【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。
【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。
【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.
