Inorganic Organic Hybrid Framework Research Articles

Cyclotriphosphazene (P3N3) derived FeOx@SPNO-C core–shell nanospheres as peroxymonosulfate activator for degradation via non-radical pathway

Though synergistic interactions between quaternary heteroatom (S, N, P, O) and FexO atoms could significantly improve catalytic performance, however, developing a robust catalyst with quaternary heteroatom-doped carbons and FexO is rarely addressed. We fabricated FeOx@SPNO-C core–shell nanospheres by using cyclotriphosphazene (P3N3)-derived covalent organic–inorganic hybrid frameworks (COIFs) and Fe3O4. The as-synthesized FeOx@SPNO-C nanospheres catalyst attained superior PMS activation for degradation of sulfamethoxazole (SMX), achieving 99.5 % removal efficiency in 18 min, 65.1 % mineralization rate, lower iron leaching (0.014 mg/L), and reaction rate constant was 73.6 % higher than sole SPNO-C, counterpart. Non-radical 1O2 generation was the dominant pathway for SMX degradation, which was confirmed by electron paramagnetic resonance (EPR), radical quenching inorganic ions addition experiments, and density functional theory (DFT) calculations. Structural defects, C = O, C = C–C groups, and N/Fe-Nx sites atoms have been revealed to be active sites. The improved degradation of SMX may be attributed to many essential characteristics. Firstly, there is a synergistic impact between FexO and SPNO-C. Additionally, the carbon charge density is high, and there are numerous structural defects present. Furthermore, there is a significant presence of C = O groups, with a higher proportion of sp2 carbon containing sufficient free-flowing π electrons. Lastly, the presence of N/Fe-Nx sites also contributes to the enhanced degradation of SMX. Several intermediate products were found, and a potential degradation mechanism was postulated. The high performance of FeOx@SPNO-C under harsh experimental conditions makes it a potential candidate for the commercial-scale Fenton-like catalyst.

Improved thermoelectric power factor of multilayered poly(3,4-ethylenedioxythiophene) polystyrene sulfonate and Cu2Se thin films

Cu2Se is a promising thermoelectric material due to its superionic behavior with superior transport properties. Here we report a facile method of spin coating for the fabrication of multilayers of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and Cu2Se thermoelectric materials for mid-temperature range applications. The synthesis of multilayered thin films with a unique organic-inorganic hybrid framework could be used in flexible thermoelectric devices. The detailed investigation of PEDOT:PSS and Cu2Se multilayered thin films reveals interaction between organic and inorganic material as inferred by AFM and FTIR. The electronic transport properties were investigated for all specimens, with the highest PF of 20.1 µW/m. K2 at 450 K was achieved from the bilayer stacking of Cu2Se and PEDOT:PSS, which is about 82 % higher as compared to that of pure PEDOT:PSS at the same temperature. These improved transport properties are the combined effect of energy filtering and interface effects. The proposed strategy opens up an avenue for research on chalcogenide based composite materials with an organic framework for flexible thermoelectric device applications.

A bifunctional 3D inorganic–organic hybrid framework constructed by [β-Mo8O26]n4n- chains and [Cu(dap)2]2+ cations for efficient electrochemical sensing and photocatalytic reduction of Cr(VI)

Under hydrothermal conditions, a new 3D inorganic–organic hybrid polyoxometalate(POM), {[Cu(dap)2]2[β-Mo8O26]}·H2O (1, dap = 1,2-diaminopropane) was synthesized and characterized. Structural analysis displays that 1 represents an interesting 3D POM-based framework constructed from the 1D infinite inorganic chains [β-Mo8O26]n4n- and [Cu(dap)2]2+ cations. 1 exhibits good electrochemical performance and acts as electrochemical sensor for the detection of Cr(VI) with low limit of detection (LOD) of 0.291 µM, high sensitivity of 0.483 μA μM−1 and good anti-interference. The LOD of Cr(VI) for 1 is lower than the maximum content of Cr(VI) in groundwater required by the World Health Organization (WHO). Interestingly, 1 also displays excellent photocatalytic activity for Cr(VI) reduction. The reduction rate of Cr(VI) by 1 can reach 96% within 80 min under the original pH condition. Furthermore, the photocatalytic process obeys the pseudo-first-order reaction kinetic with the half-life of 16.35 min.

An Inorganic-Organic Hybrid Framework Composed of Polyoxotungstate and Long-Chained Bolaamphiphile.

Surfactants are functional molecules utilized in various situations. The self-assembling property of surfactants enables several molecular arrangements that can be employed to build up nanometer-sized architectures. This is beneficial in the construction of functional inorganic-organic hybrids holding the merits of both inorganic and organic components. Among several surfactants, bolaamphiphile surfactants with two hydrophilic heads are effective, as they have multiple connecting or coordinating sites in one molecule. Here, a functional polyoxotungstate inorganic anion was successfully hybridized with a bolaamphiphile to form single crystals with anisotropic one-dimensional alignment of polyoxotungstate. Keggin-type metatungstate ([H2W12O40]6-, H2W12) was employed as an inorganic anion, and 1,12-dodecamethylenediammonium (C12N2) derived from 1,12-dodecanediamine was combined as an organic counterpart. A simple and general ion-exchange reaction provided a hybrid crystal consisting of H2W12 and C12N2 (C12N2-H2W12). Single crystal X-ray structure analyses revealed a characteristic honeycomb structure in the C12N2-H2W12 hybrid crystal, which is possibly effective for the emergence of conductivity due to the dissociative protons of C12N2.

Mechanical Properties of a New Hybrid Inorganic–Organic Framework: A Nanoindentation, High-Pressure X-ray Diffraction, and Computational Study

Mechanical Properties of a New Hybrid Inorganic–Organic Framework: A Nanoindentation, High-Pressure X-ray Diffraction, and Computational Study

Reticular chemistry for the rational design of mechanically robust mesoporous merged-net metal-organic frameworks

Reticular chemistry for the rational design of mechanically robust mesoporous merged-net metal-organic frameworks

Organoamine Templated Multifunctional Hybrid Metal Phosphonate Frameworks: Promising Candidates for Tailoring Electrochemical Behaviors and Size-Selective Efficient Heterogeneous Lewis Acid Catalysis.

The successful discovery of novel multifunctional metal phosphonate framework materials that incorporate newer organoamines and their utilization as a potential electroactive material for energy storage applications (supercapacitors) and as efficient heterogeneous catalysts are the most enduring challenges at present. From this perspective, herein, four new inorganic-organic hybrid zinc organodiphosphonate materials, namely, [C5H14N2]2[Zn6(hedp)4] (I), [C5H14N2]0.5[Zn3(Hhedp) (hedp)]·2H2O (II), [C6H16N2][Zn3(hedp)2] (III), and [C10H24N4][Zn6(Hhedp)2(hedp)2] (IV) (H4hedp = 1-hydroxyethane 1,1-diphosphonic acid), have been synthesized through the introduction of different organoamines and then structurally analyzed using various techniques. The compounds (I-IV) possess a three-dimensional network through alternate connectivity of zinc ions and diphosphonate ligands, as confirmed using single-crystal X-ray diffraction. The investigations of electrochemical charge storage behaviors of the present compounds indicate that compound III exhibits a high specific capacitance of 190 F g-1 (76 C g-1) at 1 A g-1, while compound II shows an excellent cycling stability of 90.11% even after 5000 cycles at 5 A g-1 in the 6 M KOH solution. Further, the present materials have also been utilized as active heterogeneous Lewis acid catalysts in the ketalization reaction. The screening of various substrate scopes during the catalytic process confirms the size-selective heterogeneous catalytic nature of the framework compounds. To our utmost knowledge, such a size-selective heterogeneous Lewis acid catalytic behavior has been observed for the first time in the amine templated inorganic-organic hybrid framework family. Moreover, the excellent size-selective catalytic efficiencies with the d10 metal system and recyclability performances make the compounds (I-IV) more efficient and promising Lewis acid heterogeneous catalysts.

Prediction of Large Second Harmonic Generation in the Metal-Oxide/Organic Hybrid Compound CuMoO3(p2c)

Noncentrosymmetric hybrid framework (HF) materials are an important system in discovering new practical second-order nonlinear optical materials. We calculated the second harmonic generation (SHG) response of a noncentrosymmetric (NCS) organic–inorganic HF compound, CuMoO3(p2c) (p2c = pyrazine-2-carboxylate) to find that it exhibits the largest SHG response among all known NCS HF materials with one-dimensional helical chains. Further atom response theory analysis revealed that the metal atoms Cu and Mo contribute much more strongly than do nonmetal atoms in determining the strength of the SHG response, which is a novel example in nonlinear optical materials known to date.

Magnetic interactions controlled by light in the family of Fe(II)-M(IV) (M = Mo, W, Nb) hybrid organic-inorganic frameworks.

Three new hybrid organic-inorganic frameworks employing octacyanidometallates and 4,4'-bypiridine dioxide (4,4'-bpdo) as bridging molecules were prepared and characterized. The three-dimensional coordination frameworks {[FeII(μ-4,4'-bpdo)(H2O)2]2[MIV(CN)8]·9H2O}n (Fe2Mo, Fe2W and Fe2Nb; M = Mo, W and Nb) are composed of cyanido-bridged chains, which are interconnected by the organic linkers. Magnetic measurements for Fe2Nb show a two-step transition to the antiferromagnetic state, which results from the cooperation of antiferromagnetic intra- and inter-chain interactions. Fe2Mo and Fe2W, on the other hand, behave as paramagnets at 2 K because of the diamagnetic character of the corresponding octacyanidometallate(IV) building units. However, after 450 nm light irradiation they show transition to the metastable high spin MoIV or WIV states, respectively, with distinct ferromagnetic intrachain spin interactions, as opposed to the antiferromagnetic ones observed in the Fe2Nb framework.

Porous Layered Inorganic–Organic Hybrid Frameworks Constructed from Polyoxovanadate and Bolaamphiphiles

Porous Layered Inorganic–Organic Hybrid Frameworks Constructed from Polyoxovanadate and Bolaamphiphiles

Syntheses, Crystal Structure, Theoretical Calculation and Photophysical Properties of one Inorganic–Organic Hybrid Frameworks Based on Mixed Ligands

Syntheses, Crystal Structure, Theoretical Calculation and Photophysical Properties of one Inorganic–Organic Hybrid Frameworks Based on Mixed Ligands

Halide-modulated self-assembly of metal-free perovskite single crystals for bio-friendly X-ray detection

Halide-modulated self-assembly of metal-free perovskite single crystals for bio-friendly X-ray detection

Transition metal nitroprussides: Crystal and electronic structure, and related properties

The nitroprusside ion forms 3D, 2D, 1D, 0D and Ionic solids with monovalent and divalent transition metals, which show interesting physical properties among them, spin crossover behavior and ability for the separation and storage of small molecules. • Coordination chemistry of transition metal nitroprussides. • Electronic structure of transition metal nitroprussides. • Structural diversity of transition metal nitroprussides. • Functional properties of transition metal nitroprussides. • Thermal and environmental stability of transition metal nitroprussides. This review summarizes the state of the art on the structural features, thermal and environmental stability, physical properties and potential applications of transition metal nitroprussides, for their 3D, 2D, 1D and 0D structures. The nitroprusside ion, [Fe(CN) 5 NO] 2− , forms insoluble solids with monovalent and divalent transition metals. The crystal structure for the coordination polymers obtained with divalent metals shows a marked dependence on the used preparative route, metal nature and hydration degree, which was the origin of many incongruities in studies published a few decades ago. Nowadays, the structural features and related properties for the immense majority of the solids formed with such metal ions are known and discussed in this review. The preparation of transition metal nitroprussides using co-ligands with different coordination capability to modulate the dimensionality and related properties of the resulting solids has been on the spotlight of research during the last few years, particularly those related to atypical magnetic behavior. This subject is also herein summarized, revealing the large diversity of hybrid inorganic–organic frameworks that can be obtained with some of their physical properties only recently revealed, among them, the thermal-induced spin transition in ferrous nitroprussides containing monodentate and bridging organic ligands acting as pillar or pseudo-pillars in 2D and 3D hybrid materials. This contribution also includes a general overview of the use of spectroscopic tools such as XPS, XAS, Mössbauer, UV–vis-NIR, IR and Raman, to access electronic and structural characteristics of this family of materials. We also carried out a critical analysis of those research areas that, in our opinion, require further studies, representing opportunities to make important scientific contributions on new knowledge on this family of materials. This is the first general review on transition metal nitroprussides.

A series of porous 3D inorganic–organic hybrid framework crystalline materials based on 5-aminoisophthalic acid for photocatalytic degradation of crystal violet

Seven 3D metal-organic frameworks have been designed and synthesized by the hydrothermal synthetic method based on the ligand 5-aminoisophthalic acid. Complexes 1-4 have better photocatalytic degradation properties for dyes CV.

Three Inorganic-Organic Hybrid Gallo-/Alumino-Borates with Porous-Layered Structures Containing [MB4O10(OH)] (M = Al/Ga) Cluster Units.

Three inorganic-organic hybrid gallo-/alumino-borates [Ga2B7O14(OH)]·H2dah (1, dah = 1,6-diaminohexane), K2[Ga2B7O14(OH)(en)0.5] (2, en = ethylenediamine), and K2[Al2B7O14(OH)(en)0.5]·H2O (3) were synthesized under solvothermal conditions. Compound 1 features a 3D porous-layered structure built by the alternation of [GaB4O10(OH)]6-, [B3O6]3- clusters and GaO4 tetrahedra, in which the novel [GaB4O10(OH)]6- cluster is first observed. Compounds 2 and 3 are isostructural and made by [MB4O10(OH)]6-, [B3O6(en)0.5]3- clusters and MO4 tetrahedra (M = Ga/Al); their 3D porous layers are similar to those of 1 and further bridged by en linkers through the rare B-N-C covalent bonds, resulting in the 3D inorganic-organic hybrid framework. This is the first main-group metal borate with organic molecules participating in the oxoboron frameworks through B-N bonds. Optical diffuse-reflectance spectra reveal that 1, 2, and 3 are potential wide-band-gap semiconductors.

Surfactant-Assisted Mesostructural Variation by the Molecular Structure of Frameworks.

Typical syntheses for the mesostructural design were performed with strategic deviations, being substantially powerful for changing the molecular structure of frameworks, from the synthetic conditions optimized for the preparation of lamellar and 2-d hexagonal mesostructured materials where the frameworks were constructed by aluminophosphate (AlPO) like units with and without organic groups in the molecular scale. A series of the materials such as mesostructured aluminum organophosphonate (AOP) and AlPO type ones were investigated according to the molecular structure and crystallinity of inorganic-organic hybrid and non-hybrid inorganic frameworks. Considering a uniqueness of AlPO based frameworks, a rational insight on strength of interactions between crystalline/amorphous AlPO based units and cationic surfactant molecules was surveyed as one of the most significant factors for understanding the mesostructural variation.

Cucurbit[7]uril-Mediated 2D Single-Layer Hybrid Frameworks Assembled by Tetraphenylethene and Polyoxometalate toward Modulation of the α-Chymotrypsin Activity.

Construction of large-scale single-layer two-dimensional (2D) frameworks in water is significant due to their utilities in various fields. Utilizing macrocycle-mediated supramolecular self-assembly represents a promising approach; however, challenges still remain in their practical preparation. Here, we exploited a two-step supramolecular strategy to build 2D organic-inorganic hybrid frameworks at a micrometer scale in water. Taking advantage of the high binding affinity to cucurbit[7]uril (CB[7]), mono-quaternary ammonium tetraphenylethene (MQATPE) derivatives were first included with CB[7] to form a 1:1 complex (MQATPE@CB[7]). Then, just mixing the complex with anionic polyoxometalate Na9[EuW10O36]·32H2O (denoted as Eu-POM) in a 3:1 molar ratio leads to the formation of single-layer 2D films with tens of micrometers via electrostatic and π-π stacking interactions. The most unique feature of this strategy is that the steric effect imposed by CB[7] would not only lead the modules to adopt a periodic hexagonal assembly but also forbid stacking between layers through comparison with the merely multilayered 2D nanosheets self-assembled by MQATPE/Eu-POM. Interestingly, the charge interactions between MQATPE and Eu-POM would lead to the aggregation-induced emission (AIE) fluorescence of MQATPE, and white light emission could be obtained through the simple regulation of the contents of Eu-POM and MQATPE. Furthermore, due to the high surface areas and more accessible active sites, the single-layer films can act as an effective enzyme inhibitor to modulate the activity of α-chymotrypsin (ChT). These findings suggest a simple but universal approach for single-layer hybrid materials, which may hold promise for practical applications in photophysical and biomedical fields.

Effective accommodation and conversion of polysulfides using organic-inorganic hybrid frameworks for long-life lithium-sulfur batteries.

Lithium-sulfur (Li-S) batteries are one of the most promising candidates for meeting the emerging market demands for energy storage, and have the advantages including high energy density and low cost. However, the practical application of Li-S batteries is hindered by the lithium polysulfide (LiPS) shuttle, which induces low sulfur utilization and unsatisfactory capacity retention. To address this problem, recent studies have focused on improving the transformation of LiPS into insoluble Li2S2/Li2S through methods beyond physical or chemical adsorption. Nevertheless, the commonly used host materials have limited ability to simultaneously trap and propel redox transfer of LiPS. Herein, the bottom-up construction of new organic-inorganic hybrid frameworks for sulfur cathodes is proposed to fundamentally restrict LiPS dissolution and enhance their electrochemical transformation. The synergistic integration of organic cellulose networks and inorganic ZIF-derivatives caused highly efficient LiPS mediators to suppress the shuttle effect and retain electrode stability. The resulting RCE-Co3O4@G-S cathode materials delivered a stable capacity of 726.5 mA h g-1 at 0.2 C after 350 cycles, with a very low fading rate of 0.026% per cycle and a high coulombic efficiency of 98.9%.

Amorphous covalent inorganic–organic hybrid frameworks (CIOFs) with an aggregation induced selective response to UV–Visible light and their DFT studies

Covalent inorganic–organic hybrid frameworks have been rationally designed and systematically investigated for aggregation-induced selective light response based on inorganic heterocycle cyclotriphosphazene.

Cyclotriphosphazene (P3N3) hybrid framework for aggregation induced photocatalytic hydrogen evolution and degradation of rhodamine B

Cyclotriphosphazene (P3N3) derived covalent inorganic–organic hybrid framework (CIOF) with highly crosslinked aggregation is developed, and their optical properties are realized for photocatalytic hydrogen evolution and degradation of rhodamine B.