High performance CuO-CeO2 catalysts for selective oxidation of CO in excess hydrogen： Effect of hydrothermal preparation conditions

High performance CuO-CeO₂ catalysts for selective oxidation of CO in excess hydrogen were prepared by a hydrothermal method under different preparation conditions and evaluated for catalytic activities and selectivities. By changing the n_CTAB/n_Ce ratio and hydrothermal aging time, the catalytic activity of the CuO-CeO₂ catalysts increased and the operating temperature window, in which the CO conversion was higher than 99%, was widened. XRD results showed no peaks of CuO_x species and Cu-Ce-O solid solution were observed. On the other hand, Cu⁺ species in the CuO-CeO₂ catalysts, which was associated with a strong interaction between copper oxide clusters and cerium oxide and could be favorable for improving the selective oxidation performance of CO in excess H₂, were detected by H₂-TPR and XPS techniques.     

不同CuO/CeO2催化剂上CO低温氧化反应

 分别用热解硝酸铈法和浸渍法制备了不同物性的CeO2粉体和相应的CuO/CeO2催化剂,并用XRD, HRTEM和TPR等对样品进行了表征,利用微反-色谱装置考察了其催化CO低温氧化的活性. 结果表明,热解温度影响CeO2的物性(形貌、粒度大小及分布等). 相同条件下,不同物性的CeO2载体上CuO的负载情况不同, 500 ℃热解获得的CeO2载体上非晶态CuO负载量最高,相应的CuO/CeO2催化剂活性也较高. 非晶态CuO一部分进入CeO2晶格,另一部分高度分散于CeO2表面上. 焙烧温度较低时(≤ 600 ℃), 催化剂活性受焙烧温度的影响较小,而高温(800 ℃)焙烧后,催化剂则因载体粒度增大和CuO烧结团聚等因素导致催化活性明显降低.     

0,1,3维CeO2的可控制备及CuO/CeO2催化剂上CO氧化反应

以水、乙醇和乙二醇为溶剂,采用溶剂热法可控制备了0,1,3维CeO2.结果表明,0维CeO2由0.2～0.5 μm纳米粒子组成;1维CeO2是直径为25～30 μm,长约500 μm的六方棒;松针型的3维CeO2是由以纳米粒子为单元构成的直径为1～5 μm,长约50 μm的光滑棒组成,其比表面积高达234 m2/g.将...     

Low-temperature CO oxidation over CuO-CeO2/SiO2 catalysts：Effect of CeO2 content and carrier porosity

The effects of CeO2 contents and silica carder porosity with their pore diameters ranging from 5.2 nm to 12.5 nm of CuO-CeO2/SiO2 catalysts in CO oxidation were investigated. The catalysts were characterized by N2 adsorption/desorption at low temperature, X-ray diffraction (XRD), temperature-programmed reduction by H2 (H2-TPR), oxygen temperature programmed desorption (O2-TPD) and X-ray photoelectron spectroscopy (XPS). The results suggested that, the ceria content and the porosity of SiO2 carder possessed great impacts on the structures and catalytic performances of CuO-CeO2/SiO2 catalysts. When appropriate content of CeO2(Ce content ≤8 wt%) was added, the catalytic activity was greatly enhanced. In the catalyst supported on silica carrier with larger pore diameter, higher dispersion of CuO was observed, better agglomeration-resistant capacity was displayed and more lattice oxygen could be found, thus the CuO-CeO2 supported on Si-1 showed higher catalytic activity for low-temperature CO oxidation.     

溶胶－凝胶法制备CeO2负载CuO低温CO氧化催化剂 Low-Temperature CO Oxidation on CuO/CeO2 Catalyst Prepared by Sol-Gel Method

Ceria is widely used as a promoter in “three-way catalysts“ (TWC). The promotion effect of ceria was originally supposed to be in the structural aspects and chemical ones. Precious metals are widely used for exhaust gas emission control. However, because the high cost of precious metals and their sensitivity to sulfur poisoning, attention has been given to nonprecious metal catalysts such as copper oxide.     

CeO2-TiO2混合氧化物及Pd/CeO2-TiO2催化剂的氧化还原性能

 以溶胶-凝胶-超临界流体干燥法制备了CeO2-TiO2混合氧化物(n(Ce)/n(Ti)=0.05～0.40),以其为载体,通过等体积浸渍法制备了Pd/CeO2-TiO2催化剂. XRD分析结果表明,在低Ce/Ti比的CeO2-TiO2混合氧化物中,CeO2高度分散于TiO2上; Ce/Ti比高于0.10时,大晶粒锐钛矿相TiO2和TiO2-CeO2固溶体或其前驱体无定形相共存. 采用H2-TPR对所合成材料的氧化还原性能进行了研究. H2-TPR谱中500 ℃附近的耗氢峰对应于CeO2-TiO2中CeO2的还原,还原过程中不存在表面晶格氧与体相晶格氧的差别. 由于TiO2与CeO2的协同作用,混合氧化物中形成了丰富的结构缺陷,提高了CeO2的氧化还原性能,其中Ce/Ti比为0.20时TiO2与CeO2的协同作用最显著. 负载上Pd后,载体中CeO2的还原温度(＜150 ℃)大大降低,同时随着Ce/Ti比的增大,PdO与载体间的相互作用增强,导致PdO难于还原,相应的H2-TPR还原峰向高温方向移动.     

CuO/ZrO2活性组分与载体相互作用及其TPR特性

铜基氧化物催化剂具有多种催化功能，许多催化工作者对铜基催化剂的结构、组成、活性组份与载体的作用等一直进行着细致深入地研究，人们尤其重视用TPR、XRD和XPS等手段[1-3]和考察CuO的还原活化过程．ZrO2是常用的催化剂载体之一，具有良好的热稳定性．因此近年来有关以氧化锡     

Effect of Addition of Base on Ceria and Reactivity of CuO/CeO2 Catalysts for Low-Temperature CO Oxidation

In this work, we have reported the influence of the addition of base (KOH) on the physicochemical property of ceria synthesized by alcohothermal process, and the alcohothermal mechanism was also put forward. Furthermore, the prepared CeO2 was used as the support to prepare CuO/CeO2 catalysts via the wet impregnation method. The samples were characterized by N2 adsorption-desorption, X-ray powder diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and temperature-programmed reduction by H2 (H2-TPR). The catalytic properties of the CuO/CeO2 catalysts for low-temperature CO oxidation were studied using a microreactor-GC system. The crystal size of CeO2-A was much smaller than that of CeO2-B, and the corresponding copper oxide catalysts exhibited higher catalytic activity than that of the CeO2-B-supported catalysts under the same reaction conditions. The alcohothermal mechanism indicated that KOH plays a key role in determining the physicochemical and catalytic properties of ceria-based materials.     

Influence of Pretreatment on the Interaction of Oxygen with Silver and the Catalytic Activity of Ag／SiO2 Catalysts for CO Selective Oxidation in H2

The interactions of oxygen with pre~reduced silver catalysts as well as their catalytic propertiesfor CO selective oxidation in H2 after oxygen pre-treatment are studied in this paper. It is found that the pretreatment exerts a strong influence on the activity and selectivity of the silver catalyst. A drop in activity and selectivity is observed after treating a pre-reduced catalyst with oxygen at low temperatures,whereas a converse result is obtained after an oxidizing treatment at high temperatures (T≥350℃). O2-TPD results show that surface oxygen species adsorbs on silver surface after the oxygen treatment at low temperatures. However, penetration of oxygen into the silver is enhanced by a high temperature treatment, meanwhile the surface oxygen species disappear. No other silver species except metallic silver are observed on all the catalysts by XRD, and the size of silver particle is not changed after the treatment with oxygen at low temperatures. The surface oxygen species formed by oxygen treatment can also be removed by hydrogen reduction. The strongly-adsorbed surface oxygen species prohibit the adsorption and diffusion of oxygen species in reaction gas on the surface of silver catalyst, causing the decrease in CO oxidation activity, in other words, it is important to obtain a clean silver surface for increasing the catalyst activity in CO removal from H2-rich feed gas. The differences in activity and selectivity due to the oxygen pretreatment at different temperatures axe discussed in terms of the changes in the surface/subsurface oxygen species of the silver particles.     

Selective Oxidation of CO in Excess H2 over Ru/Al2O3 Catalysts Modified with Metal Oxide

The Ru/Al_2O_3 catalysts modified with metal oxide(K_2O and La_2O_3)were prepared via incipient wetness impregnation method from RuCl_3·nH_2O mixed with nitrate loading on Al_2O3 support. The activity of catalysts was evaluated under simulative conditions for the preferential oxidation of CO (CO-PROX)from the hydrogen-rich gas streams produced by reforming gas,and the performances of catalysts were investigated by XRD and TPR.The results showed that the activity temperature of the modified catalysts Ru-K_2O/Al_2O3 and Ru-La_2O_3/Al_2O_3 were lowered approximately 30℃compared with pure Ru/Al_2O_3,and the activity temperature range was widened.The conversion of CO on Ru-K_2O/Al_2O_3 and Ru-La_2O_3/Al_2O_3 was above 99% at 140-160℃,suitable to remove CO in a hydrogen-rich gas and the selectivity of Ru-La_2O_3/Al_2O_3 was higher than that of Ru-K_2O/Al_2O_3 in the active temperature range. Slight methanation reaction was detected at 220℃and above.     

CuO-Ag2O/γ-Al2O3催化剂的TPR特性及氧化活性研究

采用程序升温还原技术(TPR)研究CuO-Ag2O/γ-Al2O3双组分及其单组分催化剂的还原特性以及热处理温度对其还原性能的影响。发现不同负载量的Cuo-Ag2O/γ-Al2O3催化剂的还原特性有明显差异, 反映出催化剂表面存在着不同种类的铜物种。Ag2O的存在, 使催化剂的TPR峰位与单组分CuO/γ-Al2O3的TPR曲线产生明显差异, 还原峰发生位移, 随Ag2O添加量的增加, 位移增大。对苯的完全氧化反应结果表明, 催化剂的氧化活性次序为:CuO-Ag2O/γ-Al2O3>CuO/γ-Al2O3>Ag2O/γ-Al2O3。热处理温度升高, 使催化剂表面铜物种分散状态及其还原性能发生变化。从500~900℃, 存在一个使铜物种达到最佳分散态的温度。讨论了负载于γ-Al2O3载体上的CuO-Ag2O双组分及其单组分催化剂在还原过程中金属与载体, 金属与金属间的相互作用以及热处理温度对其还原性能的影响。     

助剂CeO2对Co/Al2O3催化剂上F-T合成反应性能的影响

 在用于F－T合成的Co／Al2O3催化剂中加入少量助剂,能够提高CO转化率和C5＋烃选择性．主要考察了助剂CeO2添加量和催化剂焙烧温度等因素对F－T合成反应的影响,并通过程序升温还原、程序升温氧化及X射线衍射等手段对催化剂进行了表征．结果表明,在Co／Al2O3催化剂中加入少量CeO2（n（Ce）／n（Co）＝0．1～0．14）,能够有效提高催化剂的催化活性和C5＋烃选择性;焙烧温度则以相反的趋势控制F－T反应活性和链增长几率;助剂的加入降低了催化剂的起始还原温度,改善了催化剂的还原性能．但是,催化剂的积碳量有所增加,经10h反应后,催化剂上存在两种类型的积碳．     

Pd-O/CeO_2纳米管催化苯酚氧化羰基化反应

以碳纳米管(CNTs)为模板,采用液相沉积-水热法制备了管状纳米氧化铈(Ce O2-NT).利用X射线衍射、透射电镜和N2等温吸附-脱附技术对其结构进行了表征,所得Ce O2-NT外径~25 nm,长度大于300 nm,管壁由粒径4–9 nm的Ce O2晶粒组成,比表面积为108.8 m2/g.以其为载体制备了Pd-O/Ce O2-NT催化剂,程序升温还原结果发现,该催化剂表面氧在低温下即可被还原,具有较高的活性.将Pd-O/Ce O2-NT用于催化苯酚氧化羰基化反应,催化剂活性和碳酸二苯酯(DPC)选择性均高于零维CeO 2负载的Pd-O/Ce O2-P催化剂.在优化的条件下,苯酚转化率为67.7%,DPC选择性为93.3%.但该催化剂再次使用时活性下降明显,这是由于Pd-O/Ce O2-NT的管状结构在反应过程中被破坏,并且活性组分Pd流失所致.     

Direct Synthesis of Acetic Acid from CH4 and CO2 in the Presence of O2 over a V2O5-PdCl2／Al2O3 Catalyst

The possibility of synthesizing acetic acid from CH4 and CO2 in the presence of O2 over a V2O5-PdCl2/Al2O3 catalyst has been explored. The result shows that it is feasible in catalyzing a direct conversion of CH4, CO2 and O2 to acetic acid. It is concluded that both CO2 and O2 are involved in the formation of acetic acid.     

(Ag/Al2O3+Cu/Ce(x)/Al2O3)组合催化剂催化乙醇选择性还原NOx及其副产物的消除

制备了Cu/Ce(x)/Al2O3(x为Ce与Al的摩尔比)系列氧化催化剂,并考察了(Ag/Al2O3 Cu/Ce(x)/Al2O3)组合体系催化乙醇还原NOx以及氧化去除反应副产物(CO和未完全燃烧的碳氢化合物)的活性.在200～350℃温度区间,组合催化剂具有与Ag/Al2O3相似的NOx去除效率.随着Ce/Al比增加,氧化催化剂去除CO的活性逐渐提高.Cu/CeO2催化剂具有最好的氧化活性,但其对NOx的去除有较大影响.综合考虑NOx转化率以及CO和HC的去除效果,(Ag/Al2O3 Cu/Ce(0·15)/Al2O3)是最佳的催化剂组合体系.通过对此系列氧化催化剂的BET比表面积、XRD、H2-TPR以及XPS等表征结果的分析,发现Cu和Ce之间的相互作用是催化剂氧化CO能力提高的主要原因.     

Pt-CeO2/SiO2催化剂用于室温湿空气中CO氧化反应

开发室温CO氧化催化剂的主要挑战是CO自中毒和慢的表面动力学,同时湿气的存在也可导致催化剂失活.本文开发了高活性CeO2促进的Pt基催化剂4%Pt-12%CeO2/SiO2,用于室温湿气(湿度10%?90%,25°C)中CO氧化反应,在低CO浓度(<500 ppm)和高CO浓度(>2500 ppm)时,CO转化率高于99%.优化了催化剂制备变量,如Pt和CeO2负载量、CeO2沉积方法、CeO2和Pt前驱体的干燥和焙烧条件.采用CO/H2化学吸附、O2-H2滴定、X射线衍射和BET比表面积测定表征了催化剂的表面特性,并将其与催化剂活性相关联.结果表明,CeO2沉积方法对催化剂活性影响显著,当用浸渍法沉积CeO2时,所得催化剂的反应速率(5.77μmol/g/s)比用沉积沉淀法(1.96μmol g?1 s?1)或CeO2嫁接法(1.31μmol g?1 s?1)制得催化剂的高3倍.O2-H2滴定结果表明,当用浸渍法沉积CeO2时,CeO2和Pt的紧密结合导致了催化剂的高活性.催化剂载体的选择也非常重要,硅胶负载的催化剂活性(5.77μmol g?1 s?1)是氧化铝负载的(1.05μmol g?1 s?1)5倍.当反应受内扩散控制时,催化剂载体的粒径和孔结构影响非常大.另外,CeO2和Pt前驱体的干燥和焙烧条件对催化剂活性的影响至关重要.当Pt和CeO2含量分别大于2.5和15 wt%时,所得催化剂在室温条件下活性高(TOF>0.02 s?1),稳定性好(反应15 h,CO转化率≥99%).     

Pd/Hβ-zeolite catalysts for catalytic combustion of toluene: Effect of SiO2/Al2O3 ratio

The effect of pure and high silica Hβ zeolites on the catalytic performance of toluene combustion over Pd/H/3 catalyst was evaluated.Pure and high silica β zeolites were prepared by direct synthesis procedures,then 0.1 wt% of palladium was impregnated on different Hβ zeolites via incipient wetness technique using palladium nitrate as the Pd source.The Pd/Hβ catalysts were characterized by XRD,N2 adsorption/desorption,H2O adsorption,NH3-TPD,H2-TPR and XPS techniques.With increasing the SIO2/Al2O3 ratio of β zeolite,the activity of the Pd/Hβ catalysts for toluene combustion increased clearly and the pure silica β zeolite supported Pd catalyst showed the best catalytic activity.The superior catalytic performance of Pd/β catalyst prepared from pure silica β zeolite was attributed to its high hydrophobicity and the preserving ability for PdO active species.     

CuO/CeO2-MOx(M=C0,Mn,Al和La)催化剂富氢条件下CO氧化性能的研究

研究了MOx(M=Co,Mn,Al和La)对CuO/CeO2催化剂富氢条件下CO选择性氧化性能的影响,并运用XRD,XPS,BET,TPR和TPD等手段对催化剂进行了表征.结果表明,MnOx和Co3O4的引入能提高CuO/CeO2催化剂富氢条件下CO选择性氧化的活性,其中以MnOx的改性效果最好,80 ℃时CO转化率达58%,140℃为100%.与其他CuO/CeO2-MOx催化剂相比,CuO/CeO2-MnOx催化剂中活性组分与载体的相互作用较强,铜原子外电子云密度升高,表面Cu和晶格氧含量较多,CO的吸附量较大.     

Influence of NO on the Reduction of NO2 with CO over Pt/SiO2 in the Presence of O2

Reduction of NO2 with CO in the presence of NO and excess oxygen, a model mixture for flue gas, over a 0.1% Pt/SiO2 catalyst was studied. The related reaction mechanisms, such as oxidation of CO and NO, were discussed. It was found that there was a narrow temperature window （180-190 ℃） for the reduction of NO2 by CO. When the temperature was lower than the lower limit of the window, the reduction hardly occurred, while when the temperature was higher than the upper limit of the window, the direct oxidation of CO by O2 occurred and thereby NO2 could not be effectively reduced by CO. The presence of NO shifted the window to higher temperatures owing to the inhibition effect of NO on the activation of O2 on Pt, which made it possible to reduce NO2 by CO in flue gas.