Nonporous Metal-organic Frameworks Research Articles

Aptamer-functionalized MOFs and AI-driven strategies for early cancer diagnosis and therapeutics.

Metal-Organic Frameworks (MOFs) have exceptional inherent properties that make them highly suitable for diverse applications, such as catalysis, storage, optics, chemo sensing, and biomedical science and technology. Over the past decades, researchers have utilized various techniques, including solvothermal, hydrothermal, mechanochemical, electrochemical, and ultrasonic, to synthesize MOFs with tailored properties. Post-synthetic modification of linkers, nodal components, and crystallite domain size and morphology can functionalize MOFs to improve their aptamer applications. Advancements in AI and machine learning led to the development of nonporous MOFs and nanoscale MOFs for medical purposes. MOFs have exhibited promise in cancer therapy, with the successful accumulation of a photosensitizer in cancer cells representing a significant breakthrough. This perspective is focused on MOFs' use as advanced materials and systems for cancer therapy, exploring the challenging aspects and promising features of MOF-based cancer diagnosis and treatment. The paper concludes by emphasizing the potential of MOFs as a transformative technology for cancer treatment and diagnosis.

Borderline Metal Centers on Nonporous Metal-Organic FrameworkNanowire Boost Fast Li-Ion Interfacial Transport of Composite Polymer Electrolyte.

Metal-organic frameworks (MOFs) fillers are emerging for composite polymer electrolytes (CPEs). Enhancing Lewis acid-base interaction (LABI) among MOFs, polymer and Li-salt is expected to promote Li+ -transport. However, it is unclear how to customize a strong LABI interface. The large surface-area of classical MOFs also interferes with clarifying the LABI influence on Li+ -transport. Herein, Bi3+ as metal centers to design colloidal-dispersed nonporous MOFs (Bi/HMT-MOFs) nanowire with a surface-area of only 17.13 m2 g-1 to prepare polyethylene oxide (PEO)-based CPEs (BMCPE) is chosen. The nonporous feature can exclude the surface-area effect on Li+ -transport. More interestingly, Bi3+ is a typical borderline acid, which can interact with both hard-basic PEO and soft-basic Li-salt anion. Accordingly, Bi/HMT-MOFs are uniformly dispersed in the BMCPE to form a strong LABI interface with PEO and Li-salt, promoting Li-salt dissociation and providing rapid Li+ -transport channels. Despite the ultralow surface-area of Bi/HMT-MOFs, BMCPE exhibits significantly enhanced ion-conductivity and Li+ transference number, which completely rival traditional MOFs-filled CPEs. BMCPE also enables symmetric and full cells with excellent high-rate performance and long-term cycling stability. In contrast, when Bi3+ sites are obscured, electrochemical performances are obviously decreased. Therefore, employing borderline metal centers will be an effective strategy to construct a LABI interface for high-performance MOFs-filled CPEs.

Pore creation nanoarchitectonics from non-porous metal-organic framework to porous carbon for adsorptive elimination of sulfanilamide and chloroxylenol from aqueous solution

Three isomeric metal-organic frameworks (MOFs) such as MAF-5, − 6, and − 32 (with the same composition of [Zn(2-ethylimidazole)2]) were carbonized and, for the first time, activated further with KOH to prepare highly porous MOF-derived carbons (MDCs). Importantly, MDC-32 derived from non-porous MAF-32 had the highest porosity among the three MDCs although it has the lowest porosity when no KOH activation was done. Adsorption of sulfanilamide and chloroxylenol from water was investigated with the MDCs. Among the MDCs, MDC-32 showed the best adsorptive performance for sulfanilamide and chloroxylenol. Moreover, MDC-32, had the highest adsorption capacity (256 mg/g) for removing sulfanilamide from water, compared with any adsorbent reported so far. Based on the observed adsorption and properties of the adsorbate and adsorbent, π–π and hydrogen bonding interactions, with a slight contribution of repulsive electrostatic interaction, could be suggested as the mechanism for the sulfanilamide adsorption over the MDC-32. Moreover, the MDC-32 could be recycled easily for up to four cycles. It could be suggested that non-porous MOFs can be a good precursor for highly porous MDCs, if activated well using KOH, for example. Finally, MAF-32-derived carbon, MDC-32, might be suggested as a plausible adsorbent to eliminate organics such as sulfanilamide from water.

Highly N/O co-doped ultramicroporous carbons derived from nonporous metal-organic framework for high performance supercapacitors

A new nonporous Zn-based metal-organic framework (NPMOF) synthesized from a high nitrogen-containing rigid ligand was converted into porous carbon materials by direct carbonization without adding additional carbon sources. A series of NPMOF-derived porous carbons with very high N/O contents (24.1% for NPMOF-700, 20.2% for NPMOF-800, 15.1% for NPMOF-900) were prepared by adjusting the pyrolysis temperatures. The NPMOF-800 fabricated electrode exhibits a high capacitance of 220 F/g and extremely large surface area normalized capacitance of 57.7 μF/cm2 compared to other reported MOF-derived porous carbon electrodes, which could be attributed to the abundant ultramicroporosity and high N/O co-doping. More importantly, symmetric supercapacitor assembled with the MOF-derived carbon manifests prominent stability, i.e., 99.1% capacitance retention after 10,000 cycles at 1.0 A/g. This simple preparation of MOF-derived porous carbon materials not only finds an application direction for a variety of porous or even nonporous MOFs, but also opens a way for the production of porous carbon materials for superior energy storage.

Function-regeneration of non-porous hydrolyzed-MOF-derived materials

A facile synthetic strategy based on a water-based process is developed for the preparation of metal-organic framework (MOF)-derived materials by revisiting the hydrolyzed non-porous metal-organic frameworks (h-MOF). The poor water stability of MOF has been recognized as key limitations for its commercialization and large-scale applications because the hydrolysis resulted in the complete loss of their functionalities. However, we found that the negative effect of hydrolysis on MOF can be nullified during the heat treatment. As similar to the intact MOF, h-MOF can be used as a precursor for the preparation of MOF-derived materials from porous MOF-derived carbons (MDCs) to MDC@ZnO composites. The property of h-MOF-derived materials is almost equivalent to that of MOF-derived materials. In addition, h-MOF turned the weakness of water instability to the strength of facile water-based process for hybridization. With the demonstration of the hybrid composite between h-MDC@ZnO and reduced graphene oxide (rGO) as a prototype example, it exhibited superior electrochemical performance when evaluated as an electrode material for lithium-ion batteries.

Stereochemically Active and Inactive Lone Pairs in Two Room-Temperature Phosphorescence Coordination Polymers of Pb2+ with Different Tricarboxylic Acids.

Two new Pb2+-based coordination polymers (CPs), [Pb2(HBTC)2(DMF)] (1) and [Pb(HPTC)] (2), have been synthesized under solvothermal condition; herein, H3BTC and H3PTC represent 1,3,5-benzenetricarboxylic acid and 2,4,6-pyridine tricarboxylic acid, respectively. Both 1 and 2 were characterized by microanalysis, infrared spectra (IR), thermal gravimetric analyses (TGA), and powder X-ray diffraction (PXRD) techniques. Single-crystal structural analysis indicates that 1 and 2 show different coordination sphere around Pb2+ ions and distinct coordination frameworks. The I1O2 type three-dimensional (3D) nonporous metal-organic framework forms in 1, where the Pb2+ ion shows holo-directed coordination geometry, while the I0O2 type two-dimensional (2D) coordination polymeric layered structure forms in 2, where Pb2+ ion shows a hemidirected coordination sphere and the 6s2 lone electron pair in Pb2+ ion is stereochemically active. The two CPs emit intense and long-lasting greenish phosphorescence in air at room temperature, with absolute quantum yields of 1.2% for 1 and 4.7% for 2 and decay lifetimes of 0.73 ms for 1 and 1.52 ms for 2.

Enhancement of Proton Conductivity in Nonporous Metal–Organic Frameworks: The Role of Framework Proton Density and Humidity

Owing to their inherent pore structure, porous metal–organic frameworks (MOFs) can undergo postsynthetic modification, such as loading extra-framework proton carriers. However, strategies for impro...

Highly effective oxygen reduction reaction electrocatalysis: Nitrogen-doped hierarchically mesoporous carbon derived from interpenetrated nonporous metal-organic frameworks

Nitrogen-doped carbon materials with hierarchically mesoporous structure are synthesized in the present work via the pyrolysis of an interpenetrated non-porous metal-organic framework (MOF), viz. [Zn2(TPT)(BDC)2]·H2O (SCUT-11, TPT=tris(4-pyridyl)triazine, BDC=1,4-benzenedicarboxylate), as the precursor. X-ray diffraction reveals that the synthesized metal-organic framework (MOF) is of high purity of the crystalline phase, and its structure follows our previously reported SCUT-11. This triply-interpenetrated MOF features high density of Zn cations in their interwoven packing structure, which act as effective pore-forming agent to generate mesopores in final carbon. Physicochemical characterizations reveal that the resultant carbon has high specific surface area and bimodal mesopore size distribution, which originate from the removal of metal oxide and/or metal zinc. These textual features favour both oxygen mass transfer and accessibility of catalytically active sites. Electrochemical results confirm that the resultant carbon, synthesized by pyrolysis at 900°C, shows a superior oxygen reduction reaction (ORR) activity, which is associated with high onset and half-wave potential up to 1.0 and 0.88V, respectively. Further investigation suggests that the as-synthesized carbon catalyst exhibits a remarkable insensitivity towards anions, like sulphate and phosphate, compared with the Pt counterpart. The above features make this carbon catalyst promising to be widely used in different fuel cell types.

Opening of an Accessible Microporosity in an Otherwise Nonporous Metal-Organic Framework by Polymeric Guests.

The development of highly porous metal-organic frameworks (MOFs) is greatly sought after, due to their wide range of applications. As an alternative to the development of new structures, we propose to obtain new stable configurations for flexible MOFs by insertion of polymeric guests. The guests prevent the otherwise spontaneous closing of the host frameworks and result in stable opened forms. Introduced at a fraction of the maximal capacity, polymer chains cause an opening of the occupied nanochannels, and because of the MOF reticular stiffness, this opening is propagated to the neighboring nanochannels that become accessible for adsorption. Composites were obtained by in situ polymerization of vinyl monomers in the nanochannels of an otherwise nonporous MOF, resulting in homogeneously loaded materials with a significant increase of porosity (SBET = 920 m2/g). In addition, by limiting the accessible configurations for the framework and forbidding the formation of a reactive intermediate, the polymeric guest prevented the thermal degradation of the host MOF even at very low loading (as low as 3 wt %) and increased its stability domain by more than 200 °C.

A comparative study on conversion of porous and non-porous metal–organic frameworks (MOFs) into carbon-based composites for carbon dioxide capture

Nanoporous carbon-based composites derived from metal–organic frameworks (MOFs) have drawn increasing attention and hold promising potential in the application of gas adsorption and separation. Herein, we report the preparation and characterization of four novel carbon-based materials, converted from a non-porous Mg-MOF and a porous Zn-MOF which were both constructed by biphenyl-4,4′-dicarboxylic acid (BPDC) as bridging linkers in the structures. The phase transformation and structural evolution of the material were studied by in situ synchrotron powder X-ray diffraction with variable temperature. Interestingly, the results indicate the porosity generated by carbonization would be more dependent on the thermal stability rather than crystallographic intactness of the template MOFs. Moreover, the derived carbon materials selectively adsorb CO2 over N2 at moderate conditions, which would be promising for post-combustion carbon dioxide capture.

Russell Morris

Angewandte Chemie International EditionVolume 55, Issue 31 p. 8794-8794 Author ProfileFree Access Russell Morris First published: 25 February 2016 https://doi.org/10.1002/anie.201601281Citations: 2AboutSectionsPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat Graphical Abstract “When I was eighteen I wanted to be a professional cricketer. My favorite drink is cup of tea (how very British!) ...” This and more about Russell Morris can be found on page 8794. 1 Table 1. Russell E. Morris Date of birth: June 8, 1967 Position: Professor of Materials Chemistry, University of St Andrews E-mail: rem1@st-andrews.ac.uk Homepage: http://www.st-andrews.ac.uk/chemistry/contact/academic/#rem1 Education: 1989 BA in chemistry, University of Oxford 1992 DPhil supervised by Professor Anthony K. Cheetham, University of Oxford Awards: 2008 Fellow of the Royal Society of Edinburgh; 2012 Fellow of the Learned Society of Wales; 2012 Brian Mercer Award for Innovation, Royal Society; 2015 Peter Day Award for Materials, Royal Society of Chemistry Current research interests: Zeolites; metal–organic frameworks; gas storage and delivery for medicine; quantum spin liquids Hobbies: Playing the guitar (badly!), playing tennis (also badly!) When I was eighteen I wanted to be a professional cricketer. My favorite drink is a cup of tea (how very British!). In the future I see myself still enjoying my job. The most important thing I learned from my students is how they manage their supervisor. The principal aspect of my personality is optimism. Even when things go badly, success is always just around the corner (I hope!) My favorite musicians are Queen or maybe Billy Bragg, or my current favorite Caro Emerald—too many favorites! The natural talent I would like to be gifted with is for music. It must be a great thrill to captivate an audience with a virtuoso performance. I am waiting for the day when someone will discover a foolproof way to teach old-timers (like me) how to use social media. If I could be any age I would be 25—old enough to know better but young enough not to care too much. The secret of being a successful scientist is creativity and not being scared to ask a stupid question. My favorite molecules are polyhedral oligomeric silsesquioxanes—who couldn't love them with a name like that. My science “heroes” are my research group—they put up with a lot! My 5 top papers: References 1“Synthesis of ‘unfeasible’ zeolites”: M. Mazur, P. S. Wheatley, M. Navarro, W. J. Roth, M. Položij, A. Mayoral, P. Eliášová, P. Nachtigall, J. Čejka, R. E. Morris, Nat. Chem. 2016, 8, 58. (Shows how we can get around the limitations of hydrothermal synthesis.) 2“Zeolites with Continuously Tuneable Porosity”: P. S. Wheatley et al., Angew. Chem. Int. Ed. 2014, 53, 13210; Angew. Chem. 2014, 126, 13426. (Continuous control of the pore sizes in a family of zeolites all the way from small pores to extra-large ones.) 3“A family of zeolites with controlled pore size prepared using a top-down method”: W. J. Roth et al., Nat. Chem. 2013, 5, 628 (Reports the ADOR process: how to disassemble a parent zeolite into its constituent parts before reassembling them into a family of new structures.) 4“Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic–hydrophobic metal–organic framework”: M. I. H. Mohideen et al., Nat. Chem. 2011, 3, 304. (We can control the adsorption into two channels of the same MOF, and can close one channel down completely by using the right set of conditions.) 5“Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework”: B. Xiao et al., Nat. Chem. 2009, 1, 289. (A MOF that only adsorbs one particular gas, nitric oxide, and can be used in medical applications.) Citing Literature Volume55, Issue31July 25, 2016Pages 8794-8794 ReferencesRelatedInformation

Hierarchically porous carbons derived from nonporous metal-organic frameworks: Synthesis and influence of struts

It is challenging to synthesize low cost hierarchically structured porous carbons of high surface area and narrow mesopore-size distribution. In this paper we report a series of hierarchically porous carbons (HPCs) with the same mesopore size distribution but varied micropore sizes and surface areas. These HPCs were fabricated by one-pot thermal conversion of Zn-containing metal-organic framework (MOF) crystals with different “strut lengths” at high temperatures. Struts with different lengths were used as ‘modulators’ for controlling the surface area, porosity, morphology, structural ordering and conductivity of the HPCs derived, by pyrolysis of Zn-containing MOFs constructed with different linear or trident aromatic acids. The correlation between the properties of the end carbon products and the capacitive performance was studied. It is found that all MOFs-derived HPCs had higher the gravimetric specific capacitance compared to activated carbon. Among the HPCs synthesized, hierarchically porous carbon-bdc (HPC-bdc) derived from Zn-bdc (zinc benzene-1,4-dicarboxylate) exhibited the largest gravimetric specific capacitance (170F/g). This HPC can be cycled up to 5000 times with a capacitance retention ratio of 98%. This is attributed to its long-range ordered structure, largest surface area (2816m2/g) and highest porosity, and best conductivity.

Facile method to disperse nonporous metal organic frameworks: composite formation with a porous metal organic framework and application in adsorptive desulfurization.

It is generally not easy to utilize nonporous metal organic frameworks (MOFs) with a large crystal size (especially for catalysis or adsorption) because their surface area is low and the majority of the active sites exist inside the MOFs. Composing with porous materials may be one way to disperse the nonporous materials. In this study, a nonporous/nonsoluble MOF (in which the particle size was much larger than the cavity size of the porous MOFs) containing Cu(I) ((Cu2(pyz)2(SO4)(H2O)2)n, denoted as CP) was composed with typical porous MOFs such as MIL100(Fe) (iron-benzenetricarboxylate) and CuBTC (cupper-benzenetricarboxylate). The Cu(I) species of the nonporous MOF was effectively utilized for the adsorptive desulfurization (ADS) of model fuel. Even though the porosities of the composed MOFs decreased as the content of CP increased, the adsorption capacity increased as the content of CP increased (up to a certain content). Considering the negligible capacity of CP for ADS, the enhanced adsorption capacity may be a result of the well-dispersed Cu(I), which is known to be beneficial for ADS via π-complexation. The dispersed CP was also observed by transmission electron microscopy mapping. Therefore, composing a nonporous MOF with porous MOF is a new and facile way to disperse/utilize the active sites of a nonporous MOF.

Template-induced diverse metal-organic materials as catalysts for the tandem acylation-Nazarov cyclization.

In our continuing quest to develop a metal-organic framework (MOF)-catalyzed tandem pyrrole acylation-Nazarov cyclization reaction with α,β-unsaturated carboxylic acids for the synthesis of cyclopentenone[b]pyrroles, which are key intermediates in the synthesis of natural product (±)-roseophilin, a series of template-induced Zn-based (1-3) metal-organic frameworks (MOFs) have been solvothermally synthesized and characterized. Structural conversions from non-porous MOF 1 to porous MOF 2, and back to non-porous MOF 3 arising from the different concentrations of template guest have been observed. The anion-π interactions between the template guests and ligands could affect the configuration of ligands and further tailor the frameworks of 1-3. Futhermore, MOFs 1-3 have shown to be effective heterogeneous catalysts for the tandem acylation-Nazarov cyclization reaction. In particular, the unique structural features of 2, including accessible catalytic sites and suitable channel size and shape, endow 2 with all of the desired features for the MOF-catalyzed tandem acylation-Nazarov cyclization reaction, including heterogeneous catalyst, high catalytic activity, robustness, and excellent selectivity. A plausible mechanism for the catalytic reaction has been proposed and the structure-reactivity relationship has been further clarified. Making use of 2 as a heterogeneous catalyst for the reaction could greatly increase the yield of total synthesis of (±)-roseophilin.

Solid-state conversion of a MOF to a metal-organo polymeric framework (MOPF) via [2+2] cycloaddition reaction

The bpeb ligands aligned in a slip-stacked manner in a two-fold interpenetrated non-porous metal-organic framework (MOF) [Zn2(bpeb)(bdc)(fa)2] undergo [2+2] cycloaddition reaction in a single-crystal to single-crystal manner to a non-interpenetrated 3D structure with a new topology comprising an organic polymer ligand and a 2D coordination polymer.

Dimethylammonium copper formate [(CH3)2NH2]Cu(HCOO)3: A metal-organic framework with quasi-one-dimensional antiferromagnetism and magnetostriction

Metal-organic frameworks (MOFs) can exhibit many interesting properties such as multiferroic behavior, dipolar glass, gas storage, and protonic conductivity. Here we report that dimethylammonium copper formate (DMACuF) [(CH${}_{3}$)${}_{2}$NH${}_{2}$]Cu(HCOO)${}_{3}$, a cation templated nonporous MOF with perovskite topology, exhibits strong one-dimensional (1D) antiferromagnetism with a N\'eel temperature, ${T}_{N}$, of 5.2 K. These conclusions are derived from detailed magnetic susceptibility, heat capacity, dielectric constant, and high-frequency electron paramagnetic resonance measurements as well as density functional theory (DFT) calculations. The magnetic susceptibility exhibits a broad maximum at \ensuremath{\sim}50 K, suggesting low-dimensional magnetism; heat capacity measurements show a N\'eel temperature of 5.2 K. The magnetization versus field data at 1.8 K shows a spin-flop transition at ${H}_{sf}$ \ensuremath{\sim} 1.7 T. The ratio ${T}_{N}$/$J=6.5\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}2}$, where $J$ is the near-neighbor exchange constant (77.4 K), and the small value (2 K) of the interchain coupling suggests that DMACuF is close to an ideal 1D magnet. In this three-dimensional crystal lattice, the 1D magnetic behavior is made possible by the Jahn-Teller distortion of the 3${d}^{9}$ Cu${}^{2+}$ ions. Temperature dependence of the electron paramagnetic resonance field and the linewidth exhibits critical broadening for temperatures below 50 K, following a behavior quite characteristic of 1D spin systems. DFT calculations show that [(CH${}_{3}$)${}_{2}$NH${}_{2}$]Cu(HCOO)${}_{3}$ has a magnetic structure in which 1D antiferromagnetic chains parallel to the $c$ direction are weakly coupled ferromagnetically, supporting the thermomagnetic and EPR results. Dielectric measurements under applied magnetic fields of 0\ensuremath{-}7 T reveal a kink at the ${T}_{N}$, a clear indication of magnetostriction behavior.

Rapid energy transfer in non-porous metal–organic frameworks with caged Ru(bpy)32+ chromophores: oxygen trapping and luminescence quenching

Two non-porous metal–organic frameworks (MOFs) with caged Ru(bpy)32+ chromophores, [Ru(bpy)3][Zn2(C2O4)3] (1) and [Ru(bpy)3][NaAl(C2O4)3] (2), were synthesized and characterized. Their emission properties were studied by both steady-state and time-resolved luminescence measurements. Air-free microcrystals of 1 and 2 exhibit long-lived triplet metal-to-ligand charge transfer (3MLCT) excited states with lifetimes of 760 and 1305 ns, respectively. Lifetimes are significantly shortened (to 92 ns for 1 and 144 ns for 2) by trapping of trace amounts of oxygen in the non-porous MOFs, presumably due to amplified luminescence quenching of Ru(bpy)32+*. Following MLCT excitation, Ru(bpy)32+*/Ru(bpy)32+ energy transfer migration in 1 and 2 results in efficient quenching of Ru(bpy)32+* by Os(bpy)32+ added as an energy transfer trap at doping levels of 0.2–1.0%. A kinetic analysis indicates that the three-dimensional chromophore connectivity in 1 and 2 provides a network for rapid excited state energy transfer migration among Ru(bpy)32+ units, ultimately, finding an Os(bpy)32+ trap site. These crystalline frameworks with caged chromophores have proven to be ideal systems for studying light harvesting processes in artificial supramolecular systems.

Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework

Metal organic frameworks (MOFs) are among the most exciting materials discovered recently, attracting particular attention for their gas-adsorption and -storage properties. Certain MOFs show considerable structural flexibility in response to various stimuli. Although there are several examples of 'breathing' MOFs, in which structural changes occur without any bond breaking, examples of transformations in which several bonds are broken and made are much rarer. In this paper we demonstrate how a flexible MOF, Cu2(OH)(C8H3O7S)(H2O)2H2O, can be synthesized by careful choice of the organic linker ligand. The flexibility can be controlled by addition of a supplementary coordinating molecule, which increases the thermal stability of the solid sufficiently for direct imaging with electron microscopy to be possible. We also demonstrate that the MOF shows unprecedented low-pressure selectivity towards nitric oxide through a coordination-driven gating mechanism. The chemical control over these behaviours offers new possibilities for the synthesis of MOFs with unusual and potentially exploitable properties.