Dual-Functionalized Mixed Keggin- and Lindqvist-Type Cu24-Based POM@MOF for Visible-Light-Driven H2 and O2 Evolution.

The development of logical visible-light-driven heterogeneous photosystems for water splitting is a subject of new research. As the first example of a noble-metal-free photocatalyst for both H2 and O2 production, a high-nuclear {CuI24(µ3-Cl)8(µ4-Cl)6}-based polyoxometalate (POM)@metal-organic framework (MOF) (ZZULI-1) is rationally designed to serve as a robust dual-functionalized photocatalyst. ZZULI-1 exhibits highly efficient photocatalytic H2 evolution (6614 µmol g-1 h-1) and O2 evolution (1032 µmol g-1 calculated for the first 6 min). The {CuI24(µ3-Cl)8(µ4-Cl)6} clusters and mixed POMs not only work as the active units for H2 and O2 production, respectively, but also improve the effective electron transfer between the photosensitizer and ZZULI-1. The highly stable dual-functionalized ZZULI-1 affords new penetrations into the development of cost-effective high-nuclear cluster-based POM@MOFs for efficient solar-to-fuel generation.

Stable Layered Semiconductive Cu(I)-Organic Framework for Efficient Visible-Light-Driven Cr(VI) Reduction and H2 Evolution.

Metal-organic frameworks (MOFs) have gained tremendous attention in the fields of environmental restoration and sustainable energy for their potential use as photocatalyst. Herein, a new two-dimensional (2D) Cu(I)-based MOF material showing a narrow forbidden-band of 2.13 eV was successfully constructed using a visible-light-harvesting anthracene-based bipyridine ligand. The as-prepared MOF demonstrates high chemical stability and could be stable in the pH range 2-13, which is favorable for its potential application in photocatalysis. Photocatalytic experiments demonstrate that this Cu(I)-MOF exhibits high reactivity for reduction of Cr(VI) in water, with 95% Cr(VI) converting to Cr(III) in 10 min by using MeOH as scavenger under visible-light illumination. Furthermore, this MOF could behave as a highly active photocatalyst for H2 evolution without additional photosensitizers and cocatalyst. Remarkably, the as-prepared MOF shows enhanced photocatalytic Cr(VI) reduction and H2 evolution performances compared with the pristine light-harvesting ligand under the same conditions. In connection to these, the photocatalytic reaction mechanism has also been probed.

Tunable Robust pacs-MOFs: a Platform for Systematic Enhancement of the C2H2 Uptake and C2H2/C2H4 Separation Performance.

As a modulatable class of porous crystalline materials, metal-organic frameworks (MOFs) have gained intensive research attention in the domain of gas storage and separation. In this study, we report on the synthesis and gas adsorption properties of two robust MOFs with the general formula [Co3(µ3-OH)(cpt)3Co3(µ3-OH)(L)3(H2O)9](NO3)4(guests) n [L = 3-amino-1,2,4-triazole (1) and 3,5-diamino-1,2,4-triazole (2); Hcpt = 4-(4-carboxyphenyl)-1,2,4-triazole], which show the same pacs topology. Both MOFs are isostructural to each other and show MIL-88-type frameworks whose pore spaces are partitioned by different functionlized trinuclear 1,2,4-triazolate-based clusters. The similar framework components with different amounts of functional groups make them an ideal platform to permit a systematic gas sorption/separation study to evaluate the effects of distinctive parameters on the C2H2 uptake and separation performance. Because of the presence of additional amido groups, the MOF 2 equipped with a datz-based cluster (Hdatz = 3,5-diamino-1,2,4-triazole) shows a much improved C2H2 uptake capacity and separation performance over that of the MOF 1 equipped with atz-based clusters (Hatz = 3-amino-1,2,4-triazole), although the surface area of the MOF 1 is almost twice than that of the MOF 2. Moreover, the high density of open metal sites, abundant free amido groups, and charged framework give the MOF 2 an excellent C2H2 separation performance, with ideal adsorbed solution theory selectivity values reaching up to 11.5 and 13 for C2H2/C2H4 (1:99) and C2H2/CO2 (50:50) at 298 K and 1 bar, showing potential for use in natural gas purification.

Simultaneous Trapping of C2 H2 and C2 H6 from a Ternary Mixture of C2 H2 /C2 H4 /C2 H6 in a Robust Metal-Organic Framework for the Purification of C2 H4.

The removal of C2 H2 and C2 H6 from C2 H4 streams is of great significance for feedstock purification to produce polyethylene and other commodity chemicals but the simultaneous adsorption of C2 H6 and C2 H2 over C2 H4 from a ternary mixture has never been realized. Herein, a robust metal-organic framework, TJT-100, was designed and synthesized, which demonstrates remarkably selective adsorption of C2 H2 and C2 H6 over C2 H4 . Breakthrough experiments show that TJT-100 can be used as an adsorbent for high-performance purification of C2 H4 from a ternary mixture of C2 H2 /C2 H4 /C2 H6 (0.5:99:0.5) to afford a C2 H4 purity greater than 99.997 %, beyond that required for ethylene polymerization. Computational studies reveal that the uncoordinated carboxylate oxygen atoms and coordinated water molecules pointing towards the pore can trap C2 H2 and C2 H6 through the formation of multiple C-H⋅⋅⋅O electrostatic interactions, while the corresponding C2 H4 -framework interaction is unfavorable.

Quest for the Ncb-type Metal-Organic Framework Platform: A Bifunctional Ligand Approach Meets Net Topology Needs.

A custom-designed bifunctional ligand was used to connect an in situ formed Co3(OH) cluster affording a porous metal-organic framework, which represents the first case of ncb-type networks constructed from a single kind of ditopic ligand. Noticeably, the activated MOF shows high volumetric C2H2 uptake and excellent adsorption selectivity for C2H2/CO2 separation at room temperature with a low sorption heat.

Microporous Cobalt(II)-Organic Framework with Open O-Donor Sites for Effective C2H2 Storage and C2H2/CO2 Separation at Room Temperature.

The self-assembly of a bifunctional organic ligand with a formate-bridged rod-shaped secondary building unit leads to a new microporous metal-organic framework (MOF). This MOF shows a moderately high C2H2 storage capacity (145 cm3/g) and an excellent adsorption selectivity for C2H2/CO2 (11) at room temperature. Furthermore, its discriminatory sorption behavior toward C2H2 and CO2 was probed by computational analysis in detail.

A Mixed-Cluster Approach for Building a Highly Porous Cobalt(II) Isonicotinic Acid Framework: Gas Sorption Properties and Computational Analyses.

A unique channel-type metal-organic framework (MOF) built up from mixed square-planar Co4(µ2-OH)4(µ4-OH) and cuboidal Co4(µ3-OH)4 clusters with an isonicotinic acid ligand has been successfully fabricated that demonstrates the highest specific surface area and high H2 uptake capacities among all of the cobalt(II) isonicotinic acid frameworks reported so far.

Charge Control in Two Isostructural Anionic/Cationic CoII Coordination Frameworks for Enhanced Acetylene Capture.

Two isostructural CoII -based metal-organic frameworks (MOFs) with the opposite framework charges have been constructed, which can be simply controlled by changing the tetrazolyl or triazolyl terminal in two bifunctional ligands. Notably, the cationic MOF 2 can adsorb much more C2 H2 than the anionic MOF 1 with an increase of 88 % for C2 H2 uptake at 298 K in spite of more active nitrogen sites in 1. Theoretical calculations indicate that both nitrate and triazolyl play vital roles in C2 H2 binding and the C2 H2 adsorption isotherm confirms that the enhanced C2 H2 uptake for 2 (225 and 163 cm3 g-1 at 273 and 298 K) is exceptionally high for MOF materials without open metal sites or uncoordinated polar atom groups on the frameworks.

Ligand Symmetry Modulation for Designing Mixed-Ligand Metal-Organic Frameworks: Gas Sorption and Luminescence Sensing Properties.

Herein, we report the synthesis of a new mixed-linker Zn(II)-based metal-organic framework (MOF), {[Zn2(atz)2(bpydb)](DMA)8}n (1) (atz = deprotonated 3-amino-1,2,4-triazole, bpydb = deprotonated 4,4'-(4,4'-bipyridine-2,6-diyl) dibenzoic acid, DMA = N,N-dimethylacetamide), through symmetry modulation of a triazole ligand. The desymmetrized triazole linkers not only bond to the Zn(II) ions to result in a new helical Zn-triazolate chain building unit but also lead to the formation of a highly porous framework (N2 uptake: 617 cm(3)/g; BET surface area: 2393 m(2)/g) with 1D helical channels. The adsorption properties of desolved 1 were investigated by H2, C2H2, CO2, and CH4 sorption experiments, which showed that 1 exhibited high uptake capacity for H2 at 77 K and C2H2 around room temperature. More importantly, the high C2H2 uptake capacity but low binding energy makes this MOF a promising candidate for effective C2H2 capture from C2H2/CO2 and C2H2/CH4 mixed gases with low regenerative energy cost. In addition, 1 shows potential application for the luminescence sensing of small aromatic molecules picric acid (PA) and p-xylene (PX).

Microporous Metal-Organic Framework Based on a Bifunctional Linker for Selective Sorption of CO2 over N2 and CH4.

A bifunctional organic linker 4-(4-carboxyphenyl)-1,2,4-triazole (HCPT), incorporating both carboxylate and triazole groups, has been successfully used in the construction of a 2-fold interpenetrated dynamic metal-organic framework (MOF), {[Cu3(CPT)4(µ3-OH)]·NO3·7H2O·EtOH}n (1) based on a triangular Cu(II)-hydroxo cluster as secondary building unit (SBU). Upon solvation/desolvation and temperature, the crystal cell parameters of 1 could be fine-tuned. More importantly, a transformation from disordered phase to a more ordered phase after activation was observed via a single-crystal-to-single-crystal mode. Gas sorption studies reveal that the activated 1 exhibits highly selective sorption of CO2 over N2 and CH4 at room temperature.

Switching a 2D Co(II) layer to a 3D Co7-cluster-based metal-organic framework: syntheses, crystal structures, and magnetic properties.

Two 2D layered coordination networks with formulas of {[Co(TPA)Cl](H2O)2.5}n (1) and {[Co(TPA)(µ2-OH)](H2O)2}n (2) (HTPA = 4-(1,2,4-triazol-4-yl)phenylacetic acid) were solvothermally synthesized and fully characterized. Interesting 1D Co(2+)-Cl or Co(2+)-µ2-OH chain structures were observed. By carefully adjusting the reaction conditions, a new 3D metal-organic framework (MOF) with a formula of {[Co7(TPA)6(µ3-OH)4(µ2-OH)2(H2O)4](TPA)2(DMF)3(H2O)3}n (3) was obtained. MOF 3 is built from Co7 clusters and fully deprotonated TPA ligands, which display a cubic pcu topology. Factors that influence the structures of the three TPA-based complexes, as well as their magnetic properties, were investigated in detail. The heptanuclear-Co(II)-cluster-based MOF 3 shows interesting magnetization dynamics at low temperature.

A water-stable EuIII-based MOF as a dual-emission luminescent sensor for discriminative detection of nitroaromatic pollutants.

A water-stable EuIII-based metal-organic framework (MOF) with dual-emission luminescence behavior, namely {[Eu4(INO)5(µ3-OH)2Cl4(H2O)]·(NO3)·(H2O)5}n (Eu-MOF; HINO = isonicotinic acid N-oxide), was successfully constructed by the solvothermal reaction of Eu3+ ions with the organic ligand HINO. The cationic 3D framework contains microporous channels with accessible Lewis-base sites and NO3- ions as balanced anions, which all contribute to the selective detection of multifarious analytes. This MOF shows ratiometric detection of acetone, Cr2O72- ions, and nitroaromatic compounds (NACs). In particular, it shows great recognition of four NACs in water, representing the first LnIII-MOF which can display distinguishing fluorescence phenomena on NACs rather than relying on the quenching effect. Furthermore, this is also the first example of a MOF-sensor for detecting these explosives discriminatively by ratiometric methods. Additionally, the mechanisms for luminescent responses towards different analytes have been discussed in detail.

A high-activity cobalt-based MOF catalyst for [2 + 2 + 2] cycloaddition of diynes and alkynes: insights into alkyne affinity and selectivity control.

This work develops a highly efficient metal-organic framework (MOF) catalyst for the straightforward synthesis of functionalized benzenes via [2 + 2 + 2] cycloaddition. As efficient cooperative catalyst for such reactions, Co-MOF-1, shows great sustainability and efficiency. This new catalytic system can lead to the generation of a series of structurally diverse benzenes in good to excellent yields (up to 95%).

Dual-Emitting Dye@MOF Composite as a Self-Calibrating Sensor for 2,4,6-Trinitrophenol.

An anionic metal-organic framework (MOF) {(NH2Me2)[Zn3(µ3-OH)(tpt)(TZB)3](DMF)12}n (1, tpt = 2,4,6-tri(4-pyridyl)-1,3,5-triazine, H2TZB = 4-(1H-tetrazol-5-yl)benzoic acid and DMF = N,N-dimethylformamide), with both nanosized cages and partitions, has been solvothermally synthesized, which can serve as a crystalline vessel to encapsulate the fluorescent dye rhodamine 6G (Rh6G) via a "bottle around ship" approach. As a result, the obtained dye@MOF composite system features a blue emission of the ligand at 373 nm and a red emission of Rh6G at 570 nm when dispersed in solution, which could be used for decoding the trace amount of 2,4,6-trinitrophenol (TNP) by referring the peak-height ratio of each emission, even in coexistence with other potentially competitive nitroaromatic analytes. Furthermore, the observed fluorescence responses of the composite toward TNP are highly stable and reversible after recycling experiments. To the best of our knowledge, this is the first example of an MOF-implicated self-calibrated sensor for TNP detection.

An anionic Na(i)-organic framework platform: separation of organic dyes and post-modification for highly sensitive detection of picric acid.

A cage-based anionic Na(i)-organic framework with a unique Na9 cluster-based secondary building unit and a cage-in-cage structure was constructed. The selective separation of dyes with different charges and sizes was investigated. Furthermore, the Rh6G@MOF composite could be applied as a recyclable fluorescent sensor for detecting picric acid (PA) with high sensitivity and selectivity.

Pore modulation of zirconium-organic frameworks for high-efficiency detection of trace proteins.

Tunable electrochemical biosensors based on analogous Zr-MOFs were developed for protein detection, the performances of which rely on the pore sizes and surroundings of the MOFs that show diverse binding behaviors to aptamers and then the targeted proteins. The optimized Zr-MOF-based sensor has high selectivity to lysozyme in a wide concentration range and a low detection limit of 3.6 pg mL-1, with good repeatability, stability, and applicability in real samples. This work will establish a new platform for biosensing and extend the application scope of MOF materials.

Aptamer-Embedded Zirconium-Based Metal-Organic Framework Composites Prepared by De Novo Bio-Inspired Approach with Enhanced Biosensing for Detecting Trace Analytes.

A series of Zr-based metal-organic framework (MOF) composites embedded with three kinds of aptamer strands (509-MOF@Apt) were achieved by a one-step de novo synthetic approach. A platform for ultrasensitive detection of analytes, namely, thrombin, kanamycin, and carcinoembryonic antigen (CEA), was also established. Considering the conformational changes caused by the binding interactions between aptamer strands and targeted molecules, the label-free electrochemical aptasensors based on 509-MOF@Apt composites could be developed to detect various target molecules. By comparing the common fabrication approaches of aptasensors, a distinct determination mechanism was presented through analysis of the electrochemical measurements on different interaction behaviors between probe aptamer strands and 509-MOF materials. The optimized aptasensors based on 509-MOFs@Apt demonstrated excellent sensitivity (with the detection limit of 0.40, 0.37, and 0.21 pg mL-1 for CEA, thrombin, and kanamycin, respectively), stability, repeatability, and applicability. This work will provide a new platform for direct and feasible detection in biosensing related to clinical diagnostics and therapeutics, and further, extend the scope of potential applications for MOF materials.

A bracket approach to improve the stability and gas sorption performance of a metal-organic framework via in situ incorporating the size-matching molecular building blocks.

Incorporating the in situ formed size-matching molecular building blocks (MBBs) into the open channels will remarkably improve the robustness and gas sorption performance of an evacuated metal-organic framework. As a result, such MBBs can transfer the open metal sites from the framework walls to the channel centers and separate the large channels into multiple smaller voids, leading to a molecular sieving effect and high-performance gas-separation of the modified material.

Moisture-Stable Zn(II) Metal-Organic Framework as a Multifunctional Platform for Highly Efficient CO2 Capture and Nitro Pollutant Vapor Detection.

A moisture-stable three-dimensional (3D) metal-organic framework (MOF), {(Me2NH2)[Zn2(bpydb)2(ATZ)](DMA)(NMF)2}n (1, where bpydb = 4,4'-(4,4'-bipyridine-2,6-diyl)dibenzoate, ATZ = deprotonated 5-aminotetrazole, DMA = N,N-dimethylacetamide, and NMF = N-methylformamide), with uncoordinated N-donor sites and charged framework skeleton was fabricated. This MOF exhibits interesting structural dynamic upon CO2 sorption at 195 K and high CO2/N2 (127) and CO2/CH4 (131) sorption selectivity at 298 K and 1 bar. Particularly, its CO2/CH4 selectivity is among the highest MOFs for selective CO2 separation. The results of Grand Canonical Monte Carlo (GCMC) simulation indicate that the polar framework contributes to the strong framework-CO2 binding at zero loading, and the tetrazole pillar contributes to the high CO2 uptake capacity at high loading. Furthermore, the solvent-responsive luminescent properties of 1 indicate that it could be utilized as a fluorescent sensor to detect trace amounts of nitrobenzene in both solvent and vapor systems.

Solvent-induced secondary building unit (SBU) variations in a series of Cu(II) metal-organic frameworks derived from a bifunctional ligand.

The role of auxiliary solvents in the formation of metal-organic frameworks (MOFs) has been studied for a series of copper-based framework systems. Herein we show the formation of three different 3D ordered frameworks with the formulae {[Cu4(cpt)4Cl4]·2DMF·dioxane·3H2O}n (1), {[Cu8(cpt)4(Hcpt)2Cl7(µ3-OH)2(H2O)4]Cl3·4CH3CN}n (2), and {[Cu8(cpt)4Cl4(µ3-OH)2(µ4-O)2]Cl2·4H2O·2CH3CN·3MeOH}n (3) [Hcpt = 4-(4-carboxyphenyl)-1,2,4-triazole], respectively, from the same reaction mixture through varying auxiliary solvents of the medium. These MOFs were fully characterized by single-crystal X-ray diffraction, showing interesting secondary building unit (SBU) variations. The varied SBUs not only bring different framework architectures to these MOFs, but also affect their framework stability. Gas sorption studies of MOF 3 reveal high CO2-N2 selectivity at 298 K and 0.16 bar (a typical partial pressure of CO2 in an industrial flue gas). A high isosteric heat of adsorption (Qst) at zero loading (53 kJ mol(-1)) was also observed in MOF 3.