High-Efficacy Hierarchical Dy2O3/TiO2 Nanoflower toward Wastewater Reclamation: A Combined Photoelectrochemical and Photocatalytic Strategy.

Developing a sustainable photocatalyst is crucial to mitigate the foreseeable energy shortage and environmental pollution caused by the rapid advancement of global industry. We developed Dy2O3/TiO2 nanoflower (TNF) with a hierarchical nanoflower structure and a near-ideal anatase crystallite morphology to degrade aqueous rhodamine B solution under simulated solar light irradiation. The prepared photocatalyst was well-characterized using powder X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, energy-dispersive spectroscopy, scanning electron microscopy, Brunauer-Emmett-Teller, diffuse reflectance UV-vis spectra, and X-ray photoelectron spectroscopy. Further analysis was performed to highlight the photoelectrochemical activity of the prepared photocatalysts such as electrochemical impedance spectroscopy, linear sweep voltammetry, photocurrent response, and a Mott-Schottky study. The crystalline Dy2O3/TNF exhibits superb photocatalytic activity attributed to the improved charge transfer, reduced recombination rate of the electron-hole pairs, and a remarkable red-shift in light absorption.

Green construction of eco-friendly phosphotungstic acid Sr-MOF catalysts for crystal violet removal and synthesis of coumarin and xanthene compounds.

There is an urgent need to improve engineering and synthetic chemistry, either through the use of eco-friendly starting materials or the proper design of novel synthesis routes. This reduces the contamination of toxic chemicals and helps the disposal of organic dyes. In the current work, a metal-organic framework-based Sr(ii) was fabricated to achieve the desired goal for dye removal and catalysis. Sr-MOF-based phosphotungstic acid (PWA/Sr-MOF) was hydrothermally synthesized to study its adsorption and catalytic activities. Remarkably, about 99.9% of crystal violet (CV) dye was removed using PWA/Sr-MOF within 90 min at room temperature. Various factors have been studied to investigate the optimum conditions such as pH of solution, initial dye concentration, contact time, and temperature. The maximum adsorption capacity of CV dye was reached after 90 min and well fitted the pseudo-second kinetic order and Langmuir adsorption isotherm. Coumarin and xanthene reactions were chosen to test the catalytic activity of the prepared PWA/Sr-MOF at 373 K. Furthermore, structural and chemical characterization of the fabricated samples was obtained using FT-IR, XRD, TGA, DTA, TEM, EDX, and XPS. PWA/Sr-MOF can be considered as a promising and green framework in the material design used to study catalytic and adsorption performances.

Efficient removal of heavy metals from polluted water with high selectivity for Hg(ii) and Pb(ii) by a 2-imino-4-thiobiuret chemically modified MIL-125 metal-organic framework.

A highly porous adsorbent based on a metal-organic framework was successfully designed and applied as an innovative adsorbent in the solid phase for the heavy metal removal. MIL-125 was densely decorated by 2-imino-4-thiobiuret functional groups, which generated a green, rapid, and efficacious adsorbent for the uptake of Hg(ii) and Pb(ii) from aqueous solutions. ITB-MIL-125 showed a high adsorption affinity toward mercury(ii) ions of 946.0 mg g-1 due to covalent bond formation with accessible sulfur-based functionality. Different factors were studied, such as the initial concentration, pH, contact time, and competitive ions, under same circumstances at the room temperature. Moreover, the experimental adsorption data were in excellent agreement with the Langmuir adsorption isotherm and pseudo-second order kinetics. At a high concentration of 100 ppm mixture of six metals, ITB-MIL-125 exhibited a high adsorption capacity, reaching more than 82% of Hg(ii) compared to 62%, 30%, 2%, 1.9%, and 1.6% for Pb(ii), Cu(ii), Cd(ii), Ni(ii), and Zn(ii), respectively.

Heterogeneous catalysis by ultra-small bimetallic nanoparticles surpassing homogeneous catalysis for carbon-carbon bond forming reactions.

Palladium catalyzed cross-coupling reactions represent a significant advancement in contemporary organic synthesis as these reactions are of strategic importance in the area of pharmaceutical drug discovery and development. Supported palladium-based catalysts are highly sought-after in carbon-carbon bond forming catalytic processes to ensure catalyst recovery and reuse while preventing product contamination. This paper reports the development of heterogeneous Pd-based bimetallic catalysts supported on fumed silica that have high activity and selectivity matching those of homogeneous catalysts, eliminating the catalyst's leaching and sintering and allowing efficient recycling of the catalysts. Palladium and base metal (Cu, Ni or Co) contents of less than 1.0 wt% loading are deposited on a mesoporous fumed silica support (surface area SABET = 350 m2 g-1) using strong electrostatic adsorption (SEA) yielding homogeneously alloyed nanoparticles with an average size of 1.3 nm. All bimetallic catalysts were found to be highly active toward Suzuki cross-coupling (SCC) reactions with superior activity and stability for the CuPd/SiO2 catalyst. A low CuPd/SiO2 loading (Pd: 0.3 mol%) completes the conversion of bromobenzene and phenylboronic acid to biphenyl in 30 minutes under ambient conditions in water/ethanol solvent. In contrast, monometallic Pd/SiO2 (Pd: 0.3 mol%) completes the same reaction in three hours under the same conditions. The combination of Pd with the base metals helps in retaining the Pd0 status by charge donation from the base metals to Pd, thus lowering the activation energy of the aryl halide oxidative addition step. Along with its exceptional activity, CuPd/SiO2 exhibits excellent recycling performance with a turnover frequency (TOF) of 280 000 h-1 under microwave reaction conditions at 60 °C. Our study demonstrates that SEA is an excellent synthetic strategy for depositing ultra-small Pd-based bimetallic nanoparticles on porous silica for SCC. This avenue not only provides highly active and sintering-resistant catalysts but also significantly lowers Pd contents in the catalysts without compromising catalytic activity, making the catalysts very practical for large-scale applications.

Green Synthesis of Oxide-Supported Pd Nanocatalysts by Laser Methods for Room-Temperature Carbon-Carbon Cross-Coupling Reactions.

This work reports the design and development of a new class of highly active Pd nanocatalysts supported on substoichiometric oxides. These novel catalysts are generated by green laser synthesis methods to generate high-surface-area substoichiometric oxide nanoparticles followed by photoreduction in aqueous solutions to deposit highly active Pd nanocatalysts within the surface defects of the oxides. The laser methods eliminate the use of toxic chemicals, including hazardous solvents and chemical reducing agents, and allow efficient reduction of the Pd ions in aqueous solutions aided by the photogenerated electrons from the semiconductor support. The Pd catalysts incorporated within these oxides exhibit high activity for carbon-carbon bond-forming reactions. The Pd/TiO2 catalyst with 0.3 mol % Pd achieves 100% conversion in the reaction between bromobenzene and benzeneboronic acid to the biphenyl product within 240 minutes at room temperature without any external heating. With a catalyst loading of 0.3 mol % Pd in the microwave-assisted reaction between bromobenzene and benzeneboronic acid at 60 °C, 92 and 83% conversions to the biphenyl product are achieved within 5 min of reaction time using the Pd/TiO2 and Pd/ZnO catalysts, respectively. The results demonstrate a remarkable catalytic activity of the substoichiometric oxide-supported Pd catalysts with turnover frequencies (TOF, h-1) of 24 000, 10 000, and 3200 achieved under mirowave-assisted reactions at 60 °C for the 0.03 mol% Pd of the Pd/TiO2, Pd/ZnO, and Pd/ZrO2 catalysts, respectively. The high activity and good reusability of these nanocatalysts are attributed to the optimum catalyst-support interaction between the small Pd nanoparticles and the surface defects of the substoichiometric oxide support prepared by the laser vaporization-controlled condensation method.

Melamine-based functionalized graphene oxide and zirconium phosphate for high performance removal of mercury and lead ions from water.

Heavy metal ions are highly toxic and widely spread as environmental pollutants. This work reports the development of two novel chelating adsorbents, based on the chemical modifications of graphene oxide and zirconium phosphate by functionalization with melamine-based chelating ligands for the effective and selective extraction of Hg(ii) and Pb(ii) from contaminated water sources. The first adsorbent melamine, thiourea-partially reduced graphene oxide (MT-PRGO) combines the heavier donor atom sulfur with the amine and triazine nitrogen's functional groups attached to the partially reduced GO nanosheets to effectively capture Hg(ii) ions from water. The MT-PRGO adsorbent shows high efficiency for the extraction of Hg(ii) with a capacity of 651 mg g-1 and very fast kinetics resulting in a 100% removal of Hg(ii) from 500 ppb and 50 ppm concentrations in 15 second and 30 min, respectively. The second adsorbent, melamine zirconium phosphate (M-ZrP), is designed to combine the amine and triazine nitrogen's functional groups of melamine with the hydroxyl active sites of zirconium phosphate to effectively capture Pb(ii) ions from water. The M-ZrP adsorbent shows exceptionally high adsorption affinity for Pb(ii) with a capacity of 681 mg g-1 and 1000 mg g-1 using an adsorbent dose of 1 g L-1 and 2 g L-1, respectively. The high adsorption capacity is also coupled with fast kinetics where the equilibrium time required for the 100% removal of Pb(ii) from 1 ppm, 100 ppm and 1000 ppm concentrations is 40 seconds, 5 min and 30 min, respectively using an adsorbent dose of 1 g L-1. In a mixture of six heavy metal ions at a concentration of 10 ppm, the removal efficiency is 100% for Pb(ii), 99% for Hg(ii), Cd(ii) and Zn(ii), 94% for Cu(ii), and 90% for Ni(ii) while at a higher concentration of 250 ppm the removal efficiency for Pb(ii) is 95% compared to 23% for Hg(ii) and less than 10% for the other ions. Because of the fast adsorption kinetics, high removal capacity, excellent regeneration, stability and reusability, the MT-PRGO and M-ZrP are proposed as top performing remediation adsorbents for the solid phase extraction of Hg(ii) and Pb(ii), respectively from contaminated water.

Synthesis of sulfamic acid supported on Cr-MIL-101 as a heterogeneous acid catalyst and efficient adsorbent for methyl orange dye.

Typical highly porous metal-organic framework (MOFs) materials based on chromium benzenedicarboxylates (Cr-BDC) were prepared through a one-pot hydrothermal synthesis, and were then modified by loading the appropriate ratio of sulfamic acid (SA) using a simple impregnation technique. Pure and modified MIL-101 was characterized by XRD, TEM, SEM and FT-IR measurements. TEM and SEM measurements confirmed that the MIL-101 particles preserved their regular octahedral structure after loading with different weight contents of sulfamic acid. The total number of acid sites and Brønsted to Lewis acid sites ratio (B/L) were examined using potentiometric titration and pyridine adsorption. The acid strength and surface acidity of SA/MIL-101 gradually increased after the modification of Cr-MIL-101 by sulfamic acid crystals up to 55 wt%, then decreased again. The catalytic performance of the solid catalysts was confirmed in the synthesis of 14-phenyl-14H-dibenzo [a,j] xanthene and 7-hydroxy-4-methyl coumarin. In the two reactions, the sample with 55% sulfamic acid loaded on MIL-101 displayed the highest catalytic activity and acidity. The adsorption behaviors of sulfamic acid loaded on MIL-101 materials for methyl orange (MO) as an anionic dye were studied, and were exceptionally suitable for the Langmuir adsorption isotherm. All loaded adsorbents showed high adsorption capacity for methyl orange at 25 °C. The results indicate that the adsorption capacity was modified by changing the amount of sulfamic acid loaded on MIL-101.

Surface ion-imprinted amino-functionalized cellulosic cotton fibers for selective extraction of Cu(II) ions.

Surface ion-imprinted amino-functionalized cellulosic fibers (Cu-ABZ) were manufactured for efficient selective adsorption of Cu(2+) ions. The chemical modification steps had been characterized utilizing elemental analysis; Fourier transforms infrared (FTIR) along with wide angle X-ray diffraction (XRD) spectroscopy. Also, the morphological structure of the ion-imprinted and the non-imprinted (NI-ABZ) fibers were visualized and compared with that of the native cotton fibers using scanning electron microscope (SEM). In addition, the coordination mode by which the Cu(2+) ions bonded to the active sites were examined by both FTIR and X-ray photo electron spectra (XPS). Both Cu-ABZ and NI-ABZ were implemented in batch experiments for optimizing the conditions by which the Cu(2+) ions can be selectively removal from aqueous medium and pH 5 was the optimum for the metal ion extraction. Moreover, the kinetics and isotherm studies revealed that the adsorption data fitted with pseudo-second-order kinetic and Langmuir models with estimated maximum adsorption capacity 93.6mg/g. Also, the reusability studies indicated that the prepared ion-imprinted adsorbent maintains more than 95% of its original activity after fifth generation cycle.

Preparation, characterization and biological activity of novel metal-NNNN donor Schiff base complexes.

Novel Schiff base (H(2)L) ligand is prepared via condensation of benzil and triethylenetetraamine. The ligand is characterized based on elemental analysis, mass, IR and (1)H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, and thermal analyses (TG, DTG and DTA). 1:1 [M]:[H(2)L] complexes are found from the elemental analyses data having the formulae [M(H(2)L)Cl(2)]xyH(2)O (M=Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)), [Fe(H(2)L)Cl(2)]ClxH(2)O, [Th(H(2)L)Cl(2)]Cl(2)x3H(2)O and [UO(2)(H(2)L)](CH(3)COO)(2)x2H(2)O. The metal chelates are found to be non-electrolytes except Fe(III), Th(IV) and UO(2)(II) complexes are electrolytes. IR spectra show that H(2)L is coordinated to the metal ions in a neutral tetradentate manner with 4Ns donor sites of the two azomethine N and two NH groups. The geometrical structures of these complexes are found to be octahedral. The thermal behaviour of these chelates is studied where the hydrated complexes lose water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated using Coats-Redfern method. The ligand (H(2)L), in comparison to its metal complexes, is screened for its antibacterial activity. The activity data show that the metal complexes have antibacterial activity more than the parent Schiff base ligand and cefepime standard against one or more bacterial species.

Biological activity studies on metal complexes of novel tridentate Schiff base ligand. Spectroscopic and thermal characterization.

Metal complexes of novel Schiff base (HL) ligand, prepared via condensation of 4-aminoantipyrine and 2-aminophenol, are prepared. The ligand is characterized based on elemental analysis, mass, IR and (1)H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance, ESR spectra and thermal analyses (TG, DTG and DTA). From the elemental analyses, 1:1 [M]:[ligand] complexes are prepared with the general formulae [M(L)Cl(H(2)O)(2)] x yH(2)O (M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II), y = 3-4), [Fe(L)Cl(2)(H(2)O)] x 3 H(2)O and [Th(L)Cl(H(2)O)(2)]Cl(2) x 3 H(2)O. The molar conductance data reveal that all the metal chelates are non-electrolytes (except Th(IV) complex, it is 2:1 electrolyte). IR spectra show that HL is coordinated to the metal ions in a uninegatively tridentate manner with NNO donor sites of the azomethine-N, amino N and deprotonated phenolic-O. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters are calculated from the DTG curves using Coats-Redfern method. The synthesized ligand, in comparison to its metal complexes is screened for its antibacterial activity against bacterial species, Escherichia coli, Pseudomonas putida, Exiguobacterium acetylicum and Bacillus simplex. The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species.

Spectroscopic characterization of metal complexes of novel Schiff base. Synthesis, thermal and biological activity studies.

Novel Schiff base (HL) ligand is prepared via condensation of 4-aminoantipyrine and 2-aminobenzoic acid. The ligand is characterized based on elemental analysis, mass, IR and (1)H NMR spectra. Metal complexes are reported and characterized based on elemental analyses, IR, (1)H NMR, solid reflectance, magnetic moment, molar conductance and thermal analyses (TGA, DrTGA and DTA). The molar conductance data reveal that all the metal chelates are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a uninegatively tridentate manner with NNO donor sites of the azomethine N, amino N and deprotonated caroxylic-O. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia Coli, Pseudomonas aeruginosa, Staphylococcus Pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Shciff base ligand against one or more bacterial species.