Mesoporous MOFs Research Articles

Powering Hydrogen Evolution Reaction by Precise Control Over A Cu‐Ni Bimetallic Electrocatalyst

ABSTRACTPrecious metals are effective catalysts for the hydrogen evolution reaction, but their high cost with complicated operation steps drives people to search for non–noble‐metal alternatives. Building rational design concept for efficient electrocatalyst relies on the capability to control the structure and composition. Herein, a Ni/Cu bimetallic mesoporous MOFs with 4,4′,4″‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid as the robust ligand has been assembled via a one‐step solvothermal method. Due to the extensive conjugate plane and high nitrogen content, the catalyst possesses large pore size of 17 nm and fast electron transfer rate, which favors hydrogen bubble overflow and exposes more active sites to solid–liquid interfaces. The bimetallic interaction between highly conductive Cu ions and Ni ions allows it to improve charge migration and realize excellent conductivity. The functionalized electrode requires an overpotential of 132 mV to achieve 10 mA current density with a small Tafel slope (87.7 mV·dec−1) and continuous electrolysis for 24 h.

Disentangling the efficient photocatalytic reduction of CO2 by a stable UiO-66-NH2/Cs2AgBiBr6 catalyst

The compelling global warming crisis as well as extraterrestrial artificial light synthesis craves photocatalytic reduction of CO2 into fuels and value-added chemicals, for which efficient and robust catalysts with high selectivity and conversion rate is a prerequisite but hitherto a rarity. Herein we create a lead-free double metal perovskite of Cs2AgBiBr6, coupling with mesoporous/microporous UiO-66-NH2 MOF to form type-II heterojunctions for efficient photocatalytic reduction of CO2 with a high CO selectivity of 95 % at an electron consumption rate of 33 μmol g−1 h−1 (13.4 μmol g−1 h−1 for CO and 0.72 μmol g−1 h−1 for CH4). Multilayered mesoporous MOF particles manifest higher catalytic activity than their microporous counterparts due to the highly open mesoporous channels and larger pore volume of the former. Femtosecond transient absorption in combination with in situ infrared spectroscopic measurements disentangle the underlying mechanism accounting for the high product selectivity: the ultrafast electron transfer of 12.3 ps from Cs2AgBiBr6 to UiO-66-NH2-2 enables efficient charge separation; primary *COOH intermediates and rapid CO desorption from Bi-based photocatalyst lead to dominant CO product. Moreover, the MOF crystals maintain stability after γ-rays irradiation equivalent of over 45-year accumulation in a typical earth orbit, hinting their promising potential in extraterrestrial artificial light synthesis.

Efficient adsorption and desorption of elemental mercury by ordered mesoporous cerium oxide nanoparticles derived from Ce-based metal–organic frameworks

Metal oxide-based adsorbents not only exhibit effective elemental mercury (Hg0) removal capacity but also offer suitability for wet desorption, which is a green treatment method to avoid secondary contamination of deactivated adsorbents. Nevertheless, the limited dispersing capacity of the carrier restricts the loading of active substances, hindering further enhancement of adsorption capacity. The pore structure of adsorbent is also a key factor for wet desorption. In this work, we synthesized a hollow cerium-based metal–organic framework (Ce-mesoMOF) as a sacrificial precursor to obtain ordered mesoporous cerium oxide (OM-CeO₂) via a mesoporous genetic pyrolysis-oxidation mechanism. OM-CeO2 inherits the excellent structural properties of mesoporous MOF with better catalytic activity, exhibiting strong adsorption capacity in various atmospheres (97.6 % in pure N2, 98.8 % in N2 + H2S). Wet desorption of Hg compounds and reduction of the active site can be synergized in Na2S2O3 solution. The octahedral structure with an ordered mesoporous shell greatly facilitates the mass transfer process, as evidenced by the strong adsorption capacity and fast kinetic parameters of OM-CeO2. Density functional theory analysis reveals that the conversion reaction of adsorbed Hg has a low energy barrier on the pyrolytic-oxidized OM-CeO2 and the inhibitory effect of reactive S for Hg0 adsorption transforms into a facilitating effect. This study leverages the structural advantages of ordered mesoporous MOFs in the field of Hg adsorption and imparts reactivity through modification for efficient adsorption–desorption.

Site-Selective Functionalization of Outer Surface and Different Inner Spaces of Nanoscale Hierarchically Mesoporous MOFs for the Specific Detection of Cancer Cells

Site-Selective Functionalization of Outer Surface and Different Inner Spaces of Nanoscale Hierarchically Mesoporous MOFs for the Specific Detection of Cancer Cells

Fluorescence sensing probe based on functionalized mesoporous MOFs for non-invasive and detection of dopamine in human fluids

Abnormal amount of dopamine (DA) in human body is closely relate to various diseases, such as Parkinson's disease, pheochromocytoma. Real-time monitoring DA is crucial for disease warning, diagnosis and treatment. Currently, most methods rely on invasive blood testing for detecting DA, which is only completed with the aid of the medical staffs in hospitals. Herein, a non-invasive fluorescence visual strategy is developed for the real-time monitoring DA, based on luminescent nanoparticles and modified mesoporous zeolite imidazole framework (ZIF-8-NH2) dodecahedrons. During the reaction process, DA is enriched through the spatial configuration of ZIF-8-NH2 and hydrogen bonding effect. The luminescence of Cr3+-doped zinc gallate (ZnGa2O4:Cr3+, ZGC) is inhibited by the photo-induced electron transfer (PET) mechanism to realize sensitively detecting DA. The intelligent sensing platform based on the designed fluorescence probe and color recognition system is structured for real-time detection of DA in urine. Furthermore, a skin-fitting hydrogel patch is prepared by combining a fluorescent probe with chitosan, which enables sensitive and accurate detection of DA in sweat without the complex sample pretreatment. The non-invasive fluorescence detection method provides an effective strategy for quantitatively monitoring DA in human fluids.

Synergy of metallic Co and oxygen vacancy sites in Co/Ce-MOF catalysts for efficiently promoting lignin derived phenols and macromolecular lignin hydrodeoxygenation

The enhanced utilization of biomass-derived chemicals for the generation of high value aromatics through an advanced catalytic strategy has captured considerable attention within the realm of eco-friendly manufacturing. This work presented four innovative three-dimensional rod-shaped mesoporous Ce-based MOF materials, which were coupled with a H-donor solvent to facilitate vanillin hydrodeoxygenation and macromolecular lignin. Under the optimized conditions (30 mg CoCe@C catalyst, 2 MPa N2 pressure, 15 mL isopropanol, 190 °C, and 5 h), the CoCe@C catalyst achieved nearly complete conversion of vanillin and demonstrated 87.8 % selectivity in the hydrogen-donor solvent. The characterization findings suggested that the synergy between metallic Co and oxygen vacancy sites enabled the effective activation of CHO group in vanillin, leading to formation of reactive product MMP. In addition, the optimal CoCe@C catalyst could also achieve macromolecular lignin hydrodeoxygenation to obtain high yield of lignin oil products with narrower molecular weight distribution. This study presented a viable approach for the concurrent utilization of lignin derivatives in the generation of high value fuels and chemicals.

Mesoporous MOFs with ROS scavenging capacity for the alleviation of inflammation through inhibiting stimulator of interferon genes to promote diabetic wound healing

Excessive production of reactive oxygen species (ROS) and inflammation are the key problems that impede diabetic wound healing. In particular, dressings with ROS scavenging capacity play a crucial role in the process of chronic wound healing. Herein, Zr-based large-pore mesoporous metal–organic frameworks (mesoMOFs) were successfully developed for the construction of spatially organized cascade bioreactors. Natural superoxide dismutase (SOD) and an artificial enzyme were spatially organized in these hierarchical mesoMOFs, forming a cascade antioxidant defense system, and presenting efficient intracellular and extracellular ROS scavenging performance. In vivo experiments demonstrated that the SOD@HMUiO-MnTCPP nanoparticles (S@M@H NPs) significantly accelerated diabetic wound healing. Transcriptomic and western blot results further indicated that the nanocomposite could inhibit fibroblast senescence and ferroptosis as well as the stimulator of interferon genes (STING) signaling pathway activation in macrophages mediated by mitochondrial oxidative stress through ROS elimination. Thus, the biomimetic multi-enzyme cascade catalytic system with spatial ordering demonstrated a high potential for diabetic wound healing, where senescence, ferroptosis, and STING signaling pathways may be potential targets.Graphical Schematic diagram showing the proposed mechanism that S@M@H NPs promoted diabetic wound healing

Modulator Directed Synthesis of Size-Tunable Mesoporous MOFs and Their Derived Nanocarbon-Based Electrocatalysts for Oxygen Reduction

Although MOF-derived carbon materials have been widely used for electrocatalysis, it is challenging to prepare size-tunable MOF precursors through simple modulation. In this work, a series of mesoporous MOF (PCN-224) with a wide tunable particle size from micro- to nano-scale were successfully synthesized by in-situ introduction of 3-mercaptopropionic acid as the modulator. After carbonization and acid etching, the derived carbons (MAx-NC) inherit the mesoporous structure and exhibit uniform particles ranging from 30 to 900 nm. MAx-NC were used as model catalysts to explore the size effects on electrocatalysis. Considering the similar compositional and structural properties, the electrochemical activity depends on the number of accessible surface active sites. MA3-NC with optimized particle sizes (∼300 nm) would not only provide abundant surface active sites but also consist of large secondary pores between the particles for fast mass transport. Moreover, suitable Fe atom was introduced into the optimized MAx-NC, which shows comparable half-wave potential and better stability than commercial Pt/C for the typical oxygen reduction reaction. This work provides an efficient “modulation” strategy for preparing size-tunable mesoporous MOF cubes and their carbon derivatives, paving a new way to customize nanosized MOFs for wider applications.

Mesoporous MOF Based on a Hexagonal Bipyramid Co8-Cluster: High Catalytic Efficiency on the Cycloaddition Reaction of CO2 with Bulky Epoxides.

A mesoporous cobalt-based metal-organic framework (LCU-606) was synthesized based on a hexagonal bipyramid Co8(μ4-O)3 cluster and an N,N,N',N'-tetrakis-(4-benzoic acid)-1,4-phenylenediamine ligand (H4TBAP). LCU-606 featuring large pore diameters of 21.7 Å and exposed Lewis-acid metal sites could serve as an excellent heterogeneous catalyst for CO2 cycloaddition reaction with various epoxide substrates under mild conditions (1 atm CO2, 60 °C, and solvent free). In particular, when extending the substrates to bulkier ones, LCU-606 still shows high catalytic efficiency on account of the large pore aperture. Also, LCU-606 demonstrates high recyclability and stability in consecutive catalytic runs. Therefore, the high efficiency, recyclability, and generality on CO2 catalytic cycloaddition make LCU-606 a very promising heterogeneous catalyst for CO2 chemical fixation.

A cage-on-MOF strategy to coordinatively functionalize mesoporous MOFs for manipulating selectivity in adsorption and catalysis

Functionalizing porous materials with capping agents generates hybrid materials with enhanced properties, while the challenge is how to improve the selectivity and maintain the porosity of the parent framework. Herein, we developed a “Cage-on-MOF” strategy to tune the recognition and catalytic properties of MOFs without impairing their porosity. Two types of porous coordination cages (PCCs) of opposite charges containing secondary binding groups were developed to coordinatively functionalize two distinct porous MOFs, namely MOF@PCC nanocomposites. We demonstrated that the surface-capped PCCs can act as “modulators” to effectively tune the surface charge, stability, and adsorption behavior of different host MOF particles. More importantly, the MOF@PCCs can serve as selective heterogeneous catalysts for condensation reactions to achieve reversed product selectivity and excellent recyclability. This work sets the foundation for using molecular cages as porous surface-capping agents to functionalize and manipulate another porous material, without affecting the intrinsic properties of the parent framework.

Preparation of lysozyme-imprinted mesoporous Zr-based metal-organic frameworks with remarkable specific recognition

The development of high-performance protein-imprinted materials remains challenging due to defects concerning high mass transfer resistance and non-specific binding, which are crucial for protein purification and enrichment. In this paper, lysozyme-imprinted mesoporous Zr-based MOF (mesoUiO-66-NH2@MIPs) with specific and selective recognition of lysozyme (Lyz) were prepared by surface imprinting technology. In particular, the excellent hydrophilicity mesoporous MOFs (mesoUiO-66-NH2) with a pore size of 10 nm was prepared as a carrier for Lyz immobilization by an auxiliary modulation strategy to regulate the microporous structure of UiO-66-NH2 with the propionic acid solution, enabling massive loading of the macromolecular protein Lyz. The mesoUiO-66-NH2@MIPs reached a maximum saturation adsorption of 206.54 mg g−1 on Lyz in 20 min at 25 °C with an imprinting factor of 2.57 and selection factors of 2.02, 2.34, and 2.45 for cytochrome c (Cyt c), bovine serum albumin (BSA) and bovine hemoglobin (BHb), respectively. More importantly, the mesoUiO-66-NH2@MIPs could specifically recognize Lyz from the mixed protein system. The adsorption capacity of Lyz could still reach 78.55% after 5 cycles with good cyclic regeneration performance. This provides a new research option for developing and applying novel porous MOF in biomolecule imprinting technology and the specific separation of biomolecules.

Metal Doping Induced Formation and Dynamic Gas Sorption of a Highly Porous Mesoporous MetalOrganic Framework

A new high-porosity MOF of [Ni2.3Zn0.7(tzba)3 (H2 O)6 ]·12DMF (NiZn-MOF) processes 2D (3,6)-grid layers constructed from rare [M2 (tz)3 (H2 O)3 ] and [M(COO)3 ] nodes. The metal doping of Ni2+ and Zn2+ are crucial for the formation of the two kinds of metal nodes and subsequent synergistical assembly into the mesoporous MOF, in contrast to the formation of MIL-88-topology resembled compound of {(Me2 NH2 )[Ni3 (μ3 -OH)(tzba)3 (H2 O)3 ]·8DMF (Ni3-MOF) using single Ni2+ as metal source. The regular 2D layers stacked in parallel and ABAB fashion through interlayer hydrogen bonding, leading to a neutral framework with void fraction up to 72.1% and 1D mesoporous hexagonal channels sized at 24.0 Å in diameter. The large gas accessible porosity was revealed by the saturated N2 and CO2 uptake of 720 and 708 cm3 g-1, at 77 K and 195 K, respectively, giving a high Langmuir surface area of 2066 m2 g-1. The varying gas sorption amounts dependent on accommodated solvents and activation temperature, as well as the gate-opening behaviors in sorption isotherms, well confirm the dynamic structure response to guest species of the flexible framework.

Post-Synthetic Cyano-ferrate(II) Functionalization of a Metal–Organic Framework, NU-1000

Starting with ferrocyanide ions in acidic aqueous solution, cyano-ferrate(II) species are post-synthetically grafted to the nodes of a mesoporous zirconium-based MOF, NU-1000. As indicated by single-crystal X-ray crystallography, grafting occurs by substitution of cyanide ligands by node-based hydroxo and oxo ligands rather than by substitution of node aqua ligands by cyanide ligands as bridges between Fe(II) and Zr(IV). The installed moieties yield a broad absorption band that is tentatively ascribed to iron-to-zirconium charge transfer. Consistent with Fe(III/II) redox activity, a modest fraction of the installed iron complexes are directly electrochemically addressable.

Water-Stable etb-MOFs for Methane and Carbon Dioxide Storage

We utilized the etb platform of MOFs for the synthesis of two new water-stable compounds based on amide functionalized trigonal tritopic organic linkers H3BTBTB (L1), H3BTCTB (L2) and Al3+ metal ions, namely, Al(L1) and Al(L2). The mesoporous Al(L1) material exhibits an impressive methane (CH4) uptake at high pressures and ambient temperature. The corresponding values of 192 cm3 (STP) cm-3, 0.254 g g-1 at 100 bar, and 298 K are among the highest reported for mesoporous MOFs, while the gravimetric and volumetric working capacities (between 80 bar and 5 bar) can be well compared to the best MOFs for CH4 storage. Furthermore, at 298 K and 50 bar, Al(L1) adsorbs 50 wt % (304 cm3 (STP) cm-3) CO2, values among the best recorded for CO2 storage using porous materials. To gain insight into the mechanism accounting for the resultant enhanced CH4 storage capacity, theoretical calculations were performed, revealing the presence of strong CH4 adsorption sites near the amide groups. Our work demonstrates that amide functionalized mesoporous etb-MOFs can be valuable for the design of versatile coordination compounds with CH4 and CO2 storage capacities comparable to ultra-high surface area microporous MOFs.

Amide Functionalized Mesoporous MOF LOCOM-1 as a Stable Highly Active Basic Catalyst for Knoevenagel Condensation Reaction.

Acyl-amide is extensively used as functional group and is a superior contender for the design of MOFs with the guest accessible functional organic sites. A novel acyl-amide-containing tetracarboxylate ligand, bis(3,5-dicarboxy-pheny1)terephthalamide, has been successfully synthesized. The H4L linker has some fascinating attributes as follows: (i) four carboxylate moieties as the coordination sites confirm affluent coordination approaches to figure a diversity of structure; (ii) two acyl-amide groups as the guest interaction sites can engender guest molecules integrated into the MOF networks through H-bonding interfaces and have a possibility to act as functional organic sites for the condensation reaction. A mesoporous MOF ([Cu2(L)(H2O)3]·4DMF·6H2O) has been prepared in order to produce the amide FOS within the MOF, which will work as guest accessible sites. The prepared MOF was characterized by CHN analysis, PXRD, FTIR spectroscopy, and SEM analysis. The MOF showed superior catalytic activity for Knoevenagel condensation. The catalytic system endures a broad variety of the functional groups and presents high to modest yields of aldehydes containing electron withdrawing groups (4-chloro, 4-fluoro, 4-nitro), offering a yield > 98 in less reaction time as compared to aldehydes with electron donationg groups (4-methyl). The amide decorated MOF (LOCOM-1-) as a heterogeneous catalyst can be simply recovered by centrifugation and recycled again without a flagrant loss of its catalytic efficiency.

Ionic-Liquid-Assisted One-Step Construction of Mesoporous Metal-Organic Frameworks.

The synthesis of ionic-mesoporous-metal-organic frameworks (ionic-meso-MOFs) has received considerable interest in the fields of macromolecular adsorption, acid-base catalysis, ionic conductivity, etc.; yet, their synthesis still presents significant difficulties. In this study, functionalized mesoporous MIL-101-ILs (Cr) was facilely constructed via an in situ self-assembly method by using aromatic-anion-functionalized ionic liquids (ILs) as competitive ligands. It has been demonstrated that the inclusion of an aromatic moiety into an IL improves the coordination ability and is advantageous for the anchoring of ILs on Cr3+ via amino-metal coordination. Thus, ionic-meso-MOFs with a specific surface area of 441.9-624.9 cm2/g and an average pore diameter of 5.5 to 8.4 nm were successfully synthesized. Because of the presence of open Lewis acidic metal sites on the MOFs and basic active sites on the ILs, the resulting ionic-meso-MOFs demonstrated both an acid-base cooperative effect and a mesoporous structure, indicating a high potential for acid-base catalysis. This in situ synthesis procedure for ionic mesoporous MOFs offers a simple method for developing and fabricating multifunctional mesoporous materials.

Rational design of mesoporous chiral MOFs as reactive pockets in nanochannels for enzyme-free identification of monosaccharide enantiomers.

Monosaccharides play significant roles in daily metabolism in living organisms. Although various devices have been constructed for monosaccharide identification, most rely on the specificity of the natural enzyme. Herein, inspired by natural ionic channels, an asymmetrical MOF-in-nanochannel architecture is developed to discriminate monosaccharide enantiomers based on cascade reactions by combining oxidase-mimicking and Fenton-like catalysis in homochiral mesoporous CuMOF pockets. The identification performance is remarkably enhanced by the increased oxidase-mimicking activity of Au nanoparticles under a local surface plasmon resonance (LSPR) excitation. The apparent steady-state kinetic parameters and nano-fluidic simulation indicate that the different affinities induced by Au-LSPR excitation and the confinement effect from MOF pockets precipitate the high chiral sensitivity. This study offers a promising strategy for designing an enantiomer discrimination device and helps to gain insight into the origin of stereoselectivity in a natural enzyme.

Hierarchically Ultrasmall Hf-Based MOF: Mesopore Adjustment and Reconstruction by Recycle Using Acid Etching Strategy

Benefiting from their unique properties including faster mass transfer, more exposed active sites and large molecule recognition, hierarchically porous metal–organic frameworks (HP-MOFs), in the form of ultrasmall nanoparticles (NPs) and having self-assembled interparticle mesopores, have garnered greater attention in recent years that given to typical MOFs. However, controllable synthesis of HP-MOFs on the nanoscale remains a significant challenge. Herein, for the first time, a facile top-down acid etching strategy was developed to fabricate a series of nanosized (∼15 nm) mesoporous MOF, HP-UiO-66-NH2(Hf). The sizes of mesopores in this material can be effectively tuned by simply controlling the concentration of propionic acid (PA) utilized in the preparation solution. Interestingly, the generated mesoporous HP-UiO-66-NH2(Hf) has excellent stability and can be readily constructed by using PA etching solution that has been recycled at least four times. Remarkably, HP-UiO-66-NH2(Hf) displays a high size-selectivity for adsorption of enzymes. Associated with its highly matched mesopore size, the nanocomposite generated by complexation with glucose oxidase (GOD), GOD@HP-UiO-66-NH2(Hf) has a higher catalytic activity and a significantly enhanced stability (recycled at least 7 times) in promoting oxidation of glucose compared to its MOF counterpart, GOD@UiO-66-NH2(Hf) and native GOD.

The use of metal-organic frameworks as heterogeneous catalysts

Abstract This article presents an overview of some of the available research studies of MOFs as catalysts. Catalytic studies of magnetic iron oxide nanoparticles with modified surfaces, MOFs with precious metals such as palladium, platinum, and silver, with zirconium, hafnium, copper, alkaline earth metals, lanthanides are generalized. The studies of the catalytic activity of micro- and mesoporous MOF structures are described.

Photodynamic and Its Concomitant Ion-Interference Synergistic Therapies Based on Functional Hierarchically Mesoporous MOFs.

Although ion-interference therapy (IIT) has become an intriguing option for cancer treatment, the generation of interference ions on-demand remains a challenge. Herein, a nanoplatform based on hierarchically mesoporous metal-organic frameworks (HMMOFs) is adopted to integrate black phosphorus quantum dots (BPQDs) and meso-tetra(4-carboxyphenyl) porphine (TCPP) to realize controllable phosphate anions (PAs) production in a specific cancerous region for IIT. The uniform large mesopores of HMMOFs could guarantee the selective screening and immobilization of ultra-small and monodispersed BPQDs. The TCPP in microporous domains of HMMOFs could effectively produce 1 O2 , which not only serves as photosensitizer for photodynamic therapy (PDT), but also switches on the release of PAs from BPQDs in the adjacent mesoporous domains to trigger the concomitant synergetic IIT. The elaborated nanoplatform (BP@HMUiO-66-TCPP) presents good biocompatibility, biodegradability as well as enhanced synergetic therapeutic effects. In murine models treated with BP@HMUiO-66-TCPP, the tumor inhibition rate is as high as ≈98.24% as compared to that of the control group after 14 days treatment. Moreover, the tumor volumes in the synergetic group are only 19.6% of those in the PDT alone treated group. Such a concept of exogenous photo-controlled synergistic therapeutics might be extended to a broad range of IIT for an improved antitumor efficacy.