Graphene oxide-MnFe2O4 magnetic nanohybrids for efficient removal of lead and arsenic from water.

We show that the hybrids of single-layer graphene oxide with manganese ferrite magnetic nanoparticles have the best adsorption properties for efficient removal of Pb(II), As(III), and As(V) from contaminated water. The nanohybrids prepared by coprecipitation technique were characterized using atomic force and scanning electron microscopies, Fourier transformed infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and surface area measurements. Magnetic character of the nanohybrids was ascertained by a vibrating sample magnetometer. Batch experiments were carried out to quantify the adsorption kinetics and adsorption capacities of the nanohybrids and compared with the bare nanoparticles of MnFe2O4. The adsorption data from our experiments fit the Langmuir isotherm, yielding the maximum adsorption capacity higher than the reported values so far. Temperature-dependent adsorption studies have been done to estimate the free energy and enthalpy of adsorption. Reusability, ease of magnetic separation, high removal efficiency, high surface area, and fast kinetics make these nanohybrids very attractive candidates for low-cost adsorbents for the effective coremoval of heavy metals from contaminated water.

[1]  K. Kadirvelu,et al.  Removal of Lead(II) from Aqueous Solution by Adsorption on Carbon Aerogel Using a Response Surface Methodological Approach , 2005 .

[2]  Bingqing Wei,et al.  Competitive adsorption of Pb2+, Cu2+ and Cd2+ ions from aqueous solutions by multiwalled carbon nanotubes , 2003 .

[3]  J. Qu,et al.  Removal of water-soluble azo dye by the magnetic material MnFe2O4 , 2005 .

[4]  Y. Ho,et al.  Pseudo-second-order model for lead ion sorption from aqueous solutions onto palm kernel fiber. , 2006, Journal of hazardous materials.

[5]  Yali Shi,et al.  Arsenite and arsenate adsorption on coprecipitated bimetal oxide magnetic nanomaterials: MnFe2O4 and CoFe2O4 , 2010 .

[6]  H. Nesbitt,et al.  XPS study of reductive dissolution of 7Å-birnessite by H3AsO3, with constraints on reaction mechanism , 1998 .

[7]  Yongsheng Chen,et al.  Superparamagnetic graphene oxide–Fe3O4nanoparticles hybrid for controlled targeted drug carriers , 2009 .

[8]  Shifeng Hou,et al.  Adsorption behavior of EDTA-graphene oxide for Pb (II) removal. , 2012, ACS applied materials & interfaces.

[9]  W. Ngah,et al.  Pb(II) biosorption using chitosan and chitosan derivatives beads: equilibrium, ion exchange and mechanism studies. , 2010, Journal of environmental sciences.

[10]  Xingjiu Huang,et al.  Adsorption of lead(II) on O₂-plasma-oxidized multiwalled carbon nanotubes: thermodynamics, kinetics, and desorption. , 2011, ACS applied materials & interfaces.

[11]  J. Hering,et al.  Arsenic Adsorption and Oxidation at Manganite Surfaces. 1. Method for Simultaneous Determination of Adsorbed and Dissolved Arsenic Species , 2000 .

[12]  Y Al-Degs,et al.  Sorption of lead ions on diatomite and manganese oxides modified diatomite. , 2001, Water research.

[13]  M. Chaudhuri,et al.  Removal of arsenic from ground water by manganese dioxide-coated sand , 1999 .

[14]  Alexander M Puziy,et al.  Characterisation of novel modified active carbons and marine algal biomass for the selective adsorption of lead. , 2002, Water research.

[15]  Kevin R. Henke,et al.  Arsenic: Environmental Chemistry, Health Threats and Waste Treatment , 2009 .

[16]  V. Sharma,et al.  Aquatic arsenic: toxicity, speciation, transformations, and remediation. , 2009, Environment international.

[17]  J. Bollinger,et al.  As(V) retention and As(III) simultaneous oxidation and removal on a MnO2-loaded polystyrene resin. , 2004, The Science of the total environment.

[18]  K. Ahmed,et al.  Arsenic poisoning of Bangladesh groundwater , 1998, Nature.

[19]  Chao Yu,et al.  MnFe2O4-graphene nanocomposites with enhanced performances as anode materials for Li-ion batteries. , 2013, Physical chemistry chemical physics : PCCP.

[20]  P. Huang,et al.  Oxidative power of Mn(IV) and Fe(III) oxides with respect to As(III) in terrestrial and aquatic environments , 1981, Nature.

[21]  S. Ramaprabhu,et al.  Magnetite Decorated Multiwalled Carbon Nanotube Based Supercapacitor for Arsenic Removal and Desalination of Seawater , 2010 .

[22]  Xiaodong Wang,et al.  Adsorption of graphene oxide/chitosan porous materials for metal ions , 2011 .

[23]  L. Charlet,et al.  Arsenic(III) oxidation by birnessite and precipitation of manganese(II) arsenate. , 2002, Environmental science & technology.

[24]  T. Dey.  Nanotechnology for Water Purification , 2012 .

[25]  C. Chia,et al.  University of Malaya from the Selectedworks of Huang Nay Ming Simple Room-temperature Preparation of High- Yield Large-area Graphene Oxide Simple Room-temperature Preparation of High-yield Large-area Graphene Oxide , 2022 .

[26]  S. Kosa,et al.  Removal of heavy metals from aqueous solutions by multi-walled carbon nanotubes modified with 8-hydroxyquinoline , 2012 .

[27]  J. T. Mayo,et al.  Low-Field Magnetic Separation of Monodisperse Fe3O4 Nanocrystals , 2006, Science.

[28]  Yanli Chang,et al.  Folding/aggregation of graphene oxide and its application in Cu2+ removal. , 2010, Journal of colloid and interface science.

[29]  T. Nakahara.  Inductively Coupled Plasma Atomic Emission Spectrometry , 1983 .

[30]  B. Hong,et al.  Biomedical applications of graphene and graphene oxide. , 2013, Accounts of chemical research.

[31]  Nan Li,et al.  Adsorption of Pb(II) and Cu(II) from aqueous solution on magnetic porous ferrospinel MnFe2O4. , 2012, Journal of colloid and interface science.

[32]  S. Ibrahim,et al.  Graphene oxide and Ag engulfed TiO2 nanotube arrays for enhanced electron mobility and visible-light-driven photocatalytic performance , 2014 .

[33]  W. Höll,et al.  Removal of As(III) and As(V) from water using a natural Fe and Mn enriched sample. , 2005, Water research.

[34]  Benjamin Bostick,et al.  Arsenic(III) oxidation and arsenic(V) adsorption reactions on synthetic birnessite. , 2002, Environmental science & technology.

[35]  W. Lu,et al.  Improved synthesis of graphene oxide. , 2010, ACS nano.

[36]  Stephan Barcikowski,et al.  Cytotoxicity and ion release of alloy nanoparticles , 2012, Journal of Nanoparticle Research.

[37]  M. McBride.  A Critique of Diffuse Double Layer Models Applied to Colloid and Surface Chemistry , 1997 .

[38]  D. Zhao,et al.  Synthesis of MnFe2O4@Mn-Co oxide core-shell nanoparticles and their excellent performance for heavy metal removal. , 2013, Dalton transactions.

[39]  M. Shuler,et al.  Effect of oxide formation mechanisms on lead adsorption by biogenic manganese (hydr)oxides, iron (hydr)oxides, and their mixtures. , 2002, Environmental science & technology.

[40]  S. Charles,et al.  Preparation and characterization of ultra-fine MnFe2O4 and MnxFe1−xFe2O4 spinel systems: I. particles , 1994 .

[41]  S. Ramaprabhu,et al.  Functionalized graphene sheets for arsenic removal and desalination of sea water , 2011 .

[42]  Jishan Wu,et al.  Graphene oxide/ferric hydroxide composites for efficient arsenate removal from drinking water. , 2010, Journal of hazardous materials.

[43]  Min Sun,et al.  Highly selective adsorption of lead ions by water-dispersible magnetic chitosan/graphene oxide composites. , 2013, Colloids and surfaces. B, Biointerfaces.

[44]  Gaosheng Zhang,et al.  Preparation and evaluation of a novel Fe-Mn binary oxide adsorbent for effective arsenite removal. , 2007, Water research.

[45]  Krishnan Rajeshwar,et al.  Titania-based heterogeneous photocatalysis. Materials, mechanistic issues, and implications for environmental remediation , 2001 .

[46]  M. Aroua,et al.  Removal of Copper and Zinc Ions onto Biomodified Palm Shell Activated Carbon , 2011 .

[47]  D. Ghosh,et al.  Arsenic removal from groundwater and its safe containment in a rural environment: validation of a sustainable approach. , 2008, Environmental science & technology.

[48]  Guohua Chen,et al.  Fast removal and recovery of Cr(VI) using surface-modified jacobsite (MnFe2O4) nanoparticles. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[49]  M. Tadé,et al.  Adsorptive remediation of environmental pollutants using novel graphene-based nanomaterials , 2013 .

[50]  Young Chun,et al.  Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. , 2010, ACS nano.

[51]  Jianping Gao,et al.  Fabrication of highly porous biodegradable monoliths strengthened by graphene oxide and their adsorption of metal ions , 2011 .

[52]  I. Ali.  New generation adsorbents for water treatment. , 2012, Chemical reviews.

[53]  P. Uskoković,et al.  Removal of lead from water by amino modified multi-walled carbon nanotubes , 2011 .

[54]  D. Nordstrom.  Worldwide Occurrences of Arsenic in Ground Water , 2002, Science.

[55]  Keisuke Fukushi,et al.  A predictive model (ETLM) for As(III) adsorption and surface speciation on oxides consistent with spectroscopic data , 2006 .

[56]  M. Sillanpää,et al.  Adsorption mechanism of arsenate on crystal γ-Fe2O3 nanoparticles. , 2010 .

[57]  Prashant V. Kamat,et al.  A “Sense and Shoot” Approach for Photocatalytic Degradation of Organic Contaminants in Water , 2002 .

[58]  B. Pan,et al.  Preparation and preliminary assessment of polymer-supported zirconium phosphate for selective lead removal from contaminated water. , 2006, Water research.

[59]  Jun Hu,et al.  Efficient removal of arsenate by versatile magnetic graphene oxide composites , 2012 .

[60]  Jiaxing Li,et al.  Removal of Pb(II) ions from aqueous solutions on few-layered graphene oxide nanosheets. , 2011, Dalton transactions.

[61]  D. Fiorani,et al.  Manganese iron oxide superparamagnetic powder by mechanochemical processing. Nanoparticles functionalization and dispersion in a nanofluid , 2012, Journal of Nanoparticle Research.

[62]  S. Khondaker,et al.  Schottky diode via dielectrophoretic assembly of reduced graphene oxide sheets between dissimilar metal contacts , 2011 .

[63]  M. Jekel,et al.  Oxidation of arsenate(III) with manganese oxides in water treatment , 1995 .

[64]  Tianxi Liu,et al.  Synthesis of Fe nanoparticles@graphene composites for environmental applications. , 2012, Journal of hazardous materials.

[65]  R. Bowman.  Applications of surfactant-modified zeolites to environmental remediation , 2003 .

[66]  Mason B. Tomson,et al.  Effect of magnetite particle size on adsorption and desorption of arsenite and arsenate , 2005 .

[67]  Wei Lv,et al.  Adsorption of lead(II) ions from aqueous solution on low-temperature exfoliated graphene nanosheets. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[68]  Wei-xian Zhang,et al.  Nanoscale Iron Particles for Environmental Remediation: An Overview , 2003 .

[69]  A. Lu,et al.  Magnetic nanoparticles: synthesis, protection, functionalization, and application. , 2007, Angewandte Chemie.