铁改性分子筛直接催化分解一氧化二氮

采用以离子交换法制备的Fe-ZSM-5、Fe-MCM-22和Fe-Beta分子筛催化剂,系统地考察了分子筛构型、酸性和酸中心分布对N2O直接催化分解的影响.采用N2吸附、红外光谱仪(FT-IR)、NH3程序升温脱附实验(NH3-TPD)、H2程序升温还原实验(H2-TPR)和原位漫反射红外光谱(in situ DRIFTS)等方法考察了铁离子负载量、Si与Al摩尔比和分子筛构型对N2O催化分解的影响.结果表明,价键补偿Fe3 离子是N2O分解的主要活性组分;分子筛活性随Si和Al摩尔比的减少和铁离子负载量的增加而增加;Fe-Beta分子筛的催化活性明显高于Fe-ZSM-5和Fe-MCM-22分子筛;分子筛酸性和酸中心分布影响铁离子的分布,从而导致不同构型分子筛催化分解N2O的活性具有明显差异.     

铁取代介孔磷铝分子筛的合成、表征及其催化性能

以水热晶化法合成了Fe取代介孔磷铝分子筛,并用XRD, FT-IR, N2吸附等对其进行了表征. 结果表明,合成的分子筛为缺乏长程有序的介孔结构,具有较高的比表面积. 在焙烧后的分子筛中,Fe3+离子主要以四配位的形式存在于骨架中. 该分子筛能有效催化氧化水溶液中苯酚,在反应温度60℃、苯酚起始浓度3 mmol/L、加入45 mmol/L H2O2、溶液起始pH值4.5的条件下,4 h后苯酚去除率达99.5%,COD去除率达87.9%,且催化剂性能稳定,反应过程中有极少量Fe3+离子流失.     

分子筛催化剂上N2O催化分解的研究进展

氧化亚氮(N2O)会造成温室效应和臭氧层破坏,N2O的控制日益引起关注。催化分解技术是控制N2O的有效手段,分别对Fe基、Cu基和Co基分子筛催化剂催化分解N2O的研究现状进行总结和评述,并展望未来发展方向。     

Fe_2O_3可见光光催化降解水中腐殖酸的研究

采用均相沉淀法制备了Fe2O3光催化剂,并用XRD对其晶型进行了表征。研究了Fe2O3催化剂在可见光照射下对水中腐殖酸的降解行为,考察了催化剂用量、初始pH值、腐殖酸初始浓度等因素对光催化氧化过程的影响。结果表明,当Fe2O3用量为0.4 g/L,腐殖酸溶液的初始浓度为10 mg/L,pH为3.0,20 W黄色荧光灯(Em ax=548 nm)照射下反应150 m in,腐殖酸的降解率达到94.1%,说明所制备的Fe2O3光催化剂在可见光照射下对水中腐殖酸有较好的降解效果,并可多次重复使用。     

碱土金属修饰的Co/RPSA催化剂催化分解N2O

以RPSA分子筛为载体,采用浸渍法制备了一系列以Co为主活性组分和碱土金属为助剂的CoM/RPSA（M=Mg、Ca、Sr和Ba）催化剂,考察了含硫和含氧条件下直接催化分解N2O的性能。采用X射线衍射、热重-质谱联用系统、NH3-TPD和N2O-TPD等方法对催化剂进行了表征。XRD结果表明,Co物种主要以Co3O4尖晶石形态存在。NH3-TPD和N2O-TPD结果表明,碱土金属的种类影响催化剂酸性和对反应物N2O的吸附-脱附性能,催化剂活性与催化剂酸性及其对反应物N2O的吸附-脱附性能有关。催化剂活性评价结果显示,CoSr/RPSA催化剂的N2O分解活性较好,N2O转化率达到95%时的反应温度为471 ℃。     

微波强化类Fenton反应催化氧化脱色降解孔雀石绿废水

以超声浸渍-焙烧法制备的Fe2O3/Al2O3为催化剂,研究了微波促进类Fenton反应催化氧化脱色降解有机染料孔雀石绿及相关机理。考察了溶液pH、H2O2用量、催化剂用量、微波辐射功率及时间等因素对其降解效果的影响。结果表明,催化剂与微波存在协同效应,当pH为3.0时,微波可以明显加快类Fenton法催化氧化脱色降解孔雀石绿溶液,用该方法处理染料孔雀石绿,5 min色度脱除率可达到96.42%。     

非均相Fe/Al_2O_3催化H_2O_2降解偶氮染料活性黑5

以活性氧化铝为载体,制备了Fe/Al2O3负载型催化剂,用于催化H2O2分解产生羟基自由基氧化降解偶氮染料活性黑5。探讨了pH、H2O2投加量、催化剂投加量等对染料脱色率的影响。结果表明,活性黑5的脱色率随催化剂投加量的增加而升高;随H2O2投加量的增加而降低;Fe/Al2O3/H2O2体系下,活性黑5在pH为2~9之间均有一定的脱色效果,活性黑5的脱色率随初始pH的增加而先增加后减少,其中在初始pH为3时,脱色效果最佳。     

CNTs／TMO复合催化剂对含高氯酸钾烟火药剂分解反应速率的影响

采用化学沉淀法制备沉积于碳纳米管(CNTs)表面上的CuO、Fe2O3复合催化剂.用光电子能谱(XPS)对复合催化剂进行表征,研究了CuO/CNTs和Fe2O3/CNTs复合催化剂对含高氯酸钾烟火药剂分解反应的影响.结果表明,CuO和Fe2O3颗粒均匀地附着在碳纳米管表面上,Cuo/CNTs和Fe3O3/CNTs复合催化剂能够提高含高氯酸钾烟火药剂的反应速率,复合催化剂对高氯酸钾烟火药剂的催化性能明显优于Fe2O3和CuO混合物的催化性能.     

Fe-Cu-Ce/Al_2O_3 非均相Fenton催化剂的制备及活性研究

采用浸渍法制备Fe-Cu-Ce/Al2O3催化剂,探讨了催化剂的制备条件、初始pH值等因素对催化剂活性的影响。研究结果表明:Fe、Cu、Ce总离子浓度0.05mol/L,n(Fe)∶n(Cu)∶n(Ce)=1∶1∶1,前驱体在300℃下焙烧2h,反应初始pH值为5时,该催化剂对甲基橙具有良好的催化性能,反应2h后甲基橙脱色率可达97.99%。且pH=5.0~9.0均可取得良好的降解效果,拓宽了pH适用范围。     

还原石墨烯负载Fe3O4催化剂的制备及催化降解苯酚

通过水热法制备还原石墨烯负载四氧化三铁(RGO/Fe3O4)催化剂,研究了催化剂投加量、催化剂配比、H2O2投加量、体系pH值等对苯酚催化降解的影响.结果表明,当苯酚模拟废水的体系pH=3、m(催化剂)=0.2 g、V(H2O2)=20 mL、m(RGO):m(Fe3O4)=1.2时,苯酚去除效果最好,去除率最高可达8...     

Catalytic decomposition of N2O over supported Rh catalysts: effects of supports and Rh dispersion

The study of catalytic decomposition of nitrous oxide to nitrogen and oxygen over Rh catalysts supported on various supports (USY, NaY, Al₂O₃, ZrO₂, FSM-16, CeO₂, La₂O₃) showed that the activities of Rh/Al₂O₃ and Rh/USY (ultrastable Y zeolite) catalysts were comparable to or higher than the other catalysts reported in the literatures. The catalytic activity of N₂O decomposition was sensitive not only to the Rh dispersion but also to the preparation variables such as the Rh precursors and the supports used. A pulsed N₂O experiment over a Rh/USY catalyst suggested that the catalytic N₂O decomposition occurs on oxygen-covered surface and that O₂ may be freed on collision of N₂O molecules with the adsorbed oxygen atoms.     

沉淀方式对沉淀法制备Co_3O_4催化N_2O直接分解性能的影响

以Co(NO_3)_2·6H_2O为钴源,K_2CO_3为沉淀剂,采用沉淀法制备Co_3O_4催化剂,用于催化N_2O直接分解反应。利用N_2~-物理吸附、XRD、FT-IR、TEM、TPR和ICP等对其进行表征,考察沉淀方式对Co_3O_4催化剂结构及其催化性能的影响。结果表明,沉淀方式对制备的Co_3O_4催化剂织构性质、物相组成和晶粒尺寸等影响不大,但显著影响其K残留量和还原性能,进而决定催化剂直接催化分解N_2O的催化性能。反加法制得的催化剂中K残留量为1.43%,明显高于正加法,同时催化剂中Co~(3+)较正加法更易还原,因而表现出更高的催化性能。在空速10 000 h~(-1)和N_2O体积分数0.1%的条件下,反加法制备的催化剂可在280℃催化N_2O完全分解,较正加法低20℃。     

Cu-Mn氧化物催化N_2O直接分解性能

分别以Cu(NO_3)_2·3H_2O和50%Mn(NO_3)_2水溶液为铜源和锰源,K_2CO_3为沉淀剂,采用沉淀法和共沉淀法制备单一Cu、Mn氧化物催化剂和Cu-Mn-O复合氧化物催化剂,用于催化N_2O直接分解反应,并利用N_2物理吸附-脱附、XRD、FT-IR和TPR等进行表征。结果表明,单一Cu和Mn氧化物分别以体相CuO和Mn2O_3物相形式存在,Cu-Mn-O复合氧化物中除形成CuMn_2O_4尖晶石物相外,还有一定量小晶粒CuO,较单一氧化物具有更加优异的还原性能,表现出较高的催化N_2O直接分解活性。在空速10 000 h~(-1)和N_2O体积分数0.1%条件下,Cu-Mn-O复合氧化物催化剂可在440℃催化N_2O完全分解,分别较单一Cu和Mn氧化物催化剂降低了40℃和60℃。     

Catalytic decomposition of N2O and catalytic reduction of N2O and N2O + NO by NH3 in the presence of O2 over Fe-zeolite

The decomposition of N₂O, and the catalytic reduction by NH₃ of N₂O and N₂O + NO, have been studied on Fe-BEA, -ZSM-5 and -FER catalysts. These catalysts were prepared by classical ion exchange and characterized by TPR after various activation treatments. Fe-FER is the most active material in the catalytic decomposition because “oxo-species” reducible at low temperature, appearing upon interaction of Fe^II-zeolite with N₂O (-oxygen), are formed in largest amounts with this material. The decomposition of N₂O is promoted by addition of NH₃, and even more with NH₃ + NO in the case of Fe-FER and -BEA. It is proposed that the NO-promoted reduction of N₂O originated from the fast surface reaction between -oxygen O^* and NO^* to yield NO₂^*, which in turn reacts immediately with NH₃.     

单分散Co3O4@SiO2核壳催化剂的制备及N2O催化分解性能

N₂O是一种重要的温室气体,且对臭氧层有很大的破坏作用,而直接催化分解法是除去N₂O最经济有效的方法之一。针对目前报道较多的钴氧化物催化剂活性较差的问题,将包覆型Co₃O₄核壳材料引入N₂O直接催化分解反应,利用核壳结构的限域特性与壳层的多孔孔道使Co₃O₄分散性增加,粒径减小,金属载体相互作用与接触反应界面增强,从而提高了催化剂在N₂O直接催化分解反应中的低温活性。此外,还制备了一系列不同金属含量的Co₃O₄@SiO₂球形核壳催化剂来研究包覆结构对催化剂性能的影响,通过X射线荧光光谱（XRF）、透射电镜（TEM）、X射线衍射（XRD）、N₂物理吸附、H₂-程序升温还原（H₂-TPR）等表征,证实在保证稳定单分散核壳结构的前提下,活性Co₃O₄位点越多,催化剂反应活性越好。     

Co-Cu-Ce-Fe/γ-Al_2O_3催化剂催化分解N_2O的性能

以等体积浸渍法制备γ-Al_2O_3负载的Co、Cu、Ce和Fe氧化物催化剂,利用正交试验设计实验条件,采用XRD、BET和H_2-TPR等对催化剂进行表征,并考察活性组分对催化剂催化分解N_2O活性的影响。结果表明,催化剂具有尖晶石结构,其BET比表面积随着金属氧化物负载量增加而降低。催化剂中铜的氧化物可以降低还原峰温度,进而明显提高催化活性,Co和Fe的加入对活性有一定的提高,Ce对催化活性没有明显影响。     

Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: An option for automotive applications

Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH₃. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents, the activity of the mesoporous samples in NO SCR with NH₃ is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite as was confirmed by SEM analysis. Moreover, the maximum activity for the mesoporous zeolites is found at higher Fe concentrations than for the conventional zeolites. This also illustrates that the mesoporous zeolites allow a better dispersion of the metal component than the conventional zeolites. Finally, the influence of different pretreatment conditions on the catalytic activity was studied and interestingly, it was found that it is possible to increase the SCR performance significantly by preactivation of the catalysts in a 1% NH₃/N₂ mixture at 500 °C for 5 h. After preactivation, the activity of mesoporous 6 wt% Fe/HZSM-5 and 6 wt% Fe/HZSM-12 catalyst is comparable with that of traditional 3 wt% V₂O₅/TiO₂ catalyst used as a reference at temperatures below 400 °C and even more active at higher temperatures.     

Low temperature decomposition of nitrous oxide over Fe/ZSM-5: Modelling of the dynamic behaviour

The kinetics of N₂O decomposition to gaseous nitrogen and oxygen over HZSM-5 catalysts with low content of iron (<400 ppm) under transient and steady-state conditions was investigated in the temperature range of 250–380 °C. The catalysts were prepared from the HZSM-5 with Fe in the framework upon steaming at 550 °C followed by thermal activation in He at 1050 °C. The N₂O decomposition began at 280 °C. The reaction kinetics was first order towards N₂O during the transient period, and of zero order under steady-state conditions. The increase of the reaction rate with time (autocatalytic behaviour) was observed up to the steady state. This increase was assigned to the catalysis by adsorbed NO formed slowly on the zeolite surface from N₂O. The formation of NO was confirmed by temperature-programmed desorption at temperatures >360 °C. The amount of surface NO during the transient increases with the reaction temperature, the reaction time, and the N₂O concentration in the gas phase up to a maximum value. The maximum amount of surface NO was found to be independent on the temperature and N₂O concentration in the gas phase. This leads to a first-order N₂O decomposition during the transient period, and to a zero-order under steady state. A kinetic model is proposed for the autocatalytic reaction. The simulated concentration–time profiles were consistent with the experimental data under transient as well as under steady-state conditions giving a proof for the kinetic model suggested in this study.     

DeNOx reactions on Cu-zeolites Decomposition of NO, N2O and SCR of NO by C3H8 and CH4 on Cu-ZSM-5 and Cu-AlTS-1 catalysts

Cu-ZSM-5 and Cu-AlTS-1 catalysts were prepared by solid state ion exchange and studied in DeNO_x reactions. A NO₃ type surface complex was found to be an active intermediate in the decomposition of NO and N₂O. Copper was oxidized to Cu²⁺ in the decomposition reactions. Oscillations at full N₂O conversion were observed in the gas phase O₂ concentration, without any change in the N₂ concentration. The oscillation was synchronized by gas phase NO formed from the NO₃ complex. The same complex seems to be an active intermediate also in NO selective catalytic reduction (SCR) by methane, whereas carbonaceous deposits play a role in NO SCR by propane. TPD reveals that only 10–20% of the total copper in the zeolites participates in the catalytic cycles.