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1.
CeO2和Pd在Ni/γ-Al2O3催化剂中的助剂作用   总被引:6,自引:0,他引:6  
采用脉冲微反技术研究了添加n型半导体氧化物CeO2及贵金属Pd对Ni/γ Al2O3催化剂上CH4积炭/CO2消炭反应性能的影响,并运用BET、TPR、CO2 TPSR及氢吸附等技术对催化剂进行了表征.结果表明, n型半导体氧化物CeO2的添加可以降低Ni/γ Al2O3催化剂上CH4裂解积炭活性,提高CO2消炭活性,添加少量贵金属Pd可以进一步改变载体Al2O3、助剂CeO2和活性组分Ni之间的相互作用,从而改善Ni/γ Al2O3催化剂的抗积炭性能.通过Ni Ce Pd/γ Al2O3催化剂上CH4积炭/CO2消炭模型对上述作用机制作出了新的解释.  相似文献   

2.
Ni/CeO2-Al2O3催化剂上CH4-CO2转化积炭性能的研究   总被引:12,自引:0,他引:12  
采用脉冲微量反应技术研究了添加n型半导体氧化物CeO2对Ni基催化剂上CH4积炭/CO2消炭性能的影响,用TPR,XPS和氢吸附技术对催化剂进行了表征。结果表明,活性金属原子Ni与半导体氧化物CeO2之间存在金属-半导体相互作用(MScI),CeO2的添加提高了活性原子Ni^0的d电子密度,在一定程度上抑制了CH4分子中C-Hσ电子向d轨道的迁移,降低了CH4裂解积炭活性;可加强Ni^0原子d轨道向CO2空反馈π轨道的电子迁移,促进CO2分子的活化,提高CO2的消炭活性,使Ni/CeO2-Al2O3催化剂具有较强的抗积炭性能。  相似文献   

3.
Ni基催化剂上CH4、C2H6和C2H4的裂解积炭性能   总被引:2,自引:0,他引:2  
采用脉冲微反技术研究了添加半导体氧化物对Ni基催化剂上CH4、C2H6和C2H4的裂解积炭反应特性的影响。结果表明,n型半导体CeO2的添加降低了CH4和C2H6的积炭活性,而p型半导体Co3O4的添加则加速CH4和C2H6的裂解积炭;而对于与CH4和C2H6活化机制不同的C2H4分子的活化,上述影响机制正好相反,n型半导体CeO2的添加促进C2H4的裂解积炭反应,而p型半导体Co3O4的添加则抑制C2H4的裂解积炭反应。XPS分析表明,活性金属Ni与半导体氧化物之间存在的金属 半导体相互作用是这种影响机制的主要因素。  相似文献   

4.
Pd/γ-Al2O3三效催化剂中CeO2-ZrO2-La2O3的作用   总被引:1,自引:0,他引:1  
用浸渍法制备了CeO2-ZrO2-La2O3复合氧化物,用XRD,TG-DTA,拉曼光谱、H2-TPR和BET表面积测定等方法对合成的样品进行了表征,研究了在单钯Pd/γ-Al2O3催化剂中添加CeO2-ZrO2-La2O3对催化剂活性和热稳定性的影响.结果表明,在Pd/γ-Al2O3中加入三元复合氧化物有利于提高三效催化剂的热稳定性,有利于阻止γ-Al2O3在高温时的相变以稳定Al2O3结构,防止在高温条件下催化剂表面积的损失.在Pd的负载量为1 g*L-1条件下,测定了Pd/CeO2-ZrO2-La2O3/γ-Al2O3/蜂窝陶瓷催化剂对CO,C3H6和NO净化的三效活性,研究了催化剂的结构和三效催化活性之间的关系.结果表明,CeO2-ZrO2-La2O3的存在能明显提高Pd基催化剂对CO,C3H6和NO的三效净化活性,扩大催化剂的操作窗口,提高在富氧条件下对NOx的还原性能.  相似文献   

5.
Pt,Ru和Pd助剂对F-T合成中Co/γ-Al2O3催化剂性能的影响   总被引:7,自引:0,他引:7  
 采用浸渍法制备了添加贵金属Pt,Ru和Pd助剂的Co/γ-Al2O3催化剂,并考察了它们在F-T合成反应中的催化性能. 结果表明,添加贵金属助剂可以显著提高Co/γ-Al2O3催化剂的催化活性. XRD和TPR表征结果表明,贵金属助剂不但可以使催化剂的金属分散度增加,而且可以通过氢溢流促进催化剂表面活性相的Co3O4以及与载体Al2O3有相互作用的非活性相钴氧化物物种的还原,从而改善催化剂的还原性能. TPSR结果进一步表明,添加贵金属助剂后催化剂对CO的吸附解离能力增强,从而使吸附态CO的加氢活性提高.  相似文献   

6.
La2O3对沼气重整制氢催化剂Ni/γ-Al2O3的影响   总被引:4,自引:0,他引:4  
用浸渍法制备了不同La2O3含量的Ni/La2O3/γ-Al2O3催化剂,用CH4/CO2体积比为1的混合气体模拟沼气,考察了La2O3对沼气重整制氢催化剂Ni/γ-Al2O3的结构及催化性能的影响.运用XRD、H2-TPR、BET及TEM等手段对催化剂进行了表征.结果表明,La2O3对催化剂Ni/γ-Al2O3的影响主要取决于其含量.载体中La2O3的添加增强了Ni与Al2O3之间的相互作用.添加适量的La2O3能使催化剂具有更好的可还原性,并能增加金属Ni的分散性,抑制反应过程中Ni的烧结,提高载体对CO2的吸附能力,从而改善了催化剂的抗积炭性,使催化剂具有较好的活性及稳定性.反之,过量La2O3的掺杂会使催化剂的抗积炭性及活性下降.当La2O3含量为6%(ω)时,催化剂中Ni晶粒具有较好的分散性、还原性及抗积炭性,从而使催化剂具有更好的活性及稳定性.  相似文献   

7.
CH4,CO2和O2制合成气反应中载体对催化剂抗积炭性能的影响   总被引:14,自引:0,他引:14  
在CH4,CO2 和O2 催化氧化制合成气反应中 ,积炭是催化剂活性减弱的一个重要因素 .通过向Ni/Al2 O3 添加各种氧化物后 ,催化剂的抗积炭性能得到了提高 .实验结果表明 ,催化剂的抗积炭顺序为 :Ni/CaO Al2 O3 >Ni/MgO Al2 O3 >Ni/TiO2 Al2 O3>Ni/CeO2 Al2 O3 >Ni/La2 O3 Al2 O3 >Ni/Y2 O3 Al2 O3 >Ni/Fe2 O3 Al2 O3 >Ni/Al2 O3 ,并通过CO2 TPD ,O2 TPD ,XPS等方法对催化剂进行表征 ,讨论了抗积炭顺序与催化剂性能的关系 .  相似文献   

8.
La2O3对沼气重整制氢催化剂Ni/γ-Al2O3的影响   总被引:2,自引:1,他引:1  
用浸渍法制备了不同La2O3含量的Ni/La2O3/γ-Al2O3催化剂, 用CH4/CO2体积比为1的混合气体模拟沼气, 考察了La2O3对沼气重整制氢催化剂Ni/γ-Al2O3的结构及催化性能的影响. 运用XRD、H2-TPR、BET及TEM等手段对催化剂进行了表征. 结果表明, La2O3对催化剂Ni/γ-Al2O3的影响主要取决于其含量. 载体中La2O3的添加增强了Ni与Al2O3之间的相互作用. 添加适量的La2O3能使催化剂具有更好的可还原性, 并能增加金属Ni的分散性, 抑制反应过程中Ni的烧结, 提高载体对CO2的吸附能力, 从而改善了催化剂的抗积炭性, 使催化剂具有较好的活性及稳定性. 反之, 过量La2O3的掺杂会使催化剂的抗积炭性及活性下降. 当La2O3含量为6%(w)时, 催化剂中Ni晶粒具有较好的分散性、还原性及抗积炭性, 从而使催化剂具有更好的活性及稳定性.  相似文献   

9.
采用XRD、TPR和催化活性评价等技术,考察了负载型CoO催化剂的表面特征和其对CH4与CO2重整制合成气反应的催化性能.实验结果表明,采用浸渍法和焙烧温度为400℃时制备的11.0%CoO/γ-Al2O3催化剂,在反应温度为750 ℃和空速(GHSV)为2 500 h-1下,对CH4和CO2转化反应具有最佳的催化初活性,而大量的Co3O4晶粒的存在能导致催化剂因积炭而快速失去活性.CaO、MgO和La2O3助剂的添加能有效地改善其催化剂的抗积炭能力和还原性能,CoO/(CaO-γ-Al2O3)催化剂显示出最佳的催化反应稳定性,在750 ℃、GHSV=2 500 h-1、CH4/CO2原料比为1:1下,连续反应100 h催化剂活性较为稳定.CoO/(CaO-γ-Al2O3)和CoO/γ-Al2O3催化剂的表面特性本质上是不相同的.  相似文献   

10.
焙烧温度对CeO2改性Pd/Al2O3甲醇分解催化剂性能的影响   总被引:4,自引:2,他引:2  
杨成  任杰  孙予罕 《燃料化学学报》2001,29(Z1):157-159
考察了焙烧温度对Pd/Al2O3和CeO2改性Pd/Al2O3甲醇分解催化剂反应性能的影响.在300℃~700℃范围内焙烧,Pd/Al2O3和Pd/CeO2/Al2O3催化剂的活性都呈现出先升高后降低的趋势.XRD结果表明高温焙烧时活性组分Pd在γ-Al2O3载体表面发生聚集是Pd/Al2O3催化剂活性降低的原因,而XPS结果却表明,Pd在CeO2改性γ-Al2O3载体表面的浓度与Pd/CeO2/Al2O3催化剂的活性变化并非呈现一致关系,TPR表明活性组分Pd和助剂CeO2在γ-Al2O3上产生了一定的相互作用.从而认为Pd的分散度以及Pd和CeO2之间的相互作用共同决定催化剂的甲醇分解性能.  相似文献   

11.
Scandium magnesium gallide, Sc2MgGa2, and yttrium magnesium gallide, Y2MgGa2, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo2FeB2‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc2MgGa2 was determined from single‐crystal diffraction intensities and the isostructural Y2MgGa2 was identified from powder diffraction data.  相似文献   

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15.
The structures of the hypophosphites KH2PO2 (potassium hypophosphite), RbH2PO2 (rubidium hypophosphite) and CsH2PO2 (caesium hypophosphite) have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of alkali cations and hypophosphite anions, with the latter bridging four cations within the same layer. The Rb and Cs hypophosphites are isomorphous.  相似文献   

16.
Summary The ability of [MoS4]2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe2+. The present study has been restricted to linear complexes such as (NEt4)2 [Cl2FeS2MoS2] and (NEt4)2[Cl2FeS2MoS2FeCl2]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS2, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl2]2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl4Fe2MoS4]2–[Cl2FeMoS4]2–+FeCl2. The equilibrium constant, KD, was evaluated by differential pulse polarography. KD is tightly related to the donor number of the solvent.  相似文献   

17.
On Dialkali Metal Dichalcogenides β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 and Rb2Te2 The first presentation of pure samples of α- and β-Rb2S2, α- and β-K2Te2, and Rb2Te2 is described. Using single crystals of K2S2 and K2Se2, received by ammonothermal synthesis, the structure of the Na2O2 type and by using single crystals of β-Na2S2 and β-K2Te2 the Li2O2 type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na2O2 type to the Li2O2 type will be explained by means of the examples α-/β-Na2S2 and α-/β-K2Te2. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb2S2 is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.  相似文献   

18.
Wu YT  Linden A  Siegel JS 《Organic letters》2005,7(20):4353-4355
[reaction: see text] Fluoranthene 2 and heptacycle 3 are easily accessible from the reaction of diyne 1 and norbornadiene (NBD) in the presence of the rhodium catalyst. The unusual [(2+2)+(2+2)] adduct 3 was confirmed by the X-ray crystal structure analysis.  相似文献   

19.
[(n‐Bu)2Sn(O2PPh2)2] ( 1 ), and [Ph2Sn(O2PPh2)2] ( 2 ) have been synthesized by the reactions of R2SnCl2 (R=n‐Bu, Ph) with HO2PPh2 in Methanol. From the reaction of Ph2SnCl2 with diphenylphosphinic acid a third product [PhClSn(O2PPh2)OMe]2 ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P21/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)2 linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.  相似文献   

20.
The structures of isomorphous monoclinic strontium and lead bis­(di­hydrogenphosphate), Sr(H2PO2)2 and Pb(H2PO2)2, and orthorhombic barium bis­(di­hydrogen­phos­phate), Ba(H2PO2)2, consist of layers of hypophosphite anions and metal cations exhibiting square antiprismatic coordination by O atoms. The Sr and Pb atoms are located on sites with point symmetry 2, and the Ba atoms are on sites with point symmetry 222. Within the layers, each anion bridges four metal cations.  相似文献   

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