Shihabudheen M. Maliyekkal

Reduced graphene oxide–metal/metal oxide composites: Facile synthesis and application in water purification

This paper describes a versatile, and simple synthetic route for the preparation of a range of reduced graphene oxide (RGO)-metal/metal oxide composites and their application in water purification. The inherent reduction ability of RGO has been utilized to produce the composite structure from the respective precursor ions. Various spectroscopic and microscopic techniques were employed to characterize the as-synthesized composites. The data reveal that the RGO-composites are formed through a redox-like reaction between RGO and the metal precursor. RGO is progressively oxidized primarily to graphene oxide (GO) and the formed metal nanoparticles are anchored onto the carbon sheets. Metal ion scavenging applications of RGO-MnO(2) and RGO-Ag were demonstrated by taking Hg(II) as the model pollutant. RGO and the composites give a high distribution coefficient (K(d)), greater than 10 L g(-1) for Hg(II) uptake. The K(d) values for the composites are found to be about an order of magnitude higher compared to parent RGO and GO for this application. A methodology was developed to immobilize RGO-composites on river sand (RS) using chitosan as the binder. The as-supported composites are found to be efficient adsorbent candidates for field application.

Graphene from Sugar and its Application in Water Purification

This paper describes a green method for the synthesis of graphenic material from cane sugar, a common disaccharide. A suitable methodology was introduced to immobilize this material on sand without the need of any binder, resulting in a composite, referred to as graphene sand composite (GSC). Raman spectroscopy confirmed that the material is indeed graphenic in nature, having G and D bands at 1597 and 1338 cm(-1), respectively. It effectively removes contaminants from water. Here, we use rhodamine 6G (R6G) as a model dye and chloropyrifos (CP) as a model pesticide to demonstrate this application. The spectroscopic and microscopic analyses coupled with adsorption experiments revealed that physical adsorption plays a dominant role in the adsorption process. Isotherm data in batch experiments show an adsorption capacity of 55 mg/g for R6G and 48 mg/g for CP, which are superior to that of activated carbon. The adsorbent can be easily regenerated using a suitable eluent. This quick and cost-effective technique for the into a commercial water filter with appropriate engineering.

A novel cellulose-manganese oxide hybrid material by in situ soft chemical synthesis and its application for the removal of Pb(II) from water.

We report an in situ soft chemical synthesis of a novel hybrid material, cellulose-nanoscale-manganese oxide composite (C-NMOC), and its application for Pb(II) removal from aqueous solutions. For comparison, detailed Pb(II) adsorption studies were also performed with nanoscale-manganese oxide powder (NMO), prepared through a similar route. Various spectroscopic and microscopic techniques were used to characterize the as-synthesized materials. X-ray photoelectron spectroscopic (XPS) measurements confirmed the existence of Mn(IV) phase in NMO whereas C-NMOC showed largely the Mn(III) phase. The existence and uniform distribution of manganese oxide in cellulose fiber materials was confirmed by SEM and EDAX analyses. The adsorption studies reveal that the Pb(II) uptake onto C-NMOC is a fast process and >90% of the uptake occurred within the first 10 min contact time. The Sips isotherm predicted the equilibrium data well and the maximum Pb(II) uptake capacity of C-NMOC (4.64% Mn loading) was estimated to be 80.1 mg g(-1). The Pb(II) adsorption capacity of C-NMOC (per gram of Mn present) was several times higher than commercial manganese oxide (beta-MnO2) and at least twice larger than NMO. The experimental evidence reveals that physisorption plays a dominant role in Pb(II) adsorption by both NMO and C-NMOC.

Graphene: A Reusable Substrate for Unprecedented Adsorption of Pesticides

Unprecedented adsorption of chlorpyrifos (CP), endosulfan (ES), and malathion (ML) onto graphene oxide (GO) and reduced graphene oxide (RGO) from water is reported. The observed adsorption capacities of CP, ES, and ML are as high as ~1200, 1100, and 800 mg g(-1) , respectively. Adsorption is found to be insensitive to pH or background ions. The adsorbent is reusable and can be applied in the field with suitable modifications. A first-principles pseudopotential-based density functional analysis of graphene-water-pesticide interactions showed that the adsorption is mediated through water, while direct interactions between graphene and the pesticides is rather weak or unlikely.

High yield combustion synthesis of nanomagnesia and its application for fluoride removal.

We describe a novel combustion synthesis for the preparation of Nanomagnesia (NM) and its application in water purification. The synthesis is based on the self-propagated combustion of the magnesium nitrate trapped in cellulose fibers. Various characterization studies confirmed that NM formed is crystalline with high phase purity, and the particle size varied in the range of 3-7nm. The fluoride scavenging potential of this material was tested as a function of pH, contact time and adsorbent dose. The result showed that fluoride adsorption by NM is highly favorable and the capacity does not vary in the pH range usually encountered in groundwater. The effects of various co-existing ions usually found in drinking water, on fluoride removal were also investigated. Phosphate was the greatest competitor for fluoride followed by bicarbonate. The presence of other ions studied did not affect the fluoride adsorption capacity of NM significantly. The adsorption kinetics followed pseudo-second-order equation and the equilibrium data are well predicted by Frendlich equation. Our experimental evidence shows that fluoride removal happened through isomorphic substitution of fluoride in brucite. A batch household defluoridation unit was developed using precipitation-sedimentation-filtration techniques, addressing the problems of high fluoride concentration as well as the problem of alkaline pH of the magnesia treated water. The method of synthesis reported here is advantageous from the perspectives of small size of the nanoparticle, cost-effective recovery of the material and improvement in the fluoride adsorption capacity.

Biopolymer-reinforced synthetic granular nanocomposites for affordable point-of-use water purification

Creation of affordable materials for constant release of silver ions in water is one of the most promising ways to provide microbially safe drinking water for all. Combining the capacity of diverse nanocomposites to scavenge toxic species such as arsenic, lead, and other contaminants along with the above capability can result in affordable, all-inclusive drinking water purifiers that can function without electricity. The critical problem in achieving this is the synthesis of stable materials that can release silver ions continuously in the presence of complex species usually present in drinking water that deposit and cause scaling on nanomaterial surfaces. Here we show that such constant release materials can be synthesized in a simple and effective fashion in water itself without the use of electrical power. The nanocomposite exhibits river sand-like properties, such as higher shear strength in loose and wet forms. These materials have been used to develop an affordable water purifier to deliver clean drinking water at US

Luminescent, freestanding composite films of Au15 for specific metal ion sensing.

2.5/y per family. The ability to prepare nanostructured compositions at near ambient temperature has wide relevance for adsorption-based water purification.

Immobilized graphene-based composite from asphalt: facile synthesis and application in water purification.

A highly luminescent freestanding film composed of the quantum cluster, Au(15), was prepared. We studied the utility of the material for specific metal ion detection. The sensitivity of the red emission of the cluster in the composite to Cu(2+) has been used to make a freestanding metal ion sensor, similar to pH paper. The luminescence of the film was stable when exposed to several other metal ions such as Hg(2+), As(3+), and As(5+). The composite film exhibited visual sensitivity to Cu(2+) up to 1 ppm, which is below the permissible limit (1.3 ppm) in drinking water set by the U.S. environmental protection agency (EPA). The specificity of the film for Cu(2+) sensing may be due to the reduction of Cu(2+) to Cu(1+)/Cu(0) by the glutathione ligand or the Au(15) core. Extended stability of the luminescence of the film makes it useful for practical applications.

Rapid dehalogenation of pesticides and organics at the interface of reduced graphene oxide–silver nanocomposite

An in situ strategy for the preparation of graphene immobilized on sand using asphalt, a cheap carbon precursor is presented. The as-synthesized material was characterized in detail using various spectroscopic and microscopic techniques. The presence of G and D bands at 1578 cm(-1) and 1345 cm(-1) in Raman spectroscopy and the 2D sheet-like structure with wrinkles in transmission electron microscopy confirmed the formation of graphenic materials. In view of the potential applicability of supported graphenic materials in environmental application, the as-synthesized material was tested for purifying water. Removal of a dye (rhodamine-6G) and a pesticide (chlorpyrifos), two of the important types of pollutants of concern in water, were investigated in this study. Adsorption studies were conducted in batch mode as a function of time, particle size, and adsorbent dose. The continuous mode experiments were conducted in multiple cycles and they confirmed that the material can be used for water purification applications. The adsorption efficacy of the present adsorbent system was compared to other reported similar adsorbent systems and the results illustrated that the present materials are superior. The adsorbents were analyzed for post treatment and their reusability was evaluated.

Solar mediated reduction of graphene oxide

This paper reports dehalogenation of various organohalides, especially aliphatic halocarbons and pesticides at reduced graphene oxide-silver nanocomposite (RGO@Ag). Several pesticides as well as chlorinated and fluorinated alkyl halides were chosen for this purpose. The composite and the products of degradation were characterized thoroughly by means of various microscopic and spectroscopic techniques. A sequential two-step mechanism involving dehalogenation of the target pollutants by silver nanoparticles followed by adsorption of the degraded compounds onto RGO was revealed. The composite showed unusual adsorption capacity, as high as 1534 mg/g, which facilitated the complete removal of the pollutants. Irrespective of the pollutants tested, a pseudo-second-order rate equation best described the adsorption kinetics. The affinity of the composite manifested chemical differences. The high adsorption capacity and re-usability makes the composite an excellent substrate for purification of water.