A multifunctional Ag/TiO2/reduced graphene oxide with optimal surface-enhanced Raman scattering and photocatalysis

A multifunctional Ag/TiO₂/reduced graphene oxide (rGO) ternary nanocomposite was prepared by a one-step photochemical reaction with TiO₂ and Ag nanoparticles successively deposited on reduced graphene oxide. The structure, morphology, composition, optical, and photoelectrochemical properties of Ag/TiO₂/rGO were investigated in detail. Meanwhile, the ternary nanocomposite possessed much higher adsorption capacity to organic dyes compared with bare TiO₂ and binary Ag/TiO₂, which would help to its use for surface-enhanced Raman scattering detection and photocatalytic degradation. Due to the charge transfer between rGO and organic dyes and enhanced electromagnetic mechanism of Ag, Ag/TiO₂/rGO nanocomposites as surface-enhanced Raman scattering substrates demonstrated dramatically improved sensitivity and good uniformity. The detection limit of rhodamine 6G (R6G) was as low as 10⁻⁹ mol/L, and the relative standard deviation values of the intensities remained below 5%. Most importantly, the synergistic coupling effect of three components extended the photoresponse range and accelerated separation of the electron-hole pairs, leading to greatly improved photocatalytic activity under simulated sunlight. The maximum rate constant (k, 0.06243 min⁻¹) of Ag/TiO₂/rGO was 50 and four times higher than that of TiO₂ and Ag/TiO₂, respectively.     

Enhanced photoresponse and photocatalytic activities of graphene quantum dots sensitized Ag/TiO2 thin film

TiO₂ thin films were fabricated through hydrothermal method. Silver nanoparticles were loaded on TiO₂ thin films via photoreduction technique. Subsequently, the graphene quantum dots (GQDs) were spin‐coated on the Ag/TiO₂ nanocomposites thin films. The crystal structure, surface morphology and UV‐vis absorbance were tested by XRD, SEM and ultraviolet‐visible spectrophotometer. These results indicated that Ag nanoparticles and GQDs are anchored on the TiO₂ nanorods. Absorbance of Ag/TiO₂ and GQDs/Ag/TiO₂ nanocomposite thin films have been extended into the visible region. Visible‐light response of the samples were investigated by electrochemical workstation. The photoresponse of the sample can be enhanced by sensitization of the Ag nanoparticles and GQDs. The enhanced visible‐light response may be due to the surface plasmon resonance of silver nanoparticles and visible absorbance of GQDs. The highest photocatalytic activity has been observed in the 9‐GQDs/Ag/TiO₂ composite thin film. The efficient charge separation and transportation can be achieved by introducing the Ag nanoparticles and GQDs in the TiO₂ thin film.     

Ag nanoparticles loaded TiO2/MWCNT ternary nanocomposite: A visible-light-driven photocatalyst with enhanced photocatalytic performance and stability

A visible light active photocatalyst, Ag/TiO₂/MWCNT was synthesized by loading of Ag nanoparticles onto TiO₂/MWCNT nanocomposite. The photocatalytic activity of Ag/TiO₂/MWCNT ternary nanocomposite was evaluated for the degradation of methylene blue dye under UV and visible light irradiation. Ag/TiO₂/MWCNT ternary nanocomposite exhibits (~9 times) higher photocatalytic activity than TiO₂/MWCNT and (~2 times) higher than Ag/TiO₂ binary nanocomposites under visible light irradiation. The enhancement in the photocatalytic activity is attributed to the synergistic effect between Ag nanoparticles and MWCNT, which enhance the charge separation efficiency by Schottky barrier formation at Ag/TiO₂ interface and role of MWCNT as an electron reservoir. Effect of different scavengers on the degradation of methylene blue dye in the presence of catalyst has been investigated to find the role of photogenerated electrons and holes. Simultaneously, the Ag/TiO₂/MWCNT shows excellent photocatalytic stability. This work highlights the importance of Ag/TiO₂/MWCNT ternary nanocomposite as highly efficient and stable visible-light-driven photocatalyst for the degradation of organic dyes.     

Synthesis and photocatalytic performance of PVA/TiO2/graphene‐MWCNT nanocomposites for dye removal

TiO₂/graphene‐MWCNT nanocomposite was prepared using solvothermal reaction for the effective distribution of TiO₂ nanoparticles on carbonaceous materials. TiO₂/graphene‐MWCNT nanocomposite was immobilized in poly(vinyl alcohol) (PVA) matrix for a convenient recovery after wastewater purification. MWCNT was incorporated in a nanocomposite not only to prevent the restacking of graphene but also to increase the electron transfer from TiO₂. The detailed characterization of the nanocomposite was performed using SEM, EDX, XRD, XPS, and FTIR. The photocatalytic performance of PVA/TiO₂/graphene‐MWCNT nanocomposite was investigated by UV spectroscopy on the basis of degradation of organic pollutants. PVA/TiO₂/graphene‐MWCNT nanocomposite showed improved photocatalytic decomposition of more than 70% of residual dye left in case of using PVA/TiO₂/graphene nanocomposite due to the improved electron transfer and the higher adsorption of organic pollutants. PVA/TiO₂/graphene‐MWCNT nanocomposite was suitable as a promising material for the recyclable photocatalytic wastewater purification system. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40715.     

TiO2 nanofibers assembled on graphene-silver platform as a visible-light photo and bio-active nanostructure

The heterogeneous titanium oxide-reduced graphene oxide-silver (TiO₂/RGO/Ag) nanocomposites were successfully prepared by incorporation of two dimensional (2D) RGO nanosheets and spherical silver nanoparticles (NPs) into the 1D TiO₂ nanofibers. The novel TiO₂/RGO/Ag nanocomposites were synthesized by loading TiO₂ nanofibers, prepared via electrospinning technique, on the RGO/Ag platform. The resulting nanocomposites have been characterized using various techniques containing transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and ultra-violet-visible (UV–vis) spectroscopy. Microscopic studies clearly verified the existence of TiO₂ nanofibers with Ag NPs on the surface of RGO sheet and formation of TiO₂/RGO/Ag nanocomposites. Moreover, the results of UV–vis spectroscopy demonstrated that TiO₂/RGO/Ag nanocomposites extended the light absorption spectrum toward the visible region and significantly enhanced the visible-light photocatalytic performance of the prepared samples on degradation of rhodamine B (Rh. B) as a model dye. It was found that, incorporation of 50 µl RGO/Ag into the TiO₂ nanofibers lead to a maximum photocatalytic performance. Also, the improvement of the inactivation of Escherichia coli (E. coli) bacteria under visible-light irradiation was revealed by introduction of RGO/Ag into the TiO₂ matrix. The significant enhancement in the photo and bio-activity of TiO₂/RGO/Ag nanocomposites under visible-light irradiation can be ascribed to the RGO/Ag content by acting as electron traps in TiO₂ band gap.     

One-pot synthesis of CdS sensitized TiO2 decorated reduced graphene oxide nanosheets for the hydrolysis of ammonia-borane and the effective removal of organic pollutant from water

A hybrid material of reduced graphene oxide (RGO) sheets decorated with CdS-TiO₂ NPs was prepared through a facile one-pot hydrothermal method. The assembly of CdS-TiO₂ nanoparticles (NPs) on RGO sheets was in-situ produced. As-synthesized nanocomposites were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy disperse X-ray spectrum (EDS), fourier transform infrared spectroscopy (FTIR), and photoluminescence spectroscopy (PL). The obtained nanocomposites exhibited a good photocatalytic activity for the visible-light-induced decomposition of methylene blue (MB) dye and hydrolysis of ammonia borane. The results showed that by incorporation of CdS and TiO₂ NPs on graphene oxide sheets the photocatalytic efficiency was enhanced. The significant enhancement in the photocatalytic activity of CdS-TiO₂/RGO nanocomposites under visible light irradiation can be ascribed to the effect of CdS by acting as electron traps in TiO₂ band gap. Reduced graphene oxide worked as the adsorbent, electron acceptor and a photo-sensitizer to efficiently enhance the dye photo decomposition. Such nanocomposite photocatalyst might find potential application in a wide range of fields, including hydrogen energy generation, air purification, and wastewater treatment.     

Superfine and closely-packed TiO2/Bi2O3 lamination on graphene nanoplates with high photocatalytic activity

Graphene/TiO₂–Bi₂O₃ nanohybrids were synthesized by one-step PAA-assisted hydrothermal method with a low-temperature treatment. Their morphology, structure and photocatalytic property were investigated accordingly. The SEM and TEM results showed that the nanohybrids composed of TiO₂ and Bi₂O₃ nanoparticles with the size of about 10 nm were uniformly covered on the graphene sheets. Furthermore, the resultant samples presented excellent photocatalytic activity for RhB and recycle property, in which 95% RhB was degraded within 10 min and a good activity was maintained in the seven recycling tests, besides the hybrids also possess good activity in visible light. The enhancement of photocatalytic activity is attributed to efficient transfer of the photogenerated electrons from the CB of semiconductor nanoparticles to graphene and the homogeneity of nanoparticles.     

Preparation of transparent PVA/TiO2 nanocomposite films with enhanced visible-light photocatalytic activity

Polymer/semiconductor oxide nanocomposite films have been intensively investigated for various applications. In this work, we reported a simple hydrothermal method to fabricate highly transparent poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposite films with enhanced visible-light photocatalytic activity. The as-prepared PVA/TiO₂ nanocomposite films showed high optical transparency in the visible region even at a high TiO₂ content (up to 40 wt.%). The determination of photocatalytic activity by photodegradation of methyl orange (MO) and colorless phenol showed that PVA/TiO₂ nanocomposite films exhibited enhanced visible-light photocatalytic activity and excellent recycle stability. This work provided new insights into fabrication of polymer/TiO₂ nanocomposites as high performance photocatalysts in waste water treatment.     

Fabrication of TiO2‒Ag nanocomposite thin films via one-step gas-phase deposition

In this work, TiO₂‒Ag nanocomposite thin films were fabricated for the first time via simultaneous plasma-enhanced chemical vapor deposition and physical vapor deposition of TiO₂ and Ag nanoparticles in the gas-phase, respectively. The presence of Ag nanoparticles in the prepared nanocomposites has been confirmed using transmission electron microscopy and energy dispersive X-ray spectrometry techniques. The obtained electron microscopy images showed that the average size of TiO₂‒Ag nanoparticles was larger than that of pristine TiO₂. Moreover, the temperature of the anatase transformation into the rutile phase was decreased due to the presence of Ag nanoparticles in the TiO₂ matrix, while the photocatalytic activity of the produced nanocomposite (estimated by studying the degradation of methylene blue aqueous solution under UV irradiation) was 35% greater than that of pristine TiO₂. Therefore, the addition of Ag nanoparticles into the TiO₂ matrix significantly affected the morphology, phase transformation temperature, and photocatalytic performance of the fabricated material.     

One-pot synthesis of Ag-TiO2/reduced graphene oxide nanocomposite for high performance of adsorption and photocatalysis

The Ag-TiO₂/r-GO nanocomposite was synthesized via a facile one-pot solvothermal method. X-ray diffraction (XRD), Transmission electron microscopy (TEM),High resolution transmission electron microscopy(HRTEM), UV–vis diffuse reflectance spectroscopy (DRS), Fourier transformed infrared spectroscopy (FT-IR), Photoluminescence (PL) and N₂ adsorption-desorption were used for the characterization of prepared samples. The adsorbent and photocatalytic performance of prepared samples were evaluated by remove of Rh B dyes and reduction of CO₂. Both the adsorbent and photocatalytic ability of all the Ag-TiO₂/r-GO samples were much higher than pure hollow TiO₂. The excellent adsorbent capacity can be attributed to the large BET surface area and the enhanced photocatalytic activity can be assigned to the predominant properties of graphene and the localized surface plasmon(LSPR) effect of Ag nanoparticles.     

TiO2 nanoparticles loaded on graphene/carbon composite nanofibers by electrospinning for increased photocatalysis

Graphene/carbon composite nanofibers (CCNFs) with attached TiO₂ nanoparticles (TiO₂–CCNF) were prepared, and their photocatalytic degradation ability under visible light irradiation was assessed. They were characterized using scanning and transmission electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and ultraviolet–visible diffuse spectroscopy. The results suggest that the presence of graphene embedded in the composite fibers prevents TiO₂ particle agglomeration and aids the uniform dispersion of TiO₂ on the fibers. In the photodegradation of methylene blue, a significant increase in the reaction rate was observed with TiO₂–CCNF materials under visible light. This increase is due to the high migration efficiency of photoinduced electrons and the inhibition of charge–carrier recombination due to the electronic interaction between TiO₂ and graphene. The TiO₂–CCNF materials could be used for multiple degradation cycles without a decrease in photocatalytic activity.     

Ultrasonic assisted synthesis of TiO2–reduced graphene oxide nanocomposites with superior photovoltaic and photocatalytic activities

In this work, TiO₂–reduced graphene oxide (RGO) nanocomposites were successfully produced by an ultrasonication-assisted reduction process. The reduction of graphene oxide (GO) and the formation TiO₂ crystals occurred simultaneously. The synthesized nanocomposite was characterized by SEM, EDX, Raman spectroscopy, FTIR, XRD, XPS, UV–vis spectroscopy, photoluminescence spectrometer and electrochemical impedance spectroscopy. As a result of the introduction of RGO, the light absorption of octahedral TiO₂ was markedly improved. The photocatalytic results revealed that weight percent of RGO has substantial influence on degradation of Rhodamine B under visible light irradiation. The enhancement of the photocatalytic activity can be attributed to the enhancement of the visible-light irradiation harvesting and efficiently separation of the photogenerated charge carriers. Meanwhile, upon the RGO loading, the photoelectric conversion efficiency of TiO₂–RGO nanocomposite modified electrode was also highly improved.     

Preparation of WO3-reduced graphene oxide nanocomposites with enhanced photocatalytic property

In this work, WO₃-reduced graphene oxide (RGO) nanocomposite was synthesized via a simple one-pot hydrothermal method. The synthesized nanocomposite was characterized by SEM, XRD, EDX, UV–vis spectroscopy, N₂ adsorption/desorption, photocurrent response, electrochemical impedance spectroscopy and Raman spectroscopy. The superior contact between WO₃ and RGO sheets in the nanocomposite facilitates the photocatalytic degradation of methylene blue and evolution of oxygen. The cause of the enhanced photocatalytic performance could ascribe to the highly facilitated electron transport by the synergistic effect between WO₃ and RGO sheets, as well as suppressing the electron hole pair recombination in the nanocomposite.     

Graphene-supported flocculent-like TiO2 nanostructures for enhanced photoelectrochemical activity and photodegradation performance

Here, novel graphene/TiO₂ nanocomposite has been successfully prepared by loading flocculent-like titanate nanostructure in graphene sheets via hydrothermal method plus a subsequent annealing process. The as-obtained hybrid was characterized by X-ray diffraction, scanning electron microscopy with an energy dispersive spectroscope (EDS), Raman, and UV–vis diffuse reflectance spectra, respectively. The photoelectrochemical activities and photocatalytic degradation performance of methyl orange under the illumination of ultraviolet light were investigated, and the flocculent-like TiO₂/graphene composites was found to have a superior photocatalytic activity compared to flocculent-like titanate nanostructure and commercial anatase TiO₂ powder, which can be attributed to the improved light absorption and extremely efficient charge separation of the hybrid structure. The results suggest that the as-prepared flocculent-like TiO₂/graphene composite is a promising photocatalyst for photoelectrochemical hydrogen production and pollution removal.     

The role of graphene and europium on TiO2 performance for photocatalytic hydrogen evolution

Highly efficient Eu-TiO₂/graphene composites were synthesized by a two-step method such as sol-gel and hydrothermal process. The synthesized photocatalysts were characterized by XRD, TEM, XPS, UV–vis diffuse reflectance spectroscopy and photoluminescence (PL) spectroscopy. The results confirmed that anatase Eu-TiO₂ nanoparticles with average 10 nm sizes were successfully deposited on two-dimensional graphene sheets. The UV–visible spectroscopy showed a red shift in the absorption edge of TiO₂ due to Eu doping and graphene incorporation. Moreover, effective charge separation in Eu-TiO₂/graphene composites was confirmed by PL emission spectroscopy compared to TiO₂/graphene, Eu-TiO₂ and pure TiO₂. The photocatalytic activity for H₂ evolution over prepared composites was studied under visible light irradiation (λ ≥ 400 nm). The results demonstrate that photocatalytic performance of the photocatalysts for hydrogen production increases with increasing doping concentration of Eu upto 2 at%. However, further increase in doping content above this optimum level has decreased the performance of photocatalyst. The enhanced photocatalytic performance for H₂ evolution is attributed to extended visible light absorption, suppressed recombination of electron-hole pairs due to synergistic effects of Eu and graphene.     

UV-curable polyurethane acrylate–Ag/TiO2 nanocomposites with superior UV light antibacterial activity

Polyurethane acrylate (PUA)–Ag/TiO₂ nanocomposites were synthesized through in situ polymerization. The well-dispersed Ag/TiO₂ nanorods serve as photoinitiator. Meanwhile, the PUA–Ag/TiO₂ nanocomposite films exhibit superior activity toward the photocatalytic degradation of Escherichia coli under UV light. The excellent UV curing and antibacterial activities can be ascribed to the synergistic effect of Ag and TiO₂, which promotes the effective electron/hole separation and thus generates various reactive species. Thin films with these nanoparticles are more hydrophilic after UV illumination. And the antibacterial mechanism of the UV-curable PUA–Ag/TiO₂ nanocomposites was proposed.     

From AgI/TiO2 to Ag/TiO2: effects of the annealing temperature on the compositions,porous nanostructures,and visible-light photocatalytic properties

AgI/TiO₂ and Ag/TiO₂ porous nanostructures were synthesized using AgNO₃, KI, thioglycollic acid, and tetrabutyl orthotitanate as a precursor. AgI nanoparticles were used as seeds to initiate the nucleation of a precursor TiO₂ shell, and thioglycollic acid acted as a hydrolysis inhibitor and porosity promoter. The hybridized samples were annealed at different temperatures. Porous AgI/TiO₂ nanostructures were formed at low annealing temperatures (300 and 400 °C). At 600 °C, the porous Ag/TiO₂ nanostructures exhibited a plasmon resonance effect. The formation mechanism of the different porous nanostructures was also investigated. Methylene blue solutions were used as wastewater to evaluate the visible-light photocatalytic activity of the samples. The porous nanostructured photocatalyst exhibited substantially high visible-light-induced photocatalytic activity for the photodegradation of methylene blue compared with pristine AgI and TiO₂ nanoparticles.     

A general strategy for the synthesis of reduced graphene oxide-based composites

Well-exfoliated graphene oxide sheets were initially fabricated through a modified pressurized oxidation method with powdered flake graphite as raw material. A variety of inorganic-reduced graphene oxide composites have been then successfully synthesized through a general solvothermal strategy with the graphene oxide sheets as supports, ethanol as solvent, and metal salts as precursors. After the solvothermal reactions, Ni(OH)₂ nanoparticles, Fe₂O₃ nanorods, W₁₈O₄₉ nanowires, ZnO nanoparticles, and Ag nanoparticles were in situ grown on the surfaces of the graphene oxide sheets, accompanied by effective reduction of graphene oxide to reduced graphene oxide. The as-prepared products have been systematically characterized by electron microscopy, X-ray diffraction, X-ray photoelectron spectrometry, and Raman spectroscopy. The present work opens up a versatile route for preparing the reduced graphene oxide-based composites.     

Fabrication of graphene films on TiO2 nanotube arrays for photocatalytic application

Graphene film was formed on the surface of titanium dioxide nanotube (TiO₂ NT) arrays through in situ electrochemical reduction of a graphene oxide dispersion by cyclic voltammetry. The residual oxygen-containing groups and other structural defects such as sp³-hybridized carbons in the electrodeposited graphene were further removed by photo-assisted reduction of the underlying TiO₂ NTs, thus achieving the maximum restoration of π-conjugation in the graphene planes. Spectroscopic, electrochemical, and photoelectrochemical techniques were used to characterize the graphene films, and the use of the resulting graphene–TiO₂ NT material in photocatalysis was investigated. The results showed that the graphene–TiO₂ NT material exhibited a greatly improved photocatalytic activity compared with unmodified TiO₂ NTs.     

Silver nanoparticles decorated polypyrrole/graphene nanocomposite: A potential candidate for next‐generation supercapacitor electrode material

In the present study, we report a simple method to synthesize silver (Ag)‐polypyrrole (PPy)/graphene (Gr) nanocomposite as efficient electrode materials for supercapacitor application. The probable interaction between Ag nanoparticles with both PPy and Gr were characterized by FTIR, UV–visible, and Raman spectroscopies. The morphological analysis confirmed that the Gr sheets are uniformly coated by PPy and in the coated Gr sheets there is the presence of Ag nanoparticles. The Ag‐PPy/Gr nanocomposite achieved the highest specific capacitance of 472 F/g at a 0.5 A/g current density. Better energy and power density also obtained for the nanocomposite. The presence of both Ag nanoparticles and Gr is the main reason for the enhancement of the electrochemical properties of the nanocomposite. Based on the superior electrochemical properties, the nanocomposite can be used for next‐generation supercapacitor electrode material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44724.