设计了一种鱼骨形且热化学稳定的2D金属有机框架(MOF),具有多峰活性中心甲板孔壁。氧化还原活性的[Co2(COO)4]节点和噻唑并[5,4-d]噻唑官能化使这种混合配体MOF受益,在10mAcm-2电流密度和78mV/decTafel斜率下,在10mAcm-2电流密度下表现出电化学水氧化。一对相反取向的羧酸有助于过渡金属离子的后金属化,以设计异双金属材料。值得注意的是,Ni2接枝的三重氧化还原复合物的过电位降低至270mV,塔菲尔斜率比母体MOF下降两倍,在报告最好的值中排名,并优于大多数相关催化剂。重要的是,周转频率和电荷转移电阻显示35.5和1.4倍的热潮,分别,由于协同的Co(II)-Ni(II)偶联,具有更高的时间电位稳定性并增加了活性表面积。COOH和富氮部分的同时存在使该氢键键合的MOF在无溶剂的温和条件下作为可循环的脱缩醛-Knoevenagel反应的酸碱协同催化剂,产品收率>99%。除了对照实验,通过比较分子剪切方法衍生的结构相似的非官能化MOF的性能,验证了─COOH作为氢键供体位点在底物活化中的独特作用,和异双金属复合材料。为了最好的串联Knoevenagel冷凝,较大尺寸的缩醛表现出低的α产率,β-不饱和二氰化物,并证明了孔拟合介导的尺寸选择性。
A fish-bone-shaped and thermochemically stable 2D metal-organic framework (MOF) with multimodal active center-decked pore-wall is devised. Redox-active [Co2(COO)4] node and thiazolo[5,4-d]thiazole functionalization benefit this mixed-ligand MOF exhibiting electrochemical water oxidation with 375 mV overpotential at 10 mA cm-2 current density and 78 mV per dec Tafel slope in alkaline medium. Pair of oppositely oriented carboxylic acids aids postmetalation with transition metal ions to engineer heterobimetallic materials. Notably, overpotential of Ni2+ grafted triple-redox composite reduces to 270 mV with twofold declined Tafel slope than the parent MOF, ranking among the best-reported values, and outperforming majority of related catalysts. Significantly, turnover frequency and charge transfer resistance display 35.5 and 1.4-fold upsurge, respectively, with much uplifted chronopotentiometric stability and increase active surface area owing to synergistic Co(II)-Ni(II) coupling. The simultaneous presence of ─COOH and nitrogen-rich moieties renders this hydrogen-bonded MOF as acid-base synergistic catalyst for recyclable deacetalization-Knoevenagel reaction with >99% product yield under solvent-free mild condition. Besides control experiments, unique role of ─COOH as hydrogen-bond donor site in substrate activation is validated from comparing the performances of molecular-shearing approach-derived structurally similar unfunctionalized MOF, and the heterobimetallic composite. To the best of tandem Knoevenagel condensation, larger-sized acetal exhibits poor yield of α,β-unsaturated dicyanides, and demonstrates pore-fitting-mediated size-selectivity.