We report the syntheses, structures, and oxidation catalytic activities of a single-atom-based vanadium oxide incorporated in two highly crystalline MOFs, Hf-MOF-808 Zr-NU-1000. These catalysts were introduced by postsynthetic metalation, resulting materials (Hf-MOF-808-V Zr-NU-1000-V) thoroughly characterized through combination analytic spectroscopic techniques including single-crystal X-ray crystallography. Their properties investigated using 4-methoxybenzyl alcohol under an oxygen...

Protection of enzymes with synthetic materials is a viable strategy to stabilize, and hence retain, the reactivity these highly active biomolecules in non-native environments. Active supports, coupled encapsulated enzymes, can enable efficient cascade reactions which are necessary for processes like light-driven CO2 reduction, providing promising pathway alternative energy generation. Herein, semi-artificial system-containing an immobilized enzyme, formate dehydrogenase, light harvesting...

Nickel(IV) bis(dicarbollide) is incorporated in a zirconium-based metal–organic framework (MOF), NU-1000, to create an electrically conductive MOF with mesoporosity. All the nickel units are located as guest molecules microporous channels of which permits further incorporation other active species remaining mesopores. For demonstration, manganese oxide installed on nodes MOF. The electrochemically addressable fraction and specific capacitance more than 10 times higher those parent

Abstract Colloidal crystal engineering with nucleic acid-modified nanoparticles is a powerful way for preparing 3D superlattices, which may be useful in many areas, including catalysis, sensing, and photonics. To date, the building blocks studied have been primarily based upon metals, metal oxides, chalcogenide semiconductors, proteins. Here, we show that metal–organic framework (MOF NPs) densely functionalized oligonucleotides can programmed to crystallize into diverse set of superlattices...

Polyoxometalates (POMs) can benefit from immobilization on solid supports to overcome their difficulty in processability and stability. Among the reported supports, metal-organic frameworks (MOFs) offer a crystalline, versatile platform for depositing highly active POMs. The combination of these structures at times combined reactivity both POM MOF, sometimes synergistically, improve catalysis while balancing desirable properties like porosity, substrate diffusion, or In this Review, we...

A pyrene-based metal-organic framework (MOF) NU-1000 was used as a heterogeneous photocatalyst for the degradation of sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). Using irradiation from commercially available and inexpensive ultraviolet (UV) light-emitting diode (LED), singlet oxygen (1O2) is generated by selectively oxidizes CEES to nontoxic product sulfoxide (CEESO). More importantly, this method tested on warfare agent (HD) first time using 1O2 MOF catalyst, proved be...

Synthesis and activation of phase-pure defect-free metal–organic frameworks (MOFs) are essential for establishing accurate structure–property relationships.

A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting the hybrid material, PW12@NU-1000. The POM@MOF composite characterized by suite of physical methods, indicating retention crystallinity and high porosity parent MOF. material also stable to leaching media at varying pH. Finally, tested as heterogeneous catalyst for oxidation 2-chloroethyl ethyl sulfide using hydrogen peroxide oxidant....

The understanding of the catalyst-support interactions has been an important challenge in heterogeneous catalysis since supports can play a vital role controlling properties active species and hence their catalytic performance. Herein, series isostructural mesoporous metal-organic frameworks (MOFs) based on transition metals, lanthanides, actinides (Zr, Hf, Ce, Th) were investigated as for vanadium catalyst. was coordinated to oxo groups MOF node single-ion fashion, determined by...

Uremic toxins often accumulate in patients with compromised kidney function, like those chronic disease (CKD), leading to major clinical complications including serious illness and death. Sufficient removal of these from the blood increases efficacy hemodialysis, as well survival rate, CKD patients. Understanding interactions between an adsorbent uremic is critical for designing effective materials remove toxic compounds. Herein, we study adsorption behavior toxins, p-cresyl sulfate, indoxyl...

The efficient fixation of excess CO2 from the atmosphere to yield value-added chemicals remains crucial in response increasing levels carbon emission. Coupling enzymatic reactions with electrochemical regeneration cofactors is a promising technique for fixing CO2, while producing biomass which can be further transformed into biofuels. Herein, bioelectrocatalytic system was established by depositing crystallites mesoporous metal–organic framework (MOF), termed NU-1006, containing formate...

A fullerene-based photosensitizer is incorporated postsynthetically into a Zr6 -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to overall generation of from material under UV irradiation. generated by MOF/fullerene shown oxidize sulfur mustard selectively less toxic bis(2-chloroethyl)sulfoxide with half-life only 11 min.

The encapsulation of enzymes within porous materials has shown great promise, not only in protecting the from denaturation under nonbiological environments, but also, some cases, facilitating their enzymatic reaction rates at favorable conditions. While a number hypotheses have been developed to explain this phenomenon, detailed structural changes upon material, which are closely related activity, remain largely elusive. Herein, change cytochrome c (Cyt c) hierarchical metal-organic...

Single-site heterogeneous catalysts (SSHCs) play important roles in fundamental science and technology, owing to the molecular level control of structure–support interactions that is possible these systems. Recently, SSHCs supported by acidic oxides have attracted particular interest because catalytically active metal centers can be formed at surface sites. Here, we incorporated a palladium SSHC phosphated sulfated metal–organic frameworks (MOFs), hafnium-based MOF-808 (Hf-MOF-808-PO4...

Metal–organic frameworks (MOFs) have been extensively investigated as Lewis acidic catalysts for a variety of reactions. However, the identity and nature MOF nodes in catalysis remain ill-defined. Herein, series isostructural MOFs (M-NU-1008), with M being hexanuclear clusters transition metals (Zr Hf), lanthanide (Ce), or an actinide (Th), were successfully synthesized evaluated acid catalysts, CO2 cycloaddition styrene oxide was used test reaction. Superior catalytic activity observed...

The immobilization of H5PV2Mo10O40 polyoxometalates (POMs) in the mesoporous channel-type metal–organic framework (MOF), NU-1000, via simple impregnation method is reported here. Characterization composite PV2Mo10@NU-1000 activated by supercritical CO2 revealed that POMs occupy mesopore. Upon heating as low 40 °C absence bulk solvent, migrate to micropore. However, presence such cyclohexane, impedes this transformation. material was active for aerobic oxidation mustard gas simulant,...

An inexpensive, environmentally benign and scalable strategy was developed to synthesize UiO-66 derivatives in water at room temperature.

A polyoxometalate supported by the metal–organic framework, NU-1000, undergoes migration from mesopore to micropore when heated.

Acid-catalyzed skeletal C–C bond isomerizations are important benchmark reactions for the petrochemical industries. Among those, o-xylene isomerization/disproportionation is a probe reaction strong Brønsted acid catalysis, and it also sensitive to local site density pore topology. Here, we report on use of phosphotungstic (PTA) encapsulated within NU-1000, Zr-based metal–organic framework (MOF), as catalyst isomerization at 523 K. Extended X-ray absorption fine structure (EXAFS), 31P NMR, N2...

Here we describe the synthesis of two Zr-based benzothiadiazole- and benzoselenadiazole-containing metal-organic frameworks (MOFs) for selective photocatalytic oxidation mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES). The photophysical properties linkers MOFs are characterized by steady-state absorption emission, time-resolved ultrafast transient spectroscopy. MOF shows superior catalytic activity compared to that containing benzothiadiazole with a half-life 3.5 min CEES nontoxic...

The photocatalytically driven partial oxidation of a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES), was studied using the perylene-based metal–organic framework (MOF) UMCM-313 and compared to activities Zr-based MOFs: PCN-222/MOF-545 NU-1000. rates CEES positively correlated with singlet oxygen quantum yield MOF linkers, porphyrin (PCN-222/MOF-545) < pyrene (NU-1000) perylene (UMCM-313). Subsequently, thin films NU-1000 were solvothermally grown on conductive glass substrate...

Abstract The efficient fixation of excess CO 2 from the atmosphere to yield value‐added chemicals remains crucial in response increasing levels carbon emission. Coupling enzymatic reactions with electrochemical regeneration cofactors is a promising technique for fixing , while producing biomass which can be further transformed into biofuels. Herein, bioelectrocatalytic system was established by depositing crystallites mesoporous metal–organic framework (MOF), termed NU‐1006, containing...

NU-1000, a mesoporous metal–organic framework (MOF) featuring hexazirconium oxide nodes and 3 nm wide channels, was infiltrated with reactive dicobalt complex to install active sites onto the MOF nodes. The anchoring of NU-1000 occurred nearly ideal stoichiometry one bimetallic per node cobalt evenly distributed throughout particle. To access thermally robust multimetallic on an all-inorganic support, modified materials containing either complex, or analogous cobalt–aluminum species, were...