一氧化碳在高温超导体型的Ba_(2-x)Sr_xYCu_3O_(7-α)上的催化氧化

用粉末XRD法、EXAFS法,激光喇曼散射法、热重法和高真空质谱TPD法研究了超导体型氧化还原催化剂Ba_(2-x)Sr_xYCu_3O_(7-α)(x=0,0.25,0.50,0.75,1.00)的物理化学性质,并用常压连续流动法测定了它们的CO催化氧化活性,得到了催化剂氧化反应活性大小与催化剂的可失氧量(即晶胞中O_I 位置上的氧量)之间存在着线性关系的结论.     

铁的化学形态对Au/Fe-O催化剂甲醛催化氧化性能的影响

采用溶胶沉积法、共沉淀法制备了负载型Au/Fe-O催化剂,运用X-射线粉末衍射(XRD)、透射电镜(TEM)、电感耦合等离子原子发射光谱(ICP-AES),比表面和X射线光电子能谱(XPS)技术对其进行了表征,考察了Au/Fe-O催化剂对甲醛的催化氧化活性.金负载量相同的条件下,溶胶沉积法制备的样品甲醛催化氧化活性好于共沉淀法制备的样品.实验结果表明:六面体的FeOOH载体担载了较多活性组分纳米金,是影响甲醛催化氧化活性的主要原因.     

不同方法制备Pt/C催化剂对燃料电池催化活性的影响

分别采用高压有机溶剂法和回流法不同的制备方法,制备了含铂20%(w)的催化剂Pt/C-HP(高压有机溶剂法)和Pt/C-Reflux(回流法)。实验发现:对于甲醇的阳极氧化过程,高压有机溶胶法制得的催化剂活性较高,催化剂Pt/C-HP甲醇氧化峰电流密度是Pt/C-Reflux的1.5倍,且远远高于商业催化剂JM3000含铂20%(w)Pt/C催化剂,催化剂Pt/C-Reflux甲醇氧化峰电流密度与商业催化剂JM3000催化剂相当。采用X射线衍射(XRD)、透射电镜(TEM)、循环伏安法(CV)等方法对催化剂进行表征的结果表明:高压有机溶胶法制得的催化剂分散性比回流法制得的催化剂好,使得前者催化剂的电化学活性比表面积得到了显著的提高。     

Pt/Ce0.75Zr0.25O2的催化性能及其氧移动性的 18O 同位素交换表征

 采用浸渍法制备了Pt/Ce0.75Zr0.25O2催化剂,考察了催化剂对乙醇及CO的氧化活性,并采用 18O 同位素交换、乙醇程序升温表面反应(C2H5OH-TPSR)、一氧化碳程序升温脱附(CO-TPD)和程序升温还原(H2-TPR)等技术对催化剂进行了表征. 结果表明, Pt/Ce0.75Zr0.25O2催化剂表现出较高的乙醇和CO氧化活性,其催化活性随着Pt负载量的增加而提高. 当Pt负载量为3%时,活性最高. 继续增加Pt负载量,催化剂活性下降. C2H5OH-TPSR和CO-TPD结果表明,催化剂对乙醇或CO的氧化活性与从催化剂表面脱附出来的CO2量有对应关系, CO2脱附量越大,催化剂活性越高. 18O 同位素交换结果表明,表面氧交换能力与其氧化活性有一定对应关系,催化剂的表面氧交换能力越高,氧化活性越高.     

凹凸棒石负载的Cu-Mn-Ce催化剂上甲苯氧化反应性能

采用浸渍法制备了凹凸棒石(PG)负载Cu-Mn-Ce催化剂,运用X射线衍射、透射电镜和H2程序升温还原等方法对催化剂进行了表征,并将催化剂用于氧化降解甲苯反应中,考察了不同活性组分、Ce添加量以及催化剂焙烧温度对催化剂活性的影响,探讨了催化剂中活性组分的存在形式及与催化氧化活性的关联.结果表明,催化剂中Cu,Mn和Ce...     

Ce及N共掺杂改性TiO_2光催化性能及Ce组分的作用

以钛酸正丁酯、硝酸亚铈及氨水为前驱体运用溶胶-凝胶法对TiO2进行Ce及N单一和共掺杂改性,以甲基橙光催化降解为探针考察掺杂组分对催化剂的紫外、可见光活性影响,观察到了Ce及N的单一掺杂及共掺杂催化剂紫外、可见光活性的明显提升。运用X射线衍射(XRD)、低温氮气吸附(BET)、紫外-可见漫反射吸收光谱(DRS)、程序升温氧脱附(TPD)和程序升温氧化(TPO)等表征手段从催化剂的晶体结构及形貌、比表面积、紫外及可见光响应特性、表面吸附氧量及吸附氧循环性能等方面尝试理解掺杂组分的光活性影响机制。实验结果表明掺杂改性催化剂中适量Ce组分的作用在于通过抑制催化剂的晶粒长大、团聚和锐钛结构向金红石结构的相转变,提高催化剂的光相应强度和拓展光响应范围,增加催化剂表面吸附氧容量和促进催化剂的表面氧循环,有效捕获光生载流子,衍生各类高活性自由基物种和增大催化剂比表面积等方面增进催化剂的光催化性能。     

Ho~(3+)修饰的Pt/C电极对DMM的电催化氧化

通过循环伏安法(CV),计时电流法(CA)和线性扫描法(LSV)对二甲氧基甲烷的电氧化特性进行了研究.发现当用Ho3+修饰Pt/C催化剂电极后可以大幅度提高电极对DMM的电催化活性.热处理Ho3+修饰后Pt/C催化剂电极,可进一步提高该电极对DMM的电催化氧化活性.     

炭载体的表面处理对Pd/C催化剂电催化活性的影响

采用处理与未处理的活性炭制备Pd/c催化剂,运用循环伏安法(CV)和计时电流法检测两种Pd/C催化剂对甲酸的电催化氧化活性和稳定性.通过透射电镜(TEM)对催化剂进行了表征.结果表明,用硝酸处理的活性炭所制备的Pd/C催化剂中Pd粒子的分散更均匀,对甲酸的电催化氧化活性和稳定性都有不同程度的提高.     

甲苯、丙酮和乙酸乙酯在新型铂-钯/不锈钢丝网催化剂上的催化氧化

采用阳极氧化法制备了一种用于催化氧化处理挥发性有机化合物(VOCs)的0.1%Pt-0.5%Pd/不锈钢丝网(SSWM)催化剂. 活性测试结果表明, 0.1%Pt-0.5%Pd/不锈钢丝网催化剂具有较高的催化活性和热稳定性. 该催化剂上甲苯、丙酮和乙酸乙酯的完全氧化温度分别为220、260和280 ℃. 通过扫描电镜(SEM)、X射线光电子能谱(XPS)和超声波等手段对催化剂和不锈钢丝网进行了表征. SEM结果表明, 经阳极氧化工艺处理过的不锈钢金属丝网载体表面形成了一层沟壑形态的复合氧化膜. 该阳极氧化膜有利于活性组分Pd、Pt的分散.     

Ir/CeO2催化剂的表征和CO氧化性能

采用浸渍法制备了Ir/CeO2催化剂,考察了催化剂的CO氧化活性。随着Ir负载量的增加,Ir/CeO2催化剂的CO氧化活性先上升后下降,当Ir的负载量为1%时,催化剂的活性最高。Ir/CeO2催化剂中Ir以IrO2的形式存在,当低负载量(≤1%)时以高分散形式存在;高负载量(>1%)时以晶相IrO2的形式存在。随着Ir负载量增加,Ir粒子逐渐变大,反应比速率和反应转换频率(TOF)逐渐下降,表明小粒子上具有更高的CO反应活性。同时也发现金属态Ir催化剂的CO氧化活性高于氧化态IrOx催化剂。     

α-Fe2O3在Y沸石上的分散

用草酸高铁铵浸渍NaY沸石, 并在高温下焙烧, 得到α-Fe_2O_3/NaY沸石体系。经XRD相定量外推法测定, α-Fe_2O_3在NaY沸石上的最大分散量为0.060 gα-Fe_2O_3/gNaY, 仅占α-Fe_2O_3在沸石表面密置单层量的5.5%。首次尝试用正电子寿命谱方法测定α-Fe_2O_3在沸石表面的最大分散量, 所得结果与XRD方法完全吻合。由程序升温还原方法发现沸石上α-Fe_2O_3的还原分两步进行, α-Fe_2O_3先还原成Fe_3O_4, 然后再还原成金属。α-Fe_2O_3分散相与沸石之间的强相互作用, 使这两个还原反应受到阻抑。     

超导体Ba2YCu3O6.92晶格中不同位置氧的热稳定性

Studies on high-T_c superconductor Ba_2YCu_3O_(6.92) using thermogravimetry, temperature programmed decomposition, oxygen isotopic exchange method are reported. There are six steps in the thermogavimetric graph of Ba_2YCu_3O_(6.92). At the first step, 0.40 oxygen atom per unit cell is released, the amount of which corresponds to that of the oxygen released from the CuO_4 square plane when the oxidation number of copper reduced from +3 to +2. This amount of oxygen plays a key role on the influence on the T_c of superconductor. At the is 0.45, corresponding to the amount of oxygen released from CuO_4 when the oxidation number of copper changed from +2 to +1. The oxygen atom released totally at the last three steps is 1.07 per unit cell, which correspondes to the oxygen released from CuO_5 square pyramid when the oxidation number of copper changed from +2 to +1. The first three steps are almost continuous, so in TPD curve there is only one peak at 514 ℃ with respect to the three steps in TG curve and the decomposition heat of this one is 171±8 kJ mol~(-1). Another peak which is over 900 ℃ on TPD curve is the result of the loss of oxygen from the last three steps in TG curve. The sample released oxygen can recover its supeconductivity after reabsorbing oxygen. Oxygen isotopic exchange method shows that the oxygen atoms of CuO_4 and CuO_5 groups can be interexchanged under certain temperature and indicates that there is some bonding between CuO_4 square plane and CuO_5 square pyramidal groups in the crystal lattice of Ba_2YCu_3O_(6.92).     

钙钛矿型La1+X/2Sr1-x/2Co1-xCuxO3催化CO氧化活性与表征

The catalytic activity and the reactive properties of perovskite-type oxides catalysts La(1+x/2)Sr(1-x/2)Co1-xCuxO3 for CO oxidation reaction were investigated. Results showed that the catalytic activity for CO oxidation reached to a maximum when x＝0.4. The temperature for complete CO oxidation under atmospheric and experimental conditions was 168℃. According to the stoicheometry of catalyst, all catalysts were oxygen defect compounds. The active oxygen species on this catalyst was the adsorbed oxygen which was adsorbed on the surface lattice oxygen defect. It was also found that Co4+ existed in the catalysts and the sufrace active oxygen species was caused by the Co4+. It was concluded that CO oxidation reaction on this catalyst was carried out by the valence change between Co3+ and Co4+ which was adjusted by the adsorbed oxygen.     

硫物种对负载型钯催化剂上氢吸附性质的影响

用X光光电子能谱(XPS)分析了负载型Pd/Al_2O_3催化剂上硫和钯的状态。以程序升温脱附-质谱(TPD-MS)方法研究了不同硫物种及不同气氛对催化剂氢吸附性质的影响。结果表明: 硫物种对氢吸附的影响按S_2~(2-)、S~(2-)、SO_4~(2-)的顺序减小, 且前两者的影响远比SO_4~(2-)的大。这与催化剂在H_2-O_2反应中的抗硫性评价结果一致。并用原子分子轨道理论对上述结果进行了讨论。     

α-Fe2O3纳米微粒/硬脂酸交替L-B膜的结构表征

We reported in this paper FTIR linear diehroic spectroscopy and anisotropic properties of the nanoparticulate α-Fe_2O_3-stearate alternating Langmuir-Blodgett films (Fe_2O_3-St LB films) a new inorganic-organic quantum superlattice system. A new method fitted to inorganic-organic alternating films is used to study the molecular orientation and discuss the order arrangement of the nanopartieles in the films. The the results show that a configuration of stearate ions bound to the surface of the nano-particles: COO~- group are spherically bound to the surface of the nanoparticles; the hydrocarbon chains are almost perpendicular (31°±5°) to the substrate (7 nm-Fe_2O_3-St LB films). The orientation of hydrocarbon chains and CH_2 scissors vibration show the existence of trans-zigzag planar structure for C—C broken bone of the hy7drocarbon chains, which is related to high-order structure of the alternate films.     

改性介孔Al_2O_3负载的高分散铜基催化剂的结构与催化性能

采用浸渍法制备了LaCeZr或YCeZr改性的γ-Al2O3负载的系列Cu基催化剂,运用XRD、BET、EXAFS、XPS和H2-TPR等技术对催化剂的结构进行了详细表征,探讨了催化剂中Cu物种的存在形式及其还原性能,并与CO的氧化性能相关联。氮气吸附-脱附测试结果表明,催化剂具有很高的比表面积以及较均一的介孔结构。XRD结果表明,未改性的γ-Al2O3负载的Cu基催化剂经800℃高温焙烧后,Cu物种与载体作用强烈,形成了CuAl2O4尖晶石相,而EXAFS结果显示,助剂改性后的γ-Al2O3负载的Cu基催化剂上Cu物种主要以高分散的CuO形式存在,促进了催化剂对CO的低温氧化性能。H2-TPR结果表明,同一系列样品随焙烧温度提高,CuO的还原温度升高,晶格氧的活动度降低,导致活性的下降。LaCeZr改性的γ-Al2O3负载的铜基催化剂于650℃焙烧后显示出了较强的抗硫和抗水性能。     

K-MoO3/γ-Al2O3催化剂表面物种状态、组成和性能

应用XPS、XRD、ESR 和TPR技术分析了KCl助剂含量变化对MoO_3/γ-Al_2O_3催化剂表面物种状态、组成及其硫化还原性能的影响. K/Mo比小于0.8时, 钾离子完全和钼作用, 形成钾钼作用物种, 催化剂硫化后发生K~+表面富集, Cl~-游离并流失; K/Mo比0.8时, 钾钼作用达到饱和; K/Mo比大于0.8时, 多余的K~+和Cl~-结合以体相KCl形式存在. 钾钼作用减弱了Mo(Ⅵ)和载体之间的作用, 部分抑制了Mo(Ⅵ)的硫化还原. 钾钼作用物种硫化后可能产生CO合成醇的活性中心.     

纳米钙钛矿LaxSr1-xFe1-yCoyO3复合氧化物的制备和表征

用甘氨酸-硝酸盐燃烧合成法，制备La_xSr_1-xFe_1-yCo_yO₃复合氧化物的陶瓷粉末，对该钙钛矿型氧化物进行了XRD、IR、紫外漫反射光谱及循环伏安曲线分析。结果表明：该复合氧化物粉体平均晶粒为15.3～29.8 nm,为立方和正交晶系。该氧电极具有双功能催化特性，但不完全可逆。对水溶液染料进行光解实验，利用紫外-可见、人工神经网络光度法研究La_xSr_1-xFe_1-yCo_yO₃的催化性能。结果表明：CO²⁺的加入可使La_xSr_1-xFeO₃的光催化活性有所提高，B位离子(Fe³⁺，CO²⁺)改变与加入，使La_xSr_1-xFe_1-yCo_yO₃(x=0.7，0.3；y=0.3，0.9，1)光催化活性高于La_xSr_1-xFeO₃。同时，对5种染料进行紫外光解，在0.75 h，脱色率大于91%，并为动力学一级反应。     

C2H3自由基与O2反应的红外发射光谱及反应通道

The reaction of vinyl radicals with oxygen was investigated by Time-Resolved Fourier Transform infrared emission spectroscopy. The radicals were produced by the pulsed laser photolysis of C_2H_3Br at 248 nm. Vibrationally excited products of H_2CO(v1), HCO(v3), CO_2(v3, v), CH_3(v3), C_2H_2(v3), HO_2(v1), C_2H_2O_2(v3+v11), CO(v) formed in the C2H3+O_2 reaction have been observed. Four elementary reaction channels have been verified.     

Adsorptive and acidic properties, reversible lattice oxygen evolution, and catalytic mechanism of cryptomelane-type manganese oxides as oxidation catalysts

Cryptomelane-type manganese oxides have been synthesized, characterized, and tested in the total oxidation of volatile organic compounds and CO oxidation. The structural, compositional, morphological, acid-base, physisorptive-chemisorptive, and thermal stability properties (especially the reversible evolution of lattice oxygen) have been studied in detail using ICP-AES (inductively coupled plasma-atomic emission spectroscopy), HRSEM (high-resolution scanning electronic microscope), XRD (X-ray diffraction), IR (infrared) and adsorbate-IR, N2 and CO2 physisorption at 77 and 273 K, respectively, TPD-MS (temperature-programmed decomposition-mass spectroscopy), and TGA-DSC (thermogravimetric analysis-differential scanning calorimetry) techniques. Kinetic and mechanistic studies for the catalytic function have been conducted and related to the characterization results. Cryptomelane has shown to be highly microporous, by using CO2 physisorption, and highly hydrophobic, possessing both Br?nsted and Lewis acid sites. A part of the lattice oxygen atoms can be reversibly removed from the framework and recovered at elevated temperature without changing the framework structure. These lattice oxygen atoms can react with CO even at room temperature and are active sites for the oxidation of benzene. The consumed lattice oxygen atoms are replenished by gaseous oxygen to complete a catalytic cycle. The ease of reversible evolution of lattice oxygen, together with the high porosity, hydrophobicity, and acidity, leads to the excellent oxidation properties of OMS-2.