Insights into support effects on Ce-Zr-O mixed oxide-supported gold catalysts in CO oxidation

Au]Cel_xZrxO2 catalysts （x = 0-0.8） were prepared by a deposition-precipitation method using Cel_xZrxO2 nanoparticles as supports with variable Ce and Zr contents. Their structures were characterized by complimentary means such as X-ray diffraction, Raman, scanning trans- mission electron microscopy and X-ray photoelectron spectroscopy （XPS）. These Au catalysts possessed similar sizes and crystalline phases of Cel_xZrzO2 supports as well as similar sizes and oxidation states of Au nanoparticles. The oxidation state of Au nanoparticles was dominated by Au~ especially in CO oxidation. Their activities were examined in CO oxidation at different temperatures in the range of 303-333 K. The CO oxidation rates normalized per Au atoms increased with the increasing Ce contents, and reached the maximum value over Au/CeO2. Such change was in parallel with the change in the oxygen storage capacity values, i.e. the amounts of active oxygen species on Au/Cel_zZrzO2 catalysts. The excellent correlation between the two properties of the catalysts suggests that the intrinsic support effects on the CO oxidation rates is related to the effects on the adsorption and activation of O2 on Au/Cel_xZrxO2 catalysts. Such understanding on the support effects may be useful for designing more active Au catalysts, for example, by tuning the redox properties of oxide supports.

Direct gas-phase epoxidation of propylene to propylene oxide using air as oxidant on supported gold catalyst

Gold catalysts supported on SiO2, TiO2, TiO2-SiO2, and ZrO2-SiO2 supports were prepared by impregnating each support with a basic solution of tetrachloroauric acid. X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and X-ray photoelectron spectroscopy （XPS） techniques were used to characterize their structure and surface composition. The results indicated that the size of gold particles could be controlled to below 10 nm by this method of preparation. Washing gold catalysts with water could markedly enhance the dispersion of metallic gold particles on the surface, but it could not completely remove the chloride ions left on the surface. The catalytic performance of direct vapor-phase epoxidation of propylene using air as an oxidant over these catalysts was evaluated at atmospheric pressure. The selectivity to propylene oxide （PO） was found to vary with reaction time on the stream. At the reaction conditions of atmosphere pressure, temperature 325 ℃, feed gas ratio V（C3H6）/V（O2）= 1/2, and GHSV =6000h^-1, 17.9% PO selectivity with 0.9% propylene conversion were obtained at initial 10 min for Au/SiO2 catalyst. After reacting 60 min only 8.9% PO selectivity were detected, but the propylene conversion rises to 1.4% and the main product is transferred to acrolein （72% selectivity）. Washing Au/TiO2-SiO2 and Aa/ZrO2-SiO2 samples with magnesium citrate solution could markedly enhance the activity and PO selectivity because smaller gold particles were obtained.

Influence of MgO contents on silica supported nano-size gold catalyst for carbon monoxide total oxidation

A series of nano-size gold catalysts were prepared by deposition-precipitation method using silica material promoted with different amounts of MgO as the carrier. The influences of MgO addition on the structure and property of the nano-size gold catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, O2 temperature-programmed desorption （O2-TPD）, and inductively coupled with plasma atomic emission spectroscopy （ICP-AES） techniques. The total oxidation of CO was chosen as the probe reaction. The results suggest that for the gold catalysts supported on the silica material after MgO modification, the size of the gold particles is pronouncedly reduced, the oxygen mobility is enhanced, and the catalytic activity for low-temperature CO oxidation is greatly improved. The gold catalyst modified by 6 wt% MgO （Mg/SiO2 weight ratio） shows higher CO oxidation activity, over which the temperature of CO total oxidation is lower about 150 K than that over the silica directly supported gold catalyst.

Gold Catalysts Supported on Crystalline Fe_2O_3 and CeO_2/Fe_2O_3 for Low-temperature CO Oxidation

High active and stable gold catalysts supported on crystalline Fe203 and CeO2/Fe2O3 were prepared via the deposition-precipitation method. The catalyst with a Au load of 1.0% calcined at 180 ℃ showed a CO conversion of 100% at -8.9℃, while Au/CeO2/Fe2O3 converted CO completely at -16.1 ℃. Even having been calcined at 500 ℃, Au/Fe2O3 still exhibited significant catalytic activity, achieving full conversion of CO at 61.6℃. The catalyst with a low Au load of 0.5% could convert CO completely at room temperature and kept the activity unchanged for at least 150 h. N2 adsorption-desorption measurements show that the crystalline supports possessed a high specific surface area of about 200 m2/g. Characterizations of X-ray diffraction and transmission electron microscopy indicate that gold species were highly dispersed as nano or sub-nano particles on the supports. Even after the catalyst was calcined at 500 ℃, the Au particles remained in a nano-size of about 6--10 nm. X-ray photoelectron spectra reveal that the supported Au existed in metallic state Au0. The modification of Au/Fe2O3 by CeO2 proved to be beneficial to the inhibition of crystallization of Fe2O3 and the stabilization of gold particles in dispersed state, consequently promoting catalytic activity.

In situ IR, pulse reaction and TPD-ITD study of catalytic performance of room-temperature carbon monoxide oxidation on supported gold catalysts

With in situ IR, two different CO adsorption bands were detected on various chemical state gold catalysts. One band is attributed to the linear CO on an oxidized gold catalyst(2100 cm -1 ), the other one is ascribed to the bridged CO on metallic gold (2085 cm -1 ). CO pulse reaction showed that Au/Fe 2O 3 catalyst had a room temperature activity even in the presence of moisture. The produced CO 2 was detained and more easily desorbed from supported gold catalyst than support oxide. TPD IDT results indicated that the O - 2 superoxide ions are the possible active oxygen species.

THE SUPPORTED GOLD CATALYSTS FOR CLOSED CYCLE CO_2 LASER

Sealed-off carbon dioxide lasers encounter problem of dissociation of CO2, Which causes the output power to fall. Reformation of CO2 is therefore essential for long life CO2 lasers. Au/Fe2O3 and Au/NiFe2O4 are promising candidates for this application.

Promoter effect of La2O3 on gold catalyst with different textural structures

Silica supported gold nanoparticles were synthesized and promoted by lanthanum oxide as dopant. The influences of LaOand silica textural structure on the gold dispersion, formation of active species, crystalline composition and the reacting role of dopants were studied in detail. The characterization results suggested that the dispersion of gold nanoparticles depended on the textural structure of silica without lanthanum oxide doping where small mesopores are more preferable to disperse gold nanoparticles. The addition of lanthanum oxide largely increased the dispersion of gold nanoparticles and oxygen active sites independent of the textural structure of silica support. The interaction between lanthanum oxide and silica enhanced by the synergy facilitated the release of oxygen vacancies and transition of active oxygen species. In addition, the chemical properties were greatly changed after lanthanum oxide addition which was only inconspicuously impacted by the initial textural structure of silica supports, shedding light on the further design of economic gold catalyst based on simple synthesis method.

Halloysite Nanotubes Supported Gold Catalyst for Cyclohexene Oxidation with Molecular Oxygen

The selective oxidation of cyclohexene to 2-cyclohexene-1-ol and 2-cyclohexene-1-one has been investi-gated over Au/HNTs (HNTs: halloysite nanotubes) catalysts with molecular oxygen in a solvent-free system. The catalysts were prepared by deposition precipitation method and characterized by ICP-AES, TEM and XRD. The results show that the catalytic performance of Au/HNTs is quite well and the catalytic activity over recycled catalyst remains highly. Moreover, the nano-size effect of gold is also reported for the reaction.

Gold/Mg-Al mixed oxides catalysts for oxidative esterification of methacrolein:Effects of support size and composition on gold loading

Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold loading and catalytic properties are investigated.The catalysts are characterized by CO_(2)-TPD,EDS,XPS,STEM and XRD techniques.Catalysts with smaller support particle size show more uniform gold distribution and higher gold dispersion,resulting in a higher catalytic performance,and the uniformity of gold and the activity of the catalysts with larger support particle size can be improved by decreasing the concentration of HAuCl4 solution.The Mg/Al molar ratio has significant effect on the uniformity of gold and the activity of the catalyst,and the optimum Mg/Al molar ratio is 0.1–0.2.This study underlines the importance of engineering support particle size,concentration of HAuCl4 solution and density of adsorption sites for efficient gold loading on support by impregnation.

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 dis ersed both Au^3＋ and Au^δ＋ （0〈δ〈1）. For the other sample with ceria size of 5 nm （Au/CEO2-5）, Au^3＋ 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 Au^3＋ 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.

High thermal stable gold catalyst supported on La_2O_3 doped Fe_2O_3 for low-temperature CO oxidation

La2O3 doped Fe2O3 support was prepared by co-precipitation method,and gold was loaded by deposition-precipitation.Thermal stability of gold catalyst was enhanced considerably by La2O3 doping.Even when calcined at 500 oC for 12 h,the catalyst doped with La2O3 could convert 90% of CO at 28.9 oC,while the catalyst without La2O3 doping achieved 90% CO conversion at 43.5 oC.Characterization techniques,such as N2 adsorption-desorption,X-ray diffraction(XRD),transmission electron microscopic(TEM) and thermogravime...

Evolution of Gold Species in an Au/CeO_2 Catalyst and Its Impact on Activity for CO Oxidation

An Au/ceria（0.44%, mass fraction） catalyst containing gold ions was prepared by a modified deposition precipitation method, and the evolution of gold ions in the catalyst and its influence on the catalysis of CO oxidation were investigated. It was found that the as-prepared catalyst containing gold ions with high valence could fully oxidize CO at -10 ℃ initially but was deactivated gradually at low temperatures during the reaction with CO or treatment by unpurified air. The deactivation of the catalyst during CO oxidation or treatment of it by unpurified air was independent and progressive at low temperatures while the activity of the catalyst at relatively high temperatures was maintained well. During the reaction with CO or treatment by unpurified air, the XPS results indicate that gold species evolved from high valence to low valence and the diffuse reflectance UV-Vis spectra show that high valence gold was reduced to charged gold clusters, gold clusters grew to small gold crystals and small gold crystals grew to large gold particles. Accordingly, the high valence gold corresponded to the activity at low temperatures and the metallic gold was active and relatively stable at high temperatures. The turnover frequencies（TOF） of the catalysts treated by different methods at 273 K decreased with the evolution of gold species from high valence to low valence, no maximum of TOF was observed although gold particles in the catalyst attained to about 2-3 nm during the treatment. An Au/ceria catalyst with a gold load of 0.87% （mass fraction） maintained a good activity for CO oxidation within 18 h at room temperature. The catalysts were characterized via transmitted electronic microscopy（TEM）, inductively coupled plasma optical emission spectrometry（ICP-OES）, X-ray diffraction（XRD） and BET specific surface area and UV-Vis DRS as well.

Structure-activity relationship in water-gas shift reaction over gold catalysts supported on Y-doped ceria

The utilization of pure hydrogen as an energy source in fuel cells gave rise to renewed interest in developing active and stable water-gas shift catalysts. Gold catalysts have proven to be very efficient for water-gas shift reaction at low temperature. The aim of the present study was to investigate the effect of:(i) different preparation methods(impregnation and coprecipitation) to obtain a modified ceria support,and(ii) the amount of Y_2 O_3(1.0 wt%, 2.5 wt%, 5.0 wt% and 7.5 wt%) as dopant on the water-gas shift activity of Au/CeO_2 catalysts. An extended characterization by means of S_(BET), XRD, HRTEM/HAADF, FTIR,H_2-TPR and CO-TPR measurements in combination with careful evaluation of the catalyst behavior allowed to shed light on the parameters governing the water-gas shift activity. The catalysts show very high activity(>90% CO conversion) in the temperature range 180-220 ℃,with a slightly better performance of the gold catalysts on supports prepared by impregnation. The decreased activity with increasing Y_2 O_3 concentration is related to the hindering of oxygen mobility due to ordering of surface oxygen vacancies in vicinity of segregated Y^(3+). The effect of catalyst pre-treatments and the stability of the best performing samples were examined as well.

Development of Novel Supported Gold Catalysts： A Materials Perspective

自从 Haruta 等。发现了细微地在支持能展出的某些金属氧化物上驱散的那小金 nanoparticles 在在房间温度下面的公司氧化的令人惊讶地高的活动，由支持的金 nanoparticles 的异构的催化作用吸引了巨大的注意。出版物的多数处理常规金催化剂的准备和描述(例如， Au/TiO2 ) ，在各种各样的催化反应的金催化剂的使用，以及活跃地点和反应机制的性质的说明。在这概述，我们从一个材料观点加亮新奇支持的金催化剂的发展。主要从我们的组报导的那些，例子与复杂界面的结构的单个金属支持接口和 heterostructured 金牌催化剂有关简单金催化剂的开发被给。在第一个范畴的催化剂包括活跃 Au/SiO2，在第二个范畴的 Au/metal 磷酸盐催化剂，和那些包括支持的修正前在装载黄金前准备的催化剂，由支持的金催化剂修正以后，或由黄金和一个无机的部件的同时的分散到支持上。公司氧化通常作为探查反应被采用了屏蔽这些催化剂的活动。这些新奇金催化剂不仅为应用催化作用提供可能性，而且为基本研究供应根据。

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+).

Gold-iridium bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions

Carbon supported gold-iridium composite(Au Ir/C) was synthesized by a facile one-step process and was investigated as the bifunctional catalyst for oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). The physical properties of the Au Ir/C composite were characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). Although the Au and Ir in the Au Ir/C did not form alloy, it is clear that the introduction of Ir decreases the average Au particle size to 4.2 nm compared to that in the Au/C(10.1 nm). By systematical analysis on chemical state of metal surface via XPS and the electrochemical results, it was found that the Au surface for the Au/C can be activated by potential cycling from 0.12 V to 1.72 V, resulting in the increased surface roughness of Au,thus improving the ORR activity. By the same potential cycling, the Ir surface of the Ir/C was irreversibly oxidized, leading to degraded ORR activity but uninfluenced OER activity. For the Au Ir/C, Ir protects Au against being oxidized due to the lower electronegativity of Ir. Combining the advantages of Au and Ir in catalyzing ORR and OER, the Au Ir/C catalyst displays an enhanced catalytic activity to the ORR and a comparable OER activity. In the 50-cycle accelerated aging test for the ORR and OER, the Au Ir/C displayed a satisfied stability, suggesting that the Au Ir/C catalyst is a potential bifunctional catalyst for the oxygen electrode.

PEO-b-P4VP/Yttrium Hydroxide Hybrid Nanotubes as Supporter for Catalyst Gold Nanoparticles

吸附(乙烯氧化物) poly， -b-poly(4-vinylpyridine)(PEO-b-P4VP) 微粒与稠密的 P4VP 内部层和包围 YNT 的拉长的 PEO 外部层导致了到钇氢氧化物 nanotubes (YNT ) 的表面上混合 nanotubes。稠密的 P4VP 层被 crosslinking 进一步作为 crosslinker 用 1,4-dibromobutane 稳定。然后， crosslinked 混血儿 nanotubes (CHNT ) 作为一个新奇 nano 支持者被使用在 crosslinked P4VP 层以内装载催化剂金牌 nanoparticles (GNP ) 。结果的 GNPs/CHNTs (在 CHNT 上装载的 GNT ) 被使用催化 p-nitrophenol 的减小反应。结果显示这个新奇 nano 支持者在暂停，在装载 GNP (0.87 mmol/g ) 的高能力，装载 GNP (12.9 mol1min1 ) 的高催化的活动，和 GNTs/CHNTs 的好可重用性有象好 dispersity 那样的优点。

Preparation of Au/CeO_2 catalyst and its catalytic performance for HCHO oxidation

Aqueous precipitation and deposition-precipitation method were used to prepare CeO2 supports and Au/CeO2 catalysts, respectively. The effect of preparation condition of support on the catalyst activity was investigated. The catalytic combustion of HCHO was considered as the probe reaction for comparing the catalyst activity. The BET, X-ray diffraction, X-ray photoelectron spectroscopy （XPS）, and reduction （TPR） were carried out to analyze the influence factor on the catalysts activity. The results showed that the addition of dispersant and use of microwave in the support preparation procedure could be beneficial for enhancing the interaction of supports and gold species and thus improved the catalytic activity. The total conversion temperature for HCHO was 146 ℃ over AC400. With the modification during supports preparation process, the catalytic activity increased with total conversion temperature decreasing to 98 ℃. The results of XPS indicated that Au^0 and Au^＋1 species coexisted in these catalysts and the activity of catalyst correlated with Au^＋1/Au^0 ratio. Temperature-programmed reduction results demonstrated that the reduction peak appeared between 100-170 ℃ with the inducing of gold. The dependence of activity on the reduction peak temperature implied that ionic gold was catalytic activity component for HCHO oxidation.

Effects of preparation conditions of Au/FeO_x /Al_2O_3 catalysts prepared by a modified two-step method on the stability for CO oxidation

Composite oxide FeO x /Al 2 O 3 -supported gold catalysts were prepared by a modified two-step method. The effects of preparation conditions on the initial catalytic activity and long-time stability were studied for CO oxidation. XRD, XPS and in situ FTIR were employed to investigate the state of FeO x and the species on the catalyst surface. The results showed that Au/FeO x /Al 2 O 3 catalysts prepared by this method exhibited high activity and high stability in a wide pH value range. Calcination pretreatment was proved to be beneficial to improving the activity and stability. The beneficial effects of FeO x acting as a structural promoter could be ascribed to the ability to supply active oxygen species. As the precursor of FeO x , Fe（NO 3 ） 3 is superior to FeCl 3 for obtaining higher stability.

金催化乙炔氢氯化的密度泛函理论研究进展

乙炔氢氯化(AH)是生产氯乙烯的主要途径之一,传统上使用高毒性的汞催化剂,因此开发无汞催化剂迫在眉睫.金(Au)催化剂是最有潜力的替代催化剂之一,然而其活性Au物种、反应物的活化过程或反应过渡态结构等催化机理仍不够清晰.密度泛函理论(DFT)在研究由Au催化AH的反应机理中发挥了极其重要的作用.我们综述了DFT对金催化剂活性位点、反应物在催化剂上的吸附性质及反应机理的研究进展.重点讨论了DFT对阳离子金和金簇催化AH反应过程的模拟计算,包括Au电子状态、其它原子掺杂及金簇尺寸和形状对催化AH反应影响的模拟.结果表明DFT模拟计算在微观分子尺度上研究反应物的吸附、反应中间体及过渡态等方面发挥了关键作用,对理解Au催化AH反应机理做出了重要贡献.