制备方法对Co_3O_4-CeO_2催化剂催化性能的影响研究

用水热法、共沉淀法、柠檬酸络合物法和多元醇法分别合成了铈钴摩尔比1∶1的Co3O4-CeO2催化剂,并用XRD、TPR、TPD、FT-IR、BET等对催化剂的晶相结构、还原性能、吸附性能及比表面积等进行了表征.结果表明,制备方法对Co3O4-CeO2催化剂的催化性能具有较大的影响,其中多元醇法制备的催化剂能促进Co3O4和CeO2的相互作用,该催化剂还原温度较低、CO脱附面积较大,在140℃温度下,CO的转化率达到90%以上.     

不同沉淀剂对Co3O4催化剂催化分解N2O活性的影响

采用了不同沉淀剂（K2 CO3、Na2 CO3、NaOH、NaHCO3）制备了一系列 Co3 O4氧化物催化剂。通过 XRD、XPS、BET、H2-TPR、O2-TPD 表征手段,探究了催化剂物相结构和氧化还原性能对 N2 O 催化分解性能的影响。研究表明,以 K2 CO3为沉淀剂制备的 Co3 O4催化剂具有优越的氧化还原性能。此外,较低结晶度有助于提高催化剂的催化性能,催化剂表面物种与其沉淀剂相关：丰富的表面 Co 物种促进催化活性,较多氧空位有利于催化剂表面的电子传递和氧气的脱附。以 K2 CO3为沉淀剂制备的 Co3 O4催化剂表现出最佳的 N2 O 催化分解活性,在450℃达到90％以上的转化率。     

块体PdO/Co3O4-CeO2催化剂的制备与性能研究

通过共沉淀法制备出了用于CH_4气体氧化反应的块体PdO/Co_3O_4-CeO_2催化剂,并对其主要制备参数进行了详细考察,得出的最佳制备参数如下:Ce(NO_3)_3的添加量为0.05g,NH_4HCO_3溶液(0.1 g/mL)的添加量为5 mL,焙烧温度为300℃。利用X-射线衍射(XRD)和透射电子显微镜(TEM)技术对其成分、晶体结构及微观形貌进行了表征并分析了催化机理。在测试催化剂性能的过程中,发现催化剂可在250℃下促使CH_4气体被快速氧化,且该催化剂展现出了优良的重复使用性。     

整体式Co3O4/YSZ-Y-Al2O3+CYZ催化剂上的甲烷催化燃烧

用质量比为32的YSZ-γ-Al2O3和CeO2-Y2O3-ZrO2的混合物(以YSZA+CYZ表示)作载体,制备了不同Co3O4含量的整体式甲烷燃烧催化剂,同时制备了分别以YSZA和CYZ为载体的催化剂作为对比,研究了它们老化前后的反应性能,并用BET,XPS,XRD,TPR等研究了催化剂的比表面、表面状态、晶相结构和还原性能.结果表明,YSZ-γ-Al2O3和CeO2-Y2O3-ZrO2混合载体能有效地抑制CoAl2O4的生成,并能充分发挥各自的优点,因此负载一定量的钴后表现出很高的甲烷催化燃烧活性和抗老化性,尤其是含8 wt%Co3O4的样品性能最佳,有望成为实用的甲烷燃烧催化剂之一.     

Co3O4/Ce0.8Pr0.2O2催化剂用于乙醇水蒸气重整反应的研究

采用共沉淀法制备了Co3O4/Ce0.8Pr0.2O2催化剂,并将其用于乙醇水蒸气重整制氢反应,考察了Co3O4负载量以及Pr掺杂对催化剂性能的影响.采用X射线衍射、程序升温还原、热重分析和透射电子显微镜对催化剂的结构和表面性质进行表征.结果表明,催化剂中部分Co进入到载体的晶格中,使载体发生畸变产生更多的氧空位;载体中Pr掺杂有利于生成更多的氧空位,提高了催化剂的抗积碳性能,同时Pr掺杂可以增强Co3O4与载体之间的相互作用,提高金属Co的抗烧结性能;15%Co3O4/Ce0.8Pr0.2O2催化剂具有最好的催化活性,在反应温度为400℃,空速80 000 mL/(g.h),n(H2O)∶n(EtOH)=3的条件下可将乙醇完全转化;10 h稳定性测试结果表明该催化剂具有较好的稳定性.     

整体式Co3O4/YSZ—γ-Al2O3＋CYZ催化剂上的甲烷催化燃烧

用质量比为3：2的YSZ-γ-Al2O3和CeO2-Y2O3-ZrO2的混合物（以YSZA＋CYZ表示）作载体，制备了不同Co3O4含量的整体式甲烷燃烧催化剂，同时制备了分别以YSZA和CYZ为载体的催化剂作为对比。研究了它们老化前后的反应性能，并用BET，XPS，XRD，TPR等研究了催化剂的比表面、表面状态、晶相结构和还原性能．结果表明，YSZ-γ-Al2O3和CeO2-Y2O3-ZrO2混合载体能有效地抑制CoAl2O4的生成，并能充分发挥各自的优点，因此负载一定量的钴后表现出很高的甲烷催化燃烧活性和抗老化性，尤其是含8wt％Co3O4的样品性能最佳，有望成为实用的甲烷燃烧催化剂之一．     

各种形貌纳米Co3O4的制备及其应用

本文综述了各种形貌的纳米Co3O4的制备及其应用。制备纳米Co3O4的方法有很多,包括热分解、水热法、溶剂热法、化学喷雾热分解、化学气相沉积和溶胶-凝胶法。制备得到的Co3O4有各种形貌,如纳米球、纳米立方体、纳米管、纳米棒、纳米片、纳米纤维和介孔结构。Co3O4是一种重要的磁性p型半导体,在锂离子电池、超级电容器、电致变色、磁性材料、气体传感器和催化剂等诸多领域有较广泛的应用。     

CeO2和Co3O4助剂对镍基催化剂是CH4积碳和CO2消碳性能的影响

采用脉冲微反技术研究了添加CeO2和Co3O4助剂对镍基催化剂上CH4积碳和CO2消碳性能的影响，并用BET，TGA，XPS及CO2－TPSR等技术对催化剂进行了表征。结果表明，添加CeO2可以提高活性原子Ni^0中d电子的密度；Ni^0原子中d电子密度的增加在一定程度上凶制了CH4分子中C－H键σ电子向d轨道的迁移，降低了CH4裂解积碳性能；同时加强了Ni^0原子d轨道向CO2空反馈π轨道的电子迁移，促进了CO2分子的活化，提高了CO2的消碳活性。助剂Co3O4的添加则促进CH4的裂解积碳，抑制了CO2的消碳。分析表明，活性金属与半导体助剂之间存在的金属－半导体要互作用是影响这种机制的主要因素。     

各种形貌的纳米Co3O4的制备及其应用*

本文综述了各种形貌的纳米Co₃O₄的制备及其应用。制备纳米Co₃O₄的方法有很多,包括热分解、水热法、溶剂热法、化学喷雾热分解、化学气相沉积和溶胶-凝胶法。各种形貌的Co₃O₄被制备,如纳米球、纳米立方体、纳米管、纳米棒、纳米片、纳米纤维和介孔结构。Co₃O₄是一种重要的磁性P-型半导体,在锂离子电池、超级电容器、电致变色、磁性材料、气体传感器和催化剂等诸多领域有比较广泛的应用。     

聚合物燃烧方法制备Co3O4纳米粒子

纳米粒子因其独特的物理化学特性成为近年来材料科学领域的研究热点。制备方法是获得性能优越材料的关键。Co3O4具有正常的尖晶石结构，Co^2 占据八面体位置，在空气中低于800℃时十分稳定，是优良的催化剂材料^[1,2]，采用燃烧方法可通过控制反应条件在不发生沉淀的情况下获得化学组成均匀的复合氧化物粉体^[4-7]，本利用聚合物燃烧方法探索制备粒径均匀，分散性好的立方Co3O4纳米粒子，选择聚乙烯醇（PVA）的原因是其分子内包含大量的羟基极性基团，能与金属离子尤其是过渡金属离子形成良好的化学键，促使金属离子在PVA高分子的网络中均匀螯合分布，有利于最终形成分散性良好的粉体。     

Co3O4-CeO2氧化物对丙烷完全氧化的催化性能（英文）

挥发性有机化合物(VOCs)是全球大气污染物的主要来源,近年来已造成严重的环境问题.催化氧化是一种有效的、经济可行的VOCs去除技术,其研究的关键在于开发高效、稳定的催化剂.在本文中,我们采用柠檬酸法合成了一系列具有不同Co/(Ce+Co)摩尔比的Co3O4-CeO2二元氧化物催化剂,研究了其对丙烷(低碳VOCs)的催化氧化性能.在催化活性测试中,反应气的组成为0.2 vol.%C3H8和5 vol.%O2,Ar为平衡气,气体总流速为200 mL min^-1.实验结果表明,Ce的掺入能够明显提高Co3O4的丙烷催化氧化性能,Co3O4-CeO2催化剂的丙烷催化氧化活性顺序为CoCeOx-70>CoCeOx-90>Co3O4>CoCeOx-50>CoCeOx-20>CeO2.当Co/(Ce+Co)摩尔比为70%时,CoCeOx-70催化剂的丙烷催化氧化性能最好.在丙烷转化率达到90%时,CoCeOx-70催化剂的反应温度为310℃(GHSV=120000mL h^-1 g^-1),相比于单一的Co3O4催化剂的反应温度降低了25℃.XRD和TEM表征结果显示,在Co3O4-CeO2二元氧化物催化剂中存在Co3O4和CeO2两种晶型,同时随着Ce的掺入,催化剂的粒径明显降低.Raman光谱图显示,Ce的掺入使催化剂的晶格发生畸变,促进催化剂表面氧空位的产生,为催化剂中氧的迁移提供晶格位点.H2-TPR和C3H8-TPSR结果表明,Co3O4与CeO2间存在相互作用,能够提高催化剂的低温还原性能,以促进催化剂的丙烷催化氧化.O2-TPD和O 1s XPS结果表明,Ce的掺入能够增加催化剂表面活性氧物种的产生,提高催化剂中氧的移动性,从而提高了催化剂对丙烷的催化氧化活性.在对Co3O4和CoCeOx-70催化剂进行in-situ DRIFTS表征和简单的动力学研究,我们发现Ce的掺入不改变催化剂的丙烷催化氧化反应路径,其存在能够促进丙烷在催化剂表面的吸附和活化,以提高催化剂的丙烷催化氧化活性.同时,丙酮和酯作为中间物参与到丙烷的催化氧化反应过程中.此外,我们考察了反应气氛中水蒸气和CO2的存在对催化剂催化性能的影响.结果表明,CO2和水蒸气的存在都抑制了催化剂的丙烷催化氧化活性,催化性能随着CO2和水蒸气浓度的增加而降低.在相同条件下,水蒸气对催化剂催化性能的抑制作用明显大于CO2的抑制作用,但这种抑制作用会随着反应气中水蒸气和CO2的消失而消失.在稳定性测试中,CoCeOx-70催化剂表现出优异的抗水蒸气和CO2性能.在反应气中存在5 vol.%水蒸气和5 vol.%CO2的条件下,CoCeOx-70催化剂在50 h的稳定性测试中均未出现明显的失活现象.同时,经过10次加热和降温循环测试后,催化剂的催化活性也没有发生明显变化,这为CoCeOx-70催化剂的未来工业化的应用提供了可能.     

Improved catalytic properties of Co3O4-impregnated La2O3/MgO over Co3O4/MgO catalyst in the oxidative dehydrogenation of ethylbenzene

Research on Chemical Intermediates - A series of lanthanum oxide (La2O3—2–14 wt%)-encapsulated Co3O4/MgO catalysts and bare Co/MgO solid oxides were prepared by wetness...     

Preparation and bifunctional gas sensing properties of porous In2O3-CeO2 binary oxide nanotubes

The porous binary In(2)O(3)-CeO(2) oxides nanotubes (NTs) in cubic phase were first fabricated by electrospinning (ESP) method and characterized by SEM, TEM, XRD, XPS and UV-vis absorption techniques. By adjusting the In(2)O(3) and CeO(2) molar ratio, the out diameters and wall thicknesses of the final composites were tuned ranging of 90-180 nm and 15-9 nm, respectively. The band gap of the binary oxides gradually decreases, and the ratio of Ce(3+) to Ce(4+) increases with the increase of CeO(2), implying that surface oxygen vacancies gradually increase. The gas sensing test reveals that when the content of CeO(2) is appropriate, the as fabricated In(2)O(3)-CeO(2) NTs could be bifunctional gas sensors to detect H(2)S at low temperature(25-110 °C) while acetone at relative high temperature (300 °C). The In(75)Ce(25) NTs sensor is an optimum one, which exhibits the highest response of 498 to H(2)S at 80 °C and the highest response of 30 to acetone at 300 °C. In contrast to the pure In(2)O(3) sensor, the response and recovery times, as well as the sensing reaction barrier height, for In(75)Ce(25) both degrade considerably. The above temperature-dependent sensing properties were attributed to two different gas sensing mechanisms, sulfuration at low temperature and adsorption at high temperature.     

铈基与钴基Co3O4-CeO2氧载体上甲烷化学链转化特性: 产物选择性控制

采用水热法制备了Co₃O₄/CeO₂(x)[x为钴铈原子摩尔比n(Co):n(Ce)=6:49:1]和Ce_1-yCo_yO_2-δ(y=0.10.4)2个系列复合氧化物, 并表征了材料的物理化学性质, 考察了这些氧化物作为氧载体参与甲烷化学链转化(化学链燃烧和化学链部分氧化)的反应性能. 结果表明, 2类复合氧化物的甲烷反应活性均明显优于单一氧化物CeO₂或Co₃O₄, 但2类氧载体上的甲烷反应产物的选择性具有明显差异. Ce_1-yCo_yO_2-δ氧载体形成了Ce-Co-O固溶体, 储氧能力明显增强, 体相晶格氧迁移速率与甲烷活化速率匹配较好, 甲烷反应产物以CO和H₂的合成气为主, 有利于甲烷的化学链部分氧化. Co₃O₄/CeO₂(x)氧载体中CeO₂与Co₃O₄之间的相互作用改善了材料的储氧能力和氧化活性, 其与甲烷反应时主要生成CO₂, 有利于甲烷化学链燃烧. 连续性化学链循环实验表明, 2类氧载体均具有较好的再生性能和循环稳定性.     

介孔Co3O4-CeO2复合氧化物的制备及在CO选择性氧化中的应用

以硝酸钴和硝酸铈为前驱物，SBA-15为硬模板，利用双溶剂法制备了Co3O4-CeO2介孔复合氧化物，通过X-射线衍射、N2吸脱附测试、程序升温还原和透射电子显微镜等技术对活性组分及载体进行了表征，并且与浸渍法和共沉淀法所制备的催化剂进行了对比分析。结果表明，相比于浸渍法和共沉淀法，采用双溶剂法制备的介孔Co3O4-CeO2复合氧化物具有均匀的介孔结构、较小的颗粒尺寸、较大的比表面积和较高的活性组分分散度。此外，CO氧化脱除评价显示与常规的共沉淀法和浸渍法所制备的催化剂相比该介孔复合氧化物具有较高的反应活性和选择性，其高活性主要归因于较高的比表面积和活性组分的高分散度。     

In situ growth of Co3O4 nano-dodecahedeons on In2O3 hexagonal prisms for toluene catalytic combustion

In this paper, in situ growth of Co₃O₄ nano-dodecahedra on In₂O₃ hexagonal prisms were synthesized via pyrolysis of ZIF-67/MIL-68. Interestingly, the amount of Co₃O₄ dodecahedra on In₂O₃ hexagonal prisms was regularly regulated and controlled. In detail, four Co₃O₄/In₂O₃ catalysts with various Co/In molar ratio were prepared, including Co₄In₁ (Co/In molar ratio was 4:1), Co₂In₁ (Co/In molar ratio was 2:1), Co₁In₁ (Co/In molar ratio was 1:1), Co_0.5In₁ (Co/In molar ratio was 0.5:1). The catalytic performance of Co₃O₄/In₂O₃ catalysts was systematically investigated for toluene combustion. It could be noted that the Co₂In₁ sample exhibited the superior catalytic performance, and the temperatures for 90% toluene conversion (T₉₀) was 182 °C. Furthermore, the toluene conversion of Co₂In₁ sample had no significant decrease at 178 °C for 15 h, indicating that it presented superior stability for toluene oxidation reaction. Through various characterizations, it was verified that the Co/In molar ratio of Co₃O₄/In₂O₃ catalyst could obviously alter the surface atomic ratio of Co³⁺/(Co³⁺ + Co²⁺), BET surface area, the number of surface adsorbed oxygen, the interaction between In₂O₃ and Co₃O₄ of CoInO_x catalysts and so on. The lots of surface adsorbed oxygen, strong interaction between In₂O₃ and Co₃O₄ would promote the catalytic oxidation of toluene. Especially, we discovered that the catalytic activity of Co₃O₄/In₂O₃ was obviously improved with the increase of Co³⁺/(Co³⁺ + Co²⁺) surface atomic ratio.     

Effects of gamma-irradiation and Li2O-doping on surface and catalytic properties of unloaded Co3O4 solid

The effects of -irradiation (20–160 Mrad) and lithium oxide doping (0.75–6 mol%) on the surface and catalytic properties of unloaded Co₃O₄ solid have been investigated. The surface characteristics of various solids were determined from nitrogen adsorption isothems taken at –196 °C and their catalytic activities were measured by following the kinetics of CO-oxidation by O₂ at 100–150 °C using a static method. The results showed that -rays brough about a decrease of 21% inS _BET of Co₃O₄ due to widening of its pores and led also to a considerable increase in its catalytic activity. A maximum increase of 91% was observed upon exposure to a dose of 80 Mrad. Lithium oxide-doping at at 500 °C resulted in an increase of 150% inS _BET of treated solid without changing its mean pore radius. This treatment was also accompanied by an increase of about 50% in its catalytic activity measured at 150 °C. Gamma-irradiation and Li₂O-doping of unloaded Co₃O₄ did not change the magnitude of apparent activation energy of catalysis of CO-oxidation by O₂ but increased the concentration of catalytically active sites contributing in the catalytic process. In other words, -rays and lithium oxide doping did not alter the mechanism of catalytic oxidation of CO by O₂ over unloaded cobaltic oxide solid.     

Effect of gamma-irradiation on surface and catalytic properties of Co3O4 and NiO catalysts

The effects of g-irradiation (0.2-1.6 MGy) on the particle size, specific surface area and catalytic activity of Co₃O₄ and NiO solids were investigated. The investigated solids were prepared by heat treatment of cobalt carbonate at 500 and 700 °C and basic nickel carbonate at 400 °C. The techniques employed were XRD, nitrogen adsorption at -196 °C and decomposition of H₂O₂ at 30-50 °C. The results showed that g-irradiation resulted in a small decrease in the particle size of the investigated solids and effected a progressive increase in their specific surface areas. On the other hand, the exposure of Co₃O₄ and NiO catalysts to a dose of 0.2 MGy resulted in a significant decrease in their catalytic activities, which suffered further progressive decrease upon increasing the doses up to 1.6 MGy. Gamma-irradiation did not modify the activation energy of the catalyzed reaction but decreased the concentration of catalytically active sites without changing their energetic nature. These results were discussed in terms of splitting of the particles of the treated solids and removal of chemisorbed species present in nonstoichiometric cobalt and nickel oxides.     

Effect of gamma-irradiation on surface and catalytic properties of Co3O4 doped with NiO

NiO-doped Co₃O₄ samples precalcined at 500 °C were subjected to various doses of -rays within the range 0.2-1.6 MGy. The particle size and BET-surface areas of different samples were determined using XRD and nitrogen adsorption at -196 °C. The catalytic reactions studied were conversion of ethanol and isopropanol at 250-400 °C using a micropulse technique and H₂O₂ decomposition in aqueous solution at 30-50 °C. The results revealed that the -irradiation brought a significant decrease in the particle size of Co₃O₄ phase with subsequent increase in the S_BET surface areas. The treatment brought also a progressive decrease in the total conversion of both alcohol (dehydration and dehydrogenation) falling to a minimum value (about 20% of its initial activity) at a dose of 0.8 MGy. The catalysts retain their initial activity upon exposure to a dose of 1.6 MGy. On the other hand, the catalytic activity in H₂O₂ decomposition of the investigated system decreased progressively by increasing the dose of -rays and the catalysts lost more than 90% of their initial activity upon exposure to a dose of 1.6 MGy.