Guo Wenxiao, Wang Shufang, Hao Hongguo, Ma Xiaoxue, Zhao Xin, Kong Xiangjin, Yan Hui, Zhang Lu, Liu Ronghua, Li Xin, Li Xia, Zhu Hongjie, Li Yunwu, Yin Jie, Zhou Huawei, Zhong Dichang, Dai Fangna
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Pharmacy, School of Chemistry and Chemical Engineering, College of Materials Science and Engineering, Liaocheng University, Liaocheng 252059, China.
Institute for New Energy Materials and Low Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, China.
Inorg Chem. 2023 Apr 10;62(14):5757-5771. doi: 10.1021/acs.inorgchem.3c00361. Epub 2023 Mar 26.
The rational design and preparation of stable and multifunctional metal-organic frameworks (MOFs) with excellent catalysis and adsorption properties are desirable but are great challenges. The nitrophenol (NP) reduction to aminophenols (APs) by using the catalyst Pd@MOFs is an effective strategy, which has attracted extensive attention in recent years. Here, we report four stable isostructural two-dimensional (2D) rare earth metal-organic frameworks [RE(AAPA)(DMA) (HO)][DMA][HO] (namely -, RE = Eu, Gd, Tb, Y; AAPA = 5-[(anthracen-9-yl-methyl)-amino]-1,3-isophthalate), which feature a 2D layer structure with topology of point symbol {4·6} and exhibit excellent chemical stability and thermostability. The as-synthesized Pd@- was utilized for the catalytic reduction of 2/3/4-nitrophenol, which indicates high catalytic activity and recyclability attributed to the synergistic effect between Pd nanoparticles and the 2D layered structure. Of note, the turnover frequency (TOF), the reaction rate constant (), and the activation energy () of Pd@- in the reduction of 4-NP, respectively, are 1.09 s, 2.17 min, and 50.2 kJ·mol, which show that it has superior catalytic activity. Remarkably, -Eu, Gd, Tb, and Y) are multifunctional MOFs that can effectively absorb and separate mixed dyes. The appropriate interlayer spacing enables them to efficiently adsorb methylene blue (MB) and rhodamine B (RhB) in aqueous solution, with adsorption capacities of 0.97 and 0.41 g·g, respectively, which is one of the highest values among those of the reported MOF-based adsorbers. Meanwhile, - can be used for the separation of the dye mixture MB/MO and RhB/MO, and the excellent reusability enables - to be used as chromatographic column filters to quickly separate and recover dyes. Therefore, this work provides a new strategy for the exploitation of stable and efficient catalysts for NP reduction and adsorbents for dyes.
设计并制备出具有优异催化和吸附性能的稳定且多功能的金属有机框架材料(MOFs)是人们所期望的,但却面临着巨大挑战。利用催化剂Pd@MOFs将硝基苯酚(NP)还原为氨基酚(APs)是一种有效的策略,近年来受到了广泛关注。在此,我们报道了四种稳定的同构二维(2D)稀土金属有机框架材料[RE(AAPA)(DMA)(H₂O)][DMA][H₂O](即 ,RE = Eu、Gd、Tb、Y;AAPA = 5-[(蒽-9-基-甲基)-氨基]-1,3-间苯二甲酸),其具有二维层状结构,点符号拓扑为{4·6},并表现出优异的化学稳定性和热稳定性。合成的Pd@ 用于催化还原2/3/4-硝基苯酚,由于Pd纳米颗粒与二维层状结构之间的协同效应,显示出高催化活性和可回收性。值得注意的是,Pd@ 在还原4-NP时的周转频率(TOF)、反应速率常数( )和活化能( )分别为1.09 s⁻¹、2.17 min⁻¹和50.2 kJ·mol⁻¹,表明其具有优异的催化活性。值得注意的是, (Eu、Gd、Tb和Y)是多功能MOFs,能够有效吸附和分离混合染料。合适的层间距使它们能够在水溶液中高效吸附亚甲基蓝(MB)和罗丹明B(RhB),吸附容量分别为0.97和0.41 g·g⁻¹,这是已报道的基于MOF的吸附剂中的最高值之一。同时, 可用于分离染料混合物MB/MO和RhB/MO,并且优异的可重复使用性使 能够用作色谱柱过滤器以快速分离和回收染料。因此,这项工作为开发用于NP还原的稳定高效催化剂和用于染料的吸附剂提供了一种新策略。