从零维到三维的金范式: 金单质概念的新发展

含有零维金纳米球的胶体金,在古埃及就已经被用于制造彩色玻璃,但直到20世纪,人们才对其进行系统的研究。20世纪下半叶,一维金纳米棒的合成及其奇异的光学性质引起了科学家对金纳米颗粒的关注。随后,二维金纳米片、三维金纳米哑铃等金纳米颗粒的相继出现,丰富和发展了金单质的概念。几种新的金单质的发现,构建了从零维到三维的金范式,从而启发人们对“金单质”及其应用进行更加深入的探究。     

火试金法测定铅冶炼渣中的金、银含量

建立了铅冶炼渣中的金银含量的测定方法,采用火试金法富集铅冶炼渣中的金、银,铅扣经灰吹后,形成金银合粒,合粒中除有金银外,还残留微量的铅铋杂质,合粒经硝酸分金后,实现金银分离,得到金粒和分金溶液。合粒中杂质保留在分金溶液中,分金溶液经酸处理,采用电感耦合等离子体发射光谱(ICP-OES)法测定其中杂质量和微量的金量。金粒质量补正分金溶液中微量金量即为样品中的金量,合粒质量减去金粒质量和杂质量即为银量。ICP-OES法测定杂质解决了合粒中铅铋残留和分金失误造成微量金进入分金溶液现象。方法精密度较好,加标回收率分别为银98.6%～100%,金96.2%～102%。方法准确、方便、快捷,能很好地满足铅冶炼渣中金、银含量的测定。     

火试金法测定铅冶炼渣中的金、银含量

建立了铅冶炼渣中的金银含量的测定方法,采用火试金法富集铅冶炼渣中的金、银,铅扣经灰吹后,形成金银合粒,合粒中除有金银外,还残留微量的铅铋杂质,合粒经硝酸分金后,实现金银分离,得到金粒和分金溶液。合粒中杂质保留在分金溶液中,分金溶液经酸处理,采用电感耦合等离子体发射光谱(ICP-OES)法测定其中杂质量和微量的金量。金粒质量补正分金溶液中微量金量即为样品中的金量,合粒质量减去金粒质量和杂质量即为银量。ICP-OES法测定杂质解决了合粒中铅铋残留和分金失误造成微量金进入分金溶液现象。方法精密度较好,加标回收率分别为银98.6%～100%,金96.2%～102%。方法准确、方便、快捷,能很好地满足铅冶炼渣中金、银含量的测定。     

火试金重量法与AAS湿法结合测定砂金矿中金的含量

砂金矿中二氧化硅和金的含量较高,本文用传统的火试金重量法与AAS湿法相结合来测定砂金矿中的金含量,用以得到较为精确的结果。本文用科学的配料方法,调节好熔渣的硅酸度,得到品质更好的熔渣与铅扣。再通过二次补正收集分散在熔渣中的金,之后进行三次补正收集灰皿中残留的金含量,然后用原子吸收光谱—AAS湿法测定三次补正得到的金银合粒与分金液中金的含量,从而得到更精确的结果。此方法操作简便、适用性广、精密度与准确度较高。通过加标测试此方法金的回收率在99.2%～100.3% 之间,金的相对标准偏差(RSD)在0.24%～0.6%之间。     

碳质金矿中金的化学物相分析方法改进

为了解决碳质金矿金化学物相分析结果与选矿试验结果不符的问题,基于岩矿鉴定和测试结果对分析流程进行改进。方法改进后测试项目包括裸露金和半裸露金、有机碳石墨包裹金、碳酸盐包裹金、褐铁矿包裹金、黄铁矿包裹金、石英和硅酸盐包裹金6项。有机碳石墨包裹金选用Na_2S_2O_3–CuCl_2–NH_4OH–NH_4Cl体系为浸金剂,取代I_2–NH_4I体系,该体系中金的测定采用铜置换原子吸收法。裸露金半裸露金、有机碳石墨包裹金和黄铁矿包裹金的相和为82.34%,与选矿试验金精矿实际回收率(75.83%)基本吻合。改进后的方法适合碳质金矿金化学物相分析。     

Synthesis of hybrid gold-gold sulfide colloidal particles

The nucleation and growth mechanism of nanometer size gold onto gold sulfide colloidal particles by irradiation-induced reduction is reported. The process is characterized by ultraviolet-visible spectroscopy, electronic diffraction, and high-resolution transmission electron microscopy, allowing for observation of several key intermediates and characteristics of the growth mechanism. The formation mechanism of gold on the surface of the gold sulfide particles is shown to depend strongly on the deposition rate. At low dose rate, gold nucleates preferentially onto specific gold-rich Au2S facets {110}, resulting in epitaxial growth. The gold crystal lattice plastically deforms near the interface to accommodate a substantial lattice mismatch. Upon increasing gold precursor concentration, this low dose rate results in growth of elongated gold island on the gold sulfide surface. At a high dose rate, several randomly oriented gold particles are simultaneously produced on gold sulfide, resulting in a layered structure. The absorption spectra of these particles show a dominant surface plasmon band, whose peak wavelength shifts markedly to the red as layered structure is formed.     

Heat-Induced Formation of Monodisperse Gold Nanoparticles in Different Conditions

We investigate the preparation of nearly monodisperse gold nanoparticles by heat treatment in different conditions. The effects of various solvents, heating temperature, and heating time length on the monodispersity of gold nanoparticles were studied systematically and a general route to generate gold nanoparticles with uniform size was determined. The first step was to prepare gold nanoparticles with less than 3 nm and the following operation was to heat the gold nanoparticles in the present of thiolated solvents where monodispersed gold nanoparticles could be obtained easily. Our approach has enriched synthesis of monodisperse gold nanoparticles, and may provide some valuable experimental data about how the heating process affects the size evolution of gold nanoparticles.     

Geometric, electronic, and bonding properties of AuNM (N = 1-7, M = Ni, Pd, Pt) clusters

Employing first-principles methods, based on density functional theory, we report the ground state geometric and electronic structures of gold clusters doped with platinum group atoms, Au(N)M (N = 1-7, M = Ni, Pd, Pt). The stability and electronic properties of Ni-doped gold clusters are similar to that of pure gold clusters with an enhancement of bond strength. Due to the strong d-d or s-d interplay between impurities and gold atoms originating in the relativistic effects and unique properties of dopant delocalized s-electrons in Pd- and Pt-doped gold clusters, the dopant atoms markedly change the geometric and electronic properties of gold clusters, and stronger bond energies are found in Pt-doped clusters. The Mulliken populations analysis of impurities and detailed decompositions of bond energies as well as a variety of density of states of the most stable dopant gold clusters are given to understand the different effects of individual dopant atom on bonding and electronic properties of dopant gold clusters. From the electronic properties of dopant gold clusters, the different chemical reactivity toward O(2), CO, or NO molecule is predicted in transition metal-doped gold clusters compared to pure gold clusters.     

A gold nanoparticle-based immunochromatographic assay: the influence of nanoparticulate size

Four different sized gold nanoparticles (14 nm, 16 nm, 35 nm and 38 nm) were prepared to conjugate an antibody for a gold nanoparticle-based immunochromatographic assay which has many applications in both basic research and clinical diagnosis. This study focuses on the conjugation efficiency of the antibody with different sized gold nanoparticles. The effect of factors such as pH value and concentration of antibody has been quantificationally discussed using spectra methods after adding 1 wt% NaCl which induced gold nanoparticle aggregation. It was found that different sized gold nanoparticles had different conjugation efficiencies under different pH values and concentrations of antibody. Among the four sized gold nanoparticles, the 16 nm gold nanoparticles have the minimum requirement for antibody concentrations to avoid aggregation comparing to other sized gold nanoparticles but are less sensitive for detecting the real sample compared to the 38 nm gold nanoparticles. Consequently, different sized gold nanoparticles should be labeled with antibody under optimal pH value and optimal concentrations of antibody. It will be helpful for the application of antibody-labeled gold nanoparticles in the fields of clinic diagnosis, environmental analysis and so on in future.     

Catalysis by gold dispersed on supports: the importance of cationic gold

There are many examples of catalysis in solution by cationic complexes of gold, and recent results, reviewed here in this critical review, demonstrate that cationic gold species on oxide and zeolite supports are also catalytically active, for reactions including ethylene hydrogenation and CO oxidation. The catalytically active gold species on supports are evidently not restricted to isolated mononuclear gold complexes, but include gold clusters, which for at least some reactions are more active than the mononuclear complexes and for some reactions less active. Fundamental questions remain about the nature of cationic gold in supported catalysts, such as the nature of the cationic gold clusters and the nature of gold atoms at metal-support interfaces (88 references).     

Au/Al2O3催化剂的制备及其在CH4/CO2重整反应中的催化活性

采用浸渍法和沉积－沉淀法制备了四种不同的Au/Al2O3催化剂，测定了它们在氢气还原前后及催化反应后的金含量及比表面积，结果表明，制备方法明显影响催化剂的金含量，应用X－光粉末衍射技术研究了这些催化剂经还原处理及反应后的物相变化，金以Au^0物相存在，没有发现氧化态的金物相，考察了该催化剂在CH4／CO2重整反应中的催化活性，发现金催化剂的活性取决于金粒子的大小，浸渍法制备的金催化剂具有较大的金晶粒尺寸，催化活性低，沉积－沉淀法制备的金催化剂金晶粒尺寸较小，催化活性较高，以尿素为沉淀剂制备的催化剂给出1073K时的CH4和CO2转化率分别为8．1％和17．6％，高温反应不仅导致金晶粒的聚集，而且存在明显的金流失现象。     

Application of Inductively Coupled Plasma-Atomic Emission Spectrometry/Mass Spectrometry to Phase Analysis of Gold in Gold Ores

Inductively coupled plasma-atomic emission spectrometry/mass spectrometry (ICP-AES/MS) is a potentially powerful tool in chemical phase analysis of gold in batch mode, especially applicable to the low-grade gold ores with gold content of far below detection limit of the other methods, but it has not been used in gold phase analysis of gold ores. In this work, three types of typical gold deposits (altered rock type, quartz vein type, and microscopic disseminated type) and national standard reference materials of gold ores were used to establish and validate a method for gold phase analysis of gold ores using ICP-AES/MS. The optimum conditions of phase analysis were determined, including the sample granularity and preparation procedures, separation absorbent, pretreatment procedures of various phases of gold and optimized instrument parameters. Evaluation of the optimized method showed that this method had acceptable precision (RSD: 1.1%–10.6%) and accuracy (relative error, RE: 0.5%–6.3%), and the detection results of gold in ores were comparable with those obtained using the hydroquinone volumetric method-extraction flame atomic absorption spectrometry (VOL-AAS) and graphite furnace atomic absorption spectrometry (GFAAS) methods. The sum content of gold of the 4 phases (free gold, F_Au; linked gold, L_Au; sulphide-bearing gold, S_Au; and other mineral-bearing gold, A_Au) conformed to the total gold content and was consistent with the results of rock-mineral identification. The proposed method had a low detection limit (0.30 ng g^–1) and wide linear range (5.0 ng mL^–1–20.00 μg mL^–1). It is a simple, rapid, and efficient method for gold phase analysis in batch form.     

In vitro permeation of gold nanoparticles through rat skin and rat intestine: effect of particle size

Purpose of the present work was to study in vitro permeation of gold nanoparticles (NPs) through isolated rat skin and intestine. Another objective was to see the effect of particle size on permeation of the gold NP. Gold NP of 15 nm, 102 nm and 198 nm were synthesized and used for study. Franz diffusion cells were used to evaluate permeation of gold NP from rat skin whereas 'intestinal sac' method was used for assessing intestinal permeation. Number density of gold NP was analyzed by UV-vis spectroscopy whereas amount of gold permeated was measured by ICP mass spectrometry. The absorption and localization of gold NP through rat skin was studied by TEM. Qualitative analysis of gold inside of the rat skin was performed by energy dispersive X-ray spectroscopy (EDS). Gold NP showed negative zeta potential. UV-vis absorption spectra of 15 nm, 102 nm and 198 nm gold NP showed lambda(max) at 520 nm, 535 nm and 577 nm, respectively. SEM study revealed spherical morphology of NP. Gold NP showed size dependent permeation through rat skin and intestine. 15 nm gold NP showed higher permeation compared to 102 nm and 198 nm gold NP. Interestingly, 102 nm and 198 nm gold NP showed lag time of 3h and 6h in case of rat skin only. As the size of the gold NP increased, permeability coefficient and diffusion coefficient was found to be decreased. The permeation of gold NP through intestine was higher than that of skin. TEM study of rat skin revealed accumulation of smaller size gold NP in deeper region of skin whereas larger particles were observed mainly in epidermis and dermis. Presence of gold inside of rat skin was confirmed by EDS. Gold NP would be an interesting carrier for transdermal as well as for oral delivery. The study demonstrated initial proof of concept of percutaneous permeation of smaller size gold particles.     

Thermal-induced growth of gold nanoparticles conjugated with thermoresponsive polymer without chemical reduction

The growth of gold nanoparticles without chemical reduction of gold (III) ions was achieved by the disruption of thermoresponsive polymers conjugated with the gold nanoparticles through the phase transition of the polymers. When a solution of gold nanoparticles coated with thermoresponsive polymers was heated, chains of the thermoresponsive polymers were disrupted because of dehydration, resulting in the fusion of gold nanoparticles to form larger nanoparticles. The evolution of the extinction band around 550 nm evidenced the formation of these large (post-fusion) gold nanoparticles, which were characterized by transmission electron microscope (TEM) and dynamic light scattering (DLS). TEM images verified the formation of the large gold nanoparticles having particle sizes of 80-100 nm, whereas DLS indicated the existence of large nanoparticles with hydrodynamic diameters exceeding 200 nm. The deposition did not require the addition of reductants or trivalent gold ions for the formation of the large gold nanoparticles. Both the heating and the solution conditions were studied to elucidate the mechanism of the formation of large gold nanoparticles.     

金纳米粒子表面自组装巯基十一烷醇单分子层体系的制备及其光散射特性研究

采用柠檬酸钠还原法制备了水相金纳米粒子, 通过巯基的自组装, 成功获得了巯基十一烷醇(MUN)单分子层保护的金纳米粒子. 用紫外可见光谱、透射电子显微镜、激光散射粒度分析、同步散射光谱和发射光谱等手段对组装前后的金纳米粒子的性质进行了研究. 结果表明: 制备的金纳米粒子最大吸收波长518 nm, 形状规则, 粒度均匀, 平均粒径为14.6 nm, 每个粒子含有约9.64×10⁴原子; 组装之后的金纳米粒子表面等离子体共振吸收峰红移17.0 nm, 平均粒径增大为20.2 nm, 组装层的平均厚度2.8 nm, 与MUN分子长度相当, 结合量实验证明每一个金纳米粒子可以结合约7.52×10³个MUN, 表面覆盖率为83.6%, 粒子分散均匀, 稳定性增强可长期保存; 同步散射光谱变化和发射光谱中分频、差频和倍频峰的存在证明, 金纳米粒子组装前后均具有非线性光学特性.     

黄金矿的催化浸取

基于对金自溶解电化学过程的分析，提出此过程受阴极还原反应所控制，加入阴极反应催化剂，能加快金自溶速度，实验结果充分表明，我们找到的催化剂Ａ能提高金的浸出速度和浸出效率。     

Photoinduced electron transfer between chlorophyll a and gold nanoparticles

Excited-state interactions between chlorophyll a (Chla) and gold nanoparticles have been studied. The emission intensity of Chla is quenched by gold nanoparticles. The dominant process for this quenching has been attributed to the process of photoinduced electron transfer from excited Chla to gold nanoparticles, although because of a small overlap between fluorescence of Chla and absorption of gold nanoparticles, the energy-transfer process cannot be ruled out. Photoinduced electron-transfer mechanism is supported by the electrochemical modulation of fluorescence of Chla. In absence of an applied bias, Chla cast on gold film, as a result of electron transfer, exhibits a very weak fluorescence. However, upon negatively charging the gold nanocore by external bias, an increase in fluorescence intensity is observed. The negatively charged gold nanoparticles create a barrier and suppress the electron-transfer process from excited Chla to gold nanoparticles, resulting in an increase in radiative process. Nanosecond laser flash experiments of Chla in the presence of gold nanoparticles and fullerene (C60) have demonstrated that Au nanoparticles, besides accepting electrons, can also mediate or shuttle electrons to another acceptor. Taking advantage of these properties of gold nanoparticles, a photoelectrochemical cell based on Chla and gold nanoparticles is constructed. A superior performance of this cell compared to that without the gold film is due to the beneficial role of gold nanoparticles in accepting and shuttling the photogenerated electrons in Chla to the collecting electrode, leading to an enhancement in charge separation efficiency.     

Bimodal Size Distribution of Gold Nanoparticles under Picosecond Laser Pulses

The evolution of size distributions of gold nanoparticles under pulsed laser irradiation (Nd:YAG, lambda = 355 nm, pulse width 30 ps) was carefully observed by transmission electron microscopy. Interestingly, the initial monomodal size distribution of gold nanoparticles turned into a bimodal one, with two peaks in the number of particles, one at 6 nm and the other at 16-24 nm. The sizes for small particles depended very little on the irradiated laser energy. This change is attributed to laser-induced size reduction of the initial gold nanoparticles followed by the formation of small particles. In our analysis, we extracted a characteristic value for the size-reduction rate per one pulse and revealed that laser-induced size reduction of gold nanoparticles occurred even below the boiling point. When laser energy is insufficient for the boiling of particles, formation of gold vapor around liquid gold drops is thought to cause the phenomenon. With enough laser energy for the boiling, the formation of gold vapor around and inside liquid gold drops is responsible for the phenomenon. We also observed particles with gold strings after one pulse irradiation with a laser energy of 43 mJ cm(-2) pulse(-1), which is sufficient energy for the boiling. It is considered that such particles with gold strings are formed by the projection of gaseous gold from liquid gold drops with some volume of liquid gold around the bubble. On the basis of comparison with previous work, picosecond laser pulses are thought to be the most efficient way to cause laser-induced size reduction of gold nanoparticles.     

纳米金催化一氧化碳氧化反应的理论研究

近年来,纳米金催化剂独特的催化性质,特别是其优异的低温催化氧化活性,引起了人们极大的研究热情.除低温选择氧化外,在精细化学品合成、大气污染物消除、氢能的转换和利用等领域也开发出了一系列有广泛应用前景的金催化反应.此外,体相金的化学惰性和纳米金的超高活性之间差异的“鸿沟”也引起了理论工作者浓厚兴趣,试图从原理上理解体相金和纳米金活性差异的根源. CO催化氧化是最具有代表性的研究金催化活性的化学反应,本文主要综述了近十多年来金催化 CO氧化反应理论计算方面的研究工作.一般认为, CO在纳米金表面的吸附是 CO氧化反应的初始步骤.密度泛函理论研究表明, CO在金表面的吸附强度主要与被吸附金原子的配位数有关：金配位数越低, CO的吸附能越强,部分研究结果表明两者之间存在近似的线性关系.我们研究发现, CO吸附强度也与被吸附金周围配位金原子的相对位置有关,其中位于正下方的配位金原子加强 CO吸附,而位于侧位的配位金原子则弱化 CO吸附,这显然削弱了 CO吸附与金配位数线性关系的可靠性.理论研究表明,在纯金表
　　面上 O2吸附强度一般很弱,只有在一些特殊结构的金团簇上才有较强的吸附,但在 Au/TiO2界面及 CeO2表面上 O2吸附较强.金表面原子氧的吸附和金的表面结构有关.我们发现,原子氧倾向于在金的表面形成一种线性的 O–Au–O结构以增加其稳定性.当金表面的氧覆盖度增大时,会形成一种金氧化物薄膜结构,其结构依赖于氧的化学势和金的表面结构.纳米金催化 CO氧化反应机理可能因体系、载体等的差异而不同.大部分理论计算结果表明,在纯金表面上 O2很难直接解离形成原子氧,因此反应机理可能是吸附的 CO先与 O2反应形成了一种 CO–O2中间体,然后解离形成 CO2.在 Au/TiO2和 Au/CeO2催化剂上 CO催化氧化机理争议很大,均有计算结果支持 LH机理和 M–vK机理.另外,根据实验上观察到了负载型纳米金能直接活化分子氧的结果,理论上也提出了分子氧先解离为原子氧再与 CO反应的氧解离机理.针对如何解离分子氧问题,人们分别提出了低配位金模型、正方形金结构模型、Ti5c模型及 Au/Ti5c模型等.我们也提出了一种独特的双直线 O–Au–O模型来理解 Au/TiO2或 Au/CeO2界面解离活化分子氧.理论计算结果表明,低配位的金,金和载体之间的电荷转移,以及金所表现出的强相对论效应对于纳米金的活性影响很大.需要特别指出的是,金的强相对论效应有助于理解金表面的 CO吸附与金配位的关系、金表面原子氧的吸附特性、金氧化物薄膜的结构和分子氧的活化等过程.我们认为,金的强相对论作用导致了体相金的化学惰性以及纳米金的活性,因此相对论效应的深入研究将有助于理解金催化 CO氧化反应机理,从而有助于深层次理解纳米金催化活性来源.     

Gold Nanoparticle Modified Electrodes Show a Reduced Interference by Cu(II) in the Detection of As(III) Using Anodic Stripping Voltammetry

Interference by Cu(II) causes serious problems in the detection of As(III) using anodic stripping voltammetry at gold electrodes. The behavior of Cu(II) and As(III) were examined at both a gold macro electrode and two kinds of gold nanoparticle modified electrodes, one where gold particles are deposited on glassy carbon (GC) and the other where basal plane pyrolytic graphite (BPPG) is the substrate. The sensitivity of As(III) detection was higher on gold nanoparticle modified electrodes than those on a macro gold electrode by up to an order of magnitude. In addition, the stripping peak of As(III) was narrower and more symmetric on a gold nanoparticle‐modified GC electrode, leading to analytical data with a lower limit of detection. At a macro gold electrode, the peak currents of Cu(II) were higher than those on gold nanoparticle modified electrodes. Accordingly, through the use of gold nanoparticle modified electrodes, the effect of copper interference to the arsenic detection can be reduced.