Xu Xiao-Li, Wang Nian-Nian, Zou Yong-Hao, Qin Xiao, Wang Peng, Lu Xiang-Yu, Zhang Xiao-Yu, Sun Wei-Yin, Lu Yi
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, 210023, Nanjing, PR China.
Nat Commun. 2024 Aug 23;15(1):7273. doi: 10.1038/s41467-024-51552-x.
Metal-organic frameworks (MOFs), recognized as advanced catalyst carriers due to their adjustable porous, diverse structure and highly exposed active sites, have earned increasing attention for their potential to address the longevity of catalytic centers. In this manuscript, we have devised and synthesized a multifunctional amino-pyridine benzoic acid (APBA) ligand to replace the modulator ligand of the MOF-808 and disperse the palladium catalytic centers atomically on the MOF-APBA. The resulting single-site catalytic system, Pd@MOF-APBA, demonstrates preeminent efficiency and stability, as evidenced by a high average turnover number (95000) and a low metal residue (4.8 ppm) in the Heck reaction. This catalyst has exhibited recyclability for multiple runs without significant loss of reactivity for gram-scale reactions. The catalyst's high activity and efficiency can be attributed to the suitable electrical properties and structures of the N, N'-bidentate ligand for the catalytic palladium ions, postponing their deactivations, including leaching and agglomeration.
金属有机框架材料(MOFs)因其可调节的孔隙率、多样的结构和高度暴露的活性位点而被视为先进的催化剂载体,其在解决催化中心寿命问题方面的潜力已受到越来越多的关注。在本论文中,我们设计并合成了一种多功能氨基吡啶苯甲酸(APBA)配体,以取代MOF-808的调节剂配体,并将钯催化中心原子分散在MOF-APBA上。所得的单中心催化体系Pd@MOF-APBA表现出卓越的效率和稳定性,在Heck反应中具有高平均周转数(95000)和低金属残留(4.8 ppm)证明了这一点。该催化剂在克级反应中多次循环使用而无明显反应活性损失,展现出可回收性。催化剂的高活性和效率可归因于用于催化钯离子的N,N'-双齿配体具有合适的电学性质和结构,延缓了其失活,包括浸出和团聚。