Mechanistic Insights into the Stabilization of In Situ Formed γ-NiOOH Species on Ni60Nb40 Nanoglass for Effective Urea Electro-Oxidation.

The formation of NiOOH on the catalyst surface is widely considered to be the active species in electrochemical urea oxidation reactions (UOR). Though in situ-formed NiOOH species are reported to be more active than the synthesized ones, the mechanistic study of the actual active species remains a daunting task due to the possibility of different phases and instability of surface-formed NiOOH. Herein, mechanistic UOR aspects of electrochemically activated metallic Ni60Nb40 Nanoglass showing stability toward the γ-NiOOH phase are reported, probed via in situ Raman spectroscopy, supported by electron microscopy analysis and X-ray photoelectron spectroscopy in contrast with the ß-NiOOH formation favored on Ni foil. Detailed mechanistic study further reveals that γ-NiOOH predominantly follows a direct UOR mechanism while ß-NiOOH favors indirect UOR from time-dependent Raman study, and electrochemical impedance spectroscopy (EIS) analysis. The Nanoglass has shown outstanding UOR performance with a low Tafel slope of 16 mV dec-1 and stability for prolonged electrolysis (≈38 mA cm-2 for 70 h) that can be attributed to the nanostructured glassy interfaces facilitating more γ-NiOOH species formation and stabilization on the surface. The present study opens up a new direction for the development of inexpensive Ni-based UOR catalysts and sheds light on the UOR mechanism.

Flower-like Ag-decked non-stoichiometric Bi2O3-x/rGO hybrid nanocomposite SERS substrates for an effective detection of Rhodamine 6G dye molecules.

In early years, SERS-active substrates were generally noble metals. However, their practical applications were limited due to their poor biocompatibility, low uniformity and high cost. Recently, the utilization of semiconductor SERS-active substrates has greatly expanded the applications of SERS in many fields. However, metal-free SERS-active substrates have a low enhancement factor (EF), which can be overcome by adjusting their oxygen deficiency or through the effective preparation of non-stoichiometric semiconducting oxide materials. This is the key strategy and may work as an efficient and simple way to achieve high sensitivity and obtain an enhancement factor (G-factor) comparable to that of noble metals. Here, we report the preparation of flower-like rGO-Bi2O3/Bi2O2.75 and rGO-Ag-Bi2O3/Bi2O2.75 hybrid thin film nanocomposites using a liquid/liquid interface method (LLI) for the first time. In addition to the synergic effect of different enhancement mechanisms, the 3-D flower-like morphology of the substrate shows more favourable properties to improve the G-factor due to the existence of more hotspots. The rGO-Ag-Bi2O3/Bi2O2.75 hybrid thin-film nanocomposites show an EF of 1.8 × 109 with a detection ability of up to 1 nM towards Rhodamine 6G (R6G), which is highly toxic to humans and the aquatic environment.

Spontaneous Decoration of Ultrasmall Pt Nanoparticles on Size-Separated MoS2 Nanosheets.

Liquid exfoliation can be considered as a viable approach for the scalable production of 2D materials due to its various benefits, although the polydispersity in the obtained nanosheet size hinders their straightforward incorporation. Size-separation can help alleviate these concerns, however a correlation between nanosheet size and property needs to be established to bring about size-specific applicability. Herein, size-selected aqueous nanosheet dispersions have been obtained via centrifugation-based protocols, and their chemical activity in the spontaneous reduction of chloroplatinic acid is investigated. Growth of ultrasmall Pt nanoparticles was achieved on nanosheet surfaces without a need for reducing agents, and stark differences in the nanoparticle coverage were observed as a function of nanosheet size. Defects in the nanosheets were probed via Raman spectroscopy, and correlated to the observed size-activity. Additionally, the effect of reaction temperature during synthesis was investigated. The electrochemical activity of the ultrasmall Pt nanoparticle decorated MoS2 nanosheets was evaluated for the hydrogen evolution reaction, and enhancement in performance was observed with nanosheet size, and nanoparticle decoration density. These findings shine light on the significance of nanosheet size in controlling spontaneous reduction reactions, and provide a deeper insight to intrinsic properties of liquid exfoliated nanosheets.

Fabrication of sandwich structures of Ag/analyte/MoO3sea urchins for SERS detection of methylene blue dye molecules.

A substrate for surface-enhanced Raman spectroscopy (SERS) in a sandwich configuration, noble metal/analyte/defect-rich metal oxide, is demonstrated for the detection of methylene blue(MB). The sandwich structure (Ag/MB/SUMoO3) is fabricated by physical vapour deposition of Ag nanoparticles over the MB analytes that are adsorbed on sea urchin MoO3(SUMoO3). SUMoO3are grown on a glass substrate by chemical bath deposition. The morphology of the fabricated sandwich structures shows serrated spikes of MoO3from the core region decorated with strings of silver nanoparticles. The silver-decoration and the oxygen defects of SUMoO3promote absorption in the visible region and facilitate charge transfer between MB and SUMoO3, which are beneficial for achieving superior SERS properties in this configuration compared to the contribution from individual components alone. The sandwich structure is able to detect the MB molecule up to 100 nM with an enhancement factor of 8.1 × 106. The relative standard deviation of SERS intensity for the 1618 cm-1peak of MB across the substrate is 29.2%. The configuration offers stability to SERS substrate under ambient conditions. The combined effect of charge transfer, surface plasmon resonance, and MB resonance results in the improved SERS detection of MB molecules with the Ag/MB/SUMoO3sandwich structure.

Insight into the Multistate Emissive N, P-doped Carbon Nano-Onions: Emerging Visible-Light Absorption for Photocatalysis.

Carbon dots (CDs) have become one of the most emerging materials as an alternative solar light-induced photocatalyst in contrast to traditional metal-based systems. However, one of the major challenges is the lack of visible light absorption. Herein, we have fabricated unique N, P-co-doped CDs with a self-assembled onion-like layered structure by using a bottom-up facile synthesis technique from chitosan gel and phosphoric acid as molecular precursors. This typical layered structure of N, P-co-doped carbon nano onions (N, P-CNOs), with an average size of 25-50 nm, displays an enhanced visible light absorption. Detailed structural and elemental characterizations confirm the extensive aromatic domain with P-containing surface functionalities, while electrochemical study clarifies the lowering of band gaps as well as the creation of new electronic states in comparison to the pristine N-CDs. Furthermore, the intrinsic structural features are correlated with the underpinning photophysical processes by steady-state and time-resolved fluorescence spectroscopy. In addition, steady-state polarized emission and thermo-responsive PL properties have been carried out to unveil further the structure-property correlation of N, P-CNOs, and their comparative study with pristine N-CDs at the different excitation wavelengths. Finally, N, P-CNOs exhibit efficient visible-light-induced photocatalysis, and the detailed mechanistic study is carried out by trapping the photogenerated species in an aqueous medium. The prepared N, P-CNOs displayed an excellent visible-light photocatalytic performance over MB dye with a degradation efficiency of 75.8% within 120 min along with a degradation rate constant of ∼0.0109 min-1 . It is concluded that the easy to synthesize and low-cost N, P-CNOs with a unique morphology hold great potential for application in visible-light photocatalysis.

Templating effect of single-layer graphene supported by an insulating substrate on the molecular orientation of lead phthalocyanine.

The influence of single-layer graphene on top of a SiO2/Si surface on the orientation of nonplanar lead phthalocyanine (PbPc) molecules is studied using two-dimensional grazing incidence X-ray diffraction. The studies indicate the formation of a mixture of polymorphs, i.e., monoclinic and triclinic forms of PbPc with face-on (lying down) and edge-on (standing up) PbPc orientations, respectively. The formation of monoclinic fractions is attributed to the presence of the graphene layer directing the π interactions between the highly delocalized macrocycles. The competing interfacial van der Waals forces and molecule-molecule interactions lead to the formation of a small fraction of triclinic moieties. The nanoscale electrical characterization of the thin PbPc layer on graphene by means of conducting atomic force microscopy shows enhanced vertical conductance with interconnected conducting domains consisting of ordered monoclinic crystallites through which the charge transfer occurs via tunneling. These results show the importance of a templating layer to induce the formation of a required phase of PbPc suitable for specific device applications.

Gold Nanorods as an Efficient Substrate for the Detection and Degradation of Pesticides.

The rapid, ultralow detection, degradation, and complete removal of pesticides demand the design of potential substrates. Herein, we discussed gold nanorods (Au NRs) as the potential substrate for the naked eye detection and degradation of two common and broad-spectrum pesticides, chlorpyrifos (CPF) and malathion (MLT), up to 0.15 ppt concentration within 2 min. Under certain environmental conditions, both the pesticides degraded and adsorbed on the surface of Au NRs. The degraded moieties of CPF and MLT on the surface of Au NRs formed side-to-side and end-to-end interactions, respectively, leading to a long-range assembly. This shows that no external agent is required, and only CPF and MLT analytes are quite enough for the formation of assembly of Au NRs. Assembly of Au NRs is confirmed by transmission electron microscopy (TEM) analysis, and degradation is supported by Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and gas chromatography-mass spectrometry (GC-MS) analyses. Au NRs were recovered and reused for four consecutive cycles. The fast and ultralow detection of pesticides demonstrates that Au NRs are a potential substrate for the detection and degradation of pesticides.

Low-cost electrochemical detection of l-tyrosine using an rGO-Cu modified pencil graphite electrode and its surface orientation on a Ag electrode using an ex situ spectroelectrochemical method.

A low cost reduced graphene oxide-copper hybrid nano thin-film modified Pencil Graphite Electrode has been employed to detect the l-tyrosine enantiomer. The free-standing rGO-Cu hybrid nano-thin film was prepared by a simple one-step liquid-liquid interface method. Electrochemical Cyclic Voltammetry, Differential Pulse Voltammetry, pH-dependent and scan rate dependent studies on bare PGE, Cu, rGO, and rGO-Cu for l-tyrosine have been explained in detail. The rGO-Cu modified PGE based biosensor exhibits good detection of l-tyrosine. The linear range detection limit was estimated to be 1 × 10-7 M. The calculated sensitivity is 0.4 µA ppm-1 mm2. This electroactive biosensor is easily fabricated and controlled and is cost-effective. The surface orientation of l-tyrosine on the Ag electrode at a particular potential and its comparison with vibrational DFT calculations have been studied for the first time.

Current mapping of lead phthalocyanine thin films in the presence of gaseous dopants.

The structural organization and its effect on conducting pathways in lead phthalocyanine (PbPc) thin films, a nonplanar phthalocyanine, deposited on Si and highly oriented pyrolytic graphite (HOPG) substrates in the presence of iodine and ammonia vapors are presented. Two-dimensional grazing incidence X-ray diffraction studies reveal that the crystalline ordering in pristine PbPc films on Si and HOPG substrates undergoes a drastic molecular rearrangement and surface reconstruction upon iodine doping. The structural rearrangement leads to morphological changes and higher surface roughness in iodine doped PbPc (I-PbPc) films. The obvious enhancement in the current values of I-PbPc is attributed to the introduction of holes as charge carriers. Nanoscale current mapping reveals the presence of percolation pathways in I-PbPc films, on both Si and HOPG substrates, being responsible for the observed high conductance in contrast to the isolated conducting domains in the pristine PbPc system. The broad distribution of current values across various conducting domains on Si is attributed to a mixture of crystalline phases and disordered fractions of I-PbPc, while the narrow distribution of current values observed in the case of HOPG arises from the majorly disordered PbPc molecules. These films also show enhanced sensitivity towards ammonia that is almost four times higher in magnitude than for pristine PbPc films. The current maps show that the adsorption of ammonia molecules disrupts the iodine percolation pathways, thereby imposing a detrimental effect on the conductivity of the PbPc films.

Effect of Graphene and MoS2 Flakes in Industrial Oils to Enhance Lubrication.

Tribological studies of the 2D nanoadditives such as MoS2 and graphene are mostly performed in base oils such as SN500, SN150, or paraffin. We have focused on their effect in lubrication properties of industrial oils (e.g., axle, transmission, and compressor oils) along with SN500 oil employing a four-ball tester. Two types of graphene powders (GpowA with fewer defects than GpowC), MoS2 powder, and their physical mixtures are chosen as nanoadditives. The tribology performance for 0.05 wt% of additives in various industrial oils is evaluated by monitoring the coefficient of friction (COF) during rubbing and wear scar diameter (WSD) of the steel balls after rubbing. Elemental analysis and electron microscopy have been performed on the wear surfaces for evidence of any tribofilm formation. GpowA favors antifriction for axle and transmission oils with 40% reduction in axle oil, whereas it improved antiwear properties in most of the oils. GpowC shows a COF decrement by 12% only for compressor oil, but contribute to wear reduction in all oils. The observed COF reduction is attributed to the compatibility of nonfunctionalized GpowA with nonpolar axle oil and functionalized GpowC with polar compressor oil. MoS2 shows a decrease in the COF and WSD in most industrial oils; the best being 60% COF and 7% WSD reduction in axle oil. For additives in oils that favor antiwear, flakes or particles are observed on the wear surface supported by the higher elemental contribution of the constituents from the wear region. The mixtures of GpowA or C with MoS2, however, does not seem to favor improvement in the COF or WSD in industrial oils. With assistance from oleylamine surfactants, the lubrication properties of most additives are improved, particularly for the mixtures with 12-15% COF reduction and 4-7% WSD reduction in compressor oil. The study indicates that a large sheet size of high-quality graphene aids antifriction and addition of surfactant molecules facilitates a co-operative effect between MoS2 and graphene for improved tribology.

Single sea urchin-MoO3 nanostructure for surface enhanced Raman spectroscopy of dyes.

Enhancing the surface-enhanced Raman scattering (SERS) activity of semiconductor metal oxide nanostructures by controlling the morphology and oxygen vacancies towards trace detection of organics is of significant interest. In this study, MoO3 with a novel sea urchin morphology is synthesized employing chemical bath deposition and consists of hundreds of ∼15 µm long spikes originating from the core forming 20-40 micron globular structures. The spikes taper to form 20 nm sharp tips. SERS of rhodamine 6G (R6G) over MoO3 sea urchins has been investigated and compared to that of 1D h-MoO3 nanorod arrays. The SERS activity is morphology dependent and the sea urchin-like morphology exhibits higher SERS activity with an enhancement factor (EF) of the order 105 and a detection limit of 100 nM, while for h-MoO3 nanorods, the corresponding values are 103 and 1 µM, respectively. X-ray photoelectron spectroscopy reveals a high concentration of Mo+5 states in sea urchins indicating lattice oxygen vacancies. The observed EF is quite high for a metal oxide substrate and is attributed to the enhanced charge transfer between analyte molecules and the substrate promoted by the oxygen vacancies along with surface defects and hydroxyl groups on MoO3 sea urchins providing more active sites for the adsorption of probe molecules. The role of oxygen vacancies is confirmed by the lower EF value exhibited by the stoichiometric 1D h-MoO3. Raman mapping of a single sea urchin is achieved with good R6G intensity and indicates that the tips of spiky features are involved in SERS enhancement. The reusability of substrates is shown for repeated cycles of R6G adsorption by UV irradiation exploiting the photocatalytic activity of MoO3 nanostructures.

Designing Metallic MoO2 Nanostructures on Rigid Substrates for Electrochemical Water Activation.

In situ growth of metallic MoO2 films on fluorine-doped tin oxide (FTO) and MoO2 powder in solution was achieved simultaneously by a simple hydrothermal process employing citric acid as the surfactant. The growth mechanism of MoO2 nanostructures (NSs) at the heterogeneous interface and in homogeneous medium proceeds in a different manner in which seeds grow in a preferred orientation on FTO, whereas they propagate in all directions in solution. The high lattice matching of FTO and MoO2 favours the film growth which could not be obtained on other conventional substrates. The disc morphology of MoO2 nanostructures was changed to other diverse morphology by varying the synthesis conditions, particularly by the addition of nitric acid. A competitive effect of nitric acid and citric acid on the structure direction produced various shapes. The electrochemical water activation studies show that hydrogen-annealed MoO2 is an excellent hydrogen evolution reaction (HER) catalyst with good stability. H-MoO2 film/FTO displays a low onset overpotential of72 mV with a Tafel slope of 84.1 mV dec-1 , whereas the powder form exhibits an onset overpotential of 46 mV with a Tafel slope of 71.6 mV dec-1 . The large active surface area, exposure of fringe facets of (110) and the lesser electrochemical charge-transfer resistance offered by the hydrogen-annealed MoO2 NSs play a major role in the enhanced HER activity.

Improved surface-enhanced Raman and catalytic activities of reduced graphene oxide-osmium hybrid nano thin films.

Reduced graphene oxide-osmium (rGO-Os) hybrid nano dendtrites have been prepared by simple liquid/liquid interface method for the first time. The method involves the introduction of phase-transfered metal organic precursor in toluene phase and GO dispersion in the aqueous phase along with hydrazine hydrate as the reducing agent. Dendritic networks of Os nanoparticles and their aggregates decorating rGO layers are obtained. The substrate shows improved catalytic and surface-enhanced activities comparable with previous reports. The catalytic activity was tested for the reduction of p-nitroaniline into p-phenyldiamine with an excess amount of NaBH4. The catalytic activity factors of these hybrid films are 2.3 s-1 g-1 (Os film) and 4.4 s-1 g-1 (rGO-Os hybrid film), which are comparable with other noble metal nanoparticles such as Au, Ag, but lower than Pd-based catalysts. Surface-enhanced Raman spectroscopy (SERS) measurements have been done on rhodamine 6G (R6G) and methylene blue dyes. The enhancement factor for the R6G adsorbed on rGO-Os thin film is 1.0 × 105 and for Os thin film is 7 × 103. There is a 14-fold enhancement observed for Os hybrids with rGO. The enhanced catalytic and SERS activities of rGO-Os hybrid thin film prepared by simple liquid/liquid interface method open up new challenges in electrocatalytic application and SERS-based detection of biomolecules.

Films of Reduced Graphene Oxide with Metal Oxide Nanoparticles Formed at a Liquid/Liquid Interface as Reusable Surface Enhanced Raman Scattering Substrates for Dyes.

Free standing, thin films of reduced graphene oxide (rGO) with ZnO, CuO and SnO(2) nanostructures are prepared at a water/toluene interface utilizing simple interfacial reaction and self-assembly. rGO-ZnO, rGO-CuO and rGO-SnO(2) films exhibit unique morphologies such as hexagonal cylinders, elongated splinters, and balls, respectively, wrapped by rGO layers. The hybrid films exhibit surface enhanced Raman scattering (SERS) of rhodamine 6G dye with enhancement factors one order higher than bare metal oxide caused by a synergic effect of charge transfer between the dye, metal oxide and rGO. Doping with Ag+ ions improves SERS enhancement in rGO-Ag­ZnO hybrid films, exploiting the electromagnetic effect of metal surface plasmons. Detection sensitivity up to 10 µM dye with an enhancement factor of 104 is shown. The enhanced photodegradation rate by the hybrid films is utilized for UV induced regeneration of the used SERS substrate and is demonstrated for successive use of different analytes.

Hybrid materials of ZnO nanostructures with reduced graphene oxide and gold nanoparticles: enhanced photodegradation rates in relation to their composition and morphology.

Binary and ternary hybrid systems of ZnO possessing nanoparticle and nanorod morphologies on reduced graphene oxide (rGO) and rGO with Au nanoparticles are explored as photocatalysts and a comparative study of their photodegradation performance is presented. Various preparation methods such as solution phase and hydrothermal routes have been employed to produce rGO-ZnO hybrids and rGO-Au-ZnO hybrids to impart different morphologies and defect states in ZnO. All the hybrids exhibit faster photodegradation kinetics and the rGO-Au-ZnO system exhibits the highest rate, five times faster than bare ZnO, followed by the binary systems, rGO-ZnO nanoparticles and nanorods. Various factors such as structure, morphology, charge transfer and adsorption are considered to explain the observed kinetics. Excited state electron transfer from ZnO to both rGO and Au levels facilitates faster dye degradation for rGO-Au-ZnO and is reflected as highly quenched band edge and defect state photoluminescence. Intimate physical interfaces formed between rGO, Au and ZnO in the hybrid material during in situ reactions favour charge transfer across the components. The charge transfer contribution even dominates the adsorption factor and the rGO-Au-ZnO system with a slightly lower adsorption capacity than the rGO-ZnO system exhibits a higher degradation rate. A power law dependence of the photodegradation rate on light intensity is also expressed.

Cellular network formation of hydrophobic alkanethiol capped gold nanoparticles on mica surface mediated by water islands.

Dendritic and cellular networks of nanoparticles are known to form commonly either by random diffusion-limited aggregation or by solvent evaporation dynamics. Using alkanethiol capped gold nanoparticles deposited on mica imaged under ambient and controlled water vapor conditions by atomic force microscope and in situ scanning electron microscope, respectively, we show a third mechanism in action. The cellular network consisting of open and closed polygons is formed by the nucleation and lateral growth of adsorbed water islands, the contact lines of which push the randomly distributed hydrophobic nanoparticles along the growth directions, eventually leading to the polygonal structure formation as the boundaries of the growing islands meet. Such nanoparticle displacement has been possible due to the weakly adhering nature of the hydrophilic substrate, mica. These results demonstrate an important but hitherto neglected effect of adsorbed water in the structure formation on hydrophilic substrates and provide a facile tool for the fabrication of nanoparticle networks without specific particle or substrate modifications and without a tight control on particle deposition conditions during the solvent evaporation.

Evolution of surface morphology with introduction of stacking faults in zeolites.

This paper sets out to try to determine some of the nanoscopic details of template action in zeolites. The problem has been addressed by monitoring the effects of competitive templating using, in particular, atomic force microscopy and high-resolution scanning electron microscopy. Using these techniques, it is possible to determine the subtle crystal growth changes that occur as a result of altering the concentration of these competitive templating agents. This work concerns the two important intergrowth systems MFI-MEL and FAU-EMT. It was found that some organic templating agents provide much greater structure-directing specificity. So much so in the case of the MFI-MEL system that a 2 mol% doping with the highly specific tetrapropylammonium cation drastically changes the fundamental growth processes. Furthermore, the effect of template crowding is shown to reduce specificity. This work shows how extensive frustrated intergrowth structures can still be accommodated within a nominal zeolite single crystal.