Microwave-assisted green synthesis of Ag/reduced graphene oxide nanocomposite as a surface-enhanced Raman scattering substrate with high uniformity

A nanocomposite of silver nanoparticles/reduced graphene oxide (Ag/rGO) has been fabricated as a surface-enhanced Raman scattering (SERS) substrate owing to the large surface area and two-dimensional nanosheet structure of rGO. A facile and rapid microwave-assisted green route has been used for the formation of Ag nanoparticles and the reduction of graphene oxide simultaneously with L-arginine as the reducing agent. By increasing the cycle number of microwave irradiation from 1 and 4 to 8, the mean diameters of Ag nanoparticles deposited on the surface of rGO increased from 10.3 ± 4.6 and 21.4 ± 10.5 to 41.1 ± 12.6 nm. The SERS performance of Ag/rGO nanocomposite was examined using the common Raman reporter molecule 4-aminothiophenol (4-ATP). It was found that the Raman intensity of 4-ATP could be significantly enhanced by increasing the size and content of silver nanoparticles deposited on rGO. Although the Raman intensities of D-band and G-band of rGO were also enhanced simultaneously by the deposited Ag nanoparticles which limited the further improvement of SERS detection sensitivity, the detectable concentration of 4-ATP with Ag/rGO nanocomposite as the SERS substrate still could be lowered to be 10⁻¹⁰ M and the enhancement factor could be increased to 1.27 × 10¹⁰. Furthermore, it was also achievable to lower the relative standard deviation (RSD) values of the Raman intensities to below 5%. This revealed that the Ag/rGO nanocomposite obtained in this work could be used as a SERS substrate with high sensitivity and homogeneity.     

Large-area high-performance SERS substrates with deep controllable sub-10-nm gap structure fabricated by depositing Au film on the cicada wing

Noble metal nanogap structure supports strong surface-enhanced Raman scattering (SERS) which can be used to detect single molecules. However, the lack of reproducible fabrication techniques with nanometer-level control over the gap size has limited practical applications. In this letter, by depositing the Au film onto the cicada wing, we engineer the ordered array of nanopillar structures on the wing to form large-area high-performance SERS substrates. Through the control of the thickness of the Au film deposited onto the cicada wing, the gap sizes between neighboring nanopillars are fine defined. SERS substrates with sub-10-nm gap sizes are obtained, which have the highest average Raman enhancement factor (EF) larger than 2 × 10⁸, about 40 times as large as that of commercial Klarite® substrates. The cicada wings used as templates are natural and environment-friendly. The depositing method is low cost and high throughput so that our large-area high-performance SERS substrates have great advantage for chemical/biological sensing applications.     

Plasmonic Effects of Infiltrated Silver Nanoparticles Inside TiO2 Film: Enhanced Photovoltaic Performance in DSSCs

The plasmonic effects of infiltrated silver (Ag) nanoparticles, with different contents, inside a nanostructured TiO₂ film on the photovoltaic performance of dye‐sensitized solar cells (DSSCs) are explored. The synthesized Ag nanoparticles are immobilized onto deposited TiO₂ nanoparticles by a new strategy using 3‐mercaptopropionic acid (MPA), a bifunctional linker molecule. Transmission electron microscope (TEM) images show that monodispersed Ag and polydispersed TiO₂ nanoparticles have an average diameter of 12 ± 3 nm and 5 ± 1 nm, respectively. Moreover, Fourier transform infrared spectroscopy (FTIR) analysis reveals that Ag nanoparticles were successfully functionalized and capped with MPA. Optical studies on the MPA‐capped Ag nanoparticles inside TiO₂ film show an increase in the total absorbance of the electrode. Moreover, EIS measurements confirm that MPA‐capped Ag nanoparticles inhibit the charge recombination and improve the stability of nanoparticles in I₃^?/I^? electrolyte. The DSSC assembled with optimal content of MPA‐capped Ag nanoparticles demonstrated an enhanced power conversion efficiency (8.82% ± 0.07%) compared with the pure TiO₂ (7.30% ± 0.05%). The increase in cell efficiency was attributed to the enhanced dye light absorption in strength and spectral range due to the surface plasmon resonance of MPA‐capped Ag nanoparticles in the photoanode.     

Facile synthesis of mesoporous Ag-loaded TiO2 thin film and its photocatalytic properties

Ag nanoparticles highly dispersed into TiO₂ thin films are synthesized via a remarkably simple one-pot route in the presence of a P123 triblock copolymer as template directing and reducing agents, where the reduction of Ag⁺ to Ag⁰ by in situ heat-induced reduction through the oxidation of template at 400 °C and the controlled polymerization of TiO₂ take place simultaneously. The obtained mesoporous Ag/TiO₂ films deposited on soda-lime glass were optically transparent and crack-free. SEM and Kr adsorption clearly prove that Ag/TiO₂ films at different Ag contents are mesoporous with large surface area and regularly ordered mesopores and the thickness of the obtained films is ∼280 ± 20 nm. The pristine TiO₂ film exhibits a specific surface area of 63 cm²/cm² and specific pore volume of 0.013 mm³/cm² that it is decreased to 42 cm²/cm² and 0.010 mm³/cm² respectively as a result of Ag-loaded mesoporous TiO₂. The newly prepared photocatalysts Ag/TiO₂ films were evaluated for their photocatalytic degradation of 2-chlorophenol as a model reaction. It was found that the meso-ordered Ag/TiO₂ films are more photoactive 8 times than nonporous commercial photocatalysts Pilkington Glass Activ™. The recycling tests indicated that Ag/TiO₂ films was quite stable during that liquid-solid heterogeneous photocatalysis since no significant decrease in activity was observed even after being used repetitively for 10 times, showing a good potential in practical application. In general, the cubic mesoporous Ag/TiO₂ nanocomposites are stable and can be recycled without loss of their photochemical activity.     

A hybrid Ag/TiO2 nanoarray-based in situ charge transfer toward multi-functional active-platform

Designing an efficient heteronanostructure array for surface-enhanced Raman scattering (SERS) to enable ultrasensitive and reproducible detection of analytes and degrading organic contaminants provides new perspectives for chemical and biological detection at trace levels and environmental remediation. Here, we design and fabricate a heterostructure consisting of Ag nanoparticles (NPs) in-situ grown on high-density arrays of vertical TiO₂ nanorods (NRs) (denoted Ag/TiO₂ NRs). As a result, compared with pristine TiO₂ NRs, the as-obtained Ag/TiO₂ NR substrate possesses a SERS activity for detecting rhodamine 6G (R6G) with a detection limit as low as 10⁻¹² M and an enhancement factor up to 1.2 × 10¹⁰. In addition, the substrate exhibits the highest degradation rates of R6G of 82% under illumination with visible light and an excellent self-cleaning effect under UV-assisted light. Such remarkable enhanced efficacy of the binary Ag/TiO₂ NRs nanocomposites may be attributed to the i) appropriate band alignment based on the synergistic effect of Ag decorated on TiO₂ NRs; ii) a large adhesion area and the localized surface plasmon resonance (LSPR) of Ag; and iii) high-density and engineering hotspots in the active platform. These properties make the heterostructure Ag/TiO₂ NR platform promising candidate for detecting analytes and photocatalytic applications.     

Synthesis and characterization of Au/TiO2 core-shell structure nanoparticles

Au/TiO₂ core-shell structure nanoparticles were synthesized by sol-gel process, and the morphology and crystallinity of TiO₂ shell were investigated by TEM and UV-vis absorption spectrometer. Au/TiO₂ core-shell structure nanoparticles could be prepared by the hydrolysis of TOAA (titanium oxide acethylacetonate) in gold sol ethanol solution with water. The thickness of TiO₂ shell on the surface of gold particles was about 1 nm. To investigate the crystallinity of TiO, shell, UV light with 254 nm and radioactive ray of⁶⁰Co were irradiated on the TiO₂-coated gold sol ethanol solution. The surface plasmon band of gold nanoparticles appeared only when the radioactive ray was irradiated on the TiO₂-coated gold sol ethanol solution. From these results, it was found that the TiO, shell was amorphous and the MUA (mercaptoundecanoic acid) layer on the Au particle for its dispersion in ethanol did not act as an obstacle to disturb the movement of electrons onto the surface of Au particles.     

Utilization of triangle nanosilver to prepare spherical nanosilver and quantitatively detect trace titanium by SERS

The blue triangle nanosilver (BAgNP) sol was prepared by the two reducers of NaBH₄ and H₂O₂. Using BAgNP as the precursor, a small spherical nanosilver (AgNP) sol in yellow was synthesized by addition of suitable amounts of X⁻ (X = Cl, Br, and I). The oxidization process of BAgNP to AgNP was studied in detail by resonance Rayleigh scattering (RRS), surface-enhanced Raman scattering (SERS), laser scattering, surface plasmon resonance (SPR) absorption, and microscope techniques. It has been observed that NaCl accelerated the oxidizing BAgNP to form AgNP, and an oxidizing mechanism and quasi-nanograting Raman-scattering enhanced mechanism were developed to explain the phenomena. Using the BAgNP sol as substrate and based on the catalysis of Ti(IV) on the BrO₃⁻ oxidizing safranine T (ST) molecular probe with a strong SERS peak at 1,535 cm⁻¹, a new catalytic SERS quantitative method was developed for the determination of 1.0 to 100 ng/mL Ti, with a detection limit of 0.4 ng/mL.     

Controlled fabrication of Sn/TiO2 nanorods for photoelectrochemical water splitting

In this work, we investigate the controlled fabrication of Sn-doped TiO₂ nanorods (Sn/TiO₂ NRs) for photoelectrochemical water splitting. Sn is incorporated into the rutile TiO₂ nanorods with Sn/Ti molar ratios ranging from 0% to 3% by a simple solvothermal synthesis method. The obtained Sn/TiO₂ NRs are single crystalline with a rutile structure. The concentration of Sn in the final nanorods can be well controlled by adjusting the molar ratio of the precursors. Photoelectrochemical experiments are conducted to explore the photocatalytic activity of Sn/TiO₂ NRs with different doping levels. Under the illumination of solar simulator with the light intensity of 100 mW/cm², our measurements reveal that the photocurrent increases with increasing doping level and reaches the maximum value of 1.01 mA/cm² at −0.4 V versus Ag/AgCl, which corresponds to up to about 50% enhancement compared with the pristine TiO₂ NRs. The Mott-Schottky plots indicate that incorporation of Sn into TiO₂ nanorod can significantly increase the charge carrier density, leading to enhanced conductivity of the nanorod. Furthermore, we demonstrate that Sn/TiO₂ NRs can be a promising candidate for photoanode in photoelectrochemical water splitting because of their excellent chemical stability.     

Enhanced resistive switching memory characteristics and mechanism using a Ti nanolayer at the W/TaOx interface

Enhanced resistive memory characteristics with 10,000 consecutive direct current switching cycles, long read pulse endurance of >10⁵ cycles, and good data retention of >10⁴ s with a good resistance ratio of >10² at 85°C are obtained using a Ti nanolayer to form a W/TiO_x/TaO_x/W structure under a low current operation of 80 μA, while few switching cycles are observed for W/TaO_x/W structure under a higher current compliance >300 μA. The low resistance state decreases with increasing current compliances from 10 to 100 μA, and the device could be operated at a low RESET current of 23 μA. A small device size of 150 × 150 nm² is observed by transmission electron microscopy. The presence of oxygen-deficient TaO_x nanofilament in a W/TiO_x/TaO_x/W structure after switching is investigated by Auger electron spectroscopy. Oxygen ion (negative charge) migration is found to lead to filament formation/rupture, and it is controlled by Ti nanolayer at the W/TaO_x interface. Conducting nanofilament diameter is estimated to be 3 nm by a new method, indicating a high memory density of approximately equal to 100 Tbit/in.².     

Thin and long silver nanowires self-assembled in ionic liquids as a soft template: electrical and optical properties

Thin and long silver nanowires were successfully synthesized using the polyvinylpyrrolidone (PVP)-assisted polyol method in the presence of ionic liquids, tetrapropylammonium chloride and tetrapropylammonium bromide, which served as soft template salts. The first step involved the formation of Ag nanoparticles with a diameter of 40 to 50 nm through the reduction of silver nitrate. At the growing stage, the Ag nanoparticles were converted into thin and long one-dimensional wires, with uniform diameters of 30 ± 3 nm and lengths of up to 50 μm. These Ag nanowires showed an electrical conductivity of 0.3 × 10⁵ S/cm, while the sheet resistance of a two-dimensional percolating Ag nanowire network exhibited a value of 20 Ω/sq with an optical transmittance of 93% and a low haze value.     

Near-infrared optical absorption enhanced in black silicon via Ag nanoparticle-induced localized surface plasmon

Due to the localized surface plasmon (LSP) effect induced by Ag nanoparticles inside black silicon, the optical absorption of black silicon is enhanced dramatically in near-infrared range (1,100 to 2,500 nm). The black silicon with Ag nanoparticles shows much higher absorption than black silicon fabricated by chemical etching or reactive ion etching over ultraviolet to near-infrared (UV-VIS-NIR, 250 to 2,500 nm). The maximum absorption even increased up to 93.6% in the NIR range (820 to 2,500 nm). The high absorption in NIR range makes LSP-enhanced black silicon a potential material used for NIR-sensitive optoelectronic device.

PACS

78.67.Bf; 78.30.Fs; 78.40.-q; 42.70.Gi     

Simple fabrication of N-doped mesoporous TiO2 nanorods with the enhanced visible light photocatalytic activity

N-doped mesoporous TiO₂ nanorods were fabricated by a modified and facile sol–gel approach without any templates. Ammonium nitrate was used as a raw source of N dopants, which could produce a lot of gasses such as N₂, NO₂, and H₂O in the process of heating samples. These gasses were proved to be vitally important to form the special mesoporous structure. The samples were characterized by the powder X-ray diffraction, X-ray photoelectron spectrometer, nitrogen adsorption isotherms, scanning electron microscopy, transmission electron microscopy, and UV-visible absorption spectra. The average length and the cross section diameter of the as-prepared samples were ca. 1.5 μm and ca. 80 nm, respectively. The photocatalytic activity was evaluated by photodegradation of methylene blue (MB) in aqueous solution. The N-doped mesoporous TiO₂ nanorods showed an excellent photocatalytic activity, which may be attributed to the enlarged surface area (106.4 m² g^-1) and the narrowed band gap (2.05 eV). Besides, the rod-like photocatalyst was found to be easy to recycle.     

Silver(I)-directed growth of metal-organic complex nanocrystals with bidentate ligands of hydroquinine anthraquinone-1,4-diyl diethers as linkers at the water-chloroform interface

Immiscible liquid-liquid interfaces provide unique double phase regions for the design and construction of nanoscale materials. Here, we reported Ag(I)-directed growth of metal-organic complex nanocrystals by using AgNO₃ as a connector in the aqueous solution and bidentate ligand of 1,4-bis(9-O-dihydroquininyl)anthraquinone [(DHQ)₂AQN] and its enantiomer of (DHQD)₂AQN in the chloroform solutions as linkers. The Ag-(DHQ)₂AQN and Ag-(DHQD)₂AQN complex nanocrystals were formed at the liquid-liquid interfaces and characterized by using UV-vis absorption and fluorescence spectroscopy and X-ray photoelectron spectroscopy, as well as by using scanning electron microscopy. Screw-like nanocrystals were formed at the initial 30 min after the interfacial coordination reaction started, then they grew into nanorods after several days, and finally became cubic microcrystals after 2 weeks. The pure ligand showed two emission bands centered at about 363 and 522 nm in the methanol solution, the second one of which was quenched and shifted to about 470 nm in the Ag-complex nanocrystals. Two couples of reversible redox waves were recorded for the Ag-complex nanocrystals; one centered at about -0.25 V (vs. Ag/AgCl) was designated to one electron transfer process of Ag - (DHQ)₂AQN and Ag - (DHQ)₂AQN⁺, and the other one centered at about 0.2 V was designated to one electron transfer process of Ag - (DHQ)₂AQN and Ag⁺ - (DHQ)₂AQN.     

CNT@TiO2 nanohybrids for high-performance anode of lithium-ion batteries

This work describes a potential anode material for lithium-ion batteries (LIBs), namely, anatase TiO₂ nanoparticle-decorated carbon nanotubes (CNTs@TiO₂). The electrochemical properties of CNTs@TiO₂ were thoroughly investigated using various electrochemical techniques, including cyclic voltammetry, electrochemical impedance spectroscopy, galvanostatic cycling, and rate experiments. It was revealed that compared with pure TiO₂ nanoparticles and CNTs alone, the CNT@TiO₂ nanohybrids offered superior rate capability and achieved better cycling performance when used as anodes of LIBs. The CNT@TiO₂ nanohybrids exhibited a cycling stability with high reversible capacity of about 190 mAh g^-1 after 120 cycles at a current density of 100 mA g^-1 and an excellent rate capability (up to 100 mAh g^-1 at a current density of 1,000 mA g^-1).     

Plasmonic Core–Shell–Satellites with Abundant Electromagnetic Hotspots for Highly Sensitive and Reproducible SERS Detection

In this work, we develop a Ag@Al₂O₃@Ag plasmonic core–shell–satellite (PCSS) to achieve highly sensitive and reproducible surface-enhanced Raman spectroscopy (SERS) detection of probe molecules. To fabricate PCSS nanostructures, we employ a simple hierarchical dewetting process of Ag films coupled with an atomic layer deposition (ALD) method for the Al₂O₃ shell. Compared to bare Ag nanoparticles, several advantages of fabricating PCSS nanostructures are discovered, including high surface roughness, high density of nanogaps between Ag core and Ag satellites, and nanogaps between adjacent Ag satellites. Finite-difference time-domain (FDTD) simulations of the PCSS nanostructure confirm an enhancement in the electromagnetic field intensity (hotspots) in the nanogap between the Ag core and the satellite generated by the Al₂O₃ shell, due to the strong core–satellite plasmonic coupling. The as-prepared PCSS-based SERS substrate demonstrates an enhancement factor (EF) of 1.7 × 10⁷ and relative standard deviation (RSD) of ~7%, endowing our SERS platform with highly sensitive and reproducible detection of R6G molecules. We think that this method provides a simple approach for the fabrication of PCSS by a solid-state technique and a basis for developing a highly SERS-active substrate for practical applications.     

Efficiency enhancements in Ag nanoparticles-SiO2-TiO2 sandwiched structure via plasmonic effect-enhanced light capturing

TiO₂-SiO₂-Ag composites are fabricated by depositing TiO₂ films on silica substrates embedded with Ag nanoparticles. Enhancement of light absorption of the nanostructural composites is observed. The light absorption enhancement of the synthesized structure in comparison to TiO₂ originated from the near-field enhancement caused by the plasmonic effect of Ag nanoparticles, which can be demonstrated by the optical absorption spectra, Raman scattering investigation, and the increase of the photocatalytic activity. The embedded Ag nanoparticles are formed by ion implantation, which effectively prevents Ag to be oxidized through direct contact with TiO₂. The suggested incorporation of plasmonic nanostructures shows a great potential application in a highly efficient photocatalyst and ultra-thin solar cell.     

LiNi0.8Co0.15Al0.05O2 cathode materials prepared by TiO2 nanoparticle coatings on Ni0.8Co0.15Al0.05(OH)2 precursors

Synthesis, electrochemical, and structural properties of LiNi_0.8Co_0.15Al_0.05O₂ cathodes prepared by TiO₂ nanoparticles coating on a Ni_0.8Co_0.15Al_0.05(OH)₂ precursor have been investigated by the variation of coating concentration and annealing temperature. TiO₂-coated cathodes showed that Ti elements were distributed throughout the particles. Among the coated cathodes, the 0.6 wt% TiO₂-coated cathode prepared by annealing at 750 °C for 20 h exhibited the highest reversible capacity of 176 mAh g⁻¹ and capacity retention of 92% after 40 cycles at a rate of 1C (=190 mA g⁻¹). On the other hand, an uncoated cathode showed a reversible first discharge capacity of 186 mAh g⁻¹ and the same capacity retention value to the TiO₂-coated sample at a 1C rate. However, under a 1C rate cycling at 60 °C for 30 cycles, the uncoated sample showed a reversible capacity of 40 mAh g⁻¹, while a TiO₂-coated one showed 71 mAh g⁻¹. This significant improvement of the coated sample was due to the formation of a possible solid solution between TiO₂ and LiNi_0.8Co_0.15Al_0.05O₂. This effect was more evident upon annealing the charged sample while increasing the annealing temperature, and at 400 °C, the coated one showed a more suppressed formation of the NiO phase from the spinel LiNi₂O₄ phase than the uncoated sample.     

Preparation of nanosized anatase TiO2-coated kaolin composites and their pigmentary properties

Nanosized anatase TiO₂-coated kaolin composites were prepared by the chemical deposition method starting from calcined kaolin and TiCl₄. The resultant TiO₂ nanoparticles on the kaolin surfaces existed in anatase phase after calcination at 200, 400, and 900 °C for 1 h, respectively. The surfaces of the kaolin powders were uniformly coated by a monolayer of TiO₂ nanoparticles. The higher calcination temperature was beneficial to formation of well crystallized anatase TiO₂ nanoparticles. The light scattering indexes of the TiO₂-coated calcined kaolin composites were two times higher than that of the kaolin substrate. XPS analysis shows that TiO₂ coating layers anchored at the kaolin surfaces via the Ti-O-Si and Ti-O-Al bonds.     

Preparation and electrochemical properties of composites of carbon nanotubes loaded with Ag and TiO2 nanoparticle for use as anode material in lithium-ion batteries

Carbon nanotubes (CNTs) loaded with Ag and TiO₂ nanoparticles (Ag-TiO₂/CNTs) are a composite showing promise as an anode material in lithium-ion batteries. Here we prepare Ag-TiO₂/CNTs via hydrolysis and reduction processes. The morphology, structure, and electrochemical performance of the composite were investigated by transmission electron microscopy, X-ray diffraction, and a variety of electrochemical techniques. The results show that the TiO₂ and Ag nanoparticles were uniformly deposited on the surface of CNTs with crystallite sizes of ∼12 and 30 nm, respectively. The Ag-TiO₂/CNTs anode materials showed superior cycling stability and a high reversible capacity of 172 mAh/g after 30 cycles. Ag addition not only increases the electronic conductivity of the composites, but also allows convenient transfer of Li-ion in the composite structure.     

Synthesis and Photocatalytic Activity of Anatase TiO2 Nanoparticles-coated Carbon Nanotubes

A simple and straightforward approach to prepare TiO₂-coated carbon nanotubes (CNTs) is presented. Anatase TiO₂ nanoparticles (NPs) with the average size ~8 nm were coated on CNTs from peroxo titanic acid (PTA) precursor even at low temperature of 100 °C. We demonstrate the effects of CNTs/TiO₂ molar ratio on the adsorption capability and photocatalytic efficiency under UV–visible irradiation. The samples showed not only good optical absorption in visible range, but also great adsorption capacity for methyl orange (MO) dye molecules. These properties facilitated the great enhancement of photocatalytic activity of TiO₂ NPs-coated CNTs photocatalysts. The TiO₂ NPs-coated CNTs exhibited 2.45 times higher photocatalytic activity for MO degradation than that of pure TiO₂.