Phosphonate Metal-organic Framework Research Articles

A Flexible Phosphonate Metal–Organic Framework for Enhanced Cooperative Ammonia Capture

A Flexible Phosphonate Metal–Organic Framework for Enhanced Cooperative Ammonia Capture

A magnesium phosphonate metal-organic framework showing excellent performance for lead(II) sensing and removal from aqueous solutions.

A hydrogen-bonded three-dimensional porous metal-organic framework [Mg(H2PCD)2(H2O)2]·2H2O (denoted as Mg-MOF·2H2O; H3PCD = 9-(2-(ethoxy(hydroxy)phosphonyl)ethyl)-9H-carbazole-3,6-dicarboxylic acid) was synthesized by the reactions of H3PCD and Mg(II) under solvothermal conditions. The free carboxylate group was maintained in the pore surface by adjusting the acidic reaction conditions. The highly stable Mg-MOF exhibits excellent performance for lead(II) sensing and removal from aqueous solutions.

Atomically precise surface chemistry of zirconium and hafnium metal oxo clusters beyond carboxylate ligands.

The effectiveness of nanocrystals in many applications depends on their surface chemistry. Here, we leverage the atomically precise nature of zirconium and hafnium oxo clusters to gain fundamental insight into the thermodynamics of ligand binding. Through a combination of theoretical calculations and experimental spectroscopic techniques, we determine the interaction between the M6O8 8+ (M = Zr, Hf) cluster surface and various ligands: carboxylates, phosphonates, dialkylphosphinates, and monosubstituted phosphinates. We refute the common assumption that the adsorption energy of an adsorbate remains unaffected by the surrounding adsorbates. For example, dialkylphosphinic acids are too sterically hindered to yield complete ligand exchange, even though a single dialkylphosphinate has a high binding affinity. Monoalkyl or monoaryl phosphinic acids do replace carboxylates quantitatively and we obtained the crystal structure of M6O8H4(O2P(H)Ph)12 (M = Zr, Hf), giving insight into the binding mode of monosubstituted phosphinates. Phosphonic acids cause a partial structural reorganization of the metal oxo cluster into amorphous metal phosphonate as indicated by pair distribution function analysis. These results rationalize the absence of phosphonate-capped M6O8 clusters and the challenge in preparing Zr phosphonate metal-organic frameworks. We thus further reinforce the notion that monoalkylphosphinates are carboxylate mimics with superior binding affinity.

Nickel Phosphonate MOF Derived N-Doped Carbon-Coated Phosphorus-Vacancies-Rich Ni2 P Particles as Efficient Bifunctional Oxygen Electrocatalyst.

The design of non-noble metal bifunctional electrocatalysts with outstanding performance and remarkable stability for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most essential issues to the realization of rechargeable zinc-air battery, and transition metal phosphides (TMPs) have emerged as robust candidates for oxygen electrocatalysts. Herein, N-doped carbon-coated phosphorus-vacancies-rich Ni2 P particles (Vp -Ni2 P@NC) is proposed via simple carbonization and following Ar plasma treatment from a single nickel phosphonate metal-organic framework (MOF) without extra phosphine and nitrogen sources. The facile and rapid plasma treatment can achieve phosphorus vacancies which could modulate the electronic structure to enhance the inherent active and electrical conductivity. Meanwhile, the pyridine-N and graphitized-N produced during calcination also could provide more active sites and increase the electrical conductivity. The resultant Vp -Ni2 P@NC catalyst shows excellent bifunctional electrocatalytic activity (OER/ORR) based on synergistic effect of introducing P vacancies into Ni2 P and N-doped carbon. Vp -Ni2 P@NC catalyst shows more advantageous ΔE value (0.70 V) compared to Pt/C+RuO2 (0.73 V) and most reported catalysts. Additionally, the zinc-air bbatterie (ZAB) employing Vp -Ni2 P@NC as air cathode shows excellent performance. The maximum power density of 203.48 mW cm-2 , the cycling stability of more than 150 h at 10 mA cm-2 .

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.

Two Cu-Based Phosphonate Metal–Organic Frameworks as Efficient Water-Splitting Photocatalysts

Two novel three-dimensional metal–organic frameworks (MOFs) based on the photoactive pyrene tetraphosphonate ligand and copper (denoted as IEF-8 and IEF-9) have been hydrothermally synthesized and fully characterized (XRD, FTIR, TGA, SEM, XPS, etc.). Their crystal structures were unveiled by single-crystal X-ray diffraction. Remarkably, these materials exhibit coordinatively unsaturated copper (II) sites, free −PO3H2 and −PO3H acidic groups, and good thermal and chemical stability. Further, their optoelectronic characterization evidenced a photoresponse suitable for photocatalysis. In this sense, the photocatalytic activity of pyrene phosphonate MOFs was evaluated for the first time for the challenging hydrogen evolution reaction. In particular, IEF-8 exhibited a catalytic efficiency higher than that of the benchmarked Ti carboxylate photocatalyst MIL-125(Ti)–NH2, producing 1800 μmol·g–1 after 22 h under UV–vis irradiation in the absence of any co-catalyst. Furthermore, this material presented good reusability (at least up to 4 cycles), preserving its activity and structural integrity.

High Proton Conductivity of a Bismuth Phosphonate Metal–Organic Framework with Unusual Topology

Despite the interest in proton exchange membrane (PEM) technologies (fuel cells and electrolyzers) for energy applications, the low stability of the electrolyte materials under working conditions (i.e., humidity and temperature) is one of their major limitations. Metal–organic frameworks (MOFs) have recently emerged as promising electrolytes due to their higher stability compared with the currently applied organic polymers, proton conductivity, and outstanding porosity. Here, a novel robust Bi phosphonate MOF (branded as IEF-7) was successfully synthesized and fully characterized, exhibiting an unusual topology due to the irregular coordination geometry of the bismuth cations. Furthermore, IEF-7 exhibited potential porosity, very high chemical and thermal stability, and free −PO3H groups involved in its ultrahigh proton conductivity, reaching 1.39 × 10–2 S cm–1 at 90 °C and 90% relative humidity for, at least, 3 cycles. In order to improve the consolidation and shaping of the powder for testing its ion conductivity properties, a highly MOF-loaded composite (90 wt %) was prepared by adding a proton conductive sulfonated polysulfone binder. The proton conductivity of the resulting composite was in the same order of magnitude as the compacted MOF powder, making this polymeric composite electrolyte very promising for PEM technologies.

Targeted Synthesis of a Highly Stable Aluminium Phosphonate Metal–Organic Framework Showing Reversible HCl Adsorption

AbstractA concept for obtaining isoreticular compounds with tri‐ instead of tetravalent metal cations using highly acidic reaction conditions was developed and successfully applied in a high throughput study using N,N′‐piperazinebis(methylenephosphonic acid) (H4PMP), that resulted in the discovery of a new porous aluminium phosphonate denoted CAU‐60⋅6 HCl. The high‐throughput study was subsequently extended to other trivalent metal ions. Al‐CAU‐60⋅6 HCl demonstrates reversible desorption of HCl (18.3 wt % loading) with three distinct compositions observed with zero, four or six HCl molecules per formula unit. Structural changes were followed in detail by powder X‐ray diffraction, EDX analysis as well as IR spectroscopy. Rapid desorption of HCl in water within minutes and subsequent adsorption from the gas phase and from aqueous solution are shown. Furthermore, it is possible to adsorb HBr into the guest free Al‐CAU‐60 framework, demonstrating the high stability of this compound.

Targeted Synthesis of an Highly Stable Aluminium Phosphonate Metal-Organic Framework Showing Reversible HCl Adsorption.

A concept for obtaining isoreticular compounds with tri- instead of tetravalent metal cations using highly acidic reaction conditions was developed and successfully applied in a high throughput study using N,N'-piperazinebis(methylenephosphonic acid) (H4PMP), that resulted in the discovery of a new porous aluminium phosphonate denoted CAU-60 ∙ 6 HCl. The high-throughput study was subsequently extended to other trivalent metal ions. Al-CAU-60 ∙ 6 HCl demonstrates reversible desorption of HCl (18.3 wt% loading) with three distinct compositions observed with zero, four or six HCl molecules per formula unit. Structural changes were followed in detail by powder X-ray diffraction, EDX analysis as well as IR spectroscopy. Rapid desorption of HCl in water within minutes and subsequent adsorption from the gas phase and from aqueous solution are shown. Furthermore, it is possible to adsorb HBr into the guest free Al-CAU-60 framework, demonstrating the high stability of this compound.

Two luminescent phosphonate metal-organic framework as highly efficient and sensitive sensors for the detections of tetracycline antibiotic in aqueous system

The adverse effects of tetracycline (TC), chlortetracycline (CTC) and oxytetracyline (OTC) residues on human health and ecosystem have attracted much attention. Herein, two novel luminescent phosphonate metal-organic frameworks based on Zn and Cd were prepared by hydrothermal method, named MOF-1 (2[Zn2‧L·(H2O)2]) and MOF-2 (2[Cd(H2L)‧(H2O)2]), respectively. Two MOFs can specifically recognize three antibiotics and quench the fluorescence by the internal filter effect (IFE). In addition, in the presence of ions and other antibiotics, the MOFs still showed good selectivity and strong anti-interference performance. It is worth noting that the detection limits of MOF-2 for TC, CTC and OTC are 4.9, 1.21 and 2.17 ​nM respectively. These excellent sensing properties, together with easy preparation, good stability and feasibility, makes MOFs have high potential to detect tetracycline antibiotics in aqueous solution.

Coordination-Induced Band Gap Reduction in a Metal-Organic Framework.

Herein, we report on the synthesis of a microporous, three‐dimensional phosphonate metal–organic framework (MOF) with the composition Cu3(H5‐MTPPA)2 ⋅ 2 NMP (H8‐MTPPA=methane tetra‐p‐phenylphosphonic acid and NMP=N‐methyl‐2‐pyrrolidone). This MOF, termed TUB1, has a unique one‐dimensional inorganic building unit composed of square planar and distorted trigonal bipyramidal copper atoms. It possesses a (calculated) BET surface area of 766.2 m2/g after removal of the solvents from the voids. The Tauc plot for TUB1 yields indirect and direct band gaps of 2.4 eV and 2.7 eV, respectively. DFT calculations reveal the existence of two spin‐dependent gaps of 2.60 eV and 0.48 eV for the alpha and beta spins, respectively, with the lowest unoccupied crystal orbital for both gaps predominantly residing on the square planar copper atoms. The projected density of states suggests that the presence of the square planar copper atoms reduces the overall band gap of TUB1, as the beta‐gap for the trigonal bipyramidal copper atoms is 3.72 eV.

Robust Barium Phosphonate Metal–Organic Frameworks Synthesized under Aqueous Conditions

The design and discovery of three-dimensional crystalline metal–organic frameworks (MOFs) from linkers with phosphonate coordinating groups and even alkaline earth metals is largely undeveloped. Herein, we report a strategy for realizing new, stable, and robust barium phosphonate MOFs, termed Empa-1 and Empa-2. The two-dimensional (2D) Empa-1 or three-dimensional (3D) Empa-2 could be realized by way of systematically modulating the ratio of Ba2+ with a tetratopic phosphonate-based linker that was crafted to incorporate nitrogen-rich triazine units bridged by a fixed piperazine core. In addition to this synthetic approach, temperature-dependent synchrotron-radiation powder X-ray diffraction analysis demonstrated that the 2D Empa-1 undergoes an irreversible phase transition upon heating and subsequent dehydration to form the 3D Empa-2. Given the presence of uncoordinated phosphonic acid moieties within the structure of 3D Empa-2, the CO2 sorption capabilities are reported. We believe our ability to link the alkaline earth metal barium with a novel tetratopic phosphonate linker, as evidenced by the robust structures of Empa-1 and -2, paves the way for further exploration and discovery of new crystalline, porous frameworks with greater structural diversity, stability, and wide-scale practical applicability.

A Nanotubular Metal-Organic Framework with a Narrow Bandgap from Extended Conjugation*.

A one‐dimensional nanotubular metal–organic framework (MOF) [Ni(Cu‐H4TPPA)]⋅2 (CH3)2NH2 + (H8TPPA=5,10,15,20‐tetrakis[p‐phenylphosphonic acid] porphyrin) constructed by using the arylphosphonic acid H8TPPA is reported. The structure of this MOF, known as GTUB‐4, was solved by using single‐crystal X‐ray diffraction and its geometric accessible surface area was calculated to be 1102 m2 g−1, making it the phosphonate MOF with the highest reported surface area. Due to the extended conjugation of its porphyrin core, GTUB‐4 possesses narrow indirect and direct bandgaps (1.9 eV and 2.16 eV, respectively) in the semiconductor regime. Thermogravimetric analysis suggests that GTUB‐4 is thermally stable up to 400 °C. Owing to its high surface area, low bandgap, and high thermal stability, GTUB‐4 could find applications as electrodes in supercapacitors.

A 3D Cu‐Naphthalene‐Phosphonate Metal–Organic Framework with Ultra‐High Electrical Conductivity

AbstractA conductive phosphonate metal–organic framework (MOF), [{Cu(H2O)}(2,6‐NDPA)0.5] (NDPA = naphthalenediphosphonic acid), which contains a 2D inorganic building unit (IBU) comprised of a continuous edge‐sharing sheet of copper phosphonate polyhedra is reported. The 2D IBUs are connected to each other via polyaromatic 2,6‐NDPA's, forming a 3D pillared‐layered MOF structure. This MOF, known as TUB40, has a narrow band gap of 1.42 eV, a record high average electrical conductance of 2 × 102 S m−1 at room temperature based on single‐crystal conductivity measurements, and an electrical conductance of 142 S m−1 based on a pellet measurement. Density functional theory (DFT) calculations reveal that the conductivity is due to an excitation from the highest occupied molecular orbital on the naphthalene‐building unit to the lowest unoccupied molecular orbital on the copper atoms. Temperature‐dependent magnetization measurements show that the copper atoms are antiferromagnetically coupled at very low temperatures, which is also confirmed by the DFT calculations. Due to its high conductance and thermal/chemical stability, TUB40 may prove useful as an electrode material in supercapacitors.

Nickel phosphonate MOF as efficient water splitting photocatalyst

A novel microporous two-dimensional (2D) Ni-based phosphonate metal-organic framework (MOF; denoted as IEF-13) has been successfully synthesized by a simple and green hydrothermal method and fully characterized using a combination of experimental and computational techniques. Structure resolution by single-crystal X-ray diffraction reveals that IEF-13 crystallizes in the triclinic space group Pi having bi-octahedra nickel nodes and a photo/electroactive tritopic phosphonate ligand. Remarkably, this material exhibits coordinatively unsaturated nickel(II) sites, free–PO3H2 and–PO3H acidic groups, a CO2 accessible microporosity, and an exceptional thermal and chemical stability. Further, its in-deep optoelectronic characterization evidences a photoresponse suitable for photocatalysis. In this sense, the photocatalytic activity for challenging H2 generation and overall water splitting in absence of any co-catalyst using UV–Vis irradiation and simulated sunlight has been evaluated, constituting the first report for a phosphonate-MOF photocatalyst. IEF-13 is able to produce up to 2,200 µmol of H2 per gram using methanol as sacrificial agent, exhibiting stability, maintaining its crystal structure and allowing its recycling. Even more, 170 µmol of H2 per gram were produced using IEF-13 as photocatalyst in the absence of any co-catalyst for the overall water splitting, being this reaction limited by the O2 reduction. The present work opens new avenues for further optimization of the photocatalytic activity in this type of multifunctional materials.

Phosphonate metal–organic frameworks used as dye removal materials from wastewaters

A very intense study class of complex porous materials, metal–organic frameworks (MOFs), composed of diverse central metallic ions attached to organic linkers, was used in this study as adsorbant materials from wastewaters. Phosphonate MOFs were prepared by the reaction of divalent inorganic salts (CoSO4·7H2O, NiSO4·6H2O, CuSO4·5H2O,) with vinyl phosphonic acid in hydrothermal conditions, obtaining cobalt, nickel, and copper vinylphosphonate (CoVP, NiVP, and CuVP). During synthesis the experimental conditions were varied in terms of time, temperature, and pH. The synthesized materials were characterized by Fourier transform infrared, thermogravimetric analysis, scanning electron microscopy, and X‐ray crystallography. The efficiency of MOFs as adsorbents was investigated for diverse initial dye concentrations at different pH values and at three temperatures (25, 40, and 55°C). The synthesized materials presented good efficiency in the elimination of anionic as well as cationic type of dyes from aqueous solutions. The highest adsorption capacities were obtained working at optimum solution pH 4.2 for Acid Orange 7 and 10 for Basic Fuchsine, using 1 g/L of MOFs at room temperature (25°C). The adsorption capacities increase in the following order: CuVP < NiVP < CoVP.

Phosphonate Metal-Organic Frameworks: A Novel Family of Semiconductors.

Herein, the first semiconducting and magnetic phosphonate metal-organic framework (MOF), TUB75, is reported, which contains a 1D inorganic building unit composed of a zigzag chain of corner-sharing copper dimers. The solid-state UV-vis spectrum of TUB75 reveals the existence of a narrow bandgap of 1.4 eV, which agrees well with the density functional theory (DFT)-calculated bandgap of 1.77 eV. Single-crystal conductivity measurements for different orientations of the individual crystals yield a range of conductances from 10-3 to 103 S m-1 at room temperature, pointing to the directional nature of the electrical conductivity in TUB75. Magnetization measurements show that TUB75 is composed of antiferromagnetically coupled copper dimer chains. Due to their rich structural chemistry and exceptionally high thermal/chemical stabilities, phosphonate MOFs like TUB75 may open new vistas in engineerable electrodes for supercapacitors.

Probing Isoreticular Expansions in Phosphonate MOFs and their Applications

This review is divided into three different parts. In the introduction, the current applications of metal‐organic frameworks (MOFs) are shown. Furthermore, the overall stability, a comparison of phosphonate MOFs with carboxylate MOFs, the structural richness of phosphonate MOFs with the challenge in synthesis and different linker geometries is discussed. In the second part, several phosphonate MOFs with Y‐shaped planar, X‐shaped planar, and X‐shaped tetrahedral linker systems are described. The final part discusses different structures of inorganic building units (IBUs) with different metal atoms and a comparison of the formed MOF structures.

Highly Stable Phosphonate-Based MOFs with Engineered Bandgaps for Efficient Photocatalytic Hydrogen Production.

Photoactive metal-organic frameworks (MOFs) represent one of the most promising materials for photocatalytic hydrogen production, but phosphonate-based MOFs have remained largely underdeveloped compared to other conventional MOFs. Herein, a photocatalyst of 1D titanium phosphonate MOF is designed through an easy and scalable stirring hydrothermal method. Homogeneous incorporation of organophosphonic linkers can narrow the bandgap, which is due to the strong electron-donating ability of the OH functional group that can efficiently shift the top of the valence band, moving the light absorption to the visible portion of the spectrum. In addition, the unique 1D nanowire topology enhances the photoinduced charge carrier transport and separation. Accordingly, the titanium phosphonate nanowires deliver remarkably enhanced photocatalytic hydrogen evolution activity under irradiation of both visible light and a full-spectrum simulator. Such concepts of engineering both nanostructures and electronic states herald a new paradigm for designing MOF-based photocatalysts.

Effects of Secondary Anions on Proton Conduction in a Flexible Cationic Phosphonate Metal–Organic Framework

Four new phosphonate MOFs were prepared with cationic dimethylbipiperdinium units: [La2(H2L)1.5(AcO)2Br·3.25H2O], α-PCMOF-21-Br; [La2(H2L)1.5(AcO)Cl2·5.25H2O], α-PCMOF-21-Cl; [La(H2L) (AcO)Br0.5·4....