Efficient hydrogenation of CO2 realized by Ru-NNN complex
Huihua GONG, Tianhua CUI, Li JI, Liyuan ZHANG, Xueli ZHENG, Haiyan FU, Hua CHEN, Jiawei MAO, Ruixiang LI
【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.
关键词: CO2 hydrogenation, Ru complex, NNN ligands, homogeneous catalysis
人名反应在有机化学课程教学中的作用:以Roskamp-Feng反应和Ullmann-Ma反应为例
刘旭光, 李彩文, 凌宏雷, 梁茂
【大学化学】doi: 10.12461/PKU.DXHX202504079
人名反应在有机化学课程的教学中具有举足轻重的作用,每个人名反应的背后都饱含了杰出的有机化学家的重要贡献。了解有机化学中人名反应的发展脉络,挖掘人名反应背后的科学家事迹也是课程思政的重要组成部分。在众多人名反应中,以华人科学家命名的人名反应屈指可数。本文以Roskamp-Feng反应和Ullmann-Ma反应两个以华人科学家命名的人名反应为例,探讨了有机人名反应在有机化学课程教学中的作用,为国内同行开展有机化学相关课程教学研究提供了借鉴。
关键词: 有机化学, 人名反应, Roskamp-Feng反应, Ullmann-Ma反应, 教学
Ru-doped Co3O4/reduced graphene oxide: Preparation and electrocatalytic oxygen evolution property
Tian TIAN, Meng ZHOU, Jiale WEI, Yize LIU, Yifan MO, Yuhan YE, Wenzhi JIA, Bin HE
【无机化学学报】doi: 10.11862/CJIC.20240298
Binary composites (ZIF-67/rGO) were synthesized by one-step precipitation method using cobalt nitrate hexahydrate as metal source, 2-methylimidazole as organic ligand, and reduced graphene oxide (rGO) as carbon carrier. Then Ru3+ was introduced for ion exchange, and the porous Ru-doped Co3O4/rGO (Ru-Co3O4/rGO) composite electrocatalyst was prepared by annealing. The phase structure, morphology, and valence state of the catalyst were analyzed by X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). In 1 mol·L-1 KOH, the oxygen evolution reaction (OER) performance of the catalyst was measured by linear sweep voltammetry, cyclic voltammetry, and chronoamperometry. The results show that the combination of Ru doping and rGO provides a fast channel for collaborative electron transfer. At the same time, rGO as a carbon carrier can improve the electrical conductivity of Ru-Co3O4 particles, and the uniformly dispersed nanoparticles enable the reactants to diffuse freely on the catalyst. The results showed that the electrochemical performance of Ru-Co3O4/rGO was much better than that of Co3O4/rGO, and the overpotential of Ru-Co3O4/rGO was 363.5 mV at the current density of 50 mA·cm-2.
关键词: metal-organic framework, graphene, electrocatalyst, oxygen evolution reaction
Crystallinity and oxidation degree tuning of Ru for alkaline hydrogen oxidation
Yuanjun LIU, Jiayang JIANG, Rui WANG, Jiangnan HU, Chaoyi YUAN, Xingmei GUO, Junhao ZHANG, Guoxing ZHU
【无机化学学报】doi: 10.11862/CJIC.20250373
Developing high-performance electrocatalysts for the alkaline hydrogen oxidation reaction (HOR) is essential for advancing alkaline hydrogen fuel cells. Here, we report the synthesis of ruthenium (Ru) catalysts with tuned crystallinity and oxidation degree. By combining template-assisted synthesis with controlled thermal treatment, amorphous, partially crystalline, highly crystalline, and partially oxidized Ru products were successfully obtained. Catalysts with moderate crystallinity and partial oxidation exhibit enhanced catalytic activity toward the alkaline hydrogen oxidation reaction. The optimized Ru-RuO2 catalyst achieved a mass activity of 81.66 mA·mgRu-1, which was 2.27 times that of commercial Pt/C under identical conditions. The improved activity is attributed to the synergistic effect of moderate crystallinity and partial oxidation, which favors a favorable Tafel-Volmer reaction pathway.
关键词: hydrogen oxidation, Ru catalyst, crystallinity, fuel cells, catalytic activity
基于氢穿梭接力的Pd-Ru双位点催化剂用于高效电还原硝酸盐制氨
唐顺逸, 郭恒, 于波, 刘娟, 李林秋, 伍浩然, 田维俊, 张凤英, 周莹
【物理化学学报】doi: 10.1016/j.actphy.2026.100299
电催化硝酸盐还原(NO3−RR)合成氨(NH3)为含硝酸盐工业废水资源化处理利用一体化提供了一条理想的路径。然而,该反应涉及多电子/质子转移步骤,在质子供应不足时动力学缓慢,导致氨选择性与产率低。本研究基于“氢穿梭接力”策略,设计了一种负载于镍泡沫(NF)上的Pd-Ru双金属催化剂(Pd-Ru/NF),发现Pd位点主导硝酸盐活化与加氢过程,而Ru位点则高效裂解水分子产生活性氢物种(H*)。二者协同构成氢传递网络,实现反应位点间的氢溢流动态匹配,从而在加速硝酸盐加氢的同时,有效抑制析氢副反应(HER)。在−1.4 V (vs. RHE)电位下,Pd-Ru/NF催化剂的氨产率高达1.77 mmol cm−2 h−1,法拉第效率(FE)为85.95%。本工作通过构建双功能位点协同的氢接力机制,为设计高效NO3−RR催化剂提供了新范式。
关键词: 硝酸盐还原, 合成氨, 电催化, 金属负载
MA3Bi2Br9/g-C3N4 0D/2D S型异质结用于选择性光催化氧化甲苯
陈丽珊, 李雪梅, 徐向菊, 董幼青, 徐全龙
【物理化学学报】doi: 10.1016/j.actphy.2026.100258
由于sp3 C–H键的反应惰性,甲苯转化为高附加值的苯甲醛仍面临巨大挑战。本研究采用原位生长法精确构建了MA3Bi2Br9/g-C3N4异质结,并采用O2分子作为绿色氧化剂进行甲苯选择性氧化研究。能带结构分析和先进表征技术证实该异质结遵循S型机制,从而产生强氧化还原能力的光生电子-空穴对,并为生成关键活性氧物种·O2–提供强大驱动力。优化后的20%MA3Bi2Br9/g-C3N4复合材料展现出优异的甲苯转化率和产物选择性,在4 h内达到27.4%的甲苯转化率和94.2%的苯甲醛选择性。本研究为未来开发新型异质结光催化剂用于碳氢化合物向高值化学品的转化提供了普适性策略。
关键词: 无铅钙钛矿, 甲苯氧化, g-C3N4纳米片, S型异质结

出版年份

相关作者

相关热词