Rational design of the Z-scheme hollow-structure Co9S8/g-C3N4 as an efficient visible-light photocatalyst for tetracycline degradation.

The development of photocatalysts with high catalytic activity that are capable of full utilization of solar energy is a challenge in the field of photocatalysis. Accordingly, in the present study, an efficient Z-scheme cage-structured Co9S8/g-C3N4 (c-CSCN) photocatalyst was constructed for the degradation of tetracycline antibiotics under visible-light irradiation. The Z-scheme charge-transfer mechanism accelerates the separation of photogenerated charge carriers and effectively improves photocatalytic activity. Moreover, c-CSCN has a hollow structure, allowing light to be reflected multiple times inside the cavity, thereby effectively improving the utilisation efficiency of solar energy. As a result, the photocatalytic activity of c-CSCN is 1.5-, 2.5-, and 5.8-times higher than those of sheet-type Co9S8/g-C3N4 (s-CSCN), c-Co9S8, and g-C3N4, respectively, for the degradation of tetracycline. c-CSCN maintains favourable photocatalytic activity over five consecutive degradation cycles, demonstrating its excellent stability. In addition, c-CSCN performs efficient tetracycline removal in different water substrates. Moreover, c-CSCN exhibits excellent ability to remove tetracycline under direct natural sunlight. This work fully demonstrates that c-CSCN has high catalytic activity and the potential for practical application as a wastewater treatment material.

Novel CoFe2O4@ZnO-CeO2 ternary nanocomposite: Sonochemical green synthesis using Crataegus microphylla extract, characterization and their application in catalytic and antibacterial activities.

In this study, CoFe2O4@ZnO-CeO2 magnetic nanocomposite (CoFe@Zn-Ce MNC) was successfully prepared by facile sonochemical method for the first time. CoFe@Zn-Ce MNC was obtained by green and cost-effective process in the presence of Crataegus microphylla (C. microphylla) fruit extract. Influence of some parameters like capping agents (C. microphylla, SDS and CTAB), sonication time (10, 30 and 60 min) and sonication power (40, 60 and 80 W) were studied to achieve optimum condition. The as-obtained products were characterized by FT-IR, FESEM, TEM, DRS, VSM, EDS, TGA and XRD analysis. Results showed that high magnetic properties (20.38 emug-1), 70-80 nm size and spherical morphology were unique characteristics of synthesized nanocomposite. Antibacterial activity of CoFe@Zn-Ce MNC was examined against E. coli, P. aeruginoss and S. aureus bacteria. Among theme, S. aureus as gram-positive bacteria showed excellent antibacterial activity. Furthermore, photocatalytic performance of the CoFe@Zn-Ce MNC was investigated by degradation of humic acid (HA) molecules under visible and UV light irradiations. The influence of morphology of products and incorporation of cerium oxide with CoFe2O4@ZnO on photocatalytic activity of CoFe2O4@ZnO was performed. After 100 min illumination, the decomposition of HA pollutant by magnetic nanocomposite were 97.2% and 72.4% under exposure of UV and visible light irradiations, respectively. Also, CoFe@Zn-Ce MNC demonstrated high stability in the cycling decomposition experiment after six times cycling runs.

Co3O4 nanoparticles/graphitic carbon nitride heterojunction for photoelectrochemical aptasensor of oxytetracycline.

As a broad-spectrum tetracycline antibiotic, the overuse of oxytetracycline (OTC) causes antibiotics residues in the environment and seriously threats to human health owing to effective antibacterial properties. Thus, it is particularly important to design a photoelectrochemical (PEC) aptasensor to detect OTC with excellent performance. Herein, we developed a selective and stable PEC aptasensor of OTC on the basis of Co3O4 nanoparticles (Co3O4 NPs)/graphitic carbon nitride (g-CN) heterojunction, used as PEC active materials. The Co3O4 NPs were successfully grown on the g-CN via grinding and calcining mixture of Co3O4 precursors and bulk g-CN. The Co3O4/g-CN heterojunction with improved light utilization and promoted electrons/holes separation capability can exhibit higher PEC signal than that of g-CN. In order to implement the purpose of specific recognition, OTC-aptamer was introduced into modified electrode to construct highly selective PEC aptasensor for OTC determination, which can possess wide linear range (0.01-500 nM) with low detection limit (3.5 pM, S/N = 3). This PEC aptasensor platform with excellent selectivity and high stability can provide a practical application in the field of water monitoring.

Synthesis of Co3S4-SnO2/polyvinylpyrrolidone-cellulose heterojunction as highly performance catalyst for photocatalytic and antimicrobial properties under ultra-violet irradiation.

In this work, we present Co3S4-SnO2 supported polyvinylpyrrolidone-cellulose (PVPCS) nano-structure for Lidocaine degradation. The nanostructure was characterized by various techniques i.e. morphological and optical ones. The results have demonstrated that Co3S4-SnO2 nanocomposites were evenly supported on the PVPCS. Moreover, the photocatalysis performances of the catalysts were investigated under ultra-violet (UV) light irradiation. The nano-structure Co3S4-SnO2/PVPCS composite (98.72%) revealed the highest photocatalysis performance as compared to SnO2 nanoparticles, and Co3S4-SnO2 nanocomposites. The photo-stability of nano-structure Co3S4-SnO2/PVPCS composite was characterized using cyclic catalytic experimental. Results demonstrated a substantially stable performance of the nano-structure Co3S4-SnO2/PVPCS composite. The biological properties of Co3S4-SnO2/PVPCS composite were investigated through the antibacterial (versus Staphylococcus aureus, and Escherichia coli) and antifungal studies (Candida albicans). As the results declared, Co3S4-SnO2 nanocomposites have substantial biological properties as compared to SnO2 nanoparticles, and Co3S4-SnO2 nanocomposites.

Photocatalytic degradation of gemifloxacin antibiotic using Zn-Co-LDH@biochar nanocomposite.

The aim of the present study was to investigate the photocatalytic performance of biochar (BC)-incorporated Zn-Co-layered double hydroxide (LDH) nanostructures in gemifloxacin (GMF) degradation as a model pharmaceutical pollutant. The as-prepared Zn-Co-LDH@BC showed high photocatalytic efficiency due to the enhanced separation of photo-generated charge carriers using cobalt hydroxide as well as inhibiting the agglomeration of LDH nanostructures by incorporation of BC. According to the results, 92.7% of GMF was degraded through photocatalysis in the presence of Zn-Co-LDH catalyst. The photocatalytic performance of BC-incorporated Zn-Co-LDH was highly dependent on the solute concentration and photocatalyst dosage. The addition of ethanol caused more inhibiting effect than that of benzoquinone (BQ), indicating the major role of •OH in decomposition of GMF compared to the negligible role of O2•-. A greater enhancement in the photocatalytic degradation of GMF was obtained when the photoreactor containing Zn-Co-LDH@BC nanostructures was oxygenated. Less than 10% drop in the removal efficiency of GMF was observed within five successive operational runs. The results of chemical oxygen demand (COD) analysis indicated the COD removal efficiency of about 80% within 200 min, indicating the acceptable mineralization of GMF. The reaction pathways were also proposed for the photocatalytic conversion of GMF under UV light irradiation.

Photolytic Cleavage of Co-C Bond in Coenzyme B12-Dependent Glutamate Mutase.

Glutamate mutase (GLM) is a coenzyme B12-dependent enzyme that catalyzes the conversion of S-glutamate to (2 S,3 S)-3-methyl aspartate. The initial step in the catalytic process is the homolytic cleavage of the coenzyme's Co-C bond upon binding of a substrate. Alternatively, the Co-C bond can be cleaved using light. To investigate the photolytic cleavage of the Co-C bond in GLM, we applied a combined density functional theory/molecular mechanics (DFT/MM) and time-dependent-DFT/MM method to scrutinize the ground and the low-lying excited states. Potential energy surfaces (PESs) were generated as a function of axial bond lengths to describe the photodissociation mechanism. The S1 PES was characterized as the crossing of two electronic states, metal-to-ligand charge transfer (MLCT), and ligand field (LF). In GLM, radical pairs generate from the LF state. Two pathways, path A and path B, were identified as possible channels to connect the MLCT and LF electronic states. The S1 PES in GLM was compared with the S1 PES for coenzyme B12-dependent ethanolamine ammonia lyase as well as the isolated AdoCbl cofactor. Finally, the theoretical insights related to the photodissociation mechanism were compared with transient absorption spectroscopy, electron paramagnetic resonance, and resonance Raman spectroscopy.

Promoting sun light-induced photocatalytic degradation of toxic phenols by efficient and stable double metal cyanide nanocubes.

Aromatic substituted phenols and their by-products discharged from numerous industries are of environmental concern due to their toxic, carcinogenic, recalcitrant, and bioaccumulating properties. Therefore, their complete removal from waters by low-cost, efficient, environmentally friendly nanomaterial-based treatment techniques is desirable. Double metal cyanide complexes (DMCC) are the extremely useful heterogeneous and recoverable catalyst. Hence, green route has been developed for several DMCC and their photocatalytic efficiency was evaluated for degradation of toxic phenols. Herein, nanocubes for hexacyanocobaltate of iron (FeHCC ~ 200 nm), nickel (NiHCC < 10 nm), and zinc (ZnHCC ~ 500 nm) were synthesized after employing Aegle marmelos. Subsequently, at neutral pH and sunlight irradiation, 15 mg of catalysts were able to degrade the maximum extent of phenols (1 × 10-4 M) in the order: 3-aminophenol (96% ZnHCC > 94% FeHCC > 93% NiHCC) > phenol (94% ZnHCC > 92% FeHCC > 91% NiHCC) > 2,4-DNP (92% ZnHCC > 91% FeHCC > 90% NiHCC). This is attributed to highest basicity of 3-aminophenol containing excess of free electrons. Highest catalytic potential of ZnHCC (Xm = 0.54-0.43 mg/g) is because of its highest surface area and negative zeta potential along with sharp morphology and crystallinity. Adsorption of phenols over catalyst was statistically significant with Langmuir isotherms (R2 ≥ 0.96; p value ≤ 0.05). Small and non-toxic by-products like oxalic acid, benzoquinone, (Z)-hex-3-enedioic acid, (Z)-but-2-enal, and (Z)-4-oxobut-2-enoic acid were identified in GC-MS. Degradation modes involving hydroxylation, oxidative skeletal rearrangement, and ring opening clearly supported enhanced oxidation of phenols by •OH. Overall, due to greater active sites, high surface activity, low band gap, and semiconducting nature, DMCC revealed promising potential for solar photocatalytic remediation of wastewater.

A versatile CeO2/Co3O4 coated mesh for food wastewater treatment: Simultaneous oil removal and UV catalysis of food additives.

Food waste water is one of the most urgent environmental problems for the close connection between food and our daily life. Herein, we use a simple hydrothermal method to prepare a highly efficient catalyst-CeO2/Co3O4 compound on the stainless steel mesh, aiming for food waste water treatment. Possessing the superhydrophilic property and catalytic ability under ultraviolet light, CeO2/Co3O4 coated mesh has successfully processed three representative contaminants in food wastewater, which are soybean oil (food oil), AR (food dye) and VA (food flavor) simultaneously with an one-step filtration. Besides, the mesh is stable in a wide pH range and performs well in reusability. Therefore, such a multifunctional material with simple preparation method, high processing efficiency and facile operation shows a promising prospect for practical production and application for food wastewater treatment.

Solar photochemical and thermochemical splitting of water.

Artificial photosynthesis to carry out both the oxidation and the reduction of water has emerged to be an exciting area of research. It has been possible to photochemically generate oxygen by using a scheme similar to the Z-scheme, by using suitable catalysts in place of water-oxidation catalyst in the Z-scheme in natural photosynthesis. The best oxidation catalysts are found to be Co and Mn oxides with the e(1) g configuration. The more important aspects investigated pertain to the visible-light-induced generation of hydrogen by using semiconductor heterostructures of the type ZnO/Pt/Cd1-xZnxS and dye-sensitized semiconductors. In the case of heterostructures, good yields of H2 have been obtained. Modifications of the heterostructures, wherein Pt is replaced by NiO, and the oxide is substituted with different anions are discussed. MoS2 and MoSe2 in the 1T form yield high quantities of H2 when sensitized by Eosin Y. Two-step thermochemical splitting of H2O using metal oxide redox pairs provides a strategy to produce H2 and CO. Performance of the Ln0.5A0.5MnO3 (Ln = rare earth ion, A = Ca, Sr) family of perovskites is found to be promising in this context. The best results to date are found with Y0.5Sr0.5MnO3.

A Bioinspired Molecular Polyoxometalate Catalyst with Two Cobalt(II) Oxide Cores for Photocatalytic Water Oxidation.

To overcome the bottleneck of water splitting, the exploration of efficient, selective, and stable water oxidation catalysts (WOCs) is crucial. We report an all-inorganic, oxidatively and hydrolytically stable WOC based on a polyoxometalate [(A-α-SiW9 O34)2Co8(OH)6(H2O)2(CO3)3](16-) (Co8 POM). As a cobalt(II)-based cubane water oxidation catalyst, Co8POM embeds double Co(II)4O3 cores. The self-assembled catalyst is similar to the oxygen evolving complex (OEC) of photosystem II (PS II). Using [Ru(bpy)3](2+) as a photosensitizer and persulfate as a sacrificial electron acceptor, Co8POM exhibits excellent water oxidation activity with a turnover number (TON) of 1436, currently the highest among bioinspired catalysts with a cubical core, and a high initial turnover frequency (TOF). Investigation by several spectroscopy, spectrometry, and other techniques confirm that Co8POM is a stable and efficient catalyst for visible light-driven water oxidation. The results offer a useful insight into the design of water oxidation catalysts.

Co(II)-grafted Ag3PO4 photocatalysts with unexpected photocatalytic ability: Enhanced photogenerated charge separation efficiency, photocatalytic mechanism and activity.

Since the photocatalytic capability is determined by the separation and transmission efficiency of photoinduced charges, its improvement remains a challenge for development of efficient photocatalysts. Here, we made large improvement on the surface of Ag3PO4 using Co(II)-grafted Ag3PO4 by a hydrothermal method. During the photocatalytic process, Co(II) was oxidized to Co(III) by the photogenerated holes under visible light radiation, which enhanced the separation efficiency of photogenerated charges. Meanwhile, the Co(III) as-formed could oxidize dye molecules, which recovered the Co(II). The synergy of Co(II) and Ag3PO4 greatly promoted the separation and transmission efficiency of the photogenerated charges, and severely improved the photocatalytic activity of Ag3PO4. The surface grafted Co(II) on Ag3PO4 is responsible for the enhancement of photocatalytic activity.

Adsorption and photocatalytic degradation of 2-CP in wastewater onto CS/CoFe2O 4 nanocomposite synthesized using gamma radiation.

Photocatalytic degradation of 2-chlorophenol (2-CP) was studied using the photocatalyst chitosane/CoFe2O4 nanocomposite (CS/CF) under visible light. CS/CF nanocomposites were synthesized via gamma irradiation cross-linking method with the aid of sonication. Physical characteristics of CS/CF were studied using infrared spectrophotometer (IR), scanning electron microscopy (SEM), transmission electron microscope (TEM) and ultraviolet-visible (UV-vis) spectroscopy. Their photocatalytic activity was tested for the degradation of 2-CP in aqueous medium using sunlight. The effect of different parameters such as catalyst concentration, 2-CP concentration and reaction pH on degradation was also examined. It was verified that the 2-CP degradation rate fits a pseudo-first-order kinetics for initial 2-CP concentrations between 25 and 100mg/l, at 30°C. The degradation kinetics fit well Langmuir-Hinshelwood rate law. The degradation of (2-CP) follows pseudo-first-order kinetics. Results showed that after the catalyst had been used 5 times repeatedly, the degradation rate was still above 80%.

Preparation of cocrystal nanofibres of cobalt octaethylporphyrin and tetracyanoquinodimethane with good photoresponse.

Cocrystal nanofibres of cobalt octaethylporphyrin and tetracyanoquinodimethane were prepared by a facile solution method and fully characterized by SEM, AFM, XRD, Raman, EDX, and UV-vis-NIR. The as-prepared cocrystal nanofibres had smooth surfaces and uniform dimension. When incorporated into prototype devices, they exhibited good photoresponse at ambient conditions. Additionally, the phototransistor characteristics with a maximum I(on)/I(off) ratio of -460 was demonstrated. The facile synthesis and good photoresponse may boost the potential applications of cocrystal-based nanostructures in future miniaturized devices.

Synthesis and characterization of CoFe2O4/polyaniline nanocomposites for electromagnetic interference applications.

The Cobalt ferrite (CoFe2O4) powders were synthesized by Co-precipitation method. The as prepared ferrite powders were incorporated into a polyaniline matrix at various volumetric ratios. The as prepared composites of ferrite and polyaniline powders were characterized using X-ray diffraction (XRD), transmission electron microscope (TEM). The particle size of CoFe2O4 is found to be 20 nm. The saturation magnetization (M(s)) of all the composites was found to be decreasing with decrease of ferrite content, while coercivity (H(c)) remained at the value corresponding to pure cobalt ferrite nanopowders. The complex permittivity (epsilon' and epsilon") and permeability (mu' and mu") of composite samples were measured in the range of 1 MHz to 1.1 GHz. The value of epsilon' and mu' found to be increased with ferrite volume concentration.

Magnetic and ultrasonic studies on stable cobalt ferrite magnetic nanofluid.

Stable cobalt ferrite nanofluids of various concentrations have been prepared through co-precipitation method. Structural and morphological studies of nanoparticles are made with the help of X-ray diffraction technique and Transmission Electron Microscope respectively and it is found that the particles exhibit face centered cubic structure with an average size of 14 nm. The magnetic properties of the nanofluids have been analyzed at room temperature which revealed ferromagnetic behavior and also the very low value of coupling constant which ensures the negligible interparticle interaction in the absence of magnetic field. Ultrasonic investigations have been made for the nanofluids at different temperatures and magnetic fields. The temperature effects are explained with the help of open and close-packed water structure. The inter particle interactions of surface modified CoFe2O4 particles and the cluster formation at higher concentrations are realized through the variations in ultrasonic parameters.

Templated assembly of Co-Pt nanoparticles via thermal and laser-induced dewetting of bilayer metal films.

Templated dewetting of a Co/Pt metal bilayer film on a topographic substrate was used to assemble arrays of Co-Pt alloy nanoparticles, with highly uniform particle size, shape and notably composition compared to nanoparticles formed on an untemplated substrate. Solid-state and liquid-state dewetting processes, using furnace annealing and laser irradiation respectively, were compared. Liquid state dewetting produced more uniform, conformal nanoparticles but they had a polycrystalline disordered fcc structure and relatively low magnetic coercivity. In contrast, solid state dewetting enabled formation of magnetically hard, ordered L1(0) Co-Pt single-crystal particles with coercivity >12 kOe. Furnace annealing converted the nanoparticles formed by liquid state dewetting into the L1(0) phase.

Gamma ray effects on optical properties of CoS nanoparticles.

In this work, cobalt sulfide nanoparticles powder was synthesized in AlMCM-41 molecular sieve by using ion exchange method. The influence of gamma ray-radiation on the structural and optical properties of CoS/AlMCM-41 nanoparticles has been studied. Sample was irradiated by (60)Co and (137)Cs gamma ray source. The sample was characterized by X-ray diffraction (XRD), UV-Vis spectroscopy, scanning electron microscopy (SEM), FT-IR techniques and transmission electron microscopy (TEM). The XRD patterns show that nanoparticles size is increased after gamma radiation. The DRS results show that Co(2+) ions produced after gamma radiation, located in tetrahedral sites in AlMCM-41. The results indicate host materials have important role in decrease of radiation defects (RDs). The gamma ray creates free radicals and forms new bonds in CoSAlMCM-41 sample.

Graded bit patterned magnetic arrays fabricated via angled low-energy He ion irradiation.

A bit patterned magnetic array based on Co/Pd magnetic multilayers with a binary perpendicular magnetic anisotropy distribution was fabricated. The binary anisotropy distribution was attained through angled helium ion irradiation of a bit edge using hydrogen silsesquioxane (HSQ) resist as an ion stopping layer to protect the rest of the bit. The viability of this technique was explored numerically and evaluated through magnetic measurements of the prepared bit patterned magnetic array. The resulting graded bit patterned magnetic array showed a 35% reduction in coercivity and a 9% narrowing of the standard deviation of the switching field.

Large lateral photovoltaic effects in Co/Alq3 granular films on Si substrates.

A series of Co/Alq3 granular films were deposited on silicon substrates using co-evaporation technique. Under the nonuniform illumination of a laser beam, lateral photovoltaic effect (LPE) was observed in the samples, with the optimal open-circuit position sensitivity of 34.7 mV/mm. The insertion of oxide layer results in the decrease of lateral photovoltage (LPV) and the irreversible LPE. The dependence of lateral photovoltaic effect on substrates was also briefly investigated. The possible mechanism was discussed.

Production of 61Cu using natural cobalt target and its separation using ascorbic acid and common anion exchange resin.

(61)Cu was produced by (nat)Co(α, xn)(61)Cu reaction. (61)Cu production yield was 89.5 MBq/µAh (2.42 mCi/µAh) at the end of irradiation (EOI). A simple radiochemical separation method using anion exchange resin and ascorbic acid has been employed to separate the product radionuclide from inactive target material and co-produced non-isotopic impurities. The radiochemical separation yield was about 90%. Radiochemical purity of (61)Cu was >99% 1 h after EOI. Final product was suitable for making complex with N(2)S(2) type of ligands.