Pillared-layer Metal-organic Framework Research Articles

Extra-High CO2 Adsorption and Controllable C2H2/CO2 Separation Regulated by the Interlayer Stacking in Pillar-Layered Metal-Organic Frameworks.

Pillar-layered metal-organic frameworks (PLMOFs) are promising gas adsorbents due to their high designability. In this work, high CO2 storage capacity as well as controllable C2H2/CO2 separation ability are acquired by rationally manipulating the interlayer stacking in pillar-layered MOF materials. The rational construction of pillar-layered MOFs started from the 2D Ni-BTC-pyridine layer, an isomorphic structure of pioneering MOF-1 reported in 1995. The replacement of terminal pyridine groups by bridging pyrazine linkers under optimized solvothermal conditions led to three 3D PLMOFs with different stacking types between adjacent Ni-BTC layers, named PLMOF 1 (ABAB stacking), PLMOF 2 (AABB stacking), and PLMOF 3 (AAAA stacking). Regulated by the layer arrangements, CO2 and C2H2 adsorption capacities (273 K and 1 bar) of PLMOFs 1-3 vary from 173.0/153.3, 185.0/162.4, to 203.5/159.5 cm3 g-1, respectively, which surpass the values of most MOF adsorbents. Dynamic breakthrough experiments further indicate that PLMOFs 1-3 have controllable C2H2/CO2 separation performance, which can successfully overcome the C2H2/CO2 separation challenge. Specially, PLMOFs 1-3 can remove trace CO2 (3%) from the C2H2/CO2 mixture and produce high-purity ethylene (99.9%) in one step with the C2H2 productivities of 1.68, 2.45, and 3.30 mmol g-1, respectively. GCMC simulations indicate that the superior CO2 adsorption and unique C2H2/CO2 separation performance are mainly ascribed to different degrees of CO2 agglomeration in the ultramicropores of these PLMOFs.

Dielectric response of metal-organic frameworks as a function of confined guest species investigated by molecular dynamics simulations.

When using metal-organic frameworks (MOFs) as electric field-dependent sensor devices, understanding their dielectric response is crucial as the orientation of polar groups is largely affected by confinement. To shed light on this at the molecular level, the response to a static field was computationally investigated for two structurally related MOFs, depending on their loading with guest molecules. The pillared-layer MOFs differ in their pillar moiety, with one bearing a rotatable permanent dipole moment and the other being non-polar. Two guest molecules with and without polarity, namely, methanol and methane, were considered. A comprehensive picture of the response of the guest molecules could be achieved with respect to both the amount and polarity of the confined species. For both MOFs, the dielectric response is very sensitive to the introduction of methanol, showing an anisotropic and non-linear increase in the system's relative permittivity expressed by a strongly increasing polarization response to external electric fields scaling with the number of confined methanol molecules. As expected, the effect of methane in the non-dipolar MOF is negligible, whereas subtle differences can be observed for the dipolar response of the MOF with rotatable dipolar linker groups. Taking advantage of these anisotropic and guest-molecule-specific confinement effects may open pathways for future sensing applications. Finally, methanol-induced global framework dynamics were observed in both MOFs.

Rapid synthesis of ultra-microporous metal-organic framework tubular Ni-LAP membranes for H2 separation by linker salt method

Recently, the development of pillar-layered metal-organic frameworks (MOFs) is receiving more and more attention because of their pore surface chemistry tunability and designability. In this work, we firstly synthesized various sizes of high-quality Ni-LAP [Ni2(L-asp)2(pz)] (L-asp = l-aspartic acid, pz = pyrazine) crystals key for secondary growth by manipulating the crystal thermal dynamics and kinetics of Ni-LAP synthesis solution simply through choosing the Ni(OAc)2 as metal source and pretreatment at 40 °C, followed by the fabrication of defect-free Ni-LAP membranes as a model in a short time of 4 h using the linker salt method. It is found the pretreatment of Ni(OAc)2 precursor solution at 40 °C with continuous stirring for 6 h can effectively promote deprotonation to form 250 nm crystals. The linker salt method enables a greener and more rapid synthesis of Ni-LAP membranes, with continuous and compact Ni-LAP membranes, where soluble metal precursors and organic linking salts provide the synthesis solution a higher degree of supersaturation, both of which play an important role in the rapid preparation of Ni-LAP membranes. The preparation parameters of the Ni-LAP membranes were investigated in detail, and the results from the Ni-LAP membrane gas separation performance showed that the preferential (111) orientation membrane (M9) exhibited the best H2/CO2 separation performance with separation factor of 23.8 and H2 permeance of 2.11 × 10−7 mol m−2 s−1 Pa−1 compared to the preferential (002) orientations (M3), which may attributed to the preferential (111) orientation being at an angle to the optimal a-axis aperture perpendicular to the support thereby reducing the mass transfer resistance. Furthermore, the generation of corrosive nitric acid during the preparation process can be greatly reduced and replaced by eco-friendly potassium nitrate. The superiority of the pore structure and the remarkable stability of these MOF membranes show the potential for H2 purification. Moreover, our preparation route demonstrates the universality of preparing other isomorphs, such as Ni-LAB and Co-LAP membranes.

Controllable C2H2/CO2 inverse adsorption and separation in pillar-layered Zn-1,2,4-triazolate-dicarboxylate frameworks induced by the ligand aromaticity

Acetylene (C2H2) and carbon dioxide (CO2) both are linear molecules and the similarity in size and physical properties makes their separation very challenging. Compared to the C2H2-selective C2H2/CO2 separation, the inscrutable CO2-selective capture (also called inverse C2H2/CO2 separation) process is ideal as it enables one-step production of high-purity C2H2. Herein, we demonstrate the controllable C2H2/CO2 inverse adsorption and separation in a series of isomorphic Zn-1,2,4-triazolate-dicarboxylate pillar-layered frameworks (Zn-FA-TRZ, Zn-MUC-TRZ, and Zn-BDC-TRZ) based on the aromaticity modulation strategy. Compared with Zn-MUC-TRZ, the utilization of shorter FA linker only with one double bond leads to an intersection point between the isothermal adsorption curves. After the intersection points, Zn-FA-TRZ showed higher CO2 uptakes than C2H2 (thermodynamic inversion) and the intersection point moving towards the high-pressure region with the increasing temperature. When BDC involved, the enhanced ligand aromaticity enables a complete thermodynamic inversion for C2H2 and CO2 adsorption due to the much stronger interactions between the aromatic ring and CO2 molecules. The isosteric heats of adsorption for CO2 and C2H2 clearly support such inverse adsorption induced by the ligand aromaticity. Furthermore, the fixed-bed dynamic breakthrough experiments indicate that Zn-FA-TRZ and Zn-MUC-TRZ both have common C2H2-selective separation process, but Zn-BDC-TRZ adsorbent shows a prominent CO2-selective inverse C2H2/CO2 separation. Specially, with temperature increased, the inverse separation performance enhanced, and high purity C2H2 (>99.99 %) can be obtained via one-step separation from C2H2/CO2 (50/50) mixture at room temperature. Overall, inverse C2H2/CO2 separation was successfully achieved in pillar-layered metal–organic frameworks, which is helpful for the exploration of practical acetylene adsorbents.

Novel UiO-NH2-like Zr-Based MOF (Basu-DPU) as an Excellent Catalyst for Preparation of New 6H-Chromeno[4,3-b]quinolin-6-ones.

A new two-fold interpenetrated pillar-layered metal-organic framework (MOF) was designed and synthesized based on zirconium cations, an amine-functionalized ligand, and a linear exo-bidentate bis-pyridine ligand. The structure of the prepared framework was evaluated using various techniques, such as Fourier transform infrared (FTIR), 13C NMR, energy-dispersive X-ray (EDX), elemental mapping analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analysis/differential thermal analysis (TGA/DTA), and Brunauer-Emmett-Teller (BET). Then, catalytic application of the prepared zirconium-based MOF was successfully explored in the synthesis of novel 6H-chromeno[4,3-b]quinolin-6-ones 4(a-l) through a one-pot three-component condensation reaction of 4-hydroxycumarine, 1-naphthylamine, and aromatic aldehydes under solvent-free conditions at 110 °C. The pure products were obtained with high atom efficiency (AE) and short reaction times and characterized by FTIR, NMR, and mass spectrometry techniques.

Pillar-layered metal-organic frameworks with benchmark C2H2/C2H4 and C2H6/C2H4 selectivity for one-step C2H4 production

Energy-efficient adsorptive separation shows great potential for the one-step production of high-purity ethylene (C2H4) from ternary C2 hydrocarbons. However, it remains a formidable challenge to fabricate high-performance adsorbents that exhibit simultaneous high selectivity (>2) towards acetylene/ethylene (C2H2/C2H4) and ethane/ethylene (C2H6/C2H4). Herein, we report a pillar-layered metal–organic framework, Ni(sdba)(dabco)0.5 (H2sdba = 4,4′-sulfonyldibenzoic acid; dabco = 1,4-diazabicyclo [2.2.2] octane), for preferential trapping of C2H6 and C2H2 over C2H4. The abundant accessible binding sites endow Ni(sdba)(dabco)0.5 with outstanding C2H2/C2H4 (2.28) and C2H6/C2H4 (2.47) selectivity with high C2H6 (3.15 mmol g−1) and C2H2 (4.41 mmol g−1) uptake among porous materials reported for one-step C2H4 purification. Dynamic breakthrough experiments demonstrated the feasibility of producing high-purity C2H4 (>99.9%) from C2H2/C2H6/C2H4 gas-mixtures (1/1/1 and 1/9/90, v/v/v) in a single step. Computational simulations reveal that the aromatic-rich pore spaces, which decorated with accessible interlayer uncoordinated oxygen atoms of sulfonyl groups and alkyl functionalities, can provide multiple C-H···O, C-H···π, and C-H···H interactions for selectively recognizing C2H6 and C2H2 over C2H4.

Two-Dimensional Mixed-Ligand Metal–Organic Framework Constructed from Bridging Bidentate V-Shaped Ligands

A two-dimensional and bifunctional pillar-layered metal–organic framework (MOF)—with the molecular formula [Zn(cba)(bpdb)]·DMF (2DTMU-1), H2cba = 4,4′-methylenedibenzoic acid, bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene—was obtained via the reaction of zinc(II) nitrate with H2cba as the carboxylate linker and bpdb as the N-donor pillar. 2DTMU-1 is based on a binuclear paddlewheel Zn(II) unit complexed by four bridging bidentate (dicarboxylate) V-shaped ligands, which combine to from H2cba; this tetragonal array, which is connected by bpdb with a bridging azine group, presents a pore size of 18 × 12 Å2.

Combination of Low-Polar and Polar Binding Sites in Aliphatic MOFs for the Efficient C2H6/C2H4 Separation

The selective capture of C2H6 from C2H6/C2H4 mixtures is of critical importance to realize the efficient one-step purification of C2H4 but remains challenging due to their similar properties and smaller quadrupole moment of C2H6 that usually result in C2H4-preferring adsorption. Herein, we reported two isostructural pillared-layer metal-organic frameworks, ZUL-C3 and ZUL-C4, which were constructed by mixed polycycloalkane-type ligands. Their low-polar pore environment along with more accessible low-polar C-H binding sites on the pore surface are conducive to generate more van der Waals interactions with C2H6 while the carboxylic groups distributed at four corners of pores form stronger and more dipolar interactions with C2H6, cooperatively resulting in a good C2H6/C2H4 uptake ratio of 1.50 for ZUL-C3 and 1.72 for ZUL-C4 in static adsorption experiments and a high C2H4 (>99.99% purity) productivity of 10.1 L/kg for ZUL-C3 and 14.6 L/kg for ZUL-C4 from an equimolar C2H6/C2H4 mixture in breakthrough experiments.

Two pillared-layer metal-organic frameworks based on the pinwheel trinuclear carboxylate-clusters of Zn(II) and Co(II): synthesis, crystal structures, magnetic study, and Lewis acid catalysis.

Using a dicarboxylic acid, [1,1'-biphenyl]-4,4'-dicarboxylic acid (H2L1) and an exobidentate ligand, (1E,1'E)-N,N'-(1,4-phenylene)bis(1-(pyridin-4-yl)methanimine) (L2), two 3D interpenetrated networks, {[Zn3(L1)3(L2)]·9H2O}n (Zn-MOF) and {[Co3(L1)3(L2)(DMF)]·0.5DMF}n (Co-MOF), have been prepared in good yields. The crystal structure analysis of Zn-MOF and Co-MOF revealed that both have a 3D pillared-layer structure based on pinwheel trinuclear metal-carboxylate clusters as secondary building units (SBUs). Furthermore, the structures also exhibited three-fold interpenetration. Although the overall networks in Zn-MOF and Co-MOF showed significant resemblances, there are marked differences in their crystal structures, which are associated with the coordination environment of the metal centre and the binding modes of the carboxylates. Gas adsorption studies (N2 at 77 K and 1 bar) indicated that Co-MOF is more porous than Zn-MOF. Magnetic measurements on Co-MOF indicate a significant antiferromagnetic interaction (45 K to 303 K) between trimeric Co(II) S = 3/2 spins through syn-syn carboxylato bridges. Both MOFs were studied for the Lewis acid catalyzed Knoevenagel condensation reactions between benzaldehydes and malononitrile with an active methylene group, where Zn-MOF was found to be a better catalyst than Co-MOF. This was supported by the Monte Carlo simulations indicating the better substrate binding ability of Zn-MOF than Co-MOF.

Halogen-modified metal-organic frameworks for efficient separation of alkane from natural gas.

As a rich green energy source, natural gas is widely used in many fields such as the chemical industry, automobile energy, and daily life. However, it is very challenging to separate and recover C2H6 and C3H8 from natural gas. Metal-organic frameworks (MOFs) as an emerging type of multi-pore porous materials show huge potential in gas adsorption separation. Herein, we report pillar-layered MOFs, Ni (BDC)(DABCO)0.5 (DMOF-X), modified by halogen atoms (F, Cl, Br), and investigate their CH4/C2H6/C3H8 separation performance. The experimental results show that DMOF-Cl exhibited a extremely high adsorption capacity for C3H8 and C2H6. Under the conditions of 298 K and 100 kPa, the adsorption capacities for C3H8 and C2H6 on DMOF-Cl are as high as 6.23 and 4.94 mmol g-1, which are superior to the values for most of the porous materials that have been reported. In addition, DMOF-Cl also shows high C3H8/CH4 (5: 85, V/V) and C2H6/CH4 (10: 85, V/V) separation selectivities, with values of 130.9 and 12.5, respectively. Finally, DMOF-Cl also demonstrated great potential as an adsorbent for separating C3H8/C2H6/CH4.

Reduced thermal expansion by surface-mounted nanoparticles in a pillared-layered metal-organic framework

Control of thermal expansion (TE) is important to improve material longevity in applications with repeated temperature changes or fluctuations. The TE behavior of metal-organic frameworks (MOFs) is increasingly well understood, while the impact of surface-mounted nanoparticles (NPs) on the TE properties of MOFs remains unexplored despite large promises of NP@MOF composites in catalysis and adsorbate diffusion control. Here we study the influence of surface-mounted platinum nanoparticles on the TE properties of Pt@MOF (Pt@Zn2(DP-bdc)2dabco; DP-bdc2-=2,5-dipropoxy-1,4-benzenedicarboxylate, dabco=1,4-diazabicyclo[2.2.2]octane). We show that TE is largely retained at low platinum loadings, while high loading results in significantly reduced TE at higher temperatures compared to the pure MOF. These findings support the chemical intuition that surface-mounted particles restrict deformation of the MOF support and suggest that composite materials exhibit superior TE properties thereby excluding thermal stress as limiting factor for their potential application in temperature swing processes or catalysis.

Synthesis, structure, and lithium storage performance of non-conductive metal–organic frameworks for high-performance lithium-ion batteries

Some metal–organic frameworks (MOFs) cannot be used as electrode materials for lithium-ion batteries because of their inferior intrinsic electrocatalytic activity and poor conductivity. Herein, the application of two nickel (II) cluster-based pillar-layered MOFs, Ni-mba-Na ([Ni8(mba)6(Cl)2Na(OH−)3]n, H2mba is 2-mercaptobenzoic acid) and Ni-mba-K ([Ni8(mba)6(Cl)2K(OH−)3]n), as electrode materials are reported. They differ from conductive MOFs because they are insulators with small specific surface areas (<10 m2g−1) and H2mba is an inexpensive chemical raw material. The conductivities of Ni-mba-Na and Ni-mba-K at 30 ℃ are 4.002 × 10−10 and >10−11 S cm−1, respectively. They exhibit excellent lithium storage performance, stability, and high inherent density (1.835 and 1.838 g cm−3) and specific capacity (1091.6, and 905.6 mAh/g at the first cycle). Design recommendations for these MOFs are provided based on their structure and performance differences. This paper provides a novel application of non-conductive MOFs in the energy storage field and strategy for design of high-performance electrode materials for lithium-ion batteries.

Enhancing Ethane/Ethylene Separation Performance in Two Dynamic MOFs by Regulating Temperature-Controlled Structural Interpenetration.

The separation of ethane from ethylene is an important but challenging process in the chemical industry because of their similar physicochemical properties. Generally, the adsorbents for C2H6/C2H4 separation require an appropriate and relatively small aperture. Herein, we report two dynamic pillar-layered metal-organic frameworks (MOFs) BUT-111 and BUT-112 with isomorphic frameworks but different degrees of interpenetration for efficient C2H4 purification. The dynamic behavior makes both the activated MOFs exhibit ultramicropores and reversed order adsorption behavior for C2H6 and C2H4, which could obtain highly purified C2H4 in one step from the C2H6/C2H4 mixture. BUT-111 and BUT-112 could work in a wide temperature range, and with the decrease in temperature, the C2H6/C2H4 selectivity would increase. Moreover, the degree of interpenetration could be well controlled by the synthetic temperature, and the increase in the interpenetration degree of BUT-112 enhanced the C2H4 purification effectively.

Pillar-Layered Metal-Organic Frameworks for Sensing Specific Amino Acid and Photocatalyzing Rhodamine B Degradation.

Metal-organic frameworks (MOFs) have presented potential for detection of specific species and catalytic application due to their diverse framework structures and functionalities. In this work, two novel pillar-layered MOFs [Cd6(DPA)2(NTB)4(H2O)4]n·n(DPA·5DMA·H2O) (1) and [Cu2(DPA)(OBA)2]n·n(2.5DMF·H2O) (2) [DPA = 2,5-di(pyridin-4-yl)aniline, H3NTB = 4,4',4''-nitrilotribenzoic acid, H2OBA = 4,4'-oxydibenzoic acid, DMA = N,N-dimethylacetamide, DMF = N,N-dimethylformamide] were successfully synthesized and structurally characterized. Both 1 and 2 have three-dimensional framework structures. The fluorescent property of 1 makes it possible for sensing specific amino acid such as L-glutamic acid (Glu) and L-aspartic acid (Asp). While MOF 2 was found to be suitable for photocatalytic degradation of Rhodamine B (RhB) in the presence of H2O2. The results imply that MOFs are versatile and metal centers are important in determining their properties.

Synergistic effect of metal node engineering and mixed-linker-architected on the energy storage activities of pillar-layered Cu2(L)2(DABCO) metal-organic frameworks

The most promising way to increase the properties of metal-organic frameworks (MOFs) to use in supercapacitor electrodes is rational design, and defects and high porosity are introduced via the use of bimetallic MOFs. In this work, we synthesized Cu-MOF and accommodated different ions in the structure to evaluate the effect of mixed metal and mixed linker in MOF structures. Pillar-layered metal-organic frameworks, M2(L)2(DABCO), M = Cu, Co, Ni, L = BDC (1,4-benzene dicarboxylic acid), NH2BDC (2-Aminoterephthalic acid), and DABCO = 1,4-diazabicyclo [2.2.2] octane, have been designed by accommodating ions and ligands in the structures and synthesizing in a facile manner. Various characteristic and electrochemical measurements were done to investigate our samples application's performance. According to the results, the best capacitance is for the mixed metal/ligand MOF, Cu–Co (NH2/50). Moreover, the asymmetric supercapacitor was set up using our MOF and activated carbon as the positive and negative electrodes, respectively. Our synthesized electrode performed maximum specific energy of 3.39 Wh/kg, maximum specific power of 750.0 W/kg, and capacity stabilization of 86% after 10000 cycles.

Facile synthesis of dptz-CuGeF6 at room temperature and its adsorption performance for separation of CO2, CH4 and N2

Efficient capture of CO2 from flue gas and removal of CO2 from biomethane by physical adsorption are in great need. Herein, we report the facile synthesis of a new pillared-layer metal-organic frameworks, dptz-CuGeF6 for CO2 separation from the flue gas or the biomethane. The resulting samples were characterized. Structurally, the dptz-CuGeF6 possess double-interpenetrated frameworks formed by two staggered, independent sql sheets, in which the cations Cu2+ are coordinated by four dptz ligands, making the dptz-CuGeF6 exhibit narrow and uniform ultra-micropores of 5.25 Å. Its CO2 capacity reached 2.17 mmol/g at 15 kPa and 3.23 mmol/g at 100 kPa separately, and its selectivity of CO2/CH4 (50:50) and CO2/N2 (15:85) reached as high as 80 and 175.5, respectively. The stability experiments demonstrated the intact structure of dptz-CuGeF6 was retained after exposure in moisture air (RH = 50% or RH = 80%) as well as in several polar solvents. Breakthrough experiments confirmed that CO2/CH4 or CO2/N2 binary mixture were efficiently separated. Molecule simulation revealed that both F···CCO2 and multiple C-H···OCO2 interactions in the pores of dptz-CuGeF6 played an important role in enhancing its selectivity of CO2 adsorption. The dptz-CuGeF6 would be promising for CO2 capture and separation from flue gas or biomethane.

Syntheses, structures and fluorescence properties of a Zn and a Cd(II) coordination polymer based on the mixed ligands

Two new compounds, [Zn(4-npa)(btmb)]n (1) and [Cd(4-npa)(btmb)0.5(H2O)2]n (2) (H24-npa = 4-nitrophthalic acid, btmb = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) have been achieved under hydrothermal conditions and structurally characterized by elemental analysis, IR spectroscopy and single-crystal x-ray diffraction. The compound 1 crystallizes in monoclinic crystal system, space group P21/c and is characterized by a two-dimensional layer structure containing 1 D Zn-carboxylate chains. Wherein the central Zn(II) ion is coordinated by two carboxylate O atoms and two N atoms to give a distorted tetrahedral [ZnO2N2] geometry. In compound 2, The hexa-coordinated Cd(II) ion forms a slightly distorted octahedral [CdNO5] geometry. The two Cd(II) centers are bridged by pair 4-npa dianions adopting bidentate-bridging mode to form a dinuclear unit. The dinuclear units are linked together by 4-npa dianions to form a Cd-carboxylate layer, and further extend by btmb molecules to form a 3 D pillared-layer metal–organic framework. The thermogravimetric analyses and luminescent properties of two compounds are also investigated.

Tetragonal multilayered ZnO/CuO composites derived from Zn- and Cu-containing metal-organic framework: Effect of calcination temperature on physicochemical properties and photocatalytic activity

Tetragonal multilayered ZnO/CuO composites prepared by the annealing of a Zn- and Cu-containing pillar-layered metal-organic framework were characterized by using instrumental techniques and investigated as catalysts for the degradation of 4-nitrophenol (4-NP) under irradiation with UV–vis light. The as synthesized samples contained p-n junctions, amorphous-crystalline heterojunctions, which benefitted light absorption and charge separation. The calcination temperature significantly influenced both the physicochemical properties and photocatalytic activities of these composites. The sample obtained at 400 °C (TL-ZC-400) exhibited the best photocatalytic performance, achieving a 4-NP degradation efficiency of 93.93% after 40 min of illumination. The TL-ZC-400 still showed high photodegradation ability (97.2%) after four times recycling. Furthermore, the recombination of ZnO and CuO adjusted the band gap structure of TL-ZC-400. Radical trapping experiments showed that the degradation of 4-NP was mainly mediated by hydroxyl radicals and holes. A possible photocatalytic mechanism was also proposed in this study.

Constructing [Co6(μ3-OH)6]-based pillar-layered MOF with open metal sites via steric-hindrance effect on ligand for CO2 adsorption and fixation

With excellent structural tunability and well framework stability, pillar-layered metal-organic frameworks (PL-MOFs) are promising candidates as sorbents and catalysts. Yet, the open metal sites (OMSs) in PL-MOFs are usually fully occupied by the pillar ligands, mostly limiting their involvement in CO2 adsorption and fixation. Herein, in consideration of the 12-connected [Co6(μ3-OH)6]-based PL-MOFs (Co6-MOF-3), a strategy based on steric-hindrance effect on pillar linker is proposed to create OMSs on their metal cluster nodes. The 4,4′-(9,10-anthracenediyl)bis-Pyridine (ABPY) that possessed anthracene groups was selected as the pillar linker, and a new [Co6(μ3-OH)6]-based PL-MOF (DZU-6) with accessible open Co(ii) sites was successfully synthesized. Single crystal structure of DZU-6 analysis reveals that ABPY ligands which were firstly linked to the metal clusters prevented the other ABPY ligands from coordinating with the nodes due to the steric-hindrance effect on ligands, resulting that four sites on [Co6(μ3-OH)6] were occupied by the terminal solvent molecules. The coordinated solvent molecules in DZU-6 could be removed easily, meanwhile the porosity was preserved (BET surface 2566 m2 g−1). Importantly, CO2 adsorption and catalytic cycloaddition conversion of DZU-6 were performed that the CO2 uptake improved 40% and the catalytic conversion yield increased over 50% compared with isostructural Co6-MOF-3 without OMSs.

Modulating Carbon Dioxide Storage by Facile Synthesis of Nanoporous Pillared-Layered Metal-Organic Framework with Different Synthetic Routes.

A Zn(II)-based paddle wheel pillared-layered metal-organic framework, [Zn2 (DBrTPA)2(DABCO)].(DMF)2 (MUT-4), containing 1,4-diazabicyclo[2.2.2]octane (DABCO) and 2,5-dibromoterephthalic acid (DBrTPA) has been successfully synthesized with different synthetic methods, including solvothermal, sonochemical, and their mixing methods, some of which are energy-efficient, rapid, and room-temperature synthetic procedures. Structural characterization of MUT-4 with single-crystal X-ray crystallography showed that it crystallizes in the tetragonal I41/acd space group. MUT-4 has shown higher performance than known MOFs in the CO2 adsorption such as UiO-66, UiO-66-NH2, UiO-66-NO2, PCN-66, ZIF-68, UiO-67, bio-MOF-11, MIL-101, MOF-177, ZIF-8, and ZIF-82. It has shown even better CO2 adsorption performance in comparison to the previously reported DMOFs such as DMOF-1 and other DMOF analogues such as NO2-DMOF-1, NH2-DMOF-1, Br-DMOF-1, and Azo-DMOF-1. Furthermore, it has performed even better than modified known MOFs. Also, the carbon dioxide storage capacity of MUT-4 obtained using several different synthetic routes shows a significant difference. Thus, this study exhibited that CO2 gas adsorption of MUT-4 could be modulated by optimizing its synthetic methods.