CVD制备MB_2(M=Ti,Zr,Hf)研究进展

MB2(M=Ti,Zr,Hf)是ⅣB族过渡金属的硼化物,化学气相淀积(CVD)是制备MB2类薄膜材料和保护涂层的最有效技术之一。对MB2类材料CVD制备的热力学进行了简要分析。阐述了反应前驱体的选择和应用。对近年来MB2类材料的CVD合成制备的最新研究报道进行了整理和总结,对MB2类材料的CVD制备发展进程进行了概括。从CVD过程的设备工艺到产物的表征,从显微结构的定性研究到晶格常数匹配的定量分析,均进行了简要的阐述。最后,对CVD工艺制备MB2类材料的发展和应用前景进行了展望。     

介孔CuCe/M/CuCe(M=Co,Mn,Zr)催化剂富H_2中优先氧化CO的催化性能

优先氧化是去除富H2中CO最有效的方法,铜铈催化剂是该领域的研究热点。以SBA-15为模板剂,采用纳米刻蚀法合成系列介孔Cu Ce/M/Cu Ce(M=Co,Mn,Zr)催化剂,采用XRD、N2吸附-脱附、TEM、H2-TPR和O2-TPD对催化剂结构及形貌进行表征,并对其在富H2中CO优先氧化性能进行研究。结果表明,Mn有利于催化剂表面吸附氧的增加,有助于大量氧空位的产生,进而促进CO优先氧化性能的提高;Zr的加入抑制了Cu O的还原,且其表面氧脱附温度范围过宽,不利于催化剂催化氧化性能的释放。掺杂Co与Mn可以形成Ce-Cu-M-O固溶体,促进了催化剂表面氧和晶格氧之间的相互转化,最终有利于铜铈催化剂CO优先氧化性能的提高。     

Separation of Xenon and Krypton in the Metal–Organic Frameworks M2(m-dobdc) (M=Co,Ni)

The separation of Xe and Kr from air is challenging owing both to the very low atmospheric concentrations of these gases and the need for their distillation at cryogenic temperatures. Alternatively, separation processes based on adsorption could provide a less energy-intensive route to the isolation of these gases. Here, we demonstrate that the metal–organic frameworks M₂(m-dobdc) (M=Co, Ni; m-dobdc⁴⁻=4,6-dioxido-1,3-benzenedicarboxylate) effectively separate Xe and Kr at ambient temperatures based on the different adsorption enthalpies of each gas at the coordinatively-unsaturated M²⁺ sites in each material. In situ Xe- and Kr-dosed powder X-ray diffraction studies further reveal key differences in the binding of Xe and Kr within the materials. In particular, while both gases adsorb near the framework open metal sites at 200 K, much higher Xe occupancies are observed at these sites relative to Kr, corroborating a stronger interaction of the polarizing M²⁺ cations with Xe. Further, while krypton is only found located above the open metal sites, two additional adsorption sites are observed for xenon, correlating with the stronger adsorption of Xe over Kr in these materials. These results suggest the possible utility of employing M₂(m-dobdc) materials in the adsorptive separation of Xe and Kr.     

TiO2/MS(M=Cd,Zn,Cu)纳米复合光催化剂的制备及光催化活性研究

在室温下,以正丁胺为模板剂[1],通过简单的化学方法合成ZnS,CdS,CuS纳米颗粒.以钛酸丁酯为主要原料,用溶胶-凝胶法制备了TiO2/ZnS,TiO2/CdS,TiO2/CuS的纳米复合物,采用UV-Vis对其进行简单表征.并通过测定甲基橙的脱色速率,评价所有样品的光催化活性.结果表明:不同的硫化物在同一复合量时...     

Metal–metal interaction through CH2–CN bridge: synthesis and characterization of [CpM(L2)NCCH2Fc]PF6 complexes (Fc=ferrocenyl; L=1/2 dppe,PPh3; M=Fe,Ru)

The new complexes [CpM(L₂)NCCH₂Fc]PF₆ (M=Fe 1, Ru 2; Fc=ferrocenyl), have been prepared from reaction of CpM(L₂)X and the ligand Fc–CH₂CN 3 in methanol and in the presence of NH₄PF₆. The compounds were characterized by elemental analysis as well as spectroscopic methods. Electrochemical as well as near-IR measurements suggest a weak metal–metal interaction for the Fe(II)–Fe(III) complex. Hush parameters for this mixed-valence complex suggest a class II Robin–Day type with a moderate metal–metal interaction similar to that observed in the related pyridine bridged systems (η⁵-C₅H₅)Fe-η⁵-C₅H₄–C₅H₄N–ML_n. The unusual electron transfer through a insulating CH₂ group is the first such example for an asymmetric binuclear system.     

Hydrogenation of Sunflower Oil over M/SiO2 and M/Al2O3 (M = Ni,Pd, Pt,Co, Cu) Catalysts

This work is aimed at evaluating the performance of several catalysts in the partial hydrogenation of sunflower oil. The catalysts are composed of noble (Pd and Pt) and base metals (Ni, Co and Cu), supported on both silica and alumina. The following order can be proposed for the effect of the metal on the hydrogenation activity: Pd > Pt > Ni > Co > Cu. At a target iodine value of 70 (a typical value for oleomargarine), the production of trans isomers is minimum for supported nickel catalysts (25.7–32.4 %, depending on the operating conditions). Regarding the effect of the support, Al₂O₃ allows for more active catalysts based on noble metals (Pd and Pt) and Co, the effect being much more pronounced for Pt. Binary mixtures of catalysts have been studied, in order to strike a balance between catalyst activity and product distribution. The results evidence that Pd/Al₂O₃–Co/SiO₂ mixture has a good balance between activity and selectivity, and leads to a very low production of trans isomers (11.8 %) and a moderate amount of saturated stearic acid (13.5 %). Consequently, the utilization of cobalt‐based catalysts (or the addition of cobalt to other metallic catalysts) could be considered a promising alternative for the hydrogenation of edible oil.     

SiO2-Al2O3-Na2O-MO(M=Ca,Ba)玻璃在SOFC中的性能研究

从玻璃的粘结强度与气密性角度出发,对在固体氧化物燃料电池(SOFC)领域中应用较为广泛的SiO₂-Al₂O₃-Na₂O-CaO(S1)和SiO₂-Al₂O₃-Na₂O-BaO(S2)两款密封玻璃进行了研究对比。研究发现,S1与SOFC的粘结强度为2.00 MPa, 30 kPa下的气体泄漏率为0.041 sccm/cm,而S2与SOFC的粘结强度为3.93 MPa, 30 kPa下的气体泄漏率为0.027 sccm/cm,结果表明,S2的密封效果优于S1。750℃下H₂/Air=0.6/3.0 slm时,分别以S1和S2密封的SOFC开路电压(OCV)对比验证了以上结果,前者(S1)的OCV值只有0.949 V,远低于后者(S2)的1.08 V。最后结合热膨胀系数(TEC)以及微观形貌对两款密封材料进行了深入探讨分析,为Ca系和Ba系高温密封玻璃的优化提供了借鉴。     

Sm_xCe_(1-x)O_(2-x/2)(x=0.05,0.1,0.15)陶瓷的热物理性能

以Sm_2O_3和Ce(NO_3)·6H_2O为原料,采用溶胶凝胶法和固相烧结法合成了Sm_xCe_(1-x)O_(2-x/2)陶瓷材料。研究了材料的相结构和显微组织,热导率和热膨胀。结果表明:合成的Sm_xCe_(1-x)O_(2-x/2)陶瓷纯净并具有单一的萤石结构。其显微组织致密,晶界清晰。Sm_2O_3掺杂能降低CeO_2的热导率,其1000℃时的热导率在2.2~2.6 W/m·K之间,与氧化钇部分稳定氧化锆的热导率相当;Sm_xCe_(1-x)O_(2-x/2)陶瓷的热膨胀随Sm_2O_3含量的增加而降低,其1200℃时的热膨胀系数大于13×10~(-6)/K。     

M2WO3MoO4(M=Li,Na):Eu3+的发光特性

针对目前商用白光二极管普遍缺少红光部分辐射的问题,研究了M2WO3MoO4(M=Li,Na):Eu3 样品的结构和发光特性.M2WO3MoO4(M=Li,Na):Eu3 体系在长波紫外(400nm)附近有较强的吸收峰;在394nm光波长的激发下,594,617nm附近都有很强的发光峰.在电偶极子的作用下,617nm处的发光峰最强.由于阳离子半径大小的缘故,Li2(MoO4)比Na2(MoO4)发光要强;虽然W6 的离子半径比Mo6 的大,W含量的增加使Eu3 和O2-之间的距离增加,减少了离子互换的可能性,但W-O化学键对浓度淬灭的影响也随之增加并占主导作用,因此,Li2WO3MoO4比Li2(MoO4)的发光要强.     

Co-Cu-M(M=Fe,Mn,Ni,Zn,Ce)催化剂催化分解N_2O性能

采用等体积浸渍法制备了添加不同金属助剂的铜钴复合氧化物(Co/Cu质量比为0.6)催化剂,考察了其催化N_2O分解的活性。结果表明,稀土金属Ce以及过渡金属Fe对钴铜催化剂催化N_2O分解的活性有明显的促进作用。通过分析催化剂的X射线衍射(XRD)、比表面积测定(BET)、氢气程序升温还原(H_2-TPR)以及扫描电镜(SEM)等表征结果发现,助剂的添加并没有引起催化剂晶相结构的明显改变,但可以提高钴离子与铜离子的还原能力。尤其是添加Ce和Fe之后还原峰向低温区显著移动,从而提高了钴铜复合氧化物催化剂的活性。     

MxSr1-xAl2O4(M=Ca,Zn):Eu2+的微波合成及发光性能

用微波法合成了强耐水性SrAl2O4:Eu2 ,MxSr1-xAl2O4:Eu2 (M=Ca Zn)发光粉体.X射线衍射结果表明:所得SrAl2O4为α-SrAl2O4,单斜晶系,晶胞参数a=0.084 4nm,b=0.088 1 nm,c=0.051 5nm,β=93.249 1°.扫描电子显微镜观察粉体形貌的结果表明:产品微粒直径在300～700 nm之间,无需机械研磨可直接应用.在340 nm紫外光激发下,SrAl2O4:Eu2 的主发射峰位于513.4 nm处,少量钙离子(Ca2 )的掺入引起发射峰红移;少量锌离子(Zn2 )的掺入引起发射峰蓝移.Ca2 在微波场的作用下,增大了在基质中的极限浓度.     

Synthesis,sintering, and thermoelectric properties of Co1-xMxO (M = Na, 0 ≤ x ≤ 0.07; M = Ag, 0 ≤ x ≤ 0.05)

The structural and thermoelectric properties of Na- and Ag-substituted CoO dense ceramics have been investigated. X-ray diffraction shows that pure phase and Ag/CoO composites have been obtained for Na-doped and Ag-doped CoO, respectively. Raman spectroscopy shows an effect of Na dopants on the lattice disorder of CoO. The chemical composition, element distribution, and valence states of the samples have been characterized by Auger electron microscopy and X-ray photoelectron spectroscopy. Substitution of Co by 5 at. % Na enhances the power factor to 250 μW m⁻¹ K^-2 at 1000 K, similar to that of Ca₃Co₄O₉. The corresponding thermal conductivity is also reduced to 3.55 W.m⁻¹ K⁻¹ at 1000 K. Consequently, Co_0.95Na_0.05O exhibits the best thermoelectric figure of merit (ZT), which is 0.07 at 1000 K. On the other hand, the substitution of Ag into CoO leads to the formation of CoO/Ag composites and deteriorates ZT values.     

无铅或少铅钙钛矿CH3NH3M1-xPbxX3(M=Sn,Sr;X=Cl,Br,I)太阳能电池的研究进展

本文综述了Sn2+或Sr2+取代的无铅或少铅钙钛矿CH3NH3PbX3 (X=Cl,Br,I)的结构及其主要的制备方法,评述了各种方法的优缺点.简要介绍了无铅或少铅钙钛矿材料的能隙以及材料的稳定性对太阳能电池的影响,并对其发展前景进行了展望.     

固体超强酸催化剂S2O2-8/聚乙二醇-TiO2-M2O3(M=Al,Cr)制备乙酰丙酸

研制了固体超强酸催化剂S2O2-8-/聚乙二醇- TiO2 - M2O3(M=Al,Cr),并以赤砂糖为原料,催化水解法制备乙酰丙酸.通过单变量法考察了催化剂焙烧时间、催化剂用量、赤砂糖浓度、反应温度和反应时间等对乙酰丙酸收率的影响,并通过正交实验确定最佳工艺条件.结果表明,在催化剂焙烧时间120 min、赤砂糖浓度为10 g·L-1、催化剂用量为赤砂糖质量的15％、反应温度200℃和反应时间120 min条件下,乙酰丙酸收率达39.98％.     

20%BaCO_3/La_(0.8)Sr_(0.2)MO_3(M=Fe,Co,Mn)催化分解NO的研究

通过NO程序升温吸附脱附(NO-TPD)分析测试手段,研究了20%BaCO3/La0.8Sr0.2MO3(M=Fe、Co、Mn)催化分解NO的机理,解释La0.8Sr0.2MO3(M=Fe、Co、Mn)与BaCO3简单混合后催化分解NO的性能提升的原因。     

AM_2O_8(A=Zr,Hf;M=Mo,W)氧化物粉体的低温 液相合成及其结构控制(英文)

立方AM2O8氧化物(A=Zr,Hf:M=Mo,W)是最有希望的一类负热膨胀材料.为开发这类材料,期望获得高质量AM2O8粉体,而传统固相合成法不能达到这一目的.低温液相合成法是一种有望合成高质量AM2O8氧化物粉体的途径.本文介绍了1998年以来低温液相合成AM2O8粉体的研究进展,首先,概述了AM2O7(OH)2·2H2O脱水的合成工艺,其后讨论了用于制备醇盐或羧酸盐前驱体的凝胶技术.着重讨论了材料结构控制问题, 并提出了进一步研究方向.     

高镍系正极材料LiNi1-xMxO2(M=Co,Mn,Al,x≤0.4)储存性能的研究进展

高镍系正极材料LiNi1-xMxO2(M=Co, Mn, Al, x≤0.4),因其能量密度高、成本低廉以及环境友好等优点而引起研究者的广泛关注.但是,该材料也存在一些缺陷,如循环过程中结构不稳定、高温条件下稳定性差以及储存性能不佳等,这些缺点在很大程度上限制了其在锂电领域的广泛应用.着重分析了该材料储存性能不佳的根本原因,并总结了近年来研究人员关于改善高镍系正极材料储存性能的研究进展, 最后进一步针对改善高镍系正极材料的储存性能做出了展望.     

Li2MnO3·LiMO2(M=Co,Ni)的电子结构与性能

将富锂锰基正极材料Li₂MnO₃·LiMO₂(M=Co,Ni)分为LiMO₂和Li₂MnO₃两部分，基于密度泛函理论第一性原理方法对其分别进行了研究，分析和计算了LiMO₂(M=Co,Ni)的结构和性能及Li₂MnO₃的脱锂过程。结果表明：在LiMO₂(M=Co,Ni)和Li₂MnO₃中锂以离子形式存在，LiNiO₂体系的导电性优于LiCoO₂体系，Li₂MnO₃在脱锂过程中锂离子首先从锂层中脱出，之后从过渡金属层进一步脱锂，其中锂脱出造成的电荷变化主要由O的氧化来补偿。     

2M(E1)电路基本知识点浅析

文章主要介绍了2M(E1)电路的结构和类型,在本网通信系统中的使用,及一些常见故障和可能产生故障的原因分析。