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Aliphatic or aromatic diamines undergo nucleophilic attack on the epoxy groups of graphene oxide under hydrothermal conditions resulting in partial functionalization and partial reduction of the graphenic surface. The overall reaction decreases the solubility of graphene oxide and yields a hydrogel that can be dried to a 3D porous structure classified as an aerogel. This article compares the graphene aerogels derived from different aliphatic and aromatic diamines. © 2018 Vrettos, Karouta, Loginos, Donthula, Gournis and Georgakilas.
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published: 10 April 2018
doi: 10.3389/fmats.2018.00020
Frontiers in Materials | 1April 2018 | Volume 5 | Article 20
Edited by:
Emilia Morallon,
University of Alicante, Spain
Reviewed by:
Horacio Javier Salavagione,
Consejo Superior de Investigaciones
Científicas (CSIC), Spain
Tatiana S. Perova,
Trinity College, Dublin, Ireland
Vasilios Georgakilas
Specialty section:
This article was submitted to
Carbon-Based Materials,
a section of the journal
Frontiers in Materials
Received: 05 February 2018
Accepted: 22 March 2018
Published: 10 April 2018
Vrettos K, Karouta N, Loginos P,
Donthula S, Gournis D and
Georgakilas V (2018) The Role of
Diamines in the Formation of
Graphene Aerogels.
Front. Mater. 5:20.
doi: 10.3389/fmats.2018.00020
The Role of Diamines in the
Formation of Graphene Aerogels
Katerina Vrettos 1, Niki Karouta 2, Panagiotis Loginos 1, Suraj Donthula 3, Dimitrios Gournis 2
and Vasilios Georgakilas 1
1Material Science Department, University of Patras, Rio Patras, Greece, 2Department of Materials Science and Engineering,
University of Ioannina, Ioannina, Greece, 3Department of Chemistry, Missuri University of Science & Technology, Rolla, MO,
United States
Aliphatic or aromatic diamines undergo nucleophilic attack on the epoxy groups of
graphene oxide under hydrothermal conditions resulting in partial functionalization and
partial reduction of the graphenic surface. The overall reaction decreases the solubility
of graphene oxide and yields a hydrogel that can be dried to a 3D porous structure
classified as an aerogel. This article compares the graphene aerogels derived from
different aliphatic and aromatic diamines.
Keywords: graphene aerogels, diamines, conductive aerogels, carbon superstructures, porous nanostructures
Graphene Oxide (GO) is a graphene derivative with significant scientific interest that has been
expanded enormously after the isolation of single layered graphene nanosheets by Novoselov et al.
(Novoselov et al., 2004; Compton and Nguyen, 2010; Kim et al., 2010; Chen et al., 2012; Zhu
et al., 2012). GO is essentially a graphene monolayer functionalized heavily with oxygen groups,
mainly epoxides, hydroxyls, and carboxylates, although several others have been also proposed
(Hontoria-Lucas et al., 1995; He et al., 1998; Lerf et al., 1998). GO is produced via liquid exfoliation
of graphite oxide by treatment of graphite with strong acids according to established procedures
by Staudenmaier (1898),Hofmann and Konig (1937),Hummers and Offeman (1958) that followed
the first synthesis of GO by Brodie (1859), and its variants (Park and Ruoff, 2009; Mao et al., 2012).
Although the GO core consists of hydrophobic aromatic domains, the presence of surface oxygen
groups adds hydrophilic character that induces a characteristic colloidal stability of GO nanosheets
in water. Successful reductive removal of those oxygen groups, and partial reconstruction of the
aromatic system of GO results to the known-as reduced GO (rGO), which is receiving much
attention as an alternative to pure graphene due to its good electrical properties (Pei and Cheng,
2012; Chua and Pumera, 2014). In addition, removal of oxygen groups reduces the hydrophilic
character of rGO and results in aggregation in water. Thus, under appropriated conditions, the
reductive aggregation of GO may give hydrogels, which can then be transformed to aerogels by
removing pore filling water according to well-established procedures (e.g., freeze drying). Thereby,
graphene aerogels are 3D architectures consisting of a conducting network of rGO nanosheets with
large specific surface areas and micro/nano porosity (Li and Shi, 2012, 2014; Pei and Cheng, 2012;
Zhang et al., 2012; Nardecchia et al., 2013; Li et al., 2014). Graphene aerogels are attracting much
attention for applications in catalysis, environmental remediation, energy storage (supercapacitors,
Li ion batteries) as well as in sensors and biosensors (Chen et al., 2013; Hu et al., 2013; Sun et al.,
2013; Tang et al., 2014). Usually, graphene gelation is assisted by hydrophilic polymers or small
organic molecules, although rGO hydrogels without such promoters have also been reported (Liu
and Seo, 2010). The role of those promoters and their influence in the properties of the final product
Vrettos et al. The Role of Diamines in the Formation of Graphene Aerogels
FIGURE 1 | Hydrogels as prepared by hydrothermal treatment (lower), and after the addition of water (upper).
has not been studied systematically. One particular class of such
promoters, organic diamines, can act effectively as nucleophiles,
attacking the epoxy groups of GO. In that regard, they get
bonded on the surface of GO covalently, effectively bridging
(cross linking) graphene sheets. Furthermore, diamines, being
well-known reducing agents, become responsible for partial
reconstruction of the aromatic system on rGO.
In view of the aforementioned, this study describes the
preparation and characterization of a series of graphene
aerogels derived with several aliphatic and aromatic diamines
(aniline derivatives) as shown in Figure 1. Those diamines were
selected based on their solubility in water, their molecular
size and flexibility, their number of nitrogen atoms, their
basicity, and their nucleophilicity. The effectiveness of those
diamines as gelation promoters was investigated via the
morphology and other material properties of the final products
1,4-Phenylenediamine (Merck Millipore Schuchard), methylene
dianiline (Chem-Cruz), 3,3-diaminobenzidine (FluoroChem),
triethylenetetramine (Struers), 1,6 hexanediamine (Acros
Organincs Inc.) 1,2- phenylenediamine (Sigma Aldrich), para-
xylylenediamine (Fluka Chemicals) were used as received. Nitric
acid (65%), sulfuric acid (95–97%), potassium chlorate, and
powder graphite (purum) were acquired from Fluka.
Synthesis of Go
GO was prepared according to Staudenmaier’s method
(Staudenmaier, 1898) through oxidation of graphite. In a typical
procedure, graphite (5 g) was added to a cold mixture of 200 mL
H2SO4and 100 mL HNO3, in an ice-water bath. KClO3powder
(100 g) was added to the cold mixture in small portions under
continuous stirring. The reaction was quenched after 20 h by
pouring the mixture into distilled water. The oxidation product
was washed until the pH reached 6.0, and was dried at room
Synthesis of Graphene Aerogels
GO (12 mg) was dispersed in alkaline water (4 mL +60 µL of
conc. aq. ammonium hydroxide) using ultrasonication for 1 h.
After addition of diamine (0.1 mmol), the mixture was heated
in a sealed bottle at 95C for 24 h. The resulting hydrogels were
washed several times with water to remove unreacted diamine,
and then they were lyophilized for 24 h. The density of final
aerogels was determined from their weight and their physical
dimensions. (Hu et al., 2013; Tang et al., 2014).
Materials Characterization
Thermogravimetric analysis (TGA) was carried out with a TA
Instrument Q500 Thermo Gravimetric Analyzer under ambient
air with a heating rate of 10C min1up to 700C. Scanning
electron microscopy (SEM) images was carried out on a Zeiss
EVO-MA10, a Hitachi S-4700 field-emission microscope. FT-
IR spectra were obtained with a ATR technique on a FTS 3000
Excalibur Series Digilab spectrometer and on a Shimadzu FT-IR
8400 spectrometer equipped with a deuterated triglycine sulfate
detector. The samples were in the form of KBr pellets containing
ca. 2% w/w of the material.
XRD was conducted with a D8 Advance Bruker diffractometer
using a CuKa (lD1.5418) radiation source (40 kV, 40 mA) and a
secondary beam graphite monochromator. Diffraction patterns
were recorded in the 2-theta (2’) scale from 2to 80, in steps
of 0.02and with a counting time of 2 s per step. Raman spectra
were collected with a Raman system LabRam HR Evolution RM
(Horiba-Scientific) using a laser excitation line at 532 nm (laser
diode). The laser power was 1.082 mV. All Raman parameters
have carefully controlled to avoid changes in the graphene
materials. Bulk resistance was measured using a Keithley 2401
multimeter with two ITO glasses as electrodes that covered the
upper and lower surface of the aerogels. The conductivity was
estimated taking into consideration the surface of the aerogel as
shown in Table 2 and the thickness l =3 mm.
The porosity of the aerogels was estimated by the following
equation ϕ=Vpore/V where Vpore is the volume of the void-space
and Vis the volume of the bulk material and was estimated by the
dimensions of aerogel. Vpore was estimated via Vpore =V-VrGO
(VrGO =m/drGO where drGO =2 g cm3is the density of rGO and
mis the mass of the bulk material) (Chen et al., 2013).
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Vrettos et al. The Role of Diamines in the Formation of Graphene Aerogels
TABLE 1 | Diamines used as gelators for rGO hydrogels.
Aliphatics pKa1Solubility in water
HDA 11.9 800 g L1
EDA 10.7 Miscible
TETA 9.9 100 g L1
PXDA 9.2 Miscible
PPD 6.2 40 g L1
MDA 4.8 1 g L1
OPD 4.7 <1 g L1
DAB 3.6 <1 g L1
TABLE 2 | Bulk resistance (R), resistivity (ρ), dimensions, and density (d) of the
rGO aerogels.
rGO Mass
drGO (mg
S (m2)
R (k)ρ(m) Porosity %
EDA 20 12.9 3.1 6.0 620 99.4
TETA 20 22.0 1.8 3.6 200 98.9
HDA 21 21.0 2.0 40.0 2600 99.0
PXDA 22 22.0 2.0 1.6 106 98.9
MDA 26 65.0 0.8 2.0 52 96.8
OPD 16 12.8 2.5 0.3 29 99.4
PPD 20 21.0 3.1 1.2 124 99.4
DAB 21 12.0 3.6 0.3 25 99.4
The thickness was measured to 0.5 cm.
The Diamines
Diamines selected for this study are divided in two groups:
aliphatic and aromatic. The first group includes flexible
ethylenediamine (EDA), 1,6 hexanediamine (HDA),
triethylenetetramine (TETA), and a semi-flexible one, para-
xylylenediamine (PXDA). The second group includes rigid
aniline derivatives such as ortho-phenylenediamine (OPD),
para-phenylenediamine (PPD), 3,3-diaminobenzidine (DAB),
and a semi-flexible one, 4,4-methylene dianiline (MDA). The
aliphatic diamines are classified as strong bases and strong
nucleophiles, and they were water soluble (see Table 1). On the
other hand, aromatic diamines are weak bases and poorly soluble
in water. EDA (Kim et al., 2013) and PPD (Ma et al., 2012)
FIGURE 2 | The reaction mixture before (a) and after (b) the addition of TETA.
(c) Well shaped hexagonal aerogels from the hydrothermal treatment of TETA
with GO.
have been previously reported in the hydrothermal synthesis of
graphene aerogels.
Hydrogel Formation
During hydrothermal process, after the addition of diamine,
GO nanosheets agglomerated forming monolithic hydrogels as
shown in Figure 1. With the exception of MDA, hydrogels
had almost the same volume as the sol. Hydrogels with MDA
underwent excessive shrinkage (about 50% in linear dimensions).
All hydrogels were washed extensively with water and acetone to
remove unreacted diamines and ammonia, and they were dried
to aerogels using freeze-drying (see Experimental Section).
Introducing diamines as gelation promoters has the dual
advantage of using a single reagent both as a crosslinker of
GO sheets, and as a reducing agent (Herrera-Alonso et al.,
2007; Li et al., 2011; Ma et al., 2012; Kim et al., 2013). In that
regard, nucleophilic attack of diamines to an epoxide group
on the GO surface leads to fuctionalization of graphene with
diamines, which in part is followed by a second nucleophilic
attack, formation of an aziridine ring and elimination of OH as
water; eventually, elimination of the aziridine ring itself leaves
behind a double bond, in analogy to the mechanism suggested
by Stankovich et al. for the reduction of GO by hydrazine
(Stankovich et al., 2007).
Functionalization was evidenced by the presence of the
diamine on the surface. Partial reduction was accompanied by
enhanced conductivity and a drastic decrease of oxygen groups
in the final product. The first remarkable difference between the
aliphatic and aromatic diamines was observed directly after their
addition in the GO dispersion: addition of aliphatic diamines
resulted in immediate formation of GO nanosheet aggregates
(see Figures 2a,b). On the other hand, aniline derivatives were
dispersed slowly in the water phase, and GO aggregates were
formed much later during the hydrothermal heating.
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Vrettos et al. The Role of Diamines in the Formation of Graphene Aerogels
FIGURE 3 | SEM images of (a,b) rGOTETA,(c,d) rGOHDA ,(e,f) rGOEDA, and (g,h) rGOPXDA aerogels.
During hydrothermal treatment, diamines function as
crosslinkers leading to agglomeration of functionalized rGO
in well-shaped black monolithic hydrogels. The density of the
final aerogels ranged between 12 and 22 mg cm3(except for
rGOMDA). Direct aggregation of GO nanosheets via reaction of
epoxy groups with aliphatic diamines, before reduction (which
normally lead to graphitized species) led to the formation of
well-shaped gels and aerogels that kept the dimensions of the
mold as demonstrated in Figure 2c, with a hexagonal-shaped
aerogel. Hydrothermal treatment of GO, under the same
conditions, in the absence of diamine, led to the formation of
rGO aggregates, which after removal of water remained as dense
Characterization of Graphene Aerogels
The mass of functionalized rGO aerogels ranged between 16
and 26 mg, while the porosity was estimated above 96% for all
materials (see Table 2). The microstructure of final aerogels with
aliphatic diamines consists of pores with diameter between 20
and 40 µm as revealed by SEM (see Figure 3).
Similarly, GO nanosheets with aromatic diamines were partly
reduced and functionalized leading to porous 3D monolithic
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Vrettos et al. The Role of Diamines in the Formation of Graphene Aerogels
FIGURE 4 | SEM images of (a,b) rGOPPD ,(c,d) rGOOPD,(e,f) rGODAB , and (g,h) rGOMDA aerogels. (i) magnified image of the crystals that are localized on
graphene surface in rGODAB and (J) rGOMDA aerogels.
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Vrettos et al. The Role of Diamines in the Formation of Graphene Aerogels
FIGURE 5 | FT-IR spectra of aerogels with aliphatic diamines.
FIGURE 6 | FT-IR spectra of aerogels with aromatic diamines.
aerogels as shown in Figure 4. Here, pore sizes ranged from
about 50 to 200 µm in rGOPPD , rGOOPD, rGODAB aerogels, while
rGOMDA appeared to be more condensed without visible pores.
The last two aerogels were randomly decorated with crystals of
the diamines that were formed during synthesis, due to the very
low solubility of MDA and DAB in water.
FT-IR spectra of all aerogels showed, in comparison with
the spectrum of GO, a significant decrease of the characteristic
GO bands, and appearance of new bands from the incorporated
diamines (see Figures 5,6). The spectrum of pure GO showed
a broad band at 3,400–3,200 cm1due to the OH stretching
vibration (carboxyl, hydroxyl groups, or intercalated water), a
shoulder at 1,710 cm1(carboxylic C=O stretch) and bands at
1,380 cm1(carboxylic O-H deformation vibration), 1,620 cm1
(aromatic C=C stretches) (Ma et al., 2012; Hu et al., 2013;
Verma and Dutta, 2015), 1,200 cm1and 1,046 cm1[usually
assigned to phenolic C-OH stretches, as well as to epoxide (or
alcoxy) stretches (Guo et al., 2009; Ma et al., 2012; Kellici et al.,
2014)]. After reduction/functionalization, the bands assigned to
oxygen groups at 1,046, 1,200, 1,710, and 3,200–3,400 cm1were
significantly reduced in the spectra of rGO’s. Covalent grafting
of TETA on graphenic layers was indicated by the appearance
of characteristic peaks at 2,920, 2,850 cm1(-CH2- stretch),
1,550 cm1(N-H in plane scissoring vibration or bending),
(Tang et al., 2014) 1,440 cm1(-CH2- bend), 1,170 cm1and
1,100 cm1(C-N stretch). Similar spectroscopic evidence was
recorded in other aerogels with aliphatic diamines as shown in
Figure 5, indicating analogous covalent functionalization.
Regarding the FT-IR spectra of the aerogels with aromatic
diamines a similar behavior is observed. The characteristic peaks
of the oxygen groups were remarkably reduced in comparison
with GO and several new peaks have been appeared indicating
the presence of aromatic diamines in the aerogels. rGOPPD
showed peaks at 3,445 cm1(OH stretch), 1,624 cm1(C=C
bending), 1,536 cm1(bending vibration of NH, indicating –C-
NH-C- formation) (Tang et al., 2014), 1,500 cm1(phenyl ring
vibration), 1,420 (C-N stretch), 1,100, cm1(-CO stretch), (Lu
et al., 2014), and 873 cm1(CH non-planar ring vibrations; see
Figure 6).
rGOMDA showed weak bands at 3,412 cm1(NH and NH2
stretch), 1,625 cm1(C=C bending), 1,500 cm1(phenyl ring
vibration), 1,230, 1,160 cm1(C-N stretch), and 822 cm1
(CH non-planar ring vibrations). rGODAB showed peaks at
3,352 cm1(NH and NH2stretch), 1,625 cm1(C=C bending
or NH2scissors), 1,573 cm1(in plane scissoring vibrations or
bending), 1,500, 1,480 cm1(phenyl ring vibration), 1,425 cm1
(C-N stretch), 1,140 cm1(C-O stretch) (see Figure 6).
Raman Spectroscopy
Raman spectra of GO and rGO aerogels are shown in Figure 7.
D (A1g symmetry mode) and G (E2g mode of the sp2carbon
atoms) (Chen et al., 2013) bands in the modified with aliphatic
diamines rGO aerogels appeared as well-defined peaks at 1,350
and 1,580 cm1, respectively. The same bands in the GO
precursor appeared at 1,366 and 1,600 cm1. And the observed
shift is attributed to the recovery of the hexagonal network of the
carbon atoms with defects. The G band in some spectra appeared
clearly asymmetric due to the contribution of D’ band, while both
D and G bands in rGODAB, rGOOPD aerogels are contaminated
by signals probably due to the presence of aromatic diamines.
The characteristic ID/IGratio (IDand IGwere measured from
the peak height after baseline correction) was increased from 0.78
in pure GO to 0.86–1.19, similarly to other rGO products in the
literature (Stankovich et al., 2007; Pei and Cheng, 2012; Tang
et al., 2014; Abdolhosseinzadeh et al., 2015; Bo et al., 2015; Ji et al.,
2017). That change is usually attributed to the decrease of average
size of sp2domains, together with an increase of the number of
those domains after reduction (Stankovich et al., 2007; Pei and
Cheng, 2012; Chen et al., 2013; Feng et al., 2013). Moreover, the
2D band in all products appeared between 2,700 and 2,730 cm1,
while it was sharper and more intense in rGOTETA and rGOHDA
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Vrettos et al. The Role of Diamines in the Formation of Graphene Aerogels
FIGURE 7 | Raman spectra of aerogels with (A) aliphatic diamines (1:rGOEDA ,
2:rGOHDA, 3:rGOTETA, 4:rGOPXDA ), (B) aromatic diamines (1:rGOPPD ,
2:rGOMDA, 3:rGODAB , 4:rGOOPD).
indicating a higher degree of aromatization in those products,
in accordance with the results of TG analysis as shown below.
Similarly, in rGO aerogels modified with aromatic diamines,
the ID/IGratio ranged between 0.74 and 1. The 2D band
here appeared near 2,730 cm1(except in rGOOPD where it
appeared at 2,692 cm1), while it was sharper and more intense
in rGOPPD and rGOOPD indicating an analogous higher degree
of aromatization of those products.
TG Analysis
Thermogravimetric analysis of GO showed a 5% mass loss
up to 100C due to removal of water entrapped between GO
nanosheets and a 35% mass loss closer to 200C, which is
attributed to pyrolytic removal of oxygen-containing groups
(epoxides, carboxyl, and hydroxyl groups). The remaining
carbon material was removed by oxidation completely by 500C
FIGURE 8 | TG analysis of aerogels with aliphatic diamines and GO.
FIGURE 9 | TG analysis of aerogels with aromatic diamines and GO.
(see Figure 8, line 4) (Kuila et al., 2008; Abdolhosseinzadeh et al.,
Thermographs of rGO aerogels with aliphatic diamines,
as shown in Figure 8, showed a mass loss between 30 and
60%, over 600C, attributed to carbon oxidation, indicating
enhanced thermal stability of rGO nanosheets, in comparison
with GO, due to the partial aromatization during hydrogel
formation. Furthermore, rGOEDA showed a mass loss of 45%
between 100 and 200C, while the other rGO loose less mass,
gradually between 100 and 550C. This is possibly attributed
to the removal of diamine and oxygen containing groups.
HDA appeared to be the most effective in reduction of GO,
since rGOHDA was the most thermally stable (a property that
correlates with aromaticity), in accordance with its superior
basicity/nucleophilicity (see Table 1, pKavalues). At the opposite
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Vrettos et al. The Role of Diamines in the Formation of Graphene Aerogels
FIGURE 10 | XRD patterns of rGO aerogels and GO.
PXDA, the weakest base/nucleophile, was the less effective in
reduction of GO, producing less thermally stable rGOPXDA (He
et al., 2011).
The results from TGA of rGO aerogels with aromatic
diamines are shown in Figure 9. rGOPPD, showed a 35% mass
loss below 100C (water removal, which appeared in most
aerogels) and almost all the rest material (PPD and carbon mass)
was removed between 500 and 700C. rGOOPD and rGOMDA
showed similar behavior and lost about 70% between 500
and 700C showing slightly more effective reduction. rGODAB
nanosheets were the most thermally stable and consequently
most aromatic material since a 60% was removed above
700C. Comparing thermal stabilities of the four aerogel’s
nanosheets with aromatic diamines, it is observed that DAB
was the best reducing agent, although it was the weakest
base. Then, OPD and MDA followed and finally PPD, the
strongest base (according to the pKa values), was the less
effective reducing agent. That behavior could be attributed,
either to the excess amino groups of DAB, or the flexibility
of MDA due to central aliphatic carbon that could affect the
reduction mechanism, e.g., by facilitating aziridine formation
or the elimination that follows nucleophilic addition of the
Figure 10 shows the XRD patterns of GO, and rGO aerogels.
GO showed an intense peak at 2θ=11.4, which corresponds
to an interlayer distance of 0.77 nm, due to absorbed water
molecules between graphene layers and the existence of oxygen
functional groups (Ma et al., 2012; Bo et al., 2015). The
XRD patterns of rGO aerogels, showed absence of any intense
characteristic peak, which is an indication of the effective
exfoliation of rGO nanosheets. rGOOPD and rGOPXDA aerogels
showed a weak broad peak at 2θ=26.7and 26.4respectively,
which attributed to graphitic structure (d =0.34 nm). The other
aerogels showed very weak broad graphite (002) peaks with
2θ=2124, which corresponds to an interlayer spacing of
0.43–0.36 nm and is due to disordered stacking of the reduced
graphene sheets (Bourlinos et al., 2003; Chen et al., 2013; Fan
et al., 2013; Hu et al., 2013; Lan et al., 2016).
Electrical Conductivity
It is known that rGO aerogels are electrically conductive, which
is a property that is recovered only after reduction and partial
aromatization of GO (Ma et al., 2012; Nardecchia et al., 2013; Li
et al., 2014; Jun et al., 2015). However, conductivity is not always
the same and depends basically on the degree of reduction and
restoration of the aromatic system as well as the interconnections
between the rGO nanosheets.
To have a representative image of the electrical conductivity
of aerogels, bulk electric resistance was measured instead of
sheet resistance, which is preferable mainly in films, thus
avoiding problems with the roughness and the porosity of
the aerogel surfaces. Bulk resistance and resistivity of rGO
aerogels are shown in Table 2. Although the resistivity values
vary, there is a clear trend of aromatic diamines to reduce
aerogel resistivity more efficiently in comparison with aliphatic
diamines (Ma et al., 2012). Considering that electrical resistance
of a graphene superstructure is located in the interconnections
between graphene nanosheets, the reduced resistivity of the
doped with aromatic diamines aerogels could be attributed to a
positive role of the aromatic molecules as conductive pathways in
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Vrettos et al. The Role of Diamines in the Formation of Graphene Aerogels
FIGURE 11 | The compression of (a) rGOOPD (b) rGOHDA (c) rGOTETA aerogel cylinders after the placement of a 5 0 g standard precision weight.
the interconnections. Furthermore, aromatic molecules could be
placed as a bridge connecting graphene nanosheets, multiply the
number of interconnections and thus decreasing the resistivity.
In contrast to their ultralight weight, graphene aerogels
showed an outstanding mechanical strength as expressed by their
ability to support loads about 2,500 times heavier than their own
weight, without signs of deformation. As shown in Figure 11a,
the placement of a 50 g standard weight on the top of rGOOPD
aerogel cylinder, resulted in a compression of about 25%. After
the removal of the weight, rGOOPD aerogel cylinder recovered the
initial thickness. Similar elastic compression was observed with
all aerogels with aromatic diamines.
The aerogels with aliphatic diamines, under the same
conditions, showed a lower—about 11%—but inelastic
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Vrettos et al. The Role of Diamines in the Formation of Graphene Aerogels
compression, as shown in Figure 11b and rGOHDA. The
other aerogels with aliphatic diamines showed similar behavior,
with the exception of rGOTETA, which was compressed, also
inelastic, about 50%, under the same conditions (see Figure 11c).
GO was hydrothermally reduced and subsequently
functionalized with aliphatic and aromatic diamines, forming
well-defined 3D monolithic aerogels, with remarkable
mechanical strength. This study has shown that aromatic
diamines improved the conductivity of aerogels, while porosity
and density were not seriously affected by the diamine structure
or solubility. Amongst aliphatic diamines, the most nucleophilic
one (HDA) was also the most effective in reducing GO, while
among aromatic diamines, a similar correlation was not observed
since DAB, the less nucleophilic one, was the most effective in
reducing GO. Finally, it is concluded that aliphatic and aromatic
diamines are excellent gelation promoters forming stable
well-defined aerogel monoliths.
All authors listed have made a substantial, direct and intellectual
contribution to the work, and approved it for publication.
The authors thank Dr. N. Leventis for his critical reading of the
manuscript and his suggestions for improvement.
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Conflict of Interest Statement: The authors declare that the research was
conducted in the absence of any commercial or financial relationships that could
be construed as a potential conflict of interest.
Copyright © 2018 Vrettos, Karouta, Loginos, Donthula, Gournis and Georgakilas.
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Frontiers in Materials | 11 April 2018 | Volume 5 | Article 20
... Nanomaterials 2020, 10, x FOR PEER REVIEW 6 of 15 To explain the obtained trend, two effects associated to the amines must be taken into account. On the one hand, there is the thermal and chemical reduction induced by the amine [14,52] that leads to GO-COOH stacking. On the other hand, there is the effect of the amine molecules introduced between the GO-COOH sheets, which prevent their stacking by acting like spacers [53][54][55]. ...
... To explain the obtained trend, two effects associated to the amines must be taken into account. On the one hand, there is the thermal and chemical reduction induced by the amine [14,52] that leads to GO-COOH stacking. On the other hand, there is the effect of the amine molecules introduced between the GO-COOH sheets, which prevent their stacking by acting like spacers [53][54][55]. ...
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Graphene cryogels synthesis is reported by amine modification of carboxylated graphene oxide via aqueous carbodiimide chemistry. The effect of the amine type on the formation of the cryogels and their properties is presented. In this respect, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), were selected. The obtained cryogels were characterized by Fourier Transformed Infrared spectroscopy, thermogravimetric analysis, X-ray spectroscopy, and Scanning electron microscopy. The CO2 adsorption performance was evaluated as a function of amine modification. The results showed the best CO2 adsorption performance was exhibited by ethylenediamine modified aerogel, reaching 2 mmol g−1 at 1 bar and 298 K. While the total N content of the cryogels increased with increasing amine groups, the nitrogen configuration and contributions were determined to have more important influence on the adsorption properties. It is also revealed that the residual oxygen functionalities in the obtained cryogels represent another paramount factor to take into account for improving the CO2 capture properties of amine-modified graphene oxide (GO)-based cryogels.
... 3D materials prepared with the same amount of AsA and at the same temperature can give different 3D monoliths because of the heteroatoms present and the steric effects of these molecules among the graphene sheets. [41,42]. Structures obtained at 60 °C seem more porous than those prepared at 90 °C. ...
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Reduced graphene oxide is a material that has a variety of applications, especially in CO2 adsorption. The study of this research is the preparation of reduced graphene oxide with different heteroatoms and how the adsorption capacity is changed. The functionalization with other compounds bearing Si, S, N, and O was before reducing graphene oxide. Different monoliths were prepared by changing the ascorbic acid analogy and the temperature of reduction. The different porosity values, percentages of heteroatoms, and synthetic parameters show that the adsorption capacity is a complex procedure that can be affected by multiple parameters. Microporosity, different functionalities from heteroatoms, and high surface/volume of pores are the significant parameters that affect adsorption. All parameters should establish a balance among all parameters to achieve high adsorption of CO2.
... Với tiền chất GO, quá trình tổng hợp GA gồm hai giai đoạn; giai đoạn sol -gel và giai đoạn sấy [9]. Trong giai đoạn sol -gel, các chất khử có thể được sử dụng là L-ascorbic [10], etylendiamine [5,11], NaHSO3, Na2S, amoniac, HI, hydroquinone, hydrazine, borohyrides, axit hydrohalic, … [12], etylen glylcol [13,14], glutathion [15]. Chất khử được ưu tiên sử dụng là L-ascorbic do đặc tính thân thiện môi trường, không tạo sản phẩm phụ [16]. ...
Graphene Aerogel (GA) is the lightest material in over the world. This material has high surface area with many layers of single graphene and has potential applications for adsorption, catalysis and storage. In this study, graphene aerogel materials were successfully synthesized by environmentally friendly hydrothermal methods without the use of reducing agents and were dryed by supercritical CO2 to avoid secondary environmental pollution. The obtained GA materials were characterized by Brunauer- Emmett- Teller (BET) surface area measurements, scanning electron microscopy (SEM), Raman spectroscopy. Results showed that with hydrothermal time of 5 hours and GO concentration of 2,5 mg/mL, GA material has highest surface area of 941 m2/g and lowest density of 0,0226 g/cm3.
... Thus, the GA produced by different reducing agents displays different properties [67] . Vrettos and colleagues [68] demonstrated that diamines' such as EDA and PPD's double function as a reducing agent and a crosslinker between rGO nanosheets makes them excellent gelation agents for the formation of stable and welldefined aerogels with improved conductivity. Shi et al. employed glutathione as both a cross-linker and a reducing agent, producing GAs that were nitrogen and sulfur-doped [69] . ...
Graphene aerogels (GAs) are amongst the lightest materials in the world. They attracted increasing interest in academia and industry because of their exceptional and unique properties, like high mechanical strength, electrical conductivity, thermal resistance, and adsorption capacity. In this review, we describe advances in research and development of a variety of methods that lead to the synthesis of graphene-based aerogels. First, the main common methods for producing GAs are examined, such as chemical reduction, hydrothermal reduction, crosslinking, polymerization methods, and template-directed reduction. Furthermore, the advancement of the 3D printing of GAs is presented. These methods resulted in GAs with porous hierarchical textures, low densities, and improved electrical conductivities, robust mechanical properties, better stability, and excellent adsorption potential. Then, the promising potential applications of GAs in the domains of energy storage, energy conversion, and environmental protection are evaluated. Finally, the prospects and challenges associated with the manufacturing of GAs are discussed.
To increase the viability of electric vehicles for the general population, it is critically important that rechargeable batteries are designed to support rapid charging, which is as important as increasing their energy density. However, commercial lithium-ion batteries (LIBs) encounter a ceiling of rate capability due to the sluggish intercalation kinetics of graphite anodes originated from their narrow interlayer spacing. Here, we report on graphite oxide frameworks (GOFs), whose interlayers are enlarged between 7.4 and 13 Å via a solvothermal reaction employing α,ω-diamino organic fillers. The GOFs offer ultrafast charging properties with a high lithium storage capacity of 370 mA h g⁻¹ (at 3,000 mA g⁻¹). In addition, we could determine the optimum interlayer spacing of layered electrode materials, at which the barrier for Li⁺ transport could be minimized. Altogether, our findings provide deep insight for the rational design fast chargeable LIBs with electrodes based on layered materials.
Polyaniline (PANI) as a typical conductive polymer has been widely applied in cathode materials of aqueous zinc ion battery (AZIB), owing to the features of high electronic conductivity and simple synthesized methods. However, the cycling instability caused of spontaneous deprotonation still limited the extensive application of PANI cathode materials. In this work, a functionalized commercial graphene (MEG) and PANI composite (MGP-1) was successfully assembled by a facile two-step method. When the MGP-1 acted as cathode material in AZIB, it demonstrated a high capacity of 184.5 mAh/g (0.2 A/g) and excellent rate performance of 137.6 mAh/g (3 A/g) compared to the PANI cathode. The corresponding analysis revealed that the boosted electrochemical behavior of MGP-1 was attributed to the large conductive network fabricated by the MEG and PANI, and the formations of -N-Zn-O- structures during discharging process. Moreover, based on the conventional H⁺ insertion mechanism, this work furtherly provided a H⁺ and Zn²⁺ insertion mechanism. In addition, the utilization of cheap and abundant commercial graphene would allow the graphene/polyaniline composite to be a promising cathode material applied in AZIB.
The synthesis of a derivatized graphene oxide with a particularly high degree of functionalization is achieved through a facile wet‑chemistry procedure. Graphene oxide is a highly reactive graphene derivative, especially with nucleophiles or dipolarophiles. However the reductive action of nucleophiles, as well as of other reactants or solvents usually prevails over functionalization. Therefore, the reactions of graphene oxide lead almost exclusively into reduced graphene derivatives with low functionalization degree. Here we report that tuning the reaction conditions during functionalization can alter the competition outcome of the two simultaneous reactions in a 1,3 dipolar cycloaddition on graphene oxide. Under these conditions, the cycloaddition pathway was dramatically favoured against the unspecific reduction/oxygen elimination side reactions, affording a selectively and densely functionalized graphene oxide. This property can be exploited for enhancing the interactions with target molecules (very effective immobilization of pharmaceutic compounds, as demonstrated here), as well as in other applications such as in preparing catalysts with high content of active sites by coordinating metal nanoparticles or atoms.
3D graphene-based materials are promising adsorbents for environmental applications. Furthermore, increasing attention has been paid to the improvement of 3D graphene adsorbents for removing pollutants. In this article, the progress in the modification of 3D graphene materials and their performance for removing pollutants were reviewed. The modification strategies, which were classified as (1) the activation with CO2 (steam and other oxidants) and (2) the surface functionalization with polymers (metals, and metal oxides), were evaluated. The performances of modified 3D graphene materials were assessed for the removal of waste gases (such as CO2), refractory organics, and heavy metals. The challenges and future research directions were discussed for the environmental applications of 3D graphene materials.
Carbon aerogels with a three-dimensional (3D) hierarchical porous network could be promising carbon-based materials for electrochemical energy storage systems because of their rapid electron/ion transport, remarkable physicochemical stability and excellent cycling performance. They have also been used to host electrochemical active materials (transition metal oxides/sulfides/phosphides) in pores to improve the electron conductivity and to buffer large volume changes. In this review, recent advances in their synthesis, functionalization/modification and use in alkali-metal ion batteries, either alone or as composites, are summarized. The challenges for future research on carbon aerogels are discussed and development opportunities are proposed.
Full-text available
The focus of research in diamine functionalised graphene oxide (GO) has been limited to the use of diamines either as crosslinker or to achieve simultaneous functionalisation, reduction and stitching of GO sheets, especially in the case of ethylene diamine (EDA). Controlling the extent of stitching and functionalisation has to date remained a challenge. In particular, synthesis of colloidally stable monofunctionalised GO-NH2 with dangling amine groups using diamines has remained elusive. This has been the limiting factor towards the utility of EDA functionalised GO (GO-NH2) in the field of polymer-based nanocomposites. We have synthesised colloidally stable GO-NH2 with dangling amine groups and subsequently demonstrated its utility as a surfactant to synthesize colloidally stable waterborne polymer nanoparticles with innate affinity to undergo film formation at room temperature. Thermally annealed dropcast polymer/GO-NH2 nanocomposite films exhibited low surface roughness (~1 µm) due to the homogeneous distribution of functionalised GO sheets within the polymer matrix as observed from confocal laser scanning microscopy, scanning electron microscopy and transmission electron microscopy. The films exhibited considerable electrical conductivity (~0.8 S m-1), demonstrating the potential of GO-NH2/polymer nanocomposite for a wide range of applications.
Full-text available
Graphene oxide has recently emerged as an efficient adsorbent for removal of heavy metals including radionuclides from contaminated ground water. Here we demonstrate very high adsorption capacity (qe = 72.2 mg g-1) of graphene oxide for adsorption of uranyl ions. However, in the presence of common interfering cations (Ca2+, Mg2+, K+, Na+, Pb2+, Fe2+ and Zn2+) and anions (CO32-, HCO3-, Cl- and SO42-) that are expected in ground water, the adsorption capacity of uranyl ions on graphene oxide decreased drastically owing to poor selectivity. Here we also report a strategy for significantly improving selective adsorption of uranyl ions in the presence of the above interfering species. The graphene oxide is modified by liquid ammonia in the presence of a dehydrating agent (the material obtained is referred to as NH3-GO adsorbent) and thoroughly characterized by zeta potential measurement, Raman spectroscopy, Fourier transformed infrared spectroscopy, transmission electron microscopy and scanning electron microscopy. The suitability of NH3-GO as an adsorbent of uranyl ions has been studied in batch mode as a function of pH, temperature, adsorbent dose and initial concentration of uranyl ions. The maximum experimental adsorption capacity at equilibrium conditions is found to be 40.1 mg g-1 at pH 6 at 298 K, which is not affected by the presence of most of the cations and anions. This marked improvement in the selectivity of uranyl ion adsorption is attributed to amidation of graphene oxide, rendering improved selectivity as compared to carboxylic acid groups. The maximum monolayer coverage (qmax) was deduced as 80.13 mg g-1, indicating it to be an excellent adsorbent. The mechanism of adsorption is studied in terms of adsorption isotherm models, kinetic models and thermodynamic studies, which indicated a dual mechanism of chemisorption and physisorption owing to more than one type of binding site in NH3-GO. It is concluded that the ammonia modified graphene oxide exhibited a highly selective adsorption property for uranyl ions at neutral pH.
A green approach for the preparation of a stable reduced graphene oxide (RGO) suspension from graphene oxide (GO) has been developed. This method uses L-serine (L-Ser) as the reductant and yellow dextrin (YD) as the stabilizing agent. X-ray photoelectron spectroscopy, UV-vis spectroscopy, X-ray diffraction and thermogravimetric analyses showed that L-Ser can efficiently reduce GO at a comparatively low temperature, and that the YD adsorbed onto the RGO facilitating the formation of a stable RGO aqueous suspension. Since L-Ser and YD are natural environmentally friendly materials, this approach provides a green method to produce stable RGO from GO on a large scale. Sodium salicylate (SS) which has an aromatic structure was loaded onto the RGO through ?-? interactions and a maximum loading capacity of 44.6 mg/g was obtained. The release of the loaded SS can be controlled by adjusting the solution pH, and a 74.8% release was reached after 70 h at pH 7.4. The release profile of SS could be further controlled by incorporating it into RGO Dispersed carboxylated chitosan films.
We report a simple and effective approach to fabricate graphene/nickel (G/Ni) aerogels by a sol-gel method and supercritical CO2 drying technique. The crystalline structure and chemical composition of the G/Ni aerogels have been investigated using X-ray diffraction and X-ray photoelectron spectroscopy. The morphology and porous attributes of the G/Ni aerogels have been characterized by transmission electron microscopy, scanning electron microscopy and nitrogen adsorption tests. Results indicate that the resulting aerogels, in which the Ni nanoparticles are dispersed on the graphene sheets, exhibit mesoporous structure and large surface areas. The catalysis effect of the G/Ni aerogels on the thermal decomposition of ammonium perchlorate was studied by differential scanning calorimetry. When 9 wt% of the aerogels was added, the thermal decomposition temperature of ammonium perchlorate was decreased by 122 °C. The results show that the G/Ni aerogels exhibit a remarkable catalytic performance for the thermal decomposition of ammonium perchlorate due to the combination of Ni nanoparticles and graphene sheets.
The preparation of graphitic oxide by methods described in the literature is time consuming and hazardous. A rapid, relatively safe method has been developed for preparing graphitic oxide from graphite in what is essentially an anhydrous mixture of sulfuric acid, sodium nitrate and potassium permanganate.
Graphene oxide (GO) has attracted intense interest for its use as a precursor material for the mass production of graphene-based materials, which hold great potential in various applications. Insights into the structure of GO and reduced GO (RGO) are of significant interest, as their properties are dependent on the type and distribution of functional groups, defects, and holes from missing carbons in the GO carbon lattice. Modeling the structural motifs of GO can predict the structural evolution in its reduction and presents promising directions to tailor the properties of RGO. Two general reduction approaches, chemical and thermal, are proposed to achieve highly reduced GO materials. This review introduces typical chemical oxidation methods to produce GO from pure graphite, then summarizes the modeling progress on the GO structure and its oxidation and reduction dynamics, and lastly, presents the recent progress of RGO preparation through chemical and thermal reduction approaches. By summarizing recent studies on GO structural modeling and its reduction, this review leads to a deeper understanding of GO morphology and reduction path, and suggests future directions for the scalable production of graphene-based materials through atomic engineering.