稀土多核配合物[Ce4Ce6(μ3-O)4(μ4-O)4(acac)14(CH3O)6]·2CH3OH用于酰胺硼氢化还原
王诗怡, 陈超龙, 孔祥建, 郑兰荪, 龙腊生
【无机化学学报】doi: 10.11862/CJIC.20240342
酰胺还原加氢是获得高附加值有机化合物的一种高效但极具挑战性的方法。本研究中,我们利用乙酰丙酮(Hacac)构筑的稀土多核配合物[Ce4Ce6(μ3-O)4(μ4-O)4(acac)14(CH3O)6]·2CH3OH (Ce10)作为路易斯酸催化剂,实现了高效的酰胺硼氢化还原反应,产率可达50%~99%。此外,该方法成功应用于抗抑郁药物苯乙胺的克级合成。通过核磁共振、单晶X射线衍射等分析手段,对该反应的催化机理进行了深入探究。
关键词: 酰胺还原, 稀土多核配合物, 均相催化, 机理
Ce、Mn助剂对V2O5/TiO2催化剂催化氨选择性氧化的影响
岳鹏, 石丽瑶, 崔静磊, 张慧荣, 郭彦霞
【无机化学学报】doi: 10.11862/CJIC.20240210
以V2O5/TiO2催化剂为基体,制备了一系列Ce、Mn改性催化剂,并结合氮气吸附-脱附、X射线衍射、X射线光电子能谱、扫描电子显微镜分析了催化剂的结构及活性组成,探究了其反应活性。结果表明,制备的改性V2O5/TiO2催化剂分散性好,Ce-Mn双金属改性提高了催化剂的NH3转化率和N2选择性。Ce、Mn负载量(Ce或Mn与TiO2的质量比)分别为8%、6%时,310℃下改性材料的NH3转化率为100%,N2选择性为78%。原位漫反射傅里叶变换红外光谱表征显示催化剂表面羟基吸附的NH3会优先参与反应,温度升高后催化剂表面的Brønsted和Lewis酸位点上吸附的NH3开始参与反应,较高温度下Lewis酸位点是主要的NH3转化位点。
关键词: 氨选择性氧化, V2O5/TiO2, 催化剂, 氧化, 载体, 金属助剂, 反应机理
First-principles study on electronic structure, optical and magnetic properties of rare earth elements X (X=Sc, Y, La, Ce, Eu) doped with two-dimensional GaSe
Shenhao QIU, Qingquan XIAO, Huazhu TANG, Quan XIE
【无机化学学报】doi: 10.11862/CJIC.20240104
The electronic structure, magnetic, and optical properties of two-dimensional(2D) GaSe doped with rare earth elements X (X=Sc, Y, La, Ce, Eu) were calculated using the first-principles plane wave method based on density functional theory. The results show that intrinsic 2D GaSe is a p-type nonmagnetic semiconductor with an indirect bandgap of 2.661 1 eV. The spin-up and spin-down channels of Sc-, Y-, and La-doped 2D GaSe are symmetric, they are non-magnetic semiconductors. The magnetic moments of Ce- and Eu- doped 2D GaSe are 0.908μB and 7.163μB, which are magnetic semiconductors. Impurity energy levels appear in both spin-up and spin-down channels of Eu-doped 2D GaSe, which enhances the probability of electron transition. Compared with intrinsic 2D GaSe, the static dielectric constant of the doped 2D GaSe increases, and the polarization ability is strengthened. The absorption spectrum of the doped 2D GaSe shifts in the low-energy direction, and the red-shift phenomenon occurs, which extends the absorption spectral range. The optical reflection coefficient of the doped 2D GaSe is improved in the low energy region, and the improvement of Eu-doped 2D GaSe is the most obvious.
关键词: first principle, two-dimensional GaSe, electronic structure, magnetic property, optical property

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