纪念《大学化学》创刊40
段连运
【大学化学】doi: 10.12461/PKU.DXHX202508101
作为我国高等化学教育发展的见证者与推动者,《大学化学》自创刊之日起,便肩负起引领教学改革、服务一线教师的重任。四十年风雨兼程,期刊在摸索中成长,离不开几代编委、作者和读者的共同努力。展望未来,我们初心不改,将继续脚踏实地,努力提高质量,让《大学化学》更好地成为化学教师们的良师益友,为建设教育强国贡献一份力量。在此,深切缅怀创刊先驱,并向所有支持者致以最诚挚的谢意!
关键词: 《大学化学》, 创刊40周年, 化学教育, 教学改革, 传承与发展
Syntheses and photocatalytic CO2 reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters
Pu ZHANG, Youzhu YU, Yuhua GUO, Zhongyuan ZHOU
【无机化学学报】doi: 10.11862/CJIC.20250353
In this work, by using diphenylphosphonic acid as ligand and butyltin hydroxide oxide as tin source, reacting with nickel acetate and cobalt acetate respectively, two hexanuclear tin oxo clusters formulated as [(n-BuSn)4 Ni2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (1) and [(n-BuSn)4Co2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (2) were solvothermally synthesized. Both 1 and 2 were characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Spectral experiments revealed that the two complexes have absorptions in the visible region. The optical band gaps for complexes 1 and 2 are 1.90 and 1.79 eV, respectively. Complexes 1 and 2 exhibited photocatalytic CO2 reduction activity, and only CO was generated, with rates of 10.01 and 26.89 μmol·g-1·h-1, respectively. CCDC: 2505024, 1; 2505025, 2.
关键词: transitional metal ions, tin oxo clusters, band gap, photocatalytic CO2 reduction
庆祝《无机化学学报》创刊40
《大学化学》创刊40年纪念专刊 序言
邹鹏
【大学化学】doi: 10.12461/PKU.DXHX202512073
无过渡金属聚嗪酰亚胺促进的光催化Katritzky盐C-X键构建反应研究
王颖, 杨明成, 尹铸, 王英齐, 成佳佳
【物理化学学报】doi: 10.1016/j.actphy.2025.100212
针对聚合物氮化碳光催化剂缺陷调控与界面工程在有机转化中的研究空白,本研究设计并合成了一种新型无过渡金属聚庚嗪酰亚胺光催化剂(PHI-K-alk)。通过熔盐辅助碱化策略,成功构建了具有长程有序骨架结构及丰富N-K表面活性位点的π共轭体系。该策略不仅显著提升了材料电子云极化能力,还通过N-K键协同作用有效降低了Katritzky盐的还原电位(LUMO降低0.33 eV)及C(sp2)-N键裂解能垒(0.7 eV),从而克服了传统Katritzky盐体系存在的吸附能垒高、反应活性低等瓶颈问题。实验结果表明,PHI-K-alk在可见光驱动下实现了脱氨基Heck型偶联反应的高效转化(转化率90%,选择性94%),其性能可与当前最优均相光催化剂相媲美。通过原位光谱分析、电化学表征及密度泛函理论计算,揭示了材料中N缺陷位点与K+抗衡离子的协同作用机制:N空位诱导的电子云极化增强了底物吸附能力,而N-K键通过离子交换作用优化了吡啶基团的电荷密度分布,最终实现光生载流子的高效分离。该光催化体系展现出优异的底物普适性,在药物分子衍生化、氨基酸官能团修饰及Minisci反应中均表现出良好适应性,成功实现了C(sp3)-C(sp)、C(sp3)-H等多种化学键的可控构建。本研究为发展高效无金属光催化体系提供了新策略,其结晶度与缺陷态的协同调控策略对可持续光催化合成技术的开发具有重要指导意义。
关键词: 光催化, 聚庚嗪酰亚胺, C-X键构建, 界面电子转移, Katritzky盐
聚烯烃工业的先驱者——纪念德国化学家Karl Ziegler逝世50
范勋章, 赵远进, 罗淑芳, 贺爱华
【大学化学】doi: 10.3866/PKU.DXHX202312065
本文介绍了诺贝尔化学奖得主、德国化学家卡尔∙齐格勒(Karl Ziegler)的科研历程及贡献以纪念他逝世50周年。Ziegler对科学的热情、独特的思维和卓越的实验能力奠定了他的科学基础。他专注于自由基化合物、多元环化合物和有机金属化合物的研究,他与朱利奥∙纳塔共同发明命名的Ziegler-Natta催化剂对全球聚烯烃工业产生深远影响,造就了上千亿美元的市场。
关键词: Karl Ziegler, Ziegler-Natta催化剂, 人物传记
Selective electrocatalytic reduction of Sn(Ⅳ) by carbon nitrogen materials prepared with different precursors
Rui PAN, Yuting MENG, Ruigang XIE, Daixiang CHEN, Jiefa SHEN, Shenghu YAN, Jianwu LIU, Yue ZHANG
【无机化学学报】doi: 10.11862/CJIC.20230433
Graphitic carbon nitride (CN)-based materials were synthesized using melamine, urea, guanidine carbonate, and thiourea as precursors via pyrolysis. The synthesized materials underwent comprehensive characterization employing techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption test. These materials were evaluated for their performance as cathodes with platinum sheet electrodes as anodes in the selective electrocatalytic reduction of Sn(Ⅳ) in an acid solution. During the reduction of Sn(Ⅳ) to Sn(Ⅱ), Sn(Ⅱ) can also be reduced to Sn due to the similar reduction potentials of Sn(Ⅱ) and Sn(Ⅳ). The deposition of Sn on the cathode diminishes the electrode conductivity efficiency. Therefore, the electrode material must fulfill the dual requirements of reducing Sn(Ⅳ) to Sn(Ⅱ) while preventing the reduction of Sn(Ⅱ) to Sn. In comparison to conventional cathode materials such as copper plates, graphite plates, ruthenium iridium titanium plates, and platinum plates, the CN demonstrated superior performance in the selective electrocatalytic reduction of Sn(Ⅳ) in an acidic solution. In addition, CN exhibited a lower potential in a dual-electrode electrolytic cell and maintained stability under acidic conditions, enabling the selective reduction of Sn(Ⅳ) to Sn(Ⅱ).
关键词: carbon nitride, Sn(Ⅳ) reduction, electrocatalysis
两个丁二肟有机配合物的合成、结构及抗癌活性
卿菁菁, 何帆, 刘智辉, 侯帅鹏, 刘娅, 蒋一凡, 谭梦婷, 何丽芳, 张复兴, 朱小明
【无机化学学报】doi: 10.11862/CJIC.20240003
合成了2个丁二酮肟有机锡化合物:双(三(2-甲基-2-苯基丙基)锡)丁二酮肟配合物(C6H5C(CH3)2CH2)3Sn(ON=C(CH3)C(CH3)=NO)Sn(CH2C(CH3)2C6H5)3 (1)和二苄基锡氧氯丁二酮肟多核配合物[μ3-O-((C6H5CH2)2Sn)2(ON=C(CH3)C(CH3)=NOH)(O)Cl]2(2)。通过元素分析、红外光谱、核磁共振(1H、13C、119Sn)、差热分析和单晶X射线衍射对配合物进行了结构表征,对其结构进行量子化学从头计算,并进行了体外抗癌活性研究。结果显示:配合物1为通过配体丁二酮肟桥联的双锡核中心对称分子,锡原子均为四配位的畸变四面体构型;配合物2为通过氧原子和丁二酮肟配体桥联的四锡核中心对称多环聚合结构,锡原子分别为五配位的畸变三角双锥构型和六配位的畸变八面体构型。配合物对人肝癌细胞(HUH7)、人肺癌细胞(A549)、人表皮癌细胞(A431)、人结肠癌细胞(HCT-116)和人乳腺癌细胞(MDA-MB-231)均有较强的抑制活性。
关键词: 双(三(2-甲基-2-苯基丙基)锡)丁二酮肟配合物, 二苄基锡氧氯丁二酮肟多核配合物, 晶体结构, 从头计算, 体外抗肿瘤活性
Synthesis, structure, and properties of hydrated tricyclohexyltin theophylline-7-acetic acid complex
Lifang HE, Yaoze LUO, Qiying SHI, Jianxin TANG, Fuxing ZHANG, Xiaoming ZHU
【无机化学学报】doi: 10.11862/CJIC.20250244
The hydrated tricyclohexyltin theophylline-7-acetic acid (tpH) complex [Sn(C6H11)3(tp)(H2O)] was synthesized via an ethanol solvothermal method using tricyclohexyltin hydroxide and tpH in a 1∶1 molar ratio. The complex was characterized by IR, 1H (13C) NMR, elemental analysis, and powder X-ray diffraction, and the crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system with space group Iba2, and the central tin atom is in a five-coordinated trigonal bipyramidal configuration. Quantum chemistry ab initio calculations were performed to investigate the stability, molecular orbital energy, and frontier molecular orbital characteristics of the complex. Additionally, its thermal stability, electrochemical properties, and in vitro anticancer activity were evaluated.
关键词: hydrated tricyclohexyltin theophylline-7-acetic acid complex, synthesis, crystal structure, in vitro antitumor activity
第十五届全国大学化学教学研讨会暨《大学化学》创刊40年论坛在北京召开
袁梅, 邹鹏

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