Interaction of Au with titania: the role of reduced Ti

The interaction of Au with oxide supports has been found to play a vital role in determining the unique properties of Au catalysts. In this study, the binding of Au with titania was investigated using scanning tunneling microscopy (STM) and ultra-violet photoemission spectroscopy (UPS). Two support systems, rutile TiO₂(110) and an ordered TiO _x /Mo(112) thin film were used. On a highly defective TiO₂(110) surface, Au particles were found to bind first on the oxygen vacancy sites. Complete wetting of the oxide by Au was found on an ordered and reduced Ti³⁺O _x /Mo(112) film to form two ordered structures, a (1 × 1)-monolayer and a (1 × 3)-Au/TiO _x /Mo(112) bi-layer. Detailed STM images confirm the proposed structural models. Reduced titania was found to enhance the binding of Au with Ti sites and promote electron donation from Ti^δ+ to Au, leading to electron-rich Au and to enhanced CO bonding.     

Modeling heterogeneous catalysts: metal clusters on planar oxide supports

Model catalysts consisting of Au and Ag clusters of varying size have been prepared on single crystal TiO₂(110) and ultra-thin films of TiO₂, SiO₂ and Al₂O₃. The morphology, electronic structure, and catalytic properties of these Au and Ag clusters have been investigated using low-energy ion scattering spectroscopy (LEIS), temperature-programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) and spectroscopy (STS) with emphasis on the unique properties of clusters <5.0 nm in size. Motivating this work is the recent literature report that gold supported on TiO₂ is active for various reactions including low-temperature CO oxidation and the selective oxidation of propylene. These studies illustrate the novel and unique physical and chemical properties of nanosized supported metal clusters.     

Photocatalytic H2 Production from Ethanol–Water Mixtures Over Pt/TiO2 and Au/TiO2 Photocatalysts: A Comparative Study

Pt/TiO₂ (Pt loadings 0–4 wt%) and Au/TiO₂ (Au loadings 0–4 wt%) photocatalysts were synthesized, characterized and tested for H₂ production from ethanol–water mixtures (80 vol% ethanol, 20 vol% H₂O) under UV excitation. Average metal nanoparticle sizes determined by TEM were 1–3 nm for Pt in the Pt/TiO₂ photocatalysts and 5–7 nm for Au in the Au/TiO₂ photocatalysts. Au/TiO₂ showed an intense localized surface plasmon resonance feature at ~570 nm, typical for metallic Au nanoparticles of diameter ~5 nm supported on TiO₂. X-ray photoelectron spectroscopy and X-ray diffraction analyses established that Pt and Au were present in metallic form on the TiO₂ support. X-ray fluorescence revealed close accord between nominal and actual Pt and Au loadings. The Au/TiO₂ and Pt/TiO₂ photocatalysts both displayed very high activities for H₂ production under UV irradiation, with the Au/TiO₂ samples affording slightly superior rates of H₂ production at most metal loadings. The 2 wt% Au/TiO₂ and 1 wt% Pt/TiO₂ photocatalysts showed the highest H₂ production rates (32–34 mmol g^?1 h^?1). Photoluminescence studies confirmed that Pt and Au nanoparticles positively enhance the photocatalytic properties of P25 TiO₂ for H₂ production by acting as electron acceptors and thereby suppressing electron–hole pair recombination in TiO₂.     

DFT study of catalytic activity of an ultrathin TiO2(110) layer covering Au(112): O2 activation,CO oxidation,and replacing Au with Ag

As a model of Au-titania core-shell catalysts, an ultrathin rutile TiO₂(110) layer inversely supported on Au(112) has been examined by DFT. O₂ adsorbs and activates on the pentacoordinate Ti site of rutile(110) as O₂ π* orbitals accept electronic charge from the Au support via the oxide, as was found for Au/TiO₂. O₂ reacts with CO to yield CO₂ and O, which then reacts with CO to yield CO₂ (barrier ~ 0.6 eV). O₂ adsorption weakens with increasing O₂ coverage and oxide thickness. The reactivity of O₂ changes negligibly even if we replace Au with Ag.     

Mo+TiO2(110) Mixed Oxide Layer: Structure and Reactivity

We present a STM/XPS/TPD/LEED study of the structural and electronic properties of Mo+Ti mixed oxide layers on TiO₂(110), and of their interaction with water, methanol and ethanol. Several different preparation procedures were tested and layers with different degrees of Mo/Ti mixing were prepared. Ordered mixed oxide surface phases with distinct LEED patterns could not be found; for all investigated Mo concentrations a TiO₂(110) like pattern was observed. Mo tends to agglomerate on the surface where it is found predominantly as Mo⁶⁺ at low coverages and as Mo⁴⁺ at high coverages. Mo⁴⁺ was also identified in the bulk of the mixed oxide layer. The Mo3d binding energies categorize the Mo⁴⁺ species as being dimeric. A third Mo3d doublet is attributed to a Mo species (Mo ⁿ⁺) with an oxidation state between those reported for Mo in MoO₂ and metallic Mo. Two types of Mo-induced features could be identified in the STM images for low Mo concentrations (in the range of 1 %). At higher Mo concentrations (~50 %) the surface is characterized by stripes with limited lengths in [001] direction. The concentration of bridging oxygen vacancies, which are common defects on TiO₂(110), is reduced significantly even at low Mo concentrations. Methanol and ethanol TPD spectra reflect this effect by a decrease of the intensity of the features related to these surface defects. At elevated MoO _x coverages, the yield of reaction products in methanol and ethanol TPD spectra are somewhat smaller than those found for clean TiO₂(110) and the reactions occur at lower temperature.     

Effect of titanium dioxide nanoparticles on polydimethylsiloxane/polyethersulfone composite membranes for gas separation

Introducing inorganic nanoparticles into the structure of polymeric membranes is an interesting approach for the enhancement of physical, chemical, and separation properties of the membranes. In this article, the performance of a two‐layer nanocomposite membrane for gas separation was studied. Three different methods for embedding titanium dioxide (TiO₂) nanoparticle were employed for the membrane preparation. The techniques include blending TiO₂ in the polydimethylsiloxane (PDMS) coating layer, blending TiO₂ in the polyethersulfone (PES) support and dip coating of PES support with TiO₂ accompanied by PDMS coating. The aim of the current research was finding the optimum technique for introducing TiO₂ into the membrane to obtain superior performance for gas separation. The results indicated that PES support containing TiO₂ nanoparticles possessed favorable effect on gas separation capability. The optimum performance was obtained by PDMS‐coated membranes prepared with 7 wt% TiO₂‐embedded PES support. Carbon dioxide (CO₂) permeance, CO₂/nitrogen, and CO₂/methane selectivity were obtained as 188.7 GPU, 8.6, and 3.4, respectively. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Physico-Chemical Effects on the Scale-Up of Ag Photodeposition on TiO2 Nanoparticles

We have previously demonstrated that TiO₂ nanoparticles can be functionalized by photodeposition with silver or gold particles in the 1?C2 nm range presumed to be desirable for catalysis applications. However, the preparation of these samples directly on microscope grids, while conducive to particle size determinations, did not produce sufficient materials for reaction studies. We report here scale-up techniques designed to produce greater quantities of material for testing, while maintaining characteristics that contribute to uniformity in the deposition process. For the scale-up process, an irradiation source with highly uniform intensity is necessary to generate Ag/TiO₂ samples with consistent Ag loading. In addition, control of the precursor concentration is also required to produce Ag/TiO₂ samples with high Ag loading and narrow Ag size distribution. The optimum conditions for the scale-up process found in this study involved Ag photodeposition from a 5 × 10^?3 M AgNO₃ solution using a high pressure Hg lamp at 366 nm for 60 s. Under these reaction conditions, the size of Ag particles determined by TEM and HAADF-STEM imaging was within 1?C2 nm and the Ag loading was ~3.2 wt%. Achievement of this level of uniformity required control of the uniformity of illumination, as well as of the solution concentration and irradiation conditions. Higher solution concentrations and higher power led to the growth of larger (ca. 10 nm) silver particles. In contrast, the loading and size distribution of the Ag particles photodeposited were remarkably insensitive to the source and morphology of the TiO₂ nanoparticles utilized. No Ag peak was resolved in the XRD patterns for Ag/TiO₂ samples obtained from the optimized scale-up process, corroborating the size range determination of the Ag nanoparticles. XPS showed that the Ag particles in all cases were metallic Ag.     

Propene Adsorption on Gold Particles on TiO2(110)

The adsorption of propene on rutile TiO₂(110) and on gold islands dispersed on TiO₂(110) [Au/TiO₂(110)], both at 120 K, has been studied using temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and He⁺ low energy ion scattering spectroscopy (LEIS). Propene adsorbs on both TiO₂(110) and Au/TiO₂(110), with desorption peak temperatures at low coverage of 190 and 240 K, respectively. When only 16% of the TiO₂(110) surface is covered by gold islands [16% Au/TiO₂(110)], moderate propene doses populate both the 240 and 190 K TPD peaks, in that order. The 190 K peak, seen also without Au, is due to propene bound to bare Ti sites. The 240 K peak is attributed to propene adsorbed to Ti sites at the edges of gold islands. Tiny doses of propene to the 16% Au/TiO₂(110) surface give this a 240 K TPD peak but no 190 K feature, showing that the propene is mobile on TiO₂(110). A TPD feature at 150 K, which is more prominent at higher Au coverages and higher propene doses, is due to propene bound only to metallic Au islands. Propene desorption shows additional intensity at 265-310 K when the gold islands are only one atom thick, due to propene adsorbed on 2D Au islands or at Ti sites near their edges.     

Rutile TiO2(101) based plasmonic nanostructures

TiO₂/Ag and TiO₂/Au nanocrystalline multilayer thin films were deposited using pulsed laser deposition technique. Investigations have been made to understand the influence of different phases of TiO₂ on the surface plasmon characteristics of the thin films. Rutile phase of TiO₂ is found to be a good host matrix for both Ag and Au nanoparticles. Compared to silver, gold nanoparticles are found to enhance the photocatalytic activity of the films by exhibiting a broad and intense absorption with a significant shift to longer wavelength region.     

Deposition of Gold Particles on Mesoporous Catalyst Supports by Sonochemical Method, and their Catalytic Performance for CO Oxidation

Supported gold catalysts on the mesoporous (MSP) metal oxides were prepared by a one-step, ultrasound-assisted reduction method, and characterized by XRD, HRTEM, EDX, BET, and XPS analysis. Their catalytic activities were examined in the oxidation of CO. Compared to the Au/Fe₂O₃(MSP) catalyst, the Au/TiO₂(MSP) and Au/Fe₂O₃-TiO₂(MSP) catalysts exhibited higher catalytic activity in the oxidation of CO at low temperatures. The high catalytic activity of Au/TiO₂(MSP) was attributed to the metallic state of the gold nanoparticles, their small size (2–2.5 nm), and their high dispersion on the catalyst support.     

An experimental and theoretical understanding of a UV photodetector based on Ag nanoparticles decorated Er-doped TiO2 thin film

Glancing angle deposition (GLAD) was employed to synthesise plasmonic Silver (Ag) nanoparticles (NPs) on the chemically prepared Erbium-doped Titanium dioxide (Er:TiO₂) thin films (TFs). The impact of using Ag NPs on the morphological, optical, and electrical aspects of Er:TiO₂ TFs were sequentially analysed. From the field emission scanning electron microscopy (FESEM) image, the Ag NPs appeared spherical and uniformly distributed on the Er:TiO₂ TFs. The size (diameter) of the maximum number of Ag NPs was ~15 nm (calculated from FESEM image). Energy dispersive X-ray (EDX) spectra assured the presence of Ag NPs on the TFs. X-ray diffraction (XRD) pattern for Ag NPs decorated Er:TiO₂ TFs closely resembled the face centred cubic crystal structure of Ag NPs and body centred tetragonal Ag–O compound. The optical spectroscopy (UV–visible diffuse reflectance and photoluminescence) elucidated that the absorption of light was significantly enhanced in the UV–visible spectral range for the TFs in which Ag NPs were sandwiched between Er:TiO₂ TF layers (Er:TiO₂/Ag NPs/Er:TiO₂). The Schottky contact-based Au/Er:TiO₂/Si photodetector (PD) and Au/Er:TiO₂/Ag NPs/Er:TiO₂/Si (plasmonic) PD were constructed. The plasmonic PD offered a better photo-responsivity of ~4.5 fold higher as compared to Er:TiO₂ TF-based PD upon 380 nm illumination under ?6 V bias. An increase in detectivity and a decrease in noise equivalent power was observed for the plasmonic device compared to Er:TiO₂ device in the UV region. A theoretical approach had been adopted to calculate the wavelength-dependent responsivity for both devices. Further, the important parameters like photoconductive gain, electron transit time and electron mobility were calculated by simulating the experimental responsivity curves of the devices. These parameters exhibited improvement in the UV regime for the plasmonic PD. The fast temporal response with short rise and decay time proves the excellent efficiency of the plasmonic UV PD.     

Photocatalytic hydrogen production by Au–MxOy (MAg,Cu, Ni) catalysts supported on TiO2

Au–M_xO_y (MAg, Cu, Ni) nanoparticles supported on TiO₂–P25 were prepared by the deposition–precipitation method and were evaluated for the photocatalytic water splitting reaction for hydrogen production, using a mixture of water–methanol (1:1). The combinations of Au–Cu₂O/TiO₂ and Au–NiO/TiO₂ effectively increased the hydrogen production (2064 and 1636 μmol·h^− 1·g^− 1) obtained by Au/TiO₂ (1204 μmol·h^− 1·g^− 1). The higher photoactivities achieved by Au–Cu₂O and Au–NiO nanoparticles deposited on TiO₂ were attributed to an enhancement of the electron charge transfer from TiO₂ to the Au–M_xO_y systems and the effect of surface plasmon resonance of gold nanoparticles.     

The kinetics of CO oxidation by adsorbed oxygen on well‐defined gold particles on TiO2(110)

Very tiny Au particles on TiO₂ show excellent activity and selectivity in a number of oxidation reactions. We have studied the vapor deposition of Au onto a TiO₂(110) surface using XPS, LEIS, LEED and TPD and found that we can prepare Au islands with controlled thicknesses from one to several monolayers. In order to understand at the atomic level the unusual catalytic activity in oxidation reactions of this system, we have studied oxygen adsorption on Au/TiO₂(110) as a function of Au island thickness, and have measured the titration of this adsorbed oxygen with CO gas to yield CO₂, as function of Au island thickness, CO pressure and temperature. A hot filament was used to dose gaseous oxygen atoms. TPD results show higher O₂ desorption temperatures (741 K) from ultrathin gold particles on TiO₂(110) than from thicker particles (545 K). This implies that O_a bonds much more strongly to ultrathin islands of Au. Thus from Brønsted relations, ultrathin gold particles should be able to dissociatively adsorb O₂ more readily than thick gold particles. Our studies of the titration reaction of oxygen adatoms with CO (to produce CO₂) show that this reaction is extremely rapid at room temperature, but its rate is slightly slower for the thinnest Au islands. Thus the association reaction (CO_g + O_a → CO_2,g) gets faster as the oxygen adsorption strength decreases, again as expected from Brønsted relations. For islands of about two atomic layers thickness, the rate increases slowly with temperature, with an apparent activation energy of 11.4 ± 2.8 kJ/mol, and shows a first‐order rate in CO pressure and oxygen coverage, similar to bulk Au(110).     

Structure sensitivity of CO oxidation over model Au/TiO2 2 catalysts

Model catalysts of Au clusters supported on TiO₂ thin films were prepared under ultra-high vacuum (UHV) conditions with average metal cluster sizes that varied from ~2.5 to ~6.0 nm. The reactivities of these Au/TiO₂ catalysts were measured for CO oxidation at a total pressure of 40 Torr in a reactor contiguous to the surface analysis chamber. Catalyst structure and composition were monitored with Auger electron spectroscopy (AES) and scanning tunneling microscopy and spectroscopy (STM/STS). The apparent activation energy for the reaction between 350 and 450 K varied from 1.7 to 5 kcal/mol as the Au coverage was increased from 0.25 to 5 monolayers, corresponding to average cluster diameters of 2.5–6.0 nm. The specific rates of reaction ((product molecules) × (surface site)^-1 × s^-1 were dependent on the Au cluster size with a maximum occurring at 3.2 nm suggesting that CO oxidation over Au/TiO₂(001)/Mo(100) is structure sensitive. This revised version was published online in July 2006 with corrections to the Cover Date.     

Pd nanoparticle enhanced re-oxidation of non-stoichiometric TiO2: STM imaging of spillover and a new form of SMSI

We have used STM imaging in situ to demonstrate two fundamental steps in catalytic processes on model catalysts at elevated temperature. We show that Pd nanoparticles on sub-stoichiometric TiO₂(110) dissociatively adsorb O₂ at 673 K which spills over onto the support where further reaction takes place. The spillover oxygen re-oxidises the surface by removing Tiⁿ⁺ interstitial ions trapped in the crystal lattice, preferentially re-growing TiO₂ around and over the particles. The identification of the metal enhanced re-oxidation mechanism may have important and general consequences for the understanding of catalysis and gas sensing.     

Morphological and thermal properties of photodegradable biocomposite films

Biocomposites containing ultraviolet (UV) radiation absorbing inorganic nanofillers are of great interest in food packaging applications. The biodegradable polylactide (PLA) composite films were prepared by solvent casting method by incorporating 1 wt % of titanium dioxide (TiO₂) and Ag‐TiO₂ (silver nanoparticles decorated TiO₂) nanoparticles to impart the photodegradable properties. The films were exposed to UV radiation for different time periods and morphology of the composite films before and after UV exposure were investigated. The results showed that homogenous filler distribution was achieved in the case of Ag‐TiO₂ nanoparticles. The thermal properties and thermomechanical stability of the composite film containing Ag‐TiO₂ nanoparticles were found to be much higher than those of neat PLA and PLA/TiO₂ composite films. The scanning electron microscopy and X‐ray diffraction studies revealed that the photodegradability of PLA matrix was significantly improved in the presence of Ag‐TiO₂ nanoparticles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Naturally inspired SERS substrates fabricated by photocatalytically depositing silver nanoparticles on cicada wings

Densely stacked Ag nanoparticles with an average diameter of 199 nm were effectively deposited on TiO₂-coated cicada wings (Ag/TiO₂-coated wings) from a water-ethanol solution of AgNO₃ using ultraviolet light irradiation at room temperature. It was seen that the surfaces of bare cicada wings contained nanopillar array structures. In the optical absorption spectra of the Ag/TiO₂-coated wings, the absorption peak due to the localized surface plasmon resonance (LSPR) of Ag nanoparticles was observed at 440 nm. Strong Surface-enhanced Raman scattering (SERS) signals of Rhodamine 6G adsorbed on the Ag/TiO₂-coated wings were clearly observed using the 514.5-nm line of an Ar⁺ laser. The Ag/TiO₂-coated wings can be a promising candidate for naturally inspired SERS substrates.     

Hydrogen Formation in the Reactions of Methanol on Supported Au Catalysts

The adsorption and reactions of methanol have been investigated on Au metal supported by various oxides and carbon Norit of high surface area. Infrared spectroscopic studies revealed the dissociation of methanol at 300 K, which mainly occurs on the oxide-supports yielding methoxy species. The presence of Au already appeared in the increased amounts of desorbed products in the TPD spectra. The reaction pathway of the decomposition and the activity of the catalyst sensitively depend on the nature of the support. As regards the production of hydrogen the most effective catalyst is Au/CeO₂ followed by Au/MgO, Au/TiO₂ and Au/Norit. In contrast, on Au/Al₂O₃ the main process is the dehydration reaction yielding dimethyl ether. On Au/CeO₂ the decomposition of methanol starts above ~500 K and approaches total conversion at 723–773 K. The products are H₂ (~68%) and CO (~27%) with very small amounts of methane and CO₂. The decomposition of methanol follows the first order kinetics. The activation energy of this process is 87.0 kJ/mol. The selectivity of H₂ formation at 573–773 K was ~90%, this value increased to 97% using CH₃OH:H₂O (1:1) reacting mixture indicating the involvement of water in the reaction. No deactivation of Au catalysts was experienced at 773 K in ~10 h. It is assumed that the interface between Au and partially reduced ceria is responsible for the high activity of Au/CeO₂ catalyst.     

Titania and Noble Metals Deposited Titania Catalysts in the Photodegradation of Tartazine

Nanoparticles of TiO₂ were synthesised by sol–gel technique and photo deposition of about 1% noble metal (M/TiO₂, M = Ag, Au, and Pt) on TiO₂ was carried out. The catalysts were characterised by XRD, TEM, BET, FT-IR, and UV–Visible spectroscopy. Using commercial TiO₂ (P-25 Degussa), the conditions such as dye concentration, catalyst weight and pH were optimized for complete decolourisation of textile dye tartazine (TAZ) under UV and visible irradiations. Among the catalysts tested, the synthesised TiO₂ showed better photocatalytic activity than TiO₂ (P-25 Degussa). Whereas, M/TiO₂ catalysts showed remarkable photocatalytic activity towards the decolourisation of TAZ even under visible irradiation. This enhanced activity of M/TiO₂ catalyst may be attributed to the trapping of conduction band electrons by noble metals.