水相中金纳米颗粒催化的醛基选择性氧化（英文）

本文开发了一种新型的用生物质淀粉保护的金纳米颗粒作为催化剂,选择性氧化醛基得到羧酸的方法.在4-羟甲基苯甲醛的催化氧化中,金纳米颗粒对醛基表现出了压倒性的选择性,而醇羟基则保持不变.该非均相催化体系由可溶解的催化剂和不溶解的底物构成.金催化剂的制备、储存、和使用都在水相中.反应条件优化之后,双氧水被证明是最佳的氧化剂,可以得到100%转化率.此外,在不同官能团取代的醛衍生物中,金纳米颗粒也表现出了很好的普适性.反应结束之后,有机组分被有机溶剂萃取,而金颗粒被保留在水中通过分液分离以回收使用.     

亚纳米厚的氧化铝包裹层可以显著提高负载型金纳米颗粒催化剂的热稳定性

负载型金纳米颗粒催化剂在许多催化反应中展现出非常好的催化活性,但是金纳米颗粒在高温等反应条件下容易烧结团聚,极大地限制了金催化剂的应用。利用原子层沉积技术在Au/TiO₂催化剂表面分别精确沉积了一层超薄的二氧化钛和氧化铝包裹层,并对比研究了包裹层对金纳米颗粒的热稳定性影响。原位红外漫反射CO吸附和x-射线光电子能谱数据证实了氧化物包裹层的存在。发现亚纳米厚的氧化铝包裹层能够在600 C完全避免金纳米颗粒的团聚;相反,二氧化钛包裹层对金纳米颗粒稳定性的提高没有明显效果。通过CO氧化探针反应的活性测试,发现随着煅烧温度的升高氧化铝包裹的Au/TiO₂ 催化剂的活性逐渐提高,表明高温处理可以促进被包裹金原子的暴露并表现出催化活性。提供了提高金纳米颗粒稳定性的有效方法,为拓展金催化剂在条件苛刻的反应中的应用奠定了技术基础.     

甲烷氧化偶联锂/氧化镁催化剂和纳米催化剂

采用初湿浸渍和溶胶凝胶法分别制备了Li/MgO催化剂和Li/MgO纳米催化剂. 比较两种Li/MgO催化剂对于甲烷氧化偶联反应的催化性能. 采用X射线衍射、BET吸附和透射电镜进行了表征.在973-1073 K和总压力为101 kPa下对催化剂进行了测试. 实验结果表明,Li/MgO纳米催化剂比普通催化剂对于甲烷氧化偶联反应表现为更高的甲烷转换率,较高选择性和较高的的主要产品(乙烷和乙烯)的产率.     

光学相关论题 光化学

O644.12006054769纳米Ce1-xZrxO2催化剂上乙醇催化氧化发光研究=Cata-lytic oxidation cataluminescence of ethanol over catalystsCe1-xZrxO2[刊,中]/叶青(清华大学化学系,有机光电子与分子工程教育部重点实验室.北京(100084)),张新荣…//高等学校化学学报.—2006,27(4).—726-730研究了纳米Ce1-xZrxO2上乙醇催化氧化发光特性,重点考察了反应温度和催化剂组成[n(Ce)/n(Zr)]对发光强度的影响。在相近的反应条件下研究了纳米Ce1-xZrxO2上乙醇催化氧化反应的活性、选择性和可能的催化发光机理。结果表明,催化发光强度与催化反应中生成…     

免疫纳米金催化氯金酸-盐酸羟胺光度法检测免疫球蛋白G

在pH 2.27的柠檬酸钠-盐酸缓冲溶液中,纳米金对氯金酸-盐酸羟胺生成较大粒径金颗粒这一慢反应具有较强的催化作用。较大粒径金颗粒在600～1 000 nm处有一个较宽的吸收峰。将纳米金标记羊抗人IgG获得免疫纳米金,免疫纳米金也具有相同催化效果。在一定条件下,金标记羊抗人IgG与IgG发生特异性结合生成纳米金免疫复合物。以16 000 rpm速度离心分离获得未反应的纳米金标抗上层溶液。以它作为催化剂催化氯金酸-盐酸羟胺微粒反应,700 nm处的吸光度A_{700 nm}线性降低。其降低值ΔA_{700 nm}与IgG在0.1～10 ng·mL-1范围内呈良好线性关系, 检出限为0.06 ng·mL-1。本法具有灵敏、快速和较高的特异性,用于定量分析人血清IgG,结果满意。     

光敏催化氧化α-蒎烯合成桃金娘烯醛

以α-蒎烯为原料,以卤素灯为光源,在自制光化学反应器中进行反应.研究了α-蒎烯光敏催化氧化制备高附加值桃金娘烯醛的新工艺.考察了光敏催化氧化反应条件对反应转化率和选择性的影响规律.气相色谱分析结果表明:以吡啶-醋酸酐-铜盐为催化剂,在氧流速0.3L/min、原料浓度0.75mol/L、催化剂浓度0.253mol/L、反应温度45℃下反应6h,原料的转化率达97.34％,桃金娘烯醛的选择性可达48.10％.     

铜基廉价催化剂的火焰合成及甲烷催化特性研究

本文基于预混滞止弱旋火焰系统,以溶于水或乙醇的廉价硝酸盐为前驱物,采用"一步"的雾化火焰方法来合成铜基催化剂纳米颗粒。采用TEM、XRD等分析了合成颗粒的形貌及物相态,进而考察了该催化剂在甲烷催化氧化反应中的催化活性。根据TEM结果,发现乙醇做溶剂时所合成的氧化铜颗粒具有颗粒直径小且结晶度较好的特点。实验结果表明,10 nm氧化铜颗粒体现出良好的甲烷催化性能,但掺杂氧化铝后,铜基催化剂对甲烷的催化性能有所下降,其原因可归结为氧化铝对氧化铜的覆盖作用导致其有效比表面积降低。     

三维金属有机骨架/石墨烯水凝胶均相降解纤维素为小分子酸的研究

通过在三维还原氧化石墨烯孔径中原位生长ZIF-8纳米粒子,制备了三维金属有机骨架/石墨烯催化剂.这种ZIF-8/rGO纳米复合材料同时具有介孔和微孔,并且拥有高比表面积和大量催化位点,是生物质转化的理想催化剂.将纤维素溶解于氢氧化钠水溶液中,在水热条件下,使用这种催化剂,纤维素可以被充分降解转化.纤维素转化率可以达到100%,其主要产物是甲酸,产率最高可达93.66%.催化剂还可以被回收,重复使用依然具有很好的催化效果.     

调控氧空位实现高比表面积Co_3O_4纳米片上的产氧反应（英文）

电催化水分解的速率控制步骤是水的氧化反应.高活性的电催化剂可加速水氧化的反应速率从而提升水分解反应的整体效果.我们通过水热-热解法制备了一种高活性的Co304催化剂去高效电催化产氧气.电镜表征证实了Co3O4具有超薄的纳米片层结构,X射线光电子能谱及电子顺磁共振波谱确认了Co304纳米片中存在大量氧空位.大幅提高的比表面积有利于更多包括作为活性点位的氧缺陷在内的点位暴露.Co304纳米片可加速阳极与电解质之间的产氧气反应,以很低的过电势(310 mV)及电流密度(10 mA/cm~2)高效催化产氧气,在1.0 mol/L KOH中表现出突出的稳定性.     

固-液-气三相环境下非均相苯加氢反应的原位核磁共振研究

本文使用原位核磁共振（NMR）方法成功实现了对固-液-气三相环境下加氢反应的在线监测.在反应过程中,无需分离产物.以Pd纳米颗粒粉末及不同晶面形貌的Pd催化剂作为研究对象,我们研究了反应压强、反应时间,以及催化剂表面性质对加氢反应的影响.结果表明,压强和反应时间都可以影响加氢反应产物的产率,使用暴露不同晶面的Pd共催化剂时,苯加氢产物不同.该原位NMR方法为研究固-液-气三相催化环境下的加氢反应机理提供了可能.     

Cavitation intensifying bags improve ultrasonic advanced oxidation with Pd/Al2O3 catalyst

Advanced oxidation processes can potentially eliminate organic contaminants from industrial waste streams as well as persistent pharmaceutical components in drinking water. We explore for the first time the utilization of Cavitation Intensifying Bags (CIB) in combination with Pd/Al₂O₃ catalyst as possible advanced oxidation technology for wastewater streams, oxidizing terephthalic acid (TA) to 2-hydroxyterephthalic acid (HTA). The detailed characterization of this novel reaction system reveals that, during sonication, the presence of surface pits of the CIB improves the reproducibility and thus the control of the sonication process, when compared to oxidation in non-pitted bags. Detailed reaction kinetics shows that in the CIB reactor the reaction order to TA is zero, which is attributed to the large excess of TA in the system. The rate of HTA formation increased ten-fold from ~0.01 μM*min⁻¹ during sonication in the CIB, to ~0.10 μM*min⁻¹ for CIB in the presence of the Pd/Al₂O₃ catalyst. This enhancement was ascribed to a combination of improved mass transport, the creation of thermal gradients, and Pd/Al₂O₃ catalyst near the cavitating bubbles. Further analysis of the kinetics of HTA formation on Pd/Al₂O₃ indicated that initially the reaction underwent through an induction period of 20 min, where the HTA concentration was ~0.3 μM. After this, the reaction rate increased reaching HTA concentrations ~6 μM after 40 min. This behavior resembled that observed during oxidation of hydrocarbons on metal catalysts, where the slow rate formation of hydroperoxides on the metal surface is followed by rapid product formation upon reaching a critical concentration. Finally, a global analysis using the Intensification Factor (IF) reveals that CIB in combination with the Pd/Al₂O₃ catalyst is a desirable option for the oxidation of TA when considering increased oxidation rates and costs.     

Photocatalytic degradation of methyl orange by gold silver nano-core/silica nano-shell

The silica nanoparticles (SiO₂ NPs), silver (Ag) NPs and gold (Au) NPs coated with SiO₂ NPs (core-shell) were prepared. The sizes and morphology of the particles were indicated. The three prepared NPs were used for photocatalytic degradation of methyl orange (MO) dye by xenon lamp. Rate of photocatalytic degradation reaction constant and lifetime were calculated for each catalyst. Moreover, the mechanism of the photocatalytic reaction was studied.     

Comparing the Contribution of Visible‐Light Irradiation,Gold Nanoparticles,and Titania Supports in Photocatalytic Nitroaromatic Coupling and Aromatic Alcohol Oxidation

Under visible‐light irradiation, gold nanoparticles (Au NPs) supported by titania (TiO₂) nanofibers show excellent activity and high selectivity for both reductive coupling of nitroaromatics to corresponding azobenzene or azoxylbenzene and selective oxidation of aromatic alcohols to corresponding aldehydes. The Au NPs act as active centers mainly due to their localized surface plasmon resonance (LSPR) effect. They can effectively couple the photonic energy and thermal energy to enhance reaction efficiency. Visible‐light irradiation has more influence on the reduction than on the oxidation, lowering the activation energy by 24.7 kJ mol^?1 and increasing the conversion rate by 88% for the reductive coupling, compared to merely 8.7 kJ mol^?1 and 46% for the oxidation. Furthermore, it is found that the conversion of nitroaromatics significantly depends on the particle size and specific surface area of supported Au NPs; and the catalyst on TiO₂(B) support outperforms that on anatase phase with preferable ability to activate oxygen. In contrast, for the selective oxidation, the effect of surface area is less prominent and Au NPs on anatase exhibit higher photo‐catalytic activity than other TiO₂ phases. The catalysts can be recovered efficiently because the Au NPs stably attach to TiO₂ supports by forming a well‐matched coherent interface observed via high‐resolution TEM.     

Phyllanthin-assisted biosynthesis of silver and gold nanoparticles: a novel biological approach

Abstract  The anisotropic gold and spherical–quasi-spherical silver nanoparticles (NPs) were synthesized by reducing aqueous chloroauric acid (HAuCl₄) and silver nitrate (AgNO₃) solution with the extract of phyllanthin at room temperature. The rate of reduction of HAuCl₄ is greater than the AgNO₃ at constant amount of phyllanthin extract. The size and shape of the NPs can be controlled by varying the concentration of phyllanthin extract and thereby to tune their optical properties in the near-infrared region of the electromagnetic spectrum. The case of low concentration of extract with HAuCl₄ offers slow reduction rate along with the aid of electron-donating group containing extract leads to formation of hexagonal- or triangular-shaped gold NPs. Transmission electron microscopy (TEM) analysis revealed that the shape changes on the gold NPs from hexagonal to spherical particles with increasing initial concentration of phyllanthin extract. The Fourier transform infrared spectroscopy and thermogravimetric analyses reveal that the interaction between NPs and phyllanthin extract. The cyclic voltammograms of silver and gold NPs confirms the conversion of higher oxidation state to zero oxidation state. Graphical abstract  Anisotropic gold and silver nanoparticles were synthesized by a simple procedure using phyllanthin extract as reducing agent. The rate of bioreduction of AgNO₃ is lower than the HAuCl₄ at constant concentration of phyllanthin extract. The required size of the nanoparticles can be prepared by varying the concentration of phyllanthin with AgNO₃ and HAuCl₄.      

Self-assembly of water-dispersed gold nanoparticles stabilized by a thiolated glycol derivative

Two-dimensional (2D) hexagonally close-packed arrays of water-dispersed gold nanoparticles (NPs) on highly hydrophilic sputter-deposited SiO₂ surfaces were fabricated via an evaporation-induced self-assembly process. Using a non-ionic amphiphilic glycol derivative with the thiol head group, 1-mercapto-3,6,9-trioxodecane, as a stabilization ligand, high-concentration Au NPs were stably dispersed in water, and self-assembled into μm-sized well-ordered 2D arrays on SiO₂ surfaces during the solvent evaporation on SiO₂ surfaces. Due to the non-ionic character of the ligand, the particle–particle interactions may only depend on the capillary and van der Waals forces, and not on the electric double-layer forces that change with ion/electrolyte concentrations during the solvent evaporation. This study provides an approach to fabrication of close-packed 2D arrays of water-dispersed NPs instead of using toxicological organic solvent or complex water-organic phase transfer process. Meanwhile, this approach will make it easier to study their self-assembly mechanisms in a variety of solvents by simplifying ambiguous particle–particle interactions.     

NiAg Catalysts for Selective Hydrogenolysis of the Lignin C–O Bond

Several bimetallic NiAg catalysts for the lignin hydrogenolysis reaction are evaluated. NiAg catalysts are either prepared by wet chemical reduction, in which a mixture of AgNO₃ and Ni(NO₃)₂ or a mixture of AgOAc and Ni(OAc)₂ is reduced by NaBH₄ and stabilized by polyvinylpyrrolidone in water, or by the decomposition–precipitation method to obtain NiAg/SiO₂. These three catalysts exhibit distinct performances in hydrogenolysis of a lignin β‐O‐4 model compound. For colloidal catalyst from co‐reduction of AgOAc and Ni(OAc)₂, separate growths of Ag and Ni nanoparticles (NPs) are observed, and the system exhibits an undesired selectivity of 31.5% toward dimer products. On the other hand, NiAg NPs are dominant after the reduction of nitrate precursors, although the NP size is not sufficiently small (6.7 nm), resulting in high selectivity but a low reaction rate (12.6% conversion with 12.1% monomers yield). Bimetallic NiAg active phase with excellent dispersion (≈1.5 nm) is obtained on NiAg/SiO₂, which enables 72.7% substrate conversion and 65.6% yield of target monomer compounds. From these results, NiAg bimetallic catalyst is indeed superior to monometallic Ni in lignin hydrogenolysis, however, the formation of bimetallic NiAg catalyst is highly sensitive to the preparation conditions—proper selection of precursors, reductant, and support/stabilizer are all crucial.     

Self-assembly of water-dispersed gold nanoparticles stabilized by a thiolated glycol derivative

Two-dimensional (2D) hexagonally close-packed arrays of water-dispersed gold nanoparticles (NPs) on highly hydrophilic sputter-deposited SiO₂ surfaces were fabricated via an evaporation-induced self-assembly process. Using a non-ionic amphiphilic glycol derivative with the thiol head group, 1-mercapto-3,6,9-trioxodecane, as a stabilization ligand, high-concentration Au NPs were stably dispersed in water, and self-assembled into μm-sized well-ordered 2D arrays on SiO₂ surfaces during the solvent evaporation on SiO₂ surfaces. Due to the non-ionic character of the ligand, the particle–particle interactions may only depend on the capillary and van der Waals forces, and not on the electric double-layer forces that change with ion/electrolyte concentrations during the solvent evaporation. This study provides an approach to fabrication of close-packed 2D arrays of water-dispersed NPs instead of using toxicological organic solvent or complex water-organic phase transfer process. Meanwhile, this approach will make it easier to study their self-assembly mechanisms in a variety of solvents by simplifying ambiguous particle–particle interactions.This revised version was published online in August 2005 with a corrected issue number.     

Laser synthesis of aluminium nanoparticles in biocompatible polymer solutions

Pulsed laser ablation of Aluminium (Al) in pure water rapidly forms a thin alumina (Al₂O₃) layer which drastically modifies surface plasmon resonance (SPR) absorption characteristics in deep-UV region. Initially, pure aluminium nanoparticles (NPs) are generated in water without any stabilizers or surfactants at low laser fluence which gradually transform to stable Al-Al₂O₃ core-shell nanostructure with increasing either residency time or fluence. The role of laser wavelength and fluence on the SPR properties and oxidation characteristics of Al NPs has been investigated in detail. We also present a one-step in situ synthesis of oxide-free stable Al NPs in biocompatible polymer solutions using laser ablation in liquid method. We have used nonionic polymers (PVP, PVA and PEG) and anionic surfactant (SDS) stabilizer to suppress the Al₂O₃ formation and studied the effect of polymer functional group, polymeric chain length, polymer concentration and anionic surfactant on the incipient embryonic aluminium particles and their sizes. The different functional groups of polymers resulted in different oxidation states of Al. PVP and PVA polymers resulted in pure Al NPs; however, PEG and SDS resulted in alumina-modified Al NPs. The Al nanoparticles capped with PVP, PVA, and PEG show a good correlation between nanoparticle stability and monomeric length of the polymer chain.     

Origin of the selectivity in the gold-mediated oxidation of benzyl alcohol

Benzyl alcohol has received substantial attention as a probe molecule to test the selectivity and efficiency of novel metallic gold catalysts. Herein, the mechanisms of benzyl alcohol oxidation on a gold surface covered with atomic oxygen are elucidated; the results show direct correspondence to the reaction on gold-based catalysts. The selective, partial oxidation of benzyl alcohol to benzaldehyde is achieved with low oxygen surface concentrations and takes place through dehydrogenation of the alcohol to form benzaldehyde via a benzyloxy (C₆H₅–CH₂O) intermediate. While in this case atomic oxygen plays solely a dehydrogenating role, at higher concentrations it leads to the formation of intermediates from benzaldehyde, producing benzoic acid and CO₂. Facile ester (benzyl benzoate) formation also occurs at low oxygen concentrations, which indicates that benzoic acid is not a precursor of further oxidation of the ester; instead, the ester is produced by the coupling of adsorbed benzyloxy and benzaldehyde. Key to the high selectivity seen at low oxygen concentrations is the fact that the production of the aldehyde (and esters) is kinetically favored over the production of benzoic acid.     

Reaction mechanism of elemental mercury oxidation to HgSO4 during SO2/SO3 conversion over V2O5/TiO2 catalyst

Experiments and density functional theory calculations were conducted to uncover the reaction chemistry of Hg⁰ oxidation during SO₂/SO₃ conversion over V₂O₅/TiO₂ catalyst. The results show that SO₂ promotes Hg⁰ oxidation over V₂O₅/TiO₂ catalyst with the assistance of oxygen. The promotional effect is dependent on the reaction temperature, and is associated with the bimolecular reaction between Hg⁰ and SO₃ over V₂O₅/TiO₂ catalyst. SO₂ can be oxidized to SO₃ which has high oxidation ability for Hg⁰ oxidation. SO₂/SO₃ conversion proceeds through a three-step reaction process in the sequence of SO₂ adsorption → SO₂ oxidation → SO₃ desorption. SO₂ oxidation presents an activation energy barrier of 223.84 kJ/mol. HgSO₄ species is formed from the bimolecular reaction between Hg⁰ and SO₃ over V₂O₅/TiO₂ catalyst. Hg⁰ oxidation by SO₃ over V₂O₅/TiO₂ catalyst occurs through three reaction pathways, which are energetically favorable for HgSO₄ formation. SO₂* → SO₃* is identified as the rate-determining step of HgSO₄ formation. During Hg⁰ oxidation by SO₃ over V₂O₅/TiO₂ catalyst, HgSO₄ desorption is a highly endothermic reaction process and requires a higher external energy. The proposed skeletal reaction network can be used to well understand the reaction mechanism of Hg⁰ oxidation during SO₂/SO₃ conversion over V₂O₅/TiO₂ catalyst.