双波长双指示剂催化动力学光度法测定痕量Fe(Ⅲ)

研究了在HCl介质中,Fe(Ⅲ)催化H2O2氧化甲基橙和亚甲基蓝褪色的指示反应。通过测量510nm和660nm波长处催化和非催化体系吸光度的变化,基于Fe(Ⅲ)的浓度与两波长处吸光度差值的加和呈线性关系,建立了双波长双指示剂催化动力学光度法测定Fe(Ⅲ)含量的新方法。方法的线性范围为0.008~0.24μg/mL,用该法测定菠菜、紫菜、蛋黄中Fe(Ⅲ)含量,相对标准偏差为1.0%~4.6%,加标回收率为98.9%~104.6%。     

焙烧温度对Ni/CuO-ZrO2-CeO2-Al2O3催化剂在甲烷自热重整反应中积炭行为的影响

以Na₂CO₃为沉淀剂,在pH=9时,采用并流沉淀法制备了Ni/CuO-ZrO₂-CeO₂-Al₂O₃催化剂,催化剂中活性组分Ni的负载量(质量分数)为10%．采用TPO、SEM和XPS等方法研究了载体焙烧温度对催化剂积炭行为的影响．结果表明,载体焙烧温度为800 oC制备的Ni/CuO-ZrO₂-CeO₂-Al₂O₃催化剂不存在高温烧炭峰,可以避免由于积炭而降低反应的活性．反应40 h后,催化剂表面出现表面碳酸盐和非活性丝状积炭,这些物种可能会导致催化剂活性降低．     

Structural,textural and catalytic properties of pure and Li-doped NiO/Al2O3 and CuO/Al2O3 catalysts

Pure and Li-doped NiO/Al₂O₃ and CuO/Al₂O₃ catalysts were prepared to contain 2, 4 and 8 wt.% of Ni and Cu, respectively. The structural properties were determined using DTA, XRD and FTIR techniques, and the textural properties of the catalysts were determined from their adsorption–desorption isotherms of nitrogen at 77 K. The chemisorption of hydrogen at 473–823 K with the pre-reduced catalysts was measured. The data obtained allowed the determination of the metal surface area, S (m²/g); the percentage of metal distribution, R; and the diameter of metal crystallite, d (nm). The amount of surface acidity, measured in mmol/g, was determined from the amount of chemisorbed pyridine necessary to completely inhibit the catalytic dehydration (DHD) of isopropanol. The conversion of isopropanol at 533–623 K was investigated using the micro-catalytic pulse technique. DTA, XRD and FTIR indicated that NiO and CuO exist as separate phases with crystallite sizes too small to be detected. No evidence has been gathered to indicate the existence of an aluminate phase.With the increase of metal loading, the surface area decreased whereas the total pore volume and the mean pore radius increased. Conversion of iso-propanol to propene proceeded via (DHD) on surface acid sites, and conversion of isopropanol to acetone proceeded via dehydrogenation (DHG) on redox sites. DHD and DHG exhibited first-order kinetics, and the rates of both reactions increased with temperature, with the latter being more temperature-dependent.     

甲烷-二氧化碳重整制合成气与现代分析技术应用于探究性化工专业实验的设计与探索

以甲烷-二氧化碳重整制合成气为实例，设计探究性实验，将合成气的制备和现代分析技术应用于化工专业实验的教学实践中以提高学生的创新和实践能力。实验包括催化剂的制备，催化剂的性能评价和催化剂的表征等3大部分。采用工业最常用的浸渍法制备含有不同助剂的Ni/X/γ-Al2O3（X为Co，Fe，MgO，CeO2）催化剂，以甲烷-二氧化碳重整反应评价其催化性能，并采用XRD、H2-TPR、BET和TG对催化剂的微观结构进行表征。结合催化剂的性能评价结果和表征结果，探讨不同助剂对镍基催化剂性能的改善效果及机制。通过开设该实验，可以让学生了解化工学科的前沿知识以及现代分析技术的基本原理和用途，掌握专业的实验操作、数据处理和谱图绘制方法，提高学生的专业素养和综合能力。     

Effects of pyrolysis temperatures on the textural,magnetic, morphology,and catalytic properties of supported nickel nanoparticles

The development of base metal catalysts for industrially important reactions continues to be an important goal of catalysis research. Herein, the effects of pyrolysis temperature on the textural, structural, surface, magnetics properties and catalytic properties of silica-supported nickel nanoparticles (NiNPs) were thoroughly investigated. Mono-dispersed NiNPs encapsulated in graphitic shells were first successfully obtained and were characterized using a variety of methods such as BET surface area measurement, CO-pulse chemisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HR-TEM), and superconducting quantum interference device (SQUID) measurement. The findings showed that all catalysts’ properties were considerably altered with change in pyrolysis temperature. Hydrogenation of diphenylacetylene was then selected as the model reaction for the evaluation of the catalytic performance of the graphitic-shelled NiNPs. After testing, pyrolysis of a nickel at 800 °C (catalyst A) displayed tremendous activity and selectivity to produce >94% of stilbene with selectivities of 99% for the Z-isomer.     

Ultrasound-assisted fabrication of metal nano-porous shells across polymer beads and their catalytic activity for reduction of 4-nitrophenol

Metal nano-porous architectures are a novel class of nanomaterials which has been applied in the fields of catalysis, sensing and gas storage because of their high surface-to-volume ratio, high mechanical strength and long-range ordered architectures. A commonly-used synthetic strategies to achieve architectures with high precision and diverse porosity design is the seed-and-growth method. In this work, using a dual-frequency sequential sonication approach, we have demonstrated a sonochemical-assisted one-pot seeding with a successive shell growth synthetic strategy for mesoporous metal deposition via a gold (Au) nanoparticle and poly(styrene) beads system. A uniform coating of gold nanoparticle seeds with dense surface coverage was formed by first employing 300 kHz ultrasound irradiation while the nano-porous shell growth was then performed under 1 MHz ultrasonic frequency. The precise control over the process conditions and parameters allowed for the design of well-defined shell thicknesses and surface roughness and area. The catalytic property of the MNMs was evaluated for the degradation of 4-nitrophenol and a high catalytic activity was achieved for the most porous gold structures, suggesting synergistic effects between the architecture of the nanomaterials and their surface reactivity.     

Revisiting catechol derivatives as robust chromogenic hydrogen donors working in alkaline media for peroxidase mimetics

Colloidal noble metal-based nanoparticles are able to catalyze oxidation of chromogenic substrates by H₂O_2, similarly to peroxidases, even in basic media. However, lack of robust chromogens, which work in high pH impedes their real applications. Herein we demonstrate the applicability of selected catechol derivatives: bromopyrogallol red (BPR) and pyrogallol (PG) as chromogenic substrates for peroxidase-like activity assays, which are capable of working over wide range of pH, covering also basic values. Hyperbranched polyglycidol-stabilized gold nanoparticles (HBPG@AuNPs) were used as model enzyme mimetics. Efficiency of several methods of improving stability of substrates in alkaline media by means of selective suppression of their autoxidation by molecular oxygen was evaluated. In a framework of presented studies the impact of borate anion, applied as complexing agent for PG and BPR, on their stability and reactivity towards oxidation mediated by catalytic AuNPs was investigated. The key role of high concentration of hydrogen peroxide in elimination of non-catalytic oxidation of PG and improvement of optical properties of BPR in alkaline media containing borate was underlined. Described methods of peroxidase-like activity characterization with the use of BPR and PG can become universal tools for characterization of nanozymes, which gain various applications, among others, they are used as catalytic labels in bioassays and biosensors.     

Epoxidation reaction of perfluoroalkenes with tert-amine N-oxide

Straight-chain aliphatic terr-amine N-oxides were found to be useful oxidizing agent for epoxidation of tri- and tetra-substituted perfluoroalkenes under mild conditions in high yields.The process for epoxidation by employing tri-n-butylamine N-oxide gave the best result in the reagent survey.     

Novel Stereoselective Phase Transfer Catalytic Synthesis and Some Applications of ( E )-2-Chlorovinylthioarenes and Hetarenes

A novel two-step method for the preparation of ( E )-2-chlorovinylthioarenes (or hetarenes) from thiols and 1,1,2-trichloroethane in the phase transfer catalytic systems solid K 2 CO 3 /solid KI/18-crown-6/xylene and solid KOH/18-crown-6/toluene has been developed. ( E )-2-chlorovinylthioarenes were isolated in yields up to 98%. Utilization of ( E )-2-chlorovinylthioarenes in the Heck and Stille reactions has been shown.     

Methodik und Ergebnisse von Tracerexperimenten über katalytische Reaktionen von Kohlenwasserstoffen

Tracermethoden können wichtige Beiträge zur Aufklärung katalytischer Kohlenwasserstoffreaktionen liefern. In dieser Arbeit werden einige Ergebnisse mehrjähriger Untersuchungen mit ¹⁴C-markierten Verbindungen zusammenfassend dargestellt. Es wird speziell auf Benzenbildungsreaktionen bei der Leichtbenzin-Reformierung und auf Reaktionsmechanismen bei der Isomerísierung von C₈-Aromaten eingegangen.