Creating Order in Ultrastable Phosphonate Metal-Organic Frameworks via Isolable Hydrogen-Bonded Intermediates.

The stability presented by trivalent metal-organic frameworks (MOFs) makes them an attractive class of materials. With phosphonate-based ligands, crystallization is a challenge, as there are significantly more binding motifs that can be adopted due to the extra oxygen tether compared to carboxylate counterparts and the self-assembly processes are less reversible. Despite this, we have reported charge-assisted hydrogen-bonded metal-organic frameworks (HMOFs) consisting of [Cr(H2O)6]3+ and phosphonate ligands, which were crystallographically characterized. We sought to use these HMOFs as a crystalline intermediate to synthesize ordered Cr(III)-phosphonate MOFs. This can be done by dehydrating the HMOF to remove the aquo ligands around the Cr(III) center, forcing metal-phosphonate coordination. Herein, a new porous HMOF, H-CALF-50, is synthesized and then dehydrated to yield the MOF CALF-50. CALF-50 is ordered, although it is not single crystalline. It does, however, have exceptional stability, maintaining crystallinity and surface area after boiling in water for 3 weeks and soaking in 14.5 M H3PO4 for 24 h and 9 M HCl for 72 h. Computational methods are used to study the HMOF to MOF transformation and give insight into the nature of the structure and the degree of heterogeneity.

High-Density Cobalt Single-Atom Catalysts for Enhanced Oxygen Evolution Reaction.

Single atom catalysts (SACs) possess unique catalytic properties due to low-coordination and unsaturated active sites. However, the demonstrated performance of SACs is limited by low SAC loading, poor metal-support interactions, and nonstable performance. Herein, we report a macromolecule-assisted SAC synthesis approach that enabled us to demonstrate high-density Co single atoms (10.6 wt % Co SAC) in a pyridinic N-rich graphenic network. The highly porous carbon network (surface area of ∼186 m2 g-1) with increased conjugation and vicinal Co site decoration in Co SACs significantly enhanced the electrocatalytic oxygen evolution reaction (OER) in 1 M KOH (η10 at 351 mV; mass activity of 2209 mA mgCo-1 at 1.65 V) with more than 300 h stability. Operando X-ray absorption near-edge structure demonstrates the formation of electron-deficient Co-O coordination intermediates, accelerating OER kinetics. Density functional theory (DFT) calculations reveal the facile electron transfer from cobalt to oxygen species-accelerated OER.

Microporous Metal-Phosphonates with a Novel Orthogonalized Linker and Complementary Guests: Insights for Trivalent Metal Complexes from Divalent Metal Complexes.

The reliable self-assembly of microporous metal-phosphonate materials remains a longstanding challenge. This stems from, generally, more coordination modes for the functional group allowing more dense structures, and stronger bonding driving less crystalline products. Here, a novel orthogonalized aryl-phosphonate linker, 1,3,5-tris(4'-phosphono-2',6'-dimethylphenyl) benzene (H6 L3) has been used to direct formation of open frameworks. The peripheral aryl rings of H6 L3 are orthogonalized relative to the central aromatic ring giving a tri-cleft conformation of the linker in which small aromatic molecules can readily associate. When coordinated to magnesium ions, a series of porous crystalline metal-organic, and hydrogen-bonded metal-organic frameworks (MOFs, HMOFs) are formed (CALF-41 (Mg), HCALF-42 (Mg), -43 (Mg)). While most metal-organic frameworks are tailored based on choice of metal and linker, here, the network structures are highly dependent on the inclusion and structure of the guest aromatic compounds. Larger guests, and a higher stoichiometry of metal, result in increased solvation of the metal ion, resulting in networks with connectivities increasingly involving hydrogen-bonds rather than direct phosphonate coordination. Upon thermal activation and aromatic template removal, the materials exhibit surface areas ranging from 400-600 m2 /g. Self-assembly in the absence of aromatic guests yields mixtures of phases, frequently co-producing a dense 3-fold interpenetrated structure (1). Interestingly, a series of both more porous (530-900 m2 /g), and more robust solids is formed by complexing with trivalent metal ions (Al, Ga, In) with aromatic guest; however, these are only attainable as microcrystalline powders. The polyprotic nature of phosphonate linkers enables structural analogy to the divalent analogues and these are identified as CALF-41 analogues. Finally, insights to the structural transformations during metal ion desolvation in this family are gained by considering a pair of structurally related Co materials, whose hydrogen-bonded (HCALF-44 (Co)) and desolvated (CALF-44 (Co)) coordination bonded networks were fully structurally characterized.

Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal-Organic Frameworks.

The coordinative pliancy of the phosphonate functional group means that metal-phosphonate materials often self-assemble as well-packed structures with minimal porosity, as efficient inter-ligand packing is enabled. Here, we report a multistep synthesis of a novel aryl-phosphonate linker with an orthogonalized ligand core, 1,3,5-tris(4'-phosphonophenyl)-2,4,6-trimethylbenzene (H6 L2) designed to form more open structures. A series of crystalline metal-phosphonate frameworks (CALF-35 to -39) have been assembled by coordinating to divalent metals (Ba, Sr, Ca, Mg, Zn). H6 L2 is unable to pack efficiently and, as a consequence, yields several distinct microporous structures. The resulting structures are discussed in detail, with a focus on the solid-state packing of the sterically rigidified linker. Combined with larger cations (Sr, and Ba), H6 L2 packs in a parallel-offset manner, yielding isomorphous and microporous metal-organic frameworks (CALF-35 (Sr), and (Ba)). When coordinated to smaller metals (Ca, Mg, Zn), H6 L2 forms four new structures. Two Ca MOFs of different stoichiometry, (CALF-36 and 37) and a Mg MOF CALF-38 show narrow pores and have high selectivities for CO2 over N2 and CH4 . Finally, in CALF-39 (Zn), H6 L2 linkers pack in a herringbone fashion, resulting in a material with 10.9×10.1 Å2 square channels. The stability of all structures was tested, and the most porous structure, CALF-39 (Zn), was found to retain its structure and gas adsorption after immersion in water over pH 3-11.

Mechanical Properties of a Metal-Organic Framework formed by Covalent Cross-Linking of Metal-Organic Polyhedra.

Overcoming the brittleness of metal-organic frameworks (MOFs) is a challenge for industrial applications. To increase the mechanical strength, MOFs have been blended with polymers to form composites. However, this also brings challenges, such as integration and integrity of MOF in the composite, which can hamper the selectivity of gas separations. In this report, an "all MOF" material with mechanical flexibility has been prepared by covalent cross-linking of metal-organic polyhedra (MOPs). The ubiquitous Cu24 isophthalate MOP has been decorated with a long alkyl chain having terminal alkene functionalities so that MOPs can be cross-linked via olefin metathesis using Grubbs second generation catalyst. Different degrees of cross-linked MOP materials have been obtained by varying the amount of catalyst in the reaction. Rheology of these structures with varying number of cross-links was performed to assess the cross-link density and its homogeneity throughout the sample. The mechanical properties were further investigated by the nanoindentation method, which showed increasing hardness with higher cross-link density. Thus, this strategy of cross-linking MOPs with covalent flexible units allows us to create MOFs of increasing mechanical strength while retaining the MOP cavities.

Three Sequential Hydrolysis Products of the Ubiquitous Cu24 Isophthalate Metal-Organic Polyhedra.

Metal-organic polyhedra (MOPs) are increasingly studied as host-guest capsules, linked into networks, or incorporated into composite materials. As such, understanding the decomposition of MOP structures is of fundamental importance. The degradation of the ubiquitous copper(II) MOP Cu24[5-(hydroxy)isophthalate]24 (1) is studied in liquid water. At different intervals of water exposure, powder X-ray diffraction (PXRD) is performed and stepwise conversion of the MOP into three different coordination polymers is observed. First, the formation of a 2D coordination polymer, 2, is observed, which upon further exposure gives a 1D coordination polymer, 3, and finally a trinuclear copper(II) complex, 4. Compound 2 is characterized by PXRD owing to its transient nature, while 3 and 4 are characterized crystallographically. The final structure, 4, contains copper(II) trimers, and so its magnetic behavior is also investigated.

Achieving Superprotonic Conduction in Metal-Organic Frameworks through Iterative Design Advances.

Two complementary design strategies, isomorphous ligand replacement and heterocycle doping, have been applied to iteratively enhance the proton conductivity of a metal-organic framework, ß-PCMOF2. The resulting materials, PCMOF21/2(Pz) and PCMOF21/2(Tz) (Pz = 1H-pyrazole, Tz = 1H-1,2,4-triazole), have their proton conduction raised almost 2 orders of magnitude compared to ß-PCMOF2. The bulk conductivities of these materials are over 10-1 S cm-1 at 85 °C and 90% relative humidity (RH), while maintaining the parent MOF structure. A solid state synthetic route for doping 1-D channels is also presented.

Microsphere Assemblies via Phosphonate Monoester Coordination Chemistry.

By complexing a bent phosphonate monoester ligand with cobalt(II), coupled with in situ ester hydrolysis, coordination microspheres (CALS=CALgary Sphere) are formed whereas the use of the phosphonic acid directly resulted in a sheet-like structure. Manipulation of the synthetic conditions gave spheres with different sizes, mechanical stabilities, and porosities. Time-dependent studies determined that the sphere formation likely occurred through the formation of a Co2+ and ligand chain that propagates in three dimensions through different sets of interactions. The relative rates of these assembly processes versus annealing by ester hydrolysis and metal dehydration determine the growth of the microspheres. Hardness testing by nanoindentation is carried out on the spheres and sheets. Notably, no templates or capping agents are employed, the growth of the spheres is intrinsic to the ligand geometry and the coordination chemistry of cobalt(II) and the phosphonate monoester.

Single Crystal Proton Conduction Study of a Metal Organic Framework of Modest Water Stability.

A sulfonated indium (In) metal organic framework (MOF) is reported with an anionic layered structure incorporating hydrogen-bonded dimethylammonium cations and water molecules. The MOF becomes amorphous in >60% relative humidity; however, impedance analysis of pelletized powders revealed a proton conduction value of over 10-3 S cm-1 at 25 °C and 40% RH, a very high proton conduction value for low humidity and moderate temperature. Given the modest humidity stability of the MOF, triaxial impedance analyses on a single crystal was performed and confirmed bulk proton conductivity over 10-3 S cm-1 along two axes corroborating the data from the pellet.

Tuning Intrinsic and Extrinsic Proton Conduction in Metal-Organic Frameworks by the Lanthanide Contraction.

Seven isomorphous lanthanide metal-organic frameworks in the PCMOF-5 family, [Ln(H5L)(H2O)n](H2O) (L = 1,2,4,5-tetrakis(phosphonomethyl)benzene, Ln = La, Ce, Pr, Nd, Sm, Eu, Gd) have been synthesized and characterized. This family contains 1-D water-filled channels lined with free hydrogen phosphonate groups and gives a very low activation energy pathway for proton transfer. The lanthanide contraction was employed to systematically vary the unit cell dimensions and tune the proton conducting pathways. LeBail fitting of the crystalline series shows that the crystallographic a-axis, along the channel, can be varied in increments less than 0.02 Å correspondingly shortening the proton transfer pathway. The proton conductivities for the La and Pr complexes were roughly an order of magnitude higher than other members of the series (10-3 S cm-1 versus 10-4 S cm-1). Single crystal structures of the high and low conducting members of the series (La, Pr for high and Ce for low) affirm the structural similarities extend beyond the unit cell parameters to positions of free acid groups and included water molecules. Scanning electron microscopy reveals marked differences in particle size of the different members of the Ln series owing to lattice strain effects induced by changing the lanthanide. Notably, the high conducting La and Pr complexes have the largest particle sizes. This result contradicts any notion that degradation of the MOF at grain boundaries is enabling the observed conductivity as proton conduction dominated by extrinsic pathways would be enabled by small particles (i.e., the La and Pr complexes would be the worst conductors). Proton conductivity measurements of a ball milled sample of the La complex corroborate this result.

Mediating Order and Modulating Porosity by Controlled Hydrolysis in a Phosphonate Monoester Metal-Organic Framework.

A crystalline and permanently porous copper phosphonate monoester framework has been synthesized from a tetraaryl trigonal phosphonate monoester linker. This material has a surface area over 1000 m2 g-1 , as measured by N2 sorption, the highest reported for a phosphonate-based metal-organic framework (MOF). The monoesters result in hydrophobic pore surfaces that give a low heat of adsorption for CO2 and low calculated selectivity for CO2 over N2 and CH4 in binary mixtures. By careful manipulation of synthetic conditions, it is possible to selectively remove some of the monoesters lining the pore to form a hydrogen phosphonate while giving an isomorphous structure. This increases the affinity of the framework for CO2 giving higher ambient uptake, higher heat of adsorption, and much higher calculated selectivity for CO2 over both N2 and CH4 . Formation of the acid groups is noteworthy as complexation with the parent acid gives a different structure.

A Water Stable Magnesium MOF That Conducts Protons over 10(-2) S cm(-1).

From the outset of the study of MOFs as proton conductors, both conductivity and hydrolytic robustness of the materials have needed to be improved. Here, we report a layered magnesium carboxyphosphonate framework, PCMOF10, that shows an extremely high proton conductivity value of 3.55 × 10(-2) S·cm(-1) at 70 °C and 95% RH. Moreover, PCMOF10 is water stable owing to strong Mg phosphonate bonding. The 2,5-dicarboxy-1,4-benzenediphosphonic acid (H6L) linker anchors a robust backbone and has hydrogen phosphonate groups that interact with the lattice water to form an efficient proton transfer pathway.

Design of a humidity-stable metal-organic framework using a phosphonate monoester ligand.

Phosphonate monoesters are atypical linkers for metal-organic frameworks, but they offer potentially added versatility. In this work, a bulky isopropyl ester is used to direct the topology of a copper(II) network from a dense to an open framework, CALF-30. CALF-30 shows no adsorption of N2 or CH4 however, using CO2 sorption, CALF-30 was found to have a Langmuir surface area of over 300 m(2)/g and to be stable to conditions of 90% relative humidity at 353 K owing to kinetic shielding of the framework by the phosphonate ester.

MOFs as proton conductors--challenges and opportunities.

Proton conducting materials have garnered immense attention for their role as electrolytes in fuel cells. Metal Organic Frameworks (MOFs) and coordination polymers have recently been investigated as possible candidates for proton-conducting applications. Their crystallinity, chemically functionalizable pores and options for systematic structural variation are some of the factors that allow for the targeted design of better proton conductors operating over a wide variety of temperatures and/or humidity conditions. This review will examine selected examples from this nascent field, and will focus on the design and synthesis of proton conducting MOFs, their properties and conditions under which they operate.

The Challenge of Water Competition in Physical Adsorption of CO2 by Porous Solids for Carbon Capture Applications - A Short Perspective.

With ever-increasing efforts to design sorbent materials to capture carbon dioxide from flue gas and air, this perspective article is provided based on nearly a decade of collaboration across science, engineering, and industry partners. A key point learned is that a holistic view of the carbon capture problem is critical. While researchers can be inclined to value their own fields and associated metrics, often, key parameters are those that enable synergy between materials and processes. While the role of water in the chemisorption of CO2 is well-studied, in this perspective, it is hoped to highlight the often-overlooked but critical role of water in assessing the potential of a physical adsorbent for CO2 capture. This is a challenge that requires interdisciplinarity. As such, this document is written for a general audience rather than experts in any specific discipline.

A molecular extraction process for vanadium based on tandem selective complexation and precipitation.

Recycling vanadium from alternative sources is essential due to its expanding demand, depletion in natural sources, and environmental issues with terrestrial mining. Here, we present a complexation-precipitation method to selectively recover pentavalent vanadium ions, V(V), from complex metal ion mixtures, using an acid-stable metal binding agent, the cyclic imidedioxime, naphthalimidedioxime (H2CIDIII). H2CIDIII showed high extraction capacity and fast binding towards V(V) with crystal structures showing a 1:1 M:L dimer, [V2(O)3(C12H6N3O2)2]2-, 1, and 1:2 M:L non-oxido, [V(C12H6N3O2)2] ̶ complex, 2. Complexation selectivity studies showed only 1 and 2 were anionic, allowing facile separation of the V(V) complexes by pH-controlled precipitation, removing the need for solid support. The tandem complexation-precipitation technique achieved high recovery selectivity for V(V) with a selectivity coefficient above 3 × 105 from synthetic mixed metal solutions and real oil sand tailings. Zebrafish toxicity assay confirmed the non-toxicity of 1 and 2, highlighting H2CIDIII's potential for practical and large-scale V(V) recovery.

A water-stable metal-organic framework with highly acidic pores for proton-conducting applications.

Metal-organic framework (MOF) materials are a nontraditional route to ion conductors, but their crystallinity can give insight into molecular-level transport mechanisms. However, some MOFs can be structurally compromised in humid environments. A new 3D metal-organic framework, PCMOF-5, is reported which conducts protons above 10(-3) S/cm at 60 °C and 98% relative humidity. The MOF contains free phosphonic acid groups, shows high humidity stability, and resists swelling in the presence of hydration. Channels filled with crystallographically located water and acidic groups are also observed.

Enhancing proton conduction in a metal-organic framework by isomorphous ligand replacement.

Using the concept of isomorphous replacement applied to entire ligands, a C(3)-symmetric trisulfonate ligand was substituted with a C(3)-symmetric tris(hydrogen phosphonate) ligand in a proton conducting metal-organic framework (MOF). The resulting material, PCMOF2½, has its proton conduction raised 1.5 orders of magnitude compared to the parent material, to 2.1 × 10(-2) S cm(-1) at 90% relative humidity and 85 °C, while maintaining the parent MOF structure.

Zn7O2(RCOO)10 clusters and nitro aromatic linkers in a porous metal-organic framework.

A new metal-organic framework, CALF-22 comprising Zn7O2(COO)10 secondary building units and 2-nitro-1,4-benzenedicarboxylate, is reported. The porosity and gas adsorption of N2, H2, CO2, and CH4 are studied, and CALF-22 has a surface area in excess of 1000 m(2)/g. The stability of the larger zinc cluster and the effect of the nitro group on gas sorption are also studied.

Enhancing order and porosity in a highly robust tin(IV) triphosphonate framework.

Metal organic frameworks (MOFs) are noted for crystallinity, stability, and porosity. For many industrial challenges though, beyond stability to pore activation, porous materials require high thermal and moisture stability. Here, we report a Sn(IV) triphosphonate framework, CALF-28, that is highly robust and porous. CALF-28 was designed based on the known structure of a divalent metal phosphonate that was 2-fold interpenetrated. It has strong sustaining interactions but consequently rapidly precipitates, compromising crystallinity. Using methods to enhance order, and by analogy to the M(II) analogue, insights to the structure are ascertained and corroborated by PXRD and gas sorption analysis. CALF-28 has a surface area >500 m(2)/g and is stable in water.