Operando Spectroscopy Observation of Mo Clusters-Ti3 C2 TX Catalyst/Support Interface's Dynamic Evolution in Hydrogen Evolution Reaction.

The interaction between catalyst and support plays an important role in electrocatalytic hydrogen evolution (HER), which may explain the improvement in performance by phase transition or structural remodeling. However, the intrinsic behavior of these catalysts (dynamic evolution of the interface under bias, structural/morphological transformation, stability) has not been clearly monitored, while the operando technology does well in capturing the dynamic changes in the reaction process in real time to determine the actual active site. In this paper, nitrogen-doped molybdenum atom-clusters on Ti3 C2 TX (MoACs /N-Ti3 C2 TX ) is used as a model catalyst to reveal the dynamic evolution of MoAcs on Ti3 C2 TX during the HER process. Operando X-ray absorption structure (XAS) theoretical calculation and in situ Raman spectroscopy showed that the Mo cluster structure evolves to a 6-coordinated monatomic Mo structure under working conditions, exposing more active sites and thus improving the catalytic performance. It shows excellent HER performance comparable to that of commercial Pt/C, including an overpotential of 60 mV at 10 mA cm-2 , a small Tafel slope (56 mV dec-1 ), and high activity and durability. This study provides a unique perspective for investigating the evolution of species, interfacial migration mechanisms, and sources of activity-enhancing compounds in the process of electroreduction.

Chemical effects in SERS of pyrazine adsorbed on Au-Pd bimetallic nanoparticles: a theoretical investigation.

Chemical enhancement in surface-enhanced Raman scattering (SERS) of pyrazine adsorbed on Au-Pd nanoclusters is investigated by using density functional theory. Changing Pd content in the bimetallic clusters enables modulation of the direct chemical interactions between the pyrazine and the clusters. The magnitude of chemical enhancement is correlated well with the induced polarizability for the complexes with low Pd content, which fails for the complexes with high Pd content. Furthermore, the dependence of chemical enhancement on cluster size and coupling is also described by the induced polarizability. Additionally, the chemical enhancement in the cluster-molecule-cluster junction is found to account for as much as 10(3), which suggests that a chemical mechanism might be more important than previously believed, in particular for Au-Pd bimetallic nanoparticle aggregates.

In situ identification of the adsorption of 4,4'-thiobisbenzenethiol on silver nanoparticles surface: a combined investigation of surface-enhanced Raman scattering and density functional theory study.

We investigated the configuration characteristic and adsorption behavior of 4,4'-thiobisbenzenethiol (TBBT) on the surface of silver nanoparticles (NPs). Under different conditions and preparation processes, several possible surface species were produced including single-end adsorption on a silicon wafer, double-end adsorption and bridge-like adsorption. Although consisting of the same molecule and nano material, different adsorption systems exhibited different spectral characteristics in the surface-enhanced Raman spectroscopy (SERS). A density functional theory (DFT) study further verified the corresponding adsorption states. The combined SERS-DFT study provided a framework towards investigating and designing adsorption systems at a molecular level, indicating the potential use in applications such as nano-sensors.

[Preparation of Au@SiO2 core-shell nanoparticles: controlling the optical properties].

The authros developed a new approach to preparing the Au@SiO2 core-shell nanostructure. The morphology and stability of the composite were characterized by the UV-Vis absorption spectroscopy and transmission electron microscopy (TEM) methods. The stable SERS spectra were obtained from the PMBA-functionalized Au@SiO2 composite. In addition, the authros succeeded in adjusting the thickness of SiO2 layer by controlling the precursor consumption. The stability of Au@SiO2 in basic solution was studied and the results showed that the SiO2 shell was facile to be etched. The present work may provide a reference and gist for research on the preparation, storage and application of Au@SiO2.

A DFT investigation of surface-enhanced Raman scattering of adenine and 2'-deoxyadenosine 5'-monophosphate on Ag20 nanoclusters.

We present a detailed analysis of the surface-enhanced Raman scattering (SERS) of adenine and 2'-deoxyadenosine 5'-monophosphate (dAMP) adsorbed on an Ag(20) cluster by using density functional theory. Calculated Raman spectra show that spectral features of all complexes depend greatly on adsorption sites of adenine and dAMP. The complexes consisting of adenine adsorbed on the Ag(20) cluster through N3 reproduce the measured SERS spectra in silver colloids, and thus demonstrated that adenine interacts with the silver surface via N3. We also investigate the SERS spectrum of adenine at the junction between two Ag(20) clusters and demonstrate that adenine can bind to the clusters through N3 and the external amino group, while dAMP can be adsorbed on the cluster in an end-on orientation with the ribose and phosphate groups near to or away from the silver cluster. In contrast to the adenine-Ag(20) complexes, the dAMP-Ag(20) complexes produce new and strong bands in the low- or high-wavenumber region of the Raman spectra, due to vibrations of the ribose and phosphate groups. Furthermore, the spectrum of dAMP bound to the Ag(20) cluster via N7 approaches the experimental SERS spectra on silver colloids.

Controlled dispersion of silver nanoparticles into the bulk of thermosensitive polymer microspheres: tunable plasmonic coupling by temperature detected by surface enhanced Raman scattering.

By in situ reduction of Ag(+) ions pre-dispersed inside thermosensitive microspheres of poly[(N-isopropylacrylamide)-co-(methacrylic acid)] (P(NIPAM-co-MAA)), a 3D copolymer-supported network of silver nanoparticles is created and extensively characterized by surface-enhanced Raman scattering (SERS). The effective dispersion and the suitable density of the silver nanoparticles in the composite microspheres are demonstrated by the thermal-induced SERS signal and its high reproducibility during thermocycling. When the temperature of the system increases above 32 °C, spatial separation of the silver nanoparticles decreases and the numbers of Ag nanoparticles and P(NIPAM-co-MAA) microspheres under illumination spot increase as a result of the shrinkage of the P(NIPAM-co-MAA) chains, leading to the ramp of the SERS effect. By means of the high reversibility of the thermosensitive phase transition of the P(NIPAM-co-MAA) microspheres, SERS activity of the silver nanoparticle network embedded in the microsphere can be well controlled by thermal-induced variation of special separation.

Surface-enhanced Raman spectroscopy with self-assembled cobalt nanoparticle chains: Comparison of theory and experiment.

The surface-enhanced Raman scattering (SERS) properties of 4-aminothiophenol (PATP) adsorbed on self-assembled cobalt nanoparticle chains have been investigated. Based on the density functional theory (DFT), the experimental results were in good agreement with the calculated values of the characteristic bands both for normal Raman and SERS spectra. The enhancement factor (EF) of 10(4)-10(5) indicated that high quality of surface Raman signals could be obtained, which was consistent with discrete-dipole approximation (DDA) calculation results. The SERS substrate may be helpful for extending SERS to transition metals and offering some promising applications of SERS in the future.

First-principles characterization of the anisotropy of theoretical strength and the stress-strain relation for a TiAl intermetallic compound.

We perform first-principles computational tensile and compressive tests (FPCTT and FPCCT) to investigate the intrinsic bonding and mechanical properties of a γ-TiAl intermetallic compound (L 1(0) structure) using a first-principles total energy method. We found that the stress-strain relations and the corresponding theoretical tensile strengths exhibit strong anisotropy in the [001], [100] and [110] crystalline directions, originating from the structural anisotropy of γ-TiAl. Thus, γ-TiAl is a representative intermetallic compound that includes three totally different stress-strain modes. We demonstrate that all the structure transitions in the FPCTT and FPCCT result from the breakage or formation of bonds, and this can be generalized to all the structural transitions. Furthermore, based on the calculations we qualitatively show that the Ti-Al bond should be stronger than the Ti-Ti bond in γ-TiAl. Our results provide a useful reference for understanding the intrinsic bonding and mechanical properties of γ-TiAl as a high-temperature structural material.

[Structural and optical characterization of ZnO thin films grown by plasma-assisted molecular beam epitaxy].

High-quality ZnO thin films were grown by plasma-assisted molecular beam epitaxy (P-MBE) on Al2 O3 (0001) substrate with a low temperature ZnO buffer layer. Structural and optical characterization were studied for ZnO thin films. Only a peak at (0002) were observed in the X-ray reflectivity (XRD) spectra with the full-width at half maximum (FWHM) value 0.18 degrees, and two peaks 1LO (579 cm(-1)) and 2LO (1 152 cm(-1)) were detected in the resonance Raman scattering spectra at room temperature. These results indicated that ZnO thin films had single orientation of c axis and high-quality of crystal wurtzite structure. The absorption of free-exciton and exciton-LO phonon appeared in the absorption spectra, which confirmed that the exciton state in the ZnO thin films were stable even at room temperature. And the energy spacing between these two peaks is 71.2 meV, corresponds to the longitudinal optical phonon energy of 71 meV of ZnO. Besides, from the photoluminescence spectra, no defect-related deep emission were observed, but just a remarkable free-exciton emission located at 376nm were obtained at room temperature, it proved that the ZnO thin films had high-quality but low density of defect.

Fabrication of a Flexible Gold Nanorod Polymer Metafilm via a Phase Transfer Method as a SERS Substrate for Detecting Food Contaminants.

Surface enhanced Raman scattering (SERS) has been widely used in detection of food safety due to the nondestructive examination property. Here, we reported a flexible SERS film based on a polymer-immobilized gold nanorod polymer metafilm. Polystyrene-polyisoprene-polystyrene (SIS), a transparent and flexible, along with having excellent elasticity, polymer, was chosen as the main support of gold nanorods. A simple phase transfer progress was adopted to mix the gold nanorods with the polymer, which can further be used in most water-insoluble polymers. The SERS film performed satisfactorily while being tested in a series of standard Raman probes, like crystal violet (CV) and malachite green (MG). Moreover, the excellent reproducibility and elastic properties make the film a promising substrate in practical detection. Hence, the MG detection on the fish surface and trace thiram detection on orange pericarp were inspected with detection results of 1 × 10-10 and 1 × 10-6 M, which were below the demand of the National standard of China, exactly matching the realistic application requirements.

Rapid fabrication of flexible and transparent gold nanorods/poly (methyl methacrylate) membrane substrate for SERS nanosensor application.

Flexible substrates have been proposed for daily-life applications in SERS detection due to the prominent sample collection properties such as they can be wrapped around non-planar object surface. Combining the noble metals with polymers, flexible SERS substrates could be fabricated with advantages of light weight, transparency and high SERS sensitivity. Herein, we prepare a gold nanorods (AuNRs)/poly(methyl methacrylate) (PMMA) film as flexible SERS substrate by self-assembling a uniformly AuNRs array layer on PMMA template. This AuNRs/PMMA film performs excellently on thiram trace detection with the lowest detection concentration of 0.5 ppb. The fabricated substrates were applied for practical detection with cucumber by directly covering the AuNRs/PMMA flexible film on the target surface. Furthermore, the high SERS sensitivity as well as great reproducibility present a wide range of prospections for the further application of non-plane surface.

Interfacial synthesis of a three-dimensional hierarchical MoS2-NS@Ag-NP nanocomposite as a SERS nanosensor for ultrasensitive thiram detection.

Interfacial self-assembly of ordered nanostructures at oil-water interfaces towards the fabrication of nanofilms has attracted the interest of plenty of scientists, since its discovery in 2004. Herein, further developments have been achieved, and we report a new strategy for the synthesis of a three-dimensional (3D) hierarchical nanostructure, through an interfacial synthesis driven microemulsion process. Thus, the synthesis route has been simplified, with the rigorous experimental conditions of traditional compositing technology. Combined with a two-step seed-mediated growth method for preparing uniform Ag-NPs, a plasmonic 3D MoS2-NS@Ag-NP nanostructure was successfully developed as a Surface-Enhanced Raman Scattering (SERS) active substrate, with plenty of surface hot spots, leading to an enhancement factor (EF) of 1.2 × 108 derived from both electromagnetic mechanism (EM) and chemical mechanism (CM) effects. The 3D MoS2-NS@Ag-NP nanostructure can be applied to detect trace thiram in apple juice and local lake water, with a detection limit as low as 10 ppb (42 nM), which is much lower than the maximal residue limit (MRL) of 7 ppm in fruit prescribed by the U.S. Environmental Protection Agency (EPA). Furthermore, quantitative analysis was achieved in the range of 10 ppb-1 ppm with good homogeneity and selectivity.

Fabrication of Reduced Graphene Oxide (RGO)/Co3 O4 Nanohybrid Particles and a RGO/Co3 O4 /Poly(vinylidene fluoride) Composite with Enhanced Wave-Absorption Properties.

Reduced graphene oxide (RGO)/Co3 O4 nanohybrid particles, composed of reduced graphite oxide and Co3 O4 particles, have been fabricated by an in situ growth method under mild wet-chemical conditions (140 °C). A series of characterization results indicate that the as-prepared Co3 O4 particles with relatively uniform sizes are embedded in RGO layers to form unique core-shell nanostructures. The RGO/Co3 O4 /poly(vinylidene fluoride) composite was found to possess excellent absorption properties. Owing to the effect of the negative permeability, the position of the absorption peaks remains at the same frequency at different thicknesses without shifting to lower frequencies. For the composites with a filler loading of 10 wt %, the maximum peaks can reach -25.05 dB at 11.6 GHz with a thickness of 4.0 mm. These enhanced microwave absorbing properties can be explained based on the structures of the nanohybrid particles.

Three dimensional design of large-scale TiO(2) nanorods scaffold decorated by silver nanoparticles as SERS sensor for ultrasensitive malachite green detection.

We have designed a large-scale three-dimensional (3D) hybrid nanostructure as surface-enhanced Raman scattering (SERS) sensor by decorating silver nanoparticles on TiO2 nanorods scaffold (Ag/TiO2). Taking p-mercaptobenzoic acid (PMBA) as the probe molecule, the SERS signals collected by point-to-point and time mapping modes show that the relative standard deviation (RSD) in the intensity of the main Raman vibration modes (1079, 1586 cm(-1)) is less than 10%, demonstrating good spatial uniformity and time stability. This hybrid substrate also exhibits excellent SERS enhancement effect due to the formation of high-density hot spots among the AgNPs, which was proved by finite-difference time-domain (FDTD) simulations. The application of the new nanostructures as SERS sensors was demonstrated with the detection of malachite green (MG). The quantification of MG can be accomplished with the detection limit of 1 × 10(-12) M based on the Raman intensity. The results show that the Ag/TiO2 nanostructure can be a promising candidate for SERS sensor.

Quantitative analysis of mononucleotides by isotopic labeling surface-enhanced Raman scattering spectroscopy.

A novel surface-enhanced Raman scattering (SERS) approach for accurate quantification of mononucleotides of deoxyribonucleic acid (DNA) is described. Reproducible SERS measurement was achieved by using isotopically labeled internal standard. By measuring the SERS spectra of mononucleotides and its isotope internal standard in combination with multivariate data analysis, the method was successfully applied to quantify mononucleotides. The independent validation of analyte concentrations gave a standard deviation of within 2%, which is comparable to HPLC result. Finally, a mixture of four mononucleotides of DNA was prepared to explore the possibility of quantifying the concentration of label-free, sequence-specific DNA strands by this approach. As compared to liquid chromatography/mass spectrometry (LC/MS), our method can be similarly precise but the SERS measurement is simple, rapid and potentially cheap.

A highly regular hexapod structure of lead sulfide: solution synthesis and Raman spectroscopy.

A highly regular hexapod-like structure of PbS with six symmetric arms has been synthesized by a simple and mild chemical solution route. The hexapod-like PbS structure was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution TEM (HRTEM). The results show that each arm is perpendicular to the other four, and opposite to the last one. The arms are about 0.3-0.6 microm long, which have about 40-60 nm tips and 150-200 nm base. And the arm shows an icicle-like structure and some clear steps, and grows along 100 directions. The most possible growth mechanism discussed herein is based on the characterization results. The Raman spectra of the hexapod-like PbS structure were investigated. The results show that our products are sensitive to the laser and can be photodegraded easily.

Structures and stability of N13+ and N13- clusters.

The structures and stabilities of eleven N13+ and N13- isomers have been investigated with second-order Moller-Plesset (MP2) and density functional theory (DFT) methods. Five N13+ isomers and six N13- isomers are all reasonable local minima on their potential energy hypersurfaces. The most stable N13+ cation is structure C-2 with C2v symmetry, which contains a pentazole ring and two N4 open chains. It is different from those of the N7+ and N9+ clusters, but similar to the N11+ cluster. Meanwhile, the most stable N13- structure A-2 is composed of a pentazole ring and a six-membered ring connected by two nitrogen atoms. It is not only different from those of the N7- and N9- clusters, but also from the N11- cluster. The decomposition pathways of structures C-2 and A-2 were investigated at the B3LYP/(aug)-cc-pVDZ level. From the barrier heights of the structures C-2 and A-2 decomposition processes, it is suggested that C-2 is difficult to observe experimentally and A-2 may be observed as a short-lived species.