoparticles inside the channels of mesoporous carbon CMK-3.This approach combines function of the CMK-3 surface by oxidation using HNO_3 with the subsequent absorption of Ag~ . The resultant nanocomposite materials were characterized by nitrogen adsorption,X-ray diffraction,Auger electron spectroscopy and transmission electron microscopy.Compared with the conventional impregnation method,our approach shows that Ag nanoparticles of 2-4 nm can be uniformly incorporated into CMK-3.     

有序介孔碳CMK-3负载金纳米微粒复合材料的制备和表征

分别采用等体积浸渍-甲醛还原、等体积浸渍-氢气还原及溶胶负载法在介孔碳CMK-3上负载金纳米微粒;利用透射电镜和粉末X射线衍射仪对比分析了采用3种方法得到的复合材料的微结构和相组成;并测定了采用溶胶负载法得到的不同金含量的复合材料的热稳定性.结果表明,所制备的金纳米微粒的尺寸因制备方法不同而呈现明显差异;负载于复合材料中的金纳米微粒具有很好的热稳定性.     

In situ synthesis of ceria nanoparticles in the ordered mesoporous carbon as a novel electrochemical sensor for the determination of hydrazine

A novel ceria (CeO₂)–ordered mesoporous carbon (OMC) modified electrode for the sensitive amperometric determination of hydrazine was reported. CeO₂–OMC composites were synthesized via a hydrothermal method at a relatively low temperature (180 °C) and characterized by scanning electron microscopy (SEM), transmission electron microcopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The CeO₂–OMC modified glassy carbon electrode was characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) and indicated good electrocatalytic effect to the oxidation of hydrazine. Under the optimized conditions, the present sensor could be used to measure hydrazine in wide linear range from 40 nM to 192 μM (R² = 0.999) with a low detection limit of 12 nM (S/N = 3). Additionally, the sensor has been successfully applied to detect hydrazine in real water samples and the recoveries were between 98.2% and 105.6%. Eventually, the sensor exhibited an excellent stability and reproducibility as a promising method for determination of hydrazine.     

Development of amperometric glucose biosensor through immobilizing enzyme in a Pt nanoparticles/mesoporous carbon matrix

Pt nanoparticles were deposited on mesoporous carbon material CMK-3. Glucose oxidase (GOx) was immobilized in the resulting Pt nanoparticles/mesoporous carbon (Pt/CMK-3) matrix, and then the mixture was cast on a glassy carbon electrode (GCE) using gelatin as a binder. The glucose biosensor exhibited excellent current response to glucose after cross-linking with glutaraldehyde. At 0.6V (vs. SCE) the response current was linear to glucose concentration in the range of 0.04-12.2mM. The response time (time for achieving 95% of the maximum current) was 15s and the detection limit (S/N=3) was 1 microM. The Michaelis-Menten constant (K(m)(app)) and the maximum current density (i(max)) were 10.8 mM and 908 microAcm(-2), respectively. The activation energy of the enzymatic reaction was estimated to be 22.54 kJ mol(-1). The biosensor showed good stability. It achieved the maximum response current at about 52 degrees C and retained 95.1% of its initial response current after being stored for 30 days. In addition, some fabrication and operation parameters for the biosensor were optimized in this work. The biosensor was used to monitor the glucose levels of serum samples after being covered with an extra Nafion film to improve its anti-interferent ability and satisfied results were obtained.     

Preparation and characterization by surface-enhanced infrared absorption spectroscopy of silver nanoparticles formed on germanium substrates by electroless displacement

In this paper, the feasibility of applying electroless displacement to prepare silver nanoparticles (AgNPs) on the surface of germanium (Ge) substrate is demonstrated, and the performances of surfaces prepared in this manner for surface-enhanced infrared absorption (SEIRA) spectroscopy are reported. The process used to produce suitable AgNPs for SEIRA by electroless deposition is simple and effective, requiring only pretreatment of the germanium surface with hot air, immersion of the substrate in a dilute solution of silver nitrate, and washing of the resulting plate. To quantify the behavior of AgNPs on a Ge substrate and to optimize the conditions for the preparation of AgNPs on Ge substrates, a monolayer of p-nitrothiophenol (PNTP) was bonded to the surface of the AgNPs by immersion of the plate in a dilute solution of PNTP and measurement of the transmission spectrum. The factors that influenced the formation of AgNPs, and hence the SEIRA signals, included the concentration of AgNO₃, the reaction time and the temperature. Results indicated that stronger absorption bands in the SEIRA spectrum of a monolayer of PNTP were obtained if the reaction rate for the displacement of silver ions by Ge was slow. This condition was achieved by keeping the concentration of AgNO₃ and the reaction temperature low. Under the optimal conditions found in this work, an enhancement factor of approximately 100 was achieved for commonly used probe molecules in SEIRA measurements.     

Catalytic properties of Ru nanoparticles embedded on ordered mesoporous carbon with different pore size in Fischer-Tropsch synthesis

A series of 3 wt% Ru embedded on ordered mesoporous carbon (OMC) catalysts with different pore sizes were prepared by autoreduction between ruthenium precursors and carbon sources at 1123 K. Ru nanoparticles were embedded on the carbon walls of OMC. Characterization technologies including power X-ray diffraction (XRD), nitrogen adsorption-desorption, transmission electron microscopy (TEM), and hydrogen temperature-programmed reduction (H₂-TPR) were used to scrutinize the catalysts. The catalyst activity for Fischer-Tropsch synthesis (FTS) was measured in a fixed bed reactor. It was revealed that 3 wt% Ru-OMC catalysts exhibited highly ordered mesoporous structure and large surface area. Compared with the catalysts with smaller pores, the catalysts with larger pores were inclined to form larger Ru particles. These 3 wt% Ru-OMC catalysts with different pore sizes were more stable than 3 wt% Ru/AC catalyst during the FTS reactions because Ru particles were embedded on the carbon walls, suppressing particles aggregation, movement and oxidation. The catalytic activity and C₅₊ selectivity were found to increase with the increasing pore size, however, CH₄ selectivity showed the opposite trend. These changes may be explained in terms of the special environment of the active Ru sites and the diffusion of products in the pores of the catalysts, suggesting that the activity and hydrocarbon selectivity are more dependent on the pore size of OMC than on the Ru particle size.     

Self-assembling and size-selective synthesis of Ni and NiO nanoparticles embedded in ordered mesoporous carbon and polymer frameworks

We demonstrate the self-assembling and size-selective synthesis of uniform and highly dispersed Ni or NiO nanoparticles with diameters below 12 nm embedded in ordered mesoporous carbon or polymer frameworks. Self-assembly is induced by evaporation of the solvent from a mixture of metal-containing liquid crystalline (LC) mesophases of triblock copolymer and transition metal nitrate hydrate, and the carbon source is low-polymerized phenolic resol. Characterization by XRD, N(2) sorption isotherms, TEM, HRSEM, ICP-AES, TG, and XPS techniques has indicated an ordered 2D hexagonal mesostructure, high surface areas between 524 and 721 m(2) g(-1), uniform pore sizes of about 4.0 nm, large pore volumes ranging from 0.34 to 0.58 cm(3) g(-1), and metal contents ranging from 0.6 to 10.0 wt%. There is a high degree of dispersion, and a small size of nanoparticles throughout the whole framework, without aggregation outside of the pores due to the confinement effect of the mesoporous ordered matrix. The mesoporous solids show excellent adsorption properties for dyes and permit an easy magnetic separation procedure. This method is expected to be applicable to other mesoporous transition metal(oxide)-containing carbon catalysts.     

Template carbon dispersed in polyaniline matrix electrodes: evaluation and application as electrochemical sensors to low concentrations of Cu and Pb

A new electrode, obtained by the dispersion of template carbon nanoparticles onto polyaniline, is presented in this paper. Template carbon was synthesized via the pyrolysis of the polyfurfuryl alcohol inside the nanometric pores of porous Vycor glass, and the electrodes were prepared by a polyaniline-template carbon mixture. Scanning electron microscopy showed that polyaniline-template carbon films presented a wholly modified morphology when compared to polyaniline and polyaniline-graphite films. Electrochemical characterization indicated that the interconversion reactions of polyaniline were strongly facilitated in the presence of the template carbon. The new electrode also exhibited excellent chemical and physical stabilities. Finally, anodic stripping voltammetry measurements revealed that the new electrode presented a noteworthy linear response to very low concentrations of Cu²⁺ and Pb²⁺ ions, under few minutes of pre-concentration.     

Electrocatalytic oxidation of carbon monoxide and methanol at Pt nanoparticles confined in SBA-15: voltammetric and in situ infrared spectroscopic studies

Electrocatalytic oxidation of carbon monoxide and methanol at Pt nanoparticles confined in mesoporous molecular sieve SBA-15 was studied by using cyclic voltammetry and in situ FTIR spectroscopy. Cyclic voltammetric studies revealed that the Pt nanoparticles confined in SBA-15 exhibit a high activity in the presence of hydrated phase consisting of SiO₂ in the SBA-15. In situ FTIR spectroscopy results discovered that IR absorption of CO adsorbed on Pt nanoparticles confined in SBA-15 has been enhanced 11-fold, and the full-width at half-maximum of the CO band is significantly increased, in comparison with IR feature of CO adsorbed on a bulk Pt electrode. The linearly adsorbed CO species is the only intermediate derived from dissociative adsorption of methanol, which is more readily oxidized to form CO₂ in the aid of the active oxide in SBA-15.This paper is dedicated to Professor G. Horanyi on the occasion of his 70th birthday and in recognition of his outstanding contribution to electrochemistry