Catalytic oxidation of benzene over nanostructured porous Co3O4-CeO2 composite catalysts

The three-dimensional structured Co₃O₄-CeO₂ oxides with Co/Ce molar ratio 16:1 gave the highest catalytic activity, which provided more surface hydroxyl groups and more surface oxygenated species.     

聚合物辅助成型法制备纳米Co3O4/CeO2催化剂及其对CO低温氧化性能研究

采用聚合物辅助成型法,以乙二胺四乙酸(EDTA)和聚乙烯亚胺(PEI)为配位体制备了Co_3O_4/CeO_2催化剂,对其进行了氮气吸附、XRD、XPS、SEM、TEM、H2-TPR和CO-TPR等表征,并考察了材料的CO低温催化性能.结果表明,采用聚合物辅助成型法能够合成出具有三维空间网络结构的纳米Co_3O_4/CeO_2催化剂,Ce的加入有利于获得具有更小尺寸的Co_3O_4颗粒,并提高Co3+的相对含量,从而有利于CO低温催化性能的提高;Ce/Co的摩尔比为1时,样品具有最佳的CO催化性能,在催化温度为30℃时,可使初始浓度为100 ppm的CO完全转化;同时,纯氧气加热吹扫有利于催化剂的稳定再生.本研究可为CO低温催化剂的制备提供重要参考.     

Pt-Sn/Al2O3蜂窝催化剂催化氧化C6烃

采用等体积分浸法制备Pt-Sn/Al₂O₃蜂窝催化剂（Pt含量仅为0.06wt%）.运用X射线衍射（XRD）、透射电镜（TEM）等技术对催化剂理化性质进行表征,并选取4种代表性C₆烃（苯、环己酮、环己烷和正己烷）对催化剂性能进行评价.活性评价试验中,Pt/Sn比为3/1催化效果最佳.此时4种C₆烃转化率达到90%的温度（T₉₀）较Pt催化剂均降低约20℃,其原因在于Sn可将Pt分割为较小的团簇提高Pt分散度.寿命评价试验以环己烷为例同Pt-Sn蜂窝催化剂连续运行720h,催化活性无明显变化,其原因在于,Sn可有效抑制其粒径增长;Pt₃Sn合金降低表面对C₆烃的吸附,减少催化剂表面积炭.     

不同方法制备Co3O4催化剂CO-SCR性能及机制

氮氧化物(NOx)是造成细颗粒物、近地面臭氧等大气污染问题的重要前体物.随着大气污染治理行动的深入,对工业锅炉/窑炉烟气排放的NOx进行控制十分重要.采用不同方法制备了一系列Co_3O_4催化剂,考察了不同制备方法对CO选择性催化还原NO(CO-SCR)反应活性的影响,通过BET、XRD、Raman、HR-TEM和SEM等技术对该系列催化剂进行了表征.活性测试表明,以硫酸钴为前驱体用固态研磨法制备的Co_3O_4-S催化剂具有更优异的CO-SCR反应活性,且表现出较好的抗水蒸气性能,以醋酸钴为前驱体用固态研磨法制备的Co_3O_4-C催化剂显示出较好的抗水性能. NO氧化结果显示,催化剂的NO氧化效果越好,CO-SCR活性也越好. Raman表征结果显示,Co_3O_4-S表面可能含有更多的Co2+离子,从而有利于形成氧空位. H2-TPR结果表明,Co_3O_4-S催化剂的氧化还原性较好. HR-TEM表征发现Co_3O_4-S和Co_3O_4-O主要暴露(111)和(220)晶面,而更多(220)晶面的暴露可能更有利于反应的进行.     

Macroporous Ni foam-supported Co3O4 nanobrush and nanomace hybrid arrays for high-efficiency CO oxidation

Herein, we reported the synthesis of well-defined Co_3O_4 nanoarrays(NAs) supported on a monolithic three-dimensional macroporous nickel(Ni) foam substrate for use in highefficiency CO oxidation. The monolithic Co_3O_4 NAs catalysts were obtained through a generic hydrothermal synthesis route with subsequent calcination. By controlling the reaction time,solvent polarity and deposition agent, these Co_3O_4 NAs catalysts exhibited various novel morphologies(single or hybrid arrays), whose physicochemical properties were further characterized by using several analytical techniques. Based on the catalytic and characterization analyses, it was found that the Co_3O_4 NAs-6 catalyst with nanobrush and nanomace arrays displayed enhanced catalytic activity for CO oxidation, achieving an efficient 100% CO oxidation conversion at a gas hourly space velocity(GHSV) 10,000 hr~(-1) and 150°C with longterm stability. Compared with the other Co_3O_4 NAs catalysts, it had the highest abundance of surface-adsorbed oxygen species, excellent low-temperature reducibility and was rich in surface-active sites(Co~(3+)/Co~(2+)= 1.26).     

纳米Fe3O4/H2O2降解诺氟沙星

采用纳米Fe3O4催化H2O2氧化降解水环境中的诺氟沙星.考察了溶液酸度、温度、催化剂和H2O2浓度对诺氟沙星降解的影响,对比不同底物在Fe3O4/H2O2体系中的降解情况,并进一步探讨了其反应机制.结果表明,溶液酸度显著影响诺氟沙星的降解率,在酸性条件下（pH=3.5）诺氟沙星的降解效率最高.诺氟沙星的降解率随纳米F...     

碳化泡沫负载Co3O4活化过硫酸盐降解罗丹明B

Co₃O₄具有优良的活化过硫酸盐的性能而受到人们的重视,但Co₃O₄粉体易团聚、使用过程中难以分离、易流失和重复利用率差等问题严重制约了其实际应用．通过水热法制备碳化三聚氰胺泡沫负载Co₃O₄非均相催化剂．采用X-射线衍射仪（XRD）和扫描电子显微镜（SEM）对催化剂的结构和表面形貌进行分析．研究不同因素对催化剂活化过硫酸氢钾（PMS）降解罗丹明B（RhB）的性能．其最优催化工艺参数：催化剂投加量为35 mg·L^-1、PMS质量浓度为50 mg·L^-1和pH为7、RhB初始质量浓度为10 mg·L^-1,30 min反应后对RhB降解率为98%．结果表明,增大碳化泡沫负载Co₃O₄非均相催化剂投加量和PMS质量浓度能明显提高对RhB的降解率;而增加RhB初始质量浓度和提高pH值会明显抑制RhB的降解率．催化反应过程符合准一级动力学方程．温度对RhB降...     

Co3O4纳米棒的制备及其对气相甲苯的催化氧化

采用低温水热法制备棒状纳米结构的Co3O4,通过加入少量的表面活性剂（聚乙烯吡咯烷酮简称PVP）,在95℃下低温反应,并调控制备过程的老化时间、溶液的pH这2个因素合成了棒状Co3O4纳米结构.X射线衍射（XRD）、透射电镜（TEM）表明制得的是呈立方晶体的Co3O4纳米棒,氢气程序升温还原（H2-TPR）、N2吸附脱附等表征手段表明老化时间和pH会影响Co3 O4纳米棒的尺寸、孔隙结构,进而影响其比表面积大小.采用气相甲苯作为目标物,运用气相色谱（GC）对Co3 O4的催化性能进行研究.结果表明在该实验中,调控老化时间和pH制得的Co3O4纳米棒只影响其低温降解效果,在温度低于260℃,活性最好的是pH=9,老化时间为12 h的催化剂;当温度高于260℃后,其降解曲线基本一致.     

Reduction of NO by CO using Pd-CeTb and Pd-CeZr catalysts supported on SiO2 and La2O3-Al2O3

The catalytic activity of Pd catalysts supported on Ce_0.73Tb_0.27O_x/SiO₂, Ce_0.6Zr_0.4O_x/SiO₂, Ce_0.73Tb_0.27O_x/La₂O₃-Al₂O₃ and Ce_0.6Zr_0.4O_x/La₂O₃-Al₂O₃ was studied using the reduction of NO by CO. The catalysts were characterized by X-ray fluorescence, surface area, X-ray diffraction, temperature-programmed reduction, CO chemisorption and oxygen storage capacity. Temperature-programmed reduction results indicated that Tb or Zr incorporation improves the reducibility and oxygen storage capacity. CO chemisorption data suggested the presence of large PdO particles due to the low CO/Pd ratio. No significant differences were obtained in light off temperatures (T_{Light off}) for all Pd catalysts and the most active was 1.5%Pd/Ce_0.6Zr_0.4O_x/SiO₂.     

Ce-Mn/Al2O3-H2O2催化氧化皮革废水的研究

以浸渍法制备了Ce-Mn/Al_2O_3催化剂,研究该催化剂在H_2O_2非均相类Fenton体系中对皮革废水污染物的催化降解性能.在单因素试验的基础上,以COD去除率为响应值,采用Box-Behnken响应曲面法考察了催化剂投加量、H_2O_2投加量、初始pH、反应时间等4个因素之间的单独作用及交互作用,实验数据用Design-Expert 8.0.6软件进行处理,得到二次响应曲面模型.结果表明,4个独立变量对响应值的影响顺序如下:初始pHH_2O_2投加量催化剂投加量反应时间,数学模型拟合度高(R_(adj)~2=0.9349),利用该模型预测的最大COD去除率为78.86%,最佳反应条件为:催化剂投加量56.63 g·L~(-1),H_2O_2投加量315.15 mg·L~(-1),初始pH3.51,反应时间2 h,经实验验证COD去除率为80.94%,与模型预测值偏差2.08%.     

Fe3O4/FeS2活化H2O2降解典型苯胂酸类污染物

利用水热法成功制备了Fe₃O₄/FeS₂催化剂,并将其用于构建非均相芬顿体系降解典型的苯胂酸类污染物（洛克沙胂,ROX）.XRD、SEM、XPS和磁学测量系统（VSM）等表征结果表明,Fe₃O₄/FeS₂呈明显的颗粒状且具有良好的磁性.降解实验结果显示,在最优条件下（初始pH值为4.5、ROX起始浓度为20mg/L、Fe₃O₄/FeS₂投加量为0.15g/L和H₂O₂浓度为0.034g/L,Fe₃O₄/FeS₂介导的非均相芬顿体系可以超快速降解ROX,1min后的降解效率达到96.74%,明显优于单独的Fe₃O₄或FeS₂体系.此外,Fe₃O₄/FeS₂可以通过磁铁进行快速回收利用,同时也具有良好的重复利用性能,使用3次后,ROX的降解效率仍超过80%.机理分析表明,Fe₃O₄/FeS₂能够快速地催化H₂O₂产生具有强氧化性的羟基自由基（·OH）.在·OH的作-用下,ROX分子结构中C-As、C-N和C-C等化学键发生断裂,发生脱砷、脱硝和开环等反应,进而生成一系列的有机产物（如酚类、醌类、小分子有机酸等）和无机产物（As （V）和NO₃^-）.之后,无机砷能够被吸附在催化剂表面,而有机产物则进一步被矿化.     

Promoting catalytic ozonation of phenol over graphene through nitrogenation and Co3O4 compositing

Catalytic ozonation is progressively becoming an attractive technique for quick water purification but efficient and stable catalysts remains elusive. Here we solvothermally synthesized highly-dispersed Co₃O₄ nanocrystals over microscale nitrogen-doping graphene (NG) nanosheets and tested it as a synthetic catalyst in the ozonation of phenol in aqueous solutions. Transmission electron microscopy, powder X-ray diffraction, Fourier transform infrared spectra and X-ray photoelectron spectroscopy were used to determine its morphology, crystallinity, elemental composition and molecular bonds, respectively. The comparative experiments confirmed the highest catalytic activity and oxidation degree (AOSC) of Co₃O₄/NG among four nanocomposites (G, NG, Co₃O₄/G, and Co₃O₄/NG). Co₃O₄/NG also has exhibited the highest degradation rate: complete conversion of a near-saturated concentration of phenol (941.1 mg/L) was achieved within 30 min under ambient conditions with only a small dosage of Co₃O₄/NG (50 mg/L) and ozone (4 mg/L, flow rate: 0.5 L/min). It also resulted in 34.6% chemical oxygen demand (COD_Cr) and 24.2% total organic carbon (TOC) reduction. In this work, graphene nanosheets not only functioned as a support for Co₃O₄ nanocrystals but also functioned as a co-catalyst for the enhancement in phenol removal efficiency. The surface nitridation and Co₃O₄ modification treatment further improved the removal rate of the phenol pollutants and brought in the higher oxidation degree. Our finding may open new perspectives for pursuing exceptional activity for catalytic ozonation reaction.     

Co3O4/BiVO4复合阳极活化过一硫酸盐强化光电催化降解双酚A

采用静电纺丝法制备了Co_3O_4/BiVO_4复合薄膜电极,并以之为光阳极,在过一硫酸盐(PMS)辅助作用下开展了光电催化降解双酚A研究.结果表明,PMS在可见光下可显著强化Co_3O_4/BiVO_4复合阳极光电催化降解双酚A,在0.25 V外加偏压以及可见光照射下,当加入2 mmol·L-1PMS时,双酚A在2 h内的降解效率为96%.降解动力学常数为0.471 4 min-1.系统研究了PMS初始浓度、外加偏压对双酚A降解性能的影响.结果发现,双酚A在较低的PMS投加量和较低的外加偏压(0.25 V)下即可有效降解.采用电子自旋共振波谱仪鉴定体系的主要活性自由基为SO·-4和·OH.并进一步通过淬灭实验结果证明空穴、SO·-4和·OH起主要氧化作用.光电反应后的体系中未检测到金属离子溶出,可避免二次污染.     

活性炭负载Co3O4活化过一硫酸盐降解金橙G

通过浸渍煅烧法制备活性炭负载Co的活化剂(Co/AC),采用X射线衍射仪(XRD)、扫描电镜(SEM)及X射线能谱仪(EDS)技术对活化剂进行表征,发现Co主要以Co_3O_4的形式负载于活性炭表面,并利用Co/AC活化过一硫酸盐(PMS)产生硫酸根自由基(SO_4~-·)降解偶氮染料金橙G(OG),研究了活化反应机制及不同因素对OG降解的影响.结果表明,SO_4~-·在OG降解过程中起主要作用,并且随Co/AC用量、PMS浓度、温度的提高,OG降解效率明显增加.反应初始pH对降解OG有较大影响,当p H在4~8范围内,SO_4~-·均能有效降解OG,但在强酸碱条件下,则不利于OG降解.Cl~-对活化降解OG具有双重作用,低浓度时抑制降解,而在高浓度时促进降解.Co/AC在重复使用6次时仍具有较好活化性能.通过紫外可见光谱及气相色谱-质谱(GC/MS)对OG降解过程及中间产物进行了分析.     

Mo-modified Pd/Al2O3 catalysts for benzene catalytic combustion

Mo-modified Pd/Al2O3catalysts were prepared by an impregnation method and tested for the catalytic combustion of benzene. The catalysts were characterized by N2 isothermal adsorption, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, temperatureprogrammed desorption of NH3（NH3-TPD）, H2temperature-programmed reduction（H2-TPR）, and high-angle annular dark-field scanning transmission electron microscopy（HAADF-STEM）. The results showed that the addition of Mo effectively improved the activity and stability of the Pd/Al2O3catalyst by increasing the dispersion of Pd active components, changing the partial oxidation state of palladium and increasing the oxygen species concentration on the surface of catalyst. In the case of the Pd-Mo/Al2O3catalyst,benzene conversion of 90% was obtained at temperatures as low as 190°C, which was 45°C lower than that for similar performance with the Pd/Al2O3catalyst. Moreover, the 1.0% Pd-5% Mo/Al2O3catalyst was more active than the 2.0% Pd/Al2O3catalyst. It was concluded that Pd and Mo have a synergistic effect in benzene catalytic combustion.     

Fe3O4/CeO2-H2O2非均相类Fenton体系下降解TCE的研究

采用浸渍法成功合成了新型催化剂纳米Fe3O4/CeO_2,并且用Fe3O4/CeO_2-H_2O_2非均相Fenton体系对TCE进行降解研究,考察了初始pH、H_2O_2浓度、温度及催化剂投加量等因素对于TCE降解效率的影响.实验结果表明,Fe3O4/CeO_2-H_2O_2非均相Fenton体系对TCE具有较好的去除效果:在初始pH=3,温度50℃,H_2O_2浓度30 mmol·L-1和Fe3O4/CeO_2投加量0.5 mg·L-1时,TCE去除率高达97.29%.同时实验结果表明pH在2~7范围内对TCE均有降解效果,所以相对于传统Fenton体系,该体系拥有更宽pH应用范围.目标污染物的降解符合一级动力学,反应活化能为30.77 k J·mol-1,表明反应易于进行.     

Decomposition of hexachlorobenzene over Al2O3 supported metal oxide catalysts

Decomposition of hexachlorobenzene (HCB) was investigated over several metal oxides (i.e., MgO, CaO, BaO, La₂O₃, CeO₂, MnO₂, Fe₂O₃, and Co₃O₄) supported on Al₂O₃, which was achieved in closed system at a temperature of 300°C. Catalysts were prepared by incipient wetness impregnation with different metal oxides loading and impregnating solvents. The decomposition efficiency of different catalysts for this reaction depends on the nature of the metal oxide used, and Al₂O₃ supported La₂O₃ was found to be the most active one. Pentachlorobenzene (PeCB), and all tetrachlorobenzene (TeCB), trichlorobenzene (TrCB), and dichlorobenzene (DCB) isomers were detected after the decomposition reaction, indicating that the decomposition was mainly a dechlorination process. The detection of all lower chlorinated benzenes suggested the complexity of decomposition and the presence of more than one dechlorination pathway.     

Fe3O4/TiO2-H2O2非均相类Fenton体系对3，4-二氯三氟甲苯的降解

用Fe_3O_4/Ti O_2-H_2O_2体系对3,4-二氯三氟甲苯(3,4-DCBTE)进行降解反应研究,同时考察了pH值、催化剂投加量、H_2O_2投加量、温度等因素对3,4-DCBTE降解效率的影响.实验结果表明,Fe_3O_4/Ti O_2-H_2O_2非均相类Fenton体系对3,4-二氯三氟甲苯的处理效果极佳;并且在H_2O_2投加量为45.0 mg·L~(-1)、Fe_3O_4/TiO_2的物质的量比为1∶1、pH=3.0、温度为40.0℃的条件下反应效果最佳,去除率高达99.1%.同时从实验结果可以看出,pH在2.0~7.0范围内该体系对3,4-二氯三氟甲苯均有降解效果,说明该体系相比于传统的Fenton体系有较宽的pH适用范围.目标污染物的降解符合一级反应动力学,其发生反应所需的活化能为36.9 k J·mol~(-1).     

纳米Fe3O4/CeO2-H2O2非均相类Fenton体系对3,4-二氯三氟甲苯的降解

以浸渍法制备的新型纳米Fe3O4/Ce O2为催化剂,3,4-二氯三氟甲苯(3,4-DCBTE)为目标污染物,在Fe3O4/Ce O2-H2O2非均相类Fenton体系中对目标污染物的降解进行研究,考察催化剂的催化效果和温度、p H、H2O2投加量等因素对催化剂催化效果的影响.结果表明,以纳米Fe3O4/Ce O2作为催化剂的非均相类Fenton体系对3,4-二氯三氟甲苯的处理效果极佳;随着温度的升高,纳米Fe3O4/Ce O2的催化效果不断提高;在偏酸性环境中,p H越低催化效果越好,p H=2时反应去除效率可达96.67%;随着H2O2投加量的增加,3,4-二氯三氟甲苯的降解效率先提高后降低,投加量为15 mg·L-1时去除效果最好可达99.47%;随着催化剂投加量的增加,同样出现了处理效果先升高后降低的现象,投加量为0.5 g·L-1时催化效果最好可达99.64%.在以纳米Fe3O4/Ce O2为催化剂的非均相类Fenton体系中,3,4-二氯三氟甲苯的降解符合一级反应动力学,反应所需活化能较低只需30.26 k J·mol-1.     

La0.8Ca0.2FeO3/MgAl2O4丝网整体催化剂用于低浓度甲烷催化燃烧

开发了涂覆在金属丝网基体上的La_(0.8)Ca_(0.2)FeO_3/MgAl_2O_4复合整体催化剂,用于低浓度甲烷(0.5%,体积分数)催化燃烧反应.首先用沉积-沉淀法制备了La_(0.8)Ca_(0.2)FO_3(LCF)钙钛矿与Mg Al_2O_4尖晶石复合的粉末催化剂LCF/Mg Al2O4,用程序升温微反应器(TPRS)测定了粉末活性,结合XRD、BET、SEM、TPR的表征结果,筛选出了最佳复合物质的量比和最适焙烧温度.当LCF与Mg Al_2O_4复合后,抗烧结能力增强,以拟一级反应速率常数(k,L·g~(-1)·s~(-1))计的活性提高了1倍左右.然后采用浆料涂覆法,在表面改性的金属丝网蜂窝基体上分层涂覆了作为第二载体的MgAl_2O_4和LCF/Mg Al_2O_4复合粉体涂层,考察了复合粉体球磨前焙烧的温度、第二载体及活性层涂覆量的影响.最后在空速GHSV=40000 h~(-1)条件下测试了甲烷催化燃烧反应的活性.与陶瓷基体相比,涂覆在金属丝网基体上的LCF/MgAl_2O_4活性在600℃时提升了48.1%.500 h长运转试验发现,催化剂活性在初期的200 h下降了20.3%,然后基本保持稳定.