高热稳定性二氧化硅包覆的Au25纳米簇的制备和催化应用

具有独特的电子和几何结构,原子精确控制的金纳米簇(<2 nm)成为一种新的具有广泛研究和应用前景的纳米催化剂.负载在氧化物表面的金纳米簇通常会在高于300°C时聚集或长大.人们已经通过多种方法成功制备了对于非原子精确控制的热稳定性的金纳米颗粒.主要包括利用金属与载体强相互作用,用可还原的金属氧化物来稳定金纳米颗粒;利用物理阻隔作用使用高比表面积的载体或制备核壳、纳米粒子镶嵌在载体中来稳定金纳米颗粒.对于原子精确控制的金纳米簇,由于其外边包覆着一层配体,将其负载到载体上时要保证配体不被破坏才能保证金纳米簇的结构完整性,负载后通常要除去配体才能使催化活性位曝露出来.目前,高热稳定性(>300°C)的金纳米簇的制备方法还较少.由于金与 SiO2相互作用较弱,将超小(<2 nm)的金纳米粒子包覆于其中非常困难.因此,本文首先制备了1.3 nm的含有硅酯键的巯基配体(3-巯丙基三甲氧基硅烷)保护的 Au25[SC3H6Si(OCH3)3]18,然后将其在刚成核的 SiO2表面与正硅酸四乙酯共水解,得到了既保留了 Au25的完整结构,又避免了 Au25之间相互水解的 Au25(SC3H6SiO3)18@SiO2纳米材料.漫反射固体紫外-可见光谱证明了 Au25在包覆完成后结构的完整性.透射电镜结果表明, Au25纳米簇焙烧至400°C未发生明显聚集长大.对硝基苯酚还原实验结果表明,不同温度处理后的 Au25@SiO2配体在200°C开始脱除,温度高于传统的负载型 Au25催化剂,表明 Au25是在 SiO2内部而不是在表面,从而使配体不易离去.400°C处理后的 Au25@SiO2对4-硝基苯酚还原表现出最高的反应活性,表明该纳米簇在400°C处理后没有发生明显聚集长大.     

还原氧化石墨烯/Au复合微电极阵列的制备及光电特性

利用双光束干涉-无掩模光刻技术制备了周期性氧化石墨烯微结构阵列,利用肼蒸气对氧化石墨烯脱氧还原,然后蒸镀超薄Au薄膜制备了还原氧化石墨烯/Au复合微电极阵列(R-GO/Au).对复合电极在可见光波段的透过率和表面电阻进行了表征,结果表明,R-GO/Au复合微电极阵列具有良好的光电特性.将R-GO/Au复合微电极阵列引入到有机太阳电池中作为半透明阳极,器件的光电转化效率可达3.43%.     

Size‐Dependence of the Activity of Gold Nanoparticle‐Loaded Titanium(IV) Oxide Plasmonic Photocatalyst for Water Oxidation

Mesoporous TiO₂ nanocrystalline film was formed on fluorine‐doped tin oxide electrode (TiO₂/FTO) and gold nanoparticles (NPs) of different sizes were loaded onto the surface with the loading amount kept constant (Au/TiO₂/FTO). Visible‐light irradiation (λ>430 nm) of the Au/TiO₂/FTO photoanode in a photoelectrochemical cell with the structure of photoanode|0.1 m NaClO4 aqueous solution|Ag/AgCl (reference electrode)|glassy carbon (cathode) leads to the oxidation of water to oxygen (O₂). We show that the visible‐light activity of the Au/TiO₂/FTO anode increases with a decrease in Au particle size (d) at 2.9≤d≤11.9 nm due to the enhancement of the charge separation and increasing photoelectrocatalytic activity.     

Potential-dependant SERS interaction of ortho-substituted N-benzylamino(boronphenyl)methylphosphonic acid with Ag,Au, and Cu electrode surfaces

In this study we present surface-enhanced Raman spectroscopy (SERS) investigations of ortho-substituted N-benzylamino(boronphenyl)methylphosphonic acid (N-benzylamino-(2-boronphenyl)-R-methylphosphonic acid; o-PhR) adsorbed onto a roughened in oxidation–reduction cycles (ORC) Ag, Au, and Cu electrode surfaces at different applied electrode potentials. Based on the spectral changes in bandwidth and wavenumber of selected bands upon the alternation of the applied electrodes potential the manner and differences in the interaction of o-PhR with the Ag, Au, and Cu electrode surfaces were determined. Briefly, the spectral patterns on Ag and Au suggest that, generally, the both aromatic rings are involved in the o-PhR/electrode interaction, whereas the boronophenyl ring only interacts with Cu. Also, the boronic acid and phosphonic acid groups participate in the o-PhR interaction with all the types of electrodes. However, the type of the used electrode material and the applied electrode potential have influence onto the mode of adsorption.     

Surface-enhanced Raman studies of bradykinin using colloidal gold

In this paper, bradykinin (BK), an endogenous peptide hormone, which is involved in a number of physiological and pathophysiological processes was deposited onto the colloidal Au nanoparticles. The surface-enhanced Raman spectroscopy (SERS) was used to determine the adsorption mode of BK under different environmental conditions, including: excitation wavelengths (514.5 nm and 785.0 nm), pH of aqueous sol solutions (from pH = 3 to pH = 11), and size of the colloidal nanoparticles (10, 20, and 50 nm). The metal surface plasmon of the colloidal suspended Au nanoparticles was examined by ultraviolet-visible (UV–vis) spectroscopy. The results showed that the C-terminal part of BK plays a crucial role in the adsorption process onto the colloidal suspended Au particles. The Phe^5/8 and Arg⁹ residues of BK mainly participate in the interactions with the colloidal Au nanoparticles. At acidic pH of the solution (pH = 3), the BK COO⁻ terminal group through the both oxygen atoms strongly binds to the Au nanoparticles. The Phe⁵/Phe⁸ rings adopt tilted orientation with respect to the colloidal Au nanoparticles with diameters of 10 and 20 nm. As the particle size increases to 50 nm, the flat orientation of the Phe ring(s) with respect to the Au nanoparticles is observed.     

Determination of primary aromatic amines using immobilized nanoparticles based surface-enhanced Raman spectroscopy

Primary aromatic amines(PAAs) are substances with toxicity and suspected human carcinogenicity. A facile method for highly sensitive detection of PAAs using surface-enhanced Raman spectroscopy(SERS)is reported. The immobilization of Au nanoparticles(AuNPs) on the glycidyl methacrylate–ethylene dimethacrylate(GMA-EDMA) materials makes the substrate a closely packed but not aggregated AuNP arrays which provides a prominent SERS enhancement. Four PAAs with different substituent groups,namely, p-toluidine, p-nitroaniline, benzidine and 4,4-methylene-bis-(2-chloroaniline) have been successfully identified and quantified. High sensitivity and good linear relationship between SERS signals and concentrations of PAAs are obtained for all four PAAs.     

Underpotential Deposition Preparation of Pt‐loading AuNPs/Reduced Graphene Oxide and Its Catalytic Detection of Catechol

Ultralow Pt‐loading Au nanoparticles have been fabricated on the surface of reduced graphene oxide (RGO) by using underpotential deposition (UPD) monolayer redox replacement process. The Pt/Au/RGO modified electrode exhibits an excellent electrocatalytic activity toward catechol and hydroquinone. Under the optimized condition, the separation of peak‐to‐peak between hydroquinone and catechol is 197 mV, which is wide enough to distinguish the isomers of benzenediol. Catechol is detected by the Pt/Au/RGO/GCE with a low detection limit in the presence of hydroquinone.     

贵金属纳米颗粒杂化囊泡的制备及拉曼增强效果研究

以超支化聚合物囊泡为模板制备了贵金属纳米颗粒表面功能化的杂化囊泡.模板囊泡通过多巴胺修饰的超支化聚醚HSP-DA在水中自组装形成.在碱性条件下,囊泡表面的多巴胺自聚合生成聚多巴胺,实现囊泡的交联.由于聚多巴胺具有强黏附特性,因此可以将HSP-PDA交联囊泡分别与Au纳米溶胶、Ag纳米溶胶直接混合,得到Au纳米颗粒或Ag纳米颗粒功能化的杂化囊泡.分别测定了2种杂化囊泡的拉曼光谱,发现杂化囊泡产生了明显的表面增强的拉曼光谱(SERS)信号,清晰显示了对应于囊泡模板分子的拉曼信号,表明可以通过SERS来原位检测囊泡的组成.Ag纳米颗粒杂化囊泡展示出更高的SERS灵敏度,可进一步作为探针检测水中浓度为10-7mol/L罗丹明6G分子,得到了显著增强的拉曼光谱,证明所制备的Ag纳米颗粒杂化囊泡可用于目标分子的痕量检测.     

Size‐Dependent Surface Migration of Au Alloys on Si Nanowires at Different Cooling Rates

Understanding metal alloy migration in metal‐catalyzed nanowires growth is a prerequisite for improving its potential applications in the field of nanodevices. Here, we explored the surface migration of Au alloys in vertically aligned Si nanowires with different cooling rates. We varied the diameter of Au alloys by controlling the thickness of Au film as a catalyst for SiNW growth, and found that the behavior of Au alloys migration is dependent on size of Au alloys. In addition, the size‐dependent migration mechanism of Au alloys was investigated at different cooling rates, which is related to different Au‐Si eutectics.     

PVDF微孔滤膜负载金纳米粒子用于牛奶中三聚氰胺的SERS快速检测

本文报道了一种利用聚偏二氟乙烯(Polyviny Lidene Fluoride,PVDF)微孔滤膜为载体的三聚氰胺(Melamine,MAM)的简便快速痕量分析技术。通过柠檬酸钠还原法制得平均粒径为30nm的纳米金溶胶,加入不同浓度的三聚氰胺后金纳米粒子快速聚集,这种纳米金聚集体可以通过简便快捷的过滤技术截留在PVDF微孔滤膜表面,进而用于SERS检测,在水溶液中最低检测浓度为0.05mg/L。我们进一步在牛奶样品中进行检测,在牛奶中检测限可以达到1mg/L,满足大部分国家规定的婴儿配方食品中三聚氰胺的限量值为1mg/kg的参考标准。该分析方法制备过程简单、成本低廉、总分析时间短,易于实现现场快速灵敏检测,应用前景广阔。