M. Muneer

Titanium dioxide mediated photocatalytic degradation of 1,2-diethyl phthalate

Abstract The photocatalyzed degradation of 1,2-diethyl phthalate (DEP) in aqueous suspensions of titanium dioxide has been investigated under a variety of conditions employing a pH-stat technique. The degradation was studied by monitoring the change in substrate concentration employing HPLC analysis and by the decrease in the total organic carbon (TOC) content as a function of irradiation time. The depletion of DEP and TOC was studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO 2 as the photocatalyst and in the presence of several electron acceptors (H 2 O 2 , KBrO 3 and (NH 4 ) 2 S 2 O 8 ) in addition to molecular oxygen. Highest degradation rates were observed with Degussa P25 being the photocatalyst at pH 6, while with Sachtleben Hombikat UV 100 smaller decomposition rates were obtained. The degradation of DEP was found to be only slightly enhanced by the addition of electron acceptors, whereas the mineralization is markedly improved in the presence of bromate ions. The degradation products were analyzed by GC–MS technique and probable pathways for the formation of products are proposed.

Semiconductor-mediated photocatalysed degradation of two selected priority organic pollutants, benzidine and 1,2-diphenylhydrazine, in aqueous suspension

The photocatalysed degradation of two selected priority organic pollutants, namely benzidine (1) and 1,2-diphenylhydrazine (DPH, 2) has been investigated in aqueous suspensions of titanium dioxide (TiO2) under a variety of conditions employing a pH-stat technique. The degradation was studied by monitoring the change in substrate concentration of the model compound employing HPLC analysis and the decrease in total organic carbon content, respectively, as a function of irradiation time. The degradation kinetics were studied under different conditions such as reaction pH, substrate and photocatalyst concentration, type of TiO2 photocatalyst and the presence of alternative additives such as H2O2, KBrO3 and (NH4)2S2O8 besides molecular oxygen. The degradation rates and the photonic efficiencies were found to be strongly influenced by the above parameters. Toxicity tests for the irradiated samples of benzidine measuring the luminescence of bacteria Vibrio fischeri after 30 min of incubation were also performed. 4-amino-biphenyl (7) and hydroquinone (13) were identified as intermediate products by GC/MS technique and probable pathways for the formation of the products are proposed.

Synthesis, characterization, antimicrobial activity and applications of polyanilineTi(IV)arsenophosphate adsorbent for the analysis of organic and inorganic pollutants

A novel polyaniline based composite cation exchange material has been synthesized by simple chemical route and characterized on the basis of sophisticated techniques. XRD and SEM analyses reveal the amorphous morphology of the material. The partition coefficient studies of different metal ions on the material were performed in DMW and diverse concentrations of HClO4 solutions. On the basis of high Kd values some significant separations of heavy toxic metal ions were achieved from synthetic mixtures as well as tap water samples by using columns of this exchanger. For the optimum adsorption of dye on the material, the effect of various parameters along with Langmuir and Freundlich adsorption isotherm were examined. The observed result of conducting measurement indicates that the material covers semiconductor range. The photochemical degradation of industrial dyes and antimicrobial activity were also investigated which show significant results than some of the known antibiotics. On the basis of good ion exchange capacity along with photochemical degradation and microbial activity, polyanilineTi(IV)arsenophosphate can be considered as an excellent conducting material for the treatment metal ions and degradation of organic pollutants.

Heterogeneous Photocatalytic Degradation of Picloram, Dicamba, and Floumeturon in Aqueous Suspensions of Titanium Dioxide

Abstract Heterogeneous photocatalytic degradation of three-selected herbicide derivatives: (1) picloram (4-Amino-3,5,6-trichloropyridine-2-carboxylic acid, (2) dicamba (2-Methoxy-3,6-dichlorobenzoic acid, and (3) floumeturon (N,N-Dimethyl-N-[3-(trifluoromethyl)phenyl]-urea) has been investigated in aqueous suspensions of titanium dioxide under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic technique and decrease in total organic carbon (TOC) content as a function of irradiation time under a variety of conditions. The degradation of the herbicide was studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO2, and in the presence of electron acceptors such as hydrogen peroxide (H2O2), potassium bromate (KBrO3), and ammonium persulphate (NH4)2S2O8 besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with other photocatalysts in the case of dicamba (2) and floumeturon (3), whereas Hombikat UV100 was found to be better for the degradation of picloram (1). The herbicide picloram (1) was found to degrade faster as compared to dicamba (2) and floumeturon (3). The degradation products were analyzed by gas chromatography–mass spectrometry (GC/MS) technique, and plausible mechanisms for the formation of products have been proposed.

Photocatalysed degradation of a herbicide derivative, bromacil, in aqueous suspensions of titanium dioxide

The photocatalysed degradation of a herbicide, 5-bromo-3-sec-butyl-6-methyl uracil (bromacil, 1) has been investigated in aqueous suspensions of titanium dioxide under a variety of conditions. The degradation was studied by monitoring the depletion in total organic carbon (TOC) content as a function of irradiation time. The degradation kinetics of the model compound was studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO2 and in the presence of electron acceptors such as hydrogen peroxide (H2O2) and potassium bromate (KBrO3) besides molecular oxygen. The degradation rate was found to be strongly influenced by all the above factors. Higher degradation rate was observed with Degussa P25 as compared with other photocatalysts. The addition of bromate ion has been found to enhance the degradation rate markedly. 5-Hydroxy-3-sec-butyl-6-methyl uracil (2) and diisopropyl urea (16) were identified as the degradation products by GC-MS analysis and probable pathways for the formation of the products have been proposed.

Photocatalytic degradation of dimethyl terephthalate in aqueous suspensions of titanium dioxide

The photocatalytic degradation of dimethyl terephthalate (DMT, 1) has been investigated in aqueous suspensions of titanium dioxide (TiO2) by monitoring the depletion of Total Organic Carbon (TOC) content as a function of irradiation time under a variety of conditions. The degradation kinetics were studied using different parameters such as pH, substrate and photocatalyst concentration, a different kind of titanium dioxide and the presence of electron acceptors such as H2O2, KBrO3 and (NH4)2S2O8 in addition to molecular oxygen. The photocatalytic activity was better for Degussa P25 as compared to the other photocatalysts. From the obtained kinetic data a detailed account of the influence of various parameters on the degradation rate for the mineralization of the compound is given. The degradation products were analyzed using the GC/MS technique and probable pathways for the formation of different products have been proposed.

Semiconductor Mediated Photocatalysed Degradation of a Pesticide Derivative, Acephate in Aqueous Suspensions of Titanium Dioxide

Abstract The photocatalysed degradation of a pesticide derivative, acetylphosphoramidothioic acid O,S-dimethyl ester, (Acephate, 1) has been investigated in aqueous suspensions of titanium dioxide (TiO2) by monitoring the depletion in total organic carbon (TOC) content as a function of irradiation time under a variety of conditions. The degradation kinetics were studied using different parameters such as pH, substrate and photocatalyst concentration, different kind of titanium dioxide and in the presence of electron acceptors such as H2O2 and KBrO3 besides molecular oxygen. The photocatalytic activity was found to be better for Degussa P25 as compared to other photocatalysts. From the obtained data a detailed account of the influence of various parameters on the mineralization rate have been discussed. The degradation products were analyzed by GC/MS technique and the probable pathways for the formation of different products have been proposed.

Titanium-dioxide-mediated photocatalysis reaction of three selected pesticide derivatives

The photocatalysis reaction of three selected pesticide derivatives, namely methoxychlor (1), chlorothalonil (2) and disulfoton (3), has been investigated in an acetonitrile/water mixture in the presence of titanium dioxide and oxygen. The change as a function of irradiation time has been monitored using the UV spectroscopic analysis technique. An attempt has been made to identify the product formed during the photooxidation process through GC/MS analysis technique. The photolysis of methoxychlor (1) led to the formation of methoxychlor olefin (4) and 4,4′-dimethoxybenzophenone (9), whereas chlorothalonil (2) gave rise to 2,3,4,5-tetrachlorophenol (17) as the only product. On the other hand, the photolysis of disulfoton (3) under analogous conditions gave disulfoton sulfoxide (25) and phosphorodithioic acid (21). All the products have been identified by comparing the molecular ion and mass fragmentation peaks of the products with those reported in the library. A probable mechanism for the formation of the products has been proposed.

Development of PANI/MWCNTs decorated with cobalt oxide nanoparticles towards multiple electrochemical, photocatalytic and biomedical application sites

In the present work, a ternary nanocomposite of Co3O4doped/PANI/MWCNTs (cobalt oxide-doped polyaniline multi-walled carbon nanotubes) was synthesized via the in situ oxidative polymerization of aniline. The composite was fully characterized using instrumental analysis, and further tested for its potential in electrochemical, photocatalytic and biomedical applications. The Co oxide nanoparticles were first synthesized using the sol–gel approach in the presence of starch as a capping agent so as to prevent agglomeration and characterized using Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), EDX, elemental mapping and high-resolution transmission electron microscopy (HRTEM). For the measurement of electrochemical activity, the electrodes were synthesized with MWCNTs and functionalized with a conducting polymer (PANI). For the composite, the Co metal oxide provides a pseudo-capacitance which, in general, improves the performance characteristics of the electrode and has been the focus of many researchers. Further, the specific capacitance of the prepared composite was tested using cyclic voltammetry (CV) and impedance spectroscopy. The capacitive studies reveal that the composite has a synergistic effect and is observed to have the highest specific capacitance of 382 F g−1 run at a scan rate of 10 mV s−1. The composite was also found to have excellent photocatalytic degradation properties and outstanding antibacterial activity against both Gram positive and Gram negative bacterial strains. The minimum MIC (6.25 μg mL−1) and MBC (12.5 μg mL−1) values against E. coli and maximum values against B. amyloliquefaciens (25 and 50 μg mL−1) at fourth dilution were observed. Furthermore, the anticancer efficiency of the composite was tested by making use of two different cancer cell types (MCF-7 and MDA-MB-231) confirming the importance of its biological activity for biomedical applications.

Photocatalytic Degradation of Organic Pollutants: Mechanisms and Kinetics

A wide variety of organic pollutants are introduced into the water system from various sources such as industrial effluents, agricultural runoff and chemical spills (Muszkat et al., 1994; Cohen et al., 1986). Their toxicity, stability to natural decomposition and persistence in the environment has been the cause of much concern to the societies and regulation authorities around the world (Dowd et al., 1998). Development of appropriate methods for the degradation of contaminated drinking, ground, surface waters, wastewaters containing toxic or nonbiodegradable compounds is necessary. Among many processes proposed and/or being developed for the destruction of the organic contaminants, biodegradation has received the greatest attention. However, many organic chemicals, especially which are toxic or refractory, are not amendable to microbial degradation. Researcher showed their interest and started the intensive studies on heterogeneous photocatalysis, after the discovery of the photo-induced splitting of water on TiO2 electrodes (Fujishima and Honda, 1972). Semiconductor particles have been found to act as heterogeneous photocatalysts in a number of environmentally important reactions (Blake, 2001; Pirkanniemi, & Sillanpaa, 2002; Gaya & Abdullah, 2008). Materials such as colloidal TiO2 and CdS have been found to be efficient in laboratory-scale pollution abatement systems (Barni et al., 1995; Bellobono et al., 1994; Legrini et al., 1993; Mills & Hunte, 1997; Halmann, 1996), reducing both organic [e.g. halogenocarbons (Gupta & Tanaka, 1995; Martin et al., 1994; Read et al., 1996;), benzene derivatives (Blanco et al., 1996; Mao et al., 1996) detergents (Rao & Dube, 1996), PCB’s (Huang et al., 1996), pesticides (Gianturco et al., 1997; Minero et al., 1996; Lobedank et al., 1997; Haque & Muneer 2003; Muneer & Bahnemann, 2002), explosives (Schmelling et al., 1996), dyes (Vinodgopal et al., 1996), cyanobacterial toxins (Liu et al., 2002)] and inorganic [e.g. N2 (Ranjit et al., 1996), NO3and NO2(Mills et al., 1994; Ranjit et al., 1995; Kosanic & Topalov, 1990; Pollema et al., 1992), cyanides (Mihaylov et al., 1993; Frank & Bard 1977), thiocyanates (Draper & Fox, 1990), cyanates (Bravo et al., 1994), bromates (Mills et al., 1996) etc.] pollutants/impurities to harmless species. Semiconductor photocatalysts have been shown to be useful as carbon dioxide (Irvine et al., 1990) and nitrogen (Khan & Rao, 1991) fixatives and for the decomposition of O3 (Ohtani et al., 1992), destruction of microorganisms such as bacteria (Matsunaga & Okochi, 1995; Zhang et al., 1994; Dunlop et al.,