制备工艺对LaMnO3钙钛矿型催化剂性能影响的研究

采用共沉淀法、溶胶-凝胶法和燃烧法制备LaMnO3钙钛矿型催化材料,考察了不同制备方法对催化材料结构和性能的影响.用X射线衍射仪(XRD)、比表面测定仪(BET)和扫描电子显微镜(SEM)等分析手段对催化剂的微观结构进行了表征.用催化剂评价系统考察了催化剂对CO的催化氧化活性.     

La_(0.9)Rb_(0.1)Co_(1-x)Fe_xO_(3-δ)钙钛矿催化剂上NO_x辅助碳烟燃烧性能的研究

通过柠檬酸溶胶凝胶法制备了La_(0.9)Rb_(0.1)Co_(1-x)Fe_xO_(3-δ)(x=0.1～0.8)系列钙钛矿催化剂。通过X射线衍射(XRD)、氢气程序升温还原(H_2-TPR)、NO_x程序升温脱附(NO_x-TPD)及X射线光电子能谱(XPS)考察了Fe含量变化对催化剂结构、NO_x辅助碳烟燃烧反应活性、催化剂氧化还原活性、催化剂表面Fe和Co的化学状态以及NO_x储存能力的影响。结果表明:所制备的催化剂均保持钙钛矿结构,Co与Fe的共掺杂改变了B位金属的化学状态,催化剂表面存在Co~(2+)和更高价态的Fe物种。相比纯LaCoO_3和LaFeO_3,La_(0.9)Rb_(0.1)Co_(1-x)Fe_xO_(3-δ)(x=0.1～0.8)催化剂碳烟燃烧的特征温度T_(50)分别下降约30和70℃,碳烟燃烧的速度也随之加快。同时,在NO_x辅助碳烟燃烧过程中,NO氧化所生成的NO_2可与碳烟反应生成N_2,其中La_(0.9)Rb_(0.1)Co_(0.6)Fe_(0.4)O_(3-δ)催化剂具有最高的NO_x消除能力,在381℃时达到36.4%。     

金属有机框架衍生Co3O4在碳烟催化燃烧中应用

以金属有机框架材料(ZIF-67)为前驱体,通过热解制备了具有规则形貌的四氧化三钴(Co3O4)催化剂,并以紧密接触状态下的碳烟催化燃烧为模型,测试了催化剂制备条件,如结晶时间和热解温度对碳烟催化燃烧性能的影响.通过X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)和低温N2吸脱附实验发现400 ℃热解制备的Co...     

反应气氛对负载Pd催化剂上CO氧化和C3H8燃烧反应的影响

采用浸渍法制备负载Pd催化剂,并考察载体(氧化铝、铈锆复合氧化物和铈锆铝复合氧化物)以及反应气氛对其催化CO氧化和C3H8燃烧反应性能的影响.通过X射线晶体衍射(XRD)、氢气程序升温还原(H2-TPR)、NO程序升温脱附(NO-TPD)以及原位红外(in-situ DRIFTS)等手段对催化剂进行表征.研究发现PdO...     

负载型纳米金催化剂的合成、表征及性能研究

以SiO2和纳米Au颗粒为原料,采用自组装方法合成了负载型金催化剂。应用傅立叶变换红外光谱(FT-IR)、X射线能谱(EDS)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)及原子吸收光谱(AAS)等对样品进行了表征。将该催化剂用于空气氧化环己烷反应的实验结果显示,其不仅具有较高的催化活性和稳定性,而且经简单处理即可重复使用多次。     

有序介孔CeO_2基催化剂用于富H_2中CO优先氧化的研究

以介孔硅材料KIT-6为模板剂,采用纳米刻蚀法合成系列有序介孔CeO_2、CuCe、CoCuCe、MnCuCe和Co MnCuCe催化剂,考察了掺杂元素种类对有序介孔CeO_2基催化剂CO优先氧化性能的影响,并采用小角X射线衍射(SAXD)、广角X射线衍射(XRD)、扫描电子显微镜(SEM)、N2吸附-脱附、透射电子显微镜(TEM)及H2程序升温还原(H2-TPR)等手段对催化剂的结构及性能进行了表征。研究发现,采用纳米刻蚀法可以合成介孔结构规整的CeO_2基催化剂,掺杂CuO、Co3O4、MnO_2后,催化剂的CO优先氧化性能明显提高;具有较好还原能力或氧移动能力的催化剂有助于其性能的提高;催化剂的孔径及孔道结构的规整性是影响其性能的关键因素。     

钙铝石涂层对整体铜锰铈催化剂高温催化性能的影响

采用固相反应法制备了12SrO·7Al2O3钙铝石材料,采取浆液浸渍法制备了12SrO·7A12O3作为涂层的堇青石蜂窝陶瓷型Cu - Mn - Ce -O整体催化剂,以甲基丙烯酸甲酯的催化燃烧作为探针反应考察了该整体催化剂的性能,并对其进行X射线衍射(XRD)、电子扫描电镜(SEM)、能谱(EDS)表征和比表面积(BET)测试.结果表明,以12SrO·7A2O3作为涂层的整体催化剂与无涂层的Cu - Mn - Ce -O整体催化剂相比,其耐高温性能有了明显提高,SEM和EDS表明有涂层的整体催化剂活性组分较之无涂层整体催化剂更为稳定、在表面原子总数中所占比重更高.12SrO·7Al2O3涂层材料的存在不仅保持其活性组分结构,也使得其更多的保持比表面.整体催化剂高温焙烧后比表面积得以保持,成为降低催化剂高温失活程度的原因之一.     

水含量对醇盐水解制备LaMnAl11O19-δ催化剂结构及其甲烷燃烧性能的影响

采用溶胶凝胶法中的金属醇盐水解技术制备LaMnAl11O19-δ六铝酸盐催化剂,通过X射线衍射、差热-热重、扫描电镜和比表面积分析等实验技术及甲烷燃烧,对催化剂的结构和性质进行了考察.主要考察了金属醇盐水解时加入不同含量的水对催化剂结构以及对甲烷催化燃烧活性的影响.结果表明,催化剂在1200C焙烧后可以形成完整的六铝酸盐晶型,同时具有较高的催化性能和高温稳定性.水含量对催化剂的性能有较大的影响,水含量较大时催化剂的比表面积和活性明显下降.当水和醇盐的摩尔比为1.5时,所制备的LaMnAl11O19-δ具有较大的比表面积和催化活性.     

金属修饰对Cu-SAPO-34催化剂NH_3-SCR反应性能的影响

采用浸渍法引入稀土元素Ce和过渡金属Mn,考察了其对Cu-SAPO-34分子筛催化剂用于氨选择性催化还原氮氧化物(NH_3-SCR)反应性能的影响;并运用多种手段,如X射线衍射(XRD)、 N_2吸-脱附、 X射线光电子能谱(XPS)、氢气程序升温还原(H_2-TPR)、氨气程序升温脱附(NH_3-TPD)等对催化剂的物理和化学性质进行表征。稀土元素Ce的引入有效提高了Cu-SAPO-34分子筛催化剂的在高温区(375～570℃)对氮氧化合物的脱除能力;与之相反,过渡金属Mn的引入则抑制了催化剂的在高温区的反应性能。催化剂表征结果表明Ce的引入有效提高了催化剂表面的酸量、表面Cu~+/Cu~(2+)比例,以及对NO的吸附和氧化能力; Mn的引入增加了Cu-SAPO-34分子筛催化剂表面非活性中心CuO物种浓度的同时也降低了催化剂表面总酸的浓度。Mn促进高温下NH_3氧化性能的提高,从而降低了参与NH_3-SCR反应中NH_3的浓度,导致高温NH_3-SCR反应性能降低。     

MXene/磷化钴复合材料电催化制氢性能研究

针对传统电催化剂材料导电性差、活性位点易堵塞等问题,采用高导电性和优异亲水性的二维碳化钛钒(MXene)作为催化剂负载基底,在此基础上与具有高比表面积的金属有机框架衍生的磷化钴结合制备电解水制氢阴极材料。利用X射线衍射仪(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、密度泛函理论计算(DFT)和电化学测试等手段,研究了复合电极材料的晶体结构、表面形貌特征、活性位点电子结构和电化学特性。结果表明,有机配体中的碳氮元素能有效调节电极材料中活性位点的电子结构,从而改善吸脱附动力学条件;二维MXene进一步降低了电极材料电荷转移电阻,所制备的催化剂在10 mA/cm²电流密度时仅需要114 mV的过电位,且长时间工作后依然保持稳定。研究结果为制备高性能非贵金属析氢催化剂提供了参考和思路。     

Activity and deactivation behavior of Au/LaMnO3 catalysts for CO oxidation

Perovskite oxide LaMnO3 was prepared by sol-gel method and the nanosize Au/LaMnO3 catalyst was prepared by deposition-precipitation(DP) method in the paper.Characterization of the catalyst sample was made by X-ray diffractometer(XRD),atom absorption spectra(AAS) and X-ray photoelectron spectroscopy(XPS) instrumental methods.The activity,long-term stability and the reasons for deactivation of the gold catalyst in CO oxidation were investigated.The experiment results demonstrated that the Au/LaMnO3 catalyst e...     

硅钨杂多酸制备、表征及催化油酸酯化反应合成生物柴油活性研究

采用硝酸酸化-乙醚萃取法制备了一种硅钨杂多酸催化剂,应用扫描电镜(SEM)、红外光谱(FTIR)、X射线粉末衍射(XRD)、程序升温脱附(NH₃-TPD)、热重分析(TG)等手段对催化剂进行了表征,并以甲醇和油酸为反应物,研究了所制备的硅钨杂多酸在催化酯化反应时的活性,考察了催化剂用量、反应时间、反应温度等反应参数对酯化反应产品收率的影响.结果表明:当甲醇与油酸的质量比为3:2,催化剂用量为反应物总质量的1.4 %,反应时间为3.5 h,反应温度为65 ℃时,油酸甲酯的收率最高,为96.45 wt%.      

Catalytic performance of a Pt-Rh/CeO_2-ZrO_2-La_2O_3-Nd_2O_3 three-way compress nature gas catalyst prepared by a modified double-solvent method

A Pt-Rh three-way catalyst(M-DS) supported on CeO_2-ZrO_2-La_2O_3-Nd_2O_3 and its analogous supported catalyst(DS) were developed via a modified double-solvent method and conventional double-solvent method, respectively. The as-prepared catalysts were characterized by N_2 adsorption-desorption, X-ray diffraction(XRD), CO-chemisorption, X-ray photoelectron spectroscopy(XPS) and hydrogen temperature-programmed reduction(H_2-TPR). The preformed Pt nanoparticles generated using ethanol as a reducing agent on M-DS presented enhanced Pt dispersion regardless of aging treatment as confirmed by XRD and CO-chemisorption measurements. The textural properties and reduction ability of M-DS were maintained to a large extent after aging treatment. This result was consistent with those of the N_2 adsorption-desorption and H_2-TPR, respectively. Meanwhile, the XPS analysis demonstrated that higher Pt~0 species and larger Ce~(3+) concentration could be obtained for M-DS. In the conversion of a simulated compressed natural gas(CNG) vehicle exhaust, both fresh and aged M-DS showed a significant enhancement in the activity and N_2-selectivity. Particularly, the complete conversion temperature(T_(90)) of CH_4 over the aged M-DS catalyst was 65 oC lower than that over the aged catalyst by conventional double-solvent method.     

Modification of Cu/ZSM-5 catalyst with CeO_2 for selective catalytic reduction of NO_x with ammonia

Cu/ZSM-5 and CeO_2-modified Cu/ZSM-5 catalysts were prepared by a wetness impregnation method. The addition of CeO_2 was found to enhance the NO_x selective catalytic reduction(SCR) activity of the catalyst at low temperatures, but the high-temperature activity was weakened. The catalysts were characterized by X-ray diffraction(XRD), nitrogen physisorption, inductively coupled plasma optical emission spectrometry(ICP-OES), X-ray photoelectron spectroscopy(XPS), electron paramagnetic resonance(EPR), H_2 temperature-programmed reduction(TPR) and NH_3 temperature-programmed desorption(TPD). The results showed that more CuO clusters instead of isolated Cu~(2+) species were obtained on the modified catalyst. These active CuO clusters, as well as the Cu-Ce synergistic effect, improved the redox property of the catalyst and low-temperatures SCR activity via promoting the oxidation of NO to NO_2 and fast SCR reaction. The loss in high-temperatures activity was attributed to the enhanced competitive oxidation of NH_3 by O_2 and decreased surface acidity of the catalyst.     

便携式X射线荧光光谱测定车用三元催化剂中铂钯铑

采用粉末样品杯法制样, 建立了用便携式X射线荧光光谱对车用三元催化剂中贵金属铑(Rh)、钯(Pd)、铂(Pt)含量进行实时、在线定量分析的方法。比较了6种实验室常用样品薄膜对测试结果的影响, 通过透光率试验发现各样品薄膜对能量高于5.4 keV(²⁴Cr以后元素)的X射线的透光率为100％, 样品膜越薄其分析灵敏度就越好, 实验时选用厚度为4.0 μm的Ploy-4样品膜;研究了元素谱线之间的干扰重叠校正, 采用背景扫描与α经验系数法相结合的方法进行基体校正, 避免了因基体的变化对测定准确度的影响;讨论了X射线荧光光谱法中检出限的计算方法, 采用Pt、Pd、Rh含量较小样品多次测试结果的标准偏差来计算检出限, 铑、钯、铂的检出限分别为14.04 μg/g、18.17 μg/g、8.40 μg/g。对一种车用三元催化剂粉末样品进行精密度考察, 相对标准偏差(RSD)控制在4.0%之内;对8个车用三元催化剂实际样品进行分析, 经与电感耦合等离子体原子发射光谱法(ICP-AES)进行比对, 测定结果基本一致, 相对误差在10.0%之内, 方法的准确度能够满足车用三元催化剂回收要求。     

Lewis酸型固体酸催化剂Ce-Ag-PW的制备、表征及催化酯化反应合成生物柴油性能研究

通过超声浸渍法，经Ce3+和Ag+协同改性磷钨杂多酸（HPW）制备了一种以Lewis酸性活性位为主的固体酸催化剂Ce-Ag-PW。采用X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）、扫描电镜（SEM）、透射电镜（TEM）、热重（TG）、NH₃程序升温脱附（NH₃-TPD）、吡啶吸附红外光谱（Py-IR）和X射线光电子能谱（XPS）等表征手段对其物理化学性能进行了表征分析。并以Ce-Ag-PW为经甲醇和油酸酯化反应来合成生物柴油的催化剂，对其的催化活性和稳定性进行了研究。结果表明，Ce-Ag-PW具有高催化活性和稳定性，以其为催化剂，当甲醇与油酸的物质的量比为14: 1，催化剂用量为反应物总质量的2%，反应温度为65 ℃，反应6 h后，油酸的转化率即高达91%。固体酸催化剂在经过4次循环使用后，油酸的转化率仍可达到80.5%。Ce-Ag-PW的高催化活性和稳定性可归因于Ag+可置换HPW中的质子，以及Ce3+的强吸电子作用，使其由Br?nsted酸型催化剂转化为以Lewis酸型为主的催化剂。由于Br?nsted酸位易与酯化反应过程中生成的水发生水合反应而失活，因而Lewis酸位的形成有助于减少催化剂的失活现象发生。因此，当通过油酸与甲醇酯化反应合成生物柴油时，Ce-Ag-PW是一种具有高催化活性和稳定性的以Lewis酸性活性位为主的固体酸催化剂。      

Role of cerium as a promoter and process optimization studies for dehydration of glycerol to acetol over copper chromite catalyst

Cerium-promoted silica supported copper chromite catalyst was synthesized from acid hydrolysis of sodium silicate by sol-gel method.The catalyst was characterized by Brunauer-Emmett-Teller(BET)method,field-emission scanning electron microscopy(FESEM),X-ray diffraction(XRD),H₂-temperature programmed reduction(H₂-TPR),NH3-temperature programmed desorption(NH3-TPD)and pyridine adsorbed Fourier transform infrared spectroscopy(Py-FTIR).Among cerium doped catalysts,5 wt%of Ce promoted copper chromite supported by 40 wt%of silica(SiCuCr40-Ce5)shows the largest BET surface area.XRD analysis of the reduced form of the catalyst shows both CeO₂/Ce₂O₃ redox system and CuO/Cu₂O/Cu redox system.Py-FTIR shows the maximum number of Lewis acid sites for SiCuCr40-Ce5 than others.The highest acetol selectivity with analytical reagent(AR)grade glycerol conversion is observed for SiCuCr40-Ce5 at 200℃for 3 h in a batch reactor at atmospheric pressure.Cerium promotion lowers the reaction te mperature with enhanced glycerol conve rsion and increased acetol selectivity.Though the above catalyst shows higher conversion for laboratory reagent(LR)grade glycerol but it reduces acetol selectivity.The addition of glucose into the LR grade glycerol further reduces glycerol conversion and decreases the acetol selectivity to zero.This may be due to the presence of iron as impurity in LR grade glycerol.XRD analysis of spent catalyst shows the absence of redox catalytic system and the pore volume reduces identified by BET analysis.Raman analysis of the spent catalyst shows graphite-like carbon deposition in the spent catalvst.     

SO2 poisoning and regeneration of Mn-Ce/TiO2 catalyst for low temperature NOx reduction with NH_3

SO2 poisoning and regeneration of Mn-Ce/TiO2 catalyst prepared by a novel co-precipitation method for low temperature selective catalytic reduction (SCR) of NOx with ammonia were investigated in this study. When 700 ppm SO2 was fed in, the Mn-Ce/TiO2 catalyst had good resistance to SO2, but the deactivation of Mn-Ce/TiO2 poisoned by SO2 still occurred. The NO conversion of Mn-Ce/TiO2 (the molar ra-tio of Ce to Ti is 0.075) catalyst decreased from 92.5% to 34.6% in 13 h. Characterizations of fresh and SO2-poisoned Mn-Ce/TiO2 catalysts were carried out by Brunauer-Emmett-Teller method (BET), ion chromatography (IC), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The characterized results indicated that the deposition of sulfates and nitrates on the surface made the catalyst deactivated. Water washing, thermal regeneration and reductive regeneration were used to regenerate the deactivated Mn-Ce/TiO2. And water washing showed best performance on the regeneration of poisoned catalysts, especially with ultrasonic vibration. The Mn-Ce/TiO2 catalyst showed high stability under a series of deactivation-regeneration experiments for ten cycles.     

A CeFeO_x catalyst for catalytic oxidation of NO to NO_2

Catalytic oxidation of NO into NO_2 is a promising method for NO_x emission control.The aim of this study was to develop an economic and environmental-friendly catalyst for NO catalytic oxidation.Herein a CeFeO_x complex oxide catalyst for catalytic oxidation of NO was prepared by coprecipitation method.After that the catalytic performance of this catalyst was measured on a fixed-bed reactor.It was found that the intrinsic activity of CeFeO_x was higher than that of CeO_x and FeO_x.The characterization techniques of Brumauer-Emmett-Teller(BET),X-ray diffraction(XRD),temperature programmed reduction with H_2(H_2-TPR),temperature programmed desorption with NO+O_2(NO+O_2-TPD) and X-ray photoelectron spectroscopy(XPS) were performed to investigate the surface area,crystal structure,redox property and NO_x adsorption behavior of the catalyst samples.From the characterization results,it was concluded that the low crystallinity of CeFeO_x promoted the dispersion of active species,as a result,enhancing the redox ability and NO adsorption capacity of CeFeO_x catalyst,which is favorable to NO catalytic oxidation.Furthermore,the presence of much chemisorbed oxygen on CeFeO_x catalyst also made a great contribution to its good catalytic performance.     

Influence of preparation method on performance of a metal supported perovskite catalyst for combustion of methane

A different method was employed for the preparation of a metal supported perovskite catalyst for the catalytic combustion of methane.The prepared metallic catalysts were characterized by means of X-ray diffractometer(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),and also by ultrasonic and thermal shock tests and catalytic activity.It was found that the process factors during the preparation,e.g.the preparation of the catalyst precursor and the coating slurry,the calcination te...