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•Sulfonyl and amid containing dual functionalized MOF were synthesized via the solvothermal method.•The removal efficiency of the framework towards heavy metal ions such as Cd(II), ...Cu(II) and Cr(II) was studied.•The adsorption isotherms show the first isotherm plateau and adsorption capacity of about 526 mg/g is observed for Cd2+.•Recovered adsorbents after water treatment used to fabricate MOF derived porous metal/carbon materials.
Designing porous and functionalized adsorbents and achieving high efficiency in heavy metals removal from wastewater is in the spotlight of environmental science. On the other hand, upon removal, adsorbents are still highly hazardous requiring that great care be taken in its packaging, transporting and storing. A fundamental route in the synthesis of functional extended structures is the ability to combine different chemical entities in a controlled way in order to achieve high performance. Herein, we report the systematic design of dual-functionalized metal organic framework (TMU-81) by incorporating sulfonyl and amide groups for the removal of Cd(II), Cu(II) and Cr(II) ions from simulated aqueous solutions. TMU-81 showed significant enhancement in heavy metals uptake suggesting that the strong host − guest interactions between cations and the donor sites play a major role in adsorption process. The maximum adsorption capacity for Cd2+ was 526 mg/g which is among the highest values reported for similar MOFs and other porous materials. The good performance in uptake and selectivity of TMU-81 can be attributed to the network structure that shaping the void, create mono-dimensional channels, decorated by exposed oxygen atom sites selective for Cadmium ion. Environmental “compatibility” of a treated MOFs was studied in order to evaluate its possible recycling as a new template for different applications by using pyrolysis method. Engineering of the pore surface provides a potential for MOF with a hybrid interface to act as a versatile tool for the design of multifunctional nanoparticles to meet specific application requirements.
These are just examples of counter ions; solvent is also usually present.
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•Synthesis and applications of Ionic MOFs are reviewed.•Most focus is on ion exchange of ionic MOFs.•Several ...factors are influenced in Ionic-MOFs performance.
A review of the synthesis, structure and specifically the effect of counter-ions on the properties of ionic metal organic frameworks (ionic-MOFs) is presented, highlighting the important advances in this regard over the past decade. Most focus is on ionic porous metal–organic frameworks (MOFs) materials consisting of porous anionic or cationic frameworks and cationic or anionic guests. The structure and performance of cationic and anionic MOFs are influenced by several factors, such as organic ligands, metal ions and charge-balancing anions. These types of anionic and cationic materials have distinct advantages in comparison with neutral MOFs in the design of functional materials and their synthesis affords several distinct advantages over that for routine neutral frameworks by virtue of the isolated charged species in confined nano-spaces. The nanosized and charged pores in these ionic structures generate a strong interaction between the host and guest molecules, including enhanced adsorption towards small gases and solvent molecules. Ionic-MOFs can be easily modified via ion exchange and accommodate other charged guest molecules, making them an ideal platform for different applications, such as functional materials. The development of synthesis methods by ion exchange and the potential applications of such cationic or anionic structures have been discussed thoroughly in this review.
Metal-organic frameworks (MOFs) are crystalline solids formed by inorganic clusters or metal ions (generally transition metal) linked by bi- or multifunctional organic ligands. Exploiting the ...advantages of the MOFs including large surface area, high metal content, and flexibility in designing the active sites, would be an innovative idea to make novel catalysts. This review gives a useful overview on the catalytic applications of MOFs regarding their structural developments toward catalyst fabrication. The catalytic applications cited in this review include the condensation of organic reaction of two or more components involved in a verity of reactions. More specifically, the review has explored the catalytic applications of MOFs in C-C and C-X (S, N, O) bond formation reactions leading to the formation of a more complicated compounds. The emphasis has been made on discussing the stability of the MOFs, their reusability and in providing a comparison of the performance of MOFs with respect to other homogeneous and heterogeneous catalysts.
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•Heterogeneous catalytic behavior of MOFs has been reviewed.•MOFs can be manipulated by post modification methods to raises their actions.•MOFs are found to be powerful catalyzing agent to form C-C bonds.
Ferrocene and its derivatives, especially ferrocene‐based coordination polymers (Fc‐CPs), offer the benefits of high thermal stability, two stable redox states, fast electron transfer, and excellent ...charge/discharge efficiency, thus holding great promise for electrochemical applications. Herein, we describe the synthesis and electrochemical applications of Fc‐CPs and reveal how the incorporation of ferrocene units into coordination polymers containing other metals results in unprecedented properties. Moreover, we discuss the usage of Fc‐CPs in supercapacitors, batteries, and sensors as well as further applications of these polymers, for example in electrocatalysts, water purification systems, adsorption/storage systems.
Iron strength: The incorporation of ferrocene as an organometallic building block into coordination polymers containing other metals to impart certain properties can afford attractive structures denoted as ferrocene‐based coordination polymers. This Review focuses on the synthesis and electrochemical applications (e. g., supercapacitors, batteries, electrosensors, and electrocatalysts) of these coordination polymers.
Here, we applied a novel and simple strategy for high capacity heavy metal ion removal from aqueous solution by modification of urea decorated TMU-32 framework through in-situ synthesis of ...Fe3O4@TMU-32 composite with aim of controlling the surface-charge of the composite adsorbent toward Hg(II) and Pb(II) ions.
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•High capacity heavy metal ion removal by Surface-charge modulation and mult-functionalization strategies.•Fe3O4@TMU-32 hybrid nanomaterials synthesized through encapsulation of Fe3O4 nanoparticles by TMU-32 framework.•Record-breaking rates in removal of Hg(II) (905 mg.g-1) and especially Pb(II) (1600 mg.g-1) ions.•Mechanism evaluation by zeta potential and FT-IR analyses to show the critical roles of surface charge and functionality.
Water pollution by heavy metal ions especially Hg(II) and Pb(II) is one of the most important concerns because of their harmful effects on human health and environment sustainability. Here, we developed Fe3O4@TMU-32 metal-organic framework (MOF)-based nanocomposite by applying pore functionalization and surface-charge modulation strategies. Based on synergic effects of these strategies, Fe3O4@TMU-32 nanocomposite shows very high capacity toward Hg(II) and Pb(II) metal ions. TMU-32 (with formula Zn(OBA)(DPU)·2DMF·H2O where H2OBA and DPU are (4,4′-oxybis(benzoic acid)) and 1,3-di(pyridin-4-yl)urea)) is decorated with urea functional groups containing carbonyl and amine groups that can interact with metal ions. As results, TMU-32 show very high capacity toward Hg(II) and Pb(II) ions. To improve the TMU-32 capacity toward Hg(II) and Pb(II) cations, we tried to modulate the surface-charge of TMU-32 as a host-framework. Surface-charge modulation strategy had been conducted through encapsulation of Fe3O4 nanoparticles by TMU-32 in an in-situ synthesis procedure and synthesis of Fe3O4@TMU-32 nanocomposite. Fe3O4@TMU-32 nanocomposite shows improved removal capacity (45 % and 54 % toward Pb(II) and Hg(II)) rather pristine TMU-32 framework because of urea decorated framework and charge modulated surface. Fe3O4@TMU-32 nanocomposite adsorb 1600 mg.g-1 of Pb(II) and 905 mg.g-1 of Hg(II) which extremely rare in the literature. Such improvement can be related to the electrostatic interaction between cationic nature of Pb(II) and Hg(II) and negative charge of the Fe3O4@TMU-32 adsorbent.
► This review shows the variety coordination modes of carboxylate groups increase the strength and stability of the resulting architectures. ► It was found that carboxylate groups in many of lead(II) ...coordination polymers form more than one type coordination mode. ► And among all of these modes maximum number is belonged to chelating (η
2) mode.
In recent years, the chemistry of metal-coordination polymers has been advanced due to their diverse topologies and potential applications in smart optoelectronic, magnetic, microporous and biomimetic materials with specific structures, properties, and reactivities. Metal carboxylates have emerged as a large family of open framework materials. Recently, metal carboxylate chemistry has enhanced because of the increasing importance of hybrid inorganic–organic compounds with potential applications in separation, catalysis, and gas storage. So far, research on coordination polymers has considerably been concentrated on incorporation of s-, d-, and even f-block metal ions as coordination centers. As a heavy p-block metal ion, lead(II), with its large radius, flexible coordination environment, and variable stereo-chemical activity, is suitable for formation of unusual network topologies with interesting properties. This review provides an overview of all lead(II) carboxylate supramolecular compounds reported since 1990 and an investigation of their coordination modes, properties and structures. The variety of coordination modes of carboxylate groups increase the strength and stability of the resulting architectures. These modes include (η
1), (μ
2-η
1:η
1), (η
2), (μ
2-η
2), (μ
3-η
1:η
2), (μ
3-η
1:η
2), (μ
2-η
2:η
1), (μ
3-η
1:η
2:η
1) and (μ
4-η
2:η
2) that have created multiplicity polymeric structures with different dimensions. In this study it was found that carboxylate groups in many of lead(II) coordination polymers form more than a single type of coordination mode and among all of these modes maximum number belonged to chelating (η
2) mode.
Schizophrenia is a severe mental disorder characterized by impaired perception, delusions, thought disorder, abnormal emotion regulation, altered motor function, and impaired drive. The default mode ...network （DMN）, since it was first proposed in 2001, has become a central research theme in neuropsychiatric disorders, including schizophrenia. In this review, first we define the DMN and describe its functional activity, functional and anatomical connectivity, heritability, and inverse correlation with the task positive network. Second, we review empirical studies of the anatomical and functional DMN, and anti-correlation between DMN and the task positive network in schizophrenia. Finally, we review preliminary evidence about the relationship between antipsychotic medications and regulation of the DMN, review the role of DMN as a treatment biomarker for this disease, and consider the DMN effects of individualized therapies for schizophrenia.
As redox‐active based supercapacitors are known as highly desirable next‐generation supercapacitor electrodes, the targeted design of two ferrocene‐functionalized (Fc(COOH)2) clusters based on ...coinage metals, (PPh3)2AgO2CFcCO2Ag(PPh3)22⋅7 CH3OH (SC1: super capacitor) and (PPh3)3CuO2CFcCO2Cu(PPh3)3⋅3 CH3OH (SC2), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g−1 and 210 F g−1 specific capacitance at 1.5 A g−1 in Na2SO4 electrolyte, respectively. The obtained results show that the presence of CuI instead of AgI improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC2 ((PPh3)2CuO2CFcCO2∞), a polymeric structure of SC2, was synthesized and used as an energy storage electrode. PSC2 displays high conductivity and gives 455 F g−1 capacitance at 3 A g−1. The PSC2 as a supercapacitor electrode presents a high power density (2416 W kg−1), high energy density (161 Wh kg−1), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high‐performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials.
Conductive coordination polymers: Because redox‐active based supercapacitors are known as highly desirable next‐generation supercapacitor electrodes, the targeted design of two ferrocene‐functionalized (Fc(COOH)2) clusters based on coinage metals, (PPh3)2AgO2CFcCO2Ag(PPh3)22⋅7 CH3OH (SC1: super capacitor) and (PPh3)3CuO2CFcCO2Cu(PPh3)3⋅3 CH3OH (SC2), is reported.
Traditional wound dressings mainly participate in the passive healing processes and are rarely engaged in active wound healing by stimulating skin cell behaviors. Electrical stimulation (ES) has been ...known to regulate skin cell behaviors. Herein, a series of multifunctional hydrogels based on regenerated bacterial cellulose (rBC) and MXene (Ti3C2Tx) are first developed that can electrically modulate cell behaviors for active skin wound healing under external ES. The composite hydrogel with 2 wt% MXene (rBC/MXene‐2%) exhibits the highest electrical conductivity and the best biocompatibility. Meanwhile, the rBC/MXene‐2% hydrogel presents desired mechanical properties, favorable flexibility, good biodegradability, and high water‐uptake capacity. An in vivo study using a rat full‐thickness defect model reveals that this rBC/MXene hydrogel exhibits a better therapeutic effect than the commercial Tegaderm film. More importantly, in vitro and in vivo data demonstrate that coupling with ES, the hydrogel can significantly enhance the proliferation activity of NIH3T3 cells and accelerate the wound healing process, as compared to non‐ES controls. This study suggests that the biodegradable and electroactive rBC/MXene hydrogel is an appealing candidate as a wound dressing for skin wound healing, while also providing an effective synergistic therapeutic strategy for accelerating wound repair process through coupling ES with the hydrogel dressing.
In this work, a kind of novel multifunctional rBC/MXene composite hydrogel is first constructed by physical and chemical dual crosslinking. This electroactive hydrogel is an appealing candidate as a wound dressing for skin wound healing, while also realizing a local delivery of electrical stimulation at the wound site to electrically regulate skin cell behaviors for accelerating the wound healing process.
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