Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea; Analysis and Evaluation Department, Egyptian Petroleum Research Institute (EPRI), Nasr City, 11727 Cairo, Egypt; Liquid Chromatography and Water Unit, EPRI-Central Laboratories, Nasr City, 11727 Cairo, Egypt.
KU-KIST Graduate School of Converging Science and Technology, Korea University,145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea.
Adv Colloid Interface Sci. 2020 Mar;277:102108. doi: 10.1016/j.cis.2020.102108. Epub 2020 Jan 23.
Recently, as a new sub-family of porous coordination polymers (PCPs), porphyrinic-MOFs (Porph-MOFs) with biomimetic features have been developed using porphyrin macrocycles as ligands and/or pillared linkers. The control over the coordination of the porphyrin ligand and its derivatives however remains a challenge for engineering new tunable Porph-MOF frameworks by self-assembly methods. The key challenges exist in the following respects: (i) collapse of the large open pores of Porph-MOFs during synthesis, (ii) deactivation of unsaturated metal-sites (UMCs) by axial coordination, and (iii) the tendency of both coordinated moieties (at peripheral meso- and beta-carbon sites) and the N-pyridine core to coordinate with metal cations. In this respect, this review covers the advances in the design of Porph-MOFs relative to their counterpart covalent organic frameworks (Porph-COFs). The potential utility of custom-designed porphyrin/metalloporphyrins ligands is highlighted. Synthesis strategies of Porph-MOFs are also illustrated with modular design of hybrid guest@host composites (either Porph@MOFs or guest@Porph-MOFs) with exceptional topologies and stability. This review summarizes the synergistic benefits of coordinated porphyrin ligands and functional guest molecules in Porph-MOF composites for enhanced catalytic performance in various redox applications. This review shed lights on the engineering of new tunable hetero-metals open active sites within (metallo)porphyrin-MOFs as out-of-the-box platforms for enhanced catalytic processes in chemical and biological media.
最近，作为多孔配位聚合物（PCPs）的一个新亚家族，具有仿生特征的卟啉基 MOF（Porph-MOF）已通过卟啉大环作为配体和/或支柱连接体开发出来。然而，通过自组装方法控制卟啉配体及其衍生物的配位仍然是工程新可调谐 Porph-MOF 骨架的挑战。关键挑战存在于以下几个方面：（i）卟啉 MOF 在合成过程中大开口孔的塌陷，（ii）不饱和金属位点（UMCs）通过轴向配位失活，以及（iii）配位部分（在周边介孔和β-碳位）和 N-吡啶核与金属阳离子配位的趋势。在这方面，本综述涵盖了 Porph-MOF 相对于其相应的共价有机骨架（Porph-COFs）的设计进展。突出了定制卟啉/金属卟啉配体的潜在用途。还说明了 Porph-MOF 的合成策略，通过混合客体@主体复合材料（卟啉@MOFs 或客体@Porph-MOFs）的模块化设计，具有特殊的拓扑结构和稳定性。本综述总结了 Porph-MOF 复合材料中配位卟啉配体和功能客体分子在增强各种氧化还原应用中的催化性能方面的协同优势。本综述阐明了在（金属）卟啉-MOF 内工程化新的可调谐杂金属开放活性位作为在化学和生物介质中增强催化过程的现成平台。
