Well-defined Metal-organic Frameworks Research Articles

Rapid coating of polyamide, polyurea, and polythiourea on metal–organic framework surfaces

Well-defined metal–organic framework (MOF)@polymer core–shell composite particles with polyamide, polyurea, and polythiourea as the shell layer have been constructed for the first time using non-solvent-induced surface-aimed polymerization. This surface polymerization method utilizes non-solvent-induced phase separation to concentrate and direct monomers onto MOF particle surfaces, thus completing the coating process in less than 5 min. The generalizability of this method has been demonstrated with different MOFs. Coating MOF particles with any of the three polymers can effectively improve the stability of the MOF in harsh chemical environments. When used for heavy metal removal, polythiourea-coated composite particles (MOF@HDA-PDTC) exhibited a drastically improved Hg(II) removal rate and full utilization of the thione groups for Hg(II) binding compared to their neat polymer counterparts. This highlights the unique benefit of this core–shell architecture for the optimization of diffusion.

Confinement Effects in Well-Defined Metal–Organic Frameworks (MOFs) for Selective CO2 Hydrogenation: A Review

Decarbonization has become an urgent affair to restrain global warming. CO2 hydrogenation coupled with H2 derived from water electrolysis is considered a promising route to mitigate the negative impact of carbon emission and also promote the application of hydrogen. It is of great significance to develop catalysts with excellent performance and large-scale implementation. In the past decades, metal-organic frameworks (MOFs) have been widely involved in the rational design of catalysts for CO2 hydrogenation due to their high surface areas, tunable porosities, well-ordered pore structures, and diversities in metals and functional groups. Confinement effects in MOFs or MOF-derived materials have been reported to promote the stability of CO2 hydrogenation catalysts, such as molecular complexes of immobilization effect, active sites in size effect, stabilization in the encapsulation effect, and electron transfer and interfacial catalysis in the synergistic effect. This review attempts to summarize the progress of MOF-based CO2 hydrogenation catalysts up to now, and demonstrate the synthetic strategies, unique features, and enhancement mechanisms compared with traditionally supported catalysts. Great emphasis will be placed on various confinement effects in CO2 hydrogenation. The challenges and opportunities in precise design, synthesis, and applications of MOF-confined catalysis for CO2 hydrogenation are also summarized.

(Invited) Towards Broadband Solar Fuel Production

Combining nanomaterials of different properties into nanohybrids can potentially lead to improved properties/performance or multiple functions. In particular, forming nanomaterials junctions and using plasmons represent two important, promising strategies for realizing broadband photocalysis in strategically important applications such as solar fuels and photocatalytic degradation of pollutants in our environments. In this talk, I will present some of our recent work on the rational design and realization of nanohybrid materials as well as their applications in solar fuel and photocatalysis. For instance, the construction of homojunctions of nanoplates made of metal–organic frameworks (MOF) led to broadened light absorption and increased photoactivity. The well-defined MOF homojunction was prepared by a facile one-pot synthesis route directed by hollow transition metal nanoparticles. The homojunction is enabled by two concentric stacked nanoplates with slightly different crystal phases. The enhanced charge separation in the homojunction was visualized by in-situ surface photovoltage microscopy. The as-prepared nanostacks displayed a visible-light-driven carbon dioxide reduction with very high carbon monooxide selectivity, and excellent stability. Another example is about the in situ synthesis of plasmonic Ag nanoparticles (AgNPs) and Ag-MOM (metal organic matrix) using one-step facile approach. The intimate and stable interface between the AgNPs and Ag-MOM and hot electron transfer from the plasmonic AgNPs to MOM led to highly efficient visible-light photocatalytic H2 generation in aqueous solution, which surpasses most of reported MOF-based photocatalytic systems. This work sheds light on effective electronic and energy bridging between plasmonic NPs and metal organic matrix.Related

Detection of Toxic Polychlorinated Biphenyls by Nanoporous Metal–Organic Frameworks

As a class of persistent organic pollutants (POPs), polychlorinated biphenyls (PCBs) are highly hazardous to the ecosystem, and their effective and facile detection is of high importance. Herein, we present two nanoporous metal–organic frameworks (MOFs), (Me2NH2)[In(CPTTA)]·(DMF)1.5(H2O)3.5 (BUT-174) and (Et2NH2)[In(CPTTA)]·(DEF)(H2O)3 (BUT-175), constructed by In3+ ions and the aromatic-rich tetratopic carboxylate ligands, 5′-(4-carboxylatophenyl)-[1,1′:3′,1″-terphenyl]-3,4′′,5-tricarboxylate (CPTTA4–), which exhibit highly efficient turn-down fluorescence response toward 12 PCBs, especially for three highly toxic non-ortho-substituted PCBs (PCB-77, -126, and -169) with the so-called “coplanar” molecular configuration in various solvents with the limits of detection (LODs) down to the ppb level owing to the inner filter effect between MOFs and PCBs. In addition, the MOFs show high sensing selectivity toward PCBs over many relevant interferents, including hexabromocyclododecane (HBCD), decabromodiphenyl oxide (DBDPO), perfluorobutanoic acid (PFBA), and perfluorooctanoic acid (PFOA), as well as good recyclability and stability. It is demonstrated by this work that structurally well-defined MOFs could be promising sensory materials for the detection of highly toxic PCBs in a facile way.

Nanoengineering Metal-Organic Framework-Based Materials for Use in Electrochemical CO2 Reduction Reactions.

Electrocatalytic reduction of carbon dioxide to valuable chemicals is a sustainable technology that can achieve a carbon-neutral energy cycle in the environment. Electrochemical CO2 reduction reaction (CO2 RR) processes using metal-organic frameworks(MOFs), featuring atomically dispersed active sites, large surface area, high porosity, controllable morphology, and remarkable tunability, have attracted considerable research attention. Well-defined MOFs can be constructed to improve conductivity, introduce active centers, and form carbon-based single-atom catalysts (SACs) with enhanced active sites that are accessible for the development of CO2 conversion. In this review, the progress on pristine MOFs,MOF hybrids, andMOF-derivedcarbon-basedSACsis summarized for the electrocatalytic reduction of CO2 .Finally, the limitations and potential improvement directions with respect to the advancement of MOF-relatedmaterials for the field of research are discussed. These summaries are expected to provide inspiration on reasonable design to develop stable and high-efficiency MOFs-based electrocatalysts for CO2 RR.

Mitigating Global Methane Emissions Using Metal-Organic Framework Adsorbents

Global emission of methane reached a record high in 2020. Furthermore, it is expected that methane emissions will continue to rise in the coming years despite the economic slowdown stemming from the coronavirus pandemic. Adsorbents can be used to reduce methane emissions. However, the question remains as to which adsorbents perform best for enhanced methane capture. In this work, it is demonstrated that metal-organic frameworks (MOFs) exhibited the best methane uptakes at 1 bar and 298 K from experiments as compared to tested carbonaceous materials, polymers, and zeolites. In addition, the adsorption entropy, an important thermodynamic property indicating adsorption capacity and kinetics, is determined on well-defined MOFs using a global predictive equation for porous materials. A correlation was used to describe the effect of translation and rotation of methane in the porous material for methane emission abatement. This information and the entropy of adsorption of methane on MOFs has not been reported before. The predicted results were compared to experimental data obtained from adsorption isotherms. Optimum isosteric heats were calculated by the Bhatia and Myers correlation. Finally, the pre-exponential factor of desorption is determined to aid in the design of materials for global methane emissions mitigation.

Synthesis of Well-Defined Internal-Space-Controllable UiO-66 Spherical Nanostructures Used as Advanced Nanoreactor.

Controllable well-defined metal-organic frameworks (MOFs) spherical structures are expected to be potential good platforms for the heterogeneous catalysis, guest storage, and drug delivery. However, the synthesis faces a challenge. In this paper, a series of well-defined MOFs spherical structures including core-shell, yolk-shell, and hollow spheres were successfully constructed with colloidal carbon as template. Meanwhile, the shapes of MOFs unit (bricklike or octahedral) and sizes of the formed internal space can be controlled simultaneously by rationally changing the modulator and removing template in a good manner. The as-prepared structures could not only keep intact crystal textures but also be used as advanced nanoreactors for enhancing raw materials conversion in the heterogeneous reaction of synthesizing benzoin ethyl ether. Particularly, by our internal-space-controllable nanoreactors, for the first time, the quantifiable relation between nanoreactors' internal space sizes and raw material conversion was revealed.

Ferrocenyl metal-organic framework hollow microspheres for in situ loading palladium nanoparticles as a heterogeneous catalyst.

The preparation of hollow metal-organic framework (MOF) structures through a stepped dissolution-regrowth method avoids the troublesome template removal and etching process, although it still faces several challenges due to its intrinsic limitations. In this work, we reported the preparation of ferrocenyl MOF hollow microspheres by coordinating Fc(COOH)2 with Zn2+ assisted by polyvinyl pyrrolidone (PVP). It was found that PVP was beneficial for the growth of well-defined MOF hollow microspheres (2-4 μm). Both the internal and exterior morphology could be regulated by controlling the dose of PVP (0-30 equiv.). In addition, the crystallinity, thermal stability of hollow MOFs and repeatability of synthesis were improved by PVP. Owing to the excellent redox properties of the ferrocenyl ligand (1,1'-ferrocenedicarboxylic acid), the prepared MOF hollow microspheres exhibited good redox properties, and were able to reduce the Pd2+ precursor into Pd nanoparticles (diameter = 3-5 nm) under mild conditions (25 °C, aqueous solution) without extra reducing agents. The Pd-loaded MOF hollow microspheres showed remarkable catalytic activity in the reduction of 4-nitrophenol to 4-aminophenol with a reaction rate constant k of 1.82 × 10-2 s-1.

Dissolving uptake-hindering surface defects in metal-organic frameworks.

Metal-organic frameworks (MOFs) have unique properties which make them perfectly suited for various adsorption and separation applications; however, their uses and efficiencies are often hindered by their limited stability. When most MOFs are exposed to water or humid air, the MOF structure, in particular at the surface, is destroyed, creating surface defects. These surface defects are surface barriers which tremendously hinder the uptake and release of guest molecules and, thus, massively decrease the performance in any application of MOFs. Here, the destruction by exposure to water vapor is investigated by using well-defined MOF films of type HKUST-1 as a model system for uptake experiments with different-sized probe molecules as well as for spectroscopic investigations, complemented by density functional theory calculations of the defect structure. In addition to the characterization of the surface defects, it is found that the pristine MOF structure can be regenerated. We show that the surface defects can be dissolved by exposure to the synthesis solvent, here ethanol, enabling fast uptake and release of guest molecules. These findings show that the storage of MOF materials in a synthesis solvent results in healing of surface defects and enables ideal performance of MOF materials.

Uio-66 As an Effective Support of Metal Oxides for Oxygen Evolution Catalysis

The most well-known electrocatalyst for oxygen evolution reaction (OER) have been noble metals or combination of them such as ruthenium, and/or iridium.1 Due to their cost and scarcity, however, there is a persistent search for alternative materials. Metal organic frameworks (MOFs) have recently attracted significant attention due to their versatility and stability in wide range of environments that allow for post-synthetic modifications and functionalization. This tunability of MOFs has given way to the development of exceptional electrocatalyst that can have comparable performance to noble metals, and mitigate the issues found in them.2 In this study we investigated the OER performance of the zirconia-based MOF, UiO-66, as a support for metal oxides such as CoOx, MnOx and TiOx. UiO-66 has previously been used as a support for catalyst such as molybdenum, and has rendered comparable catalytic performance to that of platinum carbon for the hydrogen evolution reaction (HER).3 Having a MOF support for catalysts, such as metal oxides, can be ideal due to the well-defined MOF surrounding that will allow them to function as catalyst, but protect them from agglomeration at high temperatures. We synthesized samples containing UiO-66, graphene oxide (GO) and cobalt oxide (CoOx) using the solvothermal method. Electrochemical characterization revealed that the hybrid CoOx@UiO-66/GO affords an excellent catalytic activity for OER with an onset potential of 1.6 V versus RHE, comparable to that of Ir and Ru-based catalysts.2 Additionally, this study contains discussions on the factors of the high OER activity through a series of physical characterizations of the hybrid catalyst.

DNA-Assembled Core-Satellite Upconverting-Metal-Organic Framework Nanoparticle Superstructures for Efficient Photodynamic Therapy.

DNA-mediated assembly of core-satellite structures composed of Zr(IV)-based porphyrinic metal-organic framework (MOF) and NaYF4 ,Yb,Er upconverting nanoparticles (UCNPs) for photodynamic therapy (PDT) is reported. MOF NPs generate singlet oxygen (1 O2 ) upon photoirradiation with visible light without the need for additional small molecule, diffusional photosensitizers such as porphyrins. Using DNA as a templating agent, well-defined MOF-UCNP clusters are produced where UCNPs are spatially organized around a centrally located MOF NP. Under NIR irradiation, visible light emitted from the UCNPs is absorbed by the core MOF NP to produce 1 O2 at significantly greater amounts than what can be produced from simply mixing UCNPs and MOF NPs. The MOF-UCNP core-satellite superstructures also induce strong cell cytotoxicity against cancer cells, which are further enhanced by attaching epidermal growth factor receptor targeting affibodies to the PDT clusters, highlighting their promise as theranostic photodynamic agents.

Graphene-Templated Synthesis of Magnetic Metal Organic Framework Nanocomposites for Selective Enrichment of Biomolecules.

Successful control of homogeneous and complete coating of graphene or graphene-based composites with well-defined metal organic framework (MOF) layers is a great challenge. Herein, novel magnetic graphene MOF composites were constructed via a simple strategy for self-assembly of well-distributed, dense, and highly porous MOFs on both sides of graphene nanosheets. Graphene functionalized with magnetic nanoparticles and carboxylic groups on both sides was explored as the backbone and template to direct the controllable self-assembly of MOFs. The prepared composite materials have a relatively high specific surface area (345.4 m(2) g(-1)), and their average pore size is measured to be 3.2 nm. Their relatively high saturation magnetization (23.8 emu g(-1)) indicates their strong magnetism at room temperature. Moreover, the multifunctional composite was demonstrated to be a highly effective affinity material in selective extraction and separation of low-concentration biomolecules from biological samples, in virtue of the size-selection property of the unique porous structure and the excellent affinity of the composite materials. Besides providing a solution for the construction of well-defined functional graphene-based MOFs, this work could also contribute to selective extraction of biomolecules, in virtue of the universal affinity between immobilized metal ions and biomolecules.

Exploration of MOF nanoparticle sizes using various physical characterization methods – is what you measure what you get?

While the size of nanoparticles (NPs) seems to be a concept established in the field of NPs and is commonly used to characterize them, its definition is not that trivial as different “sizes” have to be distinguished depending on the physical characterization technique performed to measure them. Metal–organic frameworks (MOFs) are known for their crystallinity, their large variety of compositions due to a huge number of inorganic building blocks that can be combined with almost endless organic linkers, their tunable pore structure, their ultrahigh porosity, and the different ways their backbones can be functionalised. The combination of these features with the nanoworld offers manifold perspectives for the synthesis of well-defined MOF nanoparticles (NPs), whose size attribute should be accurately determined as it strongly influences their physicochemical properties (at this length scale). In order to elucidate size determination, we synthesised zirconium fumarate metal–organic framework nanoparticles (Zr-fum MOF NPs) and characterized them using various common characterization methods. Herein, we compare the results of different solid-state methods, including powder X-ray diffraction (PXRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to data obtained from dispersion-based methods, such as fluorescence correlation spectroscopy (FCS) and dynamic light scattering (DLS). In doing so, we illustrate the challenge of finding the appropriate method for obtaining a MOF NP size that is meaningful in the context of the desired application. Moreover, we demonstrate the importance of applying multiple complementary techniques as soon as the MOF NP size is considered. Throughout this paper, we highlight and define some reasonable recommendations of how the MOF NP size should be explored.

Well‐Defined Metal–Organic Framework Hollow Nanocages

Metal-organic frameworks (MOFs) have demonstrated great potentials in a variety of important applications. To enhance the inherent properties and endow materials with multifunctionality, the rational design and synthesis of MOFs with nanoscale porosity and hollow feature is highly desired and remains a great challenge. In this work, the formation of a series of well-defined MOF (MOF-5, Fe(II) -MOF-5, Fe(III) -MOF-5) hollow nanocages by a facile solvothermal method, without any additional supporting template is reported. A surface-energy-driven mechanism may be responsible for the formation of hollow nanocages. The addition of pre-synthesized poly(vinylpyrrolidone)- (PVP) capped noble-metal nanoparticles into the synthetic system of MOF hollow nanocages yields the yolk-shell noble metal@MOF nanostructures. The present strategy to fabricate hollow and yolk-shell nanostructures is expected to open up exciting opportunities for developing a novel class of inorganic-organic hybrid functional nanomaterials.