Dispersion and reactivity of copper catalysts supported on Al2O3-ZrO2

A series of CuO/Al(2)O(3)-ZrO(2) catalysts with Cu loadings varying from 1.0 to 20 wt % were prepared and characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), temperature-programmed desorption (TPD) of CO(2) and NH(3), electron spin resonance (ESR), and Brunauer-Emmett-Teller surface area measurements. The dispersion and metal area of copper were determined by the N(2)O decomposition method. XRD results suggest that the copper oxide is present in a highly dispersed amorphous state at copper loadings < 10 wt % and as a crystalline CuO phase at higher Cu loadings. ESR results suggest the presence of two types of copper species on the Al(2)O(3)-ZrO(2) support. TPR results suggest well-dispersed copper oxide species at low Cu loadings and crystalline copper oxide species at high Cu loadings. Well-dispersed copper oxide species were reduced more easily than large copper oxide species by H(2). The results of CO(2) TPD suggest that the basicity of the catalysts was found to increase with an increase of copper loading up to 5.0 wt % and decreases with a further increase of copper loading. The results of NH(3) TPD suggest that the acidity of the catalysts was found to decrease with an increase of copper loading up to 5.0 wt % and increases with a further increase of copper loading. The catalytic properties were evaluated for the vapor-phase dehydrogenation of cyclohexanol to cyclohexanone and correlated with the results of CO(2) TPD measurements and the dispersion of Cu on the Al(2)O(3)-ZrO(2) support.     

Characterization and catalytic functionalities of copper oxide catalysts supported on zirconia

A series of zirconia supported copper oxide catalysts with varying copper loadings (1.2-19.1 wt %) were prepared by impregnation method. The catalysts were characterized by X-ray diffraction, UV-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), and temperature-programmed desorption of CO2. Copper dispersion and metal area were determined by N2O decomposition method. X-ray diffraction patterns indicate the presence of crystalline CuO phase beyond 2.7 wt % of Cu on zirconia. UV-visible diffuse reflectance spectra suggest the presence of two types of copper species on the ZrO2 support. XPS peaks intensity ratio of Cu 2p3/2 and Zr 3d5/2 was compared with Cu dispersion calculated from N2O decomposition. TPR patterns reveal the presence of highly dispersed copper oxide at lower temperatures and bulk CuO at higher temperatures. The basicity of the catalysts was found to increase with Cu loading, and the activity of the catalysts was also found to increase with the increase in Cu loading up to 2.7 wt % Cu loading. The catalytic properties were evaluated for the dehydrogenation of cyclohexanol to cyclohexanone and were related to surface properties of the copper species supported on zirconia.     

Characterization of CuO supported on tetragonal ZrO2 catalysts for N2O decomposition to N2

A series of tetragonal zirconia-supported CuO oxide catalysts with various CuO loadings were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), ultraviolet and visible diffuse reflectance spectroscopy (UV/vis-DRS), and temperature-programmed reduction (TPR) measurements. The results indicate that the dispersion capacity of copper oxide on this support is approximately 8.6 Cu(2+) ions/nm(2) ZrO(2). The state of the resulting supported copper species depends on the CuO loading. At CuO loadings below the dispersion capacity, only highly dispersed copper ion species are present on the surface of t-ZrO(2). In particular, isolated Cu ions are the predominant species at low loadings. In contrast, pair Cu ions become the most abundant species at loadings near the dispersion capacity. It has been proposed that these dispersed CuO (isolated and paired Cu ions) have a symmetric 5-fold-oxygen-coordination symmetry (C(3)(v) symmetry) and can be described as distorted octahedra with a missing corner or a trigonal bipyramids. Finally, at CuO loadings above the dispersion capacity the formation of crystalline CuO is observed. TPR results reveal that the dispersed Cu ion species have a different reducibility from CuO crystallites, presumably due to strong interactions between these species and the t-ZrO(2) support. The catalytic activity of these CuO/t-ZrO(2) catalysts for the decomposition of N(2)O can also be directly correlated to CuO dispersion, with paired Cu ions being the most active species for this reaction.     

含Y或La助剂的CuO／ZrO2合成甲醇催化剂的性能和结构研究

通过ＣｕＯ／ＺｒＯ２及含Ｙ或Ｌａ助剂的ＣｕＯ／ＺｒＯ２催化剂对ＯＣ／Ｈ２合成甲醇性能的研究，发现稀土助剂能有效地提高该催化剂的活性。ＸＲＤ结果说明，ＣｕＯ｜ＺｒＯ２中加入Ｙ或Ｌａ助剂可使氧化铜处于较高的分散状态。ＴＰＲ结果揭示ＣｕＯ／ＺｒＯ２催化剂中存在着在室温就很容易被氧人的铜，它在催化剂中含量的增加导致催化剂活性的提高，是关切的活性组份。助剂的加入使这种易被氧化的铜含量增加。ＸＰＳ表面分析结果     

载体对浸渍型Cu/Mn/Mg/K甲醇裂解催化剂的影响

载体对浸渍型Cu/Mn/Mg/K甲醇裂解催化剂的影响;     

Catalytic Combustion of Methane over High Copper-Loading ZSM-5 Catalysts

Two series of Cu/ZSM-5 catalysts,loading from 5 to 20 wt% CuO,were prepared by the deposition-precipitation and impregnation methods,respectively.The catalysts prepared by the impreg- nation method showed better catalytic performances than those prepared by the deposition-precipitation method and the increase of copper loading favored methane conversion.20Cu(I)/ZSM-5 had the highest activity with T_(90%)of 746 K,and for 20Cu(D)/ZSM-5,T_(90%)was as high as 804 K.The characteriza- tion of X-ray diffraction(XRD),temperature-programmed reduction(TPR),temperature-programmed desorption(TPD),and X-ray photoelectron spectroscopy(XPS)revealed that the dispersion of cop- per species could be improved by using the deposition-precipitation method instead of the impregnation method,but the fraction of surface CuO,corresponding to active sites for methane oxidation,was larger on 20Cu(I)/ZSM-5 than 20Cu(D)/ZSM-5.The results of Pyridine-Fourier transform infrared spectrum (Py-FT-IR)showed that a majority of Lewis acidity and a minority of Brφnsted acidity were present on Cu/ZSM-5 catalysts.20Cu(I)/ZSM-5 presented more Lewis acid sites.The number of Lewis acid sites changed significantly with preadsorption of oxygen.Adsorption of methane and oxygen on acid sites was observed.The properties of Cu/ZSM-5 catalysts were correlated with the activity for methane oxidation.     

Dispersion state of CuO on CeO2

XRD and XPS are used to study the dispersion state of CuO on ceria surface. The dispersion capacity values of CuO measured by the two methods are consistent, which are of 1.20 mmol CuO/100 m² CeO₂. In addition, the results reveal that highly dispersed Cu²⁺ ions are formed at low CuO loadings and that increasing the CuO content to a value higher than its dispersion capacity produces crystalline CuO after the surface vacant sites on CeO₂ are filled. The atomic composition of the outermost layer of the CuO/CeO₂ samples has been probed by using static secondary ion mass spectroscopy (SSIMS), and the ratim of Cu/Ce are found to be 0.93 and 0.46 for the 1.22 and 0.61 mmol CuO/CeO₂ samples respectively. Temperature-programmed reduction (TPR) profile with two reduction peaks at 156 and 165°C suggests that the reduction of highly dispersed Cu²⁺ ions consists of two steps and is easier than that of CuO crystallites, in which the TPR profile has only one reduction peak at about 249°C. The above experimental results are in good agreement with the prediction of the incorporation model. Project supported by the National Natural Science Foundation of China.     

A study of thoria on the surface of gamma-Al2O3

The dispersion of thoria on the surface of gamma-Al2O3 and the surface properties of ThO2/gamma-Al2O3 samples, as well as the influence of the loading amount of thoria on the reduction behavior of copper oxide species, have been studied using XRD, XPS, FTIR, and TPR. The results indicate that the dispersion capacity of thoria, like that of ceria, is much lower than for two other tetravalent metal oxides, zirconia and titania, and the surface adsorption amount of the carbonyl compound and H2O slightly increases with increasing thoria loading. The different thoria loadings can influence the reduction behavior of the dispersed copper oxide by comparing the TPR results of CuO/ThO2/gamma-Al2O3 samples. In addition, the lower dispersion capacities of thoria and ceria on gamma-Al2O3 are tentatively discussed by considering the structural stability of the two oxides.     

Characterization and Activity of Cu‐MnOx/γ‐Al2O3 Catalyst for Hydrogenation of Carbon Dioxide

The effect of manganese on the dispersion, reduction behavior and active states of surface of supported copper oxide catalysts have been investigated by XRD, temperature‐programmed reduction and XPS. The activity of methanol synthesis from CO₂/H₂ was also investigated. The catalytic activity over CuO‐MnO_x/γ‐Al₂O₃ catalyst for CO₂ hydrogenation is higher than that of CuO/γ‐Al₂O₃. The adding of manganese is beneficial in enhancing the dispersion of the supported copper oxide and make the TPR peak of the CuO‐MnK_x/γ‐Al₂O₃ catalyst different from the individual supported copper and manganese oxide catalysts, which indicates that there exists strong interaction between the copper and manganese oxide. For the CuO/γ‐Al₂O₃ catalyst there are two reducible copper oxide species; α and β peaks are attributed to the reduction of highly dispersed copper oxide species and bulk CuO species, respectively. For the CuO‐MnO_x/γ‐Al₂O₃ catalyst, four reduction peaks are observed, α peak is attributed to the dispersed copper oxide species; β peak is ascribed to the bulk CuO; γ peak is attributed to the reduction of high dispersed CuO interacting with manganese; δ peak may be the reduction of the manganese oxide interacting with copper oxide. XPS results show that Cu⁺ mostly existed on the working surface of the Cu‐Mn/γ‐Al₂O₃ catalysts. The activity was promoted by Cu with positive charge which was formed by means of long path exchange function between Cu? O? Mn. These results indicate that there is synergistic interaction between the copper and manganese oxide, which is responsible for the high activity of CO₂ hydrogenation.     

Fe柱撑海泡石负载Cu催化剂：结构特点及其C3H6选择性催化还原NO催化性质

通过羟基铁离子柱撑将海泡石(Sep)改性成Fe柱撑海泡石(Fe-PILSEP),使用浸渍法(IM)将Cu负载在Fe-PILSEP上,制得不同铜含量的xCu/Fe-PILSEP催化剂。通过X射线衍射(XRD)、N2-吸附/脱附、H2-程序升温还原(TPR)和X射线光电子能谱(XPS)等对样品进行表征,并测定其对丙烯选择性催化还原NO的催化活性。N2-吸附/脱附和TGA结果表明,Fe-PILSEP的比表面积和孔体积较海泡石原矿Sep极大地增加,热稳定性也明显优于Sep。XRD和XPS结果表明,在xCu/Fe-PILSEP催化剂上同时存在Fe3+/Fe2+和Cu2+/Cu+不同氧化态的氧化物,而且Fe与海泡石之间存在相互作用,Fe和Cu之间存在电子迁移。H2-TPR结果表明,xCu/Fe-PILSEP催化剂上存在不同聚集状态的氧化铜物种。xCu/Fe-PILSEP催化剂的丙烯选择性催化还原NO的催化活性明显优于Fe-PILSEP催化剂,这可能与Fe和Cu的氧化还原性有关。xCu/Fe-PILSEP的催化活性与Cu负载量相关,其中10Cu/Fe-PILSEP催化剂显示出最高的活性,这与其高的比表面积、孔体积和氧化还原性能,及其具有更多有利于HC-SCR反应的孤立Cu2+((Cu2+)i)物种有关。     

Structural feature and catalytic performance of Cu species distributed over TiO2 nanotubes

Copper oxide was deposited on tubular TiO2 via Cu2+ introduction into a titanate nanotube aggregate followed by calcination. The titanate has a layered structure allowing Cu intercalation and can readily transform into anatase TiO2 via calcination for condensation of the constituting layers. The activity of the tubular catalysts, with a Cu content of 2 wt %, in selective NO reduction with NH3 was compared with those of other 2 wt % Cu/TiO2 catalysts using TiO2 nanoparticles as the support. The Cu species supported on the nanotubes showed a higher activity than those supported on the nanoparticles. X-ray absorption near-edge structure (XANES) analysis showed that the Cu species on all the TiO2 supports are in the +2 state. Extended X-ray absorption fine structure (EXAFS) investigations of these catalysts reflected higher degrees of CuO dispersion and Cu2+ dissolution into the TiO2 lattice for the tubular Cu/TiO2 catalysts. Absence of CuO bulk detection by a temperature-programmed reduction analysis for the tubular catalysts confirmed the high CuO-dispersion feature of the tubular catalysts. The dissolution of Cu2+ to form a CuxTi1-xO2 type of solid solution was improved by using an in-situ ion-intercalation method for Cu deposition on the nanotubes. A fraction as high as 40% for Cu2+ dissolution was obtained for the tubular catalysts while only 20% was obtained for the particulate catalysts. The CuxTi1-xO2 species were considered one form of the active sites on the Cu/TiO2 catalysts.     

A comparative study of CuO/TiO_2-SnO_2,Cut/Tit_2 and CuO/SnO_2 catalysts for low-temperature CO oxidation

Nanometer SnO2 particles were synthesized by sol-gel dialytic processes and used as a support to prepare CuO supported catalysts via a deposition-precipitation method. The samples were characterized by means of TG-DTA, XRD, H2-TPR and XPS. The catalytic activity of the CuO/TiO2-SnO2 catalysts was markedly depended on the loading of CuO, and the optimum CuO loading was 8 wt.% (T100 = 80 ◦C). The CuO/TiO2-SnO2 catalysts exhibited much higher catalytic activity than the CuO/TiO2 and CuO/SnO2 catalysts. H2-TPR result indicated that a large amount of CuO formed the active site for CO oxidation in 8 wt.% CuO/TiO2-SnO2 catalyst.     

Al2O3改性CuO/Fe2O3催化剂水煤气变换反应性能

采用分步共沉淀法制备了不同Al₂O₃含量(0%-15% (w))的CuO/Fe₂O₃催化剂, 并进行水煤气变换反应(WGSR)评价测试. 制得的催化剂中含有复合物CuFe₂O₄, 其晶粒尺寸, 氧化还原性质和表面Cu分散通过相应表征手段加以研究. X 射线粉末衍射(XRD), 拉曼(Raman)光谱, N₂物理吸附, N₂O分解和CO₂程序升温脱附(CO₂-TPD)等表征技术说明适量Al₂O₃的加入可以促进尖晶石CuFe₂O₄发生由四方相向立方相的转变, 阻止催化剂中Cu烧结, 增大表面Cu分散, 增加弱碱性位点的数量. 此外, 采用H₂程序升温还原(H₂-TPR)技术探究改性的CuO/Fe₂O₃催化剂的还原性能. 关联结果发现, Al₂O₃掺杂在增大铜物种的耗氢量, 降低其还原温度方面起着重要的作用. 即Al₂O₃的添加促进CuO/Fe₂O₃催化剂中铜铁物种之间的协同作用. 结合活性测试和表征结果,适量的Al₂O₃ (10%(w))改性的催化剂具有较小的Cu颗粒尺寸、较大的Cu分散、较强的还原性能、较多数量的弱碱性位点, 因此具有更好的初始活性和热稳定性.     

超细CuO/ZnO/TiO2-SiO2的表征和CO2加氢合成甲醇性能研究

用溶胶-凝胶法制备了铜、锌质量分数不同的超细Cu/ZnO/TiO2-SiO2催化剂。通过BET、TPR、XRD及FT-IR等方法对催化剂前驱体CuO/ZnO/TiO2-SiO2的物化性能进行表征。用固定床连续流动微反装置，考察催化剂CO2加氢合成甲醇的催化性能。研究结果表明，溶胶-凝胶法制备的CuO/ZnO/TiO2-SiO2催化剂比表面较大（240 m2/g～590 m2/g），孔径分布单一，晶相组成为CuO。随着铜、锌质量分数的增大，催化剂的比表面积减小，最可几孔径增大; CuO微晶结晶度增大,同时微晶尺寸逐渐增大至20 nm。催化剂具有较高的反应活性和选择性，当氧化铜、氧化锌质量分数各为25%时，在260 ℃，2 500 h－1，CO2∶H2=1∶3（mol比），2.0 MPa的反应条件下，甲醇时空收率为0.126g/(h·g)。     

Surface structure and catalytic properties of MoO3/CeO2 and CuO/MoO3/CeO2

XRD, LRS, TPR and in situ NH(3) adsorption FT-IR were used to investigate the dispersion state of the copper oxide and molybdena species of MoO(3)/CeO(2) and CuO/MoO(3)/CeO(2) catalysts as well as their surface acidity. The results showed that the molybdena monolayer modification promoted the dispersion of CuO due to the formation of new tetrahedral vacancies. Meanwhile, CuO changed the structure of molybdenum species and then influenced the surface acidity of the samples. A detail discussion about the possible model of the surface structure of the catalyst was presented. In addition, combining with the in situ NH(3) adsorption FT-IR, the relationships between the activities for 'NO + NH(3) + O(2)' reaction and surface acid properties (Br?nsted and Lewis acid sites) of the catalysts were discussed.     

CuO/TiO2的制备及对NO＋CO反应性能的研究

以三种不同的TiO2为载体，负载6%CuO，在色谱-微反装置上考察了三种Cu6-Ti催化剂对NO＋CO反应的活性。结果表明，由于制备方法不同，活性差别很大，三者活性顺序依次为：Cu6-Ti(T)> Cu6-Ti(S)> Cu6-Ti(nm)，TiO2的比表面积及晶型对活性的影响不明显。H2-TPR结果表明，Cu6-Ti在整个TPR过程中出现了3或4个还原峰，表明有多种CuO物种存在。不同预处理Cu6-Ti的TPR显示，在反应中Cu物种可能以多种价态同时存在。NO-TPD结果亦证明，Cu6-Ti对NO＋CO的反应活性与NO在催化剂表面的解离难易密切相关，而与NO的吸附量关系不大。     

V2O5-CuO/TiO2催化剂中低温选择性催化NOx还原研究

浸渍法制备了一系列V₂O₅-CuO/TiO₂催化剂,考察中低温(200~300℃)条件下,以氨为还原剂选择性催化还原NO_x的活性,并利用比表面积及微孔孔隙分析仪(BET)、X射线衍射(XRD)对催化剂进行微观表征和分析。结果表明,500℃焙烧的2V16Cu/TiO₂催化剂展示了最佳的中低温催化活性和较宽的活性温度范围,在空速6.0×10⁴ h^-1、225℃条件下,NO_x转化率达97.3%,250℃时达到100%,温度升至300℃,催化活性仍保持在100%。XRD结果表明,随着Cu负载量的增加,逐渐显现CuO的特征峰。结合活性评价数据说明,CuO是VCu/TiO₂催化剂的主要活性组分之一,是降低SCR催化反应温度的重要因素。BET结果表明,CuO的负载对钒钛催化剂的表面结构有较大影响。耐硫性实验结果表明,添加钒氧化物制备的2V16Cu/TiO₂催化剂的抗硫性能有所改善。     

Cu/SiO2催化剂结构对乙酸甲酯加氢性能的影响

采用尿素水解法制备了Cu/SiO₂催化剂, 探究其用于乙酸甲酯(MA)加氢制取乙醇的催化性能, 并通过N₂物理吸附、X射线衍射(XRD)、程序升温还原(TPR)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等表征方法分析了催化剂的物理化学特性, 探究了铜负载量和还原温度等对催化剂结构的影响, 以及与催化活性之间的关系. 发现在铜负载量分别为10%、20%和30% (质量分数, w)的催化剂中, 铜负载量为20%的催化剂因具有较多且分散均匀的活性组分而表现出最佳的加氢效果. 接着在铜负载量为20%的催化剂上研究了还原温度(270, 350, 450 ℃)对催化性能的影响, 发现在350 ℃下还原的催化剂活性最高, 在最佳的反应条件下, 乙酸甲酯转化率达到97.8%, 乙醇选择性达到64.9% (理论最大值为66.6%), 主要归属于它具有较高的铜物种分散度, 最合适的Cu⁰/(Cu⁰+Cu⁺)摩尔比例, 同时实现了解离氢气和活化乙酸甲酯的功能.     

Methane reforming With CO2 to syngas over CeO2-promoted Ni/Al2O3-ZrO2 catalysts Prepared Via a direct sol-gel process

CeO2-promoted Ni/Al2O3-ZrO2 (Ni/Al2O3-ZrO2-CeO2) catalysts were prepared by a direct sol-gel process with citric acid as gelling agent. The catalysts used for the methane reforming with CO2 was studied by infrared spectroscopy (IR), thermal gravimetric analysis (TGA), microscopic analysis, X-ray diffraction (XRD) and temperature-programmed reduction (TPR). The catalytic performance for CO2 reforming of methane to synthesis gas was investigated in a continuous-flow micro-reactor under atmospheric pressure. TGA, IR, XRD and microscopic analysis show that the catalysts prepared by the direct sol-gel process consist of Ni particles with a nanostructure of around 5 nm and an amorphous-phase composite oxide support. There exists a chemical interaction between metallic Ni particles and supports, which makes metallic Ni well dispersed, highly active and stable. The addition of CeO2 effectively improves the dispersion and the stability of Ni particles of the prepared catalysts, and enhances the adsorption of CO2 on the surface of catalysts. The catalytic tests for methane reforming with CO2 to synthesis gas show that the Ni/Al2O3-ZrO2-CeO2 catalysts show excellent activity and stability compared with the Ni/Al2O3 catalyst. The excellent catalytic activity and stability of the Ni/Al2O3-ZrO2-CeO2 are attributed to the highly, uniformly and stably dispersed small metallic Ni particles, the high reducibility of the Ni oxides and the interaction between metallic Ni particles and the composite oxide supports.     

铜基氧化锆载体合成甲醇催化剂的结构表征

以ＸＲＤ，ＥＸＡＦＳ和ＥＳＲ等手段考察了ＣｕＯ／ＺｒＯ２催化剂及其还原态的结构，结果表明，在ＣｕＯ／ＺｒＯ２中铜以ＣｕＯ的形式存在，ＺｒＯ２载体对所负载的ＣｕＯ的结构有影响，ＣｕＯ的分散度与焙烧温度有关，在适当的温度下焙烧，负载于ＺｒＯ２上的ＣｕＯ可自发分散，在还原态试样中铜主要以有金属的形式存在，但是当试样中铜的含量小，铜的分散度高时有铜的氧化物存在，其Ｃｕ－Ｏ键距介于ＣｕＯ与ＣｕＯ２之间，Ｃｕ