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Acid tolerant covalently functionalized graphene

Cite this: DOI: 10.1039/c8ta09849b
oxide for the selective extraction of Pd from high-
level radioactive liquid wastes†
Srinivasarao Kancharla and Keiko Sasaki *

Received 12th October 2018
Accepted 23rd January 2019
DOI: 10.1039/c8ta09849b
rsc.li/materials-a
The severely depleting reserves of highly demanded palladium (Pd) induce the growing pressure on its
recycling. One of the potential secondary sources of Pd is a high-level liquid waste (HLLW) produced
from spent nuclear fuel. HLLW contains several metal ions along with Pd in 3–4 M HNO3 medium. The
preparation of highly acid tolerant and efficient functional materials is a challenging task in the solid
phase recovery of noble metals. We have explored covalently functionalized graphene oxide (GO) to
overcome this issue. GO was covalently functionalized with 1-(3-aminopropyl)imidazole (ImGO) (N-
donor) and 2-methylthiophene (ThpGO) (S-donor) through amide or amine formation at different
reactive sites. The prepared materials before and after Pd recovery were thoroughly characterized using
a variety of state-of-the-art techniques. Solid-phase extraction experiments revealed that the Pd was
recovered with remarkable selectivity from HLLW-like solutions in 3 M HNO3 using both the
functionalized materials. The extraction efficiency was found to be higher than that of any of the solid-
state materials reported to date. The sorption of Pd onto ImGO and ThpGO was best expressed by the
Freundlich isotherm model. The advantages of the prepared materials are twofold: the first one is the
high tolerance to harsh acidic conditions, and the second one is the higher selectivity and efficiency for
Pd. The sorption of Pd onto ImGO was achieved by complete anion exchange with the nitrate ion,
whereas ThpGO recovered Pd through a co-ordination mechanism. The results demonstrated that the
developed covalently functionalized GO was the first choice material for the efficient and selective
recovery of Pd.

non-radioactive and/or weakly radioactive and comprise the

1. Introduction
Palladium (Pd) is widely used in various chemical industries, as
automobile catalysts, in electrical and electronic equipment, in
jewellery, in the petroleum industry, as chemical catalysts, in
pharmaceuticals etc., due to its versatile physical and chemical
properties.1–3 Platinum group metals (PGMs) exist in low levels
under the Earth's crust (0.01 g kg
1) and are globally unevenly
distributed, with South Africa (95%) and Russia (2%) as their
exclusive primary producers.4 The PGM reserves are depleting
severely every year, and the demand to supply ratio is forecast to
widen signicantly by 2020. These factors induce the growing
pressure on PGM recycling.
Palladium is present in signicant quantities in high level
liquid waste (HLLW) produced from spent nuclear fuel by the
Plutonium Uranium Redox Extraction (PUREX) process. Most of
the palladium isotopes obtained from the ssion process are
Department of Earth Resources Engineering, Faculty of Engineering, Kyushu
University, Motooka 744, Fukuoka 819-0395, Japan. E-mail: keikos@mine.kyushu-u.
ac.jp; Fax: +81 92 802 3338; Tel: +81 92 802 3338; srinivasarao@mine.kyushu-u.ac.jp
† Electronic supplementary information (ESI) available. See
10.1039/c8ta09849b
stable isotopes 104Pd (17 wt%), 105Pd (29 wt%), 106Pd (21 wt%),
108
Pd (12 wt%), and 110Pd (4 wt%) and also include a radioactive
isotope 107Pd (17 wt%) with a half-life of 6.5  106y.5 The very
weak intrinsic radioactivity of 107Pd which is a so b-emitter
with an Emax of 35 keV can be tolerated for many industrial
applications.6 Thus HLLW is a potential secondary source for
the urban mining of palladium. Further, the recovery of palla-
dium can solve the issues associated with the nuclear waste
storage technology of vitrication. Vitrication is a method for
the long term storage of radioactive waste by stabilizing it in
a form that will neither react nor degrade for extended periods;
its nal form is a glass which is highly resistant to the aqueous
chemosphere.7 The selective recovery of palladium plays a vital
role in urban mining and nuclear waste storage management
and its quality. HLLW consists of several metal ions in 3–4 M
HNO3. Most of the metal ions present in the HLLW exist in their
cationic form, whereas palladium exists in the anionic nitrate
complex form.8,9
The selective recovery of Pd from HLLW has been a subject of
great interest in the last two decades.6,8,9 Several methods such
DOI:
as solvent extraction,10–13 electro chemical methods14–16 and
solid phase extraction were employed for its efficient extraction

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Journal of Materials Chemistry A
from strong acidic medium.17 Among the different methods
employed, solid phase extraction was found advantageous
because of its operational convenience and fewer environ-
mental hazards. Solid phase extraction was performed by
developing different materials based on resins,5,18–20 meso-
porous silica,21–24 and biopolymers25,26 and recently by using
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metal–organic frameworks (MOFs).27 Pd leaching from
secondary sources oen involves treatment with strong acids
such as HCl, HNO3 or aqua regia. HLLW is oen present in 3–4
M HNO3 medium and strictly prohibits the use of chloride ions
due to its solubility issues with the molten glass used in the
vitrication process.27 Therefore development of materials
workable under such strongly acidic conditions is primarily
required for the efficient recycling of Pd from secondary sour-
ces. According to the Pearson acid–base concept, Pd(II) is cate-
gorized in a so acid; therefore so bases such as sulphur (S) or
nitrogen (N) as ligands are good choices for its selective
extraction. Sulphur donor impregnated biopolymers were
developed and employed for the extraction of Pd from high
concentrations of nitric acid. Although they show excellent
selectivity under ambient conditions, they suffer from the poor
acid stability.26 Resin and silica based materials were developed
by impregnating a variety of new kinds of extractants. Some
silica or resin based extractants showed good selectivity and
efficiency, but oen pose a serious problem of leaching of the
active species from the composite. Recently, Zr(IV)-based MOFs
with S and alkene functions were employed for the selective
extraction of Pd from HLLW-like solutions and achieved
moderate selectivity. In general, metal–organic frameworks
(MOFs) suffer from poor aqueous stability especially under low
pH conditions. Zr(IV)-based MOFs have shown some resistance
to aqueous environments but their stability depends on the
choice of the linker; a more hydrophobic linker gives better
stability in aqueous environments. Therefore, designing of
a MOF for Pd extraction under harsh acidic conditions poses
serious limitations and restricts their applicability. Hence,
a new versatile material which can withstand strongly acidic
conditions is urgently required for the development of efficient
methods for the urban mining of Pd. For this purpose, we have
looked into a recently emerged ‘wonder material’, graphene
oxide.28,29
Graphene oxide (GO) is an exotic carbon material with a large
variety of functional groups which include epoxy and hydroxyl
groups on the basal plane, and carbonyl and carboxylic groups
on its edges.30,31 Due to the presence of abundant functional
groups GO has huge potential as a precursor for the preparation
of chemically modied graphene materials such as reduced
graphene oxide (rGO)32 and functional GO. The oxygenated
functional groups allow GO to disperse well in aqueous
medium. The presence of reactive epoxy, hydroxyl and carboxyl
functional groups allows covalent functionalization of GO
through selective functionalization with organic molecules,
polymers or inorganics for targeted applications.33–37 For
example, GO can be functionalized with amines through epoxy
ring opening or amide bond formation to create new functional
materials.38,39 The idea to utilize covalently functionalized GO
has many advantages in the eld of functional materials. The
J. Mater. Chem. A
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direct formation of covalent bonds with GO gives the material
high stability under harshly acidic conditions. The abundance
and variety of reactive functional groups on GO and a variety of
functionalizable organic molecules make this strategy more
versatile and efficient for different applications including envi-
ronmental remediation and urban mining.40 Suitably function-
alized GO was found to be efficient for energy storage,41 CO2
capture,42 oil spill cleanup,43 adsorption of water-soluble dyes,44,45
and removal of toxic cations from water.46 For the metal ion
extraction under harsh acidic conditions, covalently functional-
ized GO shows promise due to its covalent functionalization and
carbon backbone. Therefore, in the present study we covalently
functionalized GO with 1-(3-aminopropyl)imidazole (ImGO)
(nitrogen donor) and 2-aminomethylthiophene (ThpGO) (sulfur
donor). Both ImGO and ThpGO were investigated for the
extraction of Pd from the HLLW-like solution in 3 M HNO3. The
structures of the materials before and aer adsorption from such
a strongly acidic medium were deeply investigated.
2. Experimental
2.1. Materials
Graphite powder of synthetic grade with particle size <20 mm
was obtained from Sigma-Aldrich. Potassium permanganate,
sulfuric acid, hydrogen peroxide, hydrochloric acid, nitric acid
(60%) and palladium(II) nitrate were obtained from Wako Pure
Chemical Industries, Japan. 1-(3-Aminopropyl)imidazole, 2-
(aminomethyl)thiophene, 1-(3-dimethylaminopropyl)-3-ethyl-
carbodiimide, and N-hydroxysuccinimide were obtained from
TCI Chemicals, Japan. Milli Q pure water with a conductivity of
18.2 MU cm at 25  C was used for the preparation of solutions.
2.2. Synthesis of graphene oxide
Graphene oxide was synthesized by the water addition modied
Hummers' method reported elsewhere,47 and briey described
as follows. 4 mL of water was mixed with 46 mL of ice-cold
concentrated sulfuric acid in a 100 mL-round bottom ask in an
ice bath (<0  C) with mechanical agitation at 300 rpm. Main-
taining the same low temperature, 1 g of graphite powder was
added to the above solution followed by the slow addition of 3 g
of KMnO4 at the same controlled temperature at intervals of 30
min and under continuous stirring for 1 h. The reaction
temperature was increased to 90  C and maintained for 12 h.
The reaction mixture was poured into a 300 mL ice/water
mixture under continuous agitation at <0  C followed by the
dropwise addition of 5 mL 30% H2O2 and stirred for 1 h. The
mixture was then ltered and washed with 50 mL of a 1 : 9 HCl
aqueous solution 3 times to remove the metallic ions. The
resulting solid was washed several times with water until it
reached neutral pH.
2.3. Synthesis of 1-(3-aminopropyl)imidazole or 2-
(aminomethyl)thiophene functionalized graphene oxide
For the functionalization, rst 500 mg of GO was dispersed in
300 mL of distilled water and ultrasonicated for 2 h. To the well
dispersed GO, 3.0 g of 1-ethyl-3-(3-dimethylaminopropyl)
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carbodiimide (EDC) and 1.6 g of N-hydroxysuccinimide (NHS)
were added, and the solution was magnetically stirred for 1 h at
room temperature to activate the carboxyl groups. 3 g of 1-(3-
aminopropyl)imidazole or 2-(aminomethyl)thiophene was
added and the mixture was ultrasonicated for another 30 min.
The reaction was transferred to an oil bath and stirred at 50  C
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for 24 h. The obtained solid products were separated from the
reaction mixture and washed 3 times with water, ethanol and
tetrahydrofuran, and then freeze-dried for 24 h. The obtained
solid products were characterized using different analytical
techniques.
2.4. Characterization of the materials
The synthesized materials were characterized by a variety of
analytical techniques such as powder X-ray diffraction (PXRD),
solid-state 13C-NMR, Fourier-transform infrared spectroscopy
(FT-IR), zeta potential measurement, atomic force microscopy
(AFM), X-ray photo electron spectroscopy (XPS), and trans-
mission electron microscopy energy-dispersive X-ray spectros-
copy (TEM-EDX). The PXRD patterns of the products were
collected using a Rigaku Ultima IV diffractometer, Japan. Cu Ka
X-ray radiation was used at 40 kV at an applied current of 40 mA
with 0.02 divergence. FT-IR spectra were measured in trans-
mittance mode on an FT/IR-670 Plus spectrometer (JASCO,
Japan) with a resolution of 4 cm
1 in the range of 4000–400
cm
1, and by averaging the data from 128 scans. Zeta potential
was measured on a Malvern Zetasizer Nano ZS. Transmission
electron microscopy (TEM) images with EDAX were observed
using a TEM-EDX (JEM-2100HCKM, JEOL, Akishima, Japan).
The samples were prepared by placing a drop of the sample
suspension on a carbon coated copper grid and drying in
a desiccator for 12 h. X-ray photoelectron spectroscopy (XPS)
was conducted on an ESCA 5800 (ULVAC-PHI, Inc., Kanagawa,
Japan). Monochromatic Al Ka X-ray operated at 200 W was used
Scheme 1 Schematic representation of the structure and preparation of GO, ImGO or ThpGO.
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as the source. The binding energy (EB) was calibrated using the
C 1s peak at 284.6 eV for the contamination carbon from the
apparatus, and peak separation was carried out with CasaXPS
soware (Version 2.3.16 PR 1.6).
2.5. Palladium sorption experiments
A simulated high level liquid waste (SHLLW) solution was
prepared by dissolving appropriate amounts of the metallic
nitrate reagents in 3 M HNO3.25,27,48 For sorption experiments,
Pd(II) solutions were prepared in the range of 2.2–702 mg Pd L
1
by dissolving Pd(NO3)2 in 3 M HNO3. The initial and equilib-
rium Pd(II) concentrations were determined using ICP-OES.
Adsorption experiments were performed at 0.5 g L
1 dosage in
10 mL volume. The samples were kept on an orbital rotary
shaker at 140 rpm for complete mixing at 25  C. Aer adsorp-
tion, the samples were ltered through a 0.2 mm membrane
syringe lter. No signicant Pd was adsorbed to the lter. All the
adsorption experiments were performed in duplicate to report
the averaged values.
3. Results and discussion
Three materials, graphene oxide (GO), 1-(3-aminopropyl)imid-
azole functionalized (ImGO) and 2-methylthiophene function-
alized (ThpGO) graphene oxide were synthesized. GO was
synthesized by oxidizing graphite powder. ImGO and ThpGO
were synthesized by covalent functionalization of 1-(3-amino-
propyl)imidazole or 2-aminomethylthiophene with the carbox-
ylic acid and epoxide functional groups of GO through amide
and amine bond formation (Scheme 1).
Elemental analyses for the GO and functionalized GO are
summarized in Table 1. The presence of nitrogen in ImGO and
ThpGO suggests the successful functionalization of GO. The
amount of nitrogen content obtained in each of the
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Table 1 Elemental composition of GO, ImGO and ThpGO

Im or Thp (mmol per g Amount of Pd extracted from HLLW

Material H (%) C (%) N (%) of functionalized GO) in 3 M HNO3 (mmol g
1)

GO 2.1 51.02 0.02

ImGO 3.4 66.68 9.78 2.33 0.61
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ThpGO 2.67 70.75 5.39 3.85 0.48

functionalized GO was evaluated to quantify the functional
groups attached to GO. The nitrogen present in the ImGO was
obtained to be 9.78% which corresponds to the nitrogen
content of 6.99 mmol g
1, that is, 2.23 mmol g
1 of 1-(3-ami-
nopropyl)imidazole functionalized to GO since three nitrogens
are present in each molecule. The nitrogen content present in
the 2-methylthiophene functionalized GO (ThpGO) is obtained
to be 5.39%, corresponding to 3.85 mmol g
1. The 2-methyl-
thiophene molecule contains one nitrogen atom for each
molecule, and therefore, it gives a direct estimation of the
number of 2-methylthiophene molecules present on ThpGO
which is 3.85 mmol g
1.
3.1. Impacts of functionalization on the intersheet spacing,
surface charge and structure of GO
Fig. 1A shows the XRD patterns of GO, ImGO and ThpGO.
Graphite displayed a sharp reection at 26.4 with a d-spacing
of 0.34 nm (Fig. S1†). When graphite was converted to GO, the
diffraction peak shied to 11.8 in 2q corresponding to d001 ¼
0.75 nm. The increase in the interlayer spacing reveals the
introduction of oxygen groups in the interlayer spaces causing
the GO sheets to stack more loosely. The large spacing between
GO sheets is also due to the presence of interlayer water. Upon
the functionalization of GO with 1-(3-aminopropyl)imidazole,
the 001 diffraction peak was shied to 10.7 in 2q resulting in
d001 ¼ 0.81 nm. Further, a new broad diffraction peak at 23.0 in
2q appeared indicating the amorphous nature in the random
arrangement of functionalized GO sheets. Similar changes were
also observed in ThpGO with a 001 diffraction peak at 11.7 in
2q, corresponding to an interlayer spacing of 0.77 nm, and
a new broad diffraction peak at 23.3 in 2q indicating the
successful functionalization and random arrangement of
ThpGO.
Solid-state 13C-NMR spectra were collected for GO and
functionalized GO and the resulting spectra are presented in
Fig. 1B. The GO spectrum showed three major peaks at 60.8, 71
and 129 ppm which were assigned to epoxy, hydroxyl and sp2
hybridized carbon of the basal sheet, respectively. Two well
resolved minor peaks were also observed at 100.5 and 167.8
ppm, respectively. The peak at 167.8 ppm was assigned to the
carbonyl group. The result of the GO spectrum is in good

Fig. 1 (A) X-ray diffraction patterns, (B) 13C NMR spectra, (C) FTIR spectra, and (D) zeta potential of GO, 1-(3-aminopropyl)imidazole func-
tionalized GO (ImGO) and 2-aminoethanethiol functional GO (ThpGO).

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accordance with that of the previous reports.31,49,50 In the 13C-
NMR spectra of functionalized GO, a new peak appeared at 36.5
ppm for ImGO and 36.3 ppm for ThpGO due to the alkyl chain
of the functional substrate indicating successful functionaliza-
tion. The epoxy and hydroxyl groups disappeared in both the
functionalized GO. The disappearance of epoxy groups was due
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to their functionalization with the selected amine containing
functional groups through ring opening reaction, whereas the
disappearance of hydroxyl groups indicates the simultaneous
partial reduction reaction. Such changes were also observed
previously in the case of highly functionalized GO with amines
and sulphur-containing functional groups.51 Another inter-
esting point in the NMR spectra is the upeld chemical shi of
the sp2 carbons in the functionalized GO. Both the functional-
ized GO showed upeld shis of the sp2 carbon peak at 121.2/
121.5 ppm, whereas that of GO was at 129 ppm. The upeld
chemical shi was likely due to the growth of graphene-like sp2
hybridized carbon sites as a consequence of partial reduction
which was further conrmed by the increased peak intensity of
sp2 carbon in the functionalized GO (Fig. 1B). The developed
graphene-like structure induces a magnetic eld that contributes
to the shielding of 13C nuclei and consequent upeld chemical
shi.50,52 Such an upeld shi was also observed previously and
was attributed to the disordered structure of functionalized GO
caused by the functionalization.53
FTIR spectra of GO and functionalized GO are presented in
Fig. 1C. The FTIR spectra of GO showed a band at 1739.5 cm
1
corresponding to the carbonyl stretching vibration mode of
carboxylic acid groups. In both the functionalized GO the
carboxylate band disappeared and a new band appeared at
1635.5 cm
1 corresponding to the carbonyl stretching vibration
mode of amide functional groups, suggesting successful func-
tionalization.35 In addition, ImGO showed new bands in the
alkyl chain region at 2965.0 and 2935.1 cm
1 corresponding to
the C–H stretching vibration mode of the alkyl chain of the 1-(3-
aminopropyl)imidazole (Im) functional group. Similar new
peaks also appeared for ThpGO at 2925.5 and 2854.1 cm
1
corresponding to the CH stretching vibration modes of 2-ami-
nomethylthiophene (Thp). The appearance of amide carbonyl
and alkyl chains in the functionalized GO indicates the
successful functionalization of GO.
The surface charges of GO, ImGO and ThpGO were
measured as shown in Fig. 1D. The zeta potential is an impor-
tant parameter that provides a measure of the magnitude and
sign of the effective surface charge associated with the double
layer around the colloid particle and is a key indicator of the
stability of colloidal dispersions. Colloids with high zeta
potential (negative or positive) are electrically stabilized while
those with low zeta potentials tend to coagulate or occulate.
Typically colloids with a zeta potential from +30 to +40 mV or

30 to
40 mV are outlined as moderately stable, whereas those
with a value higher than +40 mV or
40 mV are dened as
highly stable colloids.54 The stability of the high surface charge
colloids is due to the repulsion between the like charged
surfaces which prevents occulation. The zeta potential of the
synthesized GO was found to be
48.5 mV, indicating it to be
a negatively charged highly stable colloidal dispersion,
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consistent with the previous reports.32,55 The negative surface
charge of GO is due to the presence of carboxyl and hydroxyl
groups. Functionalization of GO resulted in a less negative zeta
potential which is
32.1 mV for ImGO and
31.6 mV for ThpGO
indicating them to be moderately stable colloids. The decrease
in the negative surface charge was due to the conversion of
carboxylic groups into amides on reaction of the selected amine
containing substrates.
The X-ray photo electron spectrum of the O 1s orbital for GO,
ImGO and ThpGO is presented in Fig. 2. The O 1s spectrum of
GO (Fig. 2A) was separated into four components. The peaks
were assigned to C]O at EB[O 1s] ¼ 529.8 eV where oxygen is
doubly bonded to aromatic carbon, C–O at EB[O 1s] ¼ 531.5 eV
where oxygen is singly bonded to aliphatic carbon, and phenolic
oxygen at EB[O 1s] ¼ 533.4 eV where oxygen is singly bonded to
aromatic carbon. An additional peak at EB[O 1s] ¼ 534.8 eV was
assigned to intercalated or chemisorbed water molecules.56–58
The O 1s spectra of the ImGO and ThpGO were separated into
three components (Fig. 2B and C) assigned to the amide
carbonyl group at EB[O 1s] ¼ 531.1 eV for both ImGO and
ThpGO, and phenolic hydroxyl groups at EB[O 1s] ¼ 533.2 eV for
ImGO, and at EB[O 1s] ¼ 533.2 eV for ThpGO. The peaks at
higher binding energy for ImGO at EB[O 1s] ¼ 534.7 eV and for
ThpGO at EB[O 1s] ¼ 535.3 eV were assigned to the adsorbed
water molecules. The changes in the O 1s spectra indicate that
imidazole or thiophene are functionalized both on the basal
plane (epoxy ring opening) and at the edges (amide bond
formation through carboxyl groups) of the GO. The N 1s spectra
of ImGO and ThpGO are presented in Fig. 2D and E. The
presence of N in the functionalized GO gives evidence for the
successful functionalization. The N 1s spectrum for ImGO was
separated into two components, which were assigned to imid-
azole nitrogen at EB[N 1s] ¼ 399.2 eV, and to amide nitrogen at
EB[N 1s] ¼ 400.5 eV.59 The N 1s spectrum of ThpGO was also
separated into two peaks, where the major peak at EB[N 1s] ¼
400.6 eV was assigned to nitrogen in amide, and a small one at
EB[N 1s] ¼ 403.9 eV was assigned to NH4+ which is formed as 2-
methylammoniumthiophene carboxylate on the edge of GO in
a small proportion.60 The S 2p spectrum of ThpGO (Fig. 2F) was
separated into two components, corresponding to EB[S 2p3/2] ¼
164.2 eV and EB[S 2p1/2] ¼ 165.5 eV, respectively.
3.2. Selective extraction of Pd from HLLW-like solutions
from 3 M HNO3, recyclability and sorption isotherms
High-level liquid waste (HLLW) was prepared to simulate spent
nuclear fuel that contains several metal ions by dissolving the
appropriate amount of metal nitrates in 3 M HNO3. The
chemical composition of the prepared HLLW-like solution is
summarized in Table 2.
An adsorption test was performed by dispersing 30 mg of
GO, 35 mg of ImGO and 40 mg of ThpGO in 10 mL of HLLW-like
solution in 3 M HNO3 and the results are shown in Fig. 3A.
Pristine GO showed no adsorption for Pd, whereas both the
functionalized GO materials have shown excellent and selective
adsorption for Pd from the HLLW-like solution. ImGO and
ThpGO showed excellent capacity for Pd with 98.8% and 96.9%
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XPS spectra of GO, ImGO and ThpGO. O 1s for (A) GO, (B) ImGO, and (C) ThpGO, N 1s for (D) ImGO and (E) ThpGO, and (F) S 2p for
Fig. 2
ThpGO.

Table 2 Concentrations of the solutes in simulated high level liquid signicantly adsorbed. The adsorption capacity and selectivity
waste (in 3 M HNO3) for Pd of both the adsorbents were superior to those of the
adsorbents reported to date.23,27,61,62 The higher adsorption
Concentration Concentration
Constituent (mg L
1) Constituent (mg L
1) capacity of both the adsorbents was due to the presence of a large
amount of reactive functional groups (carboxylic or epoxy) on GO
Al(NO3)3 124.8 Rh(NO3)3 443.1 which are functionalized to form amide/amine for the creation of
AgNO3 19.4 Ru(NO)(NO3)3 440.9 adsorption sites. These results demonstrate that GO is an excel-
Cd(NO3)2 13.8 H2SeO3 3.3
lent choice for the preparation of exotic materials for the plat-
Ce(NO3)3 525.8 Y(NO3)3 146.2
La(NO3)3 225.7 ZrO(NO3)2 172.1 inum group metal recovery. The selectivity of Pd over many other
Pd(NO3)2 223.7 Cr(NO3)3 97.1 existing ions is due to two reasons. The rst one is the anionic
Ni(NO3)2 33.3 Cu(NO3)2 19.5 form of Pd(NO3)42
and the other reason is the selectivity of
Fe(NO3)3 1770.0 Sr(NO3)2 70.2 sulphur atoms as understood by the HSAB principle.
CsNO3 432.5 Mn(NO3)2 1137.7
NaNO3 494.1
The recyclability of the ImGO or ThpGO for Pd adsorption
was estimated by performing extraction and stripping for ve
cycles. The stripping of Pd was performed by 1 M thiourea in a 1
adsorption, respectively. Both the materials also showed M HNO3 solution. In a typical experimental procedure, 25 mg of
remarkable selectivity. In the case of ImGO, Ag is found to be ImGO or ThpGO were used to extract Pd from 10 mL of SHLLW
competitively adsorbed with 22%, and other ions are also in 3 M HNO3. The adsorption experiment was performed for 9 h.
slightly adsorbed: Zr (6.9%), Ce (5.4%) and Cu (4.6%). In The Pd loaded solid materials were subjected to 35 mL of
comparison, ThpGO was more selective than ImGO. The ions stripping solution for 1 h, which resulted in Pd stripping of 94%
adsorbed other than Pd were Cu (8.6%) and Ag (6.2%) which are from ImGO/Pd and 89% from ThpGO/Pd. The obtained mate-
also in very small amounts; there are no other ions which are rials were further subjected to 25 mL of ethanol wash for 1 h

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Fig. 3 (A) Percentages of the solute elements in simulated HLLW that are adsorbed by GO, ImGO and ThpGO. (B) Adsorption capacities of Pd(II)
onto ImGO and ThpGO in five cycles of loading and stripping. (C) Isotherms of Pd adsorption onto ImGO and ThpGO from a 3 M HNO3 medium.

resulting in the complete recovery of adsorbed Pd. The mate- Qe ¼ KFCe1/n (1)
rials were washed one more time with ethanol for 30 min and
freeze-dried before employing them for the next cycle. The where Qe is the amount of Pd adsorbed onto functionalized GO
adsorption capacity of the materials was maintained without in mmol g
1, Ce is the equilibrium concentration of Pd in mmol
signicant change throughout the ve cycles (Fig. 3B). The ob-
tained adsorption capacity was 0.61–0.58 mmol g
1 for ImGO
and 0.48–0.46 mmol g
1 for ThpGO. These results indicate that
the covalently functionalized GO is a trustworthy material for
the extraction of metal ions from the highly acidic medium.
The sorption isotherm of Pd onto ImGO and ThpGO was
evaluated by performing sorption experiments in a range of 2–
700 mg L
1 of the initial Pd concentration in 3 M HNO3, as
presented in Fig. 3C. The sorption data were well tted to the
Freundlich model (eqn (1)) (Table 3), due to the heterogeneous
distribution of the active sites on functionalized GO sheets,
which was also supported by TEM-EDS observation.

Table 3 Fitting parameters of the Freundlich equation for both the

tested materials

Material KF (L·mmol
1) nF R2

ImGO 0.7835 1.9030 0.9927 Fig. 4 Powder X-ray diffraction patterns of GO, ImGO and ThpGO
ThpGO 0.6617 3.0020 0.9917 after extraction from simulated HLLW in 3 M HNO3.

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 View Article Online

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Fig. 5 XP-spectra for ImGO and ThpGO after sorption of Pd from SHLLW in 3 M HNO3: (A and B) N 1s, and (C and D) O 1s of ImGO and ThpGO,
(E) S 2p of ThpGO and (F and G) Pd 3d of ImGO and ThpGO.

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 View Article Online

Paper Journal of Materials Chemistry A

L
1, KF is the Freundlich constant and 1/n denotes the inter-

action of Pd with the ImGO or ThpGO.
At lower concentrations both the materials showed similar
adsorption capacities, whereas they largely deviated at higher
concentrations. The concentration of Pd in HLLW falls in the
marked area of the sorption isotherm which clearly explains the
Published on 24 January 2019. Downloaded by Indian Institute of Technology Chennai on 2/6/2019 1:32:25 PM.

sorption capacity of both the materials from HLLW.

3.3. Structure of the Pd adsorbed materials and sorption

mechanism
XRD reections of the solid materials aer Pd extraction from
the HLLW-like solution in 3 M HNO3 are presented in Fig. 4. All
three samples retained their characteristic patterns indicating
the high stability of the materials. The XRD peak of the 001
reection for GO shied to the lower angle 11.0 in 2q corre-
sponding to the interlayer distance of 0.81 nm indicating
a small expansion of the GO layers. Three newly obtained peaks
in the XRD pattern for GO are due to the adsorption of Ag+ onto
GO from the HLLW-like solution. The adsorption of Ag+ and
other ions leads to a further increase in the interlayer distance
of GO sheets. The XRD patterns for ImGO and ThpGO showed
the disappearance of the 001 reection indicating the complete
exfoliation of the layers. The amorphous peaks around 24.0
and 25.0 in ImGO and ThpGO, respectively, indicate the
disordered arrangement of the layers. The XRD pattern for
ImGO showed a new reection at 11.0 in 2q due to imidazolium
palladate, indicating the adsorption of Pd(NO3)22
onto ImGO
in an anionic form. The obtained XRD pattern is a good indi-
cation of the stability of the prepared materials even under
harshly acidic conditions and demonstrates that they are the
rst choice materials for Pd extraction from secondary sources.
The N 1s spectra for ImGO/Pd and ThpGO/Pd aer adsorp-
tion of Pd from HLLW in 3 M HNO3 are presented in Fig. 5A and
B. A new peak was observed in both ImGO/Pd and ThpGO/Pd at
EB[N 1s] ¼ 406.1  0.1 eV assigned to the NO3
ion63 indicating
that Pd was adsorbed either as a neutral complex [Pd(L2)(NO3)2]
and/or as anionic complexes like [Pd(NO3)3H2O)]
and
[Pd(NO3)2(H2O)2]2
which involve plenty of NO3
ions available
in the medium. The O 1s spectra of ImGO/Pd and ThpGO/Pd are
presented in Fig. 5C and D. The O 1s spectra of both the
Scheme 2 Mechanism of Pd sorption onto nitrogen active site-
materials were separated into four peaks assigned to adsorbed bearing ImGO and sulfur active site-bearing ThpGO.
water molecules, phenolic hydroxy, nitrate and amide carbonyl
for the peaks observed at EB[O 1s] ¼ 535.8  0.1, 534.3  0.2,
532.8  0.1 and 531.5  0.1 eV, respectively, for ImGO/Pd. The
ThpGO/Pd supporting its stability against oxidation in nitric
same assignment was also applicable for the peaks observed at
acid medium. Oxidation of S containing functional groups such
EB[O 1s] ¼ 535.9  0.1, 534.4  0.2, 532.9  0.1 and 531.5  0.1
as thiol is one of the serious concerns in nitric acid medium.64
eV, respectively, for ThpGO/Pd. The sustained contribution of
The XPS spectra of Pd adsorbed onto ImGO and ThpGO are
amide carbonyl is good evidence of the stability of the prepared
shown in Fig. 5F and G. The dominant peak at EB[Pd 3d5/2] ¼
functionalized GO under such strongly acidic conditions
338.1  0.2 eV in both ImGO/Pd and ThpGO/Pd was assigned to
demonstrating them to be potential materials for the extraction
the Pd2+ species.65,66 The observed higher binding energy of Pd
of Pd which oen exists in highly acidic medium. The S 2p
is characteristic of the highly oxidized state, a typical Pd2+ that
spectra of ThpGO aer Pd sorption is shown in Fig. 5E. The S 2p
exists in a complex form.66,67 The higher binding energy is also
peaks aer Pd adsorption were observed at EB[S 2p3/2] ¼ 164.1
indicative of Pd–N complexes. Another small peak at 345.5 eV in
eV, and EB[S 2p1/2] ¼ 165.2 eV, respectively, which did not show
ImGO/Pd was assigned to Zr 3p1/2 which was co-adsorbed in
any signicant change from the original. Further, no additional
a very small proportion (Table 2). The presence of Pd provides
peak was observed above 166 eV indicating no oxidation of S in

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Journal of Materials Chemistry A
a further conrmation of the successful adsorption of Pd onto
the developed materials.
Quantitative analysis of the photo electron spectra was per-
formed utilizing the peak area and the relative sensitivity factors
to understand the insights into the mechanism of Pd adsorp-
tion onto the functionalized GO having two different kinds of
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sorption sites. The details of the peak areas are provided in the
Appendix. Relative concentrations of NO3 to Pd were deter-
mined for ImGO/Pd by measuring the peak area ratio of N 1s of
NO3 and Pd which was obtained to be 4.1 indicating the pres-
ence of four nitrates for each element of Pd adsorbed suggesting
that Pd was adsorbed onto ImGO in the form of [Pd(NO3)4]2
.
The ratio of O 1s of NO3 to Pd was determined to be 12.1,
suggesting twelve oxygen atoms for each Pd which gives
a further conrmation of the [Pd(NO3)4]2
form. ImGO when
Fig. 6 TEM-EDS analysis of ThpGO/Pd and ImGO/Pd after adsorption of Pd from the SHLLW-like solution in 3 M HNO3 medium.
J. Mater. Chem. A
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dispersed into 3 M HNO3 (HLLW-like solution containing Pd)
rst formed a nitrate salt with the quaternizable N atom of
imidazole (imidazolium nitrate formation). The nitrate ion was
then exchanged with [Pd(NO3)4]2
to achieve Pd adsorption.
Therefore, the mechanism of Pd adsorption onto ImGO was
a complete anion exchange, and is schematically presented in
Scheme 2 (ImGO/Pd). The ion exchange mechanism was also
observed previously when cross-linked poly
(4-vinylpyridine-divinylbenzene) resins were used in higher
nitric acid concentrations containing Pd.68 The mechanism of
Pd adsorption onto ThpGO was also determined in a similar
manner. The molar ratio of S to Pd in ThpGO/Pd was deter-
mined to be 1.9 indicating the adsorption of Pd onto ThpGO as
[Pd(Thp)2(NO3)2] which is a neutral square planar complex
since sulphur can coordinate with Pd through a coordinate
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covalent bond. The N 1s and Pd 3d peak areas were also utilized
to determine the NO3 to Pd molar ratio which was found to be
2.1, further indicating the presence of two NO3 for each Pd
adsorbed. The presence of two NO3 and two thiophenes
(sulphur) for each adsorbed Pd conrmed its adsorption as
[Pd(Thp)2(NO3)2] attributable to the S co-ordination ability
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so bases and show good affinity with the so metal palladium
(Pd) according to Pearson's HSAB theory. Both the prepared 1-
(3-aminopropylimidazole) functionalized GO (ImGO) and 2-
methylthiophene functionalized GO (ThpGO) showed good
selectivity in the extraction of Pd from the simulated HLLW in 3
M HNO3 with ThpGO being the superior material. The better

which is schematically presented in Scheme 2 (ThpGO/Pd).
TEM-EDS images of the functionalized GO aer adsorption
of Pd from SHLLW-like solutions are presented in Fig. 6. The
distribution of N in ImGO/Pd and N and S in ThpGO/Pd shows
the successful functionalization of GO sheets. In both the
samples the distribution of Pd was overlapped with N and S all
over the sheet, which is good evidence for the adsorption of
Pd(NO3)22
onto the positively charged imidazolium group in
the prepared ImGO and through coordination with S of thio-
phene in ThpGO (Scheme 2).
4. Conclusions
Graphene oxide (GO) covalently functionalized with nitrogen
and sulphur donor moieties was developed to overcome the
vital issues of the solid state materials in the recovery of noble
metals, such as acid instability or leaching of the functional
selectivity of ThpGO was due to sulphur being more selective for
Pd than nitrogen. The 1-(3-aminopropylimidazole) functional-
ized GO (ImGO) formed corresponding to imidazolium nitrates
when dispersed in simulated HLLW in 3 M HNO3. The palla-
dium was adsorbed onto ImGO through anion exchange with
the nitrate ion in the form of [Pd(NO3)4]2
. ThpGO does not
have any ionisable groups therefore it adsorbs Pd through
coordination through the formation of a square planar complex
[Pd(Thp)2(NO3)2]. The developed covalently functionalized
materials provide a good strategy for the development of envi-
ronmental materials for the recovery of noble metals, for the
removal of heavy metal contaminants from the aqueous
samples and also for the removal of various contaminants
through suitable functionalization of GO.
5. Appendix

Pd 3d Pd 3d Pd 3d Pd 3d S 2p S 2p N 1s N 1s N 1s N 1s N 1s O 1s O 1s O 1s O 1s
Samples (1) (2) (3) (4) (1) (2) (1) (2) (3) (4) (5) (1) (2) (3) (4)

GO EB/eV 529.8 531.6 533.5 534.9

FWHM/ 2.3 2.3 2.3 2.3
eV
Area/— 305.2 586.7 1200.6 1284.8
ImGO EB/eV 399.2 400.5 531 533.2 534.7
FWHM 2.2 2.2 2.2 2.2 2.2
Area/— 339.2 240.6 677.7 714.7 483
ThpGO EB/eV 164.3 165.5 400.5 403.1 531.3 533.4 535.5
FWHM/ 1.4 1.4 2.1 2.1 2.3 2.3 2.3
eV
Area/— 1131.6 565.8 3219.5 230.7 5826.3 4329.1 2059.3
ImGO/ EB/eV 338.3 343.5 345.2 347.2 399.7 401 406.2 403 408.1 531.5 532.6 534.0 535.7
Pd FWHM/ 1.6 1.6 1.6 1.6 1.9 1.9 1.9 1.9 1.9 2.1 2.1 2.1 2.1
eV
Area/— 1653.0 1102.6 225.3 112.7 1930.1 1155.5 1094.4 123.1 79.1 9181.6 5022.3 1603.9 351.3
ThpGO/ EB/eV 338.1 343.3 164 165.1 399.8 402.2 406.1 531.5 532.9 534.3 535.8
Pd FWHM/ 1.8 1.8 1.7 1.7 2.3 2.3 2.3 2.1 2.1 2.1 2.1
eV
Area/— 2076.6 1385.1 525.9 262.9 1718.8 310.9 751.5 7628.9 5335.1 2031.7 627

moiety from the composite (active site leaching). The covalent
bond formation between the functional moiety and GO prevents
active site leaching, and the stability of the formed bond under
strongly acidic conditions made the developed material stable
under harsh conditions. The abundant reactive functional
groups present on the GO allowed the creation of large numbers
of adsorption sites on the functional materials. The functional
groups of 1-(3-aminopropylimidazole) and 2-methylthiophene
are attached to GO sheets through the formation of amine and
amide bonds which are stable against acids. The developed
functional materials contain nitrogen donor (imidazole) and
sulphur donor (thiophene) moieties as active sites which are
Conflicts of interest
There are no conicts to declare.
Acknowledgements
X-ray photoelectron spectra were collected at the Advanced
Analytical Center, Kyushu University, under the proposal No. S-
18-KU-0043 in the Nanotechnology Platform. The authors would
like to thank the Japan Society for the Promotion of Sciences
(JSPS) for providing the JSPS Postdoctoral Fellowship for

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Journal of Materials Chemistry A
Foreign Researchers to K. Srinivasarao (JP17081) and research
funding to K. Sasaki (JP16H02435 and JP17F17081).
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