Synthesis,characterization, and electrochemistry of monophosphine‐containing diiron propane‐1,2‐dithiolate complexes related to the active site of [FeFe]‐hydrogenases

Five monophosphine‐substituted diiron propane‐1,2‐dithiolate complexes as the active site models of [FeFe]‐hydrogenases have been synthesized and characterized. Reactions of complex [Fe₂(CO)₆{μ‐SCH₂CH(CH₃)S}] ( 1 ) with a monophosphine ligand tris(4‐methylphenyl)phosphine, diphenyl‐2‐pyridylphosphine, tris(4‐chlorophenyl)phosphine, triphenylphosphine, or tris(4‐fluorophenyl)phosphine in the presence of the oxidative agent Me₃NO·2H₂O gave the monophosphine‐substituted diiron complexes [Fe₂(CO)₅(L){μ‐SCH₂CH(CH₃)S}] [L = P(4‐C₆H₄CH₃)₃, 2 ; Ph₂P(2‐C₅H₄N), 3 ; P(4‐C₆H₄Cl)₃, 4 ; PPh₃, 5 ; P(4‐C₆H₄F)₃, 6 ] in 81%–94% yields. Complexes 2 – 6 have been characterized by elemental analysis, spectroscopy, and X‐ray crystallography. In addition, electrochemical studies revealed that these complexes can catalyze the reduction of protons to H₂ in the presence of HOAc.     

Correlation between Boron Isotope of Coral Acropora and pH Value of Seawater Surface

A water circulation system with the almost same element composition and socket type was adopted in coral Acropora culture under different seawater pH value conditions and the data of the relationship between boron isotopic compositions of coral and seawater pH value by thermoelectric ionization mass spectrometer were obtained. According to the correlations between α_carb-3 of coral and the pH value of cultured seawater, α_carb-3 was not a constant but related to pH value, indicating that B(OH)₃ also incorporated carbonate. Therefore, the theoretical formula could not be used to calculate the seawater pH value from the δ¹¹B_carb value of the measured marine biological carbonate. The empirical equations obtained experimentally would be an alternative method to calculate the seawater pH value. In addition, the mixed precipitation of CaCO₃ and Mg(OH)₂ was found in aquaculture tanks with high pH value, and the δ¹¹B of the solid was significantly higher than that of cultured seawater. The result indicated that the presence of Mg(OH)₂ had a significant effect on the boron isotope fractionation, which deserved our attention.     

冷冻法硝酸磷肥工艺中酸不溶物提纯研究

采用酸浸、磁选酸浸、水淬/研磨酸浸等不同工艺对冷冻法硝酸磷肥生产工艺中的废渣-酸不溶物进行了提纯处理,利用X射线荧光光谱仪(XRF测试)对酸不溶物提纯前后各成分含量的变化进行了分析,从中得出了不同工艺流程对酸不溶物纯度的影响,最终确定了最佳的酸不溶物处理工艺.结果表明:在酸浸实验中,盐酸酸浸效果最佳,可将酸不溶物中SiO2纯度达到82.43;;在酸浸工艺前加入磁选、水淬、研磨的工序均可有效提升酸不溶物的提纯效果;冷冻法硝酸磷肥工艺中酸不溶物最佳的提纯工艺路线为:干燥、筛分、水洗、磁选、研磨、盐酸酸浸,处理后酸不溶物中SiO2纯度达到88.92;,符合微硅粉的生产要求.     

La1-x CaxAl0.8Cr0.2O3/CaZrO3(0≤x≤0.2)复相陶瓷材料发射率的研究

以La2O3、Al2O3、ZrO2、Cr2O3、CaCO3为原料,通过高温固相反应法制备La1-xCaxAl0.8 Cr0.2O3/CaZrO3(0≤x≤0.2)复相陶瓷材料,分别通过XRD、SEM和EDS等仪器对试样的物相组成和显微结构进行分析,利用紫外可见近红外分光光度计测量其红外吸收曲线.结果 表明:当CaZrO3理论生成量和La1-xCaxAl0.8Cr0.2O3的摩尔比小于0.20时复相陶瓷材料在0.76～2.5 μm的发射率较La0.8 Ca0.2Al0.8Cr0.2O3得到进一步提高,当CaZrO3理论生成量和La1-xCaxAl0.8Cr0.2O3的摩尔比为0.04时发射率最佳.     

纳米硅增强纳米纤维薄膜的制备与研究

利用纳米硅粉和聚乙烯吡咯烷酮(PVP)的乙醇混合溶液,通过静电纺丝和碳化制备了Si/C纳米纤维薄膜.通过XRD、SEM、XPS、拉伸测试和TG法对样品进行表征.结果表明,纤维直径、薄膜表面元素含量、碳化薄膜强度可以通过控制Si与PVP含量而调节;当Si与PVP的质量比为0.2时,碳化薄膜拉伸强度最高其值为(6.1±0.3)MPa,继续增加硅的含量其薄膜强度明显降低.     

氮化镓单晶生长研究进展

氮化镓(GaN)作为第三代宽禁带半导体核心材料之一,具有高击穿场强、高饱和电子漂移速率、抗辐射能力强和良好的化学稳定性等优良特性,是制作宽波谱、高功率、高效率光电子、电力电子和微电子的理想材料.受制于氮化镓单晶衬底的尺寸、产能及成本的影响,当前的GaN基器件主要基于异质衬底(硅、碳化硅、蓝宝石等)制作而成,GaN单晶衬底的缺乏已成为制约GaN器件发展的瓶颈.近年来,国内外在GaN单晶衬底制备方面取得了较大的进展.本文综述了氮化镓单晶生长的最新进展,包括氢化物气相外延法、氨热法和钠助熔剂法的研究进展,分析了各生长方法面临的挑战与机遇,并对氮化镓单晶材料的发展趋势讲行了展望.     

MoSi2-SiC复合材料制备及抗热震性能研究

本文采用直接熔渗法制备二硅化钼-碳化硅(MoSi2-SiC)复合材料.以碳化硅(SiC)(粒度为0～2.5 mm、≤240目)为主要原料,水溶性树脂为结合剂,经混炼、成型、烘干后得到SiC坯体,再用二硅化钼(MoSi2)(D50 =3μm)粉末掩埋SiC坯体,在真空条件下2000℃保温3h进行熔渗烧结,制备出MoSi2-SiC复合材料.采用阿基米德排水法研究了MoSi2-SiC复合材料的显气孔率、体积密度;采用三点抗弯法测试了MoSi2-SiC复合材料1400℃抗折强度;采用热线法测试了MoSi2-SiC复合材料导热系数;采用X射线衍射测试了MoSi2-SiC复合材料的物相组成;采用SEM测试了MoSi2-SiC复合材料的显微结构;分别采用风冷法和水冷法对比研究了MoSi2-SiC复合材料、重结晶碳化硅(R-SiC)、氮化硅-碳化硅(Si3N4-SiC)三种材料抗热震性.结果表明:MoSi2在烧结过程中部分发生分解,生成了Mo5Si3,MoSi2、Mo5Si3填充于SiC的内部并实现烧结致密化,使MoSi2-SiC复合材料的显气孔率显著降低至5.7;,体积密度为3.59 g.cm-3.MoSi2-SiC复合材料中MoSi2、Mo5Si3含量分别为10wt; ～ 15wt;、3wt; ～ 5wt;.1000℃下MoSi2-SiC的导热系数为46.5W·m-1 ·K-1,显著高于R-SiC(28.3 W.m-1.K-1)材料、Si3N4-SiC(16.8 W.m-1.K-1)材料.综上所述,MoSi2-SiC复合材料的抗热震性能显著优于R-SiC材料、Si3N4-SiC材料.     

Mg/Cd共掺杂ZnO电子结构与光学性质的第一性原理研究

采用基于密度泛函理论的第一性原理平面波超软赝势法,研究了Mg/Cd(不同的Cd浓度)共掺杂ZnO的电子结构和光学性质.研究表明:Mg/Cd共掺杂ZnO,体系的晶胞尺寸变大,但结构稳定.当Mg/Cd为1:1时,吸收边略微发生蓝移.随Cd的掺杂浓度增加,导带部分逐渐下移,禁带宽度变窄,出现红移现象.除此之外体系的吸收率和反射率也减小.说明Mg/Cd共掺杂ZnO,不仅使得体系光学谱丰富,而且透射性增强.这对实验中制备出高透射率的材料具有一定的指导意义.     

SrTiO3/Mg6Ti5O16复合陶瓷的微波介电性能研究

通过传统固相烧结法制备了xSrTiO3-(1-x)Mg6Ti5O16微波介质陶瓷,并研究其晶体结构、显微结构及微波介电性能.xSrTiO3-(1-x)Mg6Ti5O16复合陶瓷主要含有MgTiO3、SrTiO3和Mg6Ti5O16三相;复合陶瓷晶粒分布紧密,尺寸大小不均匀;适当增加SrTiO3含量可以有效提高介电常数和品质因数,并使谐振频率温度系数趋于正值.1420 ℃烧结的3.8;SrTiO3-96.2;Mg6Ti5O16复合微波陶瓷可获得最佳微波介电性能:εr=17, Q×f =42729 GHz和τf=5 ppm/℃.     

热熔还原法制备超硬复合相氮化碳及其工艺探索

本文采用热熔还原法,以聚氯乙烯、氯化铵、氧化铁为原料制备复合超硬相氮化碳(α/β-C3 N4).采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)以及透射电子显微镜(TEM)对样品进行表征.在此基础上分析了不同温度和原料配比下合成复合相C3 N4的物相组成及形貌变化.结果表明样品形貌随着原料配比的不同在颗粒、棒状、纳米线之间转变.当C、N和Fe之间摩尔比为3:4:0.4时,所制备出的样品呈纳米线状,纳米线的直径约为15 nm,结晶性良好.而在其它配比下,只能获得棒状或颗粒状α/β复合相C3 N4.