Improved metal cluster deposition on a genetically engineered tobacco mosaic virus template

Improved depositions of various metal clusters onto a biomolecular template were achieved using a genetically engineered tobacco mosaic virus (TMV). Wild-type TMV was genetically altered to display multiple solid metal binding sites through the insertion of two cysteine residues within the amino-terminus of the virus coat protein. Gold, silver, and palladium clusters synthesized through in situ chemical reductions could be readily deposited onto the genetically modified template via the exposed cysteine-derived thiol groups. Metal cluster coatings on the cysteine-modified template were more densely deposited and stable than similar coatings on the unmodified wild-type template. Combined, these results confirm that the introduction of cysteine residues onto the outer surface of the TMV coat protein enhances the usefulness of this virus as a biotemplate for the deposition of metal clusters.     

Modification of the structural and electrical properties of graphene layers by Pt adsorbates

The properties of graphene are strongly affected by metal adsorbates and clusters on graphene. Here, we study the effect of a thin layer of platinum (Pt) metal on exfoliated single, bi- and trilayer graphene and on chemical vapor deposition-grown single-layer graphene by using Raman spectroscopy and transport measurements. The Raman spectra and transport measurements show that Pt affects the structure as well as the electronic properties of graphene. The shift of peak frequencies, intensities and widths of the Raman bands were analyzed after the deposition of Pt with different thicknesses (1, 3, 5 nm) on the graphene. The shifts in the G and 2D peak positions of the Raman spectra indicate the n-type doping effect by the Pt metal. The doping effect was also confirmed by gate-voltage dependent resistivity measurements. The doping effect by the Pt metal is stable under ambient conditions, and the doping intensity increases with the increasing Pt deposition without inducing a severe degradation of the charge carrier mobility.     

Catalytic properties of Pt cluster-decorated CeO2 nanostructures

Uniform clusters of Pt have been deposited on the surface of capping-agent-free CeO₂ nanooctahedra and nanorods using electron beam (e-beam) evaporation. The coverage of the Pt nanocluster layer can be controlled by adjusting the e-beam evaporation time. The resulting e-beam evaporated Pt nanocluster layers on the CeO₂ surfaces have a clean surface and clean interface between Pt and CeO₂. Different growth behaviors of Pt on the two types of CeO₂ nanocrystals were observed, with epitaxial growth of Pt on CeO₂ nanooctahedra and random growth of Pt on CeO₂ nanorods. The structures of the Pt clusters on the two different types of CeO₂ nanocrystals have been studied and compared by using them as catalysts for model reactions. The results of hydrogenation reactions clearly showed the clean and similar chemical surface of the Pt clusters in both catalysts. The support-dependent activity of these catalysts was demonstrated by CO oxidation. The Pt/CeO₂ nanorods showed much higher activity compared with Pt/CeO₂ nanooctahedra because of the higher concentration of oxygen vacancies in the CeO₂ nanorods. The structure-dependent selectivity of dehydrogenation reactions indicates that the structures of the Pt on CeO₂ nanorods and nanooctahedra are different. Thes differences arise because the metal deposition behaviors are modulated by the strong metal-metal oxide interactions.     

Materials specificity and directed assembly of a gold-binding peptide

Adsorption studies of a genetically engineered gold-binding peptide, GBP1, were carried out using a quartz-crystal microbalance (QCM) to quantify its molecular affinity to noble metals. The peptide showed higher adsorption onto and lower desorption from a gold surface compared to a platinum substrate. The material specificity, that is, the preferential adsorption, of GBP1 was also demonstrated using gold and platinum micropatterned on a silicon wafer containing native oxide. The biotinylated three-repeat units of GBP1 were preferentially adsorbed onto gold regions delineated using streptavidin-conjugated quantum dots (SAQDs). These experiments not only demonstrate that an inorganic-binding peptide could preferentially adsorb onto a metal (Au) rather than an oxide (SiO2) but also onto one noble metal (Au) over another (Pt). This result shows the utility of an engineered peptide as a molecular erector in the directed immobilization of a nanoscale hybrid entity (SAQDs) over selected regions (Au) on a fairly complex substrate (Au and Pt micropatterned regions on silica). The selective and controlled adsorption of inorganic-binding peptides may have significant implications in nano- and nanobiotechnology, where they could be genetically tailored for specific use in the development of self-assembled molecular systems.     

Biomimetic synthesis of a H2 catalyst using a protein cage architecture

A biomimetic approach has been used to develop an artificial hydrogenase that catalyses the efficient reduction of protons producing hydrogen gas. Analogous to the unique biological metal clusters found in hydrogenase enzymes, the engineered active sites are small, well-defined Pt clusters deposited on the interior of a heat shock protein cage architecture with stoichiometries of 150 to 1000 Pt per protein cage. The proton reduction reaction is driven by visible light through a coupled reaction with Ru(bpy)3(2+) and methyl viologen as an electron-transfer mediator. Hydrogen production rates are comparable to those of hydrogenase on a per protein basis and exceed production rates of other reported Pt-based catalysts. These results demonstrate the utility of a biomimetic approach toward addressing the needs of hydrogen production.     

Structure determination of chitosan-stabilized Pt and Pd based bimetallic nanoparticles by X-ray photoelectron spectroscopy and transmission electron microscopy

Chitosan (CTS)-stabilized bimetallic nanoparticles were prepared at room temperature (rt.) in aqueous solution. Palladium (Pd) and platinum (Pt) were selected as the first metals while iron (Fe) and nickel (Ni) functioned as the second metals. In order to obtain the noble metal core-transition metal shell structures, bimetallic nanoparticles were prepared in a two-step process: the preparation of mono noble metallic (Pd or Pt) nanoparticles and the deposition of transition metals (Fe or Ni) on the surface of the monometallic nanoparticles. The structures of the nanoparticles were studied using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The XPS results show that Pd and Pt exist mainly in zero valences. The presence of Fe and Ni in the bimetallic nanoparticles affects the binding energy of Pd and Pt. Moreover, the studies of O 1s spectra indicate the presence of Fe or Ni shells. The analyses of TEM micrographs give the particle size and size distributions while the high-resolution TEM (HRTEM) micrographs show the existence of noble metal core lattices. The results confirm the formation of noble metal core-transition metal shell structures.     

Nano-scaled Pt/Ag/Ni/Au contacts on p-type GaN for low contact resistance and high reflectivity

We synthesized the vertical-structured LED (VLED) using nano-scaled Pt between p-type GaN and Ag-based reflector. The metallization scheme on p-type GaN for high reflectance and low was the nano-scaled Pt/Ag/Ni/Au. Nano-scaled Pt (5 A) on Ag/Ni/Au exhibited reasonably high reflectance of 86.2% at the wavelength of 460 nm due to high transmittance of light through nano-scaled Pt (5 A) onto Ag layer. Ohmic behavior of contact metal, Pt/Ag/Ni/Au, to p-type GaN was achieved using surface treatments of p-type GaN prior to the deposition of contact metals and the specific contact resistance was observed with decreasing Pt thickness of 5 A, resulting in 1.5 x 10(-4) ohms cm2. Forward voltages of Pt (5 A)/Ag/Ni contact to p-type GaN showed 4.19 V with the current injection of 350 mA. Output voltages with various thickness of Pt showed the highest value at the smallest thickness of Pt due to its high transmittance of light onto Ag, leading to high reflectance. Our results propose that nano-scaled Pt/Ag/Ni could act as a promising contact metal to p-type GaN for improving the performance of VLEDs.     

Reversible light-controlled conductance switching of azobenzene-based metal/polymer nanocomposites

We present a new concept of light-controlled conductance switching based on metal/polymer nanocomposites with dissolved chromophores that do not have intrinsic current switching ability. Photoswitchable metal/PMMA nanocomposites were prepared by physical vapor deposition of Au and Pt clusters, respectively, onto spin-coated thin poly(methylmethacrylate) films doped with azo-dye molecules. High dye concentrations were achieved by functionalizing the azo groups with tails and branches, thus enhancing solubility. The composites show completely reversible optical switching of the absorption bands upon alternating irradiation with UV and blue light. We also demonstrate reversible light-controlled conductance switching. This is attributed to changes in the metal cluster separation upon isomerization based on model experiments where analogous conductance changes were induced by swelling of the composite films in organic vapors and by tensile stress.     

Structural and electronic studies of supported Pt and Au epitaxial clusters on tungsten oxide surface

In the present paper we investigated the growth and electronic properties of Pt or Au clusters and formation of Pt-Au bimetallic clusters prepared “in-situ” on tungsten oxide surface by physical deposition under vacuum. The epitaxial tungsten oxide thin films were prepared by oxidation of W(110) single-crystal surface using a RF oxygen plasma source followed by thermal annealing. The chemical state of the system, the interaction between deposit and substrate and formation of Pt-Al alloy were investigated by photoelectron spectroscopy excited by synchrotron radiation (SRPES) and K;α X-ray source (XPS). We found that in contrary to Au clusters the Pt ones strongly interacts with the substrate. Deposition of both Pt and Au on the surface at the substrate temperature of 300 °C gave rise to the formation of bimetallic core-shell clusters. The detail structure of the bimetallic system depends on the order of deposited metals. These findings can explain some properties of Pt/WOx and Au/WOx as well as Pt-Au/WOx bimetallic catalysts and gas sensors.     

Nanocrystalline metal/carbon composites produced by supersonic cluster beam deposition

In this work we show that supersonic cluster beam deposition is a viable method for the synthesis of nanocrystalline metal/carbon composites. By assembling carbon and metallic clusters seeded in a supersonic beam, we have grown films consisting of metal nanoparticles embedded in a nano-structured carbon matrix. Samples containing 3d transition metals (Ti, Ni) and noble metals (Au, Pd, Pt) with different metal abundances, particle size and dilution have been characterized by transmission electron microscopy. The influence of different metals on the structure of the carbon matrix has been investigated. Spatially resolved ultraviolet photoemission electron spectroscopy showed substantial surface oxidation of 3d transition metal clusters. On a micrometric scale, the spatial distribution of the metallic nanoparticles appeared to be homogeneous.     

Nanofence Stabilized Platinum Nanoparticles Catalyst via Facet‐Selective Atomic Layer Deposition

A facet‐selective atomic layer deposition method is developed to fabricate oxide nanofence structure to stabilize Pt nanoparticles. CeO_x is selectively deposited on Pt nanoparticles' (111) facets and naturally exposes Pt (100) facets. The facet selectivity is realized through different binding energies of Ce precursor fragments chemisorbed on Pt (111) and Pt (100), which is supported by in situ mass gain experiment and corroborated by density functional theory simulations. Such nanofence structure not only has exposed Pt active facets for carbon monoxide oxidation but also forms ceria–metal interfaces that are beneficial for activity enhancement. The composite catalysts show excellent sintering resistance up to 700 °C calcination. CeO_x anchors Pt nanoparticles with a strong metal oxide interaction, and nanofence structure around Pt nanoparticles provides physical blocking that suppresses particles migration. The study reveals that forming oxide nanofence structure to encapsulate precious metal nanoparticles is an effective way to simultaneously enhance catalytic activity and thermal stability.     

Stable Rhodium (IV) Oxide for Alkaline Hydrogen Evolution Reaction

Water electrolysis in alkaline electrolyte is an attractive way toward clean hydrogen energy via the hydrogen evolution reaction (HER), whereas the sluggish water dissociation impedes the following hydrogen evolution. Noble metal oxides possess promising capability for catalyzing water dissociation and hydrogen evolution; however, they are never utilized for the HER due to the instability under the reductive potential. Here it is shown that compressive strain can stabilize RhO₂ clusters and promote their catalytic activity. To this end, a strawberry-like structure with RhO₂ clusters embedded in the surface layer of Rh nanoparticles is engineered, in which the incompatibility between the oxide cluster and the metal substrate causes intensive compressive strain. As such, RhO₂ clusters remain stable at a reduction potential up to −0.3 V versus reversible hydrogen electrode and present an alkaline HER activity superior to commercial Pt/C.     

Four-probe electrical characterization of Pt-coated TMV-based nanostructures

The electrical transport and structural properties of tobacco mosaic virus (TMV)-based nanostructures have been studied. Electroless deposition was used to coat the TMV outer surface with a 13?nm thick homogeneous Pt layer. SEM, TEM and electrical characterization of the obtained nanostructures has been performed. Using four independently controlled scanning tunnelling microscope tips we were able to perform four-point probe resistance measurements on linear virus assemblies and demonstrate the continuous nature of the metallic coating. The measured resistivity values of the virial nanowires exceeded the bulk value by 10-100 times; notwithstanding this the coated structure allowed high current densities, of the order of 10(5)-10(8)?A?cm(-2). The four-probe technique proved to be useful for analysing the electrical properties of bio-inorganic nanowires.     

An Atomistic View of Platinum Cluster Growth on Pristine and Defective Graphene Supports (Small 10/2023)

Density functional theory (DFT) is used to systematically investigate the electronic structure of platinum clusters grown on different graphene substrates. Platinum clusters with 1 to 10 atoms and graphene vacancy defect supports with 0 to 5 missing C atoms are investigated. Calculations show that Pt clusters bind more strongly as the vacancy size increases. For a given defect size, increasing the cluster size leads to more endothermic energy of formation, suggesting a templating effect that limits cluster growth. The opposite trend is observed for defect-free graphene where the formation energy becomes more exothermic with increasing cluster size. Calculations show that oxidation of the defect weakens binding of the Pt cluster, hence it is suggested that oxygen-free graphene supports are critical for successful attachment of Pt to carbon-based substrates. However, once the combined material is formed, oxygen adsorption is more favorable on the cluster than on the support, indicating resistance to oxidative support degradation. Finally, while highly-symmetric defects are found to encourage formation of symmetric Pt clusters, calculations also reveal that cluster stability in this size range mostly depends on the number of and ratio between Pt C, Pt Pt, and Pt O bonds; the actual cluster geometry seems secondary.     

Confining Sub-Nanometer Pt Clusters in Hollow Mesoporous Carbon Spheres for Boosting Hydrogen Evolution Activity

Electrochemical water splitting is considered as a promising approach to produce clean and sustainable hydrogen fuel. As a new class of nanomaterials with high ratio of surface atoms and tunable composition and electronic structure, metal clusters are promising candidates as catalysts. Here, a new strategy is demonstrated to synthesize active and stable Pt-based electrocatalysts for hydrogen evolution by confining Pt clusters in hollow mesoporous carbon spheres (Pt₅/HMCS). Such a structure would effectively stabilize the Pt clusters during the ligand removal process, leading to remarkable electrocatalytic performance for hydrogen production in both acidic and alkaline solutions. Particularly, the optimal Pt₅/HMCS electrocatalyst exhibits 12 times the mass activity of Pt in commercial Pt/C catalyst with similar Pt loading. This study exemplifies a simple yet effective approach to improve the cost effectiveness of precious-metal-based catalysts with stabilized metal clusters.     

Microwave-assisted synthesis of pt nanocrystals and deposition on carbon nanotubes in ionic liquids

In this work, a simple, fast and efficient route is presented for the metal (such as Pt, Rh, etc.) nanocrystal synthesis and deposition on carbon nanotubes (CNTs) in ionic liquids (ILs) via microwave heating. In this method, inorganic salts (such as H2PtCl6.4H2O, RhCl3.2H2O, etc.) dissolved in ILs, 1,1,3,3-tetramethylguanidinium trifluoroacetate or 1,1,3,3-tetramethylguanidinium lactate, were reduced to metal nanoparticles by glycol with the aid of microwave heating, and the produced metal nanoparticles could be decorated on CNTs in the presence of CNTs in ILs. The resulting nanomaterials were characterized by means of transmission electron microscopy and X-ray diffraction. It was demonstrated that the homogeneously dispersed Pt nanocrystals with the size of 2-3 nm were obtained using H2PtCl6.4H2O as precursor, and they deposited on CNTs with the similar size when CNTs was present in ILs. This technique also can be extended to fabricate other noble metal nanocrystals (including Rh, Au, etc.) and corresponding CNT composites.     

Rational Design of Atomic Layers of Pt Anchored on Mo2C Nanorods for Efficient Hydrogen Evolution over a Wide pH Range

Transition metal carbide compound has been extensively investigated as a catalyst for hydrogenation, for example, due to its noble metal‐like properties. Herein a facile synthetic strategy is applied to control the thickness of atomic‐layer Pt clusters strongly anchored on N‐doped Mo₂C nanorods (Pt/N‐Mo₂C) and it is found that the Pt atomic layers modify Mo₂C function as a high‐performance and robust catalyst for hydrogen evolution. The optimized 1.08 wt% Pt/N‐Mo₂C exhibits 25‐fold, 10‐fold, and 15‐fold better mass activity than the benchmark 20 wt% Pt/C in neutral, acidic, and alkaline media, respectively. This catalyst also represents an extremely low overpotential of ?8.3 mV at current density of 10 mA cm^?2, much better than the majority of reported electrocatalysts and even the commercial reference catalyst (20 wt%) Pt/C. Furthermore, it exhibits an outstanding long‐term operational durability of 120 h. Theoretical calculation predicts that the ultrathin layer of Pt clusters on Mo‐Mo₂C yields the lowest absolute value of ΔG_H*. Experimental results demonstrate that the atomic layer of Pt clusters anchored on Mo₂C substrate greatly enhances electron and mass transportation efficiency and structural stability. These findings could provide the foundation for developing highly effective and scalable hydrogen evolution catalysts.     

Memory effect of reversibly thermoswitchable self-assembly-competent recombinant TMV coat protein with multi-binding moieties with potential applications in nanoparticle purification

Biomolecule-mediated assembly of novel nanoconjugates has been subjected to numerous investigations nowadays, which provides a new insight into the material science and engineering. Via the molecular biology technology, the genetically engineered polypeptide for inorganics (GEPI) can be designed as a molecular binder into the bio-scaffold to assemble hybrid functional nanoarchitectures. In the present work, we constructed a multi-functional virus-like particle (VLP) scaffold based on the Tobacco mosaic virus (TMV) (wild-type strain U1) in a facile way. The S123C site-mutated coat protein (CP) of TMV recombinated with a Ti–GEPI and 6-histidine tag (His tag) was successfully cloned, expressed and purified. The as-produced r-CP products retained both binding affinity for inorganic nanoparticles and self-assembly capability. Analysis of r-CP self-assembly during condensation polymerization was conducted. The r-CP-assembled aggregates including disc-like structures and rod-like VLPs were recovered by preparative size-exclusion chromatography (SEC) and then examined by TEM analysis. Notably, r-CP protein displayed a thermo-triggered reversibly switchable transition between bistable states of transparency and opaqueness. Western blot analysis, Immunogold labelling and TEM analysis were employed to test the existence and binding function of the His tag group in r-CP VLPs. Furthermore, dispersion of TiO₂ NPs in r-CP solution and recyclable application in bio-benefication was introduced. Here we demonstrated the possibilities of combining peptide-mediated immobilization with VLP-based biotemplate bearing multi-binding moieties for prospectful functional applications.     

Focused ion beam fabrication of novel core-shell nanowire structures

A novel method of indirect deposition by means of a focused ion beam (FIB) is utilized to develop metal/insulator/semiconductor nanowire core-shell structures. This method is based upon depositing an annular pattern centered on a nanowire, with secondary deposition then coating the wire. Typical cross-sectional deposition area increments as a function of ion doses are 1.3 × 10(-2)?μm(2)?nC(-1) for Pt and 3.5 × 10(-2)?μm(2)?nC(-1) for SiO(2). The structures are examined with a transmission electron microscope (TEM) using a new nanowire TEM sample preparation method that allows direct examinations of individually selected core-shell nanowires fabricated under different indirect FIB deposition conditions. Elemental analyses by means of energy dispersive x-ray spectroscopy and electron energy filtered TEM imaging verify the deposition of SiO(2) and Pt layers. Relatively uniform Pt and SiO(2) coatings on individual GaP nanowires can be achieved with overall thickness deviation of about 10% for deposition up to 25-30?nm thick Pt or SiO(2) shells. It should be possible to extend this approach to any nanowire/nanotube system, and to a wide range of coatings in any desired layer sequences.     

Interfacial reaction and electrical properties of HfO2 film gate dielectric prepared by pulsed laser deposition in nitrogen: role of rapid thermal annealing and gate electrode

The high-k dielectric HfO(2) thin films were deposited by pulsed laser deposition in nitrogen atmosphere. Rapid thermal annealing effect on film surface roughness, structure and electrical properties of HfO(2) film was investigated. The mechanism of interfacial reaction and the annealing atmosphere effect on the interfacial layer thickness were discussed. The sample annealed in nitrogen shows an amorphous dominated structure and the lowest leakage current density. Capacitors with high-k HfO(2) film as gate dielectric were fabricated, using Pt, Au, and Ti as the top gate electrode whereas Pt constitutes the bottom side electrode. At the gate injection case, the Pt- and Au-gated metal oxide semiconductor devices present a lower leakage current than that of the Ti-gated device, as well as similar leakage current conduction mechanism and interfacial properties at the metal/HfO(2) interface, because of their close work function and chemical properties.