Lanfang Zou

Topology-Guided Design and Syntheses of Highly Stable Mesoporous Porphyrinic Zirconium Metal–Organic Frameworks with High Surface Area

Through a topology-guided strategy, a series of Zr6-containing isoreticular porphyrinic metal-organic frameworks (MOFs), PCN-228, PCN-229, and PCN-230, with ftw-a topology were synthesized using the extended porphyrinic linkers. The bulky porphyrin ring ligand effectively prevents the network interpenetration which often appears in MOFs with increased linker length. The pore apertures of the structures range from 2.5 to 3.8 nm, and PCN-229 demonstrates the highest porosity and BET surface area among the previously reported Zr-MOFs. Additionally, by changing the relative direction of the terminal phenyl rings, this series replaces a Zr8 cluster with a smaller Zr6 cluster in a topologically identical framework. The high connectivity of the Zr6 cluster yields frameworks with enhanced stability despite high porosity and ultralarge linker. As a representative example, PCN-230, constructed with the most extended porphyrinic linker, shows excellent stability in aqueous solutions with pH values ranging from 0 to 12 and demonstrates one of the highest pH tolerances among all porphyrinic MOFs. This work not only presents a successful example of rational design of MOFs with desired topology, but also provides a strategy for construction of stable mesoporous MOFs.

Stepwise Synthesis of Robust Metal–Organic Frameworks via Postsynthetic Metathesis and Oxidation of Metal Nodes in a Single-Crystal to Single-Crystal Transformation

Utilizing PCN-426-Mg as a template, two robust metal-organic frameworks (MOFs), PCN-426-Fe(III) and PCN-426-Cr(III), have been synthesized through a strategy of postsynthetic metathesis and oxidation (PSMO) of the metal nodes step by step. The frameworks remained in their single crystal form throughout. Furthermore, the stability and porosity of the frameworks were significantly improved after PSMO. By taking advantage of both the kinetically labile metal-ligand exchange reactions prior to oxidation and the kinetically inert metal-ligand bonds after oxidation, robust MOFs, which would otherwise be difficult to synthesize, can be readily prepared.

Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs

Precise placement of multiple functional groups in a highly ordered metal-organic framework (MOF) platform allows the tailoring of the pore environment, which is required for advanced applications. To realize this, we present a comprehensive study on the linker installation method, in which a stable MOF with coordinatively unsaturated Zr6 clusters was employed and linkers bearing different functional groups were postsynthetically installed. A Zr-MOF with inherent missing linker sites, namely, PCN-700, was initially constructed under kinetic control. Twelve linkers with different substituents were then designed to study their effect on MOF formation kinetics and therefore resulting MOF structures. Guided by the geometrical analysis, linkers with different lengths were installed into a parent PCN-700, giving rise to 11 new MOFs and each bearing up to three different functional groups in predefined positions. Systematic variation of the pore volume and decoration of pore environment were realized by linker installation, which resulted in synergistic effects including an enhancement of H2 adsorption capacities of up to 57%. In addition, a size-selective catalytic system for aerobic alcohol oxidation reaction is built in PCN-700 through linker installation, which shows high activity and tunable size selectivity. Altogether, these results exemplify the capability of the linker installation method in the pore environment engineering of stable MOFs with multiple functional groups, giving an unparalleled level of control.

A Reversible Crystallinity-Preserving Phase Transition in Metal–Organic Frameworks: Discovery, Mechanistic Studies, and Potential Applications

A quenching-triggered reversible single-crystal-to-single-crystal (SC-SC) phase transition was discovered in a metal-organic framework (MOF) PCN-526. During the phase transition, the one-dimensional channel of PCN-526 distorts from square to rectangular in shape while maintaining single crystallinity. Although SC-SC transformations have been frequently observed in MOFs, most reports have focused on describing the resulting structural alterations without shedding light on the mechanism for the transformation. Interestingly, modifying the occupancy or species of metal ions in the extra-framework sites, which provides mechanistic insight into the causes for the transformation, can forbid this phase transition. Moreover, as a host scaffold, PCN-526 presents a platform for modulation of the photoluminescence properties by encapsulation of luminescent guest molecules. Through judicious choice of these guest molecules, responsive luminescence caused by SC-SC transformations can be detected, introducing a new strategy for the design of novel luminescent MOF materials.

Flexible Zirconium Metal‐Organic Frameworks as Bioinspired Switchable Catalysts

Flexible metal-organic frameworks (MOFs) are highly desirable in host-guest chemistry owing to their almost unlimited structural/functional diversities and stimuli-responsive pore architectures. Herein, we designed a flexible Zr-MOF system, namely PCN-700 series, for the realization of switchable catalysis in cycloaddition reactions of CO2 with epoxides. Their breathing behaviors were studied by successive single-crystal X-ray diffraction analyses. The breathing amplitudes of the PCN-700 series were modulated through pre-functionalization of organic linkers and post-synthetic linker installation. Experiments and molecular simulations confirm that the catalytic activities of the PCN-700 series can be switched on and off upon reversible structural transformation, which is reminiscent of sophisticated biological systems such as allosteric enzymes.

Construction of hierarchically porous metal–organic frameworks through linker labilization

A major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.

Porous Organic Polymers for Post‐Combustion Carbon Capture

One of the most pressing environmental concerns of our age is the escalating level of atmospheric CO2 . Intensive efforts have been made to investigate advanced porous materials, especially porous organic polymers (POPs), as one type of the most promising candidates for carbon capture due to their extremely high porosity, structural diversity, and physicochemical stability. This review provides a critical and in-depth analysis of recent POP research as it pertains to carbon capture. The definitions and terminologies commonly used to evaluate the performance of POPs for carbon capture, including CO2 capacity, enthalpy, selectivity, and regeneration strategies, are summarized. A detailed correlation study between the structural and chemical features of POPs and their adsorption capacities is discussed, mainly focusing on the physical interactions and chemical reactions. Finally, a concise outlook for utilizing POPs for carbon capture is discussed, noting areas in which further work is needed to develop the next-generation POPs for practical applications.

Stable Metal-Organic Frameworks: Design, Synthesis, and Applications

Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

One‐Step Synthesis of Hybrid Core–Shell Metal–Organic Frameworks

Epitaxial growth of MOF-on-MOF composite is an evolving research topic in the quest for multifunctional materials. In previously reported methods, the core-shell MOFs were synthesized via a stepwise strategy that involved growing the shell-MOFs on top of the preformed core-MOFs with matched lattice parameters. However, the inconvenient stepwise synthesis and the strict lattice-matching requirement have limited the preparation of core-shell MOFs. Herein, we demonstrate that hybrid core-shell MOFs with mismatching lattices can be synthesized under the guidance of nucleation kinetic analysis. A series of MOF composites with mesoporous core and microporous shell were constructed and characterized by optical microscopy, powder X-ray diffraction, gas sorption measurement, and scanning electron microscopy. Isoreticular expansion of microporous shells and orthogonal modification of the core was realized to produce multifunctional MOF composites, which acted as size selective catalysts for olefin epoxidation with high activity and selectivity.

Flexible monomer-based covalent organic frameworks: design, structure and functions

The design and synthesis of flexible monomer-based covalent organic frameworks (COFs) have been considered a challenge. Herein, we describe the design and synthesis of a new flexible monomer-based COF, termed PPN-30 (PPN meaning porous polymer network), by the use of a flexible alkyl amine, 1,4-cyclohexanediamine, combined with 1,3,5-triformylbenzene. The structure and gas adsorption properties of PPN-30 were carefully investigated.