Mesoporous graphene/IL Hybrid material coated

sand: an efficient mode for heavy metal detoxification

Varsha Khare, Shiva Raj Poudel, Dae Seob Song, Sung Hoon Ahn
Mechanical & Aerospace Engineering, Seoul National University
Institute of Advanced Machinery and Design

Innovative Design and Integrated Manufacturing Laboratory

The control of heavy metal pollutants and their associated toxicities remain a key environmental concern. Reduced Graphene oxide has been pursued in recent years as a leading candidate
for heavy metal remediation primarily due to its high surface area and modifiable properties. In the present work, the formation of mesoporous graphene and its applicability for heavy meta
l detoxification is discussed. Here, we demonstrate the flexible tunability of porous reduced graphene oxide (rGO) with sulfonium based ionic liquids (SIL) to generate porous rGO-SIL hybrid
nanomaterials derived from GO using glycerol as a reductant. The genesis of mesoporous graphene can be explained on the basis of opening of edges via stress strain generated by surface
and interlayer interaction of ions from ionic liquid with sp2 and sp3 bonded carbon atoms (Fig.1).The application of a facile and mild reduction process assisted by the IL environment is further
advantaged by its simplicity as a single-step chemical process that is essentially green. The complete reaction was performed in presence of sand to coat the hybrid material onto the sand.

Background
Increasing global environmental concern
Toxic bioaccumulation in humans through food consumption
Need for effective heavy metal detoxification technology

Fractionation distillation
Coated bulk materials
Crystallization

SILMG

Separation / Filtration technology

Methods

Heavy Metal Toxic Water Pollution

Limitations
High energy consumption
Complex and expensive setups
Material wastage

Sulfer doped ionic liquid

mesoporous graphene (SILMG)
coated sand Technology
Environmentally friendly materials
Simple economic low cost process
High surface area and permeability
Material recyclability

Results

Objective
Cost effective hybrid nanomaterial for water detoxification

SIL/MPrGO Hybrid materials

Structure-Microstructure : Presence of Mesoporous Graphene
Intensity (a.u.)

Develop an environmentally friendly and cost effective stable hybrid

nanomaterial with high filtration properties
Hybrid nanomaterial will combine the high surface of graphene with the
electrostatic properties of ionic liquids
Synthesize graphene-ionic liquid hybrid materials and characterize the
hybrid properties using X-ray diffraction, electron microscopy, X-ray
photoelectron spectroscopy, batch test.
Develop stable graphene coated sand filtration technique for heavy metal
removal

SIL/MPrGO

Concept

SIL/MPrGO/Fe0

SIL/MPrGO/FGR

Functionalization chemistry: Sulfur doped MPrGO

Graphene coated sand technology

SIL/MPrGO

The Concept

Applicability

Bond vibrations are

consistent with the C-S
bonds indicating the C
atom replacing by S.

Binding Energies in survey

spectrum of SIL/MPrGO are
consistent with S2p and S2s
core level excitations.

120000

CPS

FTIR XPS

160000

80000

S2p S2s
40000

0
0

200

400

600

800

1000

1200

Binding Energy

Absorption Analysis on HM Coated sand

ICPMS: Heavy Metal Absorption Efficiency: pH Effect
0

GR1
GR(SO42-)
AcBiBaCjCbAkA. . .
Anions are planar
No long range ordering betwee
n Fe(III) and anions
OH-

-Hexagonal Layer

Fe (II) ion Located at center of t

he octahedron
intercalated anion and water m
olecule should be counterbala
nced by Fe(III) in brucite like la
yer

Green Rust LDH

B
A

B
A
A
C

GR2
(CO32-), (Cl)AcBijA. . .. . .

Anions 3-D
long range ordering betw

~ 11 een Fe(III) and anions

B
A

C
B

Two anion layer at betwe

en the Hexagonal Layer
of
Fe (OH)2

~ 7.6

SEM and EDS: Surface Morphological and Elemental changes

SEM

General Formula
[Fe(1-x)2+ Fex3+x
(OH)2]x+ [(x/n)An
(mx/n)H2O]
(with3+x being the Fe3+ molar fractio
n Fe /Fetotal)

B
A

Experimental
SIL Mesoporous
Graphene/Fe HM
Coated Sand

Synthesis of Ferric Green Rust

Synthesis of green rust

Fe II-Fe III

EDAX
XPS on coated sand after absorption of Hg and Cr

mixed solution of 0.4M

Eh

Na 2CO 3 -NaOH

pH

N2

N2
Fe II SO 4 +
Fe III 2 (SO 4 ) 3

Reagents
4

Stoicheometric

GR

controlled oxidation via H

2O 2

Discussion and Conclusions

SIL Mesoporous Graphene

Simple one pot synthesis

Sulfur doped Mesoporous rGO, rGO/Fe HM were synthesized as evidenced by FTIR and XPS.
Sulfur atom occupies more space within the lattice than carbon and leads to the formation of
MPrGO due to the occurrence of lattice stress and strain events
HM combined with iron species are promising materials for coated sand and demonstrate
enhanced absorption of heavy metals
Sand coated with FGR with HM was investigated for heavy metal absorption as a function of pH
and showed Hg absorption to be independent of pH. Cr absorption however improves under both
acidic and basic conditions indicating the presence of more than one of reactive species
Formation of organometallic of Hg and Cr after absorption are good for recyclability
Present work shows almost 95% absorption of Pb

This work was supported by the National Research Foundation of Korea(NRF) grant funded by the Korea government (MEST) (No. NRF-2012R1A1A2008196, NRF-2010-0029227 and NRF-2012R1A2A2A01047189)