A位缺陷对La-Sr-Co-O钙钛矿结构和催化氧化性能的影响

采用柠檬酸络合法制备La-Sr-Co-O钙钛矿, 通过酸处理溶解Sr离子, 得到了相应的A位缺陷钙钛矿. 采用X射线衍射(XRD)、 X射线吸收精细结构(XAFS)、 电感耦合等离子体原子发射光谱(ICP-OES)、 X 射线光电子能谱(XPS)和拉曼光谱(Raman)等表征技术考察了A位缺陷钙钛矿的晶体结构、 配位环境及表面电子结构等性质, 通过CO氧化和NO氧化活性测试评价了A位缺陷钙钛矿的催化性能. 结果表明, 简单酸处理有选择性地改造了Sr富集区, 溶解了SrCO₃ 以及大部分SrO. 钙钛矿主体结构基本不变, 局域结构中Sr(A位)的缺位造成Co离子以Co₃O₄形式溶出, 并形成了更多的氧缺陷, 有效地活化了晶格氧物种, 因此其在CO氧化和NO氧化反应中均表现出更优异的低温活性.     

LaSrCo0.9B’0.1O4复合氧化物制备、氧化性能及表征

采用聚丙烯酰胺法制备了类钙钛矿LaSrCo_0.9B’_0.1O₄系列复合氧化物(B’= Mn、Fe、Ni、Cu)和LaSrCoO₄,并考察了对CO和C₃H₈催化氧化反应的活性,运用XRD、BET、TEM、TPD等方法对LaSrCo_0.9Ni_0.1O₄、LaSrCoO₄进行了表征.结果表明, LaSrCo_0.9Ni_0.1O₄和LaSrCoO₄都为四方K₂NiF₄型纳米材料. Ni的掺入提高了LaSrCoO₄的催化活性、O₂的吸附量和晶格畸变率,降低了平均晶粒度.     

LaSrMO4复合氧化物的结构及其己烷完全氧化性能

采用分解无定形柠檬酸和乙二胺四乙酸聚合体法,合成了具有类钙钛矿型结构的LaSrMO4(M=Mn,Fe,Co,N i,Cu)催化材料,以己烷完全氧化为探针反应,运用XRD、BET、TPR、TPD、FT-IR、XPS等手段进行表征.结果表明:对己烷完全氧化性能的顺序为LaSrCoO4>LaSrN iO4>LaSrCuO4>LaSrFeO4>LaSrMnO4,且氧空穴和可移动晶格氧越多、比表面积越大及颗粒度越小,均有利于提高己烷完全氧化活性.     

LaSrCo_(0.9)B'_(0.1)O_4复合氧化物制备、氧化性能及表征

采用聚丙烯酰胺法制备了类钙钛矿LaSrCo0.9B'0.1O4系列复合氧化物(B'=Mn、Fe、Ni、Cu)和LaSrCoO4,并考察了对CO和C3H8催化氧化反应的活性,运用XRD、BET、TEM、TPD等方法对LaSrCo0.9Ni0.1O4、LaSrCoO4进行了表征.结果表明,LaSrCo0.9Ni0.1O4和LaSrCoO4都为四方K2NiF4型纳米材料.Ni的掺入提高了LaSrCoO4的催化活性、O的吸附量和晶格畸变率,降低了平均晶粒度.     

Cu掺杂对LaMnO3催化剂的结构和催化氧化性能的影响

采用非晶态多核配合的方法合成了La1-xCuxMnO3(x=0、0.05、0.1、0.2、0.3、0.4、0.5)系列催化剂, 并用X射线衍射(XRD)、透射电镜(TEM)、比表面测定仪(BET)等手段对催化剂的微观结构进行了表征. 研究了Cu掺杂对钙钛矿结构及其对CO催化氧化发光性能及催化氧化CO、CH4性能的影响规律. 结果表明, 当x≤0.1 时, Cu掺杂仍可形成单相的钙钛矿结构; 当x>0.1时, 过量掺杂的Cu以CuO杂相存在. Cu掺杂可改善La1-xCuxMnO3催化剂对CO和CH4的催化氧化活性. 经700 ℃焙烧3 h制备的La0.9Cu0.1MnO3催化剂具有最高CO催化氧化活性(T100%=170 ℃), 该结果与CO催化氧化发光结果一致.而La0.95Cu0.05MnO3催化剂对CH4的催化氧化活性最高(T95%=705 ℃).     

乙烷在钛酸盐复合氧化物上的氧化脱氢Ⅰ.锂掺杂对催化性能的影响

研究了掺杂钛酸盐催化剂用于乙烷氧化脱氢的催化行为，发现适量的Ｌｉ＾＋取代Ｔｉ＾４＋后可明显改善催化剂对乙烯的选择性。催化剂ＣａＴｉ０．９Ｌｉ０．１Ｏ３－δ在８５０℃时乙烷转化率和乙烯选择性分别为８７．８％和７１．７％，乙类的单程收经为６３．０％．催化剂Ｓｒ０．９Ｃａ０．１Ｔｉ０．９Ｌｉ０．１Ｏ３－δ可在极宽的温度范围内保持很高的乙烯选择性。     

不同氧化态的离子掺杂对limn2o4电化学性能的影响

以CH3COOLi·2H2O、(CH3CO2)2Mn·4H2O、氧化物和柠檬酸为原料,采用流变相法经过2次灼烧后得到了不同氧化态离子掺杂的尖晶石化合物LiMn1.95M0.05O4(M:Li,Mg,Co,Ti,V)。通过X射线衍射测试技术对合成的产物物相进行表征,所得产物均具有纯相尖晶石结构。同时应用软件计算了其晶格常数,结果发现金属离子的掺杂不同程度地减少晶格大小。通过循环伏安法研究发现,在4V区域有2步可逆过程发生,对应于锂离子的脱嵌。掺杂的金属离子对于峰电位以及峰面积都有影响。Mn3 的含量越低,峰的面积越小。金属离子与氧的键能越大,峰电位越高。50次充放电循环测试表明,通过掺杂改性来改善尖晶石LiMn2O4的电化学性能时,在掺杂相同量阳离子的尖晶石化合物中,以选择氧化态为Co3 掺杂的化合物具有最佳的充放电容量和循环性能。     

Sr^2＋对Li0.2375＋xLa0.5875-xSrxTiO3^-LaPO4体系的性能的影响

利用循环电位沉积法从非水体系中制备了Yb-Bi薄膜。在这一沉积过程中，基体电位是在两个电位之间连续循环的。研究了沉积电位、沉积时间和扫描速率对沉积膜中Yb含量以及表面形态的影响。实验结果表明，在0．10mol．L^-1Ybcl3 0．10mol．L^-1Bi(N03)3 0．10mol．L^-1LiCl DMSO体系中，当控制恰当的沉积条件，可得到表面黑色、均匀、有金属光泽和附着力强的非晶态Yb-Bi薄膜，其中Yb的质量分数可达21．04％～36．36％(质量分数)，所得到的沉积膜通过SEM，EDS和XRD进行了表征。     

Low-temperature heterogeneous oxidation of sulfide ions on a higher Co oxide system in aqueous medium

Low-temperature heterogenous oxidation of sulfide ions on a higher Co oxide system in aqueous medium has been studied. The effects of pH, temperature and catalyst amount on the kinetic parameters as well as on the selectivity of the oxidation process were investigated. An oxidation mechanism has been proposed based on the results of kinetic investigations and on the data obtained by IR and XPS spectroscopic studies of Co oxide before and after sulfide ion oxidation.     

Co3O4-CeO2氧化物对丙烷完全氧化的催化性能（英文）

挥发性有机化合物(VOCs)是全球大气污染物的主要来源,近年来已造成严重的环境问题.催化氧化是一种有效的、经济可行的VOCs去除技术,其研究的关键在于开发高效、稳定的催化剂.在本文中,我们采用柠檬酸法合成了一系列具有不同Co/(Ce+Co)摩尔比的Co3O4-CeO2二元氧化物催化剂,研究了其对丙烷(低碳VOCs)的催化氧化性能.在催化活性测试中,反应气的组成为0.2 vol.%C3H8和5 vol.%O2,Ar为平衡气,气体总流速为200 mL min^-1.实验结果表明,Ce的掺入能够明显提高Co3O4的丙烷催化氧化性能,Co3O4-CeO2催化剂的丙烷催化氧化活性顺序为CoCeOx-70>CoCeOx-90>Co3O4>CoCeOx-50>CoCeOx-20>CeO2.当Co/(Ce+Co)摩尔比为70%时,CoCeOx-70催化剂的丙烷催化氧化性能最好.在丙烷转化率达到90%时,CoCeOx-70催化剂的反应温度为310℃(GHSV=120000mL h^-1 g^-1),相比于单一的Co3O4催化剂的反应温度降低了25℃.XRD和TEM表征结果显示,在Co3O4-CeO2二元氧化物催化剂中存在Co3O4和CeO2两种晶型,同时随着Ce的掺入,催化剂的粒径明显降低.Raman光谱图显示,Ce的掺入使催化剂的晶格发生畸变,促进催化剂表面氧空位的产生,为催化剂中氧的迁移提供晶格位点.H2-TPR和C3H8-TPSR结果表明,Co3O4与CeO2间存在相互作用,能够提高催化剂的低温还原性能,以促进催化剂的丙烷催化氧化.O2-TPD和O 1s XPS结果表明,Ce的掺入能够增加催化剂表面活性氧物种的产生,提高催化剂中氧的移动性,从而提高了催化剂对丙烷的催化氧化活性.在对Co3O4和CoCeOx-70催化剂进行in-situ DRIFTS表征和简单的动力学研究,我们发现Ce的掺入不改变催化剂的丙烷催化氧化反应路径,其存在能够促进丙烷在催化剂表面的吸附和活化,以提高催化剂的丙烷催化氧化活性.同时,丙酮和酯作为中间物参与到丙烷的催化氧化反应过程中.此外,我们考察了反应气氛中水蒸气和CO2的存在对催化剂催化性能的影响.结果表明,CO2和水蒸气的存在都抑制了催化剂的丙烷催化氧化活性,催化性能随着CO2和水蒸气浓度的增加而降低.在相同条件下,水蒸气对催化剂催化性能的抑制作用明显大于CO2的抑制作用,但这种抑制作用会随着反应气中水蒸气和CO2的消失而消失.在稳定性测试中,CoCeOx-70催化剂表现出优异的抗水蒸气和CO2性能.在反应气中存在5 vol.%水蒸气和5 vol.%CO2的条件下,CoCeOx-70催化剂在50 h的稳定性测试中均未出现明显的失活现象.同时,经过10次加热和降温循环测试后,催化剂的催化活性也没有发生明显变化,这为CoCeOx-70催化剂的未来工业化的应用提供了可能.     

A one-pot synthesis of bisarylhydrazones by Cu(I)-catalyzed aerobic oxidation

An efficient Cu(I)-catalyzed one-pot synthesis of N-substituted (or NH) bisarylhydrazones is reported. A further cyclization reaction could occur towards the synthesis of benzimidazoles or triazoles with elevated temperature. A plausible alkylation–oxidation–alkylation mechanism is proposed based on experimental results and literature.     

The composite catalysts of Cu/CuxO nanoparticles supported on the carbon fibers were prepared for styrene oxidation reaction

In this paper a novel simple method for preparing two different catalysts with various‐valences copper was reported. Carbon nanofibers supported copper‐cuprous oxide nanoparticles (Cu‐Cu₂O NPs/CNFs) and copper oxide nanoparticles (CuO NPs/CNFs) through electrospinning, adsorption and reduction in the high‐pressure hydrogenation and the high‐temperature calcination methods. These catalysts were investigated by a series of characterizations and were applied in reaction in nitrogen atmosphere, which had a good catalytic activity and selectivity of benzaldehyde for the reaction. Above all, the new study has been certified clearly, in which Cu‐Cu₂O NPs/CNFs and CuO NPs/CNFs composite catalysts enhanced the generation of benzaldehydeand the excellent catalytic properties were exhibited.     

热处理对[NiFe/Cu/Co/Cu]_n多层纳米线磁性能的影响

采用双槽控电位法在阳极氧化铝(AAO)模板中制备了有序均一的[NiFe/Cu/Co/Cu]n多层纳米线阵列,并在不同温度下进行了热处理.利用X射线衍射(XRD)对热处理前后多层线的晶体结构进行了测试.考察了不同退火温度对多层线矫顽力、剩磁比、巨磁电阻(GMR)效应、磁灵敏度的影响.随热处理温度升高,多层纳米线中磁性微晶晶型取向越来越明显,晶体结构更均匀;多层纳米线的矫顽力和剩磁比先增大后减小.300°C下多层纳米线矫顽力达到最大值,GMR最大值可达59%,对应的磁电阻灵敏度(SV)为0.233%Oe-1.     

The evaluation and use of properties of individual ions in slution

A critical examination is given of extra-thermodynamic methods for evaluation of properties of individual ions in solution. The ways in which such data may be applied, or are required in various problems concerning specific properties of electrolyte solutions and in the fields of kinetics, electrochemistry, colloid and interfacial chemistry, are outlined. Special attention is given to the problem of evaluation of individual ionic thermodynamic functions for the hydration of ions but, in some cases, corresponding data for nonaqueous solutions are available for discussion and are of interest in a comparative way. The reliability of the various methods is assessed and estimates of numerical values for various individual ionic functions are tabulated. The question of scales of individual ionic radii, on which some of the derived data depend, is also examined. The dependence of various properties for anions and for cations on ionic radius is discussed and data are plotted comparatively. It is shown that for most, but not all, properties, the values for anions are more sensitive to increasing ionic radius than are the values for cations. This behavior, as well as the exceptions, is of theoretical interest. The significance of ion-specific behavior at interfaces is considered and the importance of interactions between ions of like sign of charge is indicated.Presented at the Symposium on Electrolytes, University of Reading, September 13, 1977.     

Pt、Cu电极上Fe(CN)_6~(4-)和SCN~-电化学行为的现场FTIR反射吸收光谱研究

本文报道了一种简单有效的现场红外反射吸收光谱电解池设计。对Fe(CN)_~(4-)和SCN~-在Pt、Cu电极上的吸附及电化学反应进行了研究。     

The Stabilities of the o-Carboxyphenylhydrazo-Ethylacetoacetate OF Cu,Ni, Co,Zn, Mn and Cd Chelate Compounds in Different Solvents

The dissociation constants for o-carboxyphenylhydrazoethylacetoacetate (o-CPHEA) ligand, as well as the stability constants for the divalent metal complexes of Cu, (II), Ni (II), Co (II), Zn (II)and Cd (II) ions, have been calculated pH-meterically in different solvents. The dissociation constans pK₁=4.10 and pK₂=10.55 of the insoluble organic ligand are calculated in aqueous medium. The effect of solvents, the relation between stabilities and both electronegativities and ionization potential are studied.     

Mechanism of the oxidation reaction of Cu with N2O via nonadiabatic electron transfer

We treat the present work as an attempt to elucidate the mechanism of the oxidation reaction of the Cu atom by nitrous oxide based on our recent work (Kryachko, E. S.; Vinckier, C.; Nguyen, M. T. J Chem Phys 2001, 114, 7911) on the electron attachment to this molecule. We suggest that the title reaction in its Arrhenius regime occurs via the nonadiabatic electron transfer from Cu to the oxygen atom at the crossing of the potential energy surfaces Cu(4s ²S_1/2) + N₂O(X ¹Σ⁺) and Cu⁺ + N₂O^?, where the latter is linked to the complex N₂O^? originated from the higher‐energy T‐shape N₂O molecule and discovered in the aforementioned work. The calculations performed in the present work using a variety of quantum chemical methods support the proposed model. We also show the existence of other reaction pathways of the title reaction that, we believe, contribute to its non‐Arrhenius behavior observed experimentally at T > 1190 K. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

稀土元素铒对Al-4Cu合金组织与性能的影响

采用拉伸力学性能测试、硬度测试、金相组织观察、透射电镜与能谱分析等方法, 研究了不同量稀土元素Er对Al-4Cu合金组织与性能的影响, 结果表明 稀土Er能够细化Al-4Cu合金的枝晶网胞组织;Er元素对Al-4Cu 合金的再结晶行为起到了抑止作用, 添加0.2% Er能使Al-4Cu合金的再结晶起始温度提高80 ℃左右, 再结晶终了温度提高50 ℃左右; 不同量稀土元素Er不能改善Al-4Cu合金的拉伸力学性能, 甚至在一定程度上使合金的力学性能降低, 这是因为添加到Al-4Cu合金中的Er元素并没有与Al作用形成细小的Al3Er颗粒, 而是与Al, Cu发生交互作用形成了低熔点共晶Al8Cu4Er相, 这使合金的力学性能在一定程度上有所降低.