CoCr_2O_4/SiO_2催化剂上二氯甲烷催化氧化

采用浸渍法制备了不同CoCr_2O_4负载量x CoCr_2O_4/SiO_2催化剂(x=5%、10%、20%和30%),考察其对二氯甲烷催化燃烧性能的影响。结果表明,催化剂的整体活性顺序为:30CoCr_2O_4/SiO_220CoCr_2O_4/SiO_210CoCr_2O_4/SiO_25CoCr_2O_4/SiO_2,但按照活性组分CoCr_2O_4质量归一化后本征活性顺序为:10CoCr_2O_4/SiO_2≈5CoCr_2O_4/SiO_220CoCr_2O_4/SiO_230CoCr_2O_4/SiO_2。表征结果发现催化剂本征活性与可还原性能和表面酸性存在密切关系。10CoCr_2O_4/SiO_2和5CoCr_2O_4/SiO_2具有较高的表面酸性和耗氢量,因此具有较高的本征活性。     

M_(0.5)Co_(2.5)O_4(M=La,Ce,Pr,Nd)尖晶石型复合氧化物催化剂催化分解N_2O性能

采用共沉淀法制备了M_(0.5)Co_(2.5)O_4(M=La,Ce,Pr,Nd)钴基尖晶石型复合氧化物催化剂,运用XRD、SEM、H_2-TPR和O_2-TPD-TG等对催化剂物化性能进行表征,并在固定床微型反应器中评价催化剂催化分解N_2O性能。结果表明,稀土金属掺杂改性的钴基尖晶石型复合氧化物催化剂粒径明显减小,比表面积增加,氧化还原性能得到改善,催化分解N_2O活性提高,其中,M_(0.5)Co_(2.5)O_4催化剂催化分解N2O温度低,T10和T95分别为342℃和499℃。     

刚玉型复合氧化物催化剂Cr1.3Fe0.7O3上二氯甲烷催化燃烧

通过溶胶-凝胶法合成一系列具有刚玉结构的Cr_(1.3)Fe_(0.7)O_3复合氧化物,在二氯甲烷催化燃烧反应中进行活性评价。结果表明,复合氧化物比单金属氧化物CrO_x和FeO_x具有更高的催化活性,其催化活性与氧化物的表面酸性和可还原性密切相关,二者在反应中协同作用。与高温焙烧样品相比,低温焙烧的Cr_(1.3)Fe_(0.7)O_3催化剂具有更高的比表面积、表面酸性和可还原性,催化性能更优。以表面酸性位数量为基础计算的催化剂转化频率(TOF)表明,各Cr_(1.3)Fe_(0.7)O_3催化剂活性相近(300℃时约2.3×10~(-3) s~(-1)～2.8×10~(-3) s~(-1)),表面酸性位上发生二氯甲烷分子吸附及C-Cl键断裂,是反应活性位。300℃时Cr~(6+)的TOF为9.3×10~(-3) s~(-1),Cr~(3+)的TOF为0.59×10~(-3) s~(-1),Cr~(6+)物种比Cr~(3+)物种具有更高的活性。     

负载铜锰复合氧化物催化剂上有机废气(VOCs) 的催化燃烧性能

用不同方法制备了以Al2O3-CeO2-ZrO2为载体的负载CuMn复合氧化物催化剂,Cu和Mn的摩尔比为12.用共沉淀法、一步浸渍法和两步浸渍法制备的催化剂分别记做CuMn/ACZ(cp)、CuMn/ACZ(im)和CuMn/ACZ(im2),以乙酸乙酯和乙醇为探针反应,对各催化剂的催化燃烧活性进行了评价.结果表明,共沉淀法制备的复合氧化物具有催化燃烧活性高和二氧化碳选择性好的特点,乙酸乙酯和乙醇均可在较低温度下实现完全转化.     

尖晶石型Mn_(1-x)M_xCo_2O_4柴油车尾气处理催化剂的制备及其应用

尖晶石型复合氧化物因具有独特的结构特征而成为相对理想的柴油车尾气处理催化剂。采用溶胶-凝胶法制备尖晶石型Mn_(1-x)M_xCo_2O_4催化剂,通过X射线衍射(XRD)和程序升温氧化(TDO)等对Mn_(1-x)M_xCo_2O_4催化剂进行表征。结果表明,制备的样品Mn_(1-x)M_xCo_2O_4均为尖晶石型复合氧化物;掺杂Cu、Ce后,催化剂的氧化性能有不同程度的变化。在固定床微型反应器上对催化剂催化活性进行评价,结果表明,与纯MnCo_2O_4相比,Mn_(0.9)Ce_(0.1)Co_2O_4催化剂催化活性提高,Mn_(0.9)Cu_(0.1)Co_2O_4催化剂催化活性降低,但CO_2选择性增加。     

介孔CuCe/M/CuCe(M=Co,Mn,Zr)催化剂富H_2中优先氧化CO的催化性能

优先氧化是去除富H2中CO最有效的方法,铜铈催化剂是该领域的研究热点。以SBA-15为模板剂,采用纳米刻蚀法合成系列介孔Cu Ce/M/Cu Ce(M=Co,Mn,Zr)催化剂,采用XRD、N2吸附-脱附、TEM、H2-TPR和O2-TPD对催化剂结构及形貌进行表征,并对其在富H2中CO优先氧化性能进行研究。结果表明,Mn有利于催化剂表面吸附氧的增加,有助于大量氧空位的产生,进而促进CO优先氧化性能的提高;Zr的加入抑制了Cu O的还原,且其表面氧脱附温度范围过宽,不利于催化剂催化氧化性能的释放。掺杂Co与Mn可以形成Ce-Cu-M-O固溶体,促进了催化剂表面氧和晶格氧之间的相互转化,最终有利于铜铈催化剂CO优先氧化性能的提高。     

含氯挥发性有机物废气在CeO2基催化剂上的低温催化燃烧净化:从高活性到高稳定性再到高选择性

挥发性有机物(VOCs)造成的环境污染问题备受关注,采用高效催化剂通过催化燃烧方式在低温下后处理净化是解决VOCs污染的主要途径之一.由于VOCs种类繁多、实际应用工况复杂,因此该净化途径对催化剂的要求十分苛刻,广谱性、耐高温、抗中毒、高选择性的高效催化剂的研发仍然是该领域关注的核心问题.作为VOCs分支之一的含氯挥发...     

含能配合物Zn_4(C_4N_6O_5H_2)_4(DMSO)_4的晶体结构及催化性能(英文)

以ANPyO、Zn(CH_3COO)_2·2H_2O和DMSO作原料,通过溶液法合成了含能配合物Zn_4(C_4N_6O_5H_2)_4(DMSO)_4,采用傅立叶变换红外光谱、元素分析、X-射线单晶衍射、差示扫描量热法(DSC)和热重分析法(TG)对其结构进行了表征,用Kissinger和Ozawa法计算了配合物放热过程的表观活化能。研究了配合物对黑索今(RDX)、奥克托今(HMX)和高氯酸铵(AP)热分解的催化效果,测试了其撞击感度和摩擦感度。结果表明,配合物属单斜晶系,空间群为P2_1/C。配合物热分解过程有一个吸热峰和一个放热峰,剩余残渣质量分数为14.38%;表观活化能为225.56 kJ/mol;配合物对RDX和HMX热分解催化效果不明显,但对AP具有非常显著的催化效果;配合物对撞击和摩擦钝感。     

柠檬酸(CA)对Cu-Mn-O/γ-A1_2O_3催化燃烧苯性能的影响

以大孔拟薄水铝石为原料,添加有机助剂制备了比表面积高、孔分布宽的柱状氧化铝载体。用等体积浸渍法制备了Cu-Mn-O-CA/γ-A12O3催化剂(CuO,MnOx质量分数分别为14%,7%,n(CA)∶n(CuO)=1∶1),考察了其催化燃烧苯的活性,并利用低温氮吸附、X射线衍射(XRD)对催化剂结构进行了表征。结果表明:制备的γ-A12O3载体比表面积325m2/g,孔容0.48cm3/g,主要是中孔占总孔容的90.2%;添加柠檬酸(CA)后,活性组分均匀分散在载体表面,XRD谱图无明显CuO和MnOx特征峰;在空速1800h-1,苯进料浓度2mg/m3,反应温度350℃下苯催化燃烧转化率达到95%以上。     

合成方法对NH_4MPO_4·H_2O(M=Mn,Fe,Co,Ni,Cu)颗粒形貌的影响

采用低温固相法与常规液相法合成系列磷酸铵复盐NH4MPO4.H2O(M=Mn,Fe,Co,Ni,Cu),用XRD,FT-IR和SEM对产物进行表征,比较两种合成工艺及产物的颗粒形貌和大小。结果表明,除铜盐为斜方晶系外,其余都为正交晶系。与常规液相法相比,低温固相法不需要使用溶剂,能在低温短时间内合成磷酸铵复盐类化合物,但是需要晶化才能得到良好结晶体,合成的条件较为苛刻,容易有副反应发生,所得产品是片状结构,厚度为纳米尺寸的二维纳米材料,液相反应得到的产物颗粒是层状结构的微米级产品。     

负载型CuMnO_x/TiO_2催化剂催化燃烧甲苯

采用沉积-沉淀法制备CuMnO_x/TiO_2新型甲苯燃烧催化剂,考察焙烧温度、Cu与Mn物质的量比、Cu和Mn总负载量、空速及水蒸汽含量对催化甲苯燃烧性能的影响。研究表明,焙烧温度500℃和Cu与Mn物质的量比为1∶1时,催化剂活性最好,反应温度250℃时,甲苯去除率为100%;水蒸汽的出现明显降低了甲苯转化率。XRD和H2-TPR表征结果表明,CuMnO_x/TiO_2催化剂的主要活性相为铜锰尖晶石(Cu1.5Mn1.5O4),它的存在降低了CuMnO_x/TiO_2催化剂的还原温度,是催化活性优良的主要原因。     

负载型RuO_2/Me_xO_y(Me=La,Mg,Al)催化剂催化分解N_2O

采用共沉淀法制备LaMgAlO(简称Me_xO_y)复合金属氧化物,以Me-xO_y为载体,采用浸渍法制备系列负载型RuO_2/Me_xO_y催化剂,应用BET、TEM、XRF和SEM对代表性样品进行表征。结果表明,实验条件下,RuO_2负载质量分数2.0%时比较合适,在气体混合物中含有氧和少量水蒸汽条件下,催化剂具有较好的催化分解N_2O稳定性。     

Ce改性Pd基整体式催化剂的结构特征及其甲烷催化燃烧性能

分别以拟薄水铝石和添加Ce的拟薄水铝石制备铝溶胶,经过堇青石（Cord）表面涂覆和Pd溶液浸渍,得到浸渍法和溶胶法Ce改性的Pd/γ-Al₂O₃/Cord整体式催化剂。采用XRD、SEM和XPS等对催化剂进行表征,评价其甲烷催化燃烧反应性能,并考察Ce的不同添加方式对催化剂结构和反应性能的影响。结果表明,适量Ce的添加可提高Pd基整体式催化剂的甲烷催化燃烧性能,溶胶法优于浸渍法。随着Ce添加量的增加,浸渍法改性的Pd基催化剂催化性能有所降低,溶胶法则呈现先升高后降低的趋势。溶胶法中Ce的添加物与γ-Al₂O₃涂层充分融合,提高了涂层的热稳定性和活性组分的分散度,0.5Pd/γ-Al₂O₃(3.0Ce)/Cord催化剂催化性能最优。     

Studies on spinel cobaltites,MCo2O4 (M = Mn,Zn, Fe,Ni and Co) and their functional properties

Optimization of electrodes for charge storage with appropriate processing conditions places significant challenges in the developments for high performance charge storage devices. In this article, metal cobaltite spinels of formula MCo₂O₄ (where M = Mn, Zn, Fe, Ni and Co) are synthesized by oxalate decomposition method followed by calcination at three typical temperatures, viz. 350, 550, and 750 °C and examined their performance variation when used as anodes in lithium ion batteries. Phase and structure of the materials are studied by powder x-ray diffraction (XRD) technique. Single phase MnCo2O4,ZnCo2O4 and Co3O4 are obtained for all different temperatures 350 °C, 550 °C and 750 °C; whereas FeCo₂O₄ and NiCo₂O₄ contained their constituent binary phases even after repeated calcination. Morphologies of the materials are studied via scanning electron microscopy (SEM): needle-shaped particles of MnCo₂O₄ and ZnCo₂O₄, submicron sized particles of FeCo₂O₄ and agglomerated submicron particle of NiCo₂O₄ are observed. Galvanostatic cycling has been conducted in the voltage range 0.005–3.0 V vs. Li at a current density of 60 mA g^?1 up to 50 cycles to study their Li storage capabilities. Highest observed charge capacities are: MnCo₂O₄ – 365 mA h g^?1 (750 °C); ZnCo₂O₄ – 516 mA h g^?1 (550 °C); FeCo₂O₄ – 480 mA h g^?1 (550 °C); NiCo₂O₄ – 384 mA h g^?1 (750 °C); and Co₃O₄ – 675 mA h g^?1 (350 °C). The Co₃O₄ showed the highest reversible capacity of 675 mA h g^?1; the NiO present in NiCo₂O₄ acts as a buffer layer that results in improved cycling stability; the ZnCo₂O₄ with long needle-like shows good cycling stability.     

Preparation and characterization of partially substituted LiMyMn2−yO4 (M=Ni, Co, Fe) spinel cathodes for Li-ion batteries

The electrochemical and thermal behaviors of the spinels-LiMn₂O₄, LiCo_1/6Mn_11/6O₄, LiFe_1/6Mn_11/6O₄, and LiNi_1/6Mn_11/6O₄ were studied using electrochemical and thermochemical techniques. The electrochemical techniques included cyclic voltammetry, charge-discharge cycling of 2016 coin cells and diffusion coefficient measurements using Galvanostatic Intermittent Titration Technique. Better capacity retention was observed for the substituted spinels (0.11% loss per cycle for LiCo_1/6Mn_11/6O₄; 0.3% loss per cycle for LiFe_1/6Mn_11/6O₄; and 0.2% loss per cycle for LiNi_1/6Mn_11/6O₄) than for the lithium manganese dioxide spinel (1.6% loss per cycle for first ten cycles, 0.9% loss per cycle for 33 cycles) during 33 cycles. The Differential Scanning Calorimetry results showed that the cobalt substituted spinel has better thermal stability than the lithium manganese oxide and other substituted spinels.     

Catalytic decomposition of N2O over CeO2 promoted Co3O4 spinel catalyst

A series of CeO₂ promoted cobalt spinel catalysts were prepared by the co-precipitation method and tested for the decomposition of nitrous oxide (N₂O). Addition of CeO₂ to Co₃O₄ led to an improvement in the catalytic activity for N₂O decomposition. The catalyst was most active when the molar ratio of Ce/Co was around 0.05. Complete N₂O conversion could be attained over the CoCe0.05 catalyst below 400 °C even in the presence of O₂, H₂O or NO. Methods of XRD, FE-SEM, BET, XPS, H₂-TPR and O₂-TPD were used to characterize these catalysts. The analytical results indicated that the addition of CeO₂ could increase the surface area of Co₃O₄, and then improve the reduction of Co³⁺ to Co²⁺ by facilitating the desorption of adsorbed oxygen species, which is the rate-determining step of the N₂O decomposition over cobalt spinel catalyst. We conclude that these effects, caused by the addition of CeO₂, are responsible for the enhancement of catalytic activity of Co₃O₄.     

Reduction behaviors and catalytic properties for methanol steam reforming of Cu-based spinel compounds CuX2O4 (X=Fe,Mn, Al,La)

In this study, various Cu-based spinel compounds, i.e., CuFe₂O₄, CuMn₂O₄, CuAl₂O₄ and CuLa₂O₄, were fabricated by a solid-state reaction method. Reduction behaviors and morphological changes of these materials have been characterized by H₂ temperature-programmed reduction (H₂-TPR), X-ray diffraction (XRD), Scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Moreover, the catalytic properties for steam reforming of methanol (SRM) of these Cu-based spinel compounds were investigated. H₂-TPR results indicated that the reducibility of Cu-based spinel compounds was strongly dependent on the B-site component while the CuFe₂O₄ catalyst revealed the lowest reduction temperature (190 °C), followed respectively by CuAl₂O₄ (267 °C), CuMn₂O₄ (270 °C), and CuLa₂O₄ (326 °C). The reduced CuAl₂O₄ catalyst demonstrated the best performance in terms of catalytic activity. Based on the SEM and XRD results, pulverization of the CuAl₂O₄ particles due to gas evolution and a high concentration of nanosized Cu particles (≈50.9 nm) precipitated on the surfaces of the Al₂O₃ support were observed after reduction at 360 °C in H₂. The BET surface area of the CuAl₂O₄ catalyst escalated from 5.5 to 13.2 m²/g. Reduction of Cu-based spinel ferrites appear to be a potential synthesis route for preparing a catalyst with high catalytic activity and thermal stability. The catalytic performance of these copper-oxide composites was superior to those of conventional copper catalysts.     

g-C_3N_4在VOCs催化燃烧催化剂开发中的应用前景

金属氧化物作用下的催化燃烧可有效消除挥发性有机物(VOCs),工业前景较好,目前研究重点在于开发适宜结构的载体。石墨相氮化碳(g-C_3N_4)结构稳定,电子性能独特,其供电子特性与表面碱性位均具有促进氧气与反应物分子活化的潜能,有望成为VOCs催化燃烧催化剂的优良载体。介孔结构能改善电子特性,提高活性组分分散,促进反应物扩散,将成为g-C_3N_4研发的主要方向。     

Catalytic performance of Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite oxides for methane combustion: Influence of catalyst pretreatment temperature and oxygen concentration in the reaction mixture

The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration (λ = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ containing 30 wt.% of Co₃O₄. The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples).

Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g⁻¹ h⁻¹). The catalytic performance of Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ were compared with those of two pure Co₃O₄ oxides, a sample obtained by the precipitation method and a commercial reference. Characterization studies by X-ray diffraction (XRD), BET and temperature-programmed reduction (TPR) show that the catalytic activity is related to the dispersion of crystalline phases, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ as well as to their reducibility. Particular attention was paid to the thermal stability of the Co₃O₄ phase in the temperature range of 750–800 °C, in both static (in a furnace) and dynamic conditions (continuous flow). The results indicate that the thermal stability of the phase Co₃O₄ heated up to 800 °C depends on the size of the cobalt oxide crystallites (fresh or aged samples) and on the oxygen content (excess λ = 8, stoichiometric λ = 1) in the reaction mixture. A stabilizing effect due to the presence of ceria or ceria–zirconia against Co₃O₄ decomposition into CoO was observed.

Moreover, the role of ceria and ceria–zirconia is to maintain a good combustion activity of the cobalt composite oxides by dispersing the active phase Co₃O₄ and by promoting the reduction at low temperature.