【大学化学】doi: 10.12461/PKU.DXHX202412089
李正名院士是我国著名的教育家、化学家和农药学家。在李先生逝世3周年之际,李正名奖学金捐赠暨首届颁奖仪式在南开大学举行。本文结合一部分典型的具体事例,对李正名先生的教育家精神和科学家精神进行了介绍,从中折射出他始终如一的坚定爱国信念和无私奉献精神。青年学子通过学习李先生的光辉事迹,可以深入了解老一辈科学家浓厚的家国情怀。本文有助于激励当代大学生厚植爱国主义理想与信念,增强自主创新意识和能力,立志为中华民族的伟大复兴贡献自己的全部力量。
【无机化学学报】doi: 10.11862/CJIC.20250053
通过循环伏安法(CV)处理泡沫镍(NF)得到羟基氧化镍(NiOOH),并以此为前体构建了金纳米聚集体/NF复合催化剂(Au/RF100-NF,RF表示CV处理后表面粗糙化的NF)。NiOOH前体和金纳米聚集体的生成不仅增大了电极的电化学活性面积,同时又增强了电极界面的电荷转移,有利于电催化氧化甘油反应的进行。金纳米聚集体也促进了甘油C—C键的断裂,并显著降低了乳酸盐等C3产物的法拉第效率(FE),同时提高了乙醇酸盐和甲酸盐等C2与C1产物的FE。最终,通过脉冲电解方式抑制乙醇酸盐进一步转化为甲酸盐。在此条件下,Au/RF100-NF催化乙醇酸盐的FE高达约49.1%,较未预处理直接在NF上沉积金纳米颗粒制备的催化剂(Au/NF)提高了1.67倍。
【无机化学学报】doi: 10.11862/CJIC.20250170
To achieve efficient catalytic hydrogenation of CO₂ to formate, we employed a transmetallation strategy to develop three novel iridium(Ⅰ) complexes, which feature N-heterocyclic carbene-nitrogen-phosphine ligands (CNP) and a 1, 5-cyclooctadiene (cod) molecule: [Ir(cod)(κ3-CNimP)]Cl (1-Cl), [Ir(cod)(κ3-CNimP)]PF6 (1-PF6), and [Ir(cod)(κ3-CNHP)]Cl (2). The 1H NMR spectra, 31P NMR spectra, and high-resolution mass spectra verify the successful synthesis of these three Ir(Ⅰ)-CNP complexes. Furthermore, single-crystal X-ray diffraction analysis confirms the coordination geometry of 1-PF6. The strong Ir—C(NHC) bond suggests that the carbene carbon plays an enhanced anchoring role to iridium due to its strong σ-donating ability, which helps stabilize the active metal species during CO2 hydrogenation. As a result, the Ir(Ⅰ)-CNP complex exhibits remarkable activity and long catalytic lifetime for the hydrogenation of CO2 to formate, reaching a turnover number (TON) of 1.16×106 after 150 h at a high temperature of 170 ℃, which was a relatively high value among all the Ir complexes.
【无机化学学报】doi: 10.11862/CJIC.20250321
To develop highly stable and active Ru complex catalysts for CO2 hydrogenation, we synthesized Ru complexes bearing rigid pincer-type tridentate NNN (pyrazole-pyridine-pyrazole) ligands and weakly coordinated triphenylphosphine (PPh3) ligands. The NNN ligands can strongly chelate with the Ru metal center, contributing to the overall robustness of the catalytic system. Meanwhile, PPh3 can easily dissociate to form vacant coordination sites, thereby enhancing catalytic activity. As a result, the Ru(Ⅱ)-NNN complex [Ru(L-NNN)Cl(PPh3)2]Cl (1, L-NNN=2,6-bis(5-methyl-1H-pyrazol-3-yl)pyridine) was not only quite stable, but also showed high activity for CO2 hydrogenation to formate, achieving a TON of up to 150 000. In the mechanism study, based on the results of in-situ NMR, in-situ HPLC-HRMS spectra, and density functional theory calculations, it is speculated that the active intermediates with empty coordination sites are highly active species in CO2 hydrogenation.
