Thin film processing using S-layer proteins: biotemplated assembly of colloidal gold etch masks for fabrication of silicon nanopillar arrays

We explored the bionanofabrication of silicon nanopillar structures using ordered gold nanoparticle arrays generated from microbial surface layer (S-layer) protein templates. The S-layer template used for these thin film processing experiments was isolated from the Gram-positive bacterium Deinococcus radiodurans. In this preliminary work, S-layers preimmobilized onto chemically modified silicon substrates were initially used to template the fabrication of a nanolithographic hard mask pattern comprised of a hexagonally ordered array of 5-nm gold nanoparticles (lattice constant = 18 nm). Significantly, the use of the biotemplated gold nanoparticle mask patterns in an inductively coupled plasma (ICP) etching process successfully yielded silicon nanopillar structures. However, it was found that the resultant nanopillars (8–13 nm wide at the tip, 15–20 nm wide at half-height, 20–30 nm wide at the base, and 60–90 nm tall) appeared to lack any significant degree of translational ordering. The results suggest that further studies are needed in order to elucidate the optimal plasma processing parameters that will lead to the generation of long-range ordered arrays of silicon-based nanostructures using S-layer protein templates.     

Characterization and use of crystalline bacterial cell surface layers

Crystalline bacterial cell surface layers (S-layers) are one of the most common outermost cell envelope components of prokaryotic organisms (archaea and bacteria). S-layers are monomolecular arrays composed of a single protein or glycoprotein species and represent the simplest biological membranes developed during evolution. S-layers as the most abundant of prokaryotic cellular proteins are appealing model systems for studying the structure, synthesis, genetics, assembly and function of proteinaceous supramolecular structures. The wealth of information existing on the general principle of S-layers have revealed a broad application potential. The most relevant features exploited in applied S-layer research are: (i) pores passing through S-layers show identical size and morphology and are in the range of ultrafiltration membranes; (ii) functional groups on the surface and in the pores are aligned in well-defined positions and orientations and accessible for chemical modifications and binding functional molecules in very precise fashion; (iii) isolated S-layer subunits from a variety of organisms are capable of recrystallizing as closed monolayers onto solid supports (e.g., metals, polymers, silicon wafers) at the air–water interface, on lipid films or onto the surface of liposomes; (iv) functional domains can be incorporated in S-layer proteins by genetic engineering. Thus, S-layer technologies particularly provide new approaches for biotechnology, biomimetics, molecular nanotechnology, nanopatterning of surfaces and formation of ordered arrays of metal clusters or nanoparticles as required for nanoelectronics.     

Formation of a gold superlattice on an S-layer with square lattice symmetry

This work describes a new strategy in which a crystalline bacterial cell surface layer (S-layer) composed of a monolayer of a single protein species was used as periodic nanometric template in the nucleation of ordered arrays of gold nanoparticles. A square superlattice of uniform 4 to 5 nm sized gold particles with 12.8 nm repeat distance was fabricated by exposing the S-layer lattice of Bacillus sphaericus CCM2177, in which thiol groups had been introduced before, to a tetrachloroauric(III) acid solution. Transmission electron microscopical studies showed that the gold nanoparticles were formed in the pore region during electron irradiation of an initially grainy gold coating covering the whole S-layer lattice. The shape of the gold particles resembled the morphology of the pore region of the square S-layer lattice. By electron diffraction and energy dispersive X-ray analysis the crystallites were identified as gold (Au(0)). Electron diffraction patterns revealed that the gold nanoparticles were crystalline but in the long range order not crystallographically aligned. It is postulated that S-layers will allow the fabrication of a wide range of inorganic nanocrystal superlattice arrays.     

Controlled Assembly of Block Copolymer Coated Nanoparticles in 2D Arrays

The defined assembly of nanoparticles (NPs) in polymer matrices is an important prerequisite for next‐generation functional materials. A promising approach to control NP positions in polymer matrices at the nanometer scale is the use of block copolymers. It allows the selective deposition of NPs in nanodomains, but the final defined and ordered positioning of the NPs within the domains has not been possible. This can now be achieved by coating NPs with block copolymers. The self‐assembly of block copolymer‐coated NPs directly leads to ordered microdomains containing ordered NP arrays with exactly one NP per unit cell. By variation of the grafting density, the inter‐nanoparticle distance can be controlled from direct NP surface contact to surface separations of several nanometers, determined by the thickness of the polymer shell. The method can be applied to a wide variety of block copolymers and NPs and is thus suitable for a broad range of applications.     

Formation and grain analysis of spin-cast magnetic nanoparticle monolayers

Ligand-stabilized magnetic nanoparticles (NPs) with diameters of 4-7 nm were spin-cast into monolayers on electron-transparent silicon nitride (SiN) substrates. SiN membranes facilitate detailed high-resolution characterization of the spin-cast monolayers by transmission electron microscopy (TEM) and approximate spin-casting onto wafers. Suspending the NPs in hexanes and pretreating the substrate with ultraviolet light and ozone (UVO) gives the best results. Computer-aided analysis of the arrays elucidates their grain structures, including identification of the grain boundaries and defects and measurements of the grain orientations and translational correlation lengths. Narrow NP size distributions result in close-packed arrays with minimal defects and large grains containing thousands of NPs. Edge dislocations, interstitials, vacancies, and overlapping NPs were observed. Deviations from close packing occur as the normalized standard deviation of the sample's size distribution increases above approximately 11%. Polydisperse size distributions and deviations from spherical NP shapes frustrate assembly and prevent ordered packing.     

Enhancement of ethanol electrooxidation on plasmonic Au/TiO2 nanotube arrays

Novel electrocatalysts Au/TiO₂ nanotube arrays (Au/TiO₂NTs) were prepared by loading low-content(1.9 at.%) of Au nanoparticles (AuNPs) onto highly ordered TiO₂ nanotube arrays (TiO₂NTs). Ethanol electrooxidation indicates that visible-light (λ > 400 nm) irradiation can significantly enhance the activity as well as resistpoisoning of Au/TiO₂NTs electrocatalysts that are activated by plasmon resonance. Au/TiO₂NTs catalysts calcinated at 300 °C display the highest performance due to the strong synergistic interactions between TiO₂ and Au NPs. The combination of visible-light irradiation with a controllable potential offers a new strategyfor enhancing the performance of anodes in direct ethanol fuel cell (DEFC).     

Transformation of a close-packed Au nanoparticle/polymer monolayer into a large area array of oriented Au nanowires via E-beam promoted uniaxial deformation and room temperature sintering

Transformation of 2D Au nanoparticle (NP) arrays into large scale, ordered, and oriented nanorod/nanowire arrays supported on a transferrable polymer film has been accomplished. E-beam irradiation followed by room temperature aging of a suspended Au NP/polymethylmethacrylate (PMMA) polymer close packed monolayer results in one-dimensional nanoparticle aggregation, reorientation, and sintering into a high density array of oriented Au nanowires with coherent single-crystal-like interfaces. Molecular dynamics simulations of alkane-thiol capped Au NPs, interacting through the Vincent potential and undergoing 2D Poisson compression, account semiquantitatively for the qualitative features of the transformation. This fabrication approach should be extendable to directing 1D aggregation of highly anisotropic nanostructures in arbitrary NP systems.     

氮掺杂有序介孔碳负载超小尺寸铂纳米颗粒催化硝基苯类化合物选择加氢

氮掺杂有序介孔碳材料不仅具有高的比表面积、大的孔容和均一可调的孔径等优点,其骨架中丰富的氮原子还可以对材料的物理化学性质、配位金属电荷密度等进行调控,是一类优异的催化剂载体.本文利用软模板(嵌段共聚物F127为模板),以间氨基苯酚为碳源和氮前体,制备出较高含氮量(9.58 wt%)和比表面积(417 m2/g),以及规则孔径分布的介孔碳材料.结果表明,制备的材料具有三维立方相结构.以该碳材料作为载体,使用传统浸渍氢气还原的策略负载纳米铂颗粒.发现氮掺杂的载体能够有效控制金属纳米颗粒的尺寸,可实现超小尺寸Pt纳米颗粒的有效负载(1.0±0.5 nm),且纳米颗粒均匀分布于介孔碳材料的孔道中.相比而言,使用相同负载方法的情况下,以不掺氮的介孔碳材料为载体,纳米粒子的尺寸较难控制(4.4±1.7 nm)且会发生孔道外颗粒聚集的情况.研究表明,骨架中的氮原子与金属间弱的相互作用对纳米粒子有稳定作用.这对制备超小尺寸的金属纳米粒子催化剂具有一定的指导意义.此外,由于纳米粒子的尺寸将大大影响催化剂活性中心的暴露程度,进而影响催化剂活性.因此,我们以硝基苯类化合物的氢化反应来评价该催化剂的催化性能.在室温和1 MPa H2的温和条件下,氮掺杂的介孔碳负载催化剂表现出了优异的催化性能.反应0.5 h,对氯硝基苯可完全转化,且选择性高达99%.相比而言,商业化的Pt/C催化剂上反应的转化率和选择性分别为89%和90%.其它传统催化剂的比较,如Pt/SiO2,Pt/TiO2,同样表明,氮掺杂介孔碳负载的催化剂具有更优异的催化性能.在相同反应条件下,Pt/SiO2催化剂只能得到46%的转化率和93%的选择性,而Pt/TiO2催化剂虽然能够实现完全转化,但选择性也仅为91%.由此可见,氮掺杂的负载催化剂可大大提高反应活性和选择性,能有效抑制脱氯现象的发生.这种高的催化性能可能与催化剂的介孔结构、氮功能化载体以及超小尺寸的Pt纳米粒子的稳定有关.由于氮原子和介孔孔道的限域作用,氮掺杂介孔碳负载的催化剂也具有良好的催化稳定性,循环使用10次后,催化活性和选择性几乎没有下降.结果表明,循环使用后的催化剂金属粒子尺寸变化不大,进一步表明氮掺杂介孔碳载体对金属纳米颗粒的稳定作用.     

Nanoparticle ensemble electrodes: fabrication by short-pulse sputtering and characterization by scanning probe microscopy and voltammetry

Nanoparticle ensembles (NPEs) are useful platforms to study the electrocatalytic properties of nano-sized materials. A fabrication method that guarantees a good control over the morphological features, as well as a reliable characterization, are required for a proper analysis of electrochemical data measured on these electrodes. This work describes a simple, fast, and clean procedure for the fabrication of random arrays of Pt nanoparticles (NPs) supported on flat electrodes by sputtering of metal targets for short times. Besides, a strategy for morphological characterization of the ensembles based on a combination of scanning tunneling microscopy (STM) and voltammetric information is reported. The method permits to attain good control on the size and coverage of NPs in the ensemble through the sputtering parameters. Pt NPs sputtered on highly ordered pyrolytic graphite (HOPG) grow bidimensionally with heights in the range 0.8–1.2 nm, while the lateral diameters of NPs and the surface coverage are adjusted in the range 2–15 nm by controlling both the sputtering current and the sputtering time. The stability and electrochemical behavior for proton reduction under mixed control in acid media were evaluated on HOPG-supported Pt ensembles fabricated by the described method.     

Ordered Mesoporous Silica Incorporating Platinum Nanoparticles as Electrode Material for Paracetamol Detection

High ordered mesoporous materials (SBA-15) modified with Al and/or B and Pt nanoparticles (Pt NPs) were used for preparing modified graphite paste electrodes (Pt/M−SBA-15-GPE, where M=Al−, B− or Al−B−) and applied for paracetamol (PA) detection. The electrodes were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Square wave voltammetry (SWV) technique was used to obtain the analytical parameters for PA detection. The acquired values of electrochemical and analytical parameters recommend the mesoporous compound containing Pt NPs to be used as composite electrode material for PA detection in real samples.     

纳米粒子的精准组装

纳米材料由于其独特的光、电、磁、力学等性质,成为了构建功能材料与器件的理想基元。实现纳米粒子的精确组装,是探究粒子之间的耦合聚集性质和制备宏观功能器件的基础。但是由于纳米粒子的小尺寸以及在溶液中运动的随机性与复杂性,精准控制纳米粒子组装体的形貌以及在空间中的相对位置仍存在巨大挑战。为了将纳米粒子组装成理想的有序结构,许多控制粒子组装的策略与方法得到发展。本文首先概述了纳米粒子自组装的控制方法与典型形貌,着重分析了影响粒子精准排布的因素与控制方法,并对纳米粒子及其组装体的光学性质与器件应用的最新研究进展进行了讨论,最后对目前纳米粒子精准组装所面临的挑战以及未来发展的方向进行了展望。     

具有优异甲醇耐受性的Rh掺杂PdCu有序金属间化合物纳米粒子增强氧还原电催化

Direct methanol fuel cells (DMFCs), as one of the important energy conversion devices, are of great interest in the fields of energy, catalysis and materials. However, the application of DMFCs is presently challenged because of the limited activity and durability of cathode catalysts as well as the poisoning issues caused by methanol permeation to the cathode during operation. Herein, we report a new class of Rh-doped PdCu nanoparticles (NPs) with ordered intermetallic structure for enhancing the activity and durability of the cathode for oxygen reduction reaction (ORR) and achieving superior methanol tolerance. The disordered Rh-doped PdCu NPs can be prepared via a simple wet-chemical method, followed by annealing to convert it to ordered phases. The results of transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), power X-ray diffraction (PXRD) analysis and high resolution TEM (HRTEM) successfully demonstrate the formation of near-spherical NPs with an average size of 6.5 ± 0.5 nm and the conversion of the phase structure. The complete phase transition temperatures of Rh-doped PdCu NPs and PdCu are 500 and 400 ℃, respectively. The molar ratio of Rh/Pd/Cu in the as-synthesized Rh-doped PdCu NPs is 5/48/47. Benefitting from Rh doping and the presence of the ordered intermetallic structure, the Rh-doped PdCu intermetallic electrocatalyst achieves the maximum ORR mass activity of 0.96 A·mg^-1 at 0.9 V versus reversible hydrogen electrode (RHE) under alkaline conditions—a 7.4-fold enhancement compared to the commercial Pt/C catalyst. For different electrocatalysts, the ORR activities follow the sequence, ordered Rh-doped PdCu intermetallics > ordered PdCu intermetallics > disordered Rh-doped PdCu NPs > disordered PdCu NPs > commercial Pt/C catalyst. In addition, the distinct structure endows the Rh-doped PdCu intermetallics with highly stable ORR durability with unaltered half-wave potential (E_1/2) and mass activity after continuous 20000 cycles, which are higher than those of other electrocatalysts. Furthermore, the E_1/2 of the Rh-doped PdCu intermetallics decreases by only 5 mV after adding 0.5 mol·L^-1 methanol to the electrolyte, while the commercial Pt/C catalyst negatively shifts by 235 mV and a distinct oxidation peak can be observed. The results indicate that the ORR activity of the Rh-doped PdCu intermetallic electrocatalyst can be well maintained even in the presence of poisoning environment. Our results have demonstrated that Rh-doped PdCu NPs with ordered intermetallic structures is a potential electrocatalyst toward the next-generation high-performance DMFCs.     

Controlled fabrication of nanopillar arrays as active substrates for surface-enhanced Raman spectroscopy

Highly ordered gold nanopillar arrays were fabricated using anodized aluminum oxide (AAO) templates. Nanopillars with a dimension of 110 +/- 15 nm in vertical height and 75 +/- 10 nm in base diameter were formed with a density of 150 microm(-2). The ordered nanopillar arrays give reproducible surface-enhanced Raman scattering (SERS) at a detection limit of 10(-8) M using thionine as probing molecules. The enhancement by the Au nanopillar arrays was comparable with or better than that of dispersed gold nanoparticle SERS substrates. This work demonstrates a new technique for producing highly ordered and reproducible SERS substrates potentially applicable for chemical and biological assay.     

Oriented Gold Nanorod Arrays: Self‐Assembly and Optoelectronic Applications

Self‐assembly of anisotropic plasmonic nanomaterials into ordered superstructures has become popular in nanoscience because of their unique anisotropic optical and electronic properties. Gold nanorods (GNRs) are a well‐defined functional building block for fabrication of these superstructures. They possess important anisotropic plasmonic characteristics that result from strong local electric field and are responsive to visible and near‐IR light. There are recent examples of assembling the GNRs into ordered arrays or superstructures through processes such as solvent evaporation and interfacial assembly. In this Minireview, recent progress in the development of the self‐assembled GNR arrays is described, with focus on the formation of oriented GNR arrays on substrates. Key driving forces are discussed, and different strategies and self‐assembly processes of forming oriented GNR arrays are presented. The applications of the oriented GNR arrays in optoelectronic devices are also overviewed, especially surface enhanced Raman scattering (SERS).     

Effect of TiO2 nanoparticles on self-assembly behaviors and optical and photovoltaic properties of the P3HT-b-P2VP block copolymer

An ordered nanostructure can be created from the hybrid materials of self-assembly poly(3-hexyl thiophene-b-2-vinyl pyridine) and nicotinic acid-modified titanium dioxide nanoparticles (P3HT-b-P2VP/TiO(2)). TEM and XRD analyses reveal that the TiO(2) nanoparticles (NPs) are preferentially confined in the P2VP domain of P3HT-b-P2VP whereas TiO(2) NPs interact with either pure P3HT or a blend of P3HT and P2VP to produce microsized phase segregation. The morphologies of lamellar and cylindrical structures are disturbed when the loading of TiO(2) NPs is 40 wt % or higher. Cylindrical P3HT-b-P2VP/TiO(2) exhibits a small blue shift in absorption and photoluminescence spectra with increasing TiO(2) loading as compared to P3HT/TiO(2). The NPs cause a slightly misaligned P3HT domain in the copolymer. Furthermore, the PL quenching of P3HT-b-P2VP/TiO(2) becomes very large as a result of efficient charge separation in the ordered nanodomain at 16 nm. Solar cells fabricated from self-assembly P3HT-b-P2VP/TiO(2) hybrid materials exhibit a >30 fold improvement in power conversion efficiency as compared to the corresponding 0.3P3HT-0.7P2VP/TiO(2) polymer blend hybrid. This study paves the way for the further development of high-efficiency polymer-inorganic nanoparticle hybrid solar cells using a self-assembled block copolymer.     

SERS,AFM and Electrochemical Characterization of Metal Nanorod and Nanowire Arrays

Metal nanowires (nanorods) have novel properties and potential applications in a wide field^[1]. Many two-dimensional nanowire arrays of semiconductors and metals with different diameter and length have been made using template synthesis method^[2]. The nanorod arrays of various metals (e.g., Cu, Ag,Au, Ni and Co) with different diameters from about 15 nm to 130 nm were fabricated by electrodeposition of the metals into the highly ordered nanochannel arrays in alumina film followed by partial removal of the film in phosphoric acid or sodium hydroxide. In the present work, surface-enhanced Raman spectroscopy (SERS), AFM and electrochemical methods have been used to characterize the metal nanorod (nanowire) arrays. Tapping mode AFM and SERS were performed on Nanoscope Ⅲa (Digital Instruments) and on confocal Raman microscopy (LabRam I,Dilor) respectively.     

三维有序大孔二氧化钛表面超细钯纳米颗粒的构筑及其增强柴油炭烟催化燃烧性能（英文）

柴油机排放颗粒物(主要成分是炭烟)是城市大气PM2.5中一次颗粒物的主要来源和二次颗粒物形成的重要组分,严重危害大气环境和人类健康.利用颗粒物捕集器与催化剂相结合的连续过滤再生技术是满足柴油车国VI炭烟颗粒物排放标准的最有效技术,目前该技术所面临的挑战是研发在排气温度的柴油炭烟颗粒物催化氧化催化剂.柴油炭烟催化燃烧反应的本质是典型的气(氧气)-固(炭烟颗粒)-固(催化剂)三相深度氧化反应,因此我们研究组提出了高活性柴油炭烟燃烧催化剂设计应该遵循优化固-固接触与强化活化分子氧能力二者相结合的研究思路.为满足此设计思路的要求,本课题组前期采用孔径大于200 nm的三维有序大孔(3DOM)结构氧化物作为载体,利用大孔效应来实现PM在催化剂内部的有效扩散,从而提高催化剂与PM的接触效率.采用具有强活化分子氧能力的负载型贵金属(Au,Pt)纳米颗粒或贵金属-氧化物复合纳米颗粒作为活性位来提高催化剂对分子氧的活化能力,进而设计了多个系列高活性催化剂,并形成了担载贵金属纳米颗粒的可控制备方法与装置.然而,Au和Pt昂贵的价格限制了其广泛应用.价格相对便宜的Pd具有与Pt相似的催化性能,是其良好替代品.但是,目前关于3DOM氧化物表面负载型Pd纳米颗粒结构和尺寸与柴油炭烟催化燃烧性能之间的相关研究仍然较少.基于此,本文采用气泡辅助膜还原法制备了3DOM二氧化钛(TiO_2)担载超细Pd纳米颗粒催化剂.利用XRD,Raman,BET,SEM,TEM,ICP,XPS和H2-TPR等技术手段对催化剂进行表征,并以模拟柴油炭烟为研究对象,利用程序升温氧化反应(TPO)对催化剂的活性进行评价,深入探讨了催化剂的制备、结构及物化性质与炭烟催化燃烧反应性能之间的关系.XRD和Raman结果表明,TiO_2载体由锐钛矿(主)和金红石(次)两种物相组成.SEM照片显示,所制催化剂为规整的有序大孔结构,球形孔互相贯通,孔径均一,大孔腔平均尺寸为280 nm,孔窗尺寸为109 nm,这种三维有序大孔TiO_2的结构能够增强炭烟颗粒与催化剂之间的接触效率.TEM表征显示,平均粒径为1.1 nm的超细半球型Pd纳米颗粒高度分散于TiO_2载体的内壁上,两者间的优化界面面积有利于增加活化O2的活性位密度,这些活性位源于Pd与TiO_2间强相互作用.H2-TPR和XPS表征印证了上述观点,具有1.1 nm超细Pd颗粒的Pd/3DOM-TiO_2催化剂表现出强的低温氧化还原特性和丰富的表面吸附氧物种.在TPO测试中,相对于担载5.0 nm Pd颗粒的催化剂,具有1.1 nm尺寸超细Pd颗粒的Pd/3DOM-TiO_2催化剂展示了高的催化炭烟燃烧活性,T10,T50和T90分别为295,370和415 oC,且在5次TPO测试过程中表现出良好的催化和结构稳定性.这种具有3DOM结构和超细Pd纳米颗粒的纳米催化剂能够有效降低Pd的使用量,在催化炭烟燃烧的实际应用中大有潜力.     

Prolonged stochastic single ion channel recordings in S-layer protein stabilized lipid bilayer membranes

S-layer proteins are commonly found in bacteria and archaea as two-dimensional monomolecular crystalline arrays as the outermost cell membrane component. These proteins have the unique property that following disruption by chemical agents, monomers of the protein can re-assemble to their original lattice structure. This unique property makes S-layers interesting for utilization in bio-nanotechnological applications. Here, we show that the addition of S-layer proteins to bilayer lipid membranes increases the lifetime and the stability of the bilayer. M2delta ion channels were functionally incorporated into these S-layer stabilized membranes and we were able to record their activity for up to 20 h. Transmission electron microscopy (TEM) was used to visualize the 2D crystalline pattern of the S-layer and the M2delta ion channel characteristics in bilayer lipid membrane's were compared in the presence and absence of S-layers.     

Embedded high density metal nanoparticles with extraordinary thermal stability derived from guest-host mediated layered double hydroxides

A chemical precursor mediated process was used to form catalyst nanoparticles (NPs) with an extremely high density (10(14) to 10(16) m(-2)), controllable size distribution (3-20 nm), and good thermal stability at high temperature (900 °C). This used metal cations deposited in layered double hydroxides (LDHs) to give metal catalyst NPs by reduction. The key was that the LDHs had their intercalated anions selected and exchanged by guest-host chemistry to prevent sintering of the metal NPs, and there was minimal sintering even at 900 °C. Metal NPs on MoO(4)(2-) intercalated Fe/Mg/Al LDH flakes were successfully used as the catalyst for the double helix growth of single-walled carbon nanotube arrays. The process provides a general method to fabricate thermally stable metal NPs catalysts with the desired size and density for catalysis and materials science.