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1.
本研究采用柠檬酸溶胶-凝胶法制备了一系列不同载体负载的LaCoO3/MO2催化剂(M=Zr、Ti、Ce),研究考察其催化氧化甲苯与NO的性能及关键机制。结果发现,以CeO2为载体的LaCoO3/CeO2催化剂表现出最佳的催化氧化性能,其甲苯的t90为245℃,同时在300℃时NO转化率可达68%。通过BET、XRD、H2-TPR和XPS对各负载型钙钛矿催化剂的理化性质进行表征。结果表明,负载型钙钛矿催化剂拥有更大的比表面积,从而有效提供了更多的吸附位点,同时负载型钙钛矿催化剂具有更活跃的晶格氧和更好的氧化还原性能。其中,LaCoO3与载体CeO2在接触界面上观察到Co离子与Ce离子之间存在着相互作用,形成晶格缺陷,这有利于氧空位的形成。利用原位漫反射红外光谱进一步探寻了反应机理,LaCoO3/CeO2催化剂上NO氧化符合Langmuir-Hinsh...  相似文献   

2.
铁系复合氧化物催化性质的研究   总被引:1,自引:0,他引:1  
合成出一系列La_(1-s)A′_sFeO_3(A′=Ca、Sr、Ba;0≤2≤1)复合氧化物催化剂,并研究了Ca、Sr、Ba部分取代La后催化剂对CO氧化活性的影响。以XRD测定其晶体结构。结果表明,除含Ca>0.5和Ba=1.0外均生成钙钛矿型结构。用XPS和TPD法研究了吸附性能。指认吸附氧是CO氧化的活性物种,并初步解释了活性规律的成因。  相似文献   

3.
以钙钛矿结构锰酸镧为模型化合物,通过制造A位缺陷调控La_xMnO_(3-δ)中Mn的价态和氧缺陷,并通过电催化析氧(OER)及热催化CO氧化等反应对缺陷与催化性质的关系进行评价.所有样品均采用溶胶-凝胶法合成,并通过ICP-OES分析确定A位缺陷,再经过碘量法滴定确定Mn的价态,根据电中性原则,计算出氧缺陷(δ)值,调控所得样品的化学式分别为La_(0.85)MnO_(2.85),La_(0.80)MnO_(2.81)和La_(0.75)MnO_(2.74).分别利用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)和扫描电子显微镜(SEM)等对样品的结构、Mn结合能和形貌进行了表征,并利用物理吸附仪测得样品的比表面积.材料的电催化析氧和CO催化氧化性能测试结果表明,氧缺陷对2种催化反应均表现了很大的影响,氧缺陷的浓度与OER催化活性呈线性关系,而对于CO催化,则需要合适的氧缺陷浓度.  相似文献   

4.
采用水热合成法制备了α-MnO2、β-MnO2、γ-MnO2和δ-MnO2催化剂, 运用N2吸脱附实验、X射线衍射(XRD)、X射线光电子能谱(XPS)和H2程序升温还原(H2-TPR)等方法对催化剂进行了表征, 并将催化剂用于催化完全氧化乙醇反应中, 考察了不同晶型MnO2催化剂催化氧化乙醇活性的差异, 探讨了催化剂晶型结构与催化氧化活性的关联. 结果表明, 不同晶型的MnO2催化剂催化氧化乙醇活性差异显著, 活性顺序为α-MnO2>δ-MnO2>γ-MnO2>β-MnO2. 系列表征结果显示, 晶体结晶度和比表面积不是影响不同晶型MnO2催化剂活性的主要原因, α-MnO2催化剂具有的较高晶格氧浓度和较高的可还原性是其具有良好催化氧化乙醇活性的关键因素.  相似文献   

5.
采用非晶态配合物的方法合成了La1-xCexCoO3(x=0、0.05、0.1、0.2、0.3)催化剂, 并采用X射线衍射(XRD)、透射电镜(TEM)和比表面测定仪(BET)等手段对催化剂的微观结构进行了研究. 揭示了Ce掺杂对催化剂的钙钛矿结构, CO催化氧化以及催化氧化发光性能的影响规律. 结果表明, 在Ce4+掺杂部分取代La3+后, 催化剂形成了镧不足的La1-xCeyφx-yCoO3(φ是A位离子空位)钙钛矿相以及CeO2和Co3O4物相. 与LaCoO3催化剂相比, x=0.1催化剂的CO催化氧化活性最高(T100%=290 ℃). La1-xCexCoO3催化剂对CO催化氧化发光的响应与其催化活性密切相关.  相似文献   

6.
甲烷化学链蒸汽重整(Chemical-looping steam methane reforming,CL-SMR)是基于化学链燃烧的概念而提出的一种新颖的技术。在重整反应器中,甲烷与载氧体中的晶格氧发生部分氧化反应生成合成气(H2/CO物质的量比为2.0),还原后的载氧体进入到水蒸气反应器中,与水蒸气反应恢复晶格氧的同时生成H2。以钙钛矿型氧化物LaFeO3为载氧体用于甲烷化学链蒸气重整过程,同时通过碱金属CaO和MgO对LaFeO3进行负载,以增大载氧体的比表面积、热稳定性和抗积炭能力。通过X射线衍射(XRD)、H2程序升温还原(H2-TPR)、BET比表面积分析(BET)和X光电子能谱(XPS)对载氧体进行表征。结果表明,三种载氧体均表现出较高的反应活性和合成气选择性,循环后仍能保持钙钛矿的结构。从反应性能、选择性和抗积炭能力等方面综合考虑,LaFeO3-CaO的效果最好,五次循环后具有很好的再生性。  相似文献   

7.
采用分步沉积法制备不同Sr/Ti 摩尔比例的Sr/TiO2催化剂, 以X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、傅里叶变换红外(FT-IR) 光谱、紫外-可见漫反射光谱(UV-Vis RDS)等手段对样品进行了表征, 以可见光催化降解亚甲基蓝为模型反应考察样品光催化活性. 结果表明, 催化剂的活性和结构随Sr/Ti 摩尔比(n(Sr)/n(Ti))的变化而变化, 当n(Sr)/n(Ti)≤3/2 时, 催化剂呈由TiO2和SrTiO3组成的球状结构; 而当n(Sr)/n(Ti)在3/2 与4/1 之间时, 催化剂呈片状结构, 且随着n(Sr)/n(Ti)增大, 催化剂组成由SrTiO3 和Sr24 变为Sr24和Sr(OH)2·H2O; 当n(Sr)/n(Ti)=9/1 时, 催化剂呈以Sr(OH)2·H2O为主的针状结构. 其中, n(Sr)/n(Ti)=4/1的样品表现出最高的光催化活性, 一级反应速率为SrTiO3钙钛矿催化剂的5.0倍, 商用P25的86.7倍.  相似文献   

8.
杨祥龙  汪圣尧  陈婷  杨楠  江开  汪佩  李淑  丁星  陈浩 《催化学报》2021,42(6):1013-1023,中插37-中插45
开发具有高量子效率的半导体光催化材料是极具前景的解决能源短缺和环境污染问题的策略.在已报道的诸多光催化材料中,超薄二维(2D)材料表现突出,凭借其高效的载流子分离传输性能备受研究者的青睐.然而,苛刻的合成条件、缺乏表面活性位点等问题制约了其应用.因此,温和可控地合成具有大量活性位点的原子层厚2D材料具有重要的意义.作为典型的Aurivillius氧化物,Bi2WO6具有独特的层状晶体结构和合适的能带位置;另一方面,其表面Bi?O键的能量较低,氧原子在缺氧条件下经热处理容易逸出,进而产生氧空位.已知氧空位引入是调节半导体能带组成和电子结构的有效手段,不仅能改善其光电性能,而且能提供反应活性位点;因此,Bi2WO6是设计合成具有大量活性位点(氧空位)的原子层厚2D材料的理想平台.基于此,本文拟开发温和可控的合成策略,制备表面相对干净的含氧空位原子层厚Bi2WO6材料,并将其用于大气污染物NO的氧化去除.本文首先通过理论计算预测了卤素离子在调控Bi2WO6晶体生长和表面氧空位引入方面的作用,发现卤素离子尤其是Cl-不仅能减小原子层厚Bi2WO6的表面能(γ),使其稳定存在;而且能降低Bi2WO6(001)晶面上氧空位生成能(ΔE).受此启发,我们设计了Cl-辅助的溶剂热法,成功制备了含表面氧空位的原子层厚Bi2WO6材料;并利用高分辨透射电镜技术、X射线光电子能谱等考察了Cl-的存在形式,及其调控Bi2WO6晶体生长和表面氧空位形成的机理:Cl-因为静电作用吸附在[Bi2O2]2+层上,一方面抑制Bi2WO6原子层堆积;另一方面,Cl-与[Bi2O2]2+层上Bi原子成键,削弱相邻的Bi?O键,利于O原子逸出形成表面氧空位.在此基础上,将设计合成的含氧空位的原子层厚Bi2WO6材料用于空气污染物NO的光催化去除.结果表明,Cl-辅助合成的BWO-Cl可见光催化去除NO的效率高达64%;且其氧化NO至NO3?的选择性为98%.为了进一步分析BWO-Cl在NO氧化反应中的高活性和高选择性的原因,进行了理论计算与光电化学测试、活性物种分析、原位漫反射红外光谱(in-situ DRIFTs)等表征.结果表明,反应的高活性源于材料原子层厚2D结构及其表面丰富的氧空位对光电性质的改善;高选择性则归因于氧空位增强了Bi2WO6吸附活化O2为?O2?的能力,促使NO沿着热力学有利的路径氧化至NO3?.该工作初步展示了卤素离子在调控Bi2WO6晶体生长及表面氧空位引入方面的重要作用,对设计合成高活性的原子层厚2D材料具有指导意义;与此同时,材料在NO氧化方面展现出的高活性与高选择性也为构建高效的NO去除体系提供了新思路.  相似文献   

9.
用柠檬酸络合法制备了La1-xSrxCo1-yZryO3氧化催化剂,研究了其钙钛矿结构的生成温度,在连续流动的反应体系上测定了催化剂的CO氧化活性,用CO还原测定了晶格氧活动度, IR光谱研究了CO的吸附物种.结果表明, La1-xSrxCo1-yZryO3具有很高的CO催化氧化活性,活性中心是表面吸附的氧物种(O2-或 O-)和Con+离子.  相似文献   

10.
研究了稀土钙钛矿型氧化物La1-xA′xCo1-yBiyO3-δ(A′z=Ba0.2,Sr0.4;y=0,0.2)催化剂上一氧化碳低温氧化反应.XRD结果表明这4个催化剂均为单相立方钙钛矿结构.18O2和CO脉冲实验结果表明Sr掺杂催化剂的晶格氧活动度和反应性比Ba掺杂的强.TPR结果表明Bi的掺杂降低了催化剂的还原温度,提高了催化活性,且Sr取代部分La比Ba取代部分La更有利于增加催化活性.我们认为,Sr.(或Ba)和Bi的掺杂引起的催化活性的提高与氧空位浓度的增加,Co和Bi离子氧化-还原循环的改善以及晶格氧活动度的增加密切相关.  相似文献   

11.
This work aims to study the effect of redox property and surface morphology of perovskite oxides on the catalytic activity of CO oxidation and CO+NO reduction, with the redox property being tuned by doping Fe at the Co site of La0.8Sr0.2Co1-xFexO3 and the surface morphology being modified by supporting La0.8Sr0.2CoO3 on various mesoporous silicas(i.e., SBA-16, SBA-15, MCF). Characteristic results show that the Fe doping improves the match of redox potentials, and SBA-16 is the best support of La0.8Sr0.2CoO3 when referring to the oxidation ability(e.g., the Co3+/Co2+ molar ratio). A mechanism for oxygen desorption from perovskite oxides is proposed based on O2-TPD experiments, showing the evolution process of oxygen released from oxygen vacancy and lattice framework. Catalytic tests indicate that La0.8Sr0.2CoO3 is the best for CO oxidation, and La0.8Sr0.2FeO3 is the best for CO+NO reduction. The mechanism of CO+NO reduction changes as the reaction temperature increases, with XNO/XCO value decreases from 2.4 at 250 ℃ to 1.0 at 400 ℃. As for the surface morphology, La0.8Sr0.2CoO3 supported on SBA-16 possesses the highest surface Co3+/Co2+ molar ratio as compared to the other two, and shows the best activity for CO oxidation.  相似文献   

12.
Mesoporous SBA-15 with mesopore diameter up to 10.1 nm was prepared by a hydrothermal method, and was further functionalized to obtain different surface properties. Thus-prepared SBA-15 was employed as a template to synthesize rhombohedrally crystallized mesoporous La0.8Sr0.2CoO3 perovskite via a nanocasting method. The surface properties of the SBA-15 were adjusted by treatment with concentrated hydrochloric acid, trimethylchlorosilane (TMCS), and 3-aminopropyltriethoxysilane (APTES). A series of characterization techniques verified that all the synthesized templates possessed ordered two-dimensional hexagonal mesoporous structure, and the surface was successfully modified with methyl and amino groups. The mesoporous perovskite structure was formed in the samples and the surface properties of SBA-15 significantly influenced the structure and properties of La0.8Sr0.2CoO3 perovskite oxides. Wide-angle X-ray diffraction patterns suggested that the modified silica templates were conducive to the formation of pure perovskite frameworks with good crystallinity. The catalysts also possessed mesoporous structure, as confirmed by small-angle XRD patterns, high-resolution transmission electron microscopy images, and nitrogen adsorption analysis. Moreover, the La0.8Sr0.2CoO3 materials synthesized using surface-functionalized templates exhibited relatively higher catalytic activity and stability in CO oxidation. Complete CO conversion could be achieved at 140℃ using the thus-prepared La0.8Sr0.2CoO3 materials, and no significant loss in catalytic activity was observed after 100 h of on-stream reaction experiments. X-ray photoelectron spectroscopy, H2 temperature-programmed reduction, and O2 temperature-programmed desorption experiments revealed that the existence of Co4+, Sr enrichment in the perovskite structure, and high content of adsorbed oxygen species play a critical role in the enhanced catalytic activity of the catalysts. We also proposed the possible reasons for the effect of surface properties of the silica templates on the structure and properties of the La0.8Sr0.2CoO3 nanomaterials.  相似文献   

13.
The oxygen separation membrane having perovskite structure for the partial oxidation of methane to synthesis gas was prepared. La0.7Sr0.3Ga0.6Fe0.4O3−δ (LSGF) perovskite membrane coated with La0.6Sr0.4CoO3−δ (LSC) (M1), and the one side of M1 membrane coated with NiO (M2) was prepared to examine the partial oxidation of methane. The single oxygen permeations of the LSC + LSGF (M1) membrane and NiO coated membrane (M2) were measured. The oxygen permeation flux in M1 membrane was higher than that of M1 membrane at 850 °C.

The partial oxidation experiment of methane using the prepared membranes was examined at 850 °C. The value of CH4 conversion and CO selectivity of M2 membrane was higher than that of M1 membrane.

NiO/NiAl2O4 catalyst was used to improve the methane conversion, and the partial oxidation experiment of methane with M1 membrane was examined at 850 °C. The CH4 conversion was 88%, and CO selectivity was 100%.  相似文献   


14.
采用乙二醇溶胶-凝胶法制备了计量比LaMnO_3和非计量比LaMn_(1.2)O_3钙钛矿,并利用稀硝酸处理LaMnO_3制备得到LaMnO_3-AE,然后采用沉积沉淀法制备钙钛矿负载Au催化剂,以考察载体的结构和性质对Au的热稳定性以及催化剂活性的影响。通过X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱(XPS)和H_2程序升温还原(H_2-TPR)等表征,发现LaMnO_3和LaMn_(1.2)O_3钙钛矿载体虽然有利于Au的分散,但是Au的热稳定性相对较差。相反,经稀硝酸刻蚀的LaMnO_3钙钛矿(LaMnO_3-AE)不利于Au的分散,但是有利于提高Au的热稳定性。在CO氧化反应中,当催化剂在低于500°C焙烧时,LaMn_(1.2)O_3钙钛矿负载Au催化剂的活性要显著高于LaMnO_3和LaMnO_3-AE负载Au催化剂的活性,而当催化剂焙烧温度升高至700°C以上时,LaMnO_3-AE负载Au催化剂却要显著优于LaMnO_3和LaMn_(1.2)O_3钙钛矿负载Au催化剂的活性。  相似文献   

15.
ZrO2-supported La, Co oxide catalysts with different La, Co loading (2, 6, 8, 12 and 16 wt.% as LaCoO3) were prepared by impregnation of tetragonal ZrO2 with equimolar amounts of La and Co citrate precursors and calcination at 1073 K. The catalysts were characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and BET specific surface area determination. Catalytic CO oxidation was performed at 298–800 K. XRD revealed the presence of tetragonal zirconia with traces of the monoclinic phase. LaCoO3 perovskite was also detected for loading higher than 6%. XAS experiments suggested that at high loading LaCoO3 and Co3O4 were formed, while at low loading, La, Co oxide species interacting with support, and hard to be structurally defined, prevailed. The catalysis study evidenced that the catalytic activity was due to segregated and highly dispersed cobalt oxide species.  相似文献   

16.
The NdCoO3 perovskite has been investigated using a combination of atomistic simulation and experimental techniques to examine its possible use as an oxidation catalyst and/or sensor material. The sensing properties of NdCoO3 and Nd0.8Sr0.2CoO3 towards CO have been investigated by employing thin films deposited by means of radio-frequency (RF) magnetron sputtering onto polycrystalline Al2O3. The response of the films was monitored by performing four-probe DC-conductivity measurements. The conductivity variation induced by switching between a CO-free atmosphere (air) and a CO-rich one with the same composition of residual gas was recorded and analysed as a function of temperature; results are compared for the two samples. Simulation studies focussed on the dopant, transport and redox properties of the pure material; the results indicate that Sr and Ca on the Nd site are the most soluble dopants and that when divalent dopants are incorporated in the structure, charge compensation occurs via oxygen ion vacancies. The low activation energy for oxygen vacancy migration suggests high oxide-ion mobility through the lattice. Particular attention is paid to the electronic processes because of their importance with respect to practical applications of the material.  相似文献   

17.
采用氧化还原法合成了层状锰氧化物(OL),并以OL为载体采用离子交换法制备了不同Cu负载量的Cu_x/OL催化剂。利用X射线衍射(XRD)、电子扫描电镜(SEM)、N_2吸附/脱附、H_2~-程序升温还原(H_2-TPR)、TG(热重)、X射线光电子能谱(XPS)、O_2-程序升温脱附(O_2-TPD)等技术对所制催化剂进行结构和织构表征,并对其催化氧化CO及乙酸乙酯活性进行了评价。结果表明,OL具有典型的层状锰氧化物结构,适量掺杂Cu对OL的结构和织构影响不大,但Cu的掺杂明显影响Cu_x/OL的还原性、氧移动性及催化剂表面Cu~(2+)/CuO、(Mn~(2+)+Mn~(3+))/Mn~(4+)和Oads/Olatt的比例。Cu_x/OL的催化性能与以上因素密切相关。在Cu_x/OL样品中,Cu_5/OL催化剂具有最佳的催化活性(CO催化氧化,T_(50)=70°C和T_(90)=100°C;乙酸乙酯催化氧化T50=160°C,T90=200°C)。同时,Cu_5/OL催化剂具有最佳的还原性能、氧移动性能和最多的Cu~(2+)、(Mn~(2+)+Mn~(3+))和表面吸附氧浓度。Cu_x/OL催化性能与铜锰之间相互作用、还原性和氧移动性能密切相关。  相似文献   

18.
利用钙钛矿型复合氧化物(PTO)可以将多种金属离子限域并均匀混合于钙钛矿晶格中的特点,提出了一种构筑氧化物修饰的纳米双金属催化剂团簇的新构想。以担载于大比表面积SiO_2上的钙钛矿型复合氧化物La_(1-y)Ce_yCo_(0.87)Pt_(0.13)O_3/SiO_2作为前驱体,将La、Ce、Co和Pt多种金属离子均匀混合并限域于PTO晶粒中,还原后得到Pt-Co/La-Ce-O/SiO_2催化剂;通过氮气吸附-脱附、XRD、H2-TPR和TEM等手段对Pt-Co/La-Ce-O/SiO_2催化剂进行了表征,考察了其对CO氧化的催化性能,研究了构效关系。结果发现,La-Ce-O-Pt-Co构成了纳米团簇,担载于SiO_2表面,形成了Pt-Co纳米双金属颗粒; Co修饰Pt提高了其催化活性,而添加Ce进一步改善了其催化性能。当Ce含量(y)为0.2时,催化剂La_(0.8)Ce_(0.2)Co_(0.87)Pt_(0.13)O_3/SiO_2的活性最佳,在120℃下即可实现CO完全转化,且在含体积分数15%H_2O及12.5%CO_2的气氛中仍具有较好的催化性能。稳定性测试表明,所制得的Pt-Co/La-Ce-O/SiO_2催化剂具有良好的稳定性和抗烧结性能。  相似文献   

19.
以介孔中空碳球(HC)为载体,通过简单的吸附法吸附Ni2+/Fe3+金属离子,获得了在碱性电解液中具有高效5-羟基甲基糠醛(HMF)电催化氧化性能的Nix Fe1-x/HC催化剂.通过X射线衍射(XRD)、场发射扫描电子显微镜(SEM)和X射线光电子能谱(XPS)等手段对Nix Fe1-x/HC的物相、形貌结构及电子结构进行了表征,并通过线性扫描伏安和计时电位等方法测试了Nix Fe1-x/HC的HMF电催化氧化性能.结果显示, Nix Fe1-x/HC材料催化HMF氧化的活性随Fe引入量的增加先升高后降低, Ni0.7Fe0.3/HC拥有最优的催化活性, HMF的转化率为100%,2,5-呋喃二甲酸(FDCA)的选择性为90.5%,法拉第效率为90.2%,经历10次循环后,催化活性仅略微降低,表现出优良的催化稳定性.  相似文献   

20.
The catalytic activities for NO oxidation achieved by different amounts of CeO2-modified Pt/SiO2-Al2O3 catalysts Pt/SiO2-Al2O3-wCeO2 (the mass fraction w being 0%, 5%, 10%, 15%, 30%), prepared using step-wise impregnation, were investigated in the presence and absence of CO and C3H6. The results showed that the NO oxidation activity could be efficiently improved by modification of CeO2, wherein the 15%-CeO2-modified catalyst exhibited the maximum NO conversion of 61% even in the presence of CO and C3H6, which were proved to inhibit NO2 formation in this study. A series of characterization methods were performed over the as-prepared samples to correlate their surface and structural characteristics with their enhanced NO oxidation activities. CO-chemisorption illustrated that appropriate CeO2-loading was effective for enhancing Pt dispersion, thus enhancing Pt surface-to-volume ratio, confirmed by transmission electron microscope (TEM) images. X-Ray Diffraction (XRD) further suggested that ceria addition could suppress the growth of the Pt crystal, resulting in higher surface Pt atomic ratio. Further, H2 temperature-programmed reduction (H2-TPR), together with TEM results, implied that the presence of ceria could enhance the interaction between metal and supports, thus facilitating reducibility of both active platinum and ceria. Hence, this study displays that ceria could act as a dispersion promoter and a reducibility booster, both of which are beneficial to NO oxidation activity. The improved NO oxidation activity is significant for the efficient purification of diesel integrated catalytic system.  相似文献   

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