Metal Organic Frameworks (MOFs) represent a promising class of metallic catalysts for reduction of nitrogen-containing contaminants (NCCs), such as 4-nitrophenol (4-NP). Nevertheless, most researches involving MOFs for 4-NP reduction employ noble metals in the form of fine powders, making these powdered noble metal-based MOFs impractical and inconvenient for realistic applications. Thus, it would be critical to develop non-noble-metal MOFs which can be incorporated into macroscale and porous supports for convenient applications. Herein, the present study proposes to develop a composite material which combines advantageous features of macroscale/porous supports, and nanoscale functionality of MOFs. In particular, copper foam (CF) is selected as a macroscale porous medium, which is covered by nanoflower-structured CoO to increase surfaces for growing a cobaltic MOF, ZIF-67. The resultant composite comprises of CF covered by CoO nanoflowers decorated with ZIF-67 to form a hierarchical 3D-structured catalyst, enabling this ZIF-67@Cu foam (ZIF@CF) a promising catalyst for reducing 4-NP, and other NCCs. Thus, ZIF@CF can readily reduce 4-NP to 4-AP with a significantly lower Ea of 20 kJ/mol than reported values. ZIF@CF could be reused over 10 cycles and remain highly effective for 4-NP reduction. ZIF@CF also efficiently reduces other NCCs, such as 2-nitrophenol, 3-nitrophenol, methylene blue, and methyl orange. ZIF@CF can be adopted as catalytic filters to enable filtration-type reduction of NCCs by passing NCC solutions through ZIF@CF to promptly and conveniently reduce NCCs. https://www.selleckchem.com/products/baricitinib-ly3009104.html The versatile and advantageous catalytic activity of ZIF@CF validates that ZIF@CF is a promising and practical heterogeneous catalyst for reductive treatments of NCCs.Herein, MIL-101(Fe), CoFe2O4, novel binary (MIL-101(Fe)/CoFe2O4, MIL-101(Fe)/GO and CoFe2O4/GO), and ternary (MIL-101(Fe)/CoFe2O4/(3%)GO and MIL-101(Fe)/CoFe2O4/(7%)GO) magnetic composites based upon the MIL-101(Fe) were synthesized. The XRD, FESEM, TEM, EDX, BET-BJH, FTIR, VSM, DRS, PL, EIS and other electrochemical analyses were applied to characterize samples. The MIL/CoFe2O4/(3%)GO demonstrated the best performance compared to other samples for visible light photocatalytic and photo-Fenton-like degradation of Direct Red 23 (DtR-23), Reactive Red 198 (ReR-198) dyes as well as Tetracycline Hydrochloride (TC-H) antibiotic. Degradation of dyes using the ternary composite after 70 min of visible light irradiation was greater than that of 99%. The presence of the optimum GO as a strong electron acceptor in MIL/CoFe2O4/(3%)GO not only led to the effective separation of charge carriers and thus reduction of their recombination but also increased the absorption of visible light. The composite possessed good durability in terms of stability and reusability. The PL, EIS and electrochemical analyses indicated that the MIL/CoFe2O4/(3%)GO improved the optical properties and photocatalytic performance.The production of ammonia through electrocatalytic nitrogen reduction reaction (NRR) is environmentally friendly and energy-saving, but it still suffers from the low NH3 yield rate and poor selectivity. Herein, enlightened by the unique solubility of Fe3O4 in deep eutectic solvent (DES), we, for the first time, reported a DES-based regeneration strategy to fabricate porous Fe3O4 nanosheets utilizing commercial Fe3O4 powder as raw materials. The as-regenerated porous Fe3O4 nanosheets exhibited satisfactory electrocatalytic performance toward NRR, affording a NH3 yield rate of 12.09 μg h-1 mg-1cat along with an outstanding Faradaic efficiency (FE) of 34.38% at -0.1 V versus reversible hydrogen electrode (RHE), in the 0.1 M Na2SO4 electrolyte. The superior electrocatalytic activity of the as-regenerated Fe3O4 nanosheets mainly resulted from their unique sheet-like morphology with large active surface area, high porosity, and abundant oxygen vacancies. Our proposed DES-based regeneration strategy opens a new avenue for the construction of high-performance electrocatalyst from commercial raw materials, holding great promise in NRR.The electrochemical anodic behavior of transition metal compounds plays an undeniably non-negligible role across many electrooxidation reactions. In this work, a chronopotentiometric technique was employed to activate the multicomponent non-noble metal oxyfluorides in-situ for oxygen evolution reaction (OER). It is interesting to unravel that the increasing applied current density helps to reconstruct the catalyst into nanoporous core-shell structure and introduce metal oxyhydroxide on the surface, which guarantees more channels for efficient ion/mass transportation and thus contributes to exposing more active sites for catalytic reaction. The activated five-membered oxyfluoride shows the best catalytic activity with overpotential of 348 ± 2 mV to achieve the current density of 10 mA/cm2 and a Tafel slope of 110.3 ± 0.1 mV/dec, in contrast with the pristine one (532 ± 2 mV & 240.2 ± 0.1 mV/dec). It still maintains high stability after long time OER measurement, making it a promising succedaneum for noble metal catalysts. The high-entropy effect, amorphous state and high active sites density jointly contribute to its enhanced OER performance. This work provides new ideas for realizing the potential of inactive elements via entropy engineering and using electrochemical self-reconstruction to modify semiconductors for advanced water oxidation.Two-dimensional (2D) coordination polymers are very interesting materials for their attractive applications. A novel 2D metal-organic framework (MOF) was derived from copper(II) and amino benzoic acid under both room temperature and solvothermal reaction conditions using different solvents. From both of the synthesis methods, an identical MOF was crystalized with monoclinic crystal system having P21/c space group. Hirshfeld surface analysis is carried out to explore the non-covalent interactions obtained from single crystal XRD investigation in terms of percentage contribution of each interatomic contact involved in packing of molecules into MOF structure. The microstructure analysis and surface morphology studies revealed the 2D layered regular pattern of rhombus disks of ~5 μm thickness throng together via clustering of these rhombic shaped flakes as flowers (ranging 50-100 μm in size) having uniform elemental composition. This 2D MOF efficiently adsorbed organic dyes (methylene blue, methyl orange, and methyl red) from their aqueous solutions.
Metal Organic Frameworks (MOFs) represent a promising class of metallic catalysts for reduction of nitrogen-containing contaminants (NCCs), such as 4-nitrophenol (4-NP). Nevertheless, most researches involving MOFs for 4-NP reduction employ noble metals in the form of fine powders, making these powdered noble metal-based MOFs impractical and inconvenient for realistic applications. Thus, it would be critical to develop non-noble-metal MOFs which can be incorporated into macroscale and porous supports for convenient applications. Herein, the present study proposes to develop a composite material which combines advantageous features of macroscale/porous supports, and nanoscale functionality of MOFs. In particular, copper foam (CF) is selected as a macroscale porous medium, which is covered by nanoflower-structured CoO to increase surfaces for growing a cobaltic MOF, ZIF-67. The resultant composite comprises of CF covered by CoO nanoflowers decorated with ZIF-67 to form a hierarchical 3D-structured catalyst, enabling this ZIF-67@Cu foam (ZIF@CF) a promising catalyst for reducing 4-NP, and other NCCs. Thus, ZIF@CF can readily reduce 4-NP to 4-AP with a significantly lower Ea of 20 kJ/mol than reported values. ZIF@CF could be reused over 10 cycles and remain highly effective for 4-NP reduction. ZIF@CF also efficiently reduces other NCCs, such as 2-nitrophenol, 3-nitrophenol, methylene blue, and methyl orange. ZIF@CF can be adopted as catalytic filters to enable filtration-type reduction of NCCs by passing NCC solutions through ZIF@CF to promptly and conveniently reduce NCCs. https://www.selleckchem.com/products/baricitinib-ly3009104.html The versatile and advantageous catalytic activity of ZIF@CF validates that ZIF@CF is a promising and practical heterogeneous catalyst for reductive treatments of NCCs.Herein, MIL-101(Fe), CoFe2O4, novel binary (MIL-101(Fe)/CoFe2O4, MIL-101(Fe)/GO and CoFe2O4/GO), and ternary (MIL-101(Fe)/CoFe2O4/(3%)GO and MIL-101(Fe)/CoFe2O4/(7%)GO) magnetic composites based upon the MIL-101(Fe) were synthesized. The XRD, FESEM, TEM, EDX, BET-BJH, FTIR, VSM, DRS, PL, EIS and other electrochemical analyses were applied to characterize samples. The MIL/CoFe2O4/(3%)GO demonstrated the best performance compared to other samples for visible light photocatalytic and photo-Fenton-like degradation of Direct Red 23 (DtR-23), Reactive Red 198 (ReR-198) dyes as well as Tetracycline Hydrochloride (TC-H) antibiotic. Degradation of dyes using the ternary composite after 70 min of visible light irradiation was greater than that of 99%. The presence of the optimum GO as a strong electron acceptor in MIL/CoFe2O4/(3%)GO not only led to the effective separation of charge carriers and thus reduction of their recombination but also increased the absorption of visible light. The composite possessed good durability in terms of stability and reusability. The PL, EIS and electrochemical analyses indicated that the MIL/CoFe2O4/(3%)GO improved the optical properties and photocatalytic performance.The production of ammonia through electrocatalytic nitrogen reduction reaction (NRR) is environmentally friendly and energy-saving, but it still suffers from the low NH3 yield rate and poor selectivity. Herein, enlightened by the unique solubility of Fe3O4 in deep eutectic solvent (DES), we, for the first time, reported a DES-based regeneration strategy to fabricate porous Fe3O4 nanosheets utilizing commercial Fe3O4 powder as raw materials. The as-regenerated porous Fe3O4 nanosheets exhibited satisfactory electrocatalytic performance toward NRR, affording a NH3 yield rate of 12.09 μg h-1 mg-1cat along with an outstanding Faradaic efficiency (FE) of 34.38% at -0.1 V versus reversible hydrogen electrode (RHE), in the 0.1 M Na2SO4 electrolyte. The superior electrocatalytic activity of the as-regenerated Fe3O4 nanosheets mainly resulted from their unique sheet-like morphology with large active surface area, high porosity, and abundant oxygen vacancies. Our proposed DES-based regeneration strategy opens a new avenue for the construction of high-performance electrocatalyst from commercial raw materials, holding great promise in NRR.The electrochemical anodic behavior of transition metal compounds plays an undeniably non-negligible role across many electrooxidation reactions. In this work, a chronopotentiometric technique was employed to activate the multicomponent non-noble metal oxyfluorides in-situ for oxygen evolution reaction (OER). It is interesting to unravel that the increasing applied current density helps to reconstruct the catalyst into nanoporous core-shell structure and introduce metal oxyhydroxide on the surface, which guarantees more channels for efficient ion/mass transportation and thus contributes to exposing more active sites for catalytic reaction. The activated five-membered oxyfluoride shows the best catalytic activity with overpotential of 348 ± 2 mV to achieve the current density of 10 mA/cm2 and a Tafel slope of 110.3 ± 0.1 mV/dec, in contrast with the pristine one (532 ± 2 mV & 240.2 ± 0.1 mV/dec). It still maintains high stability after long time OER measurement, making it a promising succedaneum for noble metal catalysts. The high-entropy effect, amorphous state and high active sites density jointly contribute to its enhanced OER performance. This work provides new ideas for realizing the potential of inactive elements via entropy engineering and using electrochemical self-reconstruction to modify semiconductors for advanced water oxidation.Two-dimensional (2D) coordination polymers are very interesting materials for their attractive applications. A novel 2D metal-organic framework (MOF) was derived from copper(II) and amino benzoic acid under both room temperature and solvothermal reaction conditions using different solvents. From both of the synthesis methods, an identical MOF was crystalized with monoclinic crystal system having P21/c space group. Hirshfeld surface analysis is carried out to explore the non-covalent interactions obtained from single crystal XRD investigation in terms of percentage contribution of each interatomic contact involved in packing of molecules into MOF structure. The microstructure analysis and surface morphology studies revealed the 2D layered regular pattern of rhombus disks of ~5 μm thickness throng together via clustering of these rhombic shaped flakes as flowers (ranging 50-100 μm in size) having uniform elemental composition. This 2D MOF efficiently adsorbed organic dyes (methylene blue, methyl orange, and methyl red) from their aqueous solutions.
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