Flower-like 3D CuO microsphere acting as photocatalytic water oxidation catalyst

Flower-like 3D CuO microspheres were synthesized and used to photo-catalyze water oxidation under visible light.The structure of the CuO microspheres was characterized by scanning electron microscopy,transmission electron microscopy,infrared,powder X-ray diffraction,electron dispersive spectroscopy,Raman and X-ray photoelectron spectroscopy（XPS）.This is the first time that a copper oxide was demonstrated as a photocatalytic water oxidation catalyst under near neutral conditions.The catalytic activity of CuO microspheres in borate buffer shows the best performance with O2 yield of 11.5%.No change in the surface properties of CuO before and after the photocatalytic reaction was seen by XPS,which showed good catalyst stability.A photocatalytic water oxidation reaction mechanism catalyzed by the CuO microspheres was proposed.

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.

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.

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.

CuO/Co_(3)O_(4)Bifunctional Catalysts for Electrocatalytic 5-Hydroxymethylfurfural Oxidation Coupled Cathodic Ammonia Production

The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value-added chemicals and nitrogen cycling.Herein,in this work,CuO/Co_(3)O_(4)with heterogeneous interface is successfully constructed as a bifunctional catalyst for the electrooxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the electroreduction of nitrate to ammonia(NH_(3)).The open-circuit potential spontaneous experiment shows that more 5-hydroxymethylfurfural molecules are adsorbed in the Helmholtz layer of the CuO/Co_(3)O_(4)composite,which certifies that the CuO/Co_(3)O_(4)heterostructure is conducive to the kinetic adsorption of 5-hydroxymethylfurfural.In situ electrochemical impedance spectroscopy further shows that CuO/Co_(3)O_(4)has faster reaction kinetics and lower reaction potential in oxygen evolution reaction and 5-hydroxymethylfurfural electrocatalytic oxidation.Moreover,CuO/Co_(3)O_(4)also has a good reduction effect on NO_(3)^(-).The ex-situ Raman spectroscopy shows that under the reduction potential,the metal oxide is reduced,and the generated Cu_(2)O can be used as a new active site for the reaction to promote the electrocatalytic conversion of NO_(3)^(-)to NH_(3) synthesis.This work provides valuable guidance for the synthesis of value-added chemicals by 5-hydroxymethylfurfural electrocatalytic oxidation coupled with NO_(3)^(-)while efficiently producing NH_(3).

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.

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 CeO_(2)on Activity of Catalysts CuO/ZnO/Al_(2)O_(3)/CeO_(2)for Synthesis of Methanol

The size of the nanoparticles and the number of oxygen vacancies have a significant effect on the catalytic activity of copper-based catalysts used for the synthesis of methanol from syngas.In this study,the authors prepared a series of catalysts CuO/ZnO/Al_(2)O_(3)/CeO_(2)(CZAC)with CuO particles of different sizes and varying number of oxygen vacancies on the surface by changing the added volume of CeO2 by using the co-precipitation method.The properties of the catalysts were characterized and their activity was evaluated by using high-pressure fixed-bed reaction equipment.The results showed that the addition of CeO_(2)to CuO/ZnO/Al_(2)O_(3)not only influenced the size of the CuO particles and metal-metal interactions,but also had an effect on the concentrations of oxygen vacancies and strongly basic sites.The presence of CuO particles of small sizes and a large numbers of oxygen vacancies on the surface of the catalyst were beneficial to its activity for the synthesis of methanol.The catalyst CZAC,when modified by 5%of CeO_(2),recorded CuO particles of the smallest size(8.9 nm),strong intermetallic interactions,and the highest concentrations of oxygen vacancies and strongly basic sites.It also exhibited the highest catalytic activity,with a space-time yield of methanol of 0.315 g/(h·g)that was higher than that of the enterprise RK-5 catalyst[0.215 g/(h·g)].

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.

CuO/AC低温脱除烟气中SO_x和NO_x的研究

以水蒸气活化工业半焦得到的活性焦(AC)为载体,等体积浸渍硝酸铜溶液制得新型CuO/AC催化吸附剂,在烟气净化最经济的温度(120～250℃)下分别对其催化吸附脱除SO2和催化还原脱除NO的活性进行了考查,并与同温下活性焦(AC)和/或CuO/Al2O3的脱硫、脱氮活性进行了对比,同时对吸硫后的AC和CuO/AC进行了TPD表征。研究结果表明:CuO/AC在120～250℃时的脱硫活性明显高于同温下的AC和CuO/Al2O3,吸硫后生成CuSO4物种;有氧气氛下的硫容高于无氧情况,硫容增加的部分为化学吸附形态;CuO/AC在120～250℃的脱氮活性亦明显高于AC,因此,CuO/AC是具有潜在应用前景的烟气净化吸附催化剂。

新型低温CuO/AC脱硫剂制备——煅烧温度对脱硫活性的影响

首次将炭载型ＣｕＯ／ＡＣ用于烟气脱硫，在最经济的烟气脱硫温度窗口（１２０～２５０℃）显示出高的脱硫活性．考查了煅烧温度和煅烧后脱硫剂的预氧化对脱硫活性的影响，并对脱硫剂进行了ＴＰＤ和ＥＸＡＦＳ表征．结果表明：经２５０℃煅烧的ＣｕＯ／ＡＣ脱硫剂具有最高的脱硫活性．２００℃煅烧，前驱体Ｃｕ（ＮＯ３）２未完全分解；高于２５０℃煅烧，活性组分ＣｕＯ被载体Ｃ部分还原为金属Ｃｕ 微晶，从而发生烧结、聚集，以上均导致脱硫剂活性的下降．尽管不同温度煅烧的ＣｕＯ／ＡＣ表现出大的脱硫活性差异，但吸硫后均生成同一反应产物ＣｕＳＯ４．２５０℃煅烧的ＣｕＯ／ＡＣ脱硫剂Ｃｕ 以ＣｕＯ和Ｃｕ２Ｏ形态存在。

新型低温CuO/AC脱硫剂制备及表征──载铜量对脱硫活性的影响

工业半焦经850℃水蒸气活化、浓硝酸处理、等体积浸渍硝酸铜溶液、干燥、煅烧制得新型低温CuO/AC脱硫剂。考查了脱硫剂制备参数载铜量对脱硫活性的影响,并对不同载铜量的脱硫剂进行了TPR、EXAFS、XRD等表征。结果表明:载铜量为5～15%(w)时,脱硫剂具有较高的脱硫活性;5%的载Cu量为AC(活性焦)表面发生单层覆盖的最大量。低于5%,活性组份CuO在AC表面高度分散,无体相CuO出现,但脱硫剂过低的活性组份含量,使得脱硫活性较低;高于5%时,CuO在AC表面发生多层覆盖,且随着载铜量的继续增加,活性组份聚集和内部微孔堵塞严重,致使脱硫活性出现明显下降。

载体炭对CuO/AC(F)催化-吸附剂干法催化氧化苯酚的影响

为了探讨载体炭对CuO/AC(F)催化-吸附剂干法催化氧化苯酚的影响,选择四种性质不同的活性炭(纤维)作载体,制得双功能材料CuO/AC(F)催化-吸附剂。通过TGMS联用系统研究了CuO/AC(F)催化-吸附剂的苯酚催化氧化活性及其自身的烧蚀活性,采用BET、XRD等手段表征了载体炭和CuO/AC(F)催化-吸附剂的物理化学特性。结果表明,载体炭中的灰分影响CuO/AC(F)催化-吸附剂的苯酚催化氧化活性,中孔促进苯酚的催化氧化,表面含氧官能团对苯酚催化氧化活性的影响不大,但表面含氧官能团和灰分均能促进催化-吸附剂的烧蚀。苯酚的催化氧化和炭的催化氧化可能遵循不同的反应历程。

CuO/AC脱除烟气中SO_2机理的初步研究

通过活性焦 AC与 Cu O/AC在不同反应气氛吸硫后 ,于 Ar气氛中的程序升温脱附( TPD)实验 ,对 AC和 Cu O/AC吸附 SO2 的机理进行了初步研究 .结果表明 :常温下 AC和 Cu O/AC吸附 SO2 后 ,均分别生成两种硫物种 .并借助对 AC和 Cu O/Al2 O3 吸附 SO2 现存机理的分析 ,提出了 Cu O/AC吸附 SO2 可能的机理 .

再生气氛对CuO/AC脱硫活性的影响

本文考察了不同气氛再生后CuO/AC脱硫剂的二次脱硫活性,并藉借助XRD和XPS表征技术以及对再生后脱硫剂残硫的分析,探讨了脱硫剂以不同还原剂在不同温度下再生后二次脱硫活性差异的内在原因.结果表明:脱硫剂经H_2再生后二次脱硫活性与初活性相比出现大幅度下降,H_2气氛中添加H_2O可提高其二次脱硫活性;经NH_3在300℃再生后二次脱硫活性与初活性相当,两次再生后仍未观察到活性的明显下降,NH_3再生时脱硫活性的改善并非由于脱硫剂表面碱性含氮官能团=NH,-NH_2和NH_3浓度的增加,而应归因于还原性较弱的NH_3未将CuSO_4还原为单质Cu,活性组分铜物种在AC表面未发生明显的聚集.

金属担载量对CuO/AC干法催化氧化苯酚的影响

采用程序升温氧化（TPO）技术和吸附-催化氧化循环实验，研究了金属担载量对CuO／AC催化．吸附剂干法催化氧化苯酚的影响。结果表明，随着金属担载量的增加，CuO／AC催化一吸附剂的苯酚催化氧化活性升高，并且苯酚与催化．吸附剂之间的相互作用增强，使吸附的苯酚不易脱附／降解脱附。同时，CuO／AC催化-吸附剂自身的烧蚀活性也随金属担载量的增加而升高。对于吸附-干法催化氧化法而言，CuO／AC存在一个较佳的金属担载量范围，该范围以Cu的质量分数计为3％，5％。

CuO/AC脱硫剂的还原再生

Cu O/AC脱硫剂吸硫后 ,其中的 Cu O即转化成 Cu SO4,需对其进行再生 .本文分别考查以 Ar气氛和 H2 气氛还原再生后脱硫剂二次脱硫活性的变化 ,并通过 TG、TPR和 XRD等表征再生过程 .结果表明 :Ar气氛再生实际为载体 C对 Cu SO4的还原 ,最佳再生温度为 40 0℃ ;H2 气氛再生时 ,最佳温度为 2 50℃ ;即使在最佳温度下 ,再生后的脱硫活性仍低于新鲜脱硫剂 ,可能源于还原生成的 Cu微晶在较高温度下发生的明显聚集 .

CuO负载对V_2O_5/AC脱硝催化剂孔隙结构的影响

为了考察CuO对V_2O_5/AC脱硝催化剂孔隙结构的影响,采用N_2等温吸/脱附法测量V_2O_5/AC脱硝催化剂孔隙结构的表征参数,并研究了CuO负载量对催化剂孔隙结构的影响规律。结果表明,活性炭载体微孔结构极其发达,占据孔隙结构的绝大部分,中孔及大孔的数量较少,V_2O_5主要沉积于活性炭载体中孔内,CuO低负载量时分散性较好,主要沉积在微孔内,对催化剂孔隙结构影响较小,CuO负载量较高时在微孔和中孔内均有沉积,沉积量相差不大。CuO和V_2O_5的负载使催化剂比表面积减小,但对活性炭基催化剂孔径分布影响甚微。

新型低温CuO／AC脱硫剂制备及表征—载铜量对脱硫活性的影响

工业半焦经850℃水蒸气活化，浓硝酸处理，等体积浸渍硝酸铜溶液，干燥，煅烧制得新型低温CuO/AC脱硫剂，考查了脱硫剂制备参数－载铜量对脱硫活性的影响，并对不同载铜量的脱硫剂进行了TPR，EXAFS，XRD等表征，结果表明，载铜量为5－15％（w)时，脱硫剂具有较高的脱硫活性；5％的载Cu量为AC（活性焦）表面发生单层覆盖的最大量，低于5％，活性组份CuO在AC表面高度分散，无体相CuO出现，但脱硫剂过低的活性组份含量，使得脱硫活性较低；高于5％时，CuO在AC表面发生多层覆盖，且随着载铜量的继续增加，活性组份矣集和内部微孔堵塞严重，致使脱硫活性出现明显下降。