Search

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.

Porous materials possess high internal surface areas and void fractions that make them valuable in several applications, including gas storage, heterogeneous catalysis, and water purification. Despite the plentiful effort allocated to porous materials research annually, few methods exist to directly monitor and characterize chemical events occurring within a pore's confines. The crystalline nature of zeolites, covalent organic frameworks (COFs), and metal-organic frameworks (MOFs) permit structural characterization by X-ray diffraction; yet, quantifying the thermodynamics of chemical processes and transformations remains tedious and error ridden. Herein, we employ isothermal titration calorimetry (ITC) to determine the full thermodynamic profile of oxyanion adsorption in a zirconium-based MOF, NU-1000. To further validate this method, which we recently introduced to the field, we replicated ITC experiments as bulk adsorption measurements to demonstrate the correlation between the extracted stoichiometric parameter from ITC thermograms and the MOF uptake capacity. Moreover, based on the calculated association constants, we accurately predicted which analytes might be able to displace others. For example, dihydrogen phosphate can displace selenate and sulfate because of its higher association constant (ΔGphosphate = -5.41 kcal/mol; ΔGselenate = -4.98 kcal/mol; ΔGsulfate = -4.77 kcal/mol). We monitored the exchange processes by titrating oxyanion-functionalized MOF samples with a more strongly binding analyte.

As chemists and materials scientists, it is our duty to synthesize and utilize materials for a multitude of applications that promote the development of society and the well-being of its citizens. Since the inception of metal-organic frameworks (MOFs), researchers have proposed a variety of design strategies to rationally synthesize new MOF materials, studied their porosity and gas sorption performances, and integrated MOFs onto supports and into devices. Efforts have explored the relevance of MOFs for applications including, but not limited to, heterogeneous catalysis, guest delivery, water capture, destruction of nerve agents, gas storage, and separation. Recently, several start-up companies have undertaken MOF commercialization within industrial sectors. Herein, we provide a brief overview of the state of the MOF field from their design and synthesis to their potential applications, and finally, to their commercialization.

The performance of metal–organic frameworks (MOFs) under mechanical stress is an important consideration in the design, synthesis, and application of MOF materials in both fundamental and industria...

Krypton and xenon are important gases in many applications, including, but not limited to, electronics, lighting, and medicine. Separation of these two gases by cryogenic distillation is highly ene...

A new bismuth metal–organic framework (MOF), bismuth-NU-901 (Bi-NU-901), featuring the scu topology and a pore with a diameter of ∼11 A, was solvothermally synthesized, and its use as an X-ray comp...

Nanoscience and technology research offer exciting avenues to modernize undergraduate-level General Chemistry curricula. In particular, spherical nucleic acid (SNA) nanoconjugates, which behave as “programmable atom equivalents” (PAEs) in the context of colloidal crystals, are one system that one can use to reinforce foundational concepts in chemistry including matter and atoms, the Periodic Table, Lewis dot structures and the octet rule, valency and valence-shell electron-pair repulsion (VSEPR) theory, and Pauling’s rules, ultimately leading to enriching discussions centered on materials chemistry and biochemistry with key implications in medicine, optics, catalysis, and other areas. These lessons connect historical and modern concepts in chemistry, relate course content to current professional and popular science topics, inspire critical and creative thinking, and spur some students to continue their science, technology, engineering, and mathematics (STEM) education and attain careers in STEM fields. Ultimately, and perhaps most importantly, these lessons may expand the pool of young students interested in chemistry by making connections to a broader group of contemporary concepts and technologies that impact their lives and enhance their view of the field. Herein, a way of teaching aspects of General Chemistry in the context of modern nanoscience concepts is introduced to instructors and curricula developers at research institutions, primarily undergraduate institutions, and community colleges worldwide.

The global catalyst industry is valued at nearly 20 billion USD and demand continues to rise. Enzymes, biological macromolecules, are highly selective and efficient catalysts; however, their commercial implementation has been hindered due to their poor chemical and thermal stability and low reusability. Numerous strategies have been investigated to stabilize enzymes and improve their processability. Recently, metal–organic frameworks (MOFs) have been investigated as enzyme immobilization supports. Herein, we highlight the immobilization of enzymes in MOF cages and pores for catalysis applications and discuss the future of this enzyme encapsulation strategy.

Summary Enzymes are promising catalysts with high selectivity and activity under mild reaction conditions. However, their practical application has largely been hindered by their high cost and poor stability. Metal-organic frameworks (MOFs) as host materials show potential in protecting proteins against denaturing conditions, but a systematic study investigating the stabilizing mechanism is still lacking. In this study, we stabilized enzyme cytochrome c (cyt c) by encapsulating it in a hierarchical mesoporous zirconium-based MOF, NU-1000 against denaturing organic solvents. Cyt c@NU-1000 showed a significantly enhanced activity compared to the native enzyme, and the composite retained this enhanced activity after treatment with five denaturing organic solvents. Moreover, the composite was recyclable without activity loss for at least three cycles. Our cyt c@NU-1000 model system demonstrates that enzyme@MOF composites prepared via post-synthetic encapsulation offer a promising route to overcome the challenges of enzyme stability and recyclability that impede the widespread adoption of biocatalysis., Graphical abstract, Highlights • Catalytic activity of cytochrome c was protected against denaturing organic solvents • The mesoporous MOF stabilized cytochrome c by preventing enzyme aggregation • The enzyme@MOF composite was recyclable for at least three cycles • This enzyme@MOF system is promising for developing robust biocatalyst, Chemistry; Green chemistry; Engineering; Biocatalysis; Materials chemistry

The understanding of structure-activity relationships at the atomic level has played a profound role in heterogeneous catalysis, providing valuable insights into designing suitable heterogeneous catalysts. However, uncovering the detailed roles of how such active species' structures affect their catalytic performance remains a challenge owing to the lack of direct structural information on a specific active species. Herein, we deposited molybdenum(VI), an active species in oxidation reactions, on the Zr

Gadolinium(III) nanoconjugate contrast agents (CAs) provide significant advantages over small-molecule complexes for magnetic resonance imaging (MRI), namely increased Gd(III) payload and enhanced proton relaxation efficiency (relaxivity, r1). Previous research has demonstrated that both the structure and surface chemistry of the nanomaterial substantially influence contrast. We hypothesized that inserting Gd(III) complexes in the pores of a metal-organic framework (MOF) might offer a unique strategy to further explore the parameters of nanomaterial structure and composition, which influence relaxivity. Herein, we postsynthetically incorporate Gd(III) complexes into Zr-MOFs using solvent-assisted ligand incorporation (SALI). Through the study of Zr-based MOFs, NU-1000 (nano and micronsize particles) and NU-901, we investigated the impact of particle size and pore shape on proton relaxivity. The SALI-functionalized Gd nano NU-1000 hybrid material displayed the highest loading of the Gd(III) complex (1.9 ± 0.1 complexes per node) and exhibited the most enhanced proton relaxivity (r1 of 26 ± 1 mM-1 s-1 at 1.4 T). Based on nuclear magnetic relaxation dispersion (NMRD) analysis, we can attribute the performance of Gd nano NU-1000 to the nanoscale size of the MOF particles and larger pore size that allows for rapid water exchange. We have demonstrated that SALI is a promising method for incorporating Gd(III) complexes into MOF materials and identified crucial design parameters for the preparation of next generation Gd(III)-functionalized MOF MRI contrast agents.

Two-dimensional metal–organic frameworks (2D-MOFs) have shown promise in gas storage and separation applications due to their structural isomerism in response to external stimuli such as temperature, mechanical pressure, and/or guest molecules. Here, we report the guest-dependent phase transitions of a uranyl-based 2D-MOF, NU-1302, observed as single-crystal-to-single-crystal transformations. Different stacking configurations of the same structure were observed in DMF and ethanol, and after supercritical CO2 activation. The structural isomerism upon exposure to different solvents and when solvent-free demonstrated the ability of this system to respond to guests by shifting neighboring 2D sheets, resulting in the expansion or contraction of one-dimensional channels.

Diabetes affects millions of people worldwide and the number of diagnoses continues to climb annually. Though several effective medications and therapeutic methods have been developed to treat type 1 (T1DM) and type 2 (T2DM) diabetes mellitus, direct insulin injection remains the only effective treatment for insulin resistant (IR) diabetes patients. Here, we immobilize insulin in a crystalline mesoporous metal-organic framework (MOF), NU-1000, and obtain a high loading of ∼40 wt % in only 30 min. The acid-stable MOF capsules are found to effectively prevent insulin from degrading in the presence of stomach acid and the digestive enzyme, pepsin. Furthermore, the encapsulated insulin can be released from NU-1000 under simulated physiological conditions.

At the Hanford Site in southeastern Washington state, the U.S. Department of Energy intends to treat 56 million gallons of legacy nuclear waste by encasing it in borosilicate glass via vitrification. This process ineffectively captures radioactive pertechnetate (TcO4–) because of the ion’s volatility, thereby requiring a different remediation method for this long-lived (t1/2 = 2.1 × 105 years), environmentally mobile species. Currently available sorbents lack the desired combination of high uptake capacity, fast kinetics, and selectivity. Here, we evaluate the ability of the chemically and thermally robust Zr6-based metal–organic framework (MOF), NU-1000, to capture perrhenate (ReO4–), a pertechnetate simulant, and pertechnetate. Our material exhibits an excellent perrhenate uptake capacity of 210 mg/g, reaches saturation within 5 min, and maintains perrhenate uptake in the presence of competing anions. Additionally, experiments with pertechnetate confirm perrhenate is a suitable surrogate. Single-crystal...

Strict monitoring and control of selenium concentrations in freshwater supplies is critical to safeguarding human health and aquatic life. A handful of previously investigated sorbents exhibit noteworthy gravimetric (mg g−1) Se uptake capacities; however, often display insufficient volumetric (mg cm−3) capacities, thereby requiring large volumes of material for commercial implementation. In pursuit of mitigating this material inefficiency, we investigated the selenite (SeO32−) and selenate (SeO42−) affinity of MOF-808, a Zr-based metal–organic framework with a high density of potential Se oxyanion binding sites. MOF-808 recorded exceptional volumetric and gravimetric Se oxyanion capacities of 133 mg g−1 (127 mg cm−3) and 118 mg g−1 (112 mg cm−3) for aqueous selenite and selenate, respectively. Single-crystal X-ray diffraction studies revealed that selenite and selenate can bind at the MOF node via two distinct binding motifs, an η2μ2 motif in which the oxyanion coordinates to two different metal atoms in a single node, and a μ2 motif in which the oxyanion interacts with only a single metal atom. Furthermore, powder X-ray diffraction (PXRD) patterns and N2 adsorption/desorption isotherms confirm the retention of bulk crystallinity and porosity after the uptake of Se oxyanions.

The United States Environmental Protection Agency (EPA) recognizes atrazine, a commonly used herbicide, as an endocrine disrupting compound. Excessive use of this agrochemical results in contamination of surface and ground water supplies via agricultural runoff. Efficient removal of atrazine from contaminated water supplies is paramount. Here, the mechanism governing atrazine adsorption in Zr

Practical applications involving the magnetic bistability of single-molecule magnets (SMMs) for next-generation computer technologies require nanostructuring, organization, and protection of nanoscale materials in two- or three-dimensional networks, to enable read-and-write processes. Owing to their porous nature and structural long-range order, metal-organic frameworks (MOFs) have been proposed as hosts to facilitate these efforts. Although probing the channels of MOF composites using indirect methods is well established, the use of direct methods to elucidate fundamental structural information is still lacking. Herein we report the direct imaging of SMMs encapsulated in a mesoporous MOF matrix using high-resolution transmission electron microscopy. These images deliver, for the first time, direct and unambiguous evidence to support the adsorption of molecular guests within the porous host. Bulk magnetic measurements further support the successful nanostructuring of SMMs. The preparation of the first magnetic composite thin films of this kind furthers the development of molecular spintronics.

Summary Recent efforts have examined metal-organic frameworks (MOFs) as sorbents for removing pollutants and trace chemicals, such as pharmaceuticals, from aqueous media. To date, few studies have investigated the energetics of interactions between toxic species and MOF-based sorbents. To this end, we elected to use isothermal titration calorimetry (ITC) to quantify the thermodynamic parameters associated with the adsorption of uremic toxins, namely p-cresyl sulfate and indoxyl sulfate, onto zirconium-based MOFs. NU-1000, a mesoporous MOF comprising a pyrene-based linker, possesses two distinct adsorption sites that display dramatically different enthalpic and entropic parameters. ITC measurements further reveal that a concerted interaction that embodies both favorable enthalpic and entropic contributions is critical for designing a high-capacity MOF-based adsorbent.

A representative mesoporous metal-organic-framework (MOF) material, NU-1000, has been rendered electronically conductive via a robust inorganic approach that permits retention of MOF crystallinity and porosity. The approach is based on condensed-phase grafting of molecular tin species onto the MOF nodes via irreversible reaction with hydroxyl and aqua ligands presented at the node surface, a self-limiting process termed solvothermal installation (of metal ions) in MOFs (SIM, a solution-phase analog of atomic layer deposition in MOFs). Treatment of the modified MOF with aerated steam at 120 °C converts the grafted tin molecules to tetratin(IV)oxy clusters, with the clusters being sited between insulating pairs of zirconia-like nodes (the zirconium component being key to endowing the parent material with requisite chemical and thermal stability). By introducing new O-H presenting ligands on the modified-MOF node, the high-temperature steam step additionally serves to reset the material to reactive form, thus enabling a second self-limiting tin-grafting step to be run (and after further steam treatment, enabling a third). Difference-envelop-density (DED) analyses of synchrotron-derived X-ray scattering data, with and without installed tin species, show that the clusters formed after one cycle are spatially isolated, but that repetitive SIM cycling adds metal and oxygen ions in a way that enshrouds nodes, links clusters, and yields continuous one-dimensional strands of oxy-tin(IV), oriented exclusively along the c axis of the MOF. Two-probe conductivity measurements show that the parent MOF and the version containing isolated oxy-tin(IV) clusters are electrically insulating, but that the versions featuring continuous strands show an electrical conductivity of 1.8 × 10