Preferential oxidation of CO in excess H_2 over the CeO_2/CuO catalyst: Effect of initial support

Three series of CeO2/CuO samples were prepared by impregnation method and characterized by XRD, N2 adsorption-desorption, temperatureprogrammed reduction （TPR）, XPS and TEM techniques. In comparison with the samples prepared with CuO as initial support, the samples with Cu（OH）2 as initial support have higher reducibilities and smaller relative TPR peak areas, and also larger specific surface areas at calcina- tion temperatures of 400 ℃--600 ℃. As a result, Cu（OH）2 is better than CuO as initial support for preferential oxidation of CO in excess H2 （CO-PROX）. The best catalytic performance was achieved on the sample calcined at 600 ℃ and with an atomic ratio of Ce/Cu at 40%. XPS analyses indicate that more interface linkages Ce-O-Cu could be formed when it was calcined at 600 ℃. And the atomic ratio of Ce/Cu at 40% led to a proper reducibility for the sample as illustrated by the TPR measurements.

Ce_xTi_(1-x)O_2 Mixed Oxides Supported CuO Catalyst for NO Reduction by CO

Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effects of CuO on NO+CO reaction were investigated, and the structure and reductive properties of various CuO/Ce x Ti 1- x O 2 were characterized by the methodologies of BET, TPR and XRD. The results show that different Ce/Ti mole ratios and calcination temperatures induce changes of structure and reductive properties of the Ce x Ti 1- x O 2 mixed oxides. When x =0.1～0.5, amorphous CeTi 2O 6 phase mainly forms at 650 ℃ compared to the formation of CeTi 2O 6 which crystallizes at 800 ℃. When x >0.6, some TiO 2 enters the CeO 2 lattice and a CeO 2 TiO 2 solid solution is formed. The activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 650 ℃ is largely affected by the x values, which is the highest when x =0.3, 0.4 and 0.9. The NO conversion reaches 70% at a reaction temperature of 150 ℃. By comparison, the x values have little effect on the activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 800 ℃ . There are strong interactions between CuO and CeTi 2O 6, i.e., formation of the CeTi 2O 6 phase shifts the CuO reduction peak temperature from 380 to 200 ℃, and CuO, in turn, shifts the CeTi 2O 6 reduction peak temperature from 600 to 300 ℃.

Effects of Carrier on CuO/TiO_2 and CuO/Ti_(0.5)Zr_(0.5)O_2 Catalysts in the NO+CO Reaction

Using TiO2 and Ti0.5Zr0.5O2 as carriers, the CuO/TiO2 and CuO/Ti0.5Zr0.5O2 catalystswere prepared by the impregnation method with Cu(NO3)2 as active component. The catalyticactivities in NO+CO reaction were investigated using a microreactor-GC system, and structure andreducibility of catalysts were characterized by means of physical adsorption, TPR, XRD, NO-TPDtechnologies. It was found that the activity of CuO/Ti0.5Zr0.5O2 catalyst was higher than that ofCuO/TiO2, probably due to the large specific surface area of Ti0.5Zr0.5O2 that played an importantrole in NO+CO reaction.

Preparation, Characterization of CuO/CeO_2 and Cu/CeO_2 Catalysts and Their Applications in Low-Temperature CO Oxidation

CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were examined by means of a microreactor-GC system, HRTEM, XRD, TPR and XPS techniques. The results show that CuO has not catalytic activity and the activity of CeO2 is quite low for CO oxidation. However, the catalytic activity of CuO/CeO2 and Cu/ CeO2 catalysts increases significantly. Furthermore, the activity of CuO/CeO2 is higher than that of Cu/CeO2 catalysts.

A comparative study of CuO/TiO_2-SnO_2,CuO/TiO_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.% （Tloo = 80 ℃）. 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.

Characterization and CO Catalytic Oxidation of CuO/Ce-Zr-La-O Catalyst

The Ce-Zr-La-O solid solution was prepared by the sol-gel method. Thestructure and the redox behavior of Ce-Zr-La-O solid solution and CuO/Ce-Zr-La-O catalysts wereinvestigated by using XRD, Raman and TPR techniques. The result shows that the reduction capabilityof Ce_(0.7)Zr_(0.3-y)La_yO solid solution is related to content of La. Appropriate content of La canenhance the redox capability of the solid solution. The oxidation activity of the CuO (6 percent)/Ce_(0.7)Zr_(0.15)La_(0.15)O catalyst is the highest. CuO, which finely dispersed and interacted withthe support, is the site of oxidation activity.

Effect of Addition of Base on Ceria and Reactivity of CuO/CeO_2 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 temperatureprogrammed reduction by H2 （H2-TPR）. The catalytic properties of the CuO/CeO2 catalysts for lowtemperature 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.

High performance CuO-CeO_2 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 ^nCTAB/^nCe 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 CuOx 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.

Catalytic Oxidative Properties and Characterization of CuO/CeO_2 Catalysts

The oxidative properties and characterization of CuO, CeO 2 and CuO/CeO 2 cata lysts were examined by means of a CO micro-reactor GC system, TPR, XPS and X-r ay diffraction Rietveld methods. The results show that either CuO or CeO 2 ac tivity is quite low for CO oxidation. However, when CuO and CeO 2 are mixed, the oxidative activity of the catalyst increases significantly, probably owing to the valency status of copper species (Cu 2+ and Cu+) on the CeO 2 surfa ce, the dispersion and reducibility. XPS surface analysis shows that CuO loading is very important in forming of either Cu 2+ or Cu+. Rietveld analysis s hows that some CuO, which has smaller ion radius than Ce 4+, enters the Ce O 2 lattice after CuO and CeO 2 are mixed. When the CuO loading reaches 5.0%, the size of CuO crystals is a minimum (6.1 nm) and the micro-strain value i s a maximum (2.86×10 -3), resulting in high surface energy and the best ac tivity for CO oxidation.

Low-temperature CO oxidation over CuO-CeO_2/SiO_2 catalysts:Effect of CeO_2 content and carrier porosity

The effects of CeO2 contents and silica carrier porosity with their pore diameters ranging from 5.2 nm to 12.5 nm of CuO-CeO2/SiO2 cata-lysts 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 carrier 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.

Low CO content hydrogen production from oxidative steam reforming of ethanol over CuO-CeO_2 catalysts at low-temperature

CuO-CeO2 catalysts were prepared by a urea precipitation method for the oxidative steam reforming of ethanol at low-temperature.The catalytic performance was evaluated and the catalysts were characterized by inductively coupled plasma atomic emission spectroscopy,X-ray diffraction,temperature-programmed reduction,field emission scanning electron microscopy and thermo-gravimetric analysis.Over CuOCeO2 catalysts,H2 with low CO content was produced in the whole tested temperature range of 250–450 C.The non-noble metal catalyst 20CuCe showed higher H2production rate than 1%Rh/CeO2 catalyst at 300–400 C and the advantage was more obvious after 20 h testing at400 C.These results further confirmed that CuO-CeO2 catalysts may be suitable candidates for low temperature hydrogen production from ethanol.

Effects of ZrO_2 on the Performance of CuO-ZnO-Al_2O_3/HZSM-5 Catalyst for Dimethyl Ether Synthesis from CO_2 Hydrogenation

A series of composite catalysts were prepared by the wet mixing method, and the mass ratio of CuO-ZnO-Al2O3-ZrO2 component to HZSM-5 zeolite （molar ratio of SiO2 to Al2O3 being 25） was 2：1. The CuO-ZnO-Al2O3-ZrO2 （CuO/ZnO/Al2O3=3/6/1 by weight） component was prepared by a modified ＇two-step＇ co-precipitation method. The effects of ZrO2 on the performance of CuO-ZnO-Al2O3/HZSMo5 catalyst for dimethyl ether synthesis from CO2 hydrogenation were investigated. It was found that ZrO2 improved the properties of CuO-ZnO-Al2O3/HZSM-5 as a structural promoter.

Experimental and Kinetic Study of Selective Catalytic Reduction of NO with NH_3 over CuO/Al_2O_3/Cordierite Catalyst

The CuO/γ-Al2O3/cordierite catalyst, after being sulfated by sulfur dioxide (SO2) at 673 K, exhibits high activities for selective catalytic reduction (SCR) of nitrogen oxide (NO) with ammonia (NH3) at 573-723 K. The intrinsic kinetics of SCR of NO with NH3 over CuO/γ-Al2O3/cordierite catalyst has been measured in a fixed-bed reactor in the absence of internal and external diffusions. The experimental results show that the reaction rate can be quantified by a first-order expression with activation energy Eá of 94.01 kJ·mol-1 and the corresponding p re-exponential factor A′ of 3.39×108 cm3·g-1·s-1 when NH3 is excessive. However, when NH3 is not enough, an E ley-Rideal kinetic model based on experimental data is derived with Ea of 105.79 kJ·mol-1, the corresponding A of 2 .94×109 cm3·g-1·s-1, heat of adsorption-Hads of 87.90 kJ·mol-1 and the corresponding Aads of 9.24 cm3·mol-1. The intrinsic kinetic model obtained was incorporated in a 3D mathematical model of monolithic reactor, and the agreement of the prediction with experimental data indicates that the present kinetic model is adequate for the reac-tor design and engineering scale-up.

Effect of yttrium addition on water-gas shift reaction over CuO/CeO_2 catalysts

This paper presented a study on the role of yttrium addition to CuO/CeO2 catalyst for water-gas shift reaction. A single-step co-precipitation method was used for preparation of a series of yttrium doped CuO/CeO2 catalysts with yttrium content in the range of 0-5wt.%. Properties of the obtained samples were characterized and analyzed by X-ray diffraction （XRD）, Raman spectroscopy, H2-TPR, cyclic voltammetry （CV） and the BET method. The results revealed that catalytic activity was increased with the yttrium content at first, but then decreased with the further increase of yttrium content. Herein, CuO/CeO2 catalyst doped with 2wt.% of yttrium showed the highest catalytic activity （CO conversion reaches 93.4% at 250 ℃） and thermal stability for WGS reaction. The catalytic activity was correlated with the surface area, the area of peak γ of H2-TPR profile （i.e., the reduction of surface copper oxide （crystalline forms） interacted with surface oxygen vacancies on ceria）, and the area of peak C2 and A1 （Cu^0→←Cu^2＋ in cyclic voltammetry process）, respectively. Besides, Raman spectra provided evidences for a synergistic Cu-Ovacancy interaction, and it was indicated that doping yttrium may facilitate the formation of oxygen vacancies on ceria.

Effect of Addition of Sm_2O_3 on Property of CuO-γ-Al_2O_3 Catalyst

Effect of the addition of Sm 2O 3 on CuO γ Al 2O 3 catalyst for CO oxidation reaction was investigated. The result shows that the right amount of Sm 2O 3 can promote the adsorption of the surface oxygen and recovery of CuO γ Al 2O 3 catalyst. Sm 2O 3 plays an important role in change of γ Al 2O 3 phase into θ Al 2O 3 phase. In addition, the right amount of Sm 2O 3(5%) can improve the oxidation activity of the CuO γ Al 2O 3 catalyst. Whereas an excess of Sm 2O 3(10%) makes the CuO crystal in CuO γ Al 2O 3 catalyst become bigger and restrain the oxidation activity of the CuO γ Al 2O 3 catalyst.

Cl掺杂CuO在Cu^(+)和O空位协同作用下高效电催化还原CO_(2)为C_(2)H_(4)

通过简单的一步水热合成法合成具有富集Cu^(+)和氧空位活性位点的氯掺杂氧化铜催化剂(Cl-CuO),并通过调节氯元素的掺杂量使得Cu基催化剂对乙烯(C_(2)H_(4))拥有较高的选择性和法拉第效率(FE)。结果表明,在-1.2 V[针对可逆氢电极(RHE)]下,C_(2)H_(4)的最大法拉第效率为46.8%;并且在经过15 h电解后,法拉第效率和电流密度无明显下降。Cl-CuO中C_(2)H_(4)的生成归因于Cu^(+)与氧空位的协同作用。

CuO/BiOCl异质结催化剂的合成及其光催化性能研究

以微球状氯氧化铋(BiOCl)为模板,合成了CuO/BiOCl异质结催化剂,利用扫描电子显微镜、X射线衍射仪、荧光分光光度计等对催化剂形貌和结构进行了表征;以亚甲基蓝(MB)为降解目标,探究了CuO与BiOCl物质的量比、MB染料初始质量浓度、催化剂质量、溶液pH等对CuO/BiOCl催化性能的影响,并研究了该催化剂的循环再生能力及光催化反应机理。结果表明:在可见光照射下,当CuO与BiOCl物质的量比为1∶15,催化剂质量为0.050g,MB初始质量浓度为25mg/L时,光催化效率最高,吸附过程符合一级动力学模型,且该催化剂具有良好的循环再生能力。在催化过程中空穴h+起主要作用,羟基自由基和超氧自由基均起次要作用。

Introduction of ZnO,Sn,and P promoters in CuO/CeO_(2) catalysts for improved production of dimethyldichlorosilane in the Rochow-Müller reaction

Developing an efficiently supported Cu-based catalyst with promoters to substitute the existing non-supported Cu-based catalysts is highly desirable to the Rochow-Müller reaction. Using a simple ball-milling method and CeO_(2) support, we prepared a high-performance CuO-ZnO-P-Sn/CeO_(2) catalyst by integrating highly dispersed multicomponent promoters of ZnO, Sn, and P with the active component CuO. This catalyst shows a significantly enhanced dimethyldichlorosilane selectivity because these promoters can substantially increase the Cu+ content and the formation of an active CuxSi phase. This work provides a new approach to efficiently designing Cu-based catalysts for the Rochow-Müller reaction.

Local structural evolutions of CuO/ZnO/Al2O3 catalyst for methanol synthesis under operando conditions studied by in situ quick X-ray absorption spectroscopy

In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed Cu O and Zn O, and it was progressively transformed into Cu metal particles and dispersed Zn O species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu^+intermediate, and the active catalyst predominantly consisted of metallic Cu and Zn O evenunder higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion.This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.

CuO/活性炭催化湿式氧化甲基橙废水的研究

基于以硝酸铜为活性组分的前驱物,采取浸渍焙烧法制备了CuO/活性炭催化剂,并以H_(2)O_(2)为氧化剂,对比了在常压条件下催化湿式氧化工艺中处理质量浓度500 mg·L^(-1)甲基橙模拟废水的效果,分别考察了不同CuO/活性炭催化剂加入量、质量分数30%的H_(2)O_(2)氧化剂用量、脱色反应时间、脱色反应温度对甲基橙废水脱色率的影响。结果表明:随着CuO/活性炭催化剂加入量、30%H_(2)O_(2)氧化剂用量、反应温度的不断增加,甲基橙废水的脱色率明显增大;而增加反应时间对甲基橙废水脱色率增加幅度较小。当CuO/活性炭催化剂加入量为0.1 g、质量分数30%H_(2)O_(2)氧化剂加入量为6 mL、催化反应时间为2 h、催化反应温度为35℃时,其对甲基橙废水的脱色率可达到82.44%。