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1.  Integration of ZnO and CuO nanowires into a thermoelectric module 
Zinc oxide (ZnO, n-type) and copper oxide (CuO, p-type) nanowires have been synthesized and preliminarily investigated as innovative materials for the fabrication of a proof-of-concept thermoelectric device. The Seebeck coefficients, electrical conductivity and thermoelectric power factors (TPF) of both semiconductor materials have been determined independently using a custom experimental set-up, leading to results in agreement with available literature with potential improvement. Combining bundles of ZnO and CuO nanowires in a series of five thermocouples on alumina leads to a macroscopic prototype of a planar thermoelectric generator (TEG) unit. This demonstrates the possibility of further integration of metal oxide nanostructures into efficient thermoelectric devices.
PMCID: PMC4077393  PMID: 24991531
copper oxide; nanowires; thermoelectric; zinc oxide
2.  Optimizing the synthesis of CdS/ZnS core/shell semiconductor nanocrystals for bioimaging applications 
In this study, we report on CdS/ZnS nanocrystals as a luminescence probe for bioimaging applications. CdS nanocrystals capped with a ZnS shell had enhanced luminescence intensity, stronger stability and exhibited a longer lifetime compared to uncapped CdS. The CdS/ZnS nanocrystals were stabilized in Pluronic F127 block copolymer micelles, offering an optically and colloidally stable contrast agents for in vitro and in vivo imaging. Photostability test exhibited that the ZnS protective shell not only enhances the brightness of the QDs but also improves their stability in a biological environment. An in-vivo imaging study showed that F127-CdS/ZnS micelles had strong luminescence. These results suggest that these nanoparticles have significant advantages for bioimaging applications and may offer a new direction for the early detection of cancer in humans.
PMCID: PMC4077458  PMID: 24991530
bioimaging; CdS/ZnS quantum dots; Pluronic F127
3.  Gas sensing with gold-decorated vertically aligned carbon nanotubes 
Vertically aligned carbon nanotubes of different lengths (150, 300, 500 µm) synthesized by thermal chemical vapor deposition and decorated with gold nanoparticles were investigated as gas sensitive materials for detecting nitrogen dioxide (NO2) at room temperature. Gold nanoparticles of about 6 nm in diameter were sputtered on the top surface of the carbon nanotube forests to enhance the sensitivity to the pollutant gas. We showed that the sensing response to nitrogen dioxide depends on the nanotube length. The optimum was found to be 300 µm for getting the higher response. When the background humidity level was changed from dry to 50% relative humidity, an increase in the response to NO2 was observed for all the sensors, regardless of the nanotube length.
PMCID: PMC4077511  PMID: 24991529
alignment; carbon nanotubes; decoration; gas sensors; metal nanoparticles; thermal CVD
4.  Direct observation of microcavitation in underwater adhesion of mushroom-shaped adhesive microstructure 
In this work we report on experiments aimed at testing the cavitation hypothesis [Varenberg, M.; Gorb, S. J. R. Soc., Interface 2008, 5, 383–385] proposed to explain the strong underwater adhesion of mushroom-shaped adhesive microstructures (MSAMSs). For this purpose, we measured the pull-off forces of individual MSAMSs by detaching them from a glass substrate under different wetting conditions and simultaneously video recording the detachment behavior at very high temporal resolution (54,000–100,000 fps). Although microcavitation was observed during the detachment of individual MSAMSs, which was a consequence of water inclusions present at the glass–MSAMS contact interface subjected to negative pressure (tension), the pull-off forces were consistently lower, around 50%, of those measured under ambient conditions. This result supports the assumption that the recently observed strong underwater adhesion of MSAMS is due to an air layer between individual MSAMSs [Kizilkan, E.; Heepe, L.; Gorb, S. N. Underwater adhesion of mushroom-shaped adhesive microstructure: An air-entrapment effect. In Biological and biomimetic adhesives: Challenges and opportunities; Santos, R.; Aldred, N.; Gorb, S. N.; Flammang, P., Eds.; The Royal Society of Chemistry: Cambridge, U.K., 2013; pp 65–71] rather than by cavitation. These results obtained due to the high-speed visualisation of the contact behavior at nanoscale-confined interfaces allow for a microscopic understanding of the underwater adhesion of MSAMSs and may aid in further development of artificial adhesive microstructures for applications in predominantly liquid environments.
PMCID: PMC4077361  PMID: 24991528
bio-inspired; biomimetic; cavitation; contact mechanics; gecko; interface; negative pressure; pull-off; surface; tribology
5.  Optical modeling-assisted characterization of dye-sensitized solar cells using TiO2 nanotube arrays as photoanodes 
Photovoltaic characteristics of dye-sensitized solar cells (DSSCs) using TiO2 nanotube (TNT) arrays as photoanodes were investigated. The TNT arrays were 3.3, 11.5, and 20.6 μm long with the pore diameters of 50, 78.6, and 98.7 nm, respectively. The longest TNT array of 20.6 μm in length showed enhanced photovoltaic performances of 3.87% with significantly increased photocurrent density of 8.26 mA·cm−2. This improvement is attributed to the increased amount of the adsorbed dyes and the improved electron transport property with an increase in TNT length. The initial charge generation rate was improved from 4 × 1021 s−1·cm−3 to 7 × 1021 s−1·cm−3 in DSSCs based on optical modelling analysis. The modelling analysis of optical processes inside TNT-based DSSCs using generalized transfer matrix method (GTMM) revealed that the amount of dye and TNT lengths were critical factors influencing the performance of DSSCs, which is consistent with the experimental results.
PMCID: PMC4077540  PMID: 24991527
charge generation; dye-sensitized solar cells; generalized transfer matrix method; optical process; photocatalysis; TiO2 nanotubes
6.  Controlling mechanical properties of bio-inspired hydrogels by modulating nano-scale, inter-polymeric junctions 
Quinone tanning is a well-characterized biochemical process found in invertebrates, which produce diverse materials from extremely hard tissues to soft water-resistant adhesives. Herein, we report new types of catecholamine PEG derivatives, PEG-NH-catechols that can utilize an expanded spectrum of catecholamine chemistry. The PEGs enable simultaneous participation of amine and catechol in quinone tanning crosslinking. The intermolecular reaction between PEG-NH-catechols forms a dramatic nano-scale junction resulting in enhancement of gelation kinetics and mechanical properties of PEG hydrogels compared to results obtained by using PEGs in the absence of amine groups. Therefore, the study provides new insight into designing new crosslinking chemistry for controlling nano-scale chemical reactions that can broaden unique properties of bulk hydrogels.
PMCID: PMC4077523  PMID: 24991526
catechols; hydrogels; poly(ethylene glycol)s; quinone tanning
7.  Optical and structural characterization of oleic acid-stabilized CdTe nanocrystals for solution thin film processing 
This work presents results of the optical and structural characterization of oleic acid-stabilized cadmium telluride nanocrystals (CdTe-NC) synthesized by an organometallic route. After being cleaned, the CdTe-NC were dispersed in toluene to obtain an ink-like dispersion, which was drop-cast on glass substrate to deposit a thin film. The CdTe-NC colloidal dispersion as well as the CdTe drop-cast thin films were characterized with regard to the optical and structural properties. TEM analysis indicates that the CdTe-NC have a nearly spherical shape (3.5 nm as mean size). Electron diffraction and XRD diffraction analyses indicated the bulk-CdTe face-centered cubic structure for CdTe-NC. An additional diffraction line corresponding to the octahedral Cd3P2 was also detected as a secondary phase, which probably originates by reacting free cadmium ions with trioctylphosphine (the tellurium reducing agent). The Raman spectrum exhibits two broad bands centered at 141.6 and 162.3 cm−1, which could be associated to the TO and LO modes of cubic CdTe nanocrystals, respectively. Additional peaks located in the 222 to 324 cm−1 range, agree fairly well with the wavenumbers reported for TO modes of octahedral Cd3P2.
PMCID: PMC4077417  PMID: 24991525
cadmium telluride; Raman spectroscopy; semiconductor nanocrystals; transmission electron microscopy; X-ray diffraction
8.  Antimicrobial nanospheres thin coatings prepared by advanced pulsed laser technique 
We report on the fabrication of thin coatings based on polylactic acid-chitosan-magnetite-eugenol (PLA-CS-Fe3O4@EUG) nanospheres by matrix assisted pulsed laser evaporation (MAPLE). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) investigation proved that the homogenous Fe3O4@EUG nanoparticles have an average diameter of about 7 nm, while the PLA-CS-Fe3O4@EUG nanospheres diameter sizes range between 20 and 80 nm. These MAPLE-deposited coatings acted as bioactive nanosystems and exhibited a great antimicrobial effect by impairing the adherence and biofilm formation of Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa) bacteria strains. Moreover, the obtained nano-coatings showed a good biocompatibility and facilitated the normal development of human endothelial cells. These nanosystems may be used as efficient alternatives in treating and preventing bacterial infections.
PMCID: PMC4077416  PMID: 24991524
antimicrobial; chitosan; magnetite nanoparticles; nanospheres; P. aeruginosa; polylactic acid; S. aureus
9.  Classical molecular dynamics investigations of biphenyl-based carbon nanomembranes 
Background: Free-standing carbon nanomembranes (CNM) with molecular thickness and macroscopic size are fascinating objects both for fundamental reasons and for applications in nanotechnology. Although being made from simple and identical precursors their internal structure is not fully known and hard to simulate due to the large system size that is necessary to draw definite conclusions.
Results: We performed large-scale classical molecular dynamics investigations of biphenyl-based carbon nanomembranes. We show that one-dimensional graphene-like stripes constitute a highly symmetric quasi one-dimensional energetically favorable ground state. This state does not cross-link. Instead cross-linked structures are formed from highly excited precursors with a sufficient amount of broken phenyls.
Conclusion: The internal structure of the CNM is very likely described by a disordered metastable state which is formed in the energetic initial process of electron irradiation and depends on the process of relaxation into the sheet phase.
PMCID: PMC4077425  PMID: 24991523
biphenyls; carbon nanomembranes; classical molecular dynamics
10.  Pyrite nanoparticles as a Fenton-like reagent for in situ remediation of organic pollutants 
The Fenton reaction is the most widely used advanced oxidation process (AOP) for wastewater treatment. This study reports on the use of pyrite nanoparticles and microparticles as Fenton reagents for the oxidative degradation of copper phthalocyanine (CuPc) as a representative contaminant. Upon oxidative dissolution in water, pyrite (FeS2) particles can generate H2O2 at their surface while simultaneously promoting recycling of Fe3+ into Fe2+ and vice versa. Pyrite nanoparticles were synthesized by the hot injection method. The use of a high concentration of precursors gave individual nanoparticles (diameter: 20 nm) with broader crystallinity at the outer interfaces, providing a greater number of surface defects, which is advantageous for generating H2O2. Batch reactions were run to monitor the kinetics of CuPc degradation in real time and the amount of H2O2. A markedly greater degradation of CuPc was achieved with nanoparticles as compared to microparticles: at low loadings (0.08 mg/L) and 20 h reaction time, the former enabled 60% CuPc removal, whereas the latter enabled only 7% removal. These results confirm that the use of low concentrations of synthetic nanoparticles can be a cost effective alternative to conventional Fenton procedures for use in wastewater treatment, avoiding the potential risks caused by the release of heavy metals upon dissolution of natural pyrites.
PMCID: PMC4077362  PMID: 24991522
copper phthalocyanine; Fenton-like reagent; hydrogen peroxide; nanoparticles; pyrite
11.  Volcano plots in hydrogen electrocatalysis – uses and abuses 
Sabatier’s principle suggests, that for hydrogen evolution a plot of the rate constant versus the hydrogen adsorption energy should result in a volcano, and several such plots have been presented in the literature. A thorough examination of the data shows, that there is no volcano once the oxide-covered metals are left out. We examine the factors that govern the reaction rate in the light of our own theory and conclude, that Sabatier’s principle is only one of several factors that determine the rate. With the exception of nickel and cobalt, the reaction rate does not decrease for highly exothermic hydrogen adsorption as predicted, because the reaction passes through more suitable intermediate states. The case of nickel is given special attention; since it is a 3d metal, its orbitals are compact and the overlap with hydrogen is too low to make it a good catalyst.
PMCID: PMC4077405  PMID: 24991521
electrocatalysis; hydrogen evolution; Sabatier’s principle; volcano curve
12.  Fibrillar adhesion with no clusterisation: Functional significance of material gradient along adhesive setae of insects 
It has been recently demonstrated that adhesive tarsal setae of beetles possess material gradients along their length. These gradients presumably represent an evolutionary optimization enhancing the adaptation to rough surfaces while simultaneously preventing clusterisation of the setae by lateral collapse. The numerical experiment of the present study has clearly demonstrated that gradient-bearing fibers with short soft tips and stiff bases have greater advantage in maximizing adhesion and minimizing clusterisation in multiple attachment–detachment cycles, if compared to the fibers with longer soft tips on the stiff bases and fibers with stiff tips on the soft bases. This study not only manifests the crucial role of gradients in material properties along the setae in beetle fibrillar adhesive system, but predicts that similar gradients must have been convergently evolved in various lineages of arthropods.
PMCID: PMC4077360  PMID: 24991520
adhesion; attachment; biomechanics; computer modelling; cuticle; locomotion; material; surface
13.  Scale effects of nanomechanical properties and deformation behavior of Au nanoparticle and thin film using depth sensing nanoindentation 
Nanoscale research of bulk solid surfaces, thin films and micro- and nano-objects has shown that mechanical properties are enhanced at smaller scales. Experimental studies that directly compare local with global deformation are lacking. In this research, spherical Au nanoparticles, 500 nm in diameter and 100 nm thick Au films were selected. Nanoindentation (local deformation) and compression tests (global deformation) were performed with a nanoindenter using a sharp Berkovich tip and a flat punch, respectively. Data from nanoindentation studies were compared with bulk to study scale effects. Nanoscale hardness of the film was found to be higher than the nanoparticles with both being higher than bulk. Both nanoparticles and film showed increasing hardness for decreasing penetration depth. For the film, creep and strain rate effects were observed. In comparison of nanoindentation and compression tests, more pop-ins during loading were observed during the nanoindentation of nanoparticles. Repeated compression tests of nanoparticles were performed that showed a strain hardening effect and increased pop-ins during subsequent loads.
PMCID: PMC4077422  PMID: 24991519
gold (Au); Hall–Petch; hardness; nanoindentation; nano-objects
14.  Measuring air layer volumes retained by submerged floating-ferns Salvinia and biomimetic superhydrophobic surfaces 
Some plants and animals feature superhydrophobic surfaces capable of retaining a layer of air when submerged under water. Long-term air retaining surfaces (Salvinia-effect) are of high interest for biomimetic applications like drag reduction in ship coatings of up to 30%. Here we present a novel method for measuring air volumes and air loss under water. We recorded the buoyancy force of the air layer on leaf surfaces of four different Salvinia species and on one biomimetic surface using a highly sensitive custom made strain gauge force transducer setup. The volume of air held by a surface was quantified by comparing the buoyancy force of the specimen with and then without an air layer. Air volumes retained by the Salvinia-surfaces ranged between 0.15 and 1 L/m2 depending on differences in surface architecture. We verified the precision of the method by comparing the measured air volumes with theoretical volume calculations and could find a good agreement between both values. In this context we present techniques to calculate air volumes on surfaces with complex microstructures. The introduced method also allows to measure decrease or increase of air layers with high accuracy in real-time to understand dynamic processes.
PMCID: PMC4077374  PMID: 24991518
air layer; biomimetic; drag reduction; functional surfaces; plastron; Salvinia effect; volume measurement
15.  Enhancement of photocatalytic H2 evolution of eosin Y-sensitized reduced graphene oxide through a simple photoreaction 
A graphene oxide (GO) solution was irradiated by a Xenon lamp to form reduced graphene oxide (RGO). After irradiation, the epoxy, the carbonyl and the hydroxy groups are gradually removed from GO, resulting in an increase of sp2 π-conjugated domains and defect carbons with holes for the formed RGO. The RGO conductivity increases due to the restoration of sp2 π-conjugated domains. The photocatalytic activity of EY-RGO/Pt for hydrogen evolution was investigated with eosin Y (EY) as a sensitizer of the RGO and Pt as a co-catalyst. When the irradiation time is increased from 0 to 24 h the activity rises, and then reaches a plateau. Under optimum conditions (pH 10.0, 5.0 × 10−4 mol L−1 EY, 10 μg mL−1 RGO), the maximal apparent quantum yield (AQY) of EY-RGO24/Pt for hydrogen evolution rises up to 12.9% under visible light irradiation (λ ≥ 420 nm), and 23.4% under monochromatic light irradiation at 520 nm. Fluorescence spectra and transient absorption decay spectra of the EY-sensitized RGO confirm that the electron transfer ability of RGO increases with increasing irradiation time. The adsorption quantity of EY on the surface of RGO enhances, too. The two factors ultimately result in an enhancement of the photocatalytic hydrogen evolution over EY-RGO/Pt with increasing irradiation time. A possible mechanism is discussed.
PMCID: PMC4077509  PMID: 24991517
eosin Y sensitization; graphene oxide; H2 evolution; photocatalysis; photoreduction; sp2 conjugated domains
16.  Antimicrobial properties of CuO nanorods and multi-armed nanoparticles against B. anthracis vegetative cells and endospores 
Two different kinds of CuO nanoparticles (NPs) namely CuO nanorods (PS2) and multi-armed nanoparticles (P5) were synthesized by wet and electrochemical routes, respectively. Their structure, morphology, size and compositions were characterized by SEM, EDX and XRD. The NPs demonstrated strong bactericidal potential against Bacillus anthracis cells and endospores. PS2 killed 92.17% of 4.5 × 104 CFU/mL B. anthracis cells within 1 h at a dose of 1 mg/mL. Whereas P5 showed a higher efficacy by killing 99.92% of 7 × 105 CFU/mL B. anthracis cells within 30 min at a dose of 0.5 mg/mL and 99.6% of 1.25 × 104 CFU/mL B. anthracis cells within 5 min at a dose of 2 mg/mL. More than 99% of spores were killed within 8 h with 2 mg/mL PS2 in LB media.
PMCID: PMC4077429  PMID: 24991516
Bacillus anthracis; bactericidal nanoparticles; copper oxide; nanoparticles; spore inactivation
17.  Manipulation of isolated brain nerve terminals by an external magnetic field using D-mannose-coated γ-Fe2O3 nano-sized particles and assessment of their effects on glutamate transport 
The manipulation of brain nerve terminals by an external magnetic field promises breakthroughs in nano-neurotechnology. D-Mannose-coated superparamagnetic nanoparticles were synthesized by coprecipitation of Fe(II) and Fe(III) salts followed by oxidation with sodium hypochlorite and addition of D-mannose. Effects of D-mannose-coated superparamagnetic maghemite (γ-Fe2O3) nanoparticles on key characteristics of the glutamatergic neurotransmission were analysed. Using radiolabeled L-[14C]glutamate, it was shown that D-mannose-coated γ-Fe2O3 nanoparticles did not affect high-affinity Na+-dependent uptake, tonic release and the extracellular level of L-[14C]glutamate in isolated rat brain nerve terminals (synaptosomes). Also, the membrane potential of synaptosomes and acidification of synaptic vesicles was not changed as a result of the application of D-mannose-coated γ-Fe2O3 nanoparticles. This was demonstrated with the potential-sensitive fluorescent dye rhodamine 6G and the pH-sensitive dye acridine orange. The study also focused on the analysis of the potential use of these nanoparticles for manipulation of nerve terminals by an external magnetic field. It was shown that more than 84.3 ± 5.0% of L-[14C]glutamate-loaded synaptosomes (1 mg of protein/mL) incubated for 5 min with D-mannose-coated γ-Fe2O3 nanoparticles (250 µg/mL) moved to an area, in which the magnet (250 mT, gradient 5.5 Т/m) was applied compared to 33.5 ± 3.0% of the control and 48.6 ± 3.0% of samples that were treated with uncoated nanoparticles. Therefore, isolated brain nerve terminals can be easily manipulated by an external magnetic field using D-mannose-coated γ-Fe2O3 nanoparticles, while the key characteristics of glutamatergic neurotransmission are not affected. In other words, functionally active synaptosomes labeled with D-mannose-coated γ-Fe2O3 nanoparticles were obtained.
PMCID: PMC4077395  PMID: 24991515
extracellular level; γ-Fe2O3; glutamate uptake and release; manipulation by an external magnetic field; D-mannose; membrane potential; nanoparticles; rat brain nerve terminals; synaptic vesicle acidification
18.  Biomolecule-assisted synthesis of carbon nitride and sulfur-doped carbon nitride heterojunction nanosheets: An efficient heterojunction photocatalyst for photoelectrochemical applications 
A biomolecule-assisted pyrolysis method has been developed to synthesize sulfur-doped graphitic carbon nitride (CNS) nanosheets. During the synthesis, sulfur could be introduced as a dopant into the lattice of carbon nitride (CN). Sulfur doping changed the texture as well as relative band positions of CN. By growing CN on preformed sulfur-doped CN nanosheets, composite CN/CNS heterojunction nanosheets were constructed, which significantly enhanced the photoelectrochemical performance as compared with various control counterparts including CN, CNS and physically mixed CN and CNS (CN+CNS). The enhanced photoelectrochemical performance of CN/CNS heterojunction nanosheets could be ascribed to the efficient separation of photoexcited charge carriers across the heterojunction interface. The strategy of designing and preparing CN/CNS heterojunction photocatalysts in this work can open up new directions for the construction of all CN-based heterojunction photocatalysts.
PMCID: PMC4077510  PMID: 24991514
graphitic carbon nitride (g-C3N4); heterojunction; photoelectrochemical; photocatalysis; sulfur doping
19.  Carbon dioxide hydrogenation to aromatic hydrocarbons by using an iron/iron oxide nanocatalyst 
The quest for renewable and cleaner energy sources to meet the rapid population and economic growth is more urgent than ever before. Being the most abundant carbon source in the atmosphere of Earth, CO2 can be used as an inexpensive C1 building block in the synthesis of aromatic fuels for internal combustion engines. We designed a process capable of synthesizing benzene, toluene, xylenes and mesitylene from CO2 and H2 at modest temperatures (T = 380 to 540 °C) employing Fe/Fe3O4 nanoparticles as catalyst. The synthesis of the catalyst and the mechanism of CO2-hydrogenation will be discussed, as well as further applications of Fe/Fe3O4 nanoparticles in catalysis.
PMCID: PMC4077464  PMID: 24991513
aromatic hydrocarbons; carbon dioxide reduction; heterogenous catalysis; iron/iron oxide nanocatalyst
20.  Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates 
As part of a mechanistic study of the electrooxidation of C1 molecules we have systematically investigated the dissociative adsorption/oxidation of formaldehyde on a polycrystalline Pt film electrode under experimental conditions optimizing the chance for detecting weakly adsorbed reaction intermediates. Employing in situ IR spectroscopy in an attenuated total reflection configuration (ATR-FTIRS) with p-polarized IR radiation to further improve the signal-to-noise ratio, and using low reaction temperatures (3 °C) and deuterium substitution to slow down the reaction kinetics and to stabilize weakly adsorbed reaction intermediates, we could detect an IR absorption band at 1660 cm−1 characteristic for adsorbed formyl intermediates. This assignment is supported by an isotope shift in wave number. Effects of temperature, potential and deuterium substitution on the formation and disappearance of different adsorbed species (COad, adsorbed formate, adsorbed formyl), are monitored and quantified. Consequences on the mechanism for dissociative adsorption and oxidation of formaldehyde are discussed.
PMCID: PMC4077456  PMID: 24991512
electrocatalysis; formaldehyde adsorption; formyl intermediate; in situ spectro-electrochemistry; Pt
21.  An analytical approach to evaluate the performance of graphene and carbon nanotubes for NH3 gas sensor applications 
Carbon, in its variety of allotropes, especially graphene and carbon nanotubes (CNTs), holds great potential for applications in variety of sensors because of dangling π-bonds that can react with chemical elements. In spite of their excellent features, carbon nanotubes (CNTs) and graphene have not been fully exploited in the development of the nanoelectronic industry mainly because of poor understanding of the band structure of these allotropes. A mathematical model is proposed with a clear purpose to acquire an analytical understanding of the field-effect-transistor (FET) based gas detection mechanism. The conductance change in the CNT/graphene channel resulting from the chemical reaction between the gas and channel surface molecules is emphasized. NH3 has been used as the prototype gas to be detected by the nanosensor and the corresponding current–voltage (I–V) characteristics of the FET-based sensor are studied. A graphene-based gas sensor model is also developed. The results from graphene and CNT models are compared with the experimental data. A satisfactory agreement, within the uncertainties of the experiments, is obtained. Graphene-based gas sensor exhibits higher conductivity compared to that of CNT-based counterpart for similar ambient conditions.
PMCID: PMC4077376  PMID: 24991510
carbon nanotube (CNT); conductance; FET-based gas sensor; graphene
22.  Shape-selected nanocrystals for in situ spectro-electrochemistry studies on structurally well defined surfaces under controlled electrolyte transport: A combined in situ ATR-FTIR/online DEMS investigation of CO electrooxidation on Pt 
The suitability and potential of shape selected nanocrystals for in situ spectro-electrochemical and in particular spectro-electrocatalytic studies on structurally well defined electrodes under enforced and controlled electrolyte mass transport will be demonstrated, using Pt nanocrystals prepared by colloidal synthesis procedures and a flow cell set-up allowing simultaneous measurements of the Faradaic current, FTIR spectroscopy of adsorbed reaction intermediates and side products in an attenuated total reflection configuration (ATR-FTIRS) and differential electrochemical mass spectrometry (DEMS) measurements of volatile reaction products. Batches of shape-selected Pt nanocrystals with different shapes and hence different surface structures were prepared and structurally characterized by transmission electron microscopy (TEM) and electrochemical methods. The potential for in situ spectro-electrocatalytic studies is illustrated for COad oxidation on Pt nanocrystal surfaces, where we could separate contributions from two processes occurring simultaneously, oxidative COad removal and re-adsorption of (bi)sulfate anions, and reveal a distinct structure sensitivity in these processes and also in the structural implications of (bi)sulfate re-adsorption on the CO adlayer.
PMCID: PMC4077536  PMID: 24991511
CO oxidation; electrocatalysis; in situ spectro-electrochemistry; Pt; shape selected nanocrystals
23.  Resonance of graphene nanoribbons doped with nitrogen and boron: a molecular dynamics study 
Based on its enticing properties, graphene has been envisioned with applications in the area of electronics, photonics, sensors, bio-applications and others. To facilitate various applications, doping has been frequently used to manipulate the properties of graphene. Despite a number of studies conducted on doped graphene regarding its electrical and chemical properties, the impact of doping on the mechanical properties of graphene has been rarely discussed. A systematic study of the vibrational properties of graphene doped with nitrogen and boron is performed by means of a molecular dynamics simulation. The influence from different density or species of dopants has been assessed. It is found that the impacts on the quality factor, Q, resulting from different densities of dopants vary greatly, while the influence on the resonance frequency is insignificant. The reduction of the resonance frequency caused by doping with boron only is larger than the reduction caused by doping with both boron and nitrogen. This study gives a fundamental understanding of the resonance of graphene with different dopants, which may benefit their application as resonators.
PMCID: PMC4077460  PMID: 24991509
dopant; graphene; molecular dynamics simulation; natural frequency; quality factor; resonance
24.  Visible light photooxidative performance of a high-nuclearity molecular bismuth vanadium oxide cluster 
The visible light photooxidative performance of a new high-nuclearity molecular bismuth vanadium oxide cluster, H3[{Bi(dmso)3}4V13O40], is reported. Photocatalytic activity studies show faster reaction kinetics under anaerobic conditions, suggesting an oxygen-dependent quenching of the photoexcited cluster species. Further mechanistic analysis shows that the reaction proceeds via the intermediate formation of hydroxyl radicals which act as oxidant. Trapping experiments using ethanol as a hydroxyl radical scavenger show significantly decreased photocatalytic substrate oxidation in the presence of EtOH. Photocatalytic performance analyses using monochromatic visible light irradiation show that the quantum efficiency Φ for indigo photooxidation is strongly dependent on the irradiation wavelength, with higher quantum efficiencies being observed at shorter wavelengths (Φ395nm ca. 15%). Recycling tests show that the compound can be employed as homogeneous photooxidation catalyst multiple times without loss of catalytic activity. High turnover numbers (TON ca. 1200) and turnover frequencies up to TOF ca. 3.44 min−1 are observed, illustrating the practical applicability of the cluster species.
PMCID: PMC4077371  PMID: 24991508
photocatalysis; photooxidation; polyoxometalate; self-assembly; vanadium oxide
25.  Nanostructure sensitization of transition metal oxides for visible-light photocatalysis 
To better utilize the sunlight for efficient solar energy conversion, the research on visible-light active photocatalysts has recently attracted a lot of interest. The photosensitization of transition metal oxides is a promising approach for achieving effective visible-light photocatalysis. This review article primarily discusses the recent progress in the realm of a variety of nanostructured photosensitizers such as quantum dots, plasmonic metal nanostructures, and carbon nanostructures for coupling with wide-bandgap transition metal oxides to design better visible-light active photocatalysts. The underlying mechanisms of the composite photocatalysts, e.g., the light-induced charge separation and the subsequent visible-light photocatalytic reaction processes in environmental remediation and solar fuel generation fields, are also introduced. A brief outlook on the nanostructure photosensitization is also given.
PMCID: PMC4077394  PMID: 24991507
carbon nanostructures; nanostructure sensitization; plasmonic metal nanostructures; quantum dots; transition metal oxides; visible-light photocatalysis

Results 1-25 (433)