National Science Foundation RAPID: Novel Functionalized Nanomaterials for Effective Remediation of Spilled Oil Contaminants in the Gulf of Mexico Ashok Kumar, University of South Florida, DMR Outcome: Researchers at University of South Florida have observed the decontamination of organic including petroleum compounds using Titanium oxide (TiO 2 )-graphene and Titanium oxide (TiO 2 )-graphene-Rhamnolipid nanomaterials. G-TiO 2 - rhamnolipid composite is the better choice for remediation of organic compounds. Impact: The experimental finding shows the advantage of organic decontaminants using G-TiO 2 -Rhamnolipid over G-TiO 2 nanocomposite. Interestingly, the use of Rhamnolipid in G-TiO 2 shows the improved organic remediation in both UV-visible and visible light. Based on our results, we are using naphthalene and diesel at different concentrations for remediation from water. We feel that the use of biosurfactant with G-TiO 2 could be innovative material for water remediation. Explanation: This project finds the integration of two technologies for removal of organic pollutants using the biosurfactant (Rhamnolipid) and photocatalysts- TiO 2 containing graphene nanoparticles. Rhamnolipids are a good biosurfactant, and able to remove all the organic compounds and heavy metallic petroleum products, whereas the complete removal of organic compounds is made possible by photocatalysts graphene doped TiO 2 particles. Therefore, under this program, we have shown a suitable method to use TiO 2 -graphene and biosurfactant/TiO 2 -graphene to remove products of petroleum compounds. Dr. Ashok Kumar and Dr. Manoj K. Ram at USF have developed the nanocomposite materials, and used then them to effectively decontaminant organics from water. The experimental finding under this project have shown the advantage of organic decontaminants using G-TiO 2 -Rhamnolipid over G-TiO 2 nanocomposite. However, Figure 1 shows the use of Rhamnolipid in with G-TiO2 nanomaterials. It removes most of the methyl orange in nearly 200 minutes with light illumination intensity of 30 W/ m 2. Fig.1 The methyl orange decontamination using (a) samples collected for G-TiO 2 –rhamnolipid(0.19 gm) nanocomposite, (b) Samples collected for G-TiO 2 - rhamnolipid (0.1gm)

National Science Foundation Experimental: We synthesized and characterized graphene (G)-metal oxide (TiO 2 ) nanocomposite, and G-TiO 2 -Rhamnolipid nanocomposite materials to understand organic compounds remediation from water. The G-TiO 2 nanocomposite was made using the sol-gel technique. G -TiO 2 -Rhamnolipid composite was made using the slurry and adsorption process. Results: Figure 2 shows the TEM images G-TiO 2 where TiO 2 nanoparticles are covered with the graphene platelets. The peak at 577 cm -1 shows the Ti-O-Ti whereas 1603 cm -1 reveal the characteristics IR peak of graphene in Figure 3. Figure 4 shows the diffraction spectra of G-TiO 2 nanoparticles deposited on silicon substrate. It shows the peaks at , 44.35, , , and The observed peak at 26.51° and 48.03° are indicative of anatase phase of TiO 2 present in G- TiO 2 nanocomposite. RAPID: Novel Functionalized Nanomaterials for Effective Remediation of Spilled Oil Contaminants in the Gulf of Mexico Ashok Kumar, University of South Florida, DMR Figure 2 TEM images of G-TiO 2 for 20 nm and size 5 nm Figure 3: FTIR spectra of G-TiO 2 nanocomposites Figure 4 X-Ray diffraction pattern of G-TiO 2

National Science Foundation Publications 1. T. E Alam, M. K. Ram, Mi. Ladanov, F.Alvi, A. Mujumdar and A. Kumar (2012). MRS Proceedings, 1400, mrsf s08-07 doi: /opl Jorge Arturo Lara Viera, Manoj K. Ram, Pedro Villalba, Mikhail Ladanov and Ashok Kumar, MRS Proceedings, Volume 1395 / Manoj Kumar Ram, S. Gunti and A. Kumar, The petroleum decontamination using Graphene-Titanium oxide and graphene –TiO2-Rhamnolipid (under preparation for J. Phys Chem. ) 4. Manoj K Ram, Ajit Mujumdar, Tanvir E Alam, Ashok Kumar, The heavy metal separation using graphene-SiO 2 nanomaterials, Provisional Patent filing under progress In figure 5 shows the photocatalytic decontamination of p25, G- TiO 2 and G-SiO 2 nanomaterials. The G-TiO 2 degrades MO under the UV-visible light in 180 minutes whereas P25 to completely removes MO in 195 minutes. The presence of graphene helps in producing the free hydroxyl radical. The G-TiO 2 containing only rhamnolipid of 0.1 gm is sufficient to decontamination is organic molecules. Figure 6 shows the samples of for MO containing water decontaminated for various rhamnolipid containing G-TiO 2 nanocomposite. Figure 5 Photodegradation of MO by G-TiO 2, G- SiO 2 and commercially available P25 under irradiation of 30 W/m 2 UV-visible light. Figure 6 Change of concentration of MO as a function of time containing various concentration of Rhamnolipid Conclusions: Our goal is to understand the decontamination effect of organic molecules from TiO 2 -G and TiO 2 -G-Rhamnolipid nanocomposites. Our results shows that report shows advantage of organic decontaminants using G-TiO 2 -Rhamnolipid over G-TiO 2 and nanocomposite materials. Based on these results the petroleum decontamination is in progress using the optimized nanomaterials. RAPID: Novel Functionalized Nanomaterials for Effective Remediation of …. Ashok Kumar, University of South Florida, DMR Future Plan: Effectively remediate petroleum from the contaminated sea water.