Quenching of TiO2 photo catalysis by silver nanoparticles

The plasmon resonance of metal nanostructures affects neighboring semiconductors, quenching or enhancing optical transitions depending on various parameters. These plasmonic properties are currently investigated with respect to topics such as photovoltaics and optical detection and could also have important consequences for photocatalysis. Here the effect of silver nanoparticles of a size up to 30 nm and at maximum 0.50 monolayers on the photocatalytic oxidation of ethylene on TiO₂ is studied. Since the plasmon resonance energy of silver nanoparticles is comparable with the TiO₂ band gap, dipole-dipole interaction converts excitons into heat at the silver nanoparticle. This indicates that plasmonic interaction with TiO₂ semiconductor catalysts can reduce the photo catalytic activity considerably.     

Disinfection of Escherichia Coli Gram Negative Bacteria Using Surface Modified TiO2: Optimization of Ag Metallization and Depiction of Charge Transfer Mechanism

The antibacterial activity of silver deposited TiO₂ (Ag‐TiO₂) against Gram negative Escherichia coli bacteria was investigated by varying the Ag metal content from 0.10 to 0.50% on the surface of TiO₂. Ag depositions by the photoreduction method were found to be stable. Surface silver metallization was confirmed by EDAX and XPS studies. Photoluminescence studies show that the charge carrier recombination is less for 0.1% Ag‐TiO₂ and this catalyst shows superior bactericidal activity under solar light irradiation compared to Sol gel TiO₂ (SG‐TiO₂) due to the surface plasmon effect. The energy levels of deposited Ag are dependent on the Ag content and it varies from ?4.64 eV to ?1.30 eV with respect to the vacuum energy level based on atomic silver to bulk silver deposits. The ability of electron transfer from Ag deposit to O₂ depends on the position of the energy levels. The 0.25% and 0.50% Ag depositions showed detrimental effect on bactericidal activity due to the mismatch of energy levels. The effect of the EROS (External generation of the Reactive Oxygen Species by 0.1% Ag‐TiO₂) and IROS (Interior generation of Reactive Oxygen Species within the bacteria) on the bactericidal inactivation is discussed in detail.     

Single‐Nanoparticle Photoelectrochemistry at a Nanoparticulate TiO2‐Filmed Ultramicroelectrode

An ultrasensitive photoelectrochemical method for achieving real‐time detection of single nanoparticle collision events is presented. Using a micrometer‐thick nanoparticulate TiO₂‐filmed Au ultra‐microelectrode (TiO₂@Au UME), a sub‐millisecond photocurrent transient was observed for an individual N719‐tagged TiO₂ (N719@TiO₂) nanoparticle and is due to the instantaneous collision process. Owing to a trap‐limited electron diffusion process as the rate‐limiting step, a random three‐dimensional diffusion model was developed to simulate electron transport dynamics in TiO₂ film. The combination of theoretical simulation and high‐resolution photocurrent measurement allow electron‐transfer information of a single N719@TiO₂ nanoparticle to be quantified at single‐molecule accuracy and the electron diffusivity and the electron‐collection efficiency of TiO₂@Au UME to be estimated. This method provides a test for studies of photoinduced electron transfer at the single‐nanoparticle level.     

Preparation and Ultrafast Optical Characterization of Metal and Semiconductor Colloidal Nano-Particles

The ultrafast dynamics of photoinduced electrons in several metal and semiconductor colloidal nanoparticle systems are characterized using femtosecond laser spectroscopy. Various preparation methods are used and, in several cases, modified for making particles with long-term stability and narrow and controllable size distributions. The particle size and size distribution are determined using transmission electron microscopy and electronic absorption spectroscopy. For aqueous gold and silver colloids, spatial size confinement is found to cause substantially slower electronic relaxation due to reduction of non-equilibrium electron transport and weaker electron-phonon coupling. In gold colloids, photoejection of electrons into the liquid is observed, which is attributed to a two-photon enhanced ionization process. The effect of surfactant on the electron dynamics in CdS colloids is examined and found to be significant, substantiating the notion that electrons are dominantly trapped at the liquid-solid interface. In Ru³⁺-doped TiO₂ colloids, the electronic decay is found to be as fast as or even faster than in undoped TiO₂ and other semiconductor colloids such as CdS, suggesting that ion doping of large bandgap semiconductor colloids is not necessarily effective in lengthening the electron lifetime. In almost all cases studied, the majority of the photoinduced electrons are found to decay within a few tens of picoseconds due to non-radiative relaxation. The results are discussed in the context of the potential applications of metal and semiconductor nano-particles in areas including photocatalysis and photoelectrochemistry.     

Cu?Cu2O?TiO2 Nanojunction Systems with an Unusual Electron–Hole Transportation Pathway and Enhanced Photocatalytic Properties

Multicomponent Cu? Cu₂O? TiO₂ nanojunction systems were successfully synthesized by a mild chemical process, and their structure and composition were thoroughly analyzed by X‐ray diffraction, transmission electron microscopy, field‐emission scanning electron microscopy, and X‐ray photoelectron spectroscopy. The as‐prepared Cu? Cu₂O? TiO₂ (3 and 9 h) nanojunctions demonstrated higher photocatalytic activities under UV/Vis light irradiation in the process of the degradation of organic compounds than those of the Cu? Cu₂O, Cu? TiO₂, and Cu₂O? TiO₂ starting materials. Moreover, time‐resolved photoluminescence spectra demonstrated that the quenching times of electrons and holes in Cu? Cu₂O? TiO₂ (3 h) is higher than that of Cu? Cu₂O? TiO₂ (9 h); this leads to a better photocatalytic performance of Cu? Cu₂O? TiO₂ (3 h). The improvement in photodegradation activity and electron–hole separation of Cu? Cu₂O? TiO₂ (3 h) can be ascribed to the rational coupling of components and dimensional control. Meanwhile, an unusual electron–hole transmission pathway for photocatalytic reactions over Cu? Cu₂O? TiO₂ nanojunctions was also identified.     

Microwave‐Hydrothermal Preparation and Visible‐Light Photoactivity of Plasmonic Photocatalyst Ag‐TiO2 Nanocomposite Hollow Spheres

Visible‐light‐driven plasmonic photocatalyst Ag‐TiO₂ nanocomposite hollow spheres are prepared by a template‐free chemically‐induced self‐transformation strategy under microwave‐hydrothermal conditions, followed by a photochemical reduction process under xenon lamp irradiation. The prepared samples are characterized by using scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, N₂ adsorption‐desorption isotherms, X‐ray photoelectron spectroscopy, UV/Vis and Raman spectroscopy. Production of ?OH radicals on the surface of visible‐light illuminated TiO₂ was detected by using a photoluminescence method with terephthalic acid as the probe molecule. The photocatalytic activity of as‐prepared samples was evaluated by photocatalytic decolorization of Rhodamine B (RhB) aqueous solution at ambient temperature under visible‐light irradiation. The results show that the surface plasmon absorption band of the silver nanoparticles supported on the TiO₂ hollow spheres was red shifted, and a strong surface enhanced Raman scattering effect for the Ag‐TiO₂ nanocomposite sample was observed. The prepared nanocomposite hollow spheres exhibits a highly visible‐light photocatalytic activity for photocatalytic degradation of RhB in water, and their photocatalytic activity is higher than that of pure TiO₂ and commercial Degussa P25 (P25) powders. Especially, the as‐prepared Ag‐TiO₂ nanocomposite hollow spheres at the nominal atomic ratio of silver to titanium ( R ) of 2 showed the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2.     

Polyelectrolyte brushes as efficient platform for synthesis of Cu and Pt bimetallic nanocrystals onto TiO2 nanowires

A Cu–Pt nanoparticle catalyst supported on TiO₂ nanowires (NWs) was prepared through regenerative counterion exchange–reduction using polyelectrolyte brush as template. Cationic polydimethyl aminoethyl methacrylate brushes were grafted onto TiO₂ NWs. Cu–Pt nanocrystals were produced by anionic counterions CuCl₄^2? and PtCl₆^2? bound with the polymer brush through in situ reduction with NaBH₄ of high density and low polydispersity. The as‐prepared TiO₂ NWs/polymer brush/Cu–Pt was characterized by Fourier transform infrared spectroscopy (FT‐IR spectrometry), X‐ray photoelectron spectroscopy, transmission electron microscopy, and UV–Vis adsorption spectrometry analyses. Results showed that the highly dispersed Cu and Pt nanoparticles were present on the surface of the TiO₂ NWs/polymer brush. The resultant TiO₂ NWs/polymer brush/Cu–Pt exhibited extremely high catalytic activity and reduced p‐nitrophenol at room temperature. Copyright © 2017 John Wiley & Sons, Ltd.     

Sol–gel and impregnated prepared silver TiO<Subscript>2</Subscript> semiconductors as photocatalysts for the UV decomposition of 2,4-<Emphasis Type="SmallCaps">d</Emphasis>: a comparative study of the preparation method

UV-photocatalytic oxidation of 2,4-dichlorophenoxyacetic acid (2,4-d) was studied on Silver–TiO₂ semiconductors prepared by co-gelling silver acetylacetonate and titanium butoxide (TiO₂–Ag) or by incipient impregnation with silver acetylacetonate (0.5 wt% Ag) of bare TiO₂ sol–gel and TiO₂–P25 supports. The comparative study shows that only a slight modification on the specific surface area was obtained on the TiO₂–Ag sample (60 m²/g) as compared to the TiO₂ sol–gel bare support (65 m²/g). XRD patterns of the samples show anatase as the crystalline phase present in the sol–gel TiO₂ preparations. By means of HRTEM and HAADF-STEM electron microscopy techniques, silver nanoparticles (<12.0 nm) were identified which are very small to be detected by XRD. The photocatalytic oxidation of the herbicide 2,4-d used as a model of contaminant show for the kinetic parameter t_1/2 values of 45 min for the TiO₂–Ag sample, while for the impregnated Ag/TiO₂ and Ag/P25 nanomaterials t_1/2 was 124 and 66 min, respectively. The higher photoactivity of the TiO₂–Ag photocatalyst is attributed to a combined effect of the silver nanoparticles in interaction with the titania semiconductor.     

Wettability conversion on the liquid flame spray generated superhydrophobic TiO2 nanoparticle coating on paper and board by photocatalytic decomposition of spontaneously accumulated carbonaceous overlayer

Titanium dioxide (TiO₂) is a photoactive material with various interesting and useful properties. One of those is the perfect wettability of TiO₂ surface after ultraviolet (UV) illumination. Wettability of a solid surface plays an important role in the field of printing, coating, and adhesion among others. Here we report on a superhydrophobic and photoactive liquid flame spray (LFS) generated TiO₂ nanoparticle coating that can be applied on web-like materials such as paper and board in one-step roll-to-roll process. The LFS TiO₂ nanoparticle coated paper and board were superhydrophobic instantly after the coating procedure because of spontaneously accumulated carbonaceous overlayer on TiO₂, and thus there was no need for any type of separate hydrophobization treatment. The highly photoactive LFS TiO₂ nanoparticle coating could be converted steplessly from superhydrophobic to superhydrophilic by UV-illumination, and the coating gave strong response to natural daylight illumination even in the shade. The superhydrophobic LFS TiO₂ coated surface can be used as an intelligent substrate, where photo-generated hydrophilic patterns guide the fluid setting and figure formation. Our study reveals that the wettability changes on the LFS TiO₂ surface were primarily caused by the photocatalytic removal of the carbonaceous material from TiO₂ during the UV-illumination and spontaneous accumulation of the carbonaceous material on the surface of the metal oxide during storage in the dark. The latter mechanism was found to be a temperature activated process which could be significantly speeded up by heat treatment. If other mechanisms such as surface oxidization, increment of hydroxyl groups, or charge separation played a role in the wetting phenomena on TiO₂, their effect was rather secondary as the removal and accumulation of the carbonaceous material dominated the wettability changes on the surface. Our study gives valuable information on the complex issue of photo-induced wettability changes on TiO₂.     

Stabilization of silver nanoparticles with copolymers of maleic acid

Silver nanoparticles are obtained by reducing AgNO₃ with sodium borohydride in an aqueous solution in the presence of maleic acid copolymers with ethylene, N-vinylpyrrolidone, or styrene, as well as their octadecylamide group-containing hydrophobized derivatives, as dispersants. The influence of the structural features of the dicarboxylic acid copolymers on the silver nanoparticle formation process and the conditions for producing sols containing spherical nanoparticles with sizes of 1.5–3.5 nm (according to the data of transmission electron microscopy) are determined. It is shown that, at the equimolar copolymer/silver cation ratio, the morphology of resulting silver nanoparticles weakly depends on the nature of comonomers of maleic acid and the presence of hydrophobic fragments, which play an auxiliary role in the stabilization of dispersions of nanoparticles by increasing their stability with respect to ionic strength and oxidation. Evolution of the particle sizes in the system is monitored beginning with copolymer solutions to silver sols by the methods of light scattering, transmission electron microscopy, and atomic force microscopy. According to the light scattering data, copolymers and their complexes with silver ions in solutions are partly aggregated at concentrations corresponding to the conditions of nanosilver synthesis. Silver sols are shown to contain stabilized nanoparticles, which represent core-polyelectrolyte corona-type micelles and micellar clusters with polyelectrolyte coronas.     

Nanocomposites based on polyethylene and nanosilver particles produced by metallocenic “in situ” polymerization: synthesis, characterization, and antimicrobial behavior

Polyethylene nanocomposites containing silver nanoparticles with antimicrobial properties were produced via in situ polymerization. The silver nanoparticles were added together with the catalytic system (metallocene catalyst and methylaluminoxane, MAO, as cocatalyst) directly to the reactor. The polymerization activity did not present significant changes with the incorporation of the silver nanoparticles in comparison to the homopolymerization without filler. The effect of various silver nanoparticle contents on silver ion release and antimicrobial efficacy against Escherichia Coli were studied. Nanocomposites containing higher nanosilver concentrations (5 wt.%) showed the highest silver ion release, and after 24 h reached 99.99% of efficacy against the bacteria compared with the neat PE. Transmission electron microscopy (TEM) images showed that the nanospheres were well dispersed throughout the polyethylene matrix.     

Electrochemical application of titanium dioxide nanoparticle/gold nanoparticle/multiwalled carbon nanotube nanocomposites for nonenzymatic detection of ascorbic acid

Titanium dioxide nanoparticle/gold nanoparticle/carbon nanotube (TiO₂/Au/CNT) nanocomposites were synthesized, and then characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDX). A TiO₂/Au/CNT nanocomposite-modified glassy carbon (GC) electrode was prepared using the drop coating method and was investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), differential pulse voltammetry (DPV), and amperometric current–time response (I-T). The modified material is redox-active. The nonenzymatically detected amount of ascorbic acid (AA) on the TiO₂/Au/CNT electrode showed a linear relationship with the AA concentration, for concentrations from 0.01 to 0.08 μM; the sensitivity was 117,776.36 μA?·?cm^?2?·?(mM)^?1, and the detection limit was 0.01 μM (S/N?=?3). The results indicated that the TiO₂/Au/CNT nanocomposite-modified GC electrode exhibited high electrocatalytic activity toward AA. This paper describes materials consisting of a network of TiO₂, Au, and MWCNTs, and the investigation of their synergistic effects in the detection of AA.     

Pulsed current electrodeposition of Zn–Ag2S/TiO2 nanocomposite films as potential photoelectrodes

Nanocomposite Zn–Ag₂S/TiO₂ and Zn–TiO₂ films were prepared by pulsed current electrolysis from acidic zinc sulphate solutions on a titanium substrate. The influence of the nanoparticles' nature on the structural and morphological characteristics of the metallic electrodeposit was also investigated. The electrodeposits were characterized by X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy. Using transmission electron microscopy, it was possible to conclude that the chemical treatment applied to the commercial TiO₂ particles promotes the formation of Ag₂S/TiO₂ composite nanoparticles, with Ti, Ag, S and O in its composition. This was also was confirmed by X-ray fluorescence spectrometry. These particles absorb visible light radiation which makes them promising materials for photoelectrocatalytic processes. Moreover, the modification in nanoparticle composition plays a remarkable influence on the coating morphology and Zn crystallite size. When TiO₂ is added, a change of Zn texture was observed along with a decrease in crystallite size. In contrast, the metal matrix nanocomposites prepared with Ag₂S/TiO₂ exhibit a spongy Zn morphology with a lower average Zn crystallite size. The nanocomposite films were tested in the photoelectrodegradation of ibuprofen and the best results were obtained for Zn–Ag₂S/ TiO₂ photoelectrodes.     

Effect of the Titanium Dioxide Shell on the Plasmon Properties of Silver Nanoparticles

The results of the synthesis of Ag—TiO₂ nanostructures were presented. The optical properties of silver nanoparticles and Ag—TiO₂ structures were studied. The size and shape of Ag—TiO₂ nanostructures were determined. The electron density in silver, the damping constant of plasma oscillations, and the ratio between the masses of the Ag core and the TiO₂ shell were determined from the absorption spectra of Ag and Ag—TiO₂ solutions. It was shown that the semiconductor shell of titanium dioxide leads to a decrease in the electron density in silver nanoparticles and the damping constant of plasma oscillations.     

Consecutive Charging of a Perylene Bisimide Dye by Multistep Low‐Energy Solar‐Light‐Induced Electron Transfer Towards H2 Evolution

A photocatalytic system containing a perylene bisimide (PBI) dye as a photosensitizer anchored to titanium dioxide (TiO₂) nanoparticles through carboxyl groups was constructed. Under solar‐light irradiation in the presence of sacrificial triethanolamine (TEOA) in neutral and basic conditions (pH 8.5), a reaction cascade is initiated in which the PBI molecule first absorbs green light, giving the formation of a stable radical anion (PBI^.?), which in a second step absorbs near‐infrared light, forming a stable PBI dianion (PBI^2?). Finally, the dianion absorbs red light and injects an electron into the TiO₂ nanoparticle that is coated with platinum co‐catalyst for hydrogen evolution. The hydrogen evolution rates (HERs) are as high as 1216 and 1022 μmol h^?1 g^?1 with simulated sunlight irradiation in neutral and basic conditions, respectively.     

Tuning the properties of a black TiO2-Ag visible light photocatalyst produced by a rapid one-pot chemical reduction

A highly efficient black TiO₂-Ag photocatalytic nanocomposite, active under both UV and visible light illumination, was synthesized by decorating the surface of 25 nm TiO₂ particles with Ag nanoparticles. The material was obtained via a rapid, one-pot, simple (surfactant and complexing agent free) chemical reduction method using silver nitrate and formaldehyde as a metal salt and reducing agent, respectively. The nanocomposite shows an increase of over 800% in the rate of photocatalytic methylene blue dye degradation, compared to commercial unmodified TiO_2, under UV-VIS illumination. Unlike pure TiO₂, the nanocomposite exhibits visible light activation, with a corresponding drop in optical reflectance from 100% to less than 10%. The photocatalytic properties were shown to be strongly enhanced by post-reduction annealing heat treatments in air, which were observed to decrease, rather than coarsen, silver particle size, and increase particle distribution. This, accompanied by a variation in the silver surface oxidation states, appear to dramatically affect the photocatalytic efficiency under both UV and visible light. This highly active photocatalyst could have wide ranging applications in water and air pollution remediation and solar fuel production.     

Study of the adsorption behavior ¶of heavy metal ions on nanometer-size ¶titanium dioxide with ICP-AES

A new method using nanoparticle TiO₂ as solid-phase extractant coupled with ICP-AES was proposed for simultaneous determination of trace elements. The adsorption behavior of nanometer TiO₂ towards Cu, Cr, Mn and Ni was investigated by ICP-AES, and the adsorption pH curves, adsorption isotherms and adsorption capacities were obtained. It was found that the adsorption rates of the metal ions studied were more than 90% in pH 8.0～9.0, and 2.0 mol L^–1 HCl was sufficient for complete elution. Nanometer TiO₂ possesses a significant capacity for the sorption of the metal ions studied which is higher than the capacity of silica, the commonly used extractant. The method has been applied to the analysis of some environmental samples with satisfactory results.     

Silver-coated TiO2 nanostructured anode materials for lithium ion batteries

Anatase TiO₂ nanoribbons/nanotubes (TiO₂-NRTs) have been synthesised successfully via a reflux method followed by drying in a vacuum oven, and then, silver-coated TiO₂ NRTs (Ag/TiO₂-NRTs) were prepared by coating silver particles onto the TiO₂-NRTs surface by the traditional silver mirror reaction. The physical properties of the synthesised products were examined in detail using X-ray diffraction, field emission gun scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy, respectively. The results indicated that the Ag nanoparticles were uniformly deposited on the surface of the TiO₂ nanoribbons/nanotubes. The electrochemical properties were investigated by a variety of techniques. The rate capability and cycle durability for the Ag/TiO₂-NRTs were improved compared with TiO₂-NRTs. It is speculated that the Ag-coated TiO₂ nanoribbons/nanotubes are an effective anode candidate for lithium ion batteries.     

Facile decoration of TiO2 nanoparticles on graphene for solar degradation of organic dye

The reduced graphene oxide is interesting material for the synthesis of TiO₂-based photocatalyst. In the present investigation, blackberry fruit, which contains high levels of anthocyanins and other phenolic compounds, was employed as a reducing agent mainly due to its high antioxidant capacity. The nano-crystalline TiO₂ was decorated on different amounts of graphene oxide with sol–gel method and then the photocatalytic activity for degradation of cationic dye was evaluated by UV spectroscopy to achieve the optimum content of graphene oxide. The decoration of anatase nanoparticles on prepared reduced graphene oxide was investigated by X-ray diffraction, scanning and transmission electron microscopy techniques. The new composite gives significantly higher activity when is compared to the compositions fabricated by graphene oxide. The compact layer provides a large TiO₂-graphene contact area and reduces the electron recombination. The decoration of TiO₂ nanoparticles, 5–10 nm, on the graphene oxide reduced by blackberry juice further improves the dye removal. The results imply that the nanoparticle decoration is the key strategy to increase the degradation capacity.     

Regulation of Strong Metal-Support Interaction by Alkaline Earth Metal Salts

Classical strong metal-support interaction (SMSI) is of significant importance to heterogeneous catalysis, where electronic promotion and encapsulation of noble metal by reducible support are two main intrinsic properties of SMSI. However, the excessive encapsulation will inevitably hamper the contact between active sites and reactant, leading to reduced activity in catalysis. Herein, alkaline earth metal salts are employed to depress the encapsulation of Ru nanoparticles in Ru/TiO₂ catalyst in the present study. Thermodynamic calculation, transmission electron microscopy (TEM) and chemisorption results show that the alkaline earth metal salts could successfully prevent the migration of TiO_2-x overlayer to Ru nanoparticles in Ru/TiO₂ catalyst via in situ formation of titanates, resulting in high exposure of active metal. Meanwhile, X-ray photoelectron spectroscopy (XPS) and hydrogen temperature-programmed reduction (H₂-TPR) results reveal that an even stronger electron donation from the reduced support to Ru nanoparticles is achieved. As a result, the alkaline earth metal salts-doped Ru/TiO₂ catalysts exhibit superior activity in catalytic hydrogenation of aromatics, which is in contrast to the pristine Ru/TiO₂ catalyst that shows negligible activity under the same conditions due to the excess encapsulation of Ru nanoparticles in Ru/TiO₂ catalyst.