单原子Pd促进的Cu催化剂用于乙醇脱氢
冯乐乐, 白雪, 庞纪峰, 曹宏晨, 刘晓艳, 罗文豪, 杨小峰, 吴鹏飞, 郑明远
【物理化学学报】doi: 10.1016/j.actphy.2025.100100
乙醇脱氢是乙醇催化转化过程中的关键基元步骤,铜(Cu)基合金催化剂是该反应最具前景的候选材料。然而,由于合金催化剂在反应条件下固有的结构复杂性和动态演变特性,阐明合金组分与主体金属间协同效应的内在机制仍具挑战性。本研究设计了结构明确的单原子钯(Pd)修饰Cu-MFI催化剂用于乙醇脱氢制乙醛和氢气。通过球差校正高角环形暗场扫描透射电子显微镜(AC-HAADF-STEM)、X射线吸收光谱(XAS)、X射线光电子能谱(XPS)等系统表征结合密度泛函理论(DFT)计算表明,Pd原子被均匀分散在Cu催化剂表面并被Cu原子隔离,该单原子位点配位数为9–10、带−0.36e电荷。在乙醇脱氢反应中,新生成的Pdδ和Cuδ+位点协同作用降低了乙醇中C—H键断裂的活化能垒,同时增强了氢吸附和H—H键耦合能力,使得Pd/Cu-MFI催化剂获得更高的乙醇转化率和乙醛产率。
关键词: 乙醇, 脱氢, Pd-Cu单原子催化剂, 电子转移,
MOF模板法合成氮掺杂碳材料用于增强电化学钠离子储存和去除
王卓, 白雪, 张可新, 王鸿志, 董家宝, 高源, 赵斌
【物理化学学报】doi: 10.3866/PKU.WHXB202405002
电极材料在电容去离子技术中起到决定性作用,影响着盐离子的去除和电荷储存能力。本文通过碳化MOF-5和三聚氰胺的混合物,成功制备了氮掺杂的分级多孔碳,其中三聚氰胺起着氮源和造孔剂的双重作用。通过优化碳化温度,得到的MOF-5衍生纳米多孔碳(NPC-800),其不但保持着MOF-5原始的立方体形貌、还具有大的比表面积、高氮含量和良好的润湿性。NPC-800电极在0.2 A·g-1电流密度下具有91.8 mAh·g-1的高比容量。在5 A·g-1的电流密度下循环50000次,容量保持率为100%,展现出超长的循环稳定性。在500 mg·L-1的NaCl溶液,施加恒压1.2 V,NPC-800电极具有高的脱盐容量24.17 mg·g-1,快的脱盐速度2.8 mg·g-1·min-1和较稳定的再生循环能力。因此,以金属有机框架为模板合成氮掺杂的碳材料,能够有效增强钠离子的电化学储存和去除能力,有望成为电容去离子电极材料的最佳选择。
关键词: 金属有机框架, 电化学性能, 钠离子储存, 电容去离子, 能源储存机制
Synthesis and crystal structures of Co(Ⅱ)/Cu(Ⅱ) coordination polymers based on solvent and ligand concentration regulation strategy
Yinxia SUN, Liping LIU, Xue BAI, Yu SUN, Wanhong SUN, Zhepeng DENG, Jianghai CHEN, Jianjun WANG, Li XU, Shuzhen ZHANG
【无机化学学报】doi: 10.11862/CJIC.20250226
Four distinct coordination polymers (CPs) were successfully synthesized by altering solvent types and adjusting ligand concentrations, and their crystal structures were investigated. [Co(L)(FDCA)(H2O)2]·0.5H2O (1) was synthesized as a 2D structure using Co(Ⅱ) as the metal source, methanol-water (4∶6, V/V) as the solvent, and specific concentrations of 2, 5-furandicarboxylic acid (H2FDCA) and 1, 3, 5-triimidazole benzene (L). Adjusting to pure water and lowering the concentration of L yielded the 1D chain structure of [Co(HL)2(H2O)2](FDCA)2·6H2O (2). Using Cu(Ⅱ) as the metal source, methanol/water (9∶1, V/V) as the solvent, and specific concentrations of L and H2FDCA, the 1D chain structure of [Cu(L)(FDCA)(H2O)]·2H2O (3) was synthesized. Upon increasing the concentrations of L and H2FDCA, and switching the solvent to pure water, the 1D chain structure of [Cu(HL)2(H2O)2](FDCA)2·6H2O (4) was obtained. This shows that changing the solvent and ligand concentrations can affect the structural changes of CPs. In addition, the solid-state photoluminescence of CPs 1-4 at room temperature was studied, and their morphological changes were observed via scanning electron microscopy. Density functional theory calculations revealed that the negative charge concentrates on the O and N atoms of the ligand, facilitating ligand-metal ion coordination.
关键词: Co(Ⅱ)/Cu(Ⅱ), coordination polymer, crystal structure, solvent system, ligand concentration, regulation strategy

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