Au–TiO2 catalysts stabilised by carbon nanofibres

The catalytic activity and stability in the water–gas shift reaction have been tested for Au-based catalysts prepared by deposition of Au from colloid solutions. The supports that have been used are TiO₂, TiO₂ supported on carbon nanofibres (CNF) and CNF. Thermal treatments of the samples show that the Au particle size depends on the support material and hence the interaction between the Au particles and the support. In situ X-ray absorption spectroscopic (XAS) measurements during the water–gas shift reaction show no changes in the first Au–Au coordination number for the catalysts containing CNF. Furthermore, improved short-time stability is obtained compared to the AuTiO₂ catalysts. The improved stability is achieved by the CNF stabilising small TiO₂ particles and hence prevent subsequent sintering of the Au particles.     

Identification of valence shifts in Au during the water-gas shift reaction

In situ X-ray absorption spectroscopy (XAS) has been performed to investigate the active site on Au-based catalysts in the water-gas shift (WGS) reaction. The surface area and hence the WGS activity is higher for AuTiO₂ catalysts supported on carbon nanofibres (CNF) than TiO₂. The WGS reaction rate depends on the Au coordination number with an apparent maximum close to eight which corresponds to a particle size of approximately 2.5–3.0 nm. A likely cause for the changes in the electronic structure of Au is the adsorption of CO on the surface, which also creates a small positive charge in the Au atoms. The catalytic activity significantly improves when titania is present compared to Au deposited directly on CNF.     

Gold nanoparticles supported on ceria-modified mesoporous titania as highly active catalysts for low-temperature water-gas shift reaction

New gold catalytic system prepared on ceria-modified mesoporous titania (CeMTi) used as water-gas shift (WGS) reaction catalyst is reported. Mesoporous titania (MTi) was synthesized using surfactant templating method through a neutral [C₁₃(EO)₆–Ti(OC₃H₇)₄] assembly pathway. Ceria modifying additive was deposited on MTi by deposition precipitation (DP) method. Gold-based catalysts with different gold content (1–5 wt.%) were synthesized by DP of gold hydroxide on mixed metal oxide support. The supports and the catalysts were characterized by powder X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), N₂ adsorption analysis and temperature-programmed reduction (TPR). The catalytic behavior of the gold-based catalysts was evaluated in WGS reaction in a wide temperature range (140–300 °C) and at different space velocities and H₂O/CO ratios. The influence of gold content and particle size on the catalytic performance was investigated. The WGS activity of the new gold/ceria-modified mesoporous titania catalysts was compared with that of gold catalysts supported on simple oxides CeO₂ and mesoporous TiO₂, as well as gold/ceria-modified titania and reference catalyst Au/TiO₂ type A (World Gold Council). A high degree of synergistic interaction between ceria and mesoporous titania and a positive modification of structural and catalytic properties by ceria has been achieved. It is clearly revealed that the ceria-modified mesoporous titania is of much interest as potential support for gold-based catalyst. The Au/ceria-modified mesoporous titania catalytic system is found to be efficient catalyst for WGSR.     

Preparation of Au/TiO2 catalysts from Au(I)–thiosulfate complex and study of their photocatalytic activity for the degradation of methyl orange

Gold loaded on TiO₂ (Au/TiO₂) catalysts were prepared using Au(I)–thiosulfate complex (Au(S₂O₃)₂³⁻) as the gold precursor for the first time. The samples were characterized by UV–vis diffuse reflectance spectra, X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption flame emission spectroscopy (AAS), and X-ray photoelectron spectroscopy (XPS) methods. Using Au(S₂O₃)₂³⁻ as gold precursor, ultra-fine gold nanoparticles with a highly disperse state can be successfully formed on the surface of TiO₂. The diameter of Au nanoparticles increases from 1.8 to 3.0 nm with increasing the nominal Au loading from 1% to 8%. The photocatalytic activity of Au/TiO₂ catalysts was evaluated from the analysis of the photodegradation of methyl orange (MO). With the similar Au loading, the catalysts prepared with Au(S₂O₃)₂³⁻ precursor exhibit higher photocatalytic activity for methyl orange degradation when compared with the Au/TiO₂ catalysts prepared with the methods of deposition–precipitation (DP) and impregnation (IMP). The preparation method has decisive influences on the morphology, size and number of Au nanoparticles loaded on the surface of TiO₂ and further affects the photocatalytic activity of the obtained catalysts.     

CO oxidation activity of gold catalysts supported on various oxides and their improvement by inclusion of an iron component

A number of oxide-supported gold catalysts have been prepared by deposition–precipitation, with variation of the pH over a wide range, the optimum pH for high activity being 9 for TiO₂, 7.5 for Fe₂O₃, and 7 for SnO₂ and CeO₂. Whereas the activity shown by Au/TiO₂ and Au/Fe₂O₃ decreased linearly with time, Au/CeO₂ and Au/SnO₂ underwent an initial major deactivation. Addition of iron in the preparation lowered the rate of deactivation when TiO₂, SnO₂ and CeO₂ were used as supports, and imparted activity when as with Bi₂O₃ it was previously lacking. XPS revealed the existence of a broad multi-state iron-containing region, and TEM and STEM/EDX indicated that small gold particles (1.5–4 nm) were partly in contact with it. Improved stability is therefore due to gold particles being in contact with an iron phase such as FeO(OH); calcination removed the stabilisation.     

Supported gold catalysis derived from the interaction of a Au–phosphine complex with as-precipitated titanium hydroxide and titanium oxide

Supported gold catalysts derived from interaction of a Au–phosphine complex Au(PPh₃)(NO₃) (1) with conventional titanium oxide TiO₂ and as-precipitated titanium hydroxide (*, as-precipitated) have been characterized by means of XRD, XPS, EXAFS, and CP/MAS–NMR. The Au complex 1 was supported on TiO₂ and without loss of Au–P bonding at room temperature. The Au complex 1 on TiO₂ was readily and completely decomposed to form metallic gold particles by calcination at 473 K, whereas only a small part of the complex 1 on was transformed to metallic gold particles. By calcination of 1/ at 573 K the formation of both metallic gold particles and crystalline titanium oxides became notable as evidenced by XRD, XPS and CP/MAS–NMR. The mean diameter of Au particles in 1/ calcined at 673 K was less than 30 Å as estimated from Au(2 0 0) diffraction, which was about one-tenth of that for the corresponding 1/TiO₂. Thus the as-precipitated titanium hydroxide was able to stabilize the Au complex 1 to lead to the simultaneous decomposition of Au complex and . The catalyst 1/ calcined at 673 K afforded remarkably high catalytic activity for low-temperature CO oxidation at 273–373 K as compared to the catalyst 1/TiO₂.     

Gold catalysts supported on mesoporous zirconia for low-temperature water–gas shift reaction

Mesoporous ZrO₂ with high surface area and uniform pore size distribution, synthesized by surfactant templating through a neutral [C₁₃(EO)₆–Zr(OC₃H₇)₄] assembly pathway, was used as a support of gold catalysts prepared by deposition–precipitation method. The supports and the catalysts were characterized by powder X-ray diffraction, scanning and transmission electron microscopy, N₂ adsorption analysis, temperature programmed reduction and desorption. The catalytic activity of gold supported on mesoporous zirconia was evaluated in water–gas shift (WGS) reaction at wide temperature range (140–300 °C) and at different space velocities and H₂O/CO ratios. The catalytic behaviour and the reasons for а reversible deactivation of Au/mesoporous zirconia catalysts were studied. The influence of gold content and particle size on the catalytic performance was investigated. The WGS activity of the new Au/mesoporous zirconia catalyst was compared to the reference Au/TiO₂ type A (World Gold Council), revealing significantly higher catalytic activity of Au/mesoporous zirconia catalyst. It is found that the mesoporous zirconia is a very efficient support of gold-based catalyst for the WGS reaction.     

Development and evaluation of an alternative method for municipal wastewater treatment using homogeneous photocatalysis and constructed wetlands

In the preparation of Au/TiO₂ (P-25) catalysts by the method commonly but inaccurately known as deposition–precipitation (DP), the uptake of anionic complexes in solution onto the support is maximal close to the pH of the isoelectric point (6); below this pH, complexes are adsorbed electrostatically, but at higher pH values, especially at pH 8–9, the neutral Au(OH)₃·H₂O is reversibly adsorbed on the negatively charged surface. The specific activity (per gram of gold) peaks however at pH 8–9, because here the adsorbed complex is largely chlorine-free. The reversibility of the adsorption equilibrium is proved by alteration of the pH during the course of a single preparation through analysis of samples removed at intermediate points. This observation enables poorly dispersed precursors or sintered gold particles to be re-dispersed, and high activity restored.     

Low-temperature catalytic combustion of methanol and its decomposed derivatives over supported gold catalysts

Gold can be compared favorably with Pd and Pt in the catalytic combustion of CH₃OH, HCHO and HCOOH when it is deposited on some reducible metal oxides (-Fe₂O₃, TiO₂, etc.). While the supported gold catalysts are less active in H₂ oxidation, they exhibit much higher activities in CO oxidation. For Au/TiO₂, the effect of catalyst preparation was further investigated. Since the activity for CO oxidation of the gold catalysts is not depressed but enhanced by moisture, they are practically applicable to CO removal from air at room temperature. Gold supported on manganese oxide is especially effective in the selective CO removal from hydrogen, indicating its potential applicability to polymer electrolyte fuel cells using the reformed gas of methanol.     

A comparative study of the water-gas shift activity of Pt catalysts supported on single (MOx) and composite (MOx/Al2O3, MOx/TiO2) metal oxide carriers

The water-gas shift (WGS) activity of platinum catalysts dispersed on a variety of single metal oxides as well as on composite MO_x/Al₂O₃ and MO_x/TiO₂ supports (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, La, Ce, Nd, Sm, Eu, Gd, Ho, Er, Tm) has been investigated in the temperature range of 150–500 °C, using a feed composition consisting of 3% CO an 10% H₂O. For Pt catalysts supported on single metal oxides, it has been found that both the apparent activation energy of the reaction and the intrinsic rate depend strongly on the nature of the support. In particular, specific activity of Pt at 250 °C is 1–2 orders of magnitude higher when supported on “reducible” compared to “irreducible” metal oxides. For composite Pt/MO_x/Al₂O₃ and Pt/MO_x/TiO₂ catalysts, it is shown that the presence of MO_x results in a shift of the CO conversion curve toward lower reaction temperatures, compared to that obtained for Pt/Al₂O₃ or Pt/TiO₂, respectively. The specific reaction rate is in most cases higher for composite catalysts and varies in a manner which depends on the nature, loading, and primary crystallite size of dispersed MO_x. Results are explained by considering that reducibility of small oxide particles increases with decreasing crystallite size, thereby resulting in enhanced WGS activity. Therefore, evidence is provided that the metal oxide support is directly involved in the WGS reaction mechanism and determines to a significant extent the catalytic performance of supported noble metal catalysts. Results of catalytic performance tests obtained under realistic feed composition, consisting of 3% CO, 10% H₂O, 20% H₂ and 6% CO₂, showed that certain composite Pt/MO_x/Al₂O₃ and Pt/MO_x/TiO₂ catalysts are promising candidates for the development of active WGS catalysts suitable for fuel cell applications.     

Au对TiO2光电催化材料的改性策略研究进展

近年来,环境污染、能源枯竭问题日益严重,成为制约人类生存与发展的主要因素。光电催化技术能够同时实现污染物的降解与清洁能源的制备,有助于缓解环境污染与能源枯竭问题。作为典型的光（电）催化材料,TiO₂具有光活性强、性质稳定、廉价易得、环境友好等诸多优点,数十年来已成为光催化及相关领域的研究热点。然而,TiO₂存在的本征缺陷依然制约着其进一步推广应用,为此研究人员已提出多种方式对TiO₂进行改性。其中贵金属/TiO₂复合材料可显著提升TiO₂的光学活性并拓宽其吸收波长范围,尤其是Au/TiO₂材料体系已受到广泛关注和认可,表现出良好的应用前景。本文通过对目前Au/TiO₂复合材料的发展现状进行了总结,首先简单介绍了Au和TiO₂的化学性质及Au对TiO₂光学性能的增强原理;随后对Au/TiO₂复合材料的改性策略及相关作用机制展开讨论,包括Au对TiO₂光学性能的影响及调控、修饰方法的选择与影响等;最后总结出目前Au/TiO₂复合材料依然以克服TiO₂的两大本征缺陷为主,探讨各类新型Au/TiO₂复合材料有望使其得到逐步推广与实际应用。最后对目前Au/TiO₂复合材料的研究现状进行系统总结并探讨该材料未来的研究和发展方向。     

Synergism in methanol synthesis from carbon dioxide over gold catalysts supported on metal oxides

Gold deposited on various oxides with high dispersion was found to be active for the hydrogenation of CO₂ at temperatures between 150 and 400°C. Product selectivities greatly depended on the nature of support oxide. Acidic oxides like TiO₂ gave higher CO₂ conversions but low methanol yields. Zinc oxide component was indispensable for selective methanol synthesis. Significantly, large particle size effect of gold was observed and smaller gold particles gave higher methanol productivity per exposed surface area of gold. This can be explained by an increase in the perimeter area of gold particles with a decrease in particle size. Methanol yield was greatly enhanced in a Au/ZnO---TiO₂ catalyst probably due to an increase in gold-zinc oxide interface.     

The CO–H2 and CO–H2O reactions over TiO2 nanotubes filled with Pt metal nanoparticles

We have investigated the catalytic behavior of Pt encapsulated TiO₂ nanotubes for the water gas shift reaction as well as the hydrogenation of CO. Pt–TiO₂ nanotube catalysts were prepared by employing fine fiber shaped crystals of [Pt(NH₃)₄](HCO₃)₂ complex as a structure determining template material. The turnover frequencies (TOF) of these nanotube catalysts were more than one order of magnitude larger than conventional impregnation Pt/TiO₂ catalysts, and the selectivity for methanol in CO–H₂ reaction was extraordinary high compared to the impregnation catalysts. The XPS and XRD analyses of the nanotubes revealed characteristic electronic state of reduced TiO₂ (Ti³⁺ in rutile structure) with zerovalent Pt even after the calcination at 773 K. In WGS reaction, electron rich Ti³⁺ on the nanotube wall may play an important role to activate water molecules for the oxidation of CO. In CO–H₂ reaction, similar promotion effect of Ti³⁺ species may be operating for selective methanol formation by supplying active OH(a).     

Production of hydrogen via partial oxidation of methanol over Au/TiO2 catalysts

Selective production of hydrogen by partial oxidation of methanol (CH₃OH + (1/2)O₂ → 2H₂ + CO₂) over Au/TiO₂ catalysts, prepared by a deposition–precipitation method, was studied. The catalysts were characterized by XRD, TEM, and XPS analyses. TEM observations show that the Au/TiO₂ catalysts exhibit hemispherical gold particles, which are strongly attached to the metal oxide support at their flat planes. The size of the gold particles decreases from 3.5 to 1.9 nm during preparation of the catalysts with the rise in pH from 6 to 9 and increases from 2.9 to 4.3 nm with the rise in calcination temperature up to 673 K. XPS analyses demonstrate that in uncalcined catalysts gold existed in three different states: i.e., metallic gold (Au⁰), non-metallic gold (Au^δ+) and Au₂O₃, and in catalysts calcined at 573 K only in metallic state. The catalytic activity is strongly dependent on the gold particle size. The catalyst precipitated at pH 8 and uncalcined catalysts show the highest activity for hydrogen generation. The partial pressure of oxygen plays an important role in determining the product distribution. There is no carbon monoxide detected when the O₂/CH₃OH molar ratio in the feed is 0.3. Both hydrogen selectivity and methanol conversion increase with increasing the reaction temperature. The reaction pathway is suggested to consist of consecutive methanol combustion, partial oxidation and steam reforming.     

Investigation of the preparation and activity of gold catalysts in the total oxidation of n-hexane

The factors affecting the preparation of Au/TiO₂ catalysts and their activity in the total oxidation of n-hexane were investigated. The mechanism of gold deposition–precipitation is discussed through comparison of the samples prepared by this method and others prepared by anion adsorption method. The influence of the pH and of the origin of TiO₂ support used are additionally addressed. The difference of gold dispersion observed between the two methods is attributed to a difference of mobility of the gold precursors during the thermal treatment rather than to a difference of dispersion over the uncalcined samples. The mechanism of gold deposition–precipitation actually involves the reactions of gold hydroxy-chloride species with the surface. Another part of the work, thus, concerned the use of the deposition–precipitation method to prepare a Au/MnO₂ catalyst. It is shown that the activity of γ-MnO₂ is directly proportional to its surface area and that the deposition–precipitation procedure decreases the surface and activity of MnO₂. However, the deposition of gold allows to avoid a too deep sintering of γ-MnO₂ and, thus, helps to somehow preserve its activity.     

Plasmonic Au nanoparticles supported on both sides of TiO2 hollow spheres for maximising photocatalytic activity under visible light

A strategy of intensifying the visible light harvesting ability of anatase TiO₂ hollow spheres (HSs) was developed, in which both sides of TiO₂ HSs were utilised for stabilising Au nanoparticles (NPs) through the sacrificial templating method and convex surface-induced confinement. The composite structure of single Au NP yolk-TiO₂ shell-Au NPs, denoted as Au@Au(TiO₂, was rendered and confirmed by the transmission electron microscopy analysis. Au@Au(TiO₂ showed enhanced photocatalytic activity in the degradation of methylene blue and phenol in aqueous phase under visible light surpassing that of other reference materials such as Au(TiO₂ by 77% and Au@P25 by 52%, respectively, in phenol degradation.     

Effect of substrate on the phase transformation of TiO2 in pearlescent pigment

The TiO₂/substrate pearlescent pigments were prepared by the hydrolysis of TiOCl₂ on the substrate followed by a calcinations process. The natural mica (muscovite), synthetic mica (fluorophlogopite) and -alumina flake were selected as the substrates for pearlescent pigments. The effect of substrate on the anatase to rutile (A–R) phase transformation of TiO₂ was studied. The A–R phase transformation of TiO₂ during the preparation of pearlescent pigments and their proportion in the TiO₂ layer have been analyzed by XRD measurements. The phase compositions of TiO₂ layer in each pearlescent pigment are quite different depending on the substrates. The TiO₂ layer deposited on -alumina has higher rutile fraction than those on the natural and synthetic mica. The XPS analysis showed that the cations originally present in the substrates diffused into the TiO₂ layer. The TiO₂ layer deposited on -alumina contains Al, while those on the natural and synthetic mica substrates contain Si and K in addition to Al. The metal cations diffusing from the substrate into TiO₂ layer might retard the A–R phase transformation of TiO₂. The suppressing effect on the A–R transformation of TiO₂ by mixed cations seems to be much stronger than that of single cation, resulting in relatively higher rutile fraction in the case of TiO₂ layer deposited on -alumina.     

Insight into the free-radical chain mechanism of gold-catalyzed hydrocarbon oxidation reactions in the liquid phase

A free-radical mechanism has been evidenced in the liquid phase stereoselective epoxidation of trans-stilbene using methylcyclohexane (MCH) as solvent, limited amount of tert-butylhydroperoxide (TBHP), and supported gold catalysts. Trans-stilbene oxide is the major reaction product observed, with selectivities up to 88% when using the Au/TiO₂ reference catalyst from the World Gold Council. However the selectivity decreases significantly when using Au/C instead of oxide-supported gold catalysts or H₂O₂ instead of TBHP. HPLC and GC–MS analyses indicate that a fraction of MCH is oxidized during the epoxidation process. It seems that TBHP is the radical source while MCH is propagating the active radical. On the other hand, hydroxyl radicals are responsible for the degradation of the molecule. XPS studies show the presence of Au⁰ (90%) and Au⁺ (10%) on the Au/C catalyst and Au^δ− (90%) and Au⁺ (10%) on the Au/TiO₂ catalyst. Both gold and, to a minor extent, titania seem to be involved in the reaction cycle.     

Combinatorial investigation of Pt–Ru–M as anode electrocatalyst for direct methanol fuel cell

The addition of Au/TiO₂ and zeolites as active components to PtRu/C electrode in DMFC was investigated by using combinatorial high-throughput-screening test. Addition of Au/TiO₂ to PtRu/C electrode, especially in the ratio of PtRu/C: Au/TiO₂ 9:1, 8:2, 7:3, were effective to improve the performance of direct methanol fuel cell. The electrochemical properties of the prepared electrodes were compared using cyclic voltammetry, impedance spectroscopy and a single cell performance test of a direct methanol fuel cell (DMFC). The adsorbed CO on Pt might be easily oxidized on the surface of Au/TiO₂ by interaction between PtRu/C and Au/TiO₂. The addition of the solid acid proton conducting materials (ZSM-5) on PtRu/C anode leads to the high temperature operation. The cell performance was maintained over the cell temperature 120 °C (maximum current density was 200 mA/cm² at 160 °C) by the addition of ZSM-5 as proton conducting materials.     

Au/TiO2复合物的制备、表征及其增强光催化灭菌活性

为提升TiO₂光催化活性克服其可见光响应能力差的问题,采用沉积-沉淀法制备了Au/TiO₂复合物光催化剂,利用X射线衍射（XRD）、傅里叶红外光谱（FTIR）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-vis DRS）、荧光发射光谱等对样品进行了表征。XRD、FTIR和XPS结果表明,Au/TiO₂中TiO₂为锐钛矿相且Au成功沉积至TiO₂。UV-vis DRS和荧光发射光谱结果表明,适量Au修饰不仅能提高TiO₂对可见光的吸收,还可促进TiO₂光生电子-空穴对分离,有利于增强其光催化活性。自由基捕获实验证实,形成?OH的数量与光照时间成正比且?OH生成量越多,光催化活性越高。对比考察了Au/TiO₂和TiO₂在氙灯光源照射下对大肠杆菌的光催化杀灭作用,并探讨了Au负载量、光照时间、光照强度、光催化剂浓度等因素对灭菌性能的影响。结果表明：Au/TiO₂的光催化灭菌活性优于TiO₂,且与光照时间和光照强度均成正比;Au的适宜负载量为3%（质量分数）;3%Au/TiO₂在光照时间60min、光照强度7mW/cm²、光催化剂浓度100μg/mL的条件下,对大肠杆菌的杀灭效率高达91.3%。