A novel CuBi2O4/polyaniline composite as an efficient photocatalyst for ammonia degradation.

A novel polyaniline (PANI) coupled CuBi2O4 photocatalyst was successfully synthesized via in situ polymerization of aniline with pre-synthesized CuBi2O4 composites. The structure and morphology of the synthesized CuBi2O4/PANI composite photocatalyst were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) and the photocatalytic performance were evaluated through degradation process of ammonia in water under visible light irradiation. The resultant CuBi2O4/PANI composite showed exceptional stability as its structure and morphology persisted even after being immersed in water for 2 days. The composite photocatalyst exhibited improved charge transport properties due to the electrical conductivity of the PANI protective layer, leading to enhanced photoelectrochemical activity in water and removal of ammonia. PANI with CuBi2O4 (10% wt) heterostructure was applied for photodegradation of ammonia and exhibited a 96% ammonia removal efficiency (30 mg/l with 0.1 g photocatalyst and 180 min), as compared to PANI (78%) and CuBi2O4 (70%). The degradation was attributed to the efficient charge transfer (e- and h+) and formation of reactive oxygen species upon simulated sunlight exposure. The present work suggests that the CuBi2O4/PANI photocatalyst can be synthesized in a simple process and provides an excellent adsorption capacity, high photocatalytic activity, long term stability, and reusability making it a promising alternative for ammonia removal from wastewater.

Synthesis of Polyaniline Supported CdS/CdS-ZnS/CdS-TiO2 Nanocomposite for Efficient Photocatalytic Applications.

Photocatalytic degradation can be increased by improving photo-generated electrons and broadening the region of light absorption through conductive polymers. In that view, we have synthesized Polyaniline (PANI) with CdS, CdS-ZnS, and CdS-TiO2 nanocomposites using the chemical precipitation method, characterized and verified for the photo-degradation of Acid blue-29 dye. This paper provides a methodical conception about in what way conductive polymers "PANI" enhances the performance rate of composite photocatalysts (CdS, CdS-ZnS and CdS-TiO2). The nanocomposites charge transfer, molar ratio, surface morphology, particle size, diffraction pattern, thermal stability, optical and recombination of photo-generated charge carrier properties were determined. The production of nanocomposites and their efficient photocatalytic capabilities were observed. The mechanism of photocatalysis involved with PC, CZP and CTP nanocomposites are well presented by suitable diagrams representing the exchange of electrons and protons among themselves with supported equations. We discovered that increasing the number of nanocomposites in the membranes boosted both photocatalytic activity and degradation rate. CdS-Zinc-PANI (CZP) and CdS-TiO2-PANI(CTP) nanocomposites show entrapment at the surface defects of Zinc and TiO2 nanoparticles due to the demolition of unfavorable electron kinetics, and by reducing the charge recombination, greater photocatalytic activity than CdS-PANI (CP) with the same nanoparticle loading was achieved. With repeated use, the photocatalysts' efficiency dropped very little, hinting that they may be used to remove organic pollutants from water. The photocatalytic activity of CZP and CTP photocatalytic membranes was greater when compared to CdS-PANI, which may be due to the good compatibility between CdS and Zinc and TiO2, as well efficient charge carrier separation. PANI can also increase the split-up of photo-excited charge carriers and extend the absorption zone when combined with these nanoparticles. As a result, the development of outrageous performance photocatalysts and their potential uses in ecological purification and solar power conversion has been facilitated. The novelty of this article is to present the degradation of AB-29 Dye using nanocomposites with polymers and study the enhanced degradation rate. Few studies have been carried out on polymer nanocomposites and their application in the degradation of AB-29 dyes and remediation of water purposes. Nanoparticle CdS is a very effective photocatalyst, commonly used for water purification along with nanoparticle ZnS and TiO2; but cadmium ion-leaching makes it ineffective for practical and commercial use. In the present work, we have reduced the leaching of hazardous cadmium ions by trapping them in a polyaniline matrix, hence making it suitable for commercial use. We have embedded ZnS and TiO2 along with CdS in a polyaniline matrix and compared their photocatalytic activity, stability, and reusability, proving our nano-composites suitable for commercial purposes with enhanced activities and stabilities, which is a novelty. All synthesized nanocomposites are active within the near-ultraviolet to deep infrared (i.e., 340-850 nm). This gives us full efficiency of the photocatalysts in the sunlight and further proves the commercial utility of our nanocomposites.

Enhanced photocatalytic degradation of Acid Blue dye using CdS/TiO2 nanocomposite.

Photocatalytic degradation is essential for the successful removal of organic contaminants from wastewater, which is important for ecological and environmental safety. The advanced oxidation process of photocatalysis has become a hot topic in recent years for the remediation of water. Cadmium sulphide (CdS) nanostructures doped with Titanium oxide (CdS/TiO2) nanocomposites has manufactured under ambient conditions using a simple and modified Chemical Precipitation technique. The nanocomposites crystal structure, thermal stability, recombination of photo-generated charge carriers, bandgap, surface morphology, particle size, molar ratio, and charge transfer properties are determined. The production of nanocomposites (CdS-TiO2) and their efficient photocatalytic capabilities are observed. The goal of the experiment is to improve the photocatalytic efficiency of TiO2 in the visible region by doping CdS nanocomposites. The results showed that as-prepared CdS-TiO2 nanocomposites has exhibited the highest photocatalytic activity in the process of photocatalytic degradation of AB-29 dye, and its degradation efficiency is 84%. After 1 h 30 min of visible light irradiation, while CdS and TiO2 showed only 68% and 09%, respectively. The observed decolorization rate of AB-29 is also higher in the case of CdS-TiO2 photocatalyst ~ 5.8 × 10-4mol L-1 min-1) as compared to the reported decolorization rate of CdS ~ 4.5 × 10-4mol L-1 min-1 and TiO2 ~ 0.67 × 10-4mol L-1 min-1. This increased photocatalytic effectiveness of CdS-TiO2 has been accomplished by reduced charge carrier recombination as a result of improved charge separation and extension of TiO2 in response to visible light.

Exploring multifunctional behaviour of g-C3N4 decorated BiVO4/Ag2CO3 hierarchical nanocomposite for simultaneous electrochemical detection of two nitroaromatic compounds and water splitting applications.

Development of multifunctional ternary nanocomposite based electrocatalysts for detection of toxic elements and generation of renewable energy describes an environmentally sustainable technique to address the dual challenges of pollution and energy. Herein, we adopted microwave-assisted synthesis to design a multifunctional graphitic carbon nitride (g-C3N4) decorated BiVO4/Ag2CO3 (BVG@C) hierarchical ternary nanocomposite for sensing and water splitting applications. The morphological, structural and elemental characterizations demonstrate the successful decoration of carbon nitride on the composite surface. The electrochemical activity of BVG@C modified glassy carbon electrode reveals excellent redox behaviour towards simultaneous detection of 4-Nitrophenol (4-NP) and 4-Nitroaniline (PNA). The modified electrode shows rapid amperometric current response with high sensitivity of 2.368 µA mM cm-2 and 1.534 mA mM cm-2 and low detection limit of 0.012 µmol L-1and 0.028 µmol L-1, respectively for 4-NP and PNA. Moreover, the modified electrode was further investigated for hydrogen evolution and oxygen evolution reactions and the electrocatalytic results show admirable activity and good stability for oxygen evolution with very low overpotential of 136 mV in alkaline medium. It is worthwhile to mention that the excellent activity of electrocatalyst can be ascribed to the decoration and electronic interaction of g-C3N4 with the BiVO4/Ag2CO3 nanocomposite, increasing its surface area, active sites, charge transfer and decreasing resistance.

Visible light-conducting polymer nanocomposites as efficient photocatalysts for the treatment of organic pollutants in wastewater.

This review compiles recent advances and challenges on photocatalytic treatment of wastewater using nanoparticles, nanocomposites, and polymer nanocomposites as photocatalyst. The review provides an overview of the fundamental principles of photocatalytic treatment along the recent advances on photocatalytic treatment, especially on the modification strategies and operational conditions to enhance treatment efficiency and removal of recalcitrant organic contaminants. The different types of photocatalysts along the key factors influencing their performance are also critically discussed and recommendations for future research are provided.

Nanoremediation technologies for sustainable remediation of contaminated environments: Recent advances and challenges.

A major and growing concern within society is the lack of innovative and effective solutions to mitigate the challenge of environmental pollution. Uncontrolled release of pollutants into the environment as a result of urbanisation and industrialisation is a staggering problem of global concern. Although, the eco-toxicity of nanotechnology is still an issue of debate, however, nanoremediation is a promising emerging technology to tackle environmental contamination, especially dealing with recalcitrant contaminants. Nanoremediation represents an innovative approach for safe and sustainable remediation of persistent organic compounds such as pesticides, chlorinated solvents, brominated or halogenated chemicals, perfluoroalkyl and polyfluoroalkyl substances (PFAS), and heavy metals. This comprehensive review article provides a critical outlook on the recent advances and future perspectives of nanoremediation technologies such as photocatalysis, nano-sensing etc., applied for environmental decontamination. Moreover, sustainability assessment of nanoremediation technologies was taken into consideration for tackling legacy contamination with special focus on health and environmental impacts. The review further outlines the ecological implications of nanotechnology and provides consensus recommendations on the use of nanotechnology for a better present and sustainable future.

Investigation of CNT/PPy-Modified Carbon Paper Electrodes under Anaerobic and Aerobic Conditions for Phenol Bioremediation in Microbial Fuel Cells.

The study presents the comparative bioelectrochemical treatment of phenol in anodic and cathodic compartments of four identical dual chambered microbial fuel cells (MFCs) with bare and multiwalled carbon nanotube/polypyrrole (MWCNT/PPy)-coated electrodes, respectively. It was observed that systems performing biocathodic treatment of phenol performed better as compared to the systems performing bioanodic treatment. The maximum power densities for bioanodic phenol treatment using bare and coated electrodes were found to be 469.038 and 560.719 mW/m2, while for biocathodic treatment, they were observed to be 604.804 and 650.557 mW/m2, respectively. The MFCs performing biocathodic treatment of phenol consistently showed higher chemical oxygen demand removal efficiency, Coulombic efficiency, and power density and indicated the better performance of the biocathodic bare (B-MFC) and coated (C-MFC) MFCs as compared to the bioanodic B-MFC and C-MFC. UV/vis spectrophotometry revealed that the MWCNT/PPy-coated carbon paper worked significantly better in the treatment of phenol with admirable treatment obtained within a week of the experiment as compared to the system with bare carbon paper. Cyclic voltammetry asserted better electrochemical activity of the MFC systems with coated electrodes in the treatment of phenol. The electrochemical impedance spectroscopy data also supported the better performance of biocathodic phenol treatment with lower internal and charge transfer resistances. The scanning electron microscopy images confirmed the active biofilm formation on the electrode surface. The study indicates MFC as a viable option for the treatment of recalcitrant chemical compounds with energy recovery.

Deciphering the effects of temperature on bio-methane generation through anaerobic digestion.

Anaerobic digestion (AD) is a sustainable wastewater treatment technology which facilitates energy, nutrient, and water recovery from organic wastes. The agricultural and industrial wastes are suitable substrates for the AD, as they contain a high level of biodegradable compounds. The aim of this study was to examine the AD of three different concentrations of phenol (100, 200, and 300 mg/L) containing wastewater with and without co-substrate (acetate) at four different temperatures (25, 35, 45, and 55 °C) to produce methane (CH4)-enriched biogas. It was observed that the chemical oxygen demand (COD) and phenol removal efficiencies of up to 76% and 72%, respectively, were achieved. The CH4 generation was found higher in anaerobic batch reactors (ABRs) using acetate as co-substrate, with the highest yield of 189.1 µL CH4 from 500 µL sample injected, obtained using 200 mg/L of phenol at 35 °C. The results revealed that the performance of ABR in terms of degradation efficiency, COD removal, and biogas generation was highest at 35 °C followed by 55, 45, and 25 °C indicating 35 °C to be the optimum temperature for AD of phenolic wastewater with maximum energy recovery. Scanning electron microscopy (SEM) revealed that the morphology of the anaerobic sludge depends greatly on the temperature at which the system is maintained which in turn affects the performance and degradation of toxic contaminants like phenol. It was observed that the anaerobic sludge maintained at 35 °C showed uniform channels leading to higher permeability through enhanced mass transfer to achieve higher degradation rates. However, the denser sludge as in the case of 55 °C showed lesser permeability leading to limited transfer and thus reduced treatment. Quantitative real-time PCR (qPCR) analysis revealed a more noteworthy change in the population of the microbial communities due to temperature than the presence of phenol with the methanogens being the dominating species at 35 °C. The findings suggest that the planned operation of the ABR could be a promising choice for CH4-enriched biogas and COD removal from phenolic wastewater.

Ag2S-Sensitized NiO-ZnO Heterostructures with Enhanced Visible Light Photocatalytic Activity and Acetone Sensing Property.

Visible light-driven Ag2S-grafted NiO-ZnO ternary nanocomposites are synthesized using a facile and cost-effective homogeneous precipitation method. The structural, morphological, and optical properties were extensively studied, confirming the formation of ternary nanocomposites. The surface area of the synthesized nanocomposites was calculated by electrochemical double-layer capacitance (C dl). Ternary Ag2S/NiO-ZnO nanocomposites showed excellent visible light photocatalytic property which increases further with the concentration of Ag2S. The maximum photocatalytic activity was shown by 8% Ag2S/NiO-ZnO with a RhB degradation efficiency of 95%. Hydroxyl and superoxide radicals were found to be dominant species for photodegradation of RhB, confirmed by scavenging experiments. It is noteworthy that the recycling experiments demonstrated high stability and recyclable nature of the photocatalyst. Moreover, the electrochemical results indicated that the prepared nanocomposite exhibits remarkable activity toward detection of acetone. The fabricated nanocomposite sensor showed high sensitivity (4.0764 µA mmol L-1 cm-2) and a lower detection limit (0.06 mmol L-1) for the detection of acetone. The enhanced photocatalytic and the sensing property of Ag2S/NiO-ZnO can be attributed to the synergistic effects of strong visible light absorption, excellent charge separation, and remarkable surface properties.

Zinc oxide-decorated polypyrrole/chitosan bionanocomposites with enhanced photocatalytic, antibacterial and anticancer performance.

A bio-nanocomposite matrix of polypyrrole grafted ZnO/chitosan (Ppy/C/Z) was synthesized via the in situ polymerization of pyrrole with different weight fractions of ZnO. Incorporation of ZnO nanoparticles with polypyrrole enhances the photocatalytic, antibacterial as well as cytotoxic properties of the resultant composite. Characterizations of the synthesized product were performed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermal analysis (TGA and DTA). Surface morphology and particle size were determined by SEM and TEM. The elemental composition of the material was studied by EDX coupled with SEM. Electrochemical surface area was calculated from electrochemical double layer capacitance (EDLC) measurements using cyclic voltammetry. The photocatalytic activity of the composite material was tested by monitoring the degradation of reactive orange-16 (RO-16), Coomassie Brilliant Blue R-250 (CBB-R-250) and Methylene Blue (MB) dyes and the composite was found to be an effective catalyst in the presence of a UV light source. Various scavengers were used to detect the reactive species involved in the photocatalytic process. Furthermore, the stability of the photocatalyst was assessed by recycling experiments. Moreover, the Ppy/C/Z bio-nanocomposite shows potential application with anti-bacterial and anti-cancer activity against Gram-positive and Gram-negative bacterial pathogens and human cancer cell lines (HeLa and MCF-7). The experimental data confirm that the bio-nanocomposite of Ppy/C/Z showed excellent anti-bacterial and anti-cancer activity as compared to a pristine polypyrrole and chitosan formulation (Ppy/C). The apoptosis data with varying concentrations of Ppy/C/Z reveal the remarkable activity against these cancer cell lines.

Effect of co-substrates on biogas production and anaerobic decomposition of pentachlorophenol.

This study aims to examine the effect of different co-substrates on the anaerobic degradation of pentachlorophenol (PCP) with simultaneous production of biogas. Acetate and glucose were added as co-substrates to monitor and compare the methanogenic reaction during PCP degradation. During the experiment, a chemical oxygen demand (COD) removal efficiency of 80% was achieved. Methane (CH4) production was higher in glucose-fed anaerobic reactors with the highest amount of CH4 (303.3µL) produced at 200ppm of PCP. Scanning electron microscopy (SEM) demonstrates the high porous structure of anaerobic sludge with uniform channels confirming better mass transfer and high PCP removal. Quantitative real-time PCR (qPCR) revealed that methanogens were the dominating species while some sulfate reducing bacteria (SRBs) were also found in the reactors. The study shows that strategic operation of the anaerobic reactor can be a feasible option for efficient degradation of complex substrates like PCP along with the production of biogas.

Crystal structure of {6,6'-dihy-droxy-2,2'-[imino-bis-(propane-1,3-diyl-nitrilo-methanylyl-idene)]diphenolato-κ(5) O (1),N,N',N'',O (1')}copper(II).

The title compound, [Cu(C20H23N3O4)], crystallizes in the space group Cc with two independent mol-ecules in the asymmetric unit. The Cu(II) atoms are each coordinated by the penta-dentate Schiff base ligand in a distorted trigonal bipyramidal N3O2 geometry. The equatorial plane is formed by the two phenolic O atoms and the amine N atom, while the axial positions are occupied by the two imine N atoms. In the crystal, the two independent mol-ecules are each connected into a column along the b axis through inter-molecular O-H⋯O hydrogen bonds. The two independent columns are further linked through an N-H⋯O hydrogen bond, forming a double-column structure.

Crystal structure of {2-[({2-[(2-amino-ethyl)amino]-ethyl}imino)-meth-yl]-6-hy-droxy-phenolato-κ(4) N,N',N'',O (1)}(nitrato-κO)copper(II) ethanol 0.25-solvate.

In the crystal structure of the title mononuclear Cu(II) complex, [Cu(C11H16N3O2)(NO3)]·0.25C2H5OH, the complex molecules are linked by N-H⋯O and O-H⋯O hydrogen bonds, forming a dimer with an approximate non-crystallographic twofold rotation axis of symmetry. In the monomeric unit, the Cu(2+) ion exhibits a distorted square-pyramidal configuration, whereby the anionic [HL](-) Schiff base ligand binds in a tetradentate fashion via the O and the three N atoms which all are approximately coplanar. The O atom of a nitrate anion occupies the fifth coordination site, causing the Cu(II) atom to move slightly out of the approximate basal plane toward the bound nitrate group. The structure exhibits disorder of the ethanol solvent mol-ecule.

Bioelectricity Generation and Bioremediation of an Azo-Dye in a Microbial Fuel Cell Coupled Activated Sludge Process.

Simultaneous bioelectricity generation and dye degradation was achieved in the present study by using a combined anaerobic-aerobic process. The anaerobic system was a typical single chambered microbial fuel cell (SMFC) which utilizes acid navy blue r (ANB) dye along with glucose as growth substrate to generate electricity. Four different concentrations of ANB (50, 100, 200 and 400 ppm) were tested in the SMFC and the degradation products were further treated in an activated sludge post treatment process. The dye decolorization followed pseudo first order kinetics while the negative values of the thermodynamic parameter ∆G (change in Gibbs free energy) shows that the reaction proceeds with a net decrease in the free energy of the system. The coulombic efficiency (CE) and power density (PD) attained peak values at 10.36% and 2,236 mW/m2 respectively for 200 ppm of ANB. A further increase in ANB concentrations results in lowering of cell potential (and PD) values owing to microbial inhibition at higher concentrations of toxic substrates. Cyclic voltammetry studies revealed a perfect redox reaction was taking place in the SMFC. The pH, temperature and conductivity remain 7.5-8.0, 27(±2°C and 10.6-18.2 mS/cm throughout the operation. The biodegradation pathway was studied by the gas chromatography coupled with mass spectroscopy technique, suggested the preferential cleavage of the azo bond as the initial step resulting in to aromatic amines. Thus, a combined anaerobic-aerobic process using SMFC coupled with activated sludge process can be a viable option for effective degradation of complex dye substrates along with energy (bioelectricity) recovery.

Degradation pathway, toxicity and kinetics of 2,4,6-trichlorophenol with different co-substrate by aerobic granules in SBR.

The present study deals with cultivation of 2,4,6-trichlorophenol (TCP) degrading aerobic granules in two SBR systems based on glucose and acetate as co-substrate. Biodegradation of TCP containing wastewater starting from 10 to 360 mg L(-1) with more than 90% efficiency was achieved. Sludge volume index decreases as the operation proceeds to stabilize at 35 and 30 mL g(-1) while MLVSS increases from 4 to 6.5 and 6.2 g L(-1) for R1 (with glucose as co-substrate) and R2 (with sodium acetate as co-substrate), respectively. FTIR, GC and GC/MS spectral studies shows that the biodegradation occurred via chlorocatechol pathway and the cleavage may be at ortho-position. Haldane model for inhibitory substrate was applied to the system and it was observed that glucose fed granules have a high specific degradation rate and efficiency than acetate fed granules. Genotoxicity studies shows that effluent coming from SBRs was non-toxic.

Bioremediation of 2-chlorophenol containing wastewater by aerobic granules-kinetics and toxicity.

2-Chlorophenol (2-CP) degrading aerobic granules were cultivated in a sequencing batch reactor (SBR) in presence of glucose. The organic loading rate (OLR) was increased from 6.9 to 9.7 kg COD m(-3)d(-1) (1150-1617 mg L(-1)COD per cycle) during the experiment. The alkalinity (1000 mg L(-1) as CaCO(3)) was maintained throughout the experiment. The specific cell growth rate was found to be 0.013 d(-1). A COD removal efficiency of 94% was achieved after steady state at 8h HRT (hydraulic retention time). FTIR, UV, GC, GC/MS studies confirmed that the biodegradation of 2-CP occurs via chlorocatechol (modified ortho-cleavage) pathway. Biodegradation kinetics followed the Haldane model with kinetic parameters: V(max)=840 mg2-CPgMLVSS(-1)d(-1), K(s)=24.61 mg L(-1), K(i)=315.02 mg L(-1). Abiotic losses of 2-CP due to volatilization and photo degradation by sunlight were less than 3% and the results of genotoxicity showed that the degradation products are eco-friendly.

Biodegradation of phenol by aerobic granulation technology.

High organic load and fluctuation in organic load in terms of total phenols is fed into a SBR of higher height and diameter ratio (H/D 20) and operated at 4 h cycle basis with a volumetric exchange ratio of 50% resulting in a constant HRT of 8 h. Successful cultivation of aerobic granules was achieved. Aerobic granulation technology system withstands the inhibitory effect as well as fluctuation of organic load and a better efficiency as compared to traditional activated sludge process. Maximum phenol concentration of 650 mg l(-1) is treated efficiently in 4 h which is equal to an organic load of 3.9 kg m(-3) d(-1). After granulation the effluent phenol and COD concentrations were 3 mg l(-1) and 41 mg l(-1) respectively. Phenol removal efficiency and COD removal efficiency of 94% and 95% were achieved. Effluent O.D.(600) stabilizes at 0.15 which corresponds to minimum loss of biomass, which is the main advantage of SBR.