Rare-Earth Metal-Organic Framework with Nonplanar Porphyrin Groups for High-Efficiency Photocatalysis.

Nonplanar porphyrins play crucial roles in many biological processes and chemical reactions as catalysts. However, the preparation of artificial nonplanar porphyrins suffers from complicated organic syntheses. Herein, we present a new rare-earth porphyrinic metal-organic framework (RE-PMOF), BUT-233, which is a three-dimensional (3D) framework structure with the flu topology consisting of 4-connected BBCPPP-Ph ligands H4BBCPPP-Ph = 5',5⁗-(10,20-diphenylporphyrin-5,15-diyl)bis([1,1':3',1″-terphenyl]-4,4'' dicarboxylic acid) and 8-connected Eu6 clusters. Noteworthily, the porphyrin cores of the BBCPPP-Ph ligands in BUT-233 are nonplanar with a ruffle-like conformation. In contrast, the porphyrin core in the free ligand H4BBCPPP-Ph is in a nearly ideally planar conformation, as confirmed by its single-crystal structure. BUT-233 is microporous with 6-8 Špores and a Brunauer-Emmett-Teller (BET) surface area of 649 m2/g, as well as high stability in common solvents. The MOF was used as a photocatalyst for the oxidation degradation of a chemical warfare agent model molecule CEES (CEES = 2-chloroethyl ethyl sulfide) under the light-emitting diode (LED) irradiation and an O2 atmosphere at room temperature. CEES was almost completely converted into its nontoxic light-oxidized product CEESO (CEESO = 2-chloroethyl ethyl sulfoxide) in only 5 min with t1/2 = 2 min (t1/2: half-life). Moreover, the toxic deep-oxidized product 2-chloroethyl ethyl sulfone (CEESO2) was not detected. The catalytic activity of BUT-233 was high in comparison with those of some previously reported MOF catalysts. The results of photo/electrochemical property studies suggested that the high catalytic activity of BUT-233 was benefited from the presence of nonplanar porphyrin rings on its pore surface.

Interior and Exterior Surface Modification of Zr-Based Metal-Organic Frameworks for Trace Benzene Removal.

The emission of volatile organic compounds (VOCs) significantly contributes to air pollution and poses a serious threat to human health. Benzene, one of the most toxic VOCs, is difficult for the human body to metabolize and is classified as a Group 1 carcinogen. The development of efficient adsorbents for removing trace amounts of benzene from ambient air is thus of great importance. In this work, we studied the benzene adsorption properties of four Zr-based metal-organic frameworks (Zr-MOFs) through static volumetric and dynamic breakthrough experiments. Two previously reported Zr-MOFs, BUT-12 and STA-26, were prepared with a tritopic carboxylic acid ligand (H3L1) functionalized with three methyl groups, and STA-26 is a 2-fold interpenetrated network of BUT-12. Two new isoreticular Zr-MOFs, BUT-12-Et and STA-26-Et, were synthesized using a similar ligand, H3L2, where the methyl groups are replaced with ethyl groups. There are mesopores in BUT-12 and BUT-12-Et and micropores in STA-26 and STA-26-Et. The four Zr-MOFs all showed high stability in liquid water and acidic aqueous solutions. The microporous STA-26 and STA-26-Et showed much higher benzene uptakes than mesoporous BUT-12 and BUT-12-Et at room temperature under low pressures. Particularly, the benzene adsorption capacity of STA-26-Et was high up to 2.21 mmol/g at P/P0 = 0.001 (P0 = 12.78 kPa), higher than those of the other three Zr-MOFs and most reported solid adsorbents. Breakthrough experiments confirmed that STA-26-Et could effectively capture trace benzene (10 ppm) from dry air; however, its benzene capture capacity was reduced by 90% under humid conditions (RH = 50%). Coating of the crystals of STA-26-Et with polydimethylsiloxane (PDMS) increased the hydrophobicity of the exterior MOF surfaces, leading to a more than 2-fold improvement in its benzene capture capacity in the breakthrough experiment under humid condition. PDMS coating of STA-26-Et likely slowed down the water adsorption process, and thus, the adsorbent afforded more efficient capture of benzene. This work demonstrates that modifying both the interior and exterior surfaces of MOFs can effectively enhance their performance in capturing trace benzene from ambient air, even under humid conditions. This finding is meaningful for the development of new adsorbents for effective air purification applications.

Highly Efficient Propyne/Propylene Separation in a "Flexible-Robust" and Hydrolytically Stable Cu(II)-MOF.

Propyne/propylene separation is important in the petrochemical industry but challenging due to their similar physical properties and close molecular sizes. Metal-organic frameworks (MOFs) are a class of promising adsorbents for light hydrocarbon separations. Among them, the so-called "flexible-robust" MOFs combine the advantages of flexibility and rigidity in structure and could show enhanced gas separation selectivity as well as improved gas uptake at low pressure. Interpenetrated MOFs offer a platform to explore the "flexible-robust" feature of MOFs based on their subnetwork displacement in the process of gas adsorption. Herein, we present two hydrolytically stable MOFs (BUT-308 and BUT-309) with interpenetrated structures and fascinating propyne/propylene separation performance. BUT-308 is composed of interpenetrated 2D Cu(BDC-NH2)BPB layers (H2BDC-NH2 = 2-aminobenzene-1,4-dicarboxylic acid; BPB = 1,4-bis(4-pyridyl)benzene), while BUT-309 consists of twofold interpenetrated 3D pillared-layer Cu2(BDC-NH2)2(BPB-CF3) nets (BPB-CF3 = 2-trifluoromethyl-1,4-bis(4-pyridyl)benzene). Gas adsorption measurements showed that BUT-309 was a "flexible-robust" adsorbent with multistep adsorption isotherms for C3H4 rather than C3H6 at a wide temperature range. The guest-dependent pore-opening behavior endows BUT-309 with high potential in the C3H4/C3H6 separation. The C3H4 adsorption measurements of BUT-309 at 273-323 K showed that the lowering of the temperature induced the pore-opening action at lower pressure. Column breakthrough experiments further confirmed the capability of BUT-309 for the efficient removal of C3H4 from a C3H4/C3H6 binary gas, and the C3H6 processing capacity at 273 K (15.7 cm3 g-1) was higher than that at 298 K (35.2 cm3 g-1). This work shows a rare example of "flexible-robust" MOFs and demonstrated its high potential for C3H4/C3H6 separation.

Expanding the Structural Topologies of Rare-Earth Porphyrinic Metal-Organic Frameworks through Ligand Modulation.

Expanding the structural diversity of porphyrinic metal-organic frameworks (PMOFs) is essential to develop functional materials with novel properties or enhanced performance in different applications. Herein, we establish a strategy to construct rare-earth (RE) PMOFs with unprecedented topology via rational functionalization of porphyrinic ligands. By introducing phenyl/pyridyl groups to the meso-positions of the porphyrin core, the symmetries and connectivities of the ligands are tuned, and three RE-PMOFs (BUT-224/-225/-226) with new topologies are successfully obtained. In addition, BUT-225(Co), with both the Lewis basic and acidic sites, exhibits enhanced CO2 uptake and higher catalytic activity for the cycloaddition of CO2 and epoxides under mild conditions. This work reveals that the RE-PMOFs with novel topologies can be rationally designed and constructed through ligand functionalization, which provides insights into the construction of tailored PMOFs for various applications.

Catalytic ozone decomposition and adsorptive VOCs removal in bimetallic metal-organic frameworks.

Atmospheric ozone has long been a threat to human health, however, rational design of high-performance O3-decomposition catalysts remains challenging. Herein, we demonstrate the great potential of a series of isomorphous bimetallic MOFs denoted as PCN-250(Fe2M) (M = Co2+, Ni2+, Mn2+) in catalytic O3 decomposition. Particularly, PCN-250(Fe2Co) showed 100% O3 removal efficiency for a continuous air flow containing 1 ppm O3 over a wide humidity range (0 ‒ 80% RH) at room temperature. Mechanism studies suggested that the high catalytic performance originated from the introduction of open Co(II) sites as well as its porous structure. Additionally, at low pressures around 10 Pa, PCN-250(Fe2Co) exhibited high adsorption capacities (89 ‒ 241 mg g-1) for most VOCs, which are not only a class of hazardous air pollutants but also the precursor of O3. This work opens up a new avenue to develop advanced air purification materials for O3 and VOCs removal in one.

Construction and application of base-stable MOFs: a critical review.

Metal-organic frameworks (MOFs) are a new class of porous crystalline materials constructed from organic ligands and metal ions/clusters. Owing to their unique advantages, they have attracted more and more attention in recent years and numerous studies have revealed their great potential in various applications. Many important applications of MOFs inevitably involve harsh alkaline operational environments. To achieve high performance and long cycling life in these applications, high stability of MOFs against bases is necessary. Therefore, the construction of base-stable MOFs has become a critical research direction in the MOF field. This review gives a historic summary of the development of base-stable MOFs in the last few years. The key factors that can determine the robustness of MOFs under basic conditions are analyzed. We also demonstrate the exciting achievements that have been made by utilizing base-stable MOFs in different applications. In the end, we discuss major challenges for the further development of base-stable MOFs. Some possible methods to address these problems are presented.

Trace removal of benzene vapour using double-walled metal-dipyrazolate frameworks.

In principle, porous physisorbents are attractive candidates for the removal of volatile organic compounds such as benzene by virtue of their low energy for the capture and release of this pollutant. Unfortunately, many physisorbents exhibit weak sorbate-sorbent interactions, resulting in poor selectivity and low uptake when volatile organic compounds are present at trace concentrations. Herein, we report that a family of double-walled metal-dipyrazolate frameworks, BUT-53 to BUT-58, exhibit benzene uptakes at 298 K of 2.47-3.28 mmol g-1 at <10 Pa. Breakthrough experiments revealed that BUT-55, a supramolecular isomer of the metal-organic framework Co(BDP) (H2BDP = 1,4-di(1H-pyrazol-4-yl)benzene), captures trace levels of benzene, producing an air stream with benzene content below acceptable limits. Furthermore, BUT-55 can be regenerated with mild heating. Insight into the performance of BUT-55 comes from the crystal structure of the benzene-loaded phase (C6H6@BUT-55) and density functional theory calculations, which reveal that C-H···X interactions drive the tight binding of benzene. Our results demonstrate that BUT-55 is a recyclable physisorbent that exhibits high affinity and adsorption capacity towards benzene, making it a candidate for environmental remediation of benzene-contaminated gas mixtures.

Efficient Propylene/Ethylene Separation in Highly Porous Metal-Organic Frameworks.

Light olefins are important raw materials in the petrochemical industry for the production of many chemical products. In the past few years, remarkable progress has been made in the synthesis of light olefins (C2-C4) from methanol or syngas. The separation of light olefins by porous materials is, therefore, an intriguing research topic. In this work, single-component ethylene (C2H4) and propylene (C3H6) gas adsorption and binary C3H6/C2H4 (1:9) gas breakthrough experiments have been performed for three highly porous isostructural metal-organic frameworks (MOFs) denoted as Fe2M-L (M = Mn2+, Co2+, or Ni2+), three representative MOFs, namely ZIF-8 (also known as MAF-4), MIL-101(Cr), and HKUST-1, as well as an activated carbon (activated coconut charcoal, SUPELCO©). Single-component gas adsorption studies reveal that Fe2M-L, HKUST-1, and activated carbon show much higher C3H6 adsorption capacities than MIL-101(Cr) and ZIF-8, HKUST-1 and activated carbon have relatively high C3H6/C2H4 adsorption selectivity, and the C2H4 and C3H6 adsorption heats of Fe2Mn-L, MIL-101(Cr), and ZIF-8 are relatively low. Binary gas breakthrough experiments indicate all the adsorbents selectively adsorb C3H6 from C3H6/C2H4 mixture to produce purified C2H4, and 842, 515, 504, 271, and 181 cm3 g-1 C2H4 could be obtained for each breakthrough tests for HKUST-1, activated carbon, Fe2Mn-L, MIL-101(Cr), and ZIF-8, respectively. It is worth noting that C3H6 and C2H4 desorption dynamics of Fe2Mn-L are clearly faster than that of HKUST-1 or activated carbon, suggesting that Fe2M-L are promising adsorbents for C3H6/C2H4 separation with low energy penalty in regeneration.

A Hydrolytically Stable Cu(II)-Based Metal-Organic Framework with Easily Accessible Ligands for Water Harvesting.

Water scarcity is a critical issue in desert and arid regions, and atmospheric water harvesting is a potential solution. The challenge is lacking ideal adsorbents that can efficiently capture water from low-humidity air and be regenerated readily. Herein, we report a hydrolytically stable metal-organic framework (MOF), [Cu2(AD)2(SA)] (Cu-AD-SA), with excellent performance in water harvesting. More importantly, this material can be facilely prepared from two easily accessible ligands adenine (HAD) and succinic acid (H2SA). Cu-AD-SA has a three-dimensional (3D) framework structure with the crs topology and intersecting channels of ∼5 Å in diameter. The channel surface is decorated by uncoordinated aromatic N atoms, amine groups, and alkyl moieties. Interestingly, Cu-AD-SA shows a high water adsorption capacity of 0.16 g g-1 at low pressure of 0.2 P/P0 and 25 °C. Furthermore, dynamic water adsorption-desorption cycling experiments demonstrated a stable working capacity of 0.13 g g-1 for uptaking water from a low-humidity air (water partial pressure: 0.85 kPa, 20% RH at 30 °C, 5.3% RH at 55 °C) at 30 °C and desorption at 55 °C. The water adsorption mechanism was also studied by analyzing its single-crystal structure after water loading. The results indicated the existence of strong H-bonding interactions between water molecules and uncoordinated N atoms and amine groups on the framework, which should play an important role in the high adsorption at low pressure. All the above features suggest great potential of Cu-AD-SA for water harvesting in arid regions.

Linker Desymmetrization: Access to a Series of Rare-Earth Tetracarboxylate Frameworks with Eight-Connected Hexanuclear Nodes.

The exploration of metal-organic frameworks (MOFs) through the rational design of building units with specific sizes, geometries, and symmetries is essential for enriching the structural diversity of porous solids for applications including storage, separation, and conversion. However, it is still a challenge to directly synthesize rare-earth (RE) MOFs with less connected clusters as a thermodynamically favored product. Herein, we report a systematic investigation on the influence of size, rigidity, and symmetry of linkers over the formation of RE-tetracarboxylate MOFs and uncover the critical role of linker desymmetrization in constructing RE-MOFs with eight-connected hexanuclear clusters. Our results on nine new RE-MOFs, PCN-50X (X = 1-9), indicate that utilization of trapezoidal or tetrahedral linkers provides accesses to traditionally unattainable RE-tetracarboxylate MOFs with 8-c hexanuclear nodes, while the introduction of square or rectangular linkers during the assembly of RE-MOFs based on polynuclear clusters typically leads to the MOFs constructed from 12-c nodes with underlying shp topology. By rational linker design, MOFs with two unprecedented (4, 8)-c nets, lxl and jun, can also be obtained. This work highlights linker desymmetrization as a powerful strategy to enhance MOFs' structural complexity and access MOF materials with nondefault topologies that can be potentially used for separation and catalysis.

Construction of a mixed ligand MOF as "green catalyst" for the photocatalytic degradation of organic dye in aqueous media.

In the past few years, metal-organic frameworks (MOFs) have emerged as a class of fascinating materials for photocatalysis. Herein, a new MOF formulated as [Zn(bpe)(fdc)]·2DMF (BUT-206, bpe = 1,2-bis(4-pyridyl) ethylene, H2fdc = 2,5-furan dicarboxylic acid, DMF = N,N-dimethylformamide) is reported, which was synthesized under solvothermal conditions and applied for photocatalytic degradation of dyes (crystal violet and rhodamine B). Noteworthily, BUT-206 exhibited high photocatalytic activity toward the degradation of crystal violet without using any photosensitizer or cocatalyst under UV-irradiation. The photocatalytic degradation of crystal violet by BUT-206 was effective with a degradation efficiency of 92.5% within 120 minutes. The effects of key parameters including pH, amount of photocatalyst and initial concentration of dye on the dye degradation processes were examined, and the kinetics of dye degradation was established by the pseudo-first order kinetic equation. Furthermore, BUT-206 showed good cyclic stability in photocatalytic performance for up to five regeneration cycles, making it a potential green catalyst for dye degradation.

A Series of Mesoporous Rare-Earth Metal-Organic Frameworks Constructed from Organic Secondary Building Units.

Further development of metal-organic frameworks (MOFs) requires an establishment of hierarchical interaction within the framework. Herein, we report a series of mesoporous rare-earth (RE) MOFs that are constructed from an unusual 12-connected π-stacked pyrene secondary building unit (SBU) and a typical 12-connected RE6 cluster (RE=Eu, Y, Yb, Tb, Ce). The judicious design of a butterfly-shape pyrene ligand with a tert-butyl substituent enables the formation of the disordered 12-connected organic SBUs on its strong intermolecular π-π interactions. The assembly of 12-connected inorganic cuboctahedron SBUs and 12-connected organic distorted hexagonal prism SBUs generates an unprecedented network that can be further simplified into a 4,4-connected pts net linked from planar square and tetrahedra. This work provides fresh insights into the design and synthesis of frameworks constructed from coordinatively, covalently, and noncovalently linked building units.

A Green-Emission Metal-Organic Framework-Based Nanoprobe for Imaging Dual Tumor Biomarkers in Living Cells.

The modular nature of metal-organic frameworks (MOFs) permits their tunable structure and function for target application, such as in biomedicine. Herein, a green-emission Zr(IV)-MOF (BUT-88) was constructed from a customized luminescent carbazolyl ligand. BUT-88 represents the first bcu-type MOF with both organic linker and metal node in eight connections and shows medium-sized pores, rich accessible linking sites, and good water stability and biocompatibility. In virtue of these merits, BUT-88 was then fabricated into a MOF-based fluorescent nanoprobe, drDNA-BUT-88. Using it, the live-cell imaging of dual tumor biomarkers was achieved for the first time upon a MOF-based probe, offering enhanced detection precision in early cancer diagnosis. Particularly, the probe showed efficient ratiometric fluorescent sensing toward the cytoplasmic biomarker microRNA-21, further improving the detection accuracy at the cellular level. In this work, the elaborate combination of MOF engineering and the fluorescent detection technique has contributed a facile biosensing platform, unlocking more possibilities of MOF chemistry.

Microporous Hydrogen-Bonded Organic Framework for Highly Efficient Turn-Up Fluorescent Sensing of Aniline.

A microporous three-dimensional (3D) hydrogen-bonded organic framework (HOF-20) has been constructed from an aromatic-rich tetratopic carboxylic acid, 5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid (H4BCPIA). The activated HOF-20a has a moderately high Brunauer-Emmett-Teller (BET) surface area of 1323 m2 g-1 and excellent stability in water and HCl aqueous solution. HOF-20 exhibits highly efficient turn-up fluorescent sensing of aniline in water with a detection limit of 2.24 µM and is selective toward aniline in the presence of aromatic interferents, owing to the hydrogen bonding and edge-to-face π-π stacking interactions between the HOF-20 host and the guest aniline molecules, as demonstrated in the single-crystal X-ray structure of HOF-20⊃aniline. Density functional theory (DFT) calculations further demonstrate that the recognition of aniline molecules by HOF-20 could restrict the rotation of the aromatic rings in H4BCPIA linkers, reducing the nonradiative decay pathways upon photoexcitation and subsequently enhancing the fluorescence intensity.

Selective adsorption and separation of C2 hydrocarbons in a "flexible-robust" metal-organic framework based on a guest-dependent gate-opening effect.

The selective adsorption/separation of C2 hydrocarbons has been realized in a "flexible-robust" MOF, Zn2(Atz)2Ox. Owing to the distinctive guest-dependent multistep adsorption behaviors and suitable guest-framework interactions, this MOF shows outstanding separation performance for C2H2/C2H4 mixtures in a wide range of temperature confirmed by a column breakthrough experiment.

Hydrophobic Metal-Organic Frameworks: Assessment, Construction, and Diverse Applications.

Tens of thousands of metal-organic frameworks (MOFs) have been developed in the past two decades, and only ≈100 of them have been demonstrated as porous and hydrophobic. These hydrophobic MOFs feature not only a rich structural variety, highly crystalline frameworks, and uniform micropores, but also a low affinity toward water and superior hydrolytic stability, which make them promising adsorbents for diverse applications, including humid CO2 capture, alcohol/water separation, pollutant removal from air or water, substrate-selective catalysis, energy storage, anticorrosion, and self-cleaning. Herein, the recent research advancements in hydrophobic MOFs are presented. The existing techniques for qualitatively or quantitatively assessing the hydrophobicity of MOFs are first introduced. The reported experimental methods for the preparation of hydrophobic MOFs are then categorized. The concept that hydrophobic MOFs normally synthesized from predesigned organic ligands can also be prepared by the postsynthetic modification of the internal pore surface and/or external crystal surface of hydrophilic or less hydrophobic MOFs is highlighted. Finally, an overview of the recent studies on hydrophobic MOFs for various applications is provided and suggests the high versatility of this unique class of materials for practical use as either adsorbents or nanomaterials.

A stable zirconium based metal-organic framework for specific recognition of representative polychlorinated dibenzo-p-dioxin molecules.

Polychlorinated dibenzo-p-dioxins (PCDDs), as a class of persistent and highly toxic organic pollutants, have been posing a great threat to human health and the environment. The sensing of these compounds is important but challenging. Here, we report a highly stable zirconium-based metal-organic framework (MOF), Zr6O4(OH)8(HCOO)2(CPTTA)2 (BUT-17) with one-dimensional hexagonal channels and phenyl-rich pore surfaces for the recognition and sensing of two representative PCDDs, 2,3-dichlorodibenzo-p-dioxin (BCDD) and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), based on the fluorescence quenching. BUT-17 exhibits high sensing ability with the detection limits as low as 27 and 57 part per billion toward BCDD and TCDD, respectively, and is very selective as well without the interference of similar compounds. The recognition of BUT-17 toward BCDD is demonstrated by single-crystal structure of its guest-loaded phase, in which the fluorescence-quenched complexes form between the adsorbed BCDD molecules and the MOF host through π-π stacking and hydrogen bonding interactions.

Metal-Organic Frameworks for Food Safety.

Food safety is a prevalent concern around the world. As such, detection, removal, and control of risks and hazardous substances present from harvest to consumption will always be necessary. Metal-organic frameworks (MOFs), a class of functional materials, possess unique physical and chemical properties, demonstrating promise in food safety applications. In this review, the synthesis and porosity of MOFs are first introduced by some representative examples that pertain to the field of food safety. Following that, the application of MOFs and MOF-based materials in food safety monitoring, food processing, covering preservation, sanitation, and packaging is overviewed. Future perspectives, as well as potential opportunities and challenges faced by MOFs in this field will also be discussed. This review aims to promote the development and progress of MOF chemistry and application research in the field of food safety, potentially leading to novel solutions.

Reaction duration-dependent formation of two Cu(ii)-MOFs with selective adsorption properties of C3H4 over C3H6.

The formation of metal-organic frameworks (MOFs) under given reaction conditions depends on various factors including reaction duration, temperature, used solvent, system pH, and others. Among them, the reaction duration is relatively less investigated. In this work, based on a Cu(ii)-MOF system, the reaction duration was found to play an important role in directing the formation of two different products, (NH2(CH3)2)[Cu12(DDPN)6(H2O)10Cl] (BUT-301) on shorter reaction time and (NH2(CH3)2)2[Cu(DDPN)] (BUT-302) on longer reaction time, when CuCl2 reacted with 3,5-di(3,5-dicarboxylphenyl)nitrobenzene (H4DDPN) in a DMA/MeOH mixed solvent at 120 °C. With increasing the reaction duration, BUT-301 can transform into BUT-302. Both MOFs have three-dimensional (3D) framework structures. BUT-301 is constructed from paddle-wheel Cu2(COO)4 units and DDPN4- ligands as four-connected linkers, while BUT-302 is assembled from mononuclear Cu(ii) centers connecting the ligands as also four-connected linkers but in a monodentate coordination fashion. N2 adsorption confirmed that both MOFs are porous materials with the Brunauer-Emmett-Teller (BET) surface areas of 1953 and 561 m2 g-1, respectively. Interestingly, both BUT-301 and -302 show selective adsorption properties of C3H4 over C3H6. The C3H4/C3H6 adsorption selectivities were calculated to be 1.9 and 4.4 at 0.1 bar and 298 K by the ideal adsorbed solution theory (IAST) for a 1 : 99 C3H4/C3H6 mixture, respectively.