Adsorbents

27.10.
2011
Contents
Motivation Pollutants Overview of Adsorption Process Nanotechnology Based Adsorption Common Adsorbent Materials CNT Iron Based Nanomaterials Nano Zero Valent Iron (NZVI) Maghemite Titanium dioxide Nano ZnO Nanoclays Conclusion
Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents 2
NANOPARTICLES AS
ADSORBENTS
Reyhan ENGR Merve ZUVN
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Motivation
It is hard to reach clean water resources because both scarcity and pollution. Water pollutants like toxic chemicals, chlorinated hydrocarbons, waterborne bacteria are introduced into environment by; Natural sources Anthropogenic sources Water must be treated.
But how can we achieve this?

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents
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Pollutants
Arsenic
One of the most toxic elements Carcinogenic, Brain damage, Heart problems, Contribution to water resources from; Dissolution of natural mines/ores, Arsenic containing pesticides and insecticides Transistor and semiconductor material As(V), As(III)
Nanotechnologies for Water Environment Applications, Tian C. Zhang, Rao Y. Surampalli, Keith C. K. Lai, Zhigiang Hu, R. D. Tyagi, Irene M. C. Lo ,ASCE, pg. 138
Pollutants
Chromium
Normally non-toxic Cr(VI) must be reduced Cr(III) Cr(VI) is toxic form and can leads to, Lung cancer, Genetic damage Weakened immune system Liver and kidney damage Contribution to environment, Textile, leather and paint industry Major constituents of stainless steel and superalloys Fungicides
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Pollutants
Heavy metals such as lead, zinc, nickel, cadmium etc. Organic pollutants like Dye, phenolic solutions, CCl4 NOx, SO2, Environmental Nanotechnology application and impacts of nanomaterials, Mlanie Auffan, Heather J. Shipley, Sujin, Yean Rice, Amy etc. T. Kan, Mason Tomson, Jerome Rose Jean-Yves Bottero, McGraw Hill, 2007, chap.10
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Overview of Adsorption Process

Adsorption is a process of accumulating substances on an interface. Adsorbate is the substance that is being removed Adsorbent is the media that adsorbate accumulates. Why does adsorption occur? Because of hydrophobicity of the material Specific affinity
Solid (adsorbent)
Water (adsorbate)
interface
Wastewater Engineering Treatment and Use, Metcalf & Eddy, McGraw Hill, 1991, pg. 1038
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Overview of Adsorption Process

Physisorption: Adsorption by weak van der Waals forces Chemisorption: Adsorption by stronger chemical bonds (Ionic or covalent) Factors that affecting adsorption process Surface area, pore size of adsorbent Molecular size, solubility, concentration of adsorbate pH Competition among the solutes etc.
Nanotechnology Based Adsorption

Usage of nanoparticles increase adsorption properties; High surface area to volume ratio Strong adsorption because of interactions between cations and hydroxyl groups More ion selective Rapid and efficient Cost reduced due to less dosages Functionalization possible
Wastewater Engineering Treatment and Use, Metcalf & Eddy, McGraw Hill, 1991, pg. 1038
Applications of Nanomaterials in Environmental Science and Engineering: Review Guobin Shan; S. Yan; R. D. Tyagi; Rao Y. Surampalli; and Tian C. Zhang, 2009
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Commonly used Nanoparticles as Adsorbents

Nanoparticles Carbon nanotubes Zeolites Iron based nanoparticles Pollutant removed Dioxins, Heavy metals e.g. Cd, Pb Humic Acid, Zn Ammonium, Heavy metal e.g Hg, Pb, Ag, Cu, Cd, Cr chlorinated organic solvents, organic compounds e.g benzoic acid, anions e.g., NO3-, Cr2O7 2, heavy metals e.g. Ni, Hg, As Phosporus removal Heavy metals e.g As, organic pollutants Ag, H2S Cr, As Pb, Cr, Cu, Hg, Cd Hg
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Carbon Nanotubes
They are superior to activated carbon High specific surface area Well-defined structure and uniform Pore diameter distribution Adsorption capacity distribution
Nanoclays TiO2 NanoZnO Maghemite nanoparticles Alumina nanoparticles WO3

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Carbon nanotubes as adsorbents in environmental pollution management: A review Xuemei Rena, Changlun Chena,b, Masaaki Nagatsub, Xiangke Wanga, 2010
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Carbon Nanotubes
Xe, SF4 Figure: Different adsorption sites on a homogeneous bundle of partially open-ended SWCNTs: (1) internal, (2) interstitial channel, (3) external groove site, and (4) external surface.
Carbon Nanotubes
Kr, Methane
Carbon nanotubes as adsorbents in environmental pollution management: A review Xuemei Rena, Changlun Chena,b, Masaaki Nagatsub, Xiangke Wanga, 2010
TEM images of different CNT morphologies and lead adsorption isotherms. (a) Sample Xylene-Fe-800C-Hor, (b) Sample Benzene-Fe-1150 C-Vert; (c) Sample Propylene-Ni-750 C-Hor; (d)Sample Methane-Ni-650 C-Vert; (e) Adsorption isotherms of lead adsorbed by four kinds of the oxidized CNTs (CNT dosage: 0.02m/100ml; pH=5.0).
Carbon nanotubes the promising adsorbent in wastewater treatment Y. H. Li, Y. M. Zhao, W. B. Hu, I. Ahmad, Y. Q. Zhu, X. J. Peng, Z. K. Luan, 2006
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Carbon Nanotubes

Iron Based Nanoparticles

Nanosized iron oxide Nanosized zero-valent iron (NZVI) Bimetallic iron nanoparticles Iron sulfide nanoparticles
Carbon nanotubes the promising adsorbent in wastewater treatment Y. H. Li, Y. M. Zhao, W. B. Hu, I. Ahmad, Y. Q. Zhu, X. J. Peng, Z. K. Luan, 2006
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Nano Zero Valent Iron

They found to be a better adsorbent than TiO2 for removal of As, Cr Mostly used as an adsorbent in groundwater remediation In research As(III) is removed from contaminated water by using NZVI NZVI is produced from reduction of ferric iron in the presence of sodium borohydrid
Removal of Arsenic (III) from Contaminated Water by Synthetic Nano Size Zerovalent Iron A. R. Rahmani, H. R. Ghaffari, and M. T. Samadi, 2010
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Maghemite
- Fe2O3 for As(V) removal Advantages of using maghemite Adsorption capacity is high because of its large surface area Easily be separated using external magnetic field Creates no secondary pollutants Commercially available and easy to synthesize with different methods
As(V) adsorption on maghemite nanoparticles T. Tuutijrvi, J. Lub, M. Sillan, G. Chenb, 2008
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Maghemite

Maghemite
Max. Adsorption capacity is found at pH 3 for all samples.
Mechanochemical maghemite has the highest adsorption capacity: 50 mg/g sol-gel meghamite: 25.0 mg/g commercial maghemite: 16.7 mg/g Due to SSA of the nanoparticles pH effect And it is suitable for removing Cr(VI) as well.
a) Commercial maghemite
b) Sol-gel maghemite
c) Mechanochemical maghemite
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Photocatalysts
are used in organic contaminant degradation Photocatalysis is an advanced oxidation process Nanosized semi-conductor materials: TiO ZnO CdS
TiO
Semiconductor Stable and highly reactive photocatalyst Opaque to UV Transparent to Visible Light Band gap 3.0 to 3.2 eV
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Photocatalysis mechanism using TiO

Advantages of Photocatalytic Activity

Operation Energy friendly Environmental friendly Cost-effective Non-selectivity Short treatment time
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Challenges
Catalytic activity Efficiency Lifetime Reactor design Separation of the catalyst
For Separation
TiO can be immobilized on rigid support inexpensive cores magnetic cores eg. Immobilized TiO on foamed aluminium to decompose the benzene.
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For Separation
Iron oxide particles coated with TiO So, shell for destroying organic compounds in waste water. core for recovery of the particle from water with applying external magnetic field.
ZnO
Large surface area High surface activity Low toxicity in this work: Particle size: 14-25 nm SSA : 44-56 m/g Designed three types of particles and named snano1, snano2, and snano3.
Environmental Nanotechnology application and impacts of nanomaterials, Mlanie Auffan, Heather J. Shipley, Sujin, Yean Rice, Amy T. Kan, Mason Tomson, Jerome Rose Jean-Yves Bottero, McGraw Hill, 2007, chap.10
Removal of hydrogen sulfide by zinc oxide nanoparticles in drilling fluid M. A. Sayyadnejad; H. R. Ghaffarian; M. Saeidi, 2008
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Under same contiditons With nanoparticles removal time: 15 min amount: completely With bulk removal time: 90 min amount: 2,5%
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TEM image of snano1 sample

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Removal of Lead and Cadmium ions by modified Kaolinite Clay

Kaolinite clay PVA nanoclay adsorbent modified with PVA Specific surface area (SSA) of the materials unmodified clay PVA modified nanoclay
Unmodified vs. modified Kaolinite Clay XRD patterns
But it didnt effect the efficiency of PVA modified nanoclay. a) Unmodified clay
Removal of Lead and Cadmium Ions from Aqueous Solution by Polyvinyl alcohol-modified Kaolinite Clay: A Novel Nano-clay Adsorbent E.I. Unuabonah, B.I. Olu-Owolabi, K.O. Adebowale and L.Z. Yang, 2008
b) PVA modified clay
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Unmodified vs. modified Kaolinite Clay SEM images
Modified Kaolinite Clay
Unmodified clay
PVA modified nanoclay
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Adsorbent dosage : dosage adsorbance

Adsorption capacity of clay is increased almost three-fold by modifying it with PVA. PVA modified nanoclay is waterstable and because of that it can be recycled for ~ 5 min. Waterstability of this nanoclay allows recovery from filters easily.
pH pH % adsorbed metal ion
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Conclusion
Using nanoparticles as adsorbents in water and wastewater treatment can affect; Efficiency of remediation of pollutants Capability of adsorption Cost
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27.10.

But how can we achieve this?

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Overview of Adsorption Process

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Overview of Adsorption Process

Nanotechnology Based Adsorption

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Commonly used Nanoparticles as Adsorbents

Nanoclays TiO2 NanoZnO Maghemite nanoparticles Alumina nanoparticles WO3

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Iron Based Nanoparticles

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Nano Zero Valent Iron

Nano Zero Valent Iron

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Nano Zero Valent Iron

As(V) adsorption on maghemite nanoparticles T. Tuutijrvi, J. Lub, M. Sillan, G. Chenb, 2008

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

As(V) adsorption on maghemite nanoparticles T. Tuutijrvi, J. Lub, M. Sillan, G. Chenb, 2008

As(V) adsorption on maghemite nanoparticles T. Tuutijrvi, J. Lub, M. Sillan, G. Chenb, 2008

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Photocatalysis mechanism using TiO

Advantages of Photocatalytic Activity

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

TEM image of snano1 sample

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Removal of Lead and Cadmium ions by modified Kaolinite Clay

Unmodified vs. modified Kaolinite Clay XRD patterns

b) PVA modified clay

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Unmodified vs. modified Kaolinite Clay SEM images

Modified Kaolinite Clay

PVA modified nanoclay

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Modified Kaolinite Clay

Modified Kaolinite Clay

pH pH % adsorbed metal ion

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

Reyhan engr & Merve Zuvin Nanoparticles as Adsorbents

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