【大学化学】doi: 10.12461/PKU.DXHX202411076
在化学反应动力学研究中,动力学同位素效应(KIE)为深入理解化学反应路径和机制提供了关键信息。除了广泛应用的氢/氘同位素效应外, 碳原子以及质量更大一些原子的同位素效应也日益受到关注。值得一提的是, Singleton于1995年提出了一种基于核磁共振(NMR)技术的高精度KIE (12C/13C)测量方法,为该领域带来了重要突破。该方法无需对化合物进行昂贵且复杂的同位素标记操作,利用13C的自然丰度的样品结合高分辨率NMR实验,能够直接测量12C和13C之间的KIE数值,且具有极高的精度。本文将详细介绍这一方法的理论基础、实验步骤以及应用实例,探讨其在化学反应机理和动力学研究中的重要意义与优势。
【无机化学学报】doi: 10.11862/CJIC.20240231
A mononuclear CoⅡ complex, [Co(H2dapsc)(H2O)Cl]Cl·2H2O (1), with a pentagonal bipyramidal configuration was obtained by reflux reaction of CoCl2·6H2O and 2, 6-diacetylpyridine-bis(semicarbazone) (H2dapsc) in a mixed solvent of water and ethanol. The neutral ligand H2dapsc molecule provides five coordination atoms to form the equatorial plane of 1, while a water molecule and a Cl- ion occupy their axial positions. At the same time, the solid structure contains a valence counteranion Cl- ion and two lattice water molecules. The study of DC magnetic susceptibility indicates that complex 1 has strong magnetic anisotropy. The AC magnetic properties show the existence of slow magnetic relaxation behavior, which is dominated by both direct and Raman processes. The energy barrier for magnetization reversal was 55.55 K. Based on theoretical calculations, it can be concluded that the main reason for the slow magnetic relaxation behavior is the rhombic anisotropy of the pentagonal bipyramidal structure. The calculated D and E values were 45.68 and-0.32 cm-1.
【大学化学】doi: 10.12461/PKU.DXHX202405002
专业内的实验课程在学生实践能力和综合科学素质培养上起到承上启下的作用。将“五措并举”科教融合的实验教学模式应用于“专业实验”课程建设中,从思政教育提实效、教学项目重融合、科研习惯厚基础、教学环节强实践、实验成果促创新等方面进行教学改革。以思政引领为基,科教融合为魂,开发综合型、探究型的实验项目、培养良好的实验习惯、融入研讨式实验过程,提高学生科学素养的同时,促进学生创新意识的启蒙和科技创新能力的培养,有效提升立德树人育人成果。
【大学化学】doi: 10.12461/PKU.DXHX202407058
羰基氧鎓作为活泼中间体,很容易发生多种反应。本文介绍了大学有机化学教学中涉及到的羰基氧鎓的五类反应,即加成、取代、分解、异构和周环,讨论了羰基氧鎓作为关键中间体在各种复杂有机反应机理中扮演着重要角色。需要注意的是,羰基氧鎓的反应复杂多变,多类反应存在竞争与共存。深入学习羰基氧鎓的五类反应,有助于有机化学科学思维和科学素养的养成,践行“有机化学是科学也是艺术”的教学理念。
【大学化学】doi: 10.12461/PKU.DXHX202503063
本文是在较少学时背景下,针对大学化学中“杂化轨道理论”教学过程中存在的问题,提出以“五问”模式引导学生深入思考和理解该理论。通过对杂化轨道的理论依据、杂化条件、原因、原则及杂化类型的分析,阐述了如何运用该模式激发学生主动思考,提升教学的直观性与便捷性,培养学生解决问题的能力和科学思维。
【大学化学】doi: 10.12461/PKU.DXHX202412076
在能源化学工程专业的无机化学课程教学中,秉持“学生中心”和成果导向教育(OBE)理念,构建了“五环一心”教学新形态。通过教师主导,充分利用“互联网+”,从课程资源的精选与建设、教学方式方法的改革,到专业引领、深度融入课程思政,再到全程多元化课程评价,引导和激励学生在线上、线下和课前、课中、课后努力学习,同时提升综合能力和素养,实现了“知识传授、能力培养和价值引领浑然一体”的人才培养目标。
【无机化学学报】doi: 10.11862/CJIC.20250267
采用锌箔原位自组装法,将水合五氧化二钒(HVO)直接生长于锌箔表面,成功制备了具有HVO保护层的锌负极(VOZn)。通过调控组装时间可精确控制保护层的厚度。该原位自组装过程有利于在保护层与锌基体之间形成紧密界面,有效抑制充放电过程中保护层的剥落。更重要的是,富含含氧官能团的HVO显著增强了负极表面的亲锌性,从而使Zn2+均匀分布,促进了锌的均匀成核与沉积。此外,该保护层可作为物理屏障,有效减少电解液中自由水与锌负极的直接接触,进而抑制副反应的发生。因此,该复合电极展现出优异的电化学性能:在0.5 mA·cm-2的电流密度下,表现出较低的滞后电压(37 mV)和长达700 h的循环寿命。基于VOZn组装的全电池在1 000次循环后,容量保持率高达71%。
【大学化学】doi: 10.12461/PKU.DXHX202405037
化学国家级实验教学示范中心(哈尔滨工业大学)积极响应时代发展对人才培养的新要求,以杰出人才培养为目标,提出“思政引领、科(产)教融合、赛创同行”的人才培养模式,构建了四层次实验课程体系,“五位一体”推进实验实践教学改革,形成具有化学化工特色的杰出人才培养模式与创新创业实践教学体系。中心对实验实践教学改革的探索,取得了明显的成效,成果可为化学类实验教学中心的建设提供一定的借鉴和参考价值。
【无机化学学报】doi: 10.11862/CJIC.20240177
Different solvothermal reactions of ZnC2O4 with oxalic acid (H2ox) and 1, 2, 4-triazole (Htrz) successfully gave a new quaternary (NJTU-Bai83, NJTU-Bai=Nanjing Tech University Bai's group) and a new quinary (NJTU- Bai84) anionic metal-organic frameworks (MOFs), where NJTU-Bai83=(Me2NH2)2[Zn3(trz)2(ox)3]·2H2O and NJTU-Bai84=(Me2NH2)[Zn3(trz)3(ox)2]·H2O, respectively. With the [Zn2(ox)4(trz)2] secondary building unit (SBU) in NJTU- Bai83 replaced by the [Zn3(ox)2(trz)6] and planar [Zn(ox)2(trz)2] ones in NJTU-Bai84, 2D supramolecular building layers (SBLs) are changed from the A-layer and B-layer to another A-layer, while pillars are transformed from the tetrahedral [Zn(ox)2(trz)2] SBU to the irregular tetrahedral [Zn(ox)2(trz)2] and planar [Zn(ox)2(trz)2] SBUs. Thus, cdq-topological quaternary NJTU-Bai83 is tuned to (4, 4, 8)-c new topological quinary NJTU-Bai84. Two MOFs were well characterized by powder X-ray diffraction, thermogravimetric analysis, elemental analysis, etc.
【无机化学学报】doi: 10.11862/CJIC.20250195
The complexes 1-4 of cyclobutanocucurbit[5]uril (CyB5Q[5]) with Na+/K+ have been synthesized and characterized by single-crystal X-ray diffraction. The results show that although the inorganic salts are used when the cations are the same and the anions are different, in complex 1, Na+ closes one port of CyB5Q[5] through Na—O seven coordination bonds to form a molecular bowl; in complex 3, Na+ completely closes the two ports of CyB5Q[5] to form a molecular capsule with six Na—O coordination bonds; in complexes 2 and 4, the two ports of CyB5Q[5] are completely closed to form K—O coordinated molecular capsules, but the K+ of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated. and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.
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