Comparative studies of gold catalysts prepared via solvated metal atom impregnation and conventional impregnation: characterization and low-temperature co oxidation

Supported Au catalysts for low-temperature CO oxidation were prepared by solvated metal atom impregnation (SMAI) and conventional impregnation (CI). X-ray photoelectron spectroscopy investigations indicated that gold in all the samples was in the metallic state. TEM and XRD measurements showed that the mean diameter of Au particles prepared by SMAI was smaller than that of those prepared by CI with the same gold content. Catalytic tests showed that SMAI catalysts had higher CO oxidation activity than CI catalysts with the same compositions. Both SMAI and CI Au/TiO₂catalysts exhibited high activities in low temperature CO oxidation. Full CO conversion was obtained at 323 K for 3.1 wt.% Au/TiO₂ (SMAI) catalyst, which displayed higher activity than the 3.1 wt.% Au/D-72(SMAI) and 3.1 wt.% Au/TiO₂(CI). Although the sizes of gold particles prepared by the same method and supported on both TiO₂ and resin were comparable, the Au/TiO₂ catalysts showed significantly higher activities than the Au/resin catalysts with the same Au contents under the same reaction conditions. These results prove that not only the gold particle size, but also the support plays a key role in CO oxidation. This revised version was published online in June 2006 with corrections to the Cover Date.     

Geometrical Structure of the Gold–Iron(III) Oxide Interfacial Perimeter for CO Oxidation

The geometrical structure of the Au‐Fe₂O₃ interfacial perimeter, which is generally considered as the active sites for low‐temperature oxidation of CO, was examined. It was found that the activity of the Au/Fe₂O₃ catalysts not only depends on the number of the gold atoms at the interfacial perimeter but also strongly depends on the geometrical structure of these gold atoms, which is determined by the size of the gold particle. Aberration‐corrected scanning transmission electron microscopy images unambiguously suggested that the gold particles, transformed from a two‐dimensional flat shape to a well‐faceted truncated octahedron when the size slightly enlarged from 2.2 to 3.5 nm. Such a size‐induced shape evolution altered the chemical bonding environments of the gold atoms at the interfacial perimeters and consequently their catalytic activity. For Au particles with a mean size of 2.2 nm, the interfacial perimeter gold atoms possessed a higher degree of unsaturated coordination environment while for Au particles with a mean size of 3.5 nm the perimeter gold atoms mainly followed the atomic arrangements of Au {111} and {100} facets. Kinetic study, with respect to the reaction rate and the turnover frequency on the interfacial perimeter gold atom, found that the low‐coordinated perimeter gold atoms were intrinsically more active for CO oxidation. ¹⁸O isotopic titration and Infrared spectroscopy experiments verified that CO oxidation at room temperature occurred at the Au‐Fe₂O₃ interfacial perimeter, involving the participation of the lattice oxygen of Fe₂O₃ for activating O₂ and the gold atoms for CO adsorption and activation.     

Catalytic performance and structural characterization of ferric oxide and its composite oxides supported gold catalysts for low-temperature CO oxidation

The preparation and catalytic activity of ferric oxide and its composite oxides supported gold catalysts for low-temperature CO oxidation were investigated detailedly, and characterized extensively by XRD, XPS, TPR, EC and XAFS techniques. It was found that containing highly dispersed Au of partially oxidized state, these nano-structured oxides supported Au/Fe2O3 and Au/NiFe2O4 catalysts had higher low-temperature activities. The possible catalytic active center is the gold of partially oxidized state (Auζ+).     

Modulation of the Activity of Gold Clusters Immobilized on Functionalized Mesoporous Materials in the Oxidation of Cyclohexene via the Functional Group. The Case of Aminopropyl Moiety

Gold nanoclusters and isolated gold atoms have been produced in a two-liquid phase procedure that involves a solution of gold in aqua regia and rosemary essential oil as organic layer. These gold entities have been immobilized on the ordered mesoporous silica material SBA-15 functionalized with different amounts of aminopropyl groups. The resulting materials have been characterized by XRD, N₂ adsorption, chemical analysis, TGA, ²⁹Si MAS NMR, ¹³C CP/MAS NMR, UV-vis spectroscopy, XPS, and STEM. The Au-containing materials retain the ordering and porosity of the pristine support. Gold content varies in the range of 0.07–0.7 wt% as a function of the specific immobilization conditions, while STEM evidences the presence of isolated gold atoms. XPS shows a shift of the Au 4f BE toward values lower than those of metallic gold. The catalytic activity in the oxidation of cyclohexene with molecular oxygen at atmospheric pressure parallels the Au content of the aminopropyl-SBA-15 supports. This activity is higher than that of analogous Au entities immobilized on SBA-15 functionalized with thiol or sulfonate groups, the activity decreasing in the order Au-NH₂ > Au-SO₃⁻ > Au-SH. This behavior has been attributed to differences in the interaction strength between the functional group and the Au entities, which is optimum for the aminopropyl groups.     

Carbon Monoxide Oxidation by Polyoxometalate‐Supported Gold Nanoparticulate Catalysts: Activity,Stability, and Temperature‐ Dependent Activation Properties

Nanoparticulate gold supported on a Keggin‐type polyoxometalate (POM), Cs₄[α‐SiW₁₂O₄₀]?n H₂O, was prepared by the sol immobilization method. The size of the gold nanoparticles (NPs) was approximately 2 nm, which was almost the same as the size of the gold colloid precursor. Deposition of gold NPs smaller than 2 nm onto POM (Au/POM) was essential for a high catalytic activity for CO oxidation. The temperature for 50 % CO conversion was ?67 °C. The catalyst showed extremely high stability for at least one month at 0 °C with full conversion. The catalytic activity and the reaction mechanism drastically changed at temperatures higher than 40 °C, showing a unique behavior called a U‐shaped curve. It was revealed by IR measurement that Au^δ+ was a CO adsorption site and that adsorbed water promoted CO oxidation for the Au/POM catalyst. This is the first report on CO oxidation utilizing Au/POMs catalysts, and there is a potential for expansion to various gas‐phase reactions.     

Correlation of the Catalytic Activity for Oxidation Taking Place on Various TiO2 Surfaces with Surface OH Groups and Surface Oxygen Vacancies

Three catalytic oxidation reactions have been studied: The ultraviolet (UV) light induced photocatalytic decomposition of the synthetic dye sulforhodamine B (SRB) in the presence of TiO₂ nanostructures in water, together with two reactions employing Au/TiO₂ nanostructure catalysts, namely, CO oxidation in air and the decomposition of formaldehyde under visible light irradiation. Four kinds of TiO₂ nanotubes and nanorods with different phases and compositions were prepared for this study, and gold nanoparticle (Au‐NP) catalysts were supported on some of these TiO₂ nanostructures (to form Au/TiO₂ catalysts). FTIR emission spectroscopy (IES) measurements provided evidence that the order of the surface OH regeneration ability of the four types of TiO₂ nanostructures studied gave the same trend as the catalytic activities of the TiO₂ nanostructures or their respective Au/TiO₂ catalysts for the three oxidation reactions. Both IES and X‐ray photoelectron spectroscopy (XPS) proved that anatase TiO₂ had the strongest OH regeneration ability among the four types of TiO₂ phases or compositions. Based on these results, a model for the surface OH group generation, absorption, and activation of molecular oxygen has been proposed: The oxygen vacancies at the bridging O^2? sites on TiO₂ surfaces dissociatively absorb water molecules to form OH groups that facilitate adsorption and activation of O₂ molecules in nearby oxygen vacancies by lowering the absorption energy of molecular O₂. A new mechanism for the photocatalytic formaldehyde decomposition with the Au/TiO₂ catalysts is also proposed, based on the photocatalytic activity of the Au‐NPs under visible light. The Au‐NPs absorb the light owing to the surface plasmon resonance effect and mediate the electron transfers that the reaction needs.     

纳米结构Au/Fe_2O_3的制备、表征及催化氧化性能

分别以纳米和块状氧化铁为载体,通过沉积沉淀法制备了Au/Nano-Fe2O3和Au/Bulk-Fe2O3,并对其进行了表征和催化氧化性能测试。结果表明:对于Au/Nano-Fe2O3,5 nm Au颗粒被尺寸相当的Nano-Fe2O3所包覆,形成新颖的类似核壳结构;对于Au/Bulk-Fe2O3,3 nm Au颗粒高度分散于Bulk-Fe2O3的表面。在1-苯乙醇的氧化反应中,Au/Nano-Fe2O3显示出比Au/Bulk-Fe2O3更好的催化活性。活性的增强主要与小尺寸的Nano-Fe2O3以及Au和Nano-Fe2O3更大的接触界面有关。相比于广泛受到重视的Au的尺寸效应来说,对于Au/Nano-Fe2O3而言,Fe2O3尺寸的影响更大。     

γ-Al2O3负载的金溶胶的尺寸效应对CO催化氧化活性的影响

The relationship between particle size and catalytic activity of gold nanoparticle catalysts with γ-Al2O3 as support has been investigated. The catalysts were prepared via the gold sol with different particle sizes by micelle method, and their structures were characterized by HRTEM and XRD, respectively. Furthermore, the catalytic activities were tested by CO oxidation. Experimental results showed that the catalytic activity became much weaker when gold particles were increased from 3.2 to 6.6 nm. Additionally, the particle size was also a key factor to govern catalytic activity with regard to gold supported on TiO2 prepared by the methods of deposition-precipitation.     

纳米结构Au/Fe2O3的制备、表征及催化氧化性能

分别以纳米和块状氧化铁为载体,通过沉积沉淀法制备了Au/Nano-Fe₂O₃和Au/Bulk-Fe₂O₃,并对其进行了表征和催化氧化性能测试。结果表明：对于Au/Nano-Fe₂O₃,5nmAu颗粒被尺寸相当的Nano-Fe₂O₃所包覆,形成新颖的类似核壳结构;对于Au/Bulk-Fe₂O₃,3nmAu颗粒高度分散于Bulk-Fe₂O₃的表面。在1-苯乙醇的氧化反应中,Au/Nano-Fe₂O₃显示出比Au/Bulk-Fe₂O₃更好的催化活性。活性的增强主要与小尺寸的Nano-Fe₂O₃以及Au和Nano-Fe₂O₃更大的接触界面有关。相比于广泛受到重视的Au的尺寸效应来说,对于Au/Nano-Fe₂O₃而言,Fe₂O₃尺寸的影响更大。     

高活性Au/SnO2催化剂的制备及其在1,4-丁二醇氧化制γ-丁内酯反应中的催化应用

采用沉积沉淀法制备了一系列商业SnO₂负载的纳米Au催化剂, 通过电感耦合等离子体发射光谱、X射线粉末衍射、透射电镜和X射线光电子能谱等方法研究了溶液酸碱性、沉淀剂种类、Au负载量和焙烧温度等对催化剂性质的影响.结果表明, Au的负载量以及催化剂的焙烧温度对Au颗粒状态有较大影响.其中, 于573 K焙烧的3%Au/SnO₂催化剂在1,4-丁二醇氧化制备γ-丁内酯反应中的催化活性最好, TOF值是Au/TiO₂催化剂的15倍.这主要是由于SnO₂载体独特的性质对所负载的Au颗粒的影响.     

Au/Ce1-xZrxO2催化剂的制备、表征及其在CO氧化和水煤气变换反应中的催化性能

采用共沉淀法制备了不同锆铈摩尔比的Ce1-xZrxO2(x=0,0.1,0.3,0.5,0.7,0.9和1.0)氧化物,并以改性的浸渍法制备了金担载量为1%(质量分数)的Au/Ce1-xZrxO2催化剂.考察了催化剂在低温CO氧化和水煤气变换反应中的催化性能.应用氮物理吸附、X射线衍射、透射电镜和H2程序升温还原等技术对氧化物载体及其负载金催化剂进行了表征,并与其催化性能进行了关联.结果表明,与纯CeO2和ZrO2相比,Ce1-xZrxO2的比表面积增大而孔径减小,孔分布更加集中.Zr的加入使表面Ce4 的还原更加困难,使体相Ce4 的还原更加容易.活性组分金的加入有利于铈锆氧化物的还原.ZrO2载体较大的孔径使金在载体表面分散均匀而粒子较小,因此与Au/CeO2和Au/Ce1-xZrxO2相比,Au/ZrO2具有更好的低温CO氧化活性和水煤气变换活性,而Au/CeZrO在高温下的水煤气变换反应中表现出更好的催化性能.     

Gold catalysts supported on ZnO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> for low-temperature CO oxidation

Gold catalysts with loadings ranging from 0.5 to 7.0 wt% on a ZnO/Al₂O₃ support were prepared by the deposition–precipitation method (Au/ZnO/Al₂O₃) with ammonium bicarbonate as the precipitation agent and were evaluated for performance in CO oxidation. These catalysts were characterized by inductively coupled plasma-atom emission spectrometry, temperature programmed reduction, and scanning transmission electron microscopy. The catalytic activity for CO oxidation was measured using a flow reactor under atmospheric pressure. Catalytic activity was found to be strongly dependent on the reduction property of oxygen adsorbed on the gold surface, which related to gold particle size. Higher catalytic activity was found when the gold particles had an average diameter of 3–5 nm; in this range, gold catalysts were more active than the Pt/ZnO/Al₂O₃ catalyst in CO oxidation. Au/ZnO/Al₂O₃ catalyst with small amount of ZnO is more active than Au/Al₂O₃ catalyst due to higher dispersion of gold particles.     

高热稳定性纳米Au/TiO2催化剂的制备与表征

 采用三嵌段共聚物聚乙醚-聚丙醚-聚乙醚EO20PO70EO20 (P123)为有机模板剂合成了介孔TiO2载体,用沉积-沉淀法制得Au/TiO2催化剂. 运用N2 吸附-脱附、 X射线衍射、 X射线光电子能谱和高分辨电镜技术对催化剂的结构与形貌进行了表征. 采用P123模板剂合成的TiO2具有较均匀的介孔结构,孔径集中在6.1 nm附近,负载金后,其介孔结构保持良好,但孔径下降至5.4 nm. 400 ℃焙烧后,介孔TiO2负载的Au催化剂中Au主要以金属态存在. 负载在三种TiO2载体(介孔TiO2、溶胶-凝胶法合成的TiO2和工业TiO2)上的Au晶粒大小和分散度差异较大,其中介孔TiO2载体更有利于金的分散,以该载体制备的催化剂400 ℃焙烧后金的晶粒尺寸在1～5 nm范围内,催化剂显示了很好的CO氧化活性和抗热稳定性,即使在420 ℃焙烧,其室温下CO的转化率也在90%以上. 而溶胶-凝胶法制备的TiO2和工业TiO2负载的纳米金催化剂中,金晶粒尺寸约为10 nm,催化剂的CO氧化活性和抗热稳定性较差.     

Au/NiO 催化剂的XRD、TEM、TPR及XPS表征研究

采用XRD、TEM、TPR及XPS等表征手段，对共沉淀法制备的Au/NiO催化剂的活性中心，载体的结构及状态进行了研究。结果表明，活性中心金以纳米尺寸高度分散于载体表面，部分金可能呈现氧化状态，载体结晶适度。     

Au/γ-MnO2催化剂催化无溶剂条件下甲苯氧化反应

采用氧化还原法制备了α, δ, γ-MnO₂载体, 采用原位还原法制备了Au负载量为0.5%-3.0%的Au/γ-MnO₂催化剂, 并采用X射线衍射、扫描电镜、透射电镜和N₂物理吸附等手段对其进行了表征. 透射电镜照片表明Au/γ-MnO₂催化剂中Au颗粒的大小约为10 nm. 采用无溶剂存在下的甲苯氧化反应测试所制备样品的催化活性. 结果表明, 甲苯转化率随着Au负载量的增加而增大. 这是由于Au颗粒数量增多, 尺寸减小的缘故. 同时, 负载Au颗粒对苯甲醛具有较高的选择性. Au/γ-MnO₂催化剂具有良好的重复使用性.     

Gold Nanoclusters Confined in a Supercage of Y Zeolite for Aerobic Oxidation of HMF under Mild Conditions

Au nanoclusters with an average size of approximately 1 nm size supported on HY zeolite exhibit a superior catalytic performance for the selective oxidation of 5‐hydroxymethyl‐2‐furfural (HMF) into 2,5‐furandicarboxylic acid (FDCA). It achieved >99 % yield of 2,5‐furandicarboxylic acid in water under mild conditions (60 °C, 0.3 MPa oxygen), which is much higher than that of Au supported on metal oxides/hydroxide (TiO₂, CeO₂, and Mg(OH)₂) and channel‐type zeolites (ZSM‐5 and H‐MOR). Detailed characterizations, such as X‐ray diffraction, transmission electron microscopy, N₂‐physisorption, and H₂‐temperature‐programmed reduction (TPR), revealed that the Au nanoclusters are well encapsulated in the HY zeolite supercage, which is considered to restrict and avoid further growing of the Au nanoclusters into large particles. The acidic hydroxyl groups of the supercage were proven to be responsible for the formation and stabilization of the gold nanoclusters. Moreover, the interaction between the hydroxyl groups in the supercage and the Au nanoclusters leads to electronic modification of the Au nanoparticles, which is supposed to contribute to the high efficiency in the catalytic oxidation of HMF to FDCA.     

Nanoceria Supported Gold Catalysts for CO Oxidation

Two types of CeO₂ nanocubes (average size of 5 and 20 nm, respectively) prepared via the hydrothermal process were selected to load gold species via a deposition‐precipitation (DP) method. Various measurements, including X‐ray diffraction (XRD), Raman spectra, high resolution transmission electron microscopy (HRTEM), in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS), and temperature‐programmed reduction by hydrogen (H₂‐TPR), were applied to characterize the catalysts. It is found that the sample with ceria size of 20 nm (Au/CeO₂‐20) was covered by well dispersed both Au³⁺ and Au^δ+ (0 < δ < 1). For the other sample with ceria size of 5 nm (Au/CeO₂‐5), Au³⁺ is the dominant gold species. Au/CeO₂‐20 performed better catalytic activity for CO oxidation because of the strong CO adsorption of Au^δ+ in the catalysts. The catalytic activity of Au/CeO₂‐5 was improved due to the transformation of Au³⁺ to Au^δ+. Based on the CO oxidation and in situ DRIFTS results, Au^δ+ is likely to play a more important role in catalyzing CO oxidation reaction.     

掺杂Zr4+对纳米Au/TiO2催化剂结构和性能的影响

采用氨水反滴加沉淀法合成了Zr4+掺杂的系列TiO2载体,以尿素溶液为沉淀剂,用沉积-沉淀法制备负载金催化剂。运用N2吸附-脱附(BET)、X射线衍射(XRD)、X射线荧光(XRF)、高分辨电镜(HR-TEM)和氨吸附红外光谱(NH3-IR)等技术对催化剂的结构与形貌进行了表征,并在色谱-微反应装置上考察了催化剂对CO氧化反应的活性。结果表明:(1)少量的Zr4+掺杂可形成锐钛矿型固溶体,且载体的比表面积增大;随着Zr4+掺杂量增加至10%以上,载体逐渐向无定形转变,同时比表面积急剧增大。(2)保持规整锐钛矿晶相的Zr4+掺杂载体,其表面Lewis酸位占有率较高,且具备结构缺陷,而无定形载体表面的Lewis酸位占有率大幅度降低。(3)载体表面的Lewis酸位以及结构缺陷有利于增强载体对Au颗粒的锚定作用,从而减弱焙烧过程中的颗粒聚集。(4)少量Zr4+掺杂入TiO2载体中,可以提高Au颗粒的抗烧结能力,焙烧所得的Au颗粒尺寸较小(3.63 nm),且表现出优异的催化活性,在常温下就可以将CO完全氧化。     

A facile synthetic route for the preparation of the Au/Mox/Al2O3 catalysts towards CO oxidation

Summary A new facile single-step synthetic route is reported for the preparation of Au/MO_x/Al₂O₃ catalysts. The preparation method has the merit of facility but leads to not only the simultaneous load of both gold source and MO_x precursor on Al₂O₃ support, but also the formation of Au/MO_x/Al₂O₃ with high gold loading ratio, high dispersion and high activity for CO oxidation.     

Catalytic oxidation of carbon monoxide over Au/Fe2O3 preparations

Low temperature catalytic oxidation of carbon monoxide has been studied over Au/Fe₂O₃. On the coprecipitated samples the catalytic activity shows a maximum at a gold content of about 5%. Calcination of Au/Fe₂O₃ decreases the catalytic activity and the stability. The catalytic activity measured is the highest ever reported in the literature on Au/Fe₂O₃ preparations.