Characterization and Catalytic Properties of Combustion Synthesized Au/CeO2 Catalyst

Ceria-supported Au catalyst has been synthesized by the solution combustion method for the first time and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Au is dispersed as Au⁰ as well as Au³⁺ states on CeO₂ surface of 20-30 nm crystallites. On heating the as-prepared 1% Au/CeO₂ in air, the concentration of Au³⁺ ions on CeO₂ increases at the expense of Au⁰. Catalytic activities for CO and hydrocarbon oxidation and NO reduction over the as-prepared and the heat-treated 1% Au/CeO₂ have been carried out using a temperature-programmed reaction technique in a packed bed tubular reactor. The results are compared with nano-sized Au metal particles dispersed on -Al₂O₂ substrate prepared by the same method. All the reactions over heat-treated Au/CeO₂ occur at lower temperature in comparison with the as-prepared Au/CeO₂ and Au/Al₂O₂. The rate of NO + CO reaction over as-prepared and heat-treated 1% Au/CeO₂ are 28.3 and 54.0 mol g^-1 s^-1 at 250 and 300 °C respectively. Activation energy (E _a) values are 106 and 90 kJ mol^-1 for CO + O₂ reaction respectively over as-prepared and heat-treated 1% Au/CeO₂ respectively.     

Acetylene Hydrogenation on Au-Based Catalysts

Hydrogenation of acetylene has been investigated on Au/TiO₂, Pd/TiO₂ and Au-Pd/TiO₂ catalysts at high acetylene conversion levels. The Au/TiO₂ catalyst (avg. particle size: 4.6 nm) synthesized by the temperature-programmed reduction-oxidation of an Au-phosphine complex on TiO₂ showed a remarkably high selectivity to ethylene formation even at 100% acetylene conversion. Au/TiO₂ prepared by the conventional incipient wet impregnation method (avg. particle size: 30 nm), on the other hand, showed negligible activity for acetylene hydrogenation. Although the Au catalysts showed a high selectivity for ethylene, the acetylene conversion activity and catalyst stability were inferior to the Pd-based catalysts. Au-Pd catalysts prepared by the redox method showed high acetylene conversions as well as high selectivity for ethylene. Interestingly Au-Pd catalysts prepared by depositing Pd via the incipient wetness method on Au/TiO₂ showed very poor selectivity (comparable to mono-metallic Pd catalysts) for ethylene. High-resolution transmission electron microscopy (TEM) studies coupled with energy dispersive X-ray spectroscopy (EDS) showed that while the redox method produced bimetallic Au-Pd catalysts, the latter method produced individual Pd and Au particles on the support.     

(Ag)_核·(Au)_壳复合纳米粒子的制备

以银原子团簇作晶种,采用微波高压液相合成法制备了分散性好、规则球形的(Ag)核·(Au)壳复合纳米粒子。研究了(Ag)核·(Au)壳复合纳米粒子的紫外可见吸收光谱和共振散射光谱特性。结果表明,液相(Ag)核·(Au)壳复合纳米粒子和高压微波合成的液相金纳米粒子的最强共振散射峰均在580nm处,它们的吸收光谱图相似,最大吸收分别在518.5nm和524.8nm。     

Adsorption of mercaptopropionic acid onto Au(1 1 1): Part II. Effect on copper electrodeposition

Copper deposition in the presence of an organic additive (3-mercaptopropionic acid, MPA) was studied by cyclic voltammetry and in situ scanning tunneling microscopy (STM) and the results are compared to those for additive-free solutions. It is shown that underpotential deposition (upd) of copper onto a fully MPA-covered electrode produces a defect-rich substrate, but the defects are blocked by the dense organic film for bulk deposition, resulting in a low number of nuclei. A grain-refining effect of MPA, however, was found, when Cu deposition was initiated shortly after addition of MPA to the solution, i.e., for a low-coverage MPA adlayer.     

MOF作模板制备多孔Au/CuxO催化剂及其CO氧化性能

采用MOF材料作模板,通过在Cu-BTC材料表面预先负载贵金属Au再热解的方法,成功制备了具有正八面体结构的新型多孔Au/Cu_xO负载型催化剂。通过降低热解环境中的O₂浓度,调节氧化时间,实现了Au/Cu-BTC氧化产物组分的调节,分别制得了Au/Cu₂O、Au/Cu₂O-CuO、Au/CuO复合催化材料。将其用于CO催化氧化,发现所有Au/Cu_xO催化剂都表现出比Cu-BTC和Au/Cu-BTC更优异的催化性能,其中由于拥有较高的比表面积、Cu₂O含量以及更好的Au的分散性,Au/Cu₂O的CO氧化活性最佳,180℃即能实现CO的完全转化。     

Effects of Thiourea on Anodic Dissolution of Au and Surface Oxidation Behaviour in aq HClO4 Studied by Means of an EQCN

Anodic dissolution of Au is facilitated by the presence of thiourea owing to formation of strongly complexed Au ions. The present paper reports studies of this process using cyclic voltammetry (CV), chronopotentiometry and chronoamperometry, usefully complemented by nanogravimetry employing an electrochemical quartz-crystal nanobalance (EQCN). The molar masses per faraday for Au dissolution were determined from EQCN measurements, coupled with information derived from CV, chronopotentiometry and chronoamperometry, and clearly indicate that Au becomes dissolved over the potential range 0.45—0.65 V vs RHE via a 1e^– oxidation process in 0.5 M HClO₄ solution containing thiourea. The peak potential for Au dissolution in the presence of thiourea is about 600 mV less positive than that in the presence of Br^– or Cl^– (1.20 V vs RHE for Br^– and 1.39 V vs RHE for Cl^–). The linear relationship between anodic peak currents at about 0.630 V vs RHE and square-root of the sweep rate indicates that the Au dissolution process is diffusion-controlled. The anodic current efficiency for Au dissolution is 93%.     

Au/NaYF4 : Yb,Er Binary Superparticles: Synthesis and Optical Properties

Colloidal superparticles (SPs) are nanoparticle (NP) assemblies in the form of colloidal particles. Assembling nanoscopic objects into mesoscopic or macroscopic composite architectures allows for the bottom-up fabrication of functional nanomaterials. In this study, a method for single-step self-assembly synthesis of Au/NaYF₄ : Yb,Er SPs was developed using oil-in-water (O/W) microemulsions to simultaneously encapsulate gold nanoparticles (AuNPs) and NaYF₄ : Yb,Er upconversion nanoparticles (UCNPs) via evaporation at room temperature. The synthesized Au/NaYF₄ : Yb,Er SPs possess good dispersibility and stability. When the number of AuNPs added is increased, the SPs exhibit decreased upconversion luminescence, which can be ascribed to the Förster resonance energy transfer (FRET) from the NaYF₄ : Yb,Er UCNPs to the AuNPs. Time-resolved measurements of the green emission further confirm the existence of a new decay route corresponding to the FRET process. Our research provides a facile and versatile strategy for the synthesis of novel multifunctional nanocomposites with tunable upconversion luminescence properties, which can be of great significance in biological applications.     

Embedding Ag or Au nanoparticles within the nano-sized wall of YbPO4:Er3+ inverse opals and resulting enhanced upconversion luminescence

Metal nanoparticles preparation in the interior of nanoscale skeleton of inverse opals made up of crystallized matrix is more difficult than the preparation of pure inverse opals. In the present work, the Ag or Au nanoparticles embedded YbPO₄:Er³⁺ inverse opals were prepared by a simple approach, which involved the infiltration of opal template by using the transparent YbPO₄:Er³⁺ sol including silver nitrate or chloroauric acid and the sintering at high temperature. The 20–30?nm Au or 5–10?nm Ag nanoparticles were formed in the interior of nanoscale skeleton in the YbPO₄:Er³⁺ inverse opals, and the Ag or Au nanoparticles embedded YbPO₄:Er³⁺ inverse opals were prepared. The influence of Ag or Au nanoparticles on the upconversion photoluminescence of YbPO₄:Er³⁺ inverse opal was studied, and the upconversion luminescence enhancement induced by the Ag or Au nanoparticles was observed. The mechanisms of upconversion luminescence enhancement of YbPO₄:Er³⁺ inverse opals induced by Ag or Au nanoparticles were discussed. The enhancement of upconversion luminescence induced by Ag nanoparticles was attributed to the enhancement of the excitation field, and the enhancement of upconversion emission induced by Au nanoparticles was related to the increasing of the radiation decay rate of Er³⁺.     

Novel Flower-Like ZnO Hybridized with Acrylic Ester Resin for Enhanced Oil Absorption Properties

The acrylic ester resins have potential applications in for treatment of oily wastewater due to their high oil retention capacity and excellent cycle performance. Herein, a novel acrylic ester hybrid resins composed by poly(n-butylacrylate-co-styrene) resins and flower-like ZnO clusters were prepared using a combination of hydrothermal and suspension polymerization. The hybrid resins can remove a broad variety of oils from water with the maximum oil absorption performance of 30.87?g/g. More importantly, the hybrid resins are reversible and maintain high oil absorption properties after oils absorption-regeneration, making them promising candidates for treatment of oily wastewater.     

In/Au(111)和Ir/Au(111)面上巴豆醛选择加氢的机理研究及比较

基于巴豆醛在M/Au（111）合金表面（M=In,Ir）垂直吸附的最稳定吸附结构,采用密度泛函理论对其不完全加氢的反应机理进行探究。从不同加氢机理下各基元反应的活化能、反应热计算以及构型变化分析中可知,巴豆醛在M/Au（111）面上均优先对距离合金表面较近的C＝O进行加氢,且以C为活性中心优先进行加氢为最优机理,其中第1步加氢反应的活化能较高,是该机理的控速步骤。反应物巴豆醛的O原子与合金的掺杂原子M形成较强的化学吸附,提高了M/Au（111）面对C＝O加氢的选择性。巴豆醛按最优机理加氢的基元反应中在In/Au（111）面上最高反应能垒为0.969 eV,比在Ir/Au（111）面的最高反应能垒1.332 eV低,因此认为In/Au合金对其不完全加氢有更好的催化活性。