Defect-enabling zirconium-based metal-organic frameworks for energy and environmental remediation applications.

This comprehensive review explores the diverse applications of defective zirconium-based metal-organic frameworks (Zr-MOFs) in energy and environmental remediation. Zr-MOFs have gained significant attention due to their unique properties, and deliberate introduction of defects further enhances their functionality. The review encompasses several areas where defective Zr-MOFs exhibit promise, including environmental remediation, detoxification of chemical warfare agents, photocatalytic energy conversions, and electrochemical applications. Defects play a pivotal role by creating open sites within the framework, facilitating effective adsorption and remediation of pollutants. They also contribute to the catalytic activity of Zr-MOFs, enabling efficient energy conversion processes such as hydrogen production and CO2 reduction. The review underscores the importance of defect manipulation, including control over their distribution and type, to optimize the performance of Zr-MOFs. Through tailored defect engineering and precise selection of functional groups, researchers can enhance the selectivity and efficiency of Zr-MOFs for specific applications. Additionally, pore size manipulation influences the adsorption capacity and transport properties of Zr-MOFs, further expanding their potential in environmental remediation and energy conversion. Defective Zr-MOFs exhibit remarkable stability and synthetic versatility, making them suitable for diverse environmental conditions and allowing for the introduction of missing linkers, cluster defects, or post-synthetic modifications to precisely tailor their properties. Overall, this review highlights the promising prospects of defective Zr-MOFs in addressing energy and environmental challenges, positioning them as versatile tools for sustainable solutions and paving the way for advancements in various sectors toward a cleaner and more sustainable future.

Correction: Defect-enabling zirconium-based metal-organic frameworks for energy and environmental remediation applications.

Correction for 'Defect-enabling zirconium-based metal-organic frameworks for energy and environmental remediation applications' by Saba Daliran et al., Chem. Soc. Rev., 2024, https://doi.org/10.1039/d3cs01057k.

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.

Probing the electronic and ionic transport in topologically distinct redox-active metal-organic frameworks in aqueous electrolytes.

Three topologically distinct zirconium-based metal-organic frameworks (Zr-MOFs) constructed from redox-innocent linkers, MOF-808, defective UiO-66, and CAU-24, are synthesized, and the spatially dispersed redox-active manganese sites are post-synthetically immobilized on the hexa-zirconium nodes of these Zr-MOFs. The crystallinity, morphology, porosity, manganese loading, and bulk electrical conductivity of each material are studied. The redox-hopping-based electrochemical reaction between the installed Mn(III) and Mn(IV) occurring within the thin films of these MOFs in aqueous electrolytes is investigated, in the presence of various concentrations of Na2SO4 in the electrolytes. Cyclic voltammetry is used to qualitatively study the redox-hopping process, and chronoamperometry is used to quantify the electrochemically active fractions of manganese sites within the MOF thin film as well as the values of apparent diffusivity for the redox-hopping process. By adjusting the concentration of Na2SO4 in the electrolyte, the rate-determining step for the redox-hopping process can be tuned from ionic transport to electronic transport, and the Mn-decorated MOF-808, which possesses the largest pore size, can achieve the highest value of apparent diffusivity. Findings here shed light on the selection of Zr-MOF as well as the choice of electrolyte concentration for the applications of MOFs in supercapacitors and electrocatalysis relying on such redox-hopping processes in aqueous electrolytes.

Charge Transport in Zirconium-Based Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are a class of crystalline porous materials characterized by inorganic nodes and multitopic organic linkers. Because of their molecular-scale porosity and periodic intraframework chemical functionality, MOFs are attractive scaffolds for supporting and/or organizing catalysts, photocatalysts, chemical-sensing elements, small enzymes, and numerous other functional-property-imparting, nanometer-scale objects. Notably, these objects can be installed after the synthesis of the MOF, eliminating the need for chemical and thermal compatibility of the objects with the synthesis milieu. Thus, postsynthetically functionalized MOFs can present three-dimensional arrays of high-density, yet well-separated, active sites. Depending on the application and corresponding morphological requirements, MOF materials can be prepared in thin-film form, pelletized form, isolated single-crystal form, polycrystalline powder form, mixed-matrix membrane form, or other forms. For certain applications, most obviously catalytic hydrolysis and electro- or photocatalytic water splitting, but also many others, an additional requirement is water stability. MOFs featuring hexa-zirconium(IV)-oxy nodes satisfy this requirement. For applications involving electrocatalysis, charge storage, photoelectrochemical energy conversion, and chemiresistive sensing, a further requirement is electrical conductivity, as embodied in electron or hole transport. As most MOFs, under most conditions, are electrically insulating, imparting controllable charge-transport behavior is both a chemically intriguing and chemically compelling challenge.Herein, we describe three strategies to render zirconium-based metal-organic frameworks (MOFs) tunably electrically conductive and, therefore, capable of transporting charge on the few nanometers (i.e., several molecular units) to few micrometers (i.e., typical dimensions for MOF microcrystallites) scale. The first strategy centers on redox-hopping between periodically arranged, chemically equivalent sites, essentially repetitive electron (or hole) self-exchange. Zirconium nodes are electrically insulating, but they can function as grafting sites for (a) redox-active inorganic clusters or (b) molecular redox couples. Alternatively, charge hopping based on linker redox properties can be exploited. Marcus's theory of electron transfer has proven useful for understanding/predicting trends in redox-hopping based conductivity, most notably, in accounting for variations as great as 3000-fold depending on the direction of charge propagation through structurally anisotropic MOFs. In MOF environments, propagation of electronic charge via redox hopping is necessarily accompanied by movement of charge-compensating ions. Consequently, rates of redox hopping can depend on both the identity and concentration of ions permeating the MOF. In the context of electrocatalysis, an important goal is to transport electronic charge fast enough to match or exceed the inherent activity of MOF-based or MOF-immobilized catalysts.Bandlike electronic conductivity is the focus of an alternative strategy: one based on the introduction of molecular guests capable of forming donor-acceptor charge transfer complexes with the host framework. Theory again can be applied predictively to alter conductivity. A third strategy similarly emphasizes electronic conductivity, but it makes use of added bridges in the form of molecular oligomers or inorganic clusters that can then be linked to span the length of a MOF crystallite. For all strategies, retention of molecular-scale porosity is emphasized, as this property is key to many applications. Finally, while our focus is on Zr-MOFs, the described approaches clearly are extendable to other MOF compositions, as has already been demonstrated, in part, in studies by others.

Selective Formation of Polyaniline Confined in the Nanopores of a Metal-Organic Framework for Supercapacitors.

In this study, a strategy that can result in the polyaniline (PANI) solely confined within the nanopores of a metal-organic framework (MOF) without forming obvious bulk PANI between MOF crystals is developed. A water-stable zirconium-based MOF, UiO-66-NH2 , is selected as the MOF material. The polymerization of aniline is initiated in the acidic suspension of UiO-66-NH2 nanocrystals in the presence of excess poly(sodium 4-styrenesulfonate) (PSS). Since the pore size of UiO-66-NH2 is too small to enable the insertion of the bulky PSS, the quick formation of pore-confined solid PANI and the slower formation of well dispersed PANI:PSS occur within the MOF crystals and in the bulk solution, respectively. By taking advantage of the resulting homogeneous PANI:PSS polymer solution, the bulk PANI:PSS can be removed from the PANI/UiO-66-NH2 solid by successive washing the sample with fresh acidic solutions through centrifugation. As this is the first time reporting the PANI solely confined in the pores of a MOF, as a demonstration, the obtained PANI/UiO-66-NH2 composite material is applied as the electrode material for supercapacitors. The PANI/UiO-66-NH2 thin films exhibit a pseudocapacitive electrochemical characteristic, and their resulting electrochemical activity and charge-storage capacities are remarkably higher than those of the bulk PANI thin films.

Transport Diffusion of Linear Alkanes (C5-C16) through Thin Films of ZIF-8 as Assessed by Quartz Crystal Microgravimetry.

We report uptake capacities and transport diffusivities, D, for each of eight linear alkanes (ranging from C5 to C16) in quartz crystal-supported films of solvent-evacuated ZIF-8. Analyses of the alkane uptake profiles revealed that the transport dynamics are governed by guest diffusion through metal-organic framework (MOF) (ZIF-8) crystallites rather than by rates of entry into films at the MOF/vapor interface. The obtained diffusivities range from just over 10-18 m2/s to just under 10-14 m2/s. Notably, minimum cross-sectional widths for all guests exceed the crystallographically measured width of ZIF-8's largest apertures and imply consistently with previous experimental and computational studies that apertures expand to accommodate guest uptake. On average, each additional carbon decreases the transport diffusivity of an alkane by twofold. Closer examination, however, reveals an odd-even effect such that linear alkanes having even numbers of carbons diffuse more rapidly than alkanes featuring one more or one less carbon atom. Thus, ZIF-8's differentiation of transport diffusivities for pairs of alkanes differing in length by only one carbon atom can be significantly greater than the aforementioned factor of 2. Elucidation of the microscopic basis for the odd-even behavior, however, awaits the outcome of molecular dynamics calculations that are beyond the scope of the present study. For compact, solvothermally prepared films, guest transport is dominated by 1D diffusion from the film/vapor interface and toward the underlying quartz crystal. For much lower density, electrophoretically deposited (EPD) films, crystallites behave nearly independently, and guest transport can be adequately modeled by assuming rapid permeation of macroscopic voids between crystallites, followed by entry and rate-limiting radial diffusion into isolated crystallites. One consequence is that EPD films can be much more rapidly infiltrated by molecular guests than can compact, solvothermally grown films. The combined results have potentially favorable implications for the development of kinetic separation schemes for closely related analytes.

Anisotropic Redox Conductivity within a Metal-Organic Framework Material.

Engendering electrical conductivity in otherwise insulating metal-organic framework (MOF) materials is key to rendering these materials fully functional for a range of potential applications, including electrochemical and photo-electrochemical catalysis. Here we report that the platform MOF, NU-1000, can be made electrically conductive via reversible electrochemical oxidation of a fraction of the framework's tetraphenylpyrene linkers, where the basis for conduction is redox hopping. At a microscopic level, redox hopping is akin to electron self-exchange and is describable by Marcus' well-known theory of electron transfer. At a macroscopic level, the hopping behavior leads to diffusive charge transport and is quantifiable as an apparent diffusion coefficient, Dhopping. Theory suggests that the csq topology of NU-1000, together with its characteristic one-dimensional mesopores, will result in direction-dependent, that is, anisotropic, electrical conductivity. Detailed computations suggest that the governing factor is the strength of electronic coupling between pairs of linkers sited in the a,b plane of the MOF versus the mesopore-aligned c axis of the crystal. The notion has been put to the test experimentally by configuring the MOF as an array of selectively oriented, electrode-supported crystallites, where the rodlike crystallites are either oriented largely normal to the electrode (requiring redox hopping along the c direction) or mainly parallel (requiring redox hopping mainly through the a,b plane). The orientations are preselected by preparing MOF films either via interfacial solvothermal synthesis or via electrophoretic deposition. In semiquantitative accord with computational predictions, Dhopping is up to ∼3500 times larger in the c direction than through the a,b plane. In addition to their fundamental significance, the findings have clear implications for the design and optimization of MOFs for electrocatalysis and for other applications that rely upon electrical conductivity.

Core-Shell Gold Nanorod@Zirconium-Based Metal-Organic Framework Composites as in Situ Size-Selective Raman Probes.

Nanoparticle encapsulation inside zirconium-based metal-organic frameworks (NP@MOF) is hard to control, and the resulting materials often have nonuniform morphologies with NPs on the external surface of MOFs and NP aggregates inside the MOFs. In this work, we report the controlled encapsulation of gold nanorods (AuNRs) by a scu-topology Zr-MOF, via a room-temperature MOF assembly. This is achieved by functionalizing the AuNRs with poly(ethylene glycol) surface ligands, allowing them to retain colloidal stability in the precursor solution and to seed the MOF growth. Using this approach, we achieve core-shell yields exceeding 99%, tuning the MOF particle size via the solution concentration of AuNRs. The functionality of AuNR@MOFs is demonstrated by using the AuNRs as embedded probes for selective surface-enhanced Raman spectroscopy (SERS). The AuNR@MOFs are able to both take-up or block molecules from the pores, thereby facilitating highly selective sensing at the AuNR ends. This proof-of-principle study serves to present both the outstanding level of control in the synthesis and the high potential for AuNR@Zr-MOF composites for SERS.

Direct Imaging of Isolated Single-Molecule Magnets in Metal-Organic Frameworks.

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.

Stabilization of Formate Dehydrogenase in a Metal-Organic Framework for Bioelectrocatalytic Reduction of CO2.

The efficient fixation of excess CO2 from the atmosphere to yield value-added chemicals remains crucial in response to the increasing levels of carbon emission. Coupling enzymatic reactions with electrochemical regeneration of cofactors is a promising technique for fixing CO2 , while producing biomass which can be further transformed into biofuels. Herein, a bioelectrocatalytic system was established by depositing crystallites of a mesoporous metal-organic framework (MOF), termed NU-1006, containing formate dehydrogenase, on a fluorine-doped tin oxide glass electrode modified with Cp*Rh(2,2'-bipyridyl-5,5'-dicarboxylic acid)Cl2 complex. This system converts CO2 into formic acid at a rate of 79±3.4 mm h-1 with electrochemical regeneration of the nicotinamide adenine dinucleotide cofactor. The MOF-enzyme composite exhibited significantly higher catalyst stability when subjected to non-native conditions compared to the free enzyme, doubling the formic acid yield.

Increased Electrical Conductivity in a Mesoporous Metal-Organic Framework Featuring Metallacarboranes Guests.

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 bis(dicarbollide) units are located as guest molecules in the microporous channels of NU-1000, which permits the further incorporation of other active species in the remaining mesopores. For demonstration, manganese oxide is installed on the nodes of the electrically conductive MOF. The electrochemically addressable fraction and specific capacitance of the manganese oxide in the conductive framework are more than 10 times higher than those of the manganese oxide in the parent MOF.

Epitaxial Growth of γ-Cyclodextrin-Containing Metal-Organic Frameworks Based on a Host-Guest Strategy.

A class of metal-organic frameworks (MOFs)-namely CD-MOFs-obtained from natural products has been grown in an epitaxial fashion as films on the surfaces of glass substrates, which are modified with self-assembled monolayers (SAMs) of γ-cyclodextrin (γ-CD) molecules. The SAMs are created by host-guest complexation of γ-CD molecules with surface-functionalized pyrene units. The CD-MOF films have continuous polycrystalline morphology with a structurally out-of-plane ( c-axial) orientation, covering an area of several square millimeters, with a thickness of ∼2 µm. Furthermore, this versatile host-guest strategy has been applied successfully in the growth of CD-MOFs as the shell on the curved surface of microparticles as well as in the integration of CD-MOF films into electrochemical devices for sensing carbon dioxide. In striking contrast to the control devices prepared from CD-MOF crystalline powders, these CD-MOF film-based devices display an enhancement in proton conductance of up to 300-fold. In addition, the CD-MOF film-based device exhibits more rapid and highly reversible CO2-sensing cycles under ambient conditions, with a 50-fold decrease in conductivity upon exposure to CO2 for 3 s which is recovered within 10 s upon re-exposure to air.

Nickel-Carbon-Zirconium Material Derived from Nickel-Oxide Clusters Installed in a Metal-Organic Framework Scaffold by Atomic Layer Deposition.

Atomic layer deposition is employed to install nickel oxide into NU-1000. Upon heating to 900 °C under nitrogen, a carbon material containing ZrO2 and Ni is formed. In notable contrast to the parent metal-organic framework, the pyrolyzed material is: (a) stable in highly alkaline solutions (typical conditions for water electro-oxidation) and (b) electrically conductive and thus able to deliver oxidizing equivalents (holes) to catalytic sites located far from the underlying conductive-glass electrode. The pyrolysis-derived material was characterized and its electrocatalytic activity for oxygen evolution was investigated.

Electroactive Ferrocene at or near the Surface of Metal-Organic Framework UiO-66.

Here, we describe the installation of a ferrocene derivative on and within the archetypal metal-organic framework (MOF), UiO-66, by solvent-assisted ligand incorporation. Thin films of the resulting material show a redox peak characteristic of the Fc/Fc+ couple, as measured by cyclic voltammetry. Consistent with restriction of redox reactivity solely to Fc molecules sited at or near the external surfaces of MOF crystallites, chronoamperometry measurements indicate that less than 20% of the installed Fc molecules are electrochemically active. Charge-transport diffusion coefficients, DCT, of 6.1 ± 0.8 × 10-11 and 2.6 ± 0.2 × 10-9 cm2/s were determined from potential step measurements, stepping oxidatively and reductively, respectively. The 40-fold difference in DCT values contrasts with the expectation, for simple systems, of identical values for oxidation-driven versus reduction-driven charge transport. The findings have implications for the design of MOFs suitable for delivery of redox equivalents to framework-immobilized electrocatalysts and/or delivery of charges from a chromophoric MOF film to an underlying electrode, processes that may be central to MOF-facilitated conversion of solar energy to chemical or electrical energy.

Dendritic cells require NIK for CD40-dependent cross-priming of CD8+ T cells.

Dendritic cells (DCs) link innate and adaptive immunity and use a host of innate immune and inflammatory receptors to respond to pathogens and inflammatory stimuli. Although DC maturation via canonical NF-κB signaling is critical for many of these functions, the role of noncanonical NF-κB signaling via the serine/threonine kinase NIK (NF-κB-inducing kinase) remains unclear. Because NIK-deficient mice lack secondary lymphoid organs, we generated transgenic mice with targeted NIK deletion in CD11c(+) cells. Although these mice exhibited normal lymphoid organs, they were defective in cross-priming naive CD8(+) T cells following vaccination, even in the presence of anti-CD40 or polyinosinic:polycytidylic acid to induce DC maturation. This impairment reflected two intrinsic defects observed in splenic CD8(+) DCs in vitro, namely antigen cross-presentation to CD8(+) T cells and secretion of IL-12p40, a cytokine known to promote cross-priming in vivo. In contrast, antigen presentation to CD4(+) T cells was not affected. These findings reveal that NIK, and thus probably the noncanonical NF-κB pathway, is critical to allow DCs to acquire the capacity to cross-present antigen and prime CD8 T cells after exposure to licensing stimuli, such as an agonistic anti-CD40 antibody or Toll-like receptor 3 ligand.

Fine-Tuning the Activity of Metal-Organic Framework-Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane.

Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal-organic framework (MOF) NU-1000, have been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (<230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 followed by Co(II) ion deposition, yielding a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Using difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples, the promoter ions are sited between pairs of Zr6 nodes along the MOF c-axis, whereas the location of the cobalt ions varies with the promoter ions. These NU-1000-supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando X-ray absorption spectroscopy at the Co K-edge. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the following order: Mo(VI) < Ti(IV) < Al(III) < Zn(II) < Ni(II). The finding is attributed to increasing ease of formation of Co(III)-O• species and stabilization of a cobalt(III)-oxyl/propane transition state as the Lewis acidity of the promoter ions decreases. The results point to an increasing ability to fine-tune the structure-dependent activity of MOF-supported heterogeneous catalysts. Coupled with mechanistic studies-computational or experimental-this ability may translate into informed prediction of improved catalysts for propane ODH and other chemical reactions.

Metal-Organic Framework Colloids: Disassembly and Deaggregation.

We demonstrate a high-resolution method as an efficient tool to in situ characterize partially reversible assembly and aggregation of metal-organic framework (MOF) colloids. Based on the gas-phase electrophoresis, the primary size and the degree of aggregation of the MOF-525 crystals are tunable by pH adjustment and mobility selection. These findings allow for the further size control of MOF colloids and prove the capability of semiquantitative analysis for the MOF-based platforms in a variety of aqueous formulations (e.g., biomedical applications).

MOF functionalization via solvent-assisted ligand incorporation: phosphonates vs carboxylates.

Solvent-assisted ligand incorporation (SALI) is useful for functionalizing the channels of metal-organic framework (MOF) materials such as NU-1000 that offer substitutionally labile zirconium(IV) coordination sites for nonbridging ligands. Each of the 30 or so previous examples relied upon coordination of a carboxylate ligand to achieve incorporation. Here we show that, with appropriate attention to ligand/node stoichiometry, SALI can also be achieved with phosphonate-terminated ligands. Consistent with stronger M(IV) coordination of phosphonates versus carboxylates, this change extends the pH range for retention of incorporated ligands. The difference in coordination strength can be exploited to achieve stepwise incorporation of pairs of ligands-specifically, phosphonates species followed by carboxylate species-without danger of displacement of the first ligand type by the second. Diffuse reflectance infrared Fourier-transform spectroscopy suggests that the phosphonate ligands are connected to the MOF node as RPO2(OH)¯ species in a moiety that leaves a base-accessible -OH moiety on each bound phosphonate.

Two-dimensional metal-organic framework for post-synthetic immobilization of graphene quantum dots for photoluminescent sensing.

Immobilization of graphene quantum dots (GQDs) on a solid support is crucial to prevent GQDs from aggregation in the form of solid powder and facilitate the separation and recycling of GQDs after use. Herein, spatially dispersed GQDs are post-synthetically coordinated within a two-dimensional (2D) and water-stable zirconium-based metal-organic framework (MOF). Unlike pristine GQDs, the obtained GQDs immobilized on 2D MOF sheets show photoluminescence in both suspension and dry powder. Chemical and photoluminescent stabilities of MOF-immobilized GQDs in water are investigated, and the use of immobilized GQDs in the photoluminescent detection of copper ions is demonstrated. Findings here shed the light on the use of 2D MOFs as a platform to further immobilize GQDs with various sizes and distinct chemical functionalities for a range of applications.