Search Results (29)

The use of fibers or fabrics as frameworks for loading photocatalysts is beneficial in solving the problems of photocatalytic nanomaterials, which tend to agglomerate and are difficult to recycle. In this study, Bi₂WO₆/CFb and Bi₂WO₆/Bi₂S₃/CFb photocatalytic fibers rich in oxygen vacancies were prepared using carbon fibers as the framework by the crystal seed attachment method and in situ growth method by using the self-polymerization and strong adhesion properties of dopamine. The results of SEM, TEM and XRD tests showed that Bi₂WO₆ and Bi₂WO₆/Bi₂S₃ nanosheets were uniformly and completely encapsulated on the surface of the carbon fibers. The results of XPS and EPR tests showed that Bi₂WO₆ nanosheets were rich in oxygen vacancies. The PL, transient photocurrent responses and EIS results showed that the introduction of Bi₂S₃ significantly improved the migration efficiency of the photogenerated carriers of Bi₂WO₆/Bi₂S₃/CFb, which effectively hindered the recombination of photogenerated electron–hole pairs. By conducting degradation experiments on p-nitrophenol and analyzing the bandgap structure, it was postulated that the heterojunction structure of Bi₂WO₆/Bi₂S₃/CFb in the Bi₂WO₆/Bi₂S₃ material was not Type-II but Z-scheme. As analyzed by the active species assay, the active species that played a major role in the degradation process were O₂⁻ and h⁺. The incorporation of a small amount of Bi₂S₃ resulted in enhanced photocatalytic degradation activity of Bi₂WO₆/Bi₂S₃/CFb toward tetracycline hydrochloride compared to Bi₂WO₆/CFb. The excellent photocatalytic performance of Bi₂WO₆/Bi₂S₃/CFb photocatalytic fibers can be attributed to the rapid transmission and separation performance and the high oxidation and reduction capacities of photogenerated electron–hole pairs formed by direct Z-scheme heterojunctions. Full article

Zinc oxide nanoparticles (ZnO NPs) were synthesized using a simple and eco-friendly precipitation method, employing a capping agent derived from chia seeds (Salvia hispanica). X-ray diffraction (XRD) analysis confirmed the formation of ZnO with a hexagonal crystal structure and an average crystallite size of less than 30 nm. Scanning electron microscopy (SEM) revealed distinct quasi-spherical and nanorod-like morphologies, while energy-dispersive X-ray spectroscopy (EDX) verified the presence of zinc and oxygen. Diffuse reflectance spectroscopy (DRS) indicated significant activity in the UV region, with the nanoparticles exhibiting a band gap of 3.25 eV. The photocatalytic efficiency of the synthesized ZnO NPs was evaluated through their ability to degrade diclofenac sodium (DCF) and para-nitrophenol (4-nitrophenol, PNP) under UV-LED irradiation, achieving pollutant removal rates exceeding 98%. The degradation mechanism is clarified by a detailed characterization of the reaction intermediates. These findings highlight the potential of ZnO NPs synthesized from chia seed extract for effective environmental remediation of pharmaceutical and organic pollutants. Full article

Octahedral nickel(II) complexes are among the simplest systems that exhibit zero-field splitting by having two unpaired electrons. For the purpose of clarifying the relationship between structure and zero-field splitting in a low-symmetric system, distorted octahedral nickel(II) complexes were prepared with a tetradentate ligand, 2-[bis(2-methoxyethyl)aminomethyl]-4-nitrophenolate(1−) [(onp)⁻]. The complex [Ni(onp)(dmso)(H₂O)][BPh₄]·2dmso (1) (dmso = dimethyl sulfoxide) was characterized as a bulk sample by IR, elemental analysis, mass spectrometry, electronic spectra, and magnetic properties. The powder electronic spectral data were analyzed based on the angular overlap model to conclude that the spectra were typical of D₄-symmetric octahedral coordination geometry with a weak axial ligand field. Simultaneous analysis of the temperature-dependent susceptibility and field-dependent magnetization data yielded the positive axial zero-field splitting parameter D (H = g_uβS_uH_u + D[S_z² − S(S + 1)/3]), which was consistent with the weak axial ligand field. Single-crystal X-ray analysis revealed the crystal structures of [Ni(onp)(dmso)(H₂O)][BPh₄]·dmso (2) and [Ni(onp)(dmf)₂][BPh₄] (3) (dmf = N,N-dimethylformamide). The density functional theory (DFT) computations based on the crystal structures indicated the D₄-symmetric octahedral coordination geometries with weak axial ligand fields. This study also showed the importance of considering g-anisotropy in magnetic analysis, even if g-anisotropy is small. Full article

This work is focused on the application of lanthanide-free perovskite Ba_1−xSr_xTiO₃ (0 < x < 1) in valorization of toxic pollutants as 4-nitrophenol (4-NPh). The series of perovskites were fabricated by facile, one-step solid-state preparation method and characterized via various techniques: elemental analysis (Inductively Coupled Plasma Optical Emission Spectrometry, ICP-OES), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR) and dielectric properties (impedance spectroscopy, IS). The methods confirmed the assumed composition, structure and high purity of the materials. The results showed that substitution of Ba²⁺ by Sr²⁺ in the perovskite crystal lattice influenced the dielectric properties of samples and the size of the grains. The absorption and catalytic properties of Ba_(1−x)Sr_xTiO₃ (0 < x < 1) series were evaluated in reduction of 4-NPh in water using NaBH₄ as reducing agent. No adsorption of 4-NPh was found for all the materials during 180 min of contact (experiment without reducing agent), and the best catalytic performance was found for the Ba_(1−x)Sr_xTiO₃ (x = 0.3) sample. The catalytic transformation of 4-NPh to 4-APh follows a pseudo-first-order model, and the catalysts can be easily regenerated via mild annealing (300 °C). Full article

The water pollution caused by the release of organic pollutants has attracted remarkable attention, and solutions for wastewater treatment are being developed. In particular, the photocatalytic removal of organic pollutants in water systems is a promising strategy to realize the self-cleaning of ecosystems under solar light irradiation. However, at present the semiconductor-based nanocatalysts can barely satisfy the industrial requirements because their wide bandgaps restrict the effective absorption of solar light, which needs an energy band modification to boost the visible light harvesting via surface engineering. As an innovative approach, pulsed laser heating in liquids has been utilized to fabricate the nanomaterials in catalysis; it demonstrates multi-controllable features, such as size, morphology, crystal structure, and even optical or electrical properties, with which photocatalytic performances can be precisely optimized. In this review, focusing on the powerful heating effect of pulsed laser irradiation in liquids, the functional nanomaterials fabricated by laser technology and their applications in the catalytic degradation of various organic pollutants are summarized. This review not only highlights the innovative works of pulsed laser-prepared nanomaterials for organic pollutant removal in water systems, such as the photocatalytic degradation of organic dyes and the catalytic reduction of toxic nitrophenol and nitrobenzene, it also critically discusses the specific challenges and outlooks of this field, including the weakness of the produced yields and the relevant automatic strategies for massive production. Full article

In this article, we discuss the preparation of organic 2-chloro-5 nitroaniline (2C5NA) crystals and their different kinds of physical, chemical, and mechanical properties. The vertical Bridgman approach was used to effectively produce the bulk organic 2C5NA crystal. To produce a good-quality bulk crystal, the shape, dimensions, and cone angle of the ampoule were optimized. Also, the temperature profile was set for the 2C5NA crystal. The growth atmosphere and the lowering rate were identified to obtain a homogeneous mixture of the compounds and initiate the nucleation process. Single-crystal X-ray diffraction (XRD), powder XRD, proton Fourier transform nuclear magnetic resonance (FT-NMR), and Fourier transform infrared investigations were used to confirm the crystal structure, molecular structure, and presence of functional groups in the formed crystal. The formed crystal has a monoclinic crystal structure with the space group P21/c, according to single-crystal XRD analysis. The thermal stability and kinetic parameters were examined using thermogravimetric analysis and differential thermal curves. From dielectric analysis, the electrical conductivity and dielectric behavior of 2C5NA were investigated with variations in frequency and temperature. The organic 2-chloro-5-nitroaniline crystal demonstrates that the indentation size effect is observed in the Vickers micro-hardness test, which was also carried out. Full article

The 1:1 cocrystal of 4-nitrophenol (NP) and 2,1,3-benzoselenadiazole (BSA) was successfully synthesized. The X-ray single-crystal diffraction analysis revealed that the structure contained a [Se–N]₂ cyclic supramolecular synthon. The synthons were connected into a one-dimensional ribbon by O–H···N hydrogen bonds and N–Se···O chalcogen bonds. Furthermore, adjacent ribbons were stabilized by the π···π stacking interactions between two 2,1,3-benzoselenadiazole molecules, leading to the formation of a two-dimensional network. Full article

Nitrogen-rich porous organic polymers were fabricated through a nonreversible ring-opening reaction from polyamines and polyepoxides (PAEs). The epoxide groups reacted with both primary and secondary amines provided by the polyamines at different epoxide/amine ratios with polyethylene glycol as the solvent to form the porous materials. Fourier-transform infrared spectroscopy confirmed the occurrence of ring opening between the polyamines and polyepoxides. The porous structure of the materials was confirmed through N₂ adsorption–desorption data and scanning electron microscopy images. The polymers were found to possess both crystalline and noncrystalline structures, as evidenced by X-ray diffraction and high-resolution transmission electron microscopy (HR-TEM) results. The HR-TEM images revealed a thin, sheet-like layered structure with ordered orientations, and the lattice fringe spacing measured from these images was consistent with the interlayer of the PAEs. Additionally, the selected area electron diffraction pattern indicated that the PAEs contained a hexagonal crystal structure. The Pd catalyst was fabricated in situ onto the PAEs support by the NaBH₄ reduction of the Au precursor, and the size of the nano-Pd was about 6.9 nm. The high nitrogen content of the polymer backbone combined with Pd noble nanometals resulted in excellent catalytic performance in the reduction of 4-nitrophenol to 4-aminophenol. Full article

Nanomaterial-based catalytic conversion of hazardous organic pollutants into benign substances is one of the green methods employed for wastewater treatment. This study demonstrates the fabrication of (rGO-ZnO)/CuO nanocomposites (NCs) via a microwave (MW)-assisted method for (photo)catalytic application. The crystal structure, optical, morphological, and electrochemical characteristics were examined using X-ray diffraction (XRD), spectroscopic, microscopic, and electrochemical techniques. The analysis indicated that rod-like (rGO-ZnO)/CuO NCs having a nanoscale diameter with enhanced light absorption and well-matched band positions between rGO-ZnO and CuO were formed. Furthermore, the catalytic reduction of 4-nitrophenol (4-NP) and photocatalytic degradation of methylene blue (MB) tests showed remarkable results with rate constants of 0.468 min⁻¹ for 4-NP reduction within 8 min and 0.02213 min⁻¹ for MB degradation within 105 min. Thus, the artful decoration of ZnO nanorods (NRs) with CuO into the (rGO-ZnO)/CuO NCs interface is an effective strategy for fabricating highly efficient photocatalysts. Full article

Salicylic acid decarboxylase (SDC) from the amidohydrolase superfamily (AHS) catalyzes the reversible decarboxylation of salicylic acid to form phenol. In this study, the substrate binding mode and reaction mechanism of SDC were investigated using computational and crystallographic methods. Quantum chemical calculations show that the enzyme follows the general mechanism of AHS decarboxylases. Namely, the reaction begins with proton transfer from a metal-coordinated aspartic acid residue (Asp298 in SDC) to the C1 of salicylic acid, which is followed by the C–C bond cleavage, to generate the phenol product and release CO₂. Interestingly, the calculations show that SDC is a Mg-dependent enzyme rather than the previously proposed Zn-dependent, and the substrate is shown to be bidentately coordinated to the metal center in the catalysis, which is also different from the previous proposal. These predictions are corroborated by the crystal structure of SDC solved in complex with the substrate analogue 2-nitrophenol. The mechanistic insights into SDC in the present study provide important information for the rational design of the enzyme. Full article

Two new luminescent metal-organic frameworks (MOFs), namely [Cd₄(TFBA)₃(H₂O)₄]_n (CdMOF-1) and [Cd(TFBA) (bipy)]_n (CdMOF-2) (H₃TFBA = tris(3′-F-4′-carboxybiphenyl)amine, 4,4′-bipy = 4,4’-bipyridine), have been prepared and successfully constructed via solvothermal conditions. Single-crystal structure analysis reveals that CdMOF-1 are two-dimensional network containing [Cd₄O₂₆] units. CdMOF-2 shows a non-interpenetration 3D microporous structure with a hexagon pore of 24.6 × 25.9 Å. Notably, CdMOF-2 exhibits turn off fluorescence behavior towards picric acid (TNP) and 4-Nitrophenol (PNP) with a limit of detection (LOD) value of 9.2 × 10⁻⁶ M and 1.81 × 10⁻⁵ M, respectively. Furthermore, CdMOF-2 shows obvious turn-on luminescence responses toward acetylacetone (Acac) with luminescence red-shift and a detection limit of 19.40 ppm. Additionally, the possible quenching or enhancing mechanism during the sensing process were evaluated by PXRD, UV-vis, and luminescence decay lifetime. Full article

Silver (Ag) containing nanomaterials were successfully prepared by varying synthesis conditions to understand the influence of preparation conditions on the physicochemical and photocatalytic properties of these materials. Different analytical techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Diffuse reflectance UV-vis spectra (DR UV-vis), X-ray photoelectron spectroscopy (XPS) measurements, and N₂-physisorption were used to investigate the physicochemical properties of synthesized Ag containing nanomaterials. The samples (Ag-1 and Ag-2) prepared using AgNO₃, NaHCO₃, and polyvinylpyrrolidone (PVP) template exhibited pure Ag metal nanorods and nanoparticles; the morphology of Ag metal is influenced by the hydrothermal treatment. The Ag-3 sample prepared without PVP template and calcined at 250 °C showed the presence of a pure Ag₂O phase. However, the same sample dried at 50 °C (Ag-4) showed the presence of a pure Ag₂CO₃ phase. Interestingly, subjecting the sample to hydrothermal treatment (Ag-5) has not resulted in any change in crystal structure, but particle size was increased. All the synthesized Ag containing nanomaterials were used as photocatalysts for p-nitrophenol (p-NP) degradation under visible light irradiation. The Ag-4 sample (pure Ag₂CO₃ with small crystallite size) exhibited high photocatalytic activity (86% efficiency at pH 10, p-NP concentration of 16 mg L⁻¹, 120 min and catalyst mass of 100 mg) compared to the other synthesized Ag containing nanomaterials. The high photocatalytic activity of the Ag-4 sample is possibly due to the presence of a pure Ag₂CO₃ crystal structure with nanorod morphology with a low band gap energy of 1.96 eV and relative high surface area. Full article

We report on the design, synthesis, and characterization of the first silver hydride clusters solely protected and stabilized by dithiophosphonate ligands and their application for the in situ generation of silver nanoparticles towards the catalytic reduction of 4-nitrophenol in an aqueous system. The synthesis of the silver monohydride cluster involves the incorporation of an interstitial hydride using sodium borohydride. Poly-nuclear magnetic resonance and mass spectrometry were used to establish the structural properties. The structural properties were then confirmed with a single-crystal X-ray diffraction analysis, which showed a distorted tetracapped tetrahedron core with one hydride ion encapsulated within the core of the silver framework. Additionally, the synthesized heptanuclear silver hydride was utilized as a precursor for the in situ generation of silver nanoparticles, which simultaneously catalyzed the reduction of 4-nitrophenol. The mechanism of the catalytic activity was investigated by first synthesizing AgNPs, which was subsequently used as a catalyst. The kinetic study showed that the pseudo-first constant obtained using the cluster (2.43 × 10⁻² s⁻¹) was higher than that obtained using the synthesized AgNPs (2.43 × 10⁻² s⁻¹). This indicated that the silver monohydride cluster was more active owing to the release of the encapsulated hydride ion and greater reaction surface prior to aggregation. Full article

Metal–Organic Frameworks (MOFs) can be a good alternative to conventional catalysts because they are non-toxic and can be selective without compromising efficiency. Nano MOFs such as UiO-66 have proven themselves to be competitive in the catalytic family. In this study, we report the excellent catalytic behavior of UiO-66 MOF in the reduction of a model reaction: 4-Nitrophenol (4-NP) to 4-Aminophenol (4-AP) over MOF-5 (Zn-BDC) and MIL-101 (Fe-BDC). Nano UiO-66 crystals were synthesized by a hydrothermal process and characterized by Powder X-ray Diffraction, Diffused Reflectance UV-Vis spectroscopy, Scanning Electron Microscopy, and Transmission Electron Microscopy. The catalysts’ performance during the hydrogenation reduction reaction from 4-NP to 4-AP was investigated in the presence of a reducer, NaBH₄. The UiO-66 nano crystals exhibited excellent catalytic behavior owing to its large surface area and Lewis acidic nature at the metal nodes. Furthermore, UiO-66 showed excellent recyclability behavior, verified during repeated consecutive use in a sequence. The catalyst yielded similar catalytic behavior during the reduction of nitrophenols at each cycle, which is a novel finding. Full article

Herein, we report a facile synthesis of ethyl-2-(4-aminophenoxy)acetate 4 as a building synthon for novel dual hypoglycemic agents. This building template was synthesized by alkylation of 4-nitrophenol with ethyl bromo-acetate followed by selective reduction of the nitro group. This reduction methoddoes not require nascent hydrogen or any reaction complexity; it goes easily via consecutive reaction in NH₄Cl/Fe to yield our target synthon as very pure crystals. This product was characterized by ¹HNMR, ¹³CNMR, COSY, NOESY NMR spectroscopy, and elemental analysis. Additionally, its structure was studied and approved by X-ray single crystal structure determination. The unit cell parameters are a = 8.2104(6)Å, b = 10.3625(9)Å, c = 11.9562(9)Å, α = 101.787(7), β = 91.849(6), and γ = 102.755(7)°, indicating that 4 was crystallized in the triclinic crystal system. The cooperative non-covalent interactions are also discussed with the aid of Hirshfeld surface analysis. The H…H, H…C, and O…H interactions have a major contribution in the molecular packing of 4. Moreover, different quantum chemical parameters were computed and discussed based on DFT calculations. The experimental UV/Vis spectra showed two bands at 299 and 234 nm, which were calculated using the TD-DFT method at 286 (f = 0.068) and 226 nm (f = 0.294), respectively. These bands were assigned to HOMO→LUMO (95%) and HOMO→LUMO+2 (86%) transitions, respectively. Full article