Highly stable Ni<sub>8</sub>-pyrazolate metal–organic frameworks for adsorption of methylene blue from water

Wu, Guoqiang; Wu, Kai; Wang, Ying; Luo, Jing‐Li; Zhou, Cong‐Ying; Lü, Weigang

doi:10.1039/d3nj03052k

Cited by 2 publications

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“…[Ni 8 (OH) 4 (H 2 O) 2 (bpe) 6 ]·nSolv ( 2 ·nSolv) is a new member of the isoreticular [Ni 8 (OH) 4 (H 2 O) 2 L 6 ] series with the first representative reported by Masciocchi et al and continued by others. − ,− The new MOF 2 ·nSolv crystallizes as expected in the cubic space group . The asymmetric unit contains one Ni(II) atom, a quarter of a bpe 2– molecule and a Ni-bridging μ 4 -OH – or μ 4 -H 2 O group treated as sharing O atoms of the respective ligands in a statistical occupation ratio of 2:1, leading to the formation of [Ni 8 (OH) 4 (H 2 O) 2 ] 12+ clusters as part of a highly symmetric {Ni 8 (OH) 4 (H 2 O) 2 (pz) 12 }-SBU (Figure a,b) of cubic symmetry.…”

Section: Resultsmentioning

confidence: 95%

“…In the cubic SBU {Ni 8 (OH) 4 (H 2 O) 2 (pz) 12 }, the Ni 2+ cations are located at the corners of a cube, Ni-bridging μ 4 -OH – or μ 4 -H 2 O groups above the center of the faces and 12 Ni-bridging pyrazolate groups on the edges (Figure c). Besides a high stability due to strong Ni–N coordination bonds, the cubic nature of this SBU makes it an ideal candidate for highly porous fcu structures offering many potential applications in several fields. − An isoreticular series of MOFs with formula [Ni 8 (μ 4 -X) 6 (μ 4 -L) 6 ] and such a cubic SBU connected by linear linkers was first presented by Masciocchi et al, expanded by Padial et al and studied further by Freund et al, Zhang et al and others. − In this series the cubic SBUs form (12)-connected 3D-networks with fcu topology, resulting in octahedral and tetrahedral pores.…”

Section: Introductionmentioning

confidence: 99%

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Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Jordan,

Müller,

Oestreich

et al. 2024

Crystal Growth & Design

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The reaction of the diprotonated linker precursor in the form of the salt [H 4 bpe 2+ ](TFA − ) 2 (H 2 bpe = 1,2-bis(1Hpyrazol-4-yl)ethyne; HTFA = trifluoroacetic acid) with Zn(NO 3 ) 2 • 4H 2 O in DMF at 75 °C for 9 days led to single crystals of the metal−organic framework (MOF) [Zn(bpe)]•1.8DMF (ortho-1• 1.8DMF) (HHUD-5). The compounds crystallize in the orthorhombic space group Fddd with rhombic channels, and is a polymorph of the previously reported structure of [Zn(bpe)]• 1.2DMF (tetra-1•1.2DMF) that crystallizes in the tetragonal space group P4 2 /mmc and features square channels as established from powder X-ray diffraction (PXRD) data. Microporous ortho-1 and tetra-1 demonstrate similar porosities with surface areas (pore volumes) of 2135 m 2 /g (0.77 cm 3 /g at p/p 0 = 0.95) and 1904 m 2 /g (0.73 cm 3 /g at p/p 0 = 0.95) when an optimized activation is employed (1380 m 2 /g was reported previously for tetra-1). Reaction of the boc-protected linker precursor Boc 2 bpe with Ni(OAc) 2 • 4H 2 O in DMF/water under reflux yielded the MOF [Ni 8 (OH) 4 (H 2 O) 2 (bpe) 6 ]•nSolv (2•nSolv, HHUD-6), which crystallized in the cubic space group Fm m 3 established from PXRD. Compound 2 is the newest member of the isoreticular series of [Ni 8 (OH) 4 (H 2 O) 2 L 6 ] (L = bis-pyrazolate or carboxylate-pyrazolate) and exhibits a surface area of 1415 m 2 /g and a pore volume of 0.78 cm 3 /g at p/p 0 = 0.80. The CO 2 uptake at 273 K and 1 bar was 3.99 mmol/g for ortho-1 and 5.84 mmol/g for 2; the CH 4 uptake was 1.11 mmol/g for ortho-1 and 1.64 mmol/g for 2, all in line with the higher heat of adsorption of the gases in 2, where open metal sites are possible after activation. Above 2 bar for CO 2 , and above 6 bar for CH 4 , the uptake in ortho-1 surpasses that in 2 due to the higher surface area of ortho-1. Both MOFs show high H 2 uptakes of 11.6 mmol/g for ortho-1 and 8.7 mmol/g for 2 at 77 K and 1 bar. Comparison to the CO 2 , CH 4 , and H 2 uptake in the analogous MOFs with the slightly longer 4,4′-(1,4phenylene)bis(pyrazolate) linker (having phenylene instead of acetylene spacer) suggests an advantage of the −C�C− triple bond.Vapor adsorption experiments with volatile organic compounds at 293 K for ortho-1 yielded uptakes of 8.2 mmol/g for benzene, 6.6 mmol/g for cyclohexane, and 5.7 mmol/g for n-hexane with type I isotherms. Compound 2 gave uptakes of 10.4 mmol/g for benzene, 10.7 mmol/g for cyclohexane, and 8.8 mmol/g for n-hexane with type II isotherms. Both MOFs are water stable as indicated by water vapor sorption and stability tests which also show a hydrophobicity of the bpe 2− linker.

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Section: Resultsmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Jordan,

Müller,

Oestreich

et al. 2024

Crystal Growth & Design

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“…Thus, it is crucial to solve the environmental pollution problems caused by these species [25][26][27]. In recent years, a number of scholars have utilized metal oxides with precise atomic structures as catalysts for photodegradation of organic dye wastewater [8,28,29]. On account of this, we investigated the photocatalytic degradation performance of compounds 2 and 4 as inhomogeneous reaction photocatalysts using methylene blue (MB) as a simulated pollutant.…”

Section: Photodegradation Performance Of Compounds 2 Andmentioning

confidence: 99%

Synthesis and Properties of Cobalt/Nickel-Iron-Antimony(III, V)-Oxo Tartrate Cluster-Based Compounds

Wen,

Wang,

Pan

et al. 2024

Molecules

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Two types of isostructural iron-cobalt/nickel-antimony-oxo tartrate cluster-based compounds, namely (H3O)(Me2NH2)[M(H2O)6]2[FeII2SbIII12(μ4-O)3(μ3-O)8(tta)6]·6H2O (M = Co (1); Ni (3)), H5/3[Co2.5FeII4/3FeIII3(H2O)13SbV1/3FeIII2/3(μ4-O)2(μ3-O)4SbIII6(μ3-O)2(tta)6]·2H2O (2) and H2[Ni2.25FeII1.5FeIII3(H2O)14SbV0.25FeIII0.75(μ4-O)2(μ3-O)4SbIII6(μ3-O)2(tta)6]·2H2O (4) (H4tta = tartaric acid) were synthesized via simple solvothermal reactions. All the clusters in the structures adopt sandwich configurations, that is, bilayer sandwich configuration in 1 and 3 and monolayer sandwich configuration in 2 and 4. Interestingly, the monolayer sandwiched compounds 2 and 4 represent rare examples of cluster-based compounds containing mixed-valence Sb(III, V), whose center of the intermediate layer is the co-occupied [FexSbV1−x]. This is different from that of previously reported sandwich-type antimony-oxo clusters in which the center position is either occupied by a transition metal ion or a Sb(V) alone. Thus, the discovery of title compounds 2 and 4 makes the evolution of center metal ion more complete, that is, from M, MxSbV1−x to SbV. All the title compounds were fully characterized, and the photocatalysis, proton conduction and magnetism of compounds 2 and 4 were studied.

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Highly stable Ni₈-pyrazolate metal–organic frameworks for adsorption of methylene blue from water

Abstract: Three Ni8-pyrazolate metal-organic frameworks, namely Ni8-NiL1, Ni8-CuL1 and Ni8-CuL2, were prepared by using metallosalen-based ligands (NiL1, CuL1, CuL2). The octanuclear cubic clusters [Ni8(OH)4(H2O)2] render these materials with sufficient robustness, enabling...

Cited by 2 publications

References 54 publications

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Synthesis and Properties of Cobalt/Nickel-Iron-Antimony(III, V)-Oxo Tartrate Cluster-Based Compounds

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Highly stable Ni8-pyrazolate metal–organic frameworks for adsorption of methylene blue from water

Abstract: Three Ni8-pyrazolate metal-organic frameworks, namely Ni8-NiL1, Ni8-CuL1 and Ni8-CuL2, were prepared by using metallosalen-based ligands (NiL1, CuL1, CuL2). The octanuclear cubic clusters [Ni8(OH)4(H2O)2] render these materials with sufficient robustness, enabling...

Cited by 2 publications

References 54 publications

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Metal–Organic Azolate Frameworks with an Acetylene-bis-pyrazolate Linker: Assessing the Role of the Triple-Bond Spacer in Gas and Vapor Sorption

Synthesis and Properties of Cobalt/Nickel-Iron-Antimony(III, V)-Oxo Tartrate Cluster-Based Compounds

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Highly stable Ni₈-pyrazolate metal–organic frameworks for adsorption of methylene blue from water