Highlights in Interface of Wastewater Treatment by Utilizing Metal Organic Frameworks: Purification and Adsorption Kinetics.

Polluted water has become a concern for the scientific community as it causes many severe threats to living beings. Detection or removal of contaminants present in wastewater and attaining purity of water that can be used for various purposes are a primary responsibility. Different treatment methods have already been used for the purification of sewage. There is a need for low-cost, highly selective, and reusable materials that can efficiently remove pollutants or purify contaminated water. In this regard, MOFs have shown significant potential for applications such as supercapacitors, drug delivery, gas storage, pollutant adsorption, etc. The outstanding structural diversity, substantial surface areas, and adjustable pore sizes of MOFs make them superior candidates for wastewater treatment. This Review provides an overview of the interaction science and engineering (kinetic and thermodynamic aspects with interactions) underpinning MOFs for water purification. First, fundamental strategies for the synthesis methods of MOFs, different categories, and their applicability in wastewater treatment are summarized, followed by a detailed explanation of various interaction mechanisms. Finally, current challenges and future outlooks for research on MOF materials toward the adsorption of hazardous components are discussed. A new avenue for modifying their structural characteristics for the adsorption and separation of hazardous materials, which will undoubtedly direct future work, is also summarized.

Cu-Metal Organic Framework Derived Multilevel Hierarchy (Cu/CuxO@NC) as a Bifunctional Electrode for High-Performance Supercapacitors and Oxygen Evolution Reaction.

The development of a MOFs-derived multilevel hierarchy in a single step still remains a challenging task. Herein, we have synthesized novel Cu-MOF via a slow diffusion method at ambient temperature and further utilized it as a precursor source for MOF-derived multilevel hierarchy (Cu/CuxO@NC, x = 1 and 2). This studies suggest that the organic ligands served as a source of an N-doped carbon matrix encapsulated with metal oxide nanoparticles which were confirmed by various characterization techniques; further BET analysis reveals a surface area of 178.46 m2/g. The synthesized multilevel hierarchy was utilized as an electro-active material in a supercapacitor that achieved a specific capacitance of 546.6 F g-1 at a current density of 1 A g-1 with a higher cyclic retention of 91.81% after 10 000 GCD cycles. Furthermore, the ASC device was fabricated using Cu/CuxO@NC as the positive electrode and carbon black as the negative electrode and utilized to enlighten the commercially available LED bulb. The fabricated ASC device was further employed for a two-electrode study which achieved a specific capacitance of 68 F g-1 along with a comparable energy density of 13.6 Wh kg-1. Furthermore, the electrode material was also explored for the oxygen evolution reaction (OER) in an alkaline medium with a low overpotential of 170 mV along with a Tafel slope of 95 mV dec-1 having long-term stability. The MOF-derived material has high durability, chemical stability, and efficient electrochemical performance. This work provides some new thoughts for the design and preparation of a multilevel hierarchy (Cu/CuxO@NC) via a single precursor source in a single step and explored multifunctional applications in energy storage and an energy conversion system.

Phosphorization Engineering on a MOF-Derived Metal Phosphide Heterostructure (Cu/Cu3P@NC) as an Electrode for Enhanced Supercapacitor Performance.

A highly conductive and rationally constructed metal-organic framework (MOF)-derived metal phosphide with a carbonaceous nanostructure is a meticulous architecture toward the development of electrode materials for energy storage devices. Herein, we report a facile strategy to design and construct a new three-dimensional (3D) Cu-MOF via a solvent diffusion method at ambient temperature, which was authenticated by a single-crystal X-ray diffraction study, revealing a novel topology of (2,4,7)-connected three-nodal net named smm4. Nevertheless, the poor conductivity of pristine MOFs is a major bottleneck hindering their capacitance. To overcome this, we demonstrated an MOF-derived Cu3P/Cu@NC heterostructure via low-temperature phosphorization of Cu-MOF. The electronic and ionic diffusion kinetics in Cu3P/Cu@NC were improved due to the synergistic effects of the heterostructure. The as-prepared Cu3P/Cu@NC heterostructure electrode delivers a specific capacity of 540 C g-1 at 1 A g-1 with outstanding rate performance (190 C g-1 at 20 A g-1) and cycle stability (91% capacity retention after 10,000 cycles). Moreover, the assembled asymmetric solid-state supercapacitor (ASC) achieved a high energy density/power density of 45.5 Wh kg-1/7.98 kW kg-1 with a wide operating voltage (1.6 V). Long-term stable capacity retention (87.2%) was accomplished after 5000 cycles. These robust electrochemical performances suggest that the Cu3P/Cu@NC heterostructure is a suitable electrode material for supercapacitor applications.

Effect of Electrolytic Cations on a 3D Cd-MOF for Supercapacitive Electrodes.

A cadmium-based metal-organic framework (Cd-MOF) is synthesized in a facile manner at ambient temperature by an easy slow diffusion process. The three-dimensional (3D) structure of Cd-MOF is authenticated by single-crystal X-ray diffraction studies and exhibits a cuboid-shaped morphology with an average edge length of ∼1.13 µm. The prepared Cd-MOF was found to be electroactive in nature, which resulted in a specific capacitance of 647 F g-1 at 4 A g-1 by maintaining a retention of ∼78% over 10,000 successive cycles in the absence of any binder. Further, to distinguish the efficiency of Cd-MOF electrodes, different electrolytes (NaOH, KOH, and LiOH) were explored, wherein NaOH revealed a higher capacitive response due to its combined effect of ionic and hydrated ionic radii. To investigate the practical applicability, an asymmetric supercapacitor (ASC) device is fabricated by employing Cd-MOF as the positive electrode and activated carbon (AC) as the negative electrode, enabling it to light a commercial light-emitting diode (LED) bulb (∼1.8 V). The as-fabricated ASC device delivers comparable energy density and power density.

Recent Development of Morphology-Controlled Hybrid Nanomaterials for Triboelectric Nanogenerator: A Review.

Being cognizant of modern electronic devices, the scientists are continuing to investigate renewable green-energy resources for a decade. Amid different energy harvesting systems, the triboelectric nanogenerators (TENGs) have been found to be the most promising mechanical harvesting technology and have drawn attention to generate electrical energy. Thanks to its instant output power, choice to opt for wide-ranging materials, low maintenance cost, easy fabrication process and environmentally friendly nature. Due to numerous working modes of TENGs, it is dedicated to desired application at ambient conditions. In this review, an advance correlation of TENGs have been explained based on the variety of nanostructures, including 0D, 1D, 2D, 3D, metal organic frameworks (MOFs), coordination polymers (CPs), covalent organic frameworks (COFs), and perovskite materials. Moreover, an overview of previous and current perspectives of various nanomaterials, synthesis, fabrication and their applications in potential fields have been discussed in detail.

Progress and Perspectives on Covalent-Organic Frameworks (COFs) and Composites for Various Energy Applications.

Covalent-organic frameworks (COFs), being a new member of the crystalline porous materials family, have emerged as important materials for energy storage/conversion/generation devices. They possess high surface areas, ordered micro/mesopores, designable structures and an ability to precisely control electro-active groups in their pores, which broaden their application window. Thanks to their low weight density, long range crystallinity, reticular nature and tunable synthesis approach towards two and three dimensional (2D and 3D) networks, they have been found suitable for a range of challenging electrochemical applications. Our review focuses on the progress made on the design, synthesis and structure of COFs and their composites for various energy applications, such as metal-ion batteries, supercapacitors, water-splitting and solar cells. Additionally, attempts have been made to correlate the structural and mechanistic characteristics of COFs with their applications.

Mechanochromism and Aggregation-Induced Emission in Phenanthroimidazole Derivatives: Role of Positional Change of Different Donors in a Multichromophoric Assembly.

Organic materials possessing solid-state emission responsive to external stimuli have significance in a variety of material, biomedical, and optoelectronic applications. Organic molecules having different donor-acceptor architectures integrated with aggregation-induced emission (AIE) fluorophores have been utilized in development of mechanofluorochromic (MFC) materials. In this work, we have designed and synthesized phenanthroimidazole (PI) based derivatives TPE-PI-1, TPE-PI-2, TPE-PI-3, PTZ-PI-1, PTZ-PI-2, and PTZ-PI-3 where in donors tetraphenylethylene-TPE (D) and phenothiazine-PTZ (D') of contrasting donor abilities are attached to the N and C atom positions of PI. The position and mode of attachment of the donors have been changed, and an additional PTZ spacer has been introduced which has a direct consequence on their photophysical and electronic properties. The PI derivatives manifest AIE, solvatochromic, and mechanochromic behavior. The single crystal X-ray analysis of TPE-PI-1 and PTZ-PI-2 reveals bent structures for the PTZ unit and a twisted conformation for TPE moieties. The density functional theory calculations were used to obtain optimized ground-state structures of the PI derivatives. The work shows a comprehensive comparison of the photophysical, electronic, AIE, and MFC properties of the PI derivatives as an effect of variations in the position of donor, donor-acceptor strength, and change in molecular conformation on use of spacer.

Photocatalytic C-H Thiocyanation of Corroles: Development of Near-Infrared (NIR)-Emissive Dyes.

A new method of activating corrole macrocycles via an in situ generated SCN radical has been developed at very mild conditions at room temperature. This photoredox reaction resulted in the generation of tetrathiocyanatocorroles in good yields. The synthesis of tetrathiocyanatocorroles was never reported earlier. Single-crystal XRD analysis reveals that the insertion of four thiocyanate moieties at the four ß-pyrrolic positions has imparted significant distortion to the corrole macrocycle. The generated tetrathiocyanatocorroles are different from the parent corroles in many ways. The photophysical properties of the newly synthesized tetrathiocyanatocorroles are dramatically altered from the parent corroles. The absorption feature of these modified corrole derivatives (both position and intensity) bears a nice similarity with the chlorophyll-a macrocycle. Thus, these newly synthesized molecules can be considered as spectroscopic model systems for chlorophyll-a pigments. The observed absorption and emission spectra of these tetrathiocyanatocorroles certainly point out that these newly developed ligand scaffolds and their various metal complexes will have immense potential as pigments in solar cells and also as NIR-emissive dyes. The observed C-H···Au weak interactions in a representative Au(III)-corrole complex point out that these complexes are capable of activating the unfunctionalized C-H groups and thus will have potential implications in C-H activation reactions.

Nitrogen-Doped Mixed-Phase Cobalt Nanocatalyst Derived from a Trinuclear Mixed-Valence Cobalt(III)/Cobalt(II) Complex for High-Performance Oxygen Evolution Reaction.

Because of a continuous increase in energy demands and environmental concerns, a focus has been on the design and construction of a highly efficient, low-cost, environmentally friendly, and noble-metal free electrocatalyst for energy technology. Herein we report facile synthesis of the mixed-valence trinuclear cobalt complex 1 by the reaction of 2-amino-1-phenylethanol and CoCl2·6H2O in methanol as the solvent at room temperature. Further, 1 was reduced by using aqueous N2H4 as a simple reducing agent, followed by calcination at 300 °C for 3 h, yielding a nitrogen-doped mixed phase cobalt [ß-Co(OH)2 and CoO] nanocatalyst (N@MPCoNC). Both 1 and N@MPCoNC were characterized by various physicochemical techniques. Moreover, 1 was authenticated by single-crystal X-ray diffraction studies. The hybrid N@MPCoNC reveals a unique electronic and morphological structure, offering a low overpotential of 390 mV for a stable current density of 10 mA cm-2 with high durability. This N@MPCoNC showed excellent electrocatalytic as well as photocatalytic activity for oxygen evolution reaction compared to 1.

Construction of a Cu-Based Metal-Organic Framework by Employing a Mixed-Ligand Strategy and Its Facile Conversion into Nanofibrous CuO for Electrochemical Energy Storage Applications.

Recently, metal-organic frameworks (MOFs) have been widely employed as a sacrificial template for the construction of nanostructured materials for a range of applications including energy storage. Herein, we report a facile mixed-ligand strategy for the synthesis of a Cu-MOF, [Cu3(Azopy)3(BTTC)3(H2O)3·2H2O]n (where BTTC = 1,2,4,5-benzenetetracarboxylic acid and Azopy = 4,4'-azopyridine), via a slow-diffusion method at room temperature. X-ray analysis authenticates the two-dimensional (2D)-layered framework of Cu-MOF. Topologically, this 2D-layered structure is assigned as a 4-connected unimodal net with sql topology. Further, nanostructured CuO is obtained via a simple precipitation method by employing Cu-MOF as a precursor. After analysis of their physicochemical properties through various techniques, both materials are used as surface modifiers of glassy carbon electrodes for a comparative electrochemical study. The results reveal a superior charge storage performance of CuO (244.2 F g-1 at a current density of 0.8 A g-1) with a high rate capability compared to Cu-MOF. This observation paves the pathway for the strategic design of high-performing supercapacitor electrode materials.

Design and fabrication of cost-effective and sensitive non-enzymatic hydrogen peroxide sensor using Co-doped δ-MnO2 flowers as electrode modifier.

The development of a cost-effective and highly sensitive hydrogen peroxide sensor is of great importance. Electrochemical sensing is considered the most sensitive technique for hydrogen peroxide detection. Herein, we reported a cost-effective and highly sensitive hydrogen peroxide sensor using Co-doped δ-MnO2 (Co@δ-MnO2) flower-modified screen-printed carbon electrode. The δ-MnO2 and Co@δ-MnO2 flowers were synthesized by employing a hydrothermal approach. Advanced techniques such as PXRD, SEM, FTIR, Raman, UV, EDX, BET, and TEM were utilized to confirm the formation of δ-MnO2 and Co-doped δ-MnO2 flowers. The fabricated sensor exhibited an excellent detection limit (0.12 µM) and sensitivity of 5.3 µAµM-1 cm-2.Graphical abstract.

Directional Approach to Enantiomerically Enriched Functionalized [7]Oxa-helicenoids and Groove-Based Selective Cyanide Sensing.

Several regioselective functionalized mono- and disubstituted [7]oxa-helicenoids have been synthesized in the enantiomerically enriched (90-99% ee) form. These functionalized helicenoids exhibited pronounced spectral and chiroptical properties suitable for sensing applications. In particular, corresponding helicenoid's mono and dialdehydes have been effectively used as chemodosimeters for selective detection of cyanide anions over other anions, while simple aromatic aldehydes do not function as cyanide sensors. The groove available in the helical host plays a crucial role in the sensing. The enantiomerically enriched nature of the sensors allows the use of electronic circular dichroism as an uncommon detection tool for cyanide anions, along with conventional fluorescence and NMR methods.

Crystallographic Elucidation of Stimuli-Controlled Molecular Rotation for a Reversible Sol-Gel Transformation.

To get an idea about the most probable microporous supramolecular environment in the gel state, gelator molecule 1 has been crystallized from its gelling solvent (dimethylformamide). Crystal structure analysis of 1 shows a strong π···π stacking interaction between the electron-deficient pentafluorophenyl ring and electron-rich naphthyl ring. The gelling solvent situated in the "molecular pocket" stitches the gelators through weak H-bonding interactions to facilitate the formation of an organogel. Scanning electron microscopy analysis exhibits a ribbonlike fibrous morphology that resembles the supramolecular arrangement of 1 in its crystalline state, as evidenced by powder X-ray diffraction. In the presence of external stimuli (tetrabutylammonium fluoride), the organogel of 1 disassembles into sol. This sol-gel transformation phenomenon has been explained on the basis of X-ray single-crystal analysis. Single crystals obtained from the sol state show that naphthylic -OH of 1 gets deprotonated, resulting in C-C bond rotation that plays a major role in the sol-gel transformation. Gelator 1 exhibits weak green fluorescence in the gel state, whereas it shows highly intense yellow fluorescence in the sol state. Furthermore, a reversible sol-gel transformation associated with changes in the spectroscopic properties has been observed in the presence of acids and fluoride ions, respectively.

Mixed-Ligand Architected Unique Topological Heterometallic Sodium/Cobalt-Based Metal-Organic Framework for High-Performance Supercapacitors.

A new Na/Co-based heterometallic metal-organic framework, [Na2Co(SDCA)(µ2-OH)2(µ2-H2O)2(Azopy)]n (where Azopy = 4,4'-Azopyridine and SDCA = 2,5'-thiophenedicarboxylic acid) (1) with nanorod-shaped morphology was synthesized using mixed-ligand approach via slow-diffusion technique under ambient conditions. The crystal structure study demonstrates the proportion of Co(II) and Na(I) metal node to be 1:2 and the acquired coordination network reveals as a 3D architecture. Topologically, the 4-c Na(I) ion directs in situ assembly of 4-c SDCA linker and 6-c Co(II) ion, resulting in the formation of 4,4,6-c net with a topology named as smm3. Additionally, 1 was incorporated as a binder-free material for a glassy carbon electrode (1-GCE) to explore its supercapacitor performance, which reveals a high specific capacitance of 321.8 F g-1 at 4 A g-1 and notable rate performance (∼78.9% of initial capacitance up to 16 A g-1) as well as excellent cycling stability (retains 97.4% after 5000 cycles). The demonstrated strategy of employing different heterometallic clusters with mixed ligands markedly increases MOF's complexity and induces synergistic properties, which is highly favorable for electrochemical applications. Hence, the present approach can be extended to build a wide range of MOFs and synergistically enhanced electrochemical performance can be achieved.

Insights into the Aggregation Behaviour of a Benzoselenadiazole-Based Compound and Generation of White Light Emission.

We have designed and synthesized the benzoselenadiazole (BDS) based donor-acceptor-donor (D-A-D) π-conjugated compound 4,7-di((E)styryl)benzo[2,1,3]selenadiazole (1). A single-crystal study of 1 shows J-type molecular aggregation in the solid state. The crystal packing of 1 shows head-to-head dimeric intermolecular assembly via Se⋅⋅⋅N interactions while staircase-type interlock molecular packing has occurred via Se⋅⋅⋅π interaction. The staircase-type interlock packing of dimeric molecular arrangement induces sheet-type, herringbone type architecture along crystallographic a axis and ab plane via CH⋅⋅⋅π interactions. Interestingly, the J-type aggregation of 1 in solid state changes to H-type aggregation upon UV-irradiation. Moreover, our spectroscopic findings in solution state reveal H-type of aggregation of 1 in 90 % aqueous THF. We have further demonstrated white light emission in the binary mixture of 1 and 1-pyrenemethanol (2) in 90 % aqueous THF. Our study reveals solvent specific co-assembly of H-aggregated 1 and 2 in 90 % aqueous THF solution, which shows white light emissive properties with the Commission Internationale de l'Eclairage (CIE) chromaticity coordinates (0.32, 0.31). The observed white light emission arises mainly due to the combination of red light from H-aggregated 1, blue light from monomeric 2 and green light from excimers of 2.

Benzyne-Mediated Nonconcerted Pathway toward Synthesis of Sterically Crowded [5]- and [7]Oxahelicenoids, Stereochemical and Theoretical Studies, and Optical Resolution of Helicenoids.

Synthesis of [5]- and [7]oxahelicenoids via Diels-Alder reaction of sterically crowded bichromenes with benzyne is presented. Studies carried out on Diels-Alder addition product establish the unusual preference for a stepwise mechanism over the concerted reaction pathway. This high yielding general synthetic protocol affords unexpected anti cycloadducts [5]- and [7]oxahelicenoids, as confirmed by crystallographic analysis. To rationalize these intriguing antiaddition products, the reaction mechanism was elucidated by means of DFT analysis. Additionally, hydroxy-functionalized [7]oxahelicenoid has been resolved in its optically pure forms.

Dual Functionalized CuMOF-Based Composite for High-Performance Supercapacitors.

Herein, we utilized our previously reported highly porous CuMOF, {[Cu2(L)(H2O)2]·(5DMF)·(4H2O)}n, decorated with amine and trifluoromethyl functional groups for energy storage application. This robust framework in CuMOF enhances the chemical and thermal stabilities as well as improves the interfacial binding interactions. The poor conductivity of CuMOF usually restricts its practical utility in energy storage systems, due to which rGO was introduced along with CuMOF to form a CuMOF/rGO composite (1) through a facile ultrasonication technique. The synergistic effects between CuMOF and rGO induce a dramatic enhancement in specific capacitance (462 F g-1 at 0.8 A g-1) of 1 with a cycle life of 93.75% up to 1000 cycles. The results highlight 1 as an emerging contestant for next generation supercapacitors.

Dy(III)-Based Metal-Organic Framework as a Fluorescent Probe for Highly Selective Detection of Picric Acid in Aqueous Medium.

A dysprosium metal-organic framework, {[Dy(µ2-FcDCA)1.5(MeOH)(H2O)]·0.5H2O}n (1), where FcDCA = 1,1'-ferrocene dicarboxylic acid, was prepared by slow-diffusion technique at room temperature. The crystal structure analysis of 1 by single-crystal X-ray diffraction reveals different binding modes of FcDCA linkers coordinated with Dy(III) metal ions, which forms continuous porous two-dimensional (2D) infinite framework. The resulting 2D layers are linked by π···π interactions to build three-dimensional (3D) supramolecular framework. Observably, this thermally stable 3D architecture was topologically simplified as a three-connected uninodal net with fes topology. Furthermore, the practical applicability of 1 was investigated as a fluorescence sensor for the sensitive detection of picric acid in aqueous medium with an impressive detection limit of 0.71 µM with quenching constant (KSV) quantified to be 8.55 × 104 M-1. The distinguished selectivity in the presence of other nitroaromatics suggests the possible incorporation of 1 in real-world futuristic diagnostic kits. Additionally, the electrochemical behavior of 1 exhibits reversible in nature attributed to the ferrocene/ferrocenium cation.

Catalytic CO2 Fixation over a Robust Lactam-Functionalized Cu(II) Metal Organic Framework.

A porous, Cu(II)-metal organic framework (Cu-MOF) constituted of a rigid lactam functionalized ditopic ligand (H2L) was synthesized at room temperature under slow evaporation conditions {H2L = (5-(1-oxo-2,3-dihydro-1H-inden-2-yl)isophthalic acid)}. The single crystal X-ray structure revealed the formation of a 3D framework of Cu-MOF with one-dimensional (1D) channels decorated with lactam groups and exposed metal centers in the crystallographic c-axis. Interestingly, Cu(II) coordinated DMF molecules were eliminated from the Cu(II) metal center on activation of Cu-MOF at a temperature of 150 °C under high vacuum to generate a solvent free framework with pores lined with unsaturated Lewis acidic Cu(II) ions, i.e., Cu-MOF'. The lactam functionalized channels inclined toward the CO2, which interact with the Cu(II) metal sites lined in the channels of Cu-MOF' and exhibit fascinating solvent-free heterogeneous catalytic conversion of CO2 to cyclic carbonates at atmospheric pressure of CO2, under mild conditions. Furthermore, the Cu-MOF' catalyst was easily recycled and reused for several cycles without a significant loss in catalytic activity.

Mitochondrial Localization of Highly Fluorescent and Photostable BODIPY-Based Ruthenium(II), Rhodium(III), and Iridium(III) Metal Complexes.

A new N,O-based BODIPY ligand was synthesized and further utilized to develop highly fluorescent and photostable Ru(II), Rh(III), and Ir(III) metal complexes. The complexes were fully characterized by different analytical techniques including single-crystal XRD studies. The photostabilities and live cell imaging capabilities of the complexes were investigated via confocal microscopy. The complexes localized specifically in the mitochondria of live cells and showed negligible cytotoxicities at a concentration used for imaging purposes. They also exhibited high photostabilities, with fluorescence intensities remaining above 50% after 1800 scans.