乐果的振动光谱及其在金/银核-壳复合粒子表面的SERS研究

联合FTIR,FT-拉曼表征了乐果的振动光谱,获得了固态及不同酸碱条件下饱和液态乐果的振动特征信息;以金/银核-壳复合粒子为基底,获得了乐果在酸碱条件下一系列浓度的表面增强拉曼散射(SERS)光谱,考察了乐果分子在该基底表面的吸附状态及其酸碱影响,推测了乐果与金/银核-壳复合粒子作用机理;结果表明:νas(NH),νas(CH3),ν(O=C-N),τ(O=C-N),ν(P—O),ν(P S),ν(C—C),δ(P—O—C)为乐果分子特征振动;酸、碱条件下,在1.0×10-3mol.L-1为乐果与基底作用的最佳浓度;乐果主要以P—O—C,O=C-C,(S—CH2),P=S,CH3与金/银核-壳复合粒子基底相作用,探讨了酸碱条件下磷酸酯键不同离解历程对吸附的影响。为研究有机磷农药的形态变化提供有益参考。     

光激发作用下分子与多金属纳米粒子间的电荷转移研究

金属纳米粒子在光激发作用下的增强作用是纳米科学领域的一个研究热点. 针对分子和多个不同位形下的金属纳米粒子在光激发下的相互作用展开了理论研究. 应用密度矩阵理论描述分子和金属纳米粒子同时激发产生表面等离激元后的电荷输运过程. 研究发现, 表面等离激元增强效应与分子和各个金属纳米粒子的相对位置有密切关系. 详细分析了金属纳米粒子间的耦合强度、分子和金属纳米粒子间的耦合强度、表面等离激元能级杂化、分子激发能和外场频率对表面等离激元增强效应的影响.     

第一性原理研究气体小分子吸附的石墨烯负载金属原子体系

石墨烯负载的单个金属原子体系(M-gra)具有高的结构稳定性,显正电性的金属原子可作为活性位用在气敏器件和催化材料.本文采用基于密度泛函理论的第一性原理方法研究单个有毒气体小分子(NO和CO)在M-gra表面的吸附特性.研究结果表明:单个NO分子吸附的稳定性高于CO分子,由于其能够从反应衬底获得更多的转移电荷,因此,M-gra衬底对NO分子表现出高的灵敏度.此外,不同小分子吸附能够改变M-gra体系的电荷密度和自旋电荷分布,进而使得气体分子吸附体系表现出不同大小的磁矩.通过对比气体分子吸附前后M-gra体系的磁矩变化,能够有效判断吸附分子和反应衬底的类型.     

A first-principles study on the interaction of CO molecules with VIII transition metals-embedded graphitic carbon nitride as an excellent candidate for CO sensor

We studied the adsorption behavior of CO molecules over graphitic carbon nitride (gCN) and VIII transition metals (TM)-embedded gCN systems (TM=Ni, Pd, and Pt atoms) using density functional theory. The results indicated that the Pt-embedded gCN is excellent candidate for adsorption of CO molecules with adsorption energy of −2.77 eV, which is much better than those of the other adsorbents. Furthermore, it was observed that the band gap energies of TM-embedded systems were less than that of pristine gCN and decoration of transition metal atoms leads to the formation of mid gap impurity states, resulting in increase of electrical conductivity. Additionally, the Lowdin charges displayed that upon adsorption of CO molecules, this molecule acts as an electron acceptor and gCN systems behave as an electron donor with electron transfer from d-orbitals of transition metal atoms to the states of CO molecule. The results of spin polarized band structure indicated that the pristine gCN, Ni and Pd-embedded systems are non-magnetic, whereas Pt-embedded gCN induces non-zero magnetic moment equal to 1.35 μB. Therefore, our results revealed that among the TM-embedded systems, Pt-embedded gCN is more effective than those of the other adsorbents in sensing and removing of this gas from the atmosphere.     

Oxidation of metal nanoparticles: Experiment and model

Studies of oxygen adsorption on a metal surface are reviewed. The relationship between oxygen adsorption and the initial stage of oxidation is considered. Current theories of low-temperature oxidation and experimental data obtained during recent decades are reviewed. Thermodynamic aspects of low-temperature oxidation of metal nanoparticles and their relationship with the physical properties of metal nanoparticles are discussed. An original method for investigating the oxidation kinetics of ferromagnetic nanoparticles is described. The technique is based on continuous measurements of magnetization in the course of oxidation under controlled conditions. A stochastic model of oxidation is presented, which is based on the atomistic concepts of Cabrera-Mott theory. Oxidation is regarded as a random sequence of elementary acts (oxygen adsorption, oxygen ionization, metal ionization, metal ion migration, etc.).     

FT-SERS研究非极性R侧链氨基酸在银胶体系中的吸附状态

利用傅里叶变换表面增强拉曼光谱(FT-SERS)研究了以L-蛋氨酸为代表的非极性R侧链氨基酸在纳米银衬底上的吸附状态和相互作用的特性,并结合浓度、pH值的变化探讨了吸附作用的特点和规律。实验结果表明, L-蛋氨酸在银胶上的最佳FT-SERS的浓度范围为10-3～10-4 mol·L-1;其pH范围以酸性、等电点、碱性而分段,当pH值在等电点附近及酸碱度过大时的FT-SERS都较差;L-蛋氨酸与纳米银的作用是通过氨基、羧基、硫与银的物理、化学吸附,其吸附态随着pH值的变化而改变。结合文献,对非极性R侧链氨基酸与纳米银的吸附特性作了总结,以期有助于对氨基酸、蛋白质、多肽、酶等相关领域更深入的研究。     

Adsorption of 4,4′‐thiobisbenzenethiol on silver surfaces: surface‐enhanced Raman scattering study

Adsorption of 4,4′‐thiobisbenzenethiol (4,4′‐TBBT) on a colloidal silver surface and a roughened silver electrode surface was investigated by means of surface‐enhanced Raman scattering (SERS) for the first time, which indicates that 4,4′‐TBBT is chemisorbed on the colloidal silver surface as dithiolates by losing two H‐atoms of the S H bond, while as monothiolates on the roughened silver electrode. The different orientations of the molecules on both silver surfaces indicate the different adsorption behaviors of 4,4′‐TBBT in the two systems. It is inferred from the SERS signal that the two aromatic rings in 4,4′‐TBBT molecule are parallel to the colloidal silver surface as seen from the disappearance of ν_{C H} band (3054 cm⁻¹), which is a vibrational mode to be used to determine the orientation of a molecule on metals according to the surface selection rule, while on the roughened silver electrode surface they are tilted to the surface as seen from the enhanced signal of ν_{C H}. The orientation of the C‐S bond is tilted with respect to the silver surface in both cases as inferred from the strong enhancement of the ν_{C S}. SERS spectra of 4,4′‐TBBT on the roughened silver electrode with different applied potentials reveal that the enhancement of 4,4′‐TBBT on the roughened silver electrode surface may be related to the chemical mechanism (CM). More importantly, the adsorption of 4,4′‐TBBT on the silver electrode is expected to be useful to covalently adsorb metal nanoparticles through the free S H bond to form two‐ or three‐ dimensional nanostructures. Copyright © 2007 John Wiley & Sons, Ltd.     

Dynamic changes of optical characteristics of resonant domains in metal nanoparticle aggregates under pulsed laser fields

A systematic analysis of the impact of laser radiation on disordered metal nanoparticle aggregates has been carried out using the simplest model of a resonance domain in the form of a bisphere. Such aggregates can be considered as a set of elementary domains with different eigen-resonant frequencies. The model is basically a pair of bound spherical nanoparticles having equal radii and covered with a polymer adsorption layer. A significant change in the resonance properties of the domain occurs due to the change of interparticle gaps under applied radiation. We investigated the temporal variation of parameters and hence optical characteristics of coupled Ag nanoparticles under pulsed laser radiation for different wavelengths, intensities and pulse durations and for different initial values of the interparticle gap.     

Surface enhanced Raman spectroscopic readout on heavy metal ions based on surface self assembly

A new method is reported for detecting heavy metal ions by using the self assembled monolayer (SAM) technique and surface enhanced Raman spectroscopy (SERS). The p‐mercaptobenzoic acid (MBA) served as the SERS readout molecule and the modified tag to attach on the smooth gold substrate as well as the tag of nanoparticles by the SAM method. Two carboxyl groups from MBA molecules which were attached respectively to gold substrate and gold nanoparticles were linked through the heavy metal ions (Cu²⁺, Pb²⁺ and Zn²⁺) as bridge, and thus sandwich structure of ‘MBA modified gold substrate/heavy metal ions/MBA modified gold nanoparticles’ was built for detection. The observation of the oxidation peak of metal nanoparticles from cyclic voltammetry (CV) curve, gold nanoparticles from scanning electron microscopy (SEM) images and SERS signal of MBA from the sandwich structure indicated the existence of heavy metal ions. The difference in the wavenumbers of vibrational modes from MBA in the sandwich structure constructed by different could be used to identify different heavy metal ions. The assembled structure was rinsed by strong chelator of EDTA solution to remove the heavy metal ions from the sandwich structure and thus to obtain a fresh gold substrate modified with MBA for the cyclic detection. Copyright © 2007 John Wiley & Sons, Ltd.     

Superparamagnetic silica nanoparticles with immobilized metal affinity ligands for protein adsorption

Superparamagnetic silica-coated magnetite (Fe₃O₄) nanoparticles with immobilized metal affinity ligands were prepared for protein adsorption. First, magnetite nanoparticles were synthesized by co-precipitating Fe²⁺ and Fe³⁺ in an ammonia solution. Then silica was coated on the Fe₃O₄ nanoparticles using a sol–gel method to obtain magnetic silica nanoparticles. The condensation product of 3-Glycidoxypropyltrimethoxysilane (GLYMO) and iminodiacetic acid (IDA) was immobilized on them and after charged with Cu²⁺, the magnetic silica nanoparticles with immobilized Cu²⁺ were applied for the adsorption of bovine serum albumin (BSA). Scanning electron micrograph showed that the magnetic silica nanoparticles with an average size of 190 nm were well dispersed without aggregation. X-ray diffraction showed the spinel structure for the magnetite particles coated with silica. Magnetic measurement revealed the magnetic silica nanoparticles were superparamagnetic and the saturation magnetization was about 15.0 emu/g. Protein adsorption results showed that the nanoparticles had high adsorption capacity for BSA (73 mg/g) and low nonspecific adsorption. The regeneration of these nanoparticles was also studied.     

Interaction and local magnetic moments of metal phthalocyanine and tetraphenylporphyrin molecules on noble metal surfaces

In order to understand the Kondo effect observed in molecular systems, first-principles calculations have been widely used to predict the ground state properties of molecules on metal substrates. In this work, the interaction and the local magnetic moments of magnetic molecules （3d-metal phthalocyanine and tetraphenylporphyrin molecules） on noble metal surfaces are investigated based on the density functional theory. The calculation results show that the dz2 orbital of the transition metal atom of the molecule plays a dominant role in the molecule-surface interaction and the adsorption energy exhibits a simple declining trend as the adsorption distance increases. In addition, the Au（111） surface generally has a weak interaction with the adsorbed molecule compared with the Cu（ll 1） surface and thus serves as a better candidate substrate for studying the Kondo effect. The relation between the local magnetic moment and the Coulomb interaction U is examined by carrying out the GGA＋U calculation according to Dudarev＇s scheme. We find that the Coulomb interaction is essential for estimating the local magnetic moment in molecule-surface systems, and we suggest that the reference values of parameter U are 2 eV for Fe and 2-3 eV for Co.     

Inverse oxide/metal catalysts: A versatile approach for activity tests and mechanistic studies

There is a general desire to improve the configuration of industrial catalysts to take advantage of the intrinsic properties of metal oxides. In recent years, a series of studies has been published examining the growth of oxide nanoparticles on metal substrates. These studies have revealed structures for the supported oxide which are different from those found in bulk phases. In addition, the oxide ? metal interactions can alter the electronic states of the oxide producing new chemical properties. On an inverse oxide/metal catalyst, the reactants can interact with defect sites of the oxide nanoparticles, metal sites, and the metal–oxide interface. In these systems, one can couple the special reactivity of the oxide nanoparticles to the reactivity of the metal to obtain high catalytic activity. Furthermore, an oxide/metal system is also an attractive model for fundamental studies. It can be used to investigate the role of the oxide in a catalytic process, and how the stability of different reaction intermediates depends on the nature of the oxide.     

Elucidation of surface structure and bonding by photoelectron spectroscopy?

Information obtained on the adsorption of small and medium-sized molecules (CO, O₂, CO₂, NO, C₂H₄, C₆H₆) at three metal surfaces (Mo, W, Ni) by X-ray photoelectron spectroscopy (XPS) and ultra-violet photoelectron spectroscopy (UPS) is discussed in an attempt to establish what has been achieved, and what might be achieved in the elucidation of adsorption bonding at metal surfaces. Some of the individual results have been published by the present author with co-workers, and by other authors, but some results represent new work. Emphasis is placed on the detection of different states of adsorption, and then on interpretations of structure and bonding. The latter is divided into two areas, empirical interpretation by analogy between different adsorption systems, and in more absolute terms by consideration of the differences in electronic energy levels between the absorbate molecule in its gaseous and adsorbed state as well as differences between the metal levels in the clean and surface bonded state. Note is made of the problems of suitable reference levels and the phenomena of relaxation energies. Mo and W are taken as representative examples of adsorption confined usually to the monolayer regime; Ni is taken as an example of the situation where further reaction may occur. Most of the work described refers to polycrystalline films since little work has yet been done by XPS on adsorption at single crystal surfaces. A short general review of the quantitative aspects of XPS and UPS for analysis is given.     

纳米银/丝素复合材料的制备及其光谱性质研究

开发可靠、生态友好的纳米材料合成方法是当今纳米技术发展的一个重要方面,基于天然生物材料如丝素蛋白原位合成来制备纳米贵金属溶胶是一种具有极大发展潜力的方法之一。文章在室温下以丝素原位还原硝酸银制得了纳米银/丝素复合溶胶,通过紫外-可见光谱、原子力显微镜、荧光光谱和共振光散射对其制备过程和光谱性质进行了表征。实验表明丝素链中的酪氨酸残基对AgNO₃还原生成纳米银颗粒起了主要作用,制得的纳米银粒子均匀地包埋在丝素胶体中,具有很好的分散性和稳定性,可长期保存。丝素蛋白与纳米银复合后,荧光强度明显增加,证明了丝素蛋白与纳米银表面之间形成了较强的化学吸附,在银表面形成了一个相对稳定的络合物致密层。同时利用共振散射光谱分析实验进一步证实了纳米银粒子的形成。     

Chitosan magnetic microspheres for technological applications: Preparation and characterization

One of the major applications of chitosan and its many derivatives are based on its ability to bind strongly heavy and toxic metal ions. In this study chitosan magnetic microspheres have been synthesized. Acetic acid (1%w/v) solution was used as solvent for the chitosan polymer solution (2%w/v) where magnetite nanoparticles were suspended in order to obtain a stable ferrofluid. Glutaraldehyde was used as cross-linker. The magnetic characteristic of these materials allows an easy removal after use if is necessary. The morphological characterization of the microspheres shows that they can be produced in the size range 800–1100 μm.The adsorption of Cu(II) onto chitosan–magnetite nanoparticles was studied in batch system. A second-order kinetic model was used to fit the kinetic data, leading to an equilibrium adsorption capacity of 19 mg Cu/g chitosan.     

纳米增强激光诱导击穿光谱的苹果表面农药残留检测

水果表面的农药残留严重危害身体健康,而常规检测方法需要采样处理,耗时、费力。激光诱导击穿光谱技术具有多元素分析和原位测量的能力,在水果表面农药残留检测方面潜力巨大。但是较差的检测灵敏度,限制了此技术在水果表面微量有害元素检测方面的应用。提高激光诱导击穿光谱系统的检测能力是目前的研究热点领域,研究了纳米粒子表面增强技术对苹果表面残留的毒死蜱农药的激光诱导击穿光谱信号的增强效果。通过在被测样品表面涂抹币族金属纳米粒子,然后利用激光诱导击穿光谱激发样品表面,对诱导出的原子发射光谱信号进行测量,实验结果表明,苹果表面涂抹金属纳米粒子后毒死蜱农药中磷元素的特征峰有4倍的增强。此方法的应用对提高果蔬表面微量有害元素的检测能力具有重要意义。然后我们对币族金属纳米粒子的增强效果进行了优化。研究了金纳米粒子和银纳米粒子的增强能力,同时对纳米粒子的粒径的增强效果进行了比较,通过对20 nm的金纳米粒子、20 nm的银纳米粒子和80 nm的银纳米粒子的增强效果比较,发现80 nm的银纳米粒子对苹果表面毒死蜱农药光谱的增强效果最好。研究了信号采集延时时间对光谱信噪比的影响,确定了0.2 μs的延时时间可以获得较为理想的信噪比。在以上研究的基础上,采用最优的实验参数(80 nm银粒子增强、0.2 μs的延时时间),以毒死蜱中磷元素在213.62,214.91,253.56和255.33 nm处的特征峰峰强作为依据,对苹果表面残留的毒死蜱农药进行了定量化分析。分别采集了毒死蜱残留浓度分别为30,20,15,12,10和6 μg·cm-2的苹果表面的LIBS光谱,然后分别利用磷元素的四个特征峰峰强进行了定量化曲线拟合,结果发现LIBS对残留的毒死蜱具有很好的定量化预测能力,R2在0.89以上。根据定量化拟合曲线,探讨了纳米增强LIBS的检测限,计算得到,利用纳米增强LIBS技术测量苹果表面的毒死蜱农药最低可以做到1.61 μg·cm-2的检测限。研究证明了金属纳米粒显著提高了LIBS对苹果表面农药残留的检测灵敏度。     

Ultrasound-assisted synthesis of nanocomposites based on aromatic polyamide and modified ZnO nanoparticle for removal of toxic Cr(VI) from water

In this study, novel nanocomposites (NCs) of aromatic polyamide (PA) and surface modified ZnO nanoparticle with s-triazine heterocyclic ring was introduced for efficient removal of toxic hexavalent chromium (VI) from aqueous solution. The surface of ZnO nanoparticle was modified by s-triazine core silane coupling agent (ZnO-TSC) and PA/ZnO-TSC NCs with different amount of ZnO-TSC nanoparticles (0, 5, 10 and 15 wt%) were prepared by ultrasonic irradiation. The synthesized PA/ZnO-TSC NCs were characterized by FT-IR, XRD, FE-SEM, TEM and TGA methods. TEM images showed that ZnO nanoparticles were dispersed homogeneously in the polymer matrix. The adsorption experiments were carried out in batch mode to optimize various parameters like contact time, pH and concentration of metal ion that influence the adsorption rate. The maximum uptakes of Cr(VI) at pH 4.0 was 72%, 81%, 89% and 91% for pure PA, NC5%, NC10% and NC15%, respectively. The kinetic of adsorption was investigated and the pseudo second-order model is an appropriate model for interpretation of adsorption mechanism of Cr(VI) ions.     

Surface atomic distribution and water adsorption on Pt-Co alloys

Density functional theory is used to study surface atomic distributions on slabs of PtCo and Pt₃Co overall compositions, as well as water molecule adsorption on PtCo(1 1 1) and Pt-skin structures. Pt-rich surfaces are energetically favored under vacuum in the PtCo and Pt₃Co alloys. The adsorption trend on the studied structures agrees with the d-band model, with stronger adsorption at higher surface Co composition. The most stable adsorption site for a water molecule on PtCo surfaces is on top of Co atoms, with the dipole vector parallel to the surface. This water/surface interaction is as strong as that of water molecule on Pt(1 1 1), whereas bonding to Pt-skin monolayers is found much weaker than that on Pt(1 1 1). It is found that water interacts mainly through its 1b₁ and 3a₁ orbitals with d orbitals of the Pt(1 1 1), PtCo(1 1 1) and Pt-skin surface atoms. Compared to the sum of the electron densities of the separated systems, the electron density of the water/surface gets depleted along O-Pt on Pt-skin surfaces while it becomes richer in the O-Co bonding region of PtCo.     

基于密度泛函理论的CO2吸附微观机理比较研究

为探究吸附法捕获CO₂过程中的微观机理和吸附剂材料间的作用关系，基于密度泛函理论方法，综合比较了典型吸附剂包括煤基官能团、Fe、限域离子液体、Na₂CO₃、SrTiO₃与CO₂的吸附过程和差异性.根据不同计算策略，着重分析比较了吸附能、结构优化参数、吸附构型以及原子分布等参数.结果表明，化学吸附中CO₂分子与吸附面呈平行关系时通常吸附能最大；在一种材料的同类型官能团中，吸附能大小与氧原子的数量呈正相关关系；吸附过程中C-O键的伸长活化会生成一种重要的中间产物CO₂^-.提出在探寻CO₂吸附材料时可以在含氧原子较多的官能团、活性金属表面等方面进一步探究.最后对基于密度泛函理论的CO₂的吸附机理的进一步研究方向进行了展望.