新型杂合四烯光控分子开关的设计合成与性能测试
高睿, 周颖, 胡一凡, 陈思远, 徐首红, 罗千福, 张文清
【大学化学】doi: 10.3866/PKU.DXHX202310050
围绕分子开关及聚集诱导发光的科研热点领域进行本科教学实验设计,将光致变色二芳烯巧妙嵌合于具有聚集诱导发光性能的四芳烯体系中,制备得到兼具变色和发光功能的新型杂合四芳烯光控荧光分子开关,科教融合,将科研前沿引入到本科实验教学。从物质的制备、分离提纯、结构表征和性能测试等方面进行了综合实验探索。本实验分子设计简练新颖,内容丰富,现象明显,在综合运用和巩固本科学习的基本理论和基本操作的基础上,激发学生的科研兴趣,培养团结协作和突破创新的科学精神。
关键词: 光致变色, 聚集诱导发光, 荧光分子开关, 本科实验教学
一锅多组分反应选择性合成二基甲胺和三基甲烷——推荐一个有机化学综合实验
王一诺, 王思然, 赵奕龙, 徐大振
【大学化学】doi: 10.3866/PKU.DXHX202401063
本文介绍了一个有机化学综合实验,实验以水杨醛、苯硼酸和芳胺为反应底物,通过芳胺上取代基控制亲核性选择性地制备二芳基甲胺和三芳基甲烷,并利用核磁共振氢谱(1H NMR)和碳谱(13C NMR)对产物结构进行表征。本实验与理论知识相结合,启发学生进行机理方面的思考,帮助他们开拓知识视野,更好地树立“绿色化学”理念和环保意识。
关键词: 多组分反应, 苯胺, 苯硼酸, 绿色化学
酚类衍生物作为基自由基前体参与的高选择性反应进展
曹中艳, 金胜男, 王玉霞, 陈依漪, 孔宪强, 徐元清
【大学化学】doi: 10.12461/PKU.DXHX202405186
酚是年产超千万吨的廉价化工原料,广泛应用于有机合成中的各类重要转化。大学基础化学中关于酚类化合物反应类型的介绍主要是富电子芳环和酚羟基氧上的取代反应,两类产物中均保留了酚的惰性C―O键。为进一步拓展酚类化合物的应用价值,人们通过在酚氧原子上引入不同活化基,借助金属催化打断C―O键,实现了各类高效的脱氧偶联反应。然而,该策略的反应条件通常较为苛刻,并且可能导致产物中有金属残留,限制了其在制药等领域的广泛应用。为挑战上述难题,化学家们发现利用光、电等手段,在温和条件下可将酚的一些简单衍生物通过C―O键的选择性断裂产生芳基自由基。借助芳基自由基的高反应活性和选择性,实现一些新颖和高效的化学转化,为酚的合成应用提供新的策略和方法。本文介绍了利用酚的三氟甲基磺酸酯、磷酸酯和碳酸酯等作为芳基自由基前体的挑战和难点,以及如何实现一些精细化学品精准构建的最新研究进展,期望可以为学有余力的同学们拓宽知识面。
关键词: , 惰性C-O键, 选择性断裂, 芳基自由基, 光合成, 电合成
铜催化氧化偶联反应合成基砜类化合物——适合本科生的基础探究教学实验
江黎黎, 郑少瑜, 刘雪娇, 谢小敏
【大学化学】doi: 10.12461/PKU.DXHX202408004
过渡金属催化偶联反应是非常重要的现代有机合成方法,但由于一些反应条件及催化剂的价格限制,尚未在本科实验教学中大规模推广。为了让学生切身体会现代有机化学的发展及绿色化学理念,我们设计了一个反应条件温和、操作步骤简单、原料及催化剂廉价易得的过渡金属催化偶联反应——铜催化芳基硼酸与烷基亚磺酸盐的氧化偶联反应合成芳基砜类化合物。以醋酸铜和N-甲基咪唑为催化剂、空气作为氧化剂,催化4-乙酰基苯硼酸及甲基亚磺酸钠的偶联反应,以中等产率得到4-甲砜基苯乙酮。本实验包括无水实验操作、微量试剂的称量及加料、薄层色谱及旋转蒸发技术、熔点测定等实验操作。此外,本实验可以拓展为探究实验,让学生初步学习有机合成实验研究方法及数据处理、分析方法,了解过渡金属催化有机反应中主要的影响因素,培养学生科学研究的思维,提高学生的综合化学素养。本实验已经在本科生实验教学中进行了验证。
关键词: 过渡金属催化偶联反应, 铜催化氧化偶联反应, 芳基砜类化合物, 基础实验教学, 探究实验教学
Syntheses, crystal structures and Hirshfeld surface analyses of three 3-pyridazinyl-substituted triaryltriazoles and their Cu(Ⅱ) complexes
Ran ZHUANG, Xinru WANG, Ruwei SHEN, Dunru ZHU
【无机化学学报】doi: 10.11862/CJIC.20260136
Three new 3-pyridazinyl-substituted triaryltriazoles, 4-(4-R-phenyl)-3-(2-pyridyl)-5-(3-pyridazinyl)-1,2,4-triazole (L1: R=OCH3; L2: R=H; L3: R=F) and their Cu(Ⅱ) complexes, trans-[Cu(L1)2(NO3)2]·H2O (1), trans-[Cu(L2)2(NO3)2] (2) and trans-[Cu(L3)2(H2O)2](NO3)2 (3), have been synthesized and characterized by FTIR, 1H NMR, elemental analysis and single crystal X-ray crystallography. Crystal structure analyses reveal that the supramolecular trimer (L1)3 and complex 3 crystallize in the triclinic P1 space group, the ligand L2 and complexes 1 and 2 belong to the monoclinic P21/c space group, while the ligand L3 crystallizes in the monoclinic P21/n space group. There is a hydrogen-bonded trimer (L1)3 in the asymmetric unit of the ligand L1. In the complexes 1-3, there is a distorted [CuN4O2] octahedron with two NO3- ions located in the axial positions in 1 and 2, whereas the two water molecules occupy the axial sites in 3. In the equatorial plane of 1-3, each L ligand adopts a chelating bidentate mode to bind the Cu(Ⅱ) ion through the pyridyl N atom and one triazole N atom, leaving the pyridazinyl group uncoordinated. The intermolecular interactions in the free ligands and the complexes have been explored by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main intermolecular interactions are H…H and C…H/H…C contacts in (L1)3, H…H and N…H/H…N contacts in L2, H…H, N…H/H…N and C…H/H…C in L3, H…H and O…H/H…O contacts in both 1 and 2, H…H, N…H/H…N and O…H/H…O contacts in 3.
关键词: synthesis, crystal structure, pyridazine, triaryltriazole, Cu(Ⅱ) complex, Hirshfeld surface analysis
Application of double-side modified separator with hollow carbon material in high-performance Li-S battery
Yu ZHANG, Fangfang ZHAO, Cong PAN, Peng WANG, Liangming WEI
【无机化学学报】doi: 10.11862/CJIC.20230412
To reduce the "shuttle effects" of lithium polysulfides (LIPs) and the lithium dendrites in Li-S batteries, the separator modified by hollow carbon material was prepared by the simple scraping method. It can be found from the contact angle tests that the layers formed by the porous carbon of uniform width exhibited both stronger attractions to LIPs and better permeability of electrolytes than the bare polypropylene (PP) separator. Permeation tests further showed an effective block over LIPs by the modification layers. Cathode symmetrical batteries with Celgard 3501 separator were assembled and the current response tests implied a conversion of LIPs to Li2S catalyzed by hollow carbon materials. Lithium symmetrical batteries with modified separators were assembled and the voltage-time profile of charge-discharge processes showed better stability owing to the prevention of lithium dendrites. The Li-S batteries were assembled with sulfur loading of 1.8-2.0 mg·cm-2 and with the bare PP, single-side modified, and double-side modified separators. Calculations of the diffusion coefficient of lithium-ion from galvanostatic intermittent titration technique (GITT) tests and Nyquist plots both indicated the faster ion transportation for the modified separators. Smaller semicircles for impedance were also found in the plots. Nyquist plots after the 1st, 5th, 10th, 50th, and 100th cycles were analyzed to show a stable diffusion behavior of lithium ions, which should be caused by the multichannel from hollow carbon material to provide more paths for Li+ ion transportation. Li-S batteries with double-side modified separators presented a high specific capacity of 1 035 mAh·g-1 in the first cycle and 500 mAh·g-1 after 700 cycles at the current density of 0.2C, 630 mAh·g-1 after 100 cycles at 1C, and 505 mAh·g-1 after 100 cycles at 2C. The rate performance also behaved superior to the cells with bare PP as the separator. The cell assembled with higher sulfur content (3.2 mg·cm-2) also presented the reverse specific capacity of 500 mAh·g-1 at 0.2C. These battery performances could be ascribed to the porous hollow carbon materials for their adsorption and conversion of LIPs and their prevention of dendrites. Thus, the physicochemical interaction between hollow carbon and LIPs effectively alleviates the shuttle effect and the bifunctional modification of the separator could prevent the growth of lithium dendrites to improve the safety of the Li-S batteries.
关键词: Li-S battery, porous carbon, polysulfide, separator modification
高等学校化学类专业化工原理实验相关教学内容与教学要求建议
张树永, 杨延钊, 郭栋才, 周爱东, 王少飞, 黄镇, 应惠娟, 钟亚兰, 赵芳, 常彦龙, 王小华
【大学化学】doi: 10.12461/PKU.DXHX202602078
为推进化学类专业本科教学质量国家标准和教育部化学类专业教学指导委员会相关要求的全面落实,推动化工原理实验的教学改革与建设,落实学生中心、产出导向理念,提升化工原理实验教学的创新性、高阶性和挑战度,本建议明确了化学类专业化工原理实验的教学目标和相关教学要求,通过示例,明确了化工原理实验相关教学内容所应达到的知识、能力与素质目标;对化工原理实验改革与建设具有指导意义。
关键词: 化学类专业, 化工原理实验, 教学内容, 教学要求, 建议
PtRu/氮掺杂碳纳米纤维的制备及其电解水析氢性能
李艳秋, 赵芳, 杨阳, 于静
【无机化学学报】doi: 10.11862/CJIC.20250238
采用静电纺丝技术制备了多孔氮掺杂碳纳米纤维(PNCNFs),随后通过高温碳化及还原处理,成功合成了一系列PNCNFs锚定PtRu合金材料(PtRu/PNCNFs)。碳纳米纤维中氮的掺杂引入了大量的亲水性基团,能够显著增强材料与电解液之间的润湿性,有助于离子传输和整体电化学性能的进一步改善;同时PNCNFs具有较大的比表面积,PtRu合金的存在从一定程度上增加了其活性位点。此外,高温下形成的多孔结构使得PtRu合金能够均匀分散在材料表面,有利于调节材料的电子结构,促进电子转移,提升析氢反应(HER)性能。结果显示,经过500 ℃处理的PNCNFs(PtRu/PNCNFs-500)在1 mol·L-1 KOH和含1 mol·L-1 KOH的海水溶液中均表现出优异的HER性能。在电流密度为10 mA·cm-2时,PtRu/PNCNFs-500的析氢过电位分别为15.8和18.3 mV,塔菲尔(Tafel)斜率分别为20.58和20.65 mV·dec-1,性能显著优于经300、400和600 ℃处理的PNCNFs,并均展现出良好的HER稳定性。
关键词: 静电纺丝, 多孔碳纳米纤维, 铂钌合金, 电催化, 析氢反应

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