焙烧温度对Mn/Al2O3-TiO2催化剂结构及氧化NO性能的影响

采用溶胶凝胶法和浸渍法制备10% Mn/Al₂O₃-TiO₂催化剂,借助TPO、XRD、O₂-TPD、Raman、XPS等手段,考察焙烧温度(450~650 ℃)对催化剂结构以及氧化NO性能的影响。TPO结果表明催化剂活性随焙烧温度的升高先增后减,其中焙烧温度为550 ℃时催化剂活性最好。XPS结果显示随着焙烧温度的升高(450~550 ℃),催化剂表面Mn³⁺的含量逐渐升高,与催化剂活性的强弱成对应关系,并且催化剂晶格氧含量下降,而表面化学吸附氧从40.9%增加到64.8%。Raman分析显示550 ℃焙烧时,催化剂表面存在丰富的Mn₂O₃活性物种,并且O₂-TPD分析也表明随着焙烧温度的升高,晶格氧向表面化学吸附氧流动,提高了化学吸附态氧物种的含量。这些结果表明Mn₂O₃可能是NO氧化起主要作用的活性Mn物种,释放更多的表面化学吸附氧物种,将有助于促进NO的催化氧化。     

不同金属负载对Cr/Al2O3-TiO2催化剂结构及氧化NO性能的影响

采用溶胶-凝胶法和浸渍法制备Cr/Al_2O_3-TiO_2催化剂,在考察不同Cr负载量的基础上,研究不同金属负载与焙烧温度对Cr/Al_2O_3-TiO_2催化剂结构与性能影响。程序升温氧化(TPO)结果表明,当Cr负载量为10%(w/w)时具有较好的催化活性;不同金属负载Cr/Al_2O_3-TiO_2时,负载Co及在焙烧温度为550℃时催化剂具有较好的活性。通过程序升温还原(H_2-TPR)表征发现,Co的负载使催化剂的低温氧化还原能力逐渐提高,表明Co-Cr具有较好的协同催化作用。X射线光电子能谱(XPS)表征表明,Co增加了Cr~(6+)和表面吸附氧(O_β)含量,随着焙烧温度的升高(450～550℃),晶格氧不断向催化剂表面流动,表面化学吸附氧O_β比例逐渐增加,导致催化活性不断升高,说明Cr~(6+)和O_β是催化氧化NO的重要活性物种。     

La2Zr2O7催化剂结构相变对甲烷氧化偶联反应性能的影响

采用共沉淀法并通过改变焙烧温度制备了一系列具有不同晶相结构的La_2Zr_2O_7催化剂,在微型固定床反应器上评价其甲烷氧化偶联反应性能,并利用XRD、Raman、CO_2-TPD、XPS等表征手段,探究催化剂的物相结构、表面碱性以及表面氧物种的变化规律。结果表明,随着焙烧温度从700℃逐渐升高到1200℃,La_2Zr_2O_7催化剂结晶度不断提高,晶相发生明显变化,从无定形结构逐渐向缺陷萤石结构过渡,最终转变成烧绿石结构。焙烧温度提高促使La_2Zr_2O_7晶相转变过程中,催化剂表面的碱性强度减弱,中等碱性位数量以及具有催化活性的表面氧物种O_2~(2-)和O_2~-的相对含量不断减少,致使催化剂的CH_4转化率和C_(2+)选择性不断降低。其中,无定形LZO-CP-700催化剂表现出最佳的甲烷氧化偶联反应性能。     

CeO2-WO3催化剂表面酸性和氧化还原性能在脱硝反应中的研究

本研究利用原位合成法成功制备CeO₂-WO₃催化剂并用于脱硝反应，焙烧温度为550℃的CW-550催化剂活性最佳，200℃时CW-550脱硝活性达到90%以上。CW-550催化剂具有优越的催化剂性能可归结为较大的比表面积、较多的Ce³⁺物种、丰富的表面酸性和优越的氧化还原性能。Ce³⁺增多，有利于氧空位的形成，可促进氧化还原性能。WO₃的引入，在550℃的焙烧条件下可显著提升催化剂的Br?nsted酸量，有利于氨气的吸附与活化，提升其催化性能。CW催化剂上吸附的NH₃物种能与气态的NO反应，而吸附态的NH₃与吸附态的NO_x不能进行高效反应，因此，CW催化剂的SCR反应主要遵循Eley-Rideal反应机理。     

NO对LaMnO3与La0.8K0.2MnO3催化氧化碳烟活性影响

采用柠檬酸络合法制备LaMnO3和La0.8K0.2MnO3钙钛矿催化剂,运用程序升温氧化(TPO)考察在不同反应气氛下催化燃烧碳烟的活性,并通过XRD,O2-TPD,NO-TPD,XPS以及NO预处理后O2-TPD等技术对催化剂进行表征和分析。结果表明,NO的存在促进了碳烟的催化氧化,但是对LaMnO3和La0.8K0.2MnO3氧化碳烟的促进效果不同。这与催化剂表面氧空位和活性氧物种有密切联系。     

焙烧温度对Mn-Fe/CeO2-TiO2催化剂低温NH3选择性催化还原NO的影响

采用等体积浸渍法制备了Mn-Fe/CeO2-TiO2催化剂,考察了不同焙烧温度对其NH3选择性催化还原(SCR)NO活性及催化剂性能的影响。并用N2吸附-脱附,X射线衍射(XRD)和X射线光电子能谱(XPS)等手段对催化剂进行了表征。活性结果表明,随着焙烧温度的升高,Mn-Fe/CeO2-TiO2催化剂的催化活性先升高后降低。其中焙烧温度为500℃时Mn/CeO2-TiO2的NH3-SCR活性最佳,该催化剂在113～250℃之间表现出了良好NO去除效率。表征结果表明,500℃焙烧时,催化剂中Fe和Mn物种在CeO2-TiO2表面的分散效果最好。500℃焙烧时Mn-Fe/CeO2-TiO2表面Mn以+4价存在,Fe以+3、+2价存在,而Ce以+4、+3存在。     

V_2O_5/Ti-Ce-PILC在H_2S选择性催化氧化过程中的催化性能

合成了TiO_2-CeO_2柱撑黏土负载V_2O_5催化剂,通过XRD、氮气吸附脱附、TG、FT-IR、H_2-TPR、NH_3-TPD、XPS等方法对其物理化学性质进行了表征,研究了该催化剂在H2S选择性催化氧化反应中的活性。结果表明,负载5%V_2O_5的TiO_2-CeO_2柱撑黏土在180℃下催化效果最好,且尾气中不含SO_2。V_2O_5、TiO_2和CeO_2之间的相互作用提高了催化剂的活性,CeO_2提高了催化剂的热稳定性,同时提供大量晶格氧,加强了V_2O_5的氧化还原作用,降低了反应温度;TiO_2加强了VO_x和CeO_x的再氧化,降低了硫酸盐的覆盖率,从而降低了催化剂的失活速率。     

载体焙烧温度对RuO_2/TiO_2催化HCl氧化性能的影响

以不同温度焙烧TiO(OH)_2得到的TiO_2为载体,采用湿法浸渍法制备RuO_2/TiO_2-C(C=450、550、650及750℃)催化剂,利用XRD、N_2吸附-脱附、TEM和H_2-TPR等表征手段研究催化剂的物理化学性质,并对其在HCl氧化反应中的催化性能进行考察.结果表明:载体焙烧温度对催化剂的结构与活性有显著影响.随着载体焙烧温度(≤650℃)的升高,RuO_2与TiO_2之间的晶面匹配度逐渐变高,促进了RuO_2在TiO_2表面的分散,其中RuO_2/TiO_2-650催化剂表现出最优的催化性能.而当载体焙烧温度过高时,RuO_2/TiO_2-750催化剂的反应活性大大下降,可能是由于过高的焙烧温度导致载体出现严重的烧结团聚现象,以及RuO_2与TiO_2之间过强的相互作用,阻碍了HCl氧化反应的进行.此外,减小RuO_2的粒径可以促进HCl氧化活性的提升.动力学结果显示,催化剂表面的HCl氧化反应主要受O_2分压的影响,表明O_2从催化剂表面的解离吸附为决速步骤.     

焙烧温度对柴油车氧化催化剂Pt-Pd-（x）ZrO2/Ce0.3Zr0.7O2-Al2O3性能的影响

制备了氧化铝、铈锆固溶体复合氧化物负载铂、钯的双金属催化剂Pt-Pd/ Ce0.3Zr0.7O2-Al2O3,并添加3% ZrO2助剂改性,用于柴油车尾气中CO、HC和NO的催化氧化,其中贵金属负载量仅为0.68 wt%。考察了制备过程中焙烧温度对催化剂性能的影响。催化剂活性评价结果表明,与未添加ZrO2的催化剂比较。添加ZrO2明显提高了催化剂的低温氧化活性,而且焙烧温度对催化剂的氧化性能有较大影响。焙烧温度为800 ?C时,CO和C3H6的起燃温度最低,分别为168、189 ?C,焙烧温度为700 ?C时,NO转化为NO2的转化率最高,最大转化率为36%,具有较好的热稳定性。通过XRD、N2吸附-脱附、CO化学吸附、XPS、H2-TPR等表征手段考察了催化剂物理化学性质随焙烧温度的变化情况,并分析了与催化剂活性之间的关系,得到贵金属分散度、表面化学吸附氧含量、催化剂的还原性质对氧化性能有重要影响,发挥协同作用。进而可以通过优化焙烧温度提升柴油车氧化催化剂性能,对提高工业应用柴油车尾气后处理系统的净化效率有重要意义。     

尿素研磨燃烧法合成Ce_(0.8)Zr_(0.2)O_2固溶体对乙硫醇催化分解的研究

采用尿素研磨燃烧法快速制备Ce_(0.8)Zr_(0.2)O_2固溶体催化剂,考察不同焙烧温度下Ce_(0.8)Zr_(0.2)O_2固溶体常压下催化分解乙硫醇的活性。利用XRD,TEM,BET,H2-TPR,XPS和Raman等方法对催化剂的物化性质、表面结构进行研究。结果表明:Ce_(0.8)Zr_(0.2)O_2固溶体对乙硫醇催化降解有较好活性。在一定范围内升高焙烧温度有利于更多Zr4+进入Ce O2晶格,从而增加氧空位浓度,但过高的温度会使催化剂颗粒团聚,并降低催化剂表面吸附氧的相对含量,导致催化剂比表面积降低。600℃焙烧的Ce0.8Zr0.2O2固溶体表现出对乙硫醇催化分解最佳活性,得益于催化剂表面Ce3+浓度、氧空位浓度与比表面积的协同作用。一方面,这些表面Ce3+浓度与催化剂氧空位浓度,有利于氧迁移,对催化分解反应有促进作用,另一方面催化剂比表面积越大,越有利于反应物吸附、暴露更多活性位点,进而增加催化活性。     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

Ion-beam irradiation of lanthanum compounds in the systems La2O3-Al2O3 and La2O3-TiO2

Thin crystals of La₂O₃, LaAlO₃, La_2/3TiO₃, La₂TiO₅, and La₂Ti₂O₇ have been irradiated in situ using 1 MeV Kr²⁺ ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La₂O₃ remained crystalline to a fluence greater than 3.1×10¹⁶ ions cm⁻² at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (T_c) of 647 K for LaAlO₃, 840 K for La₂Ti₂O₇, 865 K for La_2/3TiO₃, and 1027 K for La₂TiO₅. The T_c values observed in this study, together with previous data for Al₂O₃ and TiO₂, are discussed with reference to the melting points for the La₂O₃-Al₂O₃ and La₂O₃-TiO₂ systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between T_c and melting temperature (T_m) in the two systems. More complex relationships exist between T_c and crystal structure, with the stoichiometric perovskite LaAlO₃ being the most resistant to amorphisation.     

Preparation of ZrO2-TiO2-CeO2 and Its Application in the Selective Catalytic Reduction of NO with NH3

TiO₂,ZrO₂-TiO₂,andZrO₂-TiO₂-CeO₂ were prepared by co-precipitation method and characterized by X-ray diffraction (XRD), specific surface area measurements (BET), temperature programmed desorption (NH₃-TPD), oxygen storage capacity (OSC), and temperature programmed reduction (H₂-TPR). The results showed that ZrO₂-TiO₂-CeO₂ exhibited large number of surface strong acid, possessed some oxygen storage capacity, and strong redox property. The three materials were used as supports and the monolith catalysts were prepared with 1% (w) V₂O₅ and 9% (w)WO₃ for selective catalytic reduction (SCR) of NO with ammonia in the presence of excessive O₂, and the results of catalytic activity showed that the catalyst used ZrO₂-TiO₂-CeO₂ as support yielded nearly 100% NO conversion at 275 °C at a gas hourly space velocity (GHSV) of 10000 h⁻¹, and it had the best catalytic activity and showed great potential for practical application.     

CeO2改性Ag-V2O5/TiO2催化剂的甲基吡啶氧化脱甲基性能

以锐钛矿TiO_2为载体,考察了CeO_2改性对Ag-CeO_2-V_2O_5/TiO_2催化3-甲基吡啶氧化脱甲基性能的影响,并优化了催化剂组成与制备条件.结果表明:Ce掺杂改性不仅能够与V物种作用形成Ce VO_4,而且促进V_2O_5分散,改善活性组分的氧化还原性能,从而提高3-甲基吡啶脱甲基转化率与选择性,改善Ag-V_2O_5/TiO_2催化性能.适宜的催化剂组成为V_2O_5负载量15%,Ce/V的摩尔比0.33,Ag质量分数1.0%.过高的焙烧温度将导致TiO_2载体向金红石型转变,Ag-CeO_2-V_2O_5/TiO_2适宜制备条件为450℃焙烧4 h.     

XRD and Si MAS-NMR spectroscopy across the β-Lu2Si2O7-β-Y2Si2O7 solid solution

Samples in the system Lu_2−xY_xSi₂O₇ (0?x?2) have been synthesized following the sol-gel method and calcined to 1300 °C, a temperature at which the β-polymorph is known to be the stable phase for the end-members Lu₂Si₂O₇ and Y₂Si₂O₇. The XRD patterns of all the compositions studied are compatible with the structure of the β-polymorph. Unit cell parameters are calculated as a function of composition from XRD patterns. They show a linear change with increasing Y content, which indicates a solid solubility of β-Y₂Si₂O₇ in β-Lu₂Si₂O₇ at 1300 °C. ²⁹Si MAS NMR spectra of the different members of the system agree with the XRD results, showing a linear decrease of the ²⁹Si chemical shift with increasing Y content. Finally, a correlation reported in the literature to predict ²⁹Si chemical shifts in silicates is applied here to obtain the theoretical variation in ²⁹Si chemical shift values in the system Lu₂Si₂O₇-Y₂Si₂O₇ and the results compare favorably with the values obtained experimentally.     

The reaction of MgCl2·4H2O with CCl2F2

A new reaction of MgCl₂·4H₂O with CCl₂F₂ is investigated by DTA and TG from room temperature to 350 °C. It is observed that MgF₂ was obtained between 252 and 350 °C, Below the temperature, MgCl₂·4H₂O dehydrates and hydrolyzes to MgCl₂ and Mg(OH)Cl, which are the real reactants of the reaction with CCl₂F₂. The formation of MgF₂ is ascribed to the reaction of MgCl₂ and Mg(OH)Cl with HF, which forms by decomposition of CCl₂F₂ with the taking part in of H₂O released from dehydration of hydrated magnesium chloride on the surface of MgCl₂ and Mg(OH)Cl, which catalyzes the decomposition of CCl₂F₂ in this case. Consequently, the reactions are tested in the fluid-bed condition. It is found that MgF₂ formed at temperatures down to 200 °C in a fluid-bed reactor. This reaction may be used as a method of disposing of the environmentally sensitive CCl₂F₂ (rather than release into the atmosphere). It is also a method for the preparation of MgF₂.     

Li2ZrO3材料吸收CO2性能的进一步研究

用不同结构的ZrO₂合成了一系列在高温下吸收CO₂的Li₂ZrO₃材料，并详细的研究了反应物质的物理和化学性质对生成物吸收CO₂性能的影响。采用SEM、XRD以及TG分析法分别进行了材料结构及其吸收CO₂性能的表征，并使用XPS法测定了材料表面的元素组成。实验结果表明，使用不同结构的ZrO₂合成的Li₂ZrO₃，其吸收CO₂的性能明显的不同。用ZrO₂(t)(四方)合成的Li₂ZrO₃吸收CO₂的速度快，在500 ℃下，20% CO₂（80%空气）的气氛中保持3h，其吸收量可达25（±0.6）%（wt），而以ZrO₂(m)(单斜)为原料制备的Li₂ZrO₃在上述吸收条件下重量仅增加9（±0.6）%（wt）。此外，实验结果还表明化学元素的掺杂对用ZrO₂(m)合成的Li₂ZrO₃的CO₂吸收速度及吸收容量影响较大。     

(Cl2AlNH2)n和(H2AlNH2)n(n=1～5)簇结构及其热力学性质

用HF自洽场理论和密度泛函理论(DFT)的B3LYP方法,在6 31G水平上研究了低聚物(Cl2AlNH2)n和(H2AlNH2)n(n=1～5)簇的几何构型、电子结构和聚合反应热力学性质,比较了两个系列化合物中化学键的强度.结果表明,Cl2AlNH2和H2AlNH2分子为C2 (EC)平面型结构,其中Al－N为由一个σ键和一个键组成的双键.(Cl2AlNH2)n和(H2AlNH2)n(n=1～5)分子为Dnh对称,Al－N是典型的σ单键 .低聚物(Cl2AlNH2)n和(H2AlNH2)n的稳定性顺序分别为: 3 > 2 > 4> 5 > 1和8 > 7 > 9 > 11 > 6.     

Mn-Na2WO4/SiO2催化剂表面活性中心结构的DFT研究

Mn Na2WO4/SiO2 is one of the best catalysts for oxidative coupling of methane.To investigate the nature of active centers and the reaction mechanism,the structure of possible metal sites formed by tungsten and manganese over the silica surface were studied using molecular simulation method and ab initio DFT calculations.Silica support exists in the catalyst as 岐瞔ristobalite and its (111) face exposes preferentially to the surface.The calculated results show that tungsten interacts with the silica surface by three or one bridge oxygen atoms to form tetrahedral [WO4],and manganese interacts with single bridge oxygen to form dispersed [MnO4] or exists as oxide clusters.The nature of the molecular orbitals and the electronic structure suggest that the tetrahedral [WO4] site with single bridge oxygen is the most probable active center responsible for methane activation.     

The crystal structure determinations and refinements of K2S2O7, KNaS2O7 and Na2S2O7 from X-ray powder and single crystal diffraction data

The crystal structures of K₂S₂O₇, KNaS₂O₇ and Na₂S₂O₇ have been solved and/or refined from X-ray synchrotron powder diffraction data and conventional single-crystal data. K₂S₂O₇: From powder diffraction data, monoclinic C2/c, Z=4, a=12.3653(2), b=7.3122(1), , β=93.0792(7)°, R_Bragg=0.096. KNaS₂O₇: From powder diffraction data; triclinic , Z=2, a=5.90476(9), b=7.2008(1), , α=101.7074(9), β=90.6960(7), γ=94.2403(9)°, R_Bragg=0.075. Na₂S₂O₇: From single-crystal data; triclinic , Z=2, a=6.7702(9), b=6.7975(10), , α=116.779(2), β=96.089(3), γ=84.000(3)°, R_F=0.033. The disulphate anions are essentially eclipsed. All three structures can be described as dichromate-like, where the alkali cations coordinate oxygens of the isolated disulphate groups in three-dimensional networks. The K-O and Na-O coordinations were determined from electron density topology and coordination geometry. The three structures have a cation-disulphate chain in common. In K₂S₂O₇ and Na₂S₂O₇ the neighbouring chains are antiparallel, while in KNaS₂O₇ the chains are parallel. The differences between the K₂S₂O₇ and Na₂S₂O₇ structures, with double-, respectively single-sided chain connections and straight, respectively, corrugated structural layers can be understood in terms of the differences in size and coordinating ability of the cations.