Pd/La0.5Pb0.5Mn0.9Sn0.1O3对甲苷伯羟基的选择催化氧化

用柠檬酸络合法制备了掺杂钙钛矿型复合金属氧化物载体, 采用沉淀法负载活性组分钯得到催化剂Pd/La0.5Pb0.5Mn0.9Sn0.1O3, 用XRD, SEM和XPS对载体和催化剂结构进行了表征分析, 考察了催化剂和氧化工艺条件对甲基葡萄糖苷的伯羟基选择氧化合成葡萄糖醛酸及其内酯的催化活性的影响. 结果表明, 载体La0.5Pb0.5Mn0.9Sn0.1O3由于掺杂效应而具有较强的助氧化还原能力, 有利于实现活性组分Pd在催化过程中的氧化还原循环. 在Pd负载量为1%、温度70 ℃、pH值为9的条件下, 葡萄糖醛酸及内酯的总收率达到60%, 反应选择性良好.     

CuO/Ce0.5Ti0.5O2的制备与表征及其对NO+CO反应的催化活性

以Ce0.5Ti0.5O2为载体, 采用浸渍法制备了不同负载量的CuO/Ce0.5Ti0.5O2催化剂, 通过TPR、XRD和激光Raman光谱等技术对其进行了表征, 并在色谱-微反装置上考察了催化剂对NO+CO反应催化性能. 结果表明, CuO/Ce0.5Ti0.5O2催化剂对NO+CO反应的活性与CuO负载量有关; 500 ℃焙烧的催化剂, 当CuO的负载量(w)为22%时, 催化剂的活性最好; 14%CuO/Ce0.5Ti0.5O2在700 ℃焙烧具有最佳催化活性, 这可能与复合载体形成了CeTi2O6的结构有关. TPR结果表明, CuO在Ce0.5Ti0.5O2上出现了四种还原能力不同的物种, α和β峰是载体表面高度分散的CuO物种, γ峰是与Ce0.5Ti0.5O2相互作用较强的孤立CuO晶簇的还原峰, δ峰是载体表面晶相CuO的还原峰; XRD结果表明700 ℃焙烧的样品中已出现了新复合氧化物CeTi2O6的晶相峰, 随焙烧温度的升高, 此晶相峰也变得更加明显, 这说明高温焙烧有利于Ce与Ti发生固相反应而形成CeTi2O6结构; Raman结果表明, 焙烧后的Ce0.5Ti0.5O2并不是简单的TiO2和CeO2的复合, 而是形成了新的晶相结构, 这也进一步验证了CeTi2O6结构的生成.     

离子排斥色谱法同时测定葡萄糖醛酸和内酯及葡萄糖醛酸稳定性

建立了同时检测葡萄糖醛酸和葡萄糖醛酸内酯的离子排斥色谱法。 采用Boston HC-B75 H+色谱柱进行分离,以5 mmol/L H2SO4水溶液为流动相,流速0.6 mL/min,柱温25 ℃,紫外检测波长220 nm;根据外标法定量,葡萄糖醛酸和内酯分别在10～1200 mg/L和5～600 mg/L范围内线性良好（r＞0.9999）;葡萄糖醛酸、葡萄糖醛酸内酯的最低检测限及定量限均分别为0.1和0.3 mg/L,精密度实验RSD分别为1.00%和0.35%,平均回收率分别为99.69%和98.21%。 该检测方法简便、快速、灵敏,可用于葡萄糖醛酸和葡萄糖醛酸内酯的同时测定。 温度、pH值和溶剂对葡萄糖醛酸稳定性有影响,可为葡萄糖醛酸的分析与制备研究提供参考依据。     

CuO/Ti0.5Zr0.5 O2催化剂上NO+CO反应活性的研究

以Ti0.5Zr0.5O2复合氧化物为载体，采用浸渍法制备了不同负载量的CuO／Ti0.5Zr0.5O2(TZ)催化剂，考察了催化剂对NO的反应活性，并用TPR、TG-DTA和NO-TPD等技术对催化剂进行了表征。结果表明，CuO的负载量和焙烧温度对催化剂的活性均有影响。30％CuO／Ti0.5Zr0.5O2(500℃，2h)在反应温度为400℃时NO转化率为100％。TPR结果表明，CuO负载量≤12％时，在TPR上出现了2个还原峰(即α和β峰)；而进一步提高CuO的负载量，出现了γ还原峰，推测α峰为高度分散Cu物种的还原，β峰为孤立的Cu物种的还原，γ峰则为晶相CuO的还原峰。TG-DTA图谱显示在725℃左右的放热峰是ZrTiO4晶化过程的完成。NO-TPD结果表明NO吸附在TZ上的热脱附过程中，出现2个脱附峰；而NO吸附在12％CuO／TZ上，500℃和750℃焙烧的催化剂上出现3个脱附峰；而在850℃和950℃焙烧的催化剂上只出现2个脱附峰，且NO在上述不同焙烧温度的催化剂上的脱附峰温均低于载体，这表明NO吸附在CuO／TZ催化剂上比吸附在Ti0.5Zr0.5O2上更容易脱出和分解。     

由钯纳米溶胶制备Pd/Ce_(0.5)Zr_(0.5)O_2催化剂及其表征研究

采用超声膜扩散还原法制备出金属Pd纳米溶胶,然后从Pd纳米溶胶出发,采用不同方法制备出系列纳米Pd/Ce0.5Zr0.5O2催化剂。采用TEM观察Pd纳米粒子的形貌,采用N2吸/脱附,XRD,TPR和ICP对Pd/Ce0.5Zr0.5O2催化剂进行表征,并考察比较了各催化剂对CO+O2的催化活性差别,结果表明:先制备Pd纳米溶胶,再负载于载体上的方法制得的催化剂金属负载量较低,但是其活性最高,CO在150℃就能完全转化,金属分散度较高,活性Pd物种还原温度低,催化剂的CO低温活性与H2还原温度和金属分散度有关。这种催化剂制备方法为在提高催化剂活性的同时降低贵金属用量提供了可能。     

Co/Ce0.5Zr0.5O2催化剂的制备及甲烷部分氧化制合成气

利用共沉淀法制备了具有介孔结构的Ce_0.5Zr_0.5O₂固溶体载体,然后浸渍不同质量分数(10%、20%、30%)的活性组分钴,制备了系列Co/Ce_0.5Zr_0.5O₂催化剂。利用N₂物理吸附(BET)、X射线粉末衍射(XRD)、H₂-程序升温还原(H₂-TPR)、扫描电子显微镜(SEM) 、透射电子显微镜(TEM) 、 程序升温氧化(TPO)和热重(TG)等手段对制备和反应后的催化剂进行了表征,研究了它们对甲烷部分氧化制合成气反应的催化性能。研究结果表明,铈锆固溶体负载的钴比较容易被还原,该系列催化剂具有较高的活性和对H₂及CO的选择性,且随Co含量的增加,催化剂的活性和对H₂和CO的选择性得到提高的同时,也增强了催化剂的抗积炭性能。     

钨酸钠/过氧化氢体系对葡甲苷伯羟基的选择催化氧化

采用钨酸钠/过氧化氢体系对甲基葡萄糖苷的伯羟基进行选择催化氧化制备葡萄糖醛酸及其内酯,考察了不同催化氧化工艺条件对反应收率的影响,产物用HPLC检测,同时对反应机理进行了初步探讨。 结果表明, 该体系对葡甲苷伯羟基的氧化具有较好的催化活性和反应选择性,葡萄糖醛酸及其内酯总收率可达到74.07%。 与传统的淀粉硝酸氧化法工艺相比,该方法具有资源节约、环境友好的特点。     

B掺杂Cd0.5Zn0.5S光催化剂制氢性能研究

采用浸渍法制备了B掺杂的Cd0.5Zn0.5S光催化剂,考察了不同B掺杂量的Cd0.5Zn0.5S催化剂在可见光光照下的放氢活性和稳定性.实验结果表明,B掺杂可以显著提高催化剂的活性和稳定性.B的掺杂量对催化剂的活性有显著影响,最佳担载量为2%.在利用XRD、PL、XPS、UV-V is等手段对催化剂表征的基础上,结合光催化性能测定结果与催化剂表征结果,初步探讨了B掺杂对Cd0.5Zn0.5S光催化剂性能的影响机制.结果表明,B掺杂显著地增强了B/Cd0.5Zn0.5S催化剂的紫外-可见漫反射和荧光光谱强度.XPS结果表明,催化剂中的B物种不是以简单氧化物的形式存在,而可能是通过某种化学反应与Cd0.5Zn0.5S光催化剂作用,使催化剂的性能得以改善.     

K-Ce_(0.5)Zr_(0.5)O_2催化碳颗粒物燃烧性能

用等体积浸渍法制备了不同K负载量的xKNO3-Ce0.5Zr0.5O2系列催化剂,用程序升温氧化反应(TPO)考察催化剂对碳颗粒物(soot)燃烧的催化活性.并采用XRD、BET、FT-IR、XPS等技术对KNO3负载催化剂进行表征.结果表明KNO3负载量对催化剂的比表面、表面化学环境有显著的影响;KNO3能使催化剂对soot的催化燃烧活性有较大提高,且存在最佳负载量,当x=0.5时,催化剂的活性最好,碳颗粒物的起燃温度(T)i和峰顶温度(Tp)分别为290℃和360℃.在反应过程中,KNO3熔融状态的形成和K2CO3的生成,使催化活性明显提高.     

CuO/Ce0.5Zr0.5O2的结构特征及催化性能表征

以硝酸铈和硝酸锆为原料,采用共沉淀法制备了不同摩尔比(X=0,0.1,0～1.0)的CexZr1-xO2样品.并以Ce0.5Zr0.5O2为载体,采用浸渍法负载不同含量的CuO,用色谱流动法考察其对CO的氧化活性.并用XRD,TPR和BET等技术对CuO/Ce0.5Zr0.5O2各样品进行了表征,结果表明,当CuO负载量为10.0%时,催化剂CO的氧化活性最高;XRD测定表明催化剂氧化活性的高低与铜物种在Ce0.5Zr0.5O2上的分散状态有关;TPR结果亦显示活性的高低与Ce0.5Zr0.5O2上分散较好的铜物种的α还原峰及分散较差的γ还原峰的峰温及形状有关.     

Magnetoresistance in La0.5Sr0.5MnO2.5

Resistance measurements indicate the presence of magnetoresistance in the La_0.5Sr_0.5MnO_2.5 brownmillerite related compound. An 80 % of magnetoresistance is found at 75 K. In spite of the partial break‐up occurring at the 3D network of octahedra sharing corners, characteristic of the full oxygen content perovskite phase, the oxygen deficient compound exhibits complex magnetic and electric properties. Such behavior can be explained on the basis of ferromagnetic and metallic clusters randomly distributed at the octahedral layers separated from each other by an insulating antiferromagnetic matrix. AC susceptibility measurements suggest spin glass behavior at low temperature as a consequence of the competition between different magnetic interactions.     

Amorphous Mo-doped NiS0.5Se0.5 Nanosheets@Crystalline NiS0.5Se0.5 Nanorods for High Current-density Electrocatalytic Water Splitting in Neutral Media

It is vitally important to develop highly active, robust and low-cost transition metal-based electrocatalysts for overall water splitting in neutral solution especially at large current density. In this work, amorphous Mo-doped NiS_0.5Se_0.5 nanosheets@crystalline NiS_0.5Se_0.5 nanorods (Am−Mo−NiS_0.5Se_0.5) was synthesized using a facil one-step strategy. In phosphate buffer saline solution, the Am−Mo−NiS_0.5Se_0.5 shows tiny overpotentials of 48 and 209 mV for hydrogen evolution reaction (HER), 238 and 514 mV for oxygen evolution reaction (OER) at 10 and 1000 mA cm⁻², respectively. Moreover, Am−Mo−NiS_0.5Se_0.5 delivers excellent stability for at least 300 h without obvious degradation. Theoretical calculations revealed that the Ni sites in the defect-rich amorphous structure of Am−Mo−NiS_0.5Se_0.5 owns higher electron state density and strengthened the binding energy of H₂O, which will optimize H adsorption/desorption energy barriers and reduce the adsorption energy of OER determining step.     

SrAu0.5Pt0.5 and CaAu0.5Pt0.5, analogues to the respective Ba compound,but featuring purely intermetallic behaviour

Both, SrAu_0.5Pt_0.5 and CaAu_0.5Pt_0.5, have been synthesized by reaction of corresponding mixtures of the pure elements at 1223 K in an argon atmosphere, and characterized by single-crystal X-ray analysis as well as by magnetic susceptibility and electric resistivity measurements. The new compounds crystallize in the CrB type of structure and thus are isostructural to BaAu_0.5Pt_0.5 (SrAu_0.5Pt_0.5: Cmcm; a = 4.262(1) Å; b = 11.435(3) Å; c = 4.632(1) Å; Z = 4; CaAu_0.5Pt_0.5: Cmcm; a = 3.9858(4) Å; b = 10.920(1) Å; c = 4.5249(5) Å; Z = 4). SrAu_0.5Pt_0.5 as well as CaAu_0.5Pt_0.5 are poor metallic conductors with ρ_300K = 0.95 mΩ.cm and ρ_300K = 3.93 mΩ.cm, respectively, and featuring diamagnetic behaviour.According to ESCA measurements SrAu_0.5Pt_0.5 and CaAu_0.5Pt_0.5 both can be formulated as having intermetallic character, showing a negligible electron transfer from alkaline earth metals to the noble metals.     

Magnetoelectric perovskite (Bi0.5Pb0.5)(Fe0.5Zr0.5)O3: Preparation,structural and magnetic properties

The perovskite (Bi_0.5Pb_0.5)(Fe_0.5Zr_0.5)O₃ was synthesized by solid-state reaction in an attempt to find magnetoelectric materials, in which ferroelectricity and ferromagnetism coexist. This complex perovskite has been studied by X-ray and neutron powder diffraction in combination with magnetic measurements. The compound crystallizes in the orthorhombic space group Pbam with a ～ √2a_p, b ～ 2√2a_p and c ～ 2a_p (with a_p ～ 4.057 Å). The field and temperature dependence of the magnetization combined with neutron diffraction data showed antiferromagnetic behavior with the Neel temperature, T_N ～ 450 K. Rietveld refinements of neutron powder diffraction data collected at different temperatures, between 10 and 700 K, have been carried out in order to extract information about the thermal evolution of the nuclear and magnetic structures. A distorted orthorhombic perovskite structure was found within the whole temperature interval. The Bi/Pb and Fe/Zr ions were found to be partially ordered over the perovskite A-site and disordered over the B-site. The neutron diffraction patterns of the (Bi_0.5Pb_0.5)(Fe_0.5Zr_0.5)O₃ sample showed evidence of a long-range magnetic ordering below T_N with a propagation vector k = (0,0,0) and an antiferromagnetic arrangement of the magnetic moments of the Fe³⁺ cations in the B-site. This is consistent with an A_y-type magnetic structure. The factors governing the structural and magnetic properties of (1 ? x)BiFeO₃–xPbZrO₃ solid solutions are discussed and compared with those of pure BiFeO₃ and PbZrO₃. A solid solution strategy for developing magnetoelectric properties in BiFeO₃-based compounds is described, with the aim of realizing both a spontaneous polarization and magnetization at room temperature.     

Ultra-incompressible Ternary Diborides Re_（0.5）Ir_（0.5）B_2,Re_（0.5）Tc_（0.5）B_2,Os_（0.5）W_（0.5）B_2 and Os_（0.5）Ru_（0.5）B_2：Density Functional Calculation

In this paper, density functional computations have been applied to the structural, elastic and electronic properties of ternary transition metal diborides Re0.5Ir0.5B2, Re0.5Tc0.5B2, Os0.5W0.5B2 and Os0.5Ru0.5B2 in hexagonal (P63/mmc) and orthorhombic (Pmmn) structures with both local density approximation and generalized gradient approximation. LDA gives smaller lattice parameters and larger elastic moduli than GGA. Both results show that the hexagonal ones are more stable than orthorhombic ones except Os0.5Ru0.5B2. Moreover, the hexagonal structure has superior elastic property than orthorhombic one. Generally speaking, the calculated elastic moduli of Re0.5Ir0.5B2 and Os0.5Ru0.5B2 are smaller than those values of Re0.5Tc0.5B2 and Os0.5W0.5B2 within the same structure because of the filling of antibonding states. The relativistic effects result in weaker bonds of Tc-B (Ru-B) than those of Re-B (Os-B). All the diborides are ultra-incompressible. Re0.5Tc0.5B2 has the largest shear modulus and it is a promising superhard diboride like Os0.5W0.5B2. The elastic properties are in high correlation with the bond strength. The shear moduli are more sensitive than the bulk moduli to the bond strength.     

Effect of ZnO on sintering and microwave dielectric properties of 0.5CaTiO3-0.5 (Li0.5La0.5) TiO3 ceramics

The novel calcium titanate-lithium lanthanum titanate doped with zinc oxide (0.10, 0.30, and 0.50 mol. %) ceramic samples were prepared by solid-state reaction route. The phase formation, microstructure, densification, and microwave dielectric properties were investigated. It was found that the doping with zinc oxide led to a decrease in sintering temperature by 25 ^oC as compared with pure calcium titanate lithium lanthanum titanate due to the liquid phase effect. Also, the calcium titanate lithium lanthanum titanate (10ZCTLLT&30ZCTLLT)) doped with lower zinc oxide (0.10 and 0.30 mol. %) led to higher densification parameter. This was followed by increasing the zinc oxide doping up to (0.50 mol. %) which resulted in a decrease in densification and microwave dielectric properties which may be attributed to increase in porosity and grain growth upon the evaporation of zinc and oxygen vacancy. This led to the increase in dielectric loss (≈10 × 10^?4) value with 50ZCTLLT. Hence, the best result of microwave dielectric characteristics was obtained for 0.5CaTiO₃–0.5(Li_0.5La_0.5)TiO₃ with (0.10 and 0.30 mol. % ZnO) 10ZCTLLT and 30ZCTLLT ceramic samples sintered at 1175 ^oC/2h, with low dielectric constant (ε_r) = 4.4–10.5, very low dielectric loss = 1.07-2.23 × 10^?4 and high quality factor (Q x ?) ≈59-55 × 10⁴ at 8 GHz. Consequently, they can be used not only in wireless satellite communications technology but also can be used in the fifth-generation telecommunication 5G technology construction.     

稀土取代的复合氧化物Eu_（0．5）RE_（0．5）Fe_（0．5）Mn_（0．

利用固相反应合成了稀土取代的复合氧化物Ｅｕ_（０．５）ＲＥ_（０．５）Ｆｅ_（０．５）Ｍｎ_（０．５）Ｏ_３（ＲＥ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ）．测量了这些化合物的ＸＲＤ和ＸＰＳ谱。在ＸＰＳ研究中发现，稀土取代而使稀土元素本身的结合能相对于其倍半氧化物中的有所降低；在取代的复合氧化物中，随着ＲＥ离子半径的减小，Ｆｅ、Ｍｎ的结合能随之增加。     

Synthesis and structure of CsLi0.5Al0.5PO4

A new phosphate CsLi_0.5Al_0.5PO₄ with a structure related to the β-tridymite structure has been synthesized by a precipitation method. X-ray powder diffraction, electron probe microanalysis, second harmonic generation of laser radiation, and IR spectroscopy have been used for studying the compound. Differential scanning calorimetry shows that the synthesized phosphate undergoes phase transitions at T _tr = 68 and 130°C. The crystal structure of CsLi_0.5Al_0.5PO₄ was refined on the basis of X-ray powder diffraction data by the Rietveld method in space group P2₁/a (Z = 8) with the unit cell parameters a = 17.8323(3) Å, b = 5.4250(1) Å, c = 9.3666(2) Å, β = 89.984(8)°, V = 906.10(9) ų.