经过氧化预处理的Ru／Al2O3催化剂的表征

对由Ru_3(CO)_(12)和RuCl_2制备的Ru/Al_2O_3催化剂进行的氧化预处理,显著地改变了催化剂在CO加氢反应中的选择性.在未经过氧化预处理或氧化预处理温度低于200℃时,主产物是C_2以上的烃类;而当氧化预处理温度在300℃或300℃以上时,主产物是甲烷.用H_2化学吸附法、TEM和XRD对y—Al_2O_3 载体上Ru粒子表征的结果表明:在H_2还原之后,载体上的Ru是一些粒径为10(?)左右的超微粒子或者这种超微粒子的聚集体,而在经过300℃或者更高温度下的氧化预处理及随后的还原之后,这些超微粒子或其聚集体转变成大的单晶.Ru粒子的这一微观形态的变化是引起催化剂选择性显著改变的根本原因.这—结果表明,对于负载型金属催化剂,不仅载体上金属粒子的分散度,而且这些金属粒子的微观形态也是决定催化剂在某些反应中的选择性的一个重要因素.     

PdO-CeO2复合氧化物催化剂的CO低温氧化

采用共沉淀法制备了一系列不同Pd含量的PdO-CeO2复合氧化物催化剂, 并考察了该催化剂的CO低温氧化反应催化性能. 运用X射线衍射(XRD), 物理吸附(BET), CO化学吸附, 程序升温还原(TPR), 脉冲反应等技术对催化剂进行了表征. XRD结果表明, 焙烧温度从400 ℃升高到800 ℃, 有利于CexPd1-xO2-δ固溶体的形成. 然而焙烧温度升至1000 ℃时, 导致Pd从固溶体中析出. 催化剂的CO氧化活性(TOF)与CexPd1-xO2-δ固溶体的含量存在一定的对应关系. 随着CexPd1-xO2-δ固溶体含量的增加, CO氧化的TOF值大, 可见CexPd1-xO2-δ固溶体的形成对CO氧化活性有着主要的贡献. 在催化剂焙烧温度相同的条件下, 催化剂的CO氧化活性与Pd粒子大小无对应关系. 脉冲反应进一步说明PdOx的CO氧化活性高于金属Pd.     

负载Ru催化剂金属表面活性结构的研究

运用原位FT-IR光谱和TPSR-MS等技术研究了负载Ru催化剂的金属表面状态. 结果表明催化剂中存在二类静态活性中心: (1)体现金属Ru本征特性的S_1中心, (2)金属与载体相互作用而产生的S_2中心. 在吸附CO及其加氢反应过程中, S_1中心上处于边、角、棱位置等配位不饱和的金属Ru原子或原子簇经CO剥蚀而产生的动态S_3活性中心. CO在S_1中心上以Ru~0—CO线式态吸附的, 其IR谱带位于1980～2060 cm~(-1)之间. Ru~0—CO在H_2流中进行程序升温加氢反应的TPSR-MS图上出现450 K左右的低温甲烷峰. 焙烧温度升高, 则在TPSR-MS谱图上出现两个甲烷峰, 600±50 K的高温甲烷峰归属为S_2中心上以Ru~(δ+)-CO线式态吸附CO加氢所致. IR谱图中的2075±50 cm~(-1)峰代表Ru~(δ+)-CO. IR谱中2135±5和2075±5 cm~(-1)这对峰的出现反映了S_3中心的形成.     

CO在担载Ru催化剂上的吸脱附作用及其表面加氢反应

研究了担载于Al_2O_3和ZrO_2上的以Ru_3(CO)_(12)为前体的[Ru]和以RuCl_3为前体的Ru催化剂的TPR特性、CO吸脱附行为及其表面加H_2反应。担载于Al_2O_3上的[Ru]和Ru催化剂上部分物相较担载于ZrO_2上者难于还原。CO在氧化[Ru]催化剂上主要以Ru(CO)yO_2表面络合物形式存在,在还原[Ru]和Ru、以及氧化Ru催化剂上CO以吸附物种形式存在。在Ru离子上的CO比在Ru原子上者难于脱附。以ZrO_2为载体的[Ru]和Ru催化剂上的CO加H_2生成CH_4的性能显著优于以Al_2O_3为载体者,担载[Ru]催化剂上的CO加H_2性能略优于担载Ru催化剂。     

预处理方法对Ru/SBA-15催化丙三醇氢解反应性能的影响(英)

使用浸渍法结合不同预处理方法制备了一系列的Ru/SBA-15催化剂,并将其应用于丙三醇氢解反应中.使用N_2吸附-脱附、X射线衍射、CO化学吸附以及透射电子显微镜等方法对所制备Ru/SBA-15进行了表征.结果表明,催化剂前驱体经过空气焙烧后再经H_2还原的Ru/SBA-15催化剂上Ru的分散度较低,而直接使用H_2处理较高.同时,随着H_2还原温度提高,Ru分散度逐渐降低.保持反应活性接近时,随着Ru分散度的降低,TOF增加.表明Ru/SBA-15催化剂上丙三醇氢解是结构敏感反应.     

丙酸水相加氢反应中Ru负载量对C—C键断裂的影响

考察了(1.0%、4.0%、6.0%)Ru/ZrO2催化剂的丙酸水相加氢性能.采用N2物理吸附、CO脉冲化学吸附、H2程序升温还原(H2-TPR)、CO和丙酸吸附傅里叶变换红外光谱(FTIR)研究了Ru/ZrO2催化剂的物理化学性质.COFTIR表明,Ru负载量增加,催化剂表面Ru粒子的富电子程度增加,更接近金属Ru的本征特性.丙酸FTIR表明,丙酸分子在Ru/ZrO2催化剂表面经解离吸附主要形成丙酰基和丙酸盐物种.随Ru含量增加,丙酰基更容易发生脱羰反应,导致C—C键断裂.     

丙酸水相加氢反应中Ru负载量对C-C键断裂的影响

考察了（1.0、4.0、6.0 wt.%）Ru/ZrO2催化剂的丙酸水相加氢性能。采用N2物理吸附、CO脉冲化学吸附、H2程序升温还原（H2-TPR）、CO和丙酸吸附傅里叶变换红外光谱（FTIR）研究了Ru/ZrO2催化剂的物理化学性质。CO-FTIR表明,Ru负载量增加,催化剂表面Ru粒子的富电子程度增加,更接近金属Ru的本征特性。丙酸FTIR表明,丙酸分子在Ru/ZrO2催化剂表面经解离吸附主要形成丙酰基和丙酸盐物种。随Ru含量增加,丙酰基更容易发生脱羰反应,导致C-C键断裂。     

Ru/Ba-ZrO2催化剂的制备及其氨合成性能研究

分别采用柠檬酸络合法、改性共沉淀法和湿浸渍法制备了掺Ba纳米ZrO2材料,负载Ru后用于催化氨合成反应.采用X射线衍射、CO2程序升温脱附(CO2-TPD)、N2物理低温吸附、H2程序升温还原技术(H2-TPR)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)和CO化学吸附对载体材料和催化剂进行了表征.结果表明,不同方法制备载体的物相结构和织构性能均有明显差别,负载Ru后催化剂的氨合成性能差别也较大.其中,以柠檬酸络合法制备的载体材料中Ba以BaZrO3的形式存在,钙钛矿型BaZrO3具有较强的供电子能力,电子可以通过Ru与载体间强相互作用传递到Ru表面,有效地促进N≡N的断裂,使催化剂的低温活性显著提高.在425℃,3 MPa,空速为10000 h-1条件下,出口氨浓度为5.72%.其氨合成活性分别是改性共沉淀法和湿浸渍法制备催化剂的3.8倍和14.3倍.     

柠檬酸凝胶法合成Ni-ZrO_2催化剂及其低温浆态床甲烷化性能研究

采用柠檬酸凝胶法制备不同温度焙烧的Ni-ZrO_2催化剂,考察了催化剂的表面性质和结构对低温浆态床CO甲烷化性能的影响.结果表明,随着焙烧温度的升高,催化剂的比表面积和孔容逐渐减小,金属Ni分散度先增加后减小,Ni晶粒先减小后增大.450℃焙烧的Ni-ZrO_2催化剂金属Ni分散度最高、Ni物种与载体ZrO_2的相互作用最强、对反应物CO分子的吸附作用适中且脱附量大,在260℃、1.0 MPa和H_2/CO摩尔比为3的条件下,CO转化率达到61.6%,且催化活性稳定,750℃焙烧的催化剂反应后金属Ni团聚且晶粒长大,导致催化剂失活.     

PdO-CeO2复合氧化物催化剂的CO低温氧化

采用共沉淀法制备了一系列不同Pd含量的PdO-CeO2复合氧化物催化剂,并考察了该催化剂的CO低温氧化反应催化性能.运用X射线衍射(XRD),物理吸附(BET),CO化学吸附,程序升温还原(TAR),脉冲反应等技术对催化剂进行了表征.XRD结果表明,焙烧温度从400 ℃升高到800℃,有利于CexPd1-xO2-δ固溶体的形成.然而焙烧温度升至1000℃时,导致Pd从固溶体中析出.催化剂的CO氧化活性(TOF)与CexPd1-xO2-δ固溶体的含量存在一定的对应关系.随着CexPd,1-xO2-δ固溶体含量的增加,CO氧化的TOF值大,可见CexPd1-xO2-δ固溶体的形成对CO氧化活性有着主要的贡献.在催化剂焙烧温度相同的条件下,催化剂的CO氧化活性与Pd粒子大小无对应关系.脉冲反应进一步说明PdOx的CO氧化活性高于金属Pd.     

泡沫铝负载钌基催化剂应用于N2O的低温催化分解研究

将导热性能良好的泡沫铝作为载体,羰基钌为前驱体制备了一系列不同形态的钌基催化剂应用于N2O的低温催化分解研究.采用XRD、XPS、SEM、TEM、BET、H2-TPR等方法对催化剂进行了表征,于石英管固定床反应器上对催化剂性能进行了评价.重点考察了泡沫铝作为催化剂载体的可行性、载体的处理方法对催化剂活性的影响以及RuO2、Ru、Ru3(CO)12所表现出的活性差异.结果表明:泡沫铝作为催化剂载体,能够促进N2O的催化分解;泡沫铝经H2O2处理有利于提高其对活性中心的附着力,提高催化活性;N2O浓度为1%,Ru负载量为0.3%,活性中心分别为Ru3(CO)12、Ru、RuO2时,N2O完全转化温度依次为285、380和415℃;活性较高的Ru3(CO)12/泡沫铝催化剂在长时间作用后活性组分转变为RuO2.     

Supported Ru catalysts prepared by two sonication-assisted methods for preferential oxidation of CO in H2

The preferential oxidation (PROX) of CO in the presence of H(2) is an important step in the production of pure H(2) for industrial applications. In this report, two sonochemical methods (S1 and S2) were used to prepare highly dispersed Ru catalysts supported on mesoporous TiO(2) (TiO(2)(MSP)) for the PROX reaction, in which a reaction gas mixture containing 1% CO + 1% O(2) + 18% CO(2) + 78% H(2) was used. The supported Ru catalysts performed better than the supported Au and Pt catalysts, and the S1 and S2 methods are superior to the impregnation method. The Ru/TiO(2)(MSP) catalysts were active for the PROX reaction below 200 °C and good for the methanation reactions of CO and CO(2) above 200 °C. The presence of residual chlorine in the catalysts severely suppressed their PROX reaction activity, and a higher dispersion of Ru particles led to better catalytic performances. The addition of Au in the Ru/TiO(2)(MSP) catalyst also caused a poorer catalytic activity for both the PROX and the methanation reactions. TPR results showed that in the active catalysts prepared by the S1 and S2 methods, the well dispersed Ru particles, after calcination in air, had a stronger interaction with the support than those in the catalyst prepared by the impregnation method and in the Au-Ru/TiO(2)(MSP) catalyst. In situ CO absorption experiments performed with the diffusion reflectance Fourier transform infra red (DRIFT) method showed that the bridged adsorbed CO species on isolated Ru(0) sites correlated with the catalytic performances, indicating that these isolated Ru(0) sites are the most active sites of the Ru/TiO(2)(MSP) catalysts in the PROX reaction.     

Effects of Thermal Activation on the El ectrocatalysis of the Ru(O001) Surface

Variable-temperature in-situ FTIR spectroscopy has been used as the primary tool to investigate the effects of temperature (10 to 50 C ) on formaldehyde dissociative adsorption and electro-oxidation on the Ru (0001) electrode in perchloric acid solution, and the results were interpreted in terms of the surface chemistry of the Ru (0001) electrode and compared to those obtained during our previous studies on the adsorption of CO under the same conditions. It was found that formaldehyde did undergo dissociative adsorption, even at -200 mV vs. Ag/AgCl, to form linear (COL) and 3-fold-hollow(COH) binding CO adsorbates. In contrast to the adsorption of .CO, it was found that increasing the temperature to 50℃ markedly increased the amount of CO adsorbates formed on the Ru(0001) surface from the adsorption of formaldehyde. On increasing the potential, the electrooxidation of the CO adsorbates to CO2 took place via reaction with the active (1×1)-O oxide. A significant increase in the surface reactivity was observed on the RuO2(100) phase formed at higher potentials. Formic acid was detected as a partial oxidation product during formaldehyde electro-oxidation. The data obtained at 50℃are markedly different from those collected at 10 and 25℃ in terms of the amount of both CO2 and formic acid formed and the adsorbed COL and COH species observed. These results were rationalized by the thermal effects on both the loosening of the CO adlayer and the activation of surface oxide on increasing the temperature.     

共浸渍制备高效的Ru/AC氨合成催化剂

通过钌的络合物前驱体和硝酸钡的共浸渍制备的Ru Ba K/AC催化剂氨合成转化效率高,其氨合成转化频率在0.87～1.30 s-1之间,与氯化钌制备的Ru/AC催化剂相比,其转化频率提高幅度在26%～88%。共浸渍法制备的催化剂氨合成转化效率高,其主要原因可能是共浸渍法制备的催化剂钌粒子粒径分布区间较窄,易形成更多的活性位;钌表面氢的吸附受到抑制,氮更易活化,因而催化效率更高。     

Pt3Ru6 clusters supported on gamma-Al2O3: synthesis from Pt3Ru6(CO)21(mu3-H)(mu-H)3, structural characterization, and catalysis of ethylene hydrogenation and n-butane hydrogenolysis

The supported clusters Pt-Ru/gamma-Al2O3 were prepared by adsorption of the bimetallic precursor Pt3Ru6(CO)21(mu3-H)(mu-H)3 from CH2Cl2 solution onto gamma-Al2O3 followed by decarbonylation in He at 300 degrees C. The resultant supported clusters were characterized by infrared (IR) and extended X-ray absorption fine structure (EXAFS) spectroscopies and as catalysts for ethylene hydrogenation and n-butane hydrogenolysis. After adsorption, the nu(CO) peaks characterizing the precursor shifted to lower wavenumbers, and some of the hydroxyl bands of the support disappeared or changed, indicating that the CO ligands of the precursor interacted with support hydroxyl groups. The EXAFS results show that the metal core of the precursor remained essentially unchanged upon adsorption, but there were distortions of the metal core indicated by changes in the metal-metal distances. After decarbonylation of the supported clusters, the EXAFS data indicated that Pt and Ru atoms interacted with support oxygen atoms and that about half of the Pt-Ru bonds were maintained, with the composition of the metal frame remaining almost unchanged. The decarbonylated supported bimetallic clusters reported here are the first having essentially the same metal core composition as that of a precursor metal carbonyl, and they appear to be the best-defined supported bimetallic clusters. The material was found to be an active catalyst for ethylene hydrogenation and n-butane hydrogenolysis under conditions mild enough to prevent substantial cluster disruption.     

In situ FTIR studies on the effect of temperature on the electro-oxidation of small organic molecules at the Ru(0001) electrode

The adsorption and electro-oxidation of formaldehyde, formic acid and methanol at the Ru(0001) electrode in perchloric acid solution have been studied as a function of temperature, potential and time using in situ FTIR spectroscopy, and the results interpreted in terms of the surface chemistry of the Ru(000 1) electrode and compared to those obtained during our previous studies on the adsorption of CO under the same conditions. It was found that no dissociative adsorption or electro-oxidation of methanol takes place at Ru(0001) at potentials < 900 mV vs. Ag/AgCl, and at all three temperatures employed, 10, 25 and 50 degrees C. However, both formaldehyde and formic acid did undergo dissociative adsorption, even at -200 mV, to form linear (CO(L)) and 3-fold-hollow (COH) binding CO adsorbates. In contrast to the adsorption of CO, it was found that increasing the temperature to 50 degrees C markedly increased the amount of CO adsorbates formed on the Ru(0001) surface from the adsorption of both formaldehyde and formic acid. On increasing the potential, the electro-oxidation of the CO adsorbates to CO2 took place via reaction with the active (1 x 1)-O oxide. Formic acid was detected as a partial oxidation product during formaldehyde electro-oxidation. At all three temperatures employed, it was found that adsorbed CO species were formed from the adsorption of both formic acid and formaldehyde, and were oxidised to CO2 faster than was observed in the experiments involving CO adsorbed from CO(g), suggesting a higher mobility of the CO adsorbates formed from the adsorption of the HCOOH and HCHO. At potentials > 1000 mV, both the oxidation of formic acid to CO2 and the oxidation of formaldehyde to both CO2 and formic acid were significantly increased, and the oxidation of methanol to CO2 and methyl formate was observed, all of which were attributed to the formation of an active RuO2 phase on the Ru(0001) surface.     

Structures and catalytic properties of PtRu electrocatalysts prepared via the reduced RuO2 nanorods array

Structures and properties of PtRu electrocatalyts, derived from the aligned RuO2 nanorods (RuO2NR), are investigated using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and cyclic voltammetry toward COads and methanol oxidation. The catalytic activity of methanol oxidation and the CO tolerance are promoted significantly by reducing RuO2 into Ru metal before decorating with Pt. Reduction of RuO2NR was carried out by either thermal decomposition at 650 degrees C in vacuum or H2-reduction at 130 degrees C in low-pressure hydrogen. Reduction assisted by hydrogen allows infiltrating decomposition at low temperature and produces an array of nanorods with rugged walls featuring small Ru nuclei and larger surface area. Pt-RuNR, whose surface Pt:Ru ratio=0.58:0.42 was prepared by decorating with 0.1 mg cm(-2) Pt on the H2-reduced array containing 0.39 mg cm(-2) Ru, demonstrates a favorable combination of CO tolerance and high methanol oxidation activity superior to other RuO2NR-derived catalysts. When compared with a commercial electrocatalyst of PtRu (1:1) alloy (<4 nm), the activity of Pt-RuNR in methanol oxidation is shown to be somewhat lower at potential<0.48 V and higher at potential>or=0.48 V.     

载体焙烧温度对RuO_2/TiO_2催化HCl氧化性能的影响

以不同温度焙烧TiO(OH)_2得到的TiO_2为载体,采用湿法浸渍法制备RuO_2/TiO_2-C(C=450、550、650及750℃)催化剂,利用XRD、N_2吸附-脱附、TEM和H_2-TPR等表征手段研究催化剂的物理化学性质,并对其在HCl氧化反应中的催化性能进行考察.结果表明:载体焙烧温度对催化剂的结构与活性有显著影响.随着载体焙烧温度(≤650℃)的升高,RuO_2与TiO_2之间的晶面匹配度逐渐变高,促进了RuO_2在TiO_2表面的分散,其中RuO_2/TiO_2-650催化剂表现出最优的催化性能.而当载体焙烧温度过高时,RuO_2/TiO_2-750催化剂的反应活性大大下降,可能是由于过高的焙烧温度导致载体出现严重的烧结团聚现象,以及RuO_2与TiO_2之间过强的相互作用,阻碍了HCl氧化反应的进行.此外,减小RuO_2的粒径可以促进HCl氧化活性的提升.动力学结果显示,催化剂表面的HCl氧化反应主要受O_2分压的影响,表明O_2从催化剂表面的解离吸附为决速步骤.     

制备方法对Ru/CeO2催化剂结构和性能的影响

以K2RuO4和Ce(NO3)3为原料,利用物质的氧化还原特性制备了Ru/CeO2氨合成催化剂,并运用N2物理吸附、X射线衍射(XRD)、FE-SEM、CO吸附和H2程序升温还原(H2-TPR)等技术对其进行了表征,考察了还原剂和制备方法对所制备的Ru/CeO2氨合成催化剂结构和性能的影响。结果表明由自身氧化还原法制备的催化剂,其比表面积最大,达到了120 m2.g-1,钌分散度最高,为45.6%,且催化剂活性最高,在10 MPa,10000 h-1,425℃反应时,出口氨浓度达到了12.6%。