Research Article

pubs.acs.org/journal/ascecg

Sustainable Carbon Nanodots with Tunable Radical Scavenging

Activity for Elastomers
Siwu Wu, Peijin Weng, Zhenghai Tang, and Baochun Guo*
Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou, 510640, P. R. China
*
S Supporting Information

ABSTRACT: The application of polymers as an essential

class of material was greatly inhibited due to the aging failure
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of these versatile materials during normal use. Hence, it is

generally recognized that stabilization against thermo-oxidative
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aging is indispensable to extend the service life of polymers for

long-term applications. However, toxicity and pollution of the
state-of-the-art antiaging technologies have long been puzzles
in the polymer industry. Herein, sustainable carbon nanodots
(CDs), synthesized by facile and cost-effective microwave-
assisted pyrolysis, are used for first time as radical scavengers
to resist the thermo-oxidative aging of elastomers. We have
demonstrated that incorporation of the resultant CDs could be
green and generic radical scavengers toward highly aging-resistant elastomers. Furthermore, by controlling the photoluminescent
quantum yield of the CDs with various passivated agents, tunable radical scavenging activity was achieved. We established for the
first time that the aging resistance originates from the prominent reactive radical scavenging activity of the CDs, which was
rationally controlled by their photoluminescent quantum yield.
KEYWORDS: Carbon nanodots, Radical-scavenging, Antioxidants, Photoluminescence, Elastomer

■ INTRODUCTION
The aging of polymeric materials greatly increases resource
consumption and may be disastrous in some cases. As an
important class of polymers in modern industries, dienic
elastomers such as natural rubber (NR) and styrene butadiene
rubber (SBR) are susceptible to thermo-oxidative aging due to
the unsaturated chains and allylic hydrogens in their backbone
chains.1 To increase the aging resistance and hence the
reliability of polymers, a general solution is to include
antioxidants to prolong their lifetime. However, most of the
antioxidants are congenitally toxic inherited from their raw
materials.2−7 Moreover, the industrialized processes for the
manufacture of most antioxidants are quite complicated, time-
demonstrated that CDs can not only act as electron donors but
also as electron acceptors and accelerate the electron transfer
process that originates from the high electron density and
mobility of the π−π inner structure and peripheral function-
alized moieties.22 Furthermore, CDs exhibited efficient radical
scavenging property and antioxidant activity through in vitro
assay.23 Herein, inspired by the unique characteristics of CDs,
we synthesized several kinds of CDs via facile microwave-
assisted pyrolysis and, for the first time, utilized CDs as novel
radical scavengers for typical dienic rubber. Furthermore, the
mechanism of antioxidation by amine-passivated CDs was
analyzed by correlating the aging resistance of the rubbers to
the CDs’ PL properties which originated from their inherent
structure.

consuming, and eco-unfriendly. These inevitable puzzles inspire
researchers to seek sustainable antioxidants with generic
processing methods.8−15 As an alternative solution, several
kinds of nanofillers, such as clays, carbon nanotubes, fullerene,
and graphene, have been explored as new antioxidants. This
approach has offered us an alternative insight into the design of
the antiaging polymeric materials.16−19 Unfortunately, the high
fabrication costs and sophisticated processing required for these
materials (e.g., graphene-based composites) impede their
applications in real-world application.
Recently, carbon nanodots (CDs), as quasi-spherical carbon-
based nanoparticles, have been widely reported because of their
fantastic properties, such as strong photoluminescence (PL)
emission, low toxicity, excellent biocompatibility, facile syn-
thesis, and wide materials sources.20,21 Some studies have
■
EXPERIMENTAL SECTION
Materials and Chemicals. Citric acid (CA, 99%), 1,2-ethylenedi-
amine (EDA, 98%), urea (99.3%), 1,4-butanediamine (BDA, 98%),
triethylamine (TEA, 99%), L-ascorbic acid (≥99%), quinine sulfate
(≥95%), and 2,2-diphenyl-1-picrylhydrazyl (DPPH, 95%) were
purchased from Beijing InnoChem Science & Technology Co., Ltd.,
Beijing, China. All chemicals were used as received without further
purification. Styrene−butadiene rubber (Trademark: SBR1502,
styrene content 23.5 wt %) was purchased from Jilin Chemical
Industry Co., Jilin, China. Nature rubber (Trademark: NR RSS3) was
Received: September 13, 2015
Revised: November 8, 2015
Published: November 25, 2015

© 2015 American Chemical Society 247 DOI: 10.1021/acssuschemeng.5b01069

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ACS Sustainable Chemistry & Engineering
Figure 1. Schematic showing the synthesis of CDs with various passivation agents.
purchased from Guangzhou Rubber Institute, Guangzhou, China. The
other rubber additives were industrial grade and were used as received.
Synthesis Procedure for the Amine-Passivated CDs. The
amine-passivated CDs were synthesized by a facile microwave-assisted
pyrolysis method that has been described elsewhere.24,25 Briefly, 1.0 g
of CA was dissolved in a 100 mL beaker containing 10 mL phosphate
solution, and 0.313 g of EDA was added under stirring. The mixture
was heated in a domestic 750 W microwave oven for 3 min, during
which the colorless solution changed to a red−brown solid, indicating
the formation of amine-passivated CDs. The resulting solid was
dissolved in the minimum amount of distilled water. The red−brown
aqueous solution was then precipitated and washed with excess
anhydrous ethanol several times to remove soluble residue. The
purified resultant CDs were dried in vacuum at 50 °C and were stored
for further use.
Other CDs passivated with urea, BDA, or TEA were synthesized
through a similar procedure by microwave-assisted pyrolysis of a mixed
solution containing CA and urea, BDA or TEA, respectively; the molar
ratio between −COOH and −NH2 was maintained at 3:2. The
reaction time of the UREA-CDs, BDA-CDs, and TEA-CDs was 4, 3,
and 4 min, respectively.
Preparation of Rubber Composites. Various purified amine-
passivated CDs were mixed with SBR in an open two-roll mill. The
aforementional compounds were then subjected to isothermal DSC
analysis to measure the oxidative induction time (OIT). The curing
agents were then incorporated with the remaining compounds,
followed by hot-pressing at 150 °C for the optimum vulcanizing
time, as determined by a U-CAN UR-2030 vulcameter. The samples
are referred to as SBR/xy, where x denotes x parts of the amine-
passivated CDs (relative to 100 parts of SBR: phr) and y corresponds
to the type of amine-passivated CDs. The specific formulations are
expressed as parts per hundreds of rubber and are listed as SBR 100,
amine-passivated CD variable, zinc oxide 5, stearic acid 2, N-
cyclohexyl-2-benzothiazole sulfonamide (CZ) 1.5, and sulfur 1.5.
In addition, NR composites with various EDA-CDs were prepared
according to the aforementioned process and basic recipe. The well-
mixed compounds were hot-pressed at 143 °C for the optimum
vulcanizing time determined by a U-CAN UR-2030 vulcameter.
For comparison, SBR and NR were mixed with 1.5 phr commercial
antioxidant N-isopropyl-N′-phenyl-p-phenylenediamine (4010NA);
the resulting samples were SBR/1.5 phr 4010NA and NR/1.5 phr
4010NA, respectively.
All the rubber samples suffered thermo-aging in a UA-2071A aging
oven tester with hot air at 100 °C for various times.
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Research Article
Characterization. High-resolution transmission electron micros-
copy (HRTEM) was performed on a Philips Tecnai F20 TEM
microscope (Philips, Netherlands) operated at an accelerating voltage
of 200 kV. The samples for HRTEM were prepared by dropping an
aqueous solution onto a copper grid coated with carbon film. UV−vis
absorption spectra were recorded at room temperature using a Scinco
S3100 UV−vis spectrophotometer (Scinco, Korea). Photolumines-
cence emission spectra were measured on an Edinburgh FL920
fluorescence spectrometer (Edinburgh Instruments, Britain). Iso-
thermal differential scanning calorimetry (DSC) analysis was
performed on a Q200 differential scanning calorimeter (TA Instru-
ments, USA) at 180 °C following ISO standard 11357-6:2005.
Electron spin resonance (ESR) spectra were obtained using a JES-FA
200 X-band electron spin resonance spectrometer (JEOL, Japan) with
a temperature accessory (JEOL, Japan). To collimate the center and
strength of magnetic field, manganese (Mn2+) was inserted beside the
specimen as external standard. Fourier transform infrared spectra
(FTIR) were measured on a Bruker Vertex 70 FTIR spectrometer
(Bruker, German). X-ray photoelectron spectroscopy (XPS) analysis
was conducted on an ESCALAB 250 equipped with an Al Kα radiation
source (Thermo Fisher Scientific, USA). Tensile tests were conducted
at room temperature with a Gotech AI-7000 S servo control system
Universal testing machine (Gotech, Taiwan) following ISO standard
37-2005. The cross-link density of the composites was determined by
the equilibrium swelling method and was calculated using the Flory−
Rehner equation. Dynamic mechanical analysis was performed on a
TA Q800 dynamic mechanical analyzer (TA Instruments, USA). The
tests were performed in tensile mode at a frequency of 1 Hz and a
strain of 0.5%. The scanning temperature ranged from −80 to 100 °C
with a heating rate of 3 °C/min under flowing liquid nitrogen.
The quantum yield (QY) of the resultant amine-passivated CDs was
determined by a comparative method involving quinine sulfate with a
known QY (54%) as a standard sample. All samples were dissolved in
distilled water at different concentrations, and the corresponding UV−
vis absorbance was not allowed to exceed 0.1 in the 10 mm
fluorescence cell to minimize reabsorption effects. The fluorescence
spectra of solutions were recorded at their maximum excitation
wavelength (for EDA-CDs, 360 nm; UREA-CDs, 340 nm; BDA-CDs,
360 nm; TEA-CDs, 380 nm). The integrated fluorescence intensity
was calculated from the whole range of the spectra. A graph of the
integrated fluorescence intensity vs the corresponding absorbance was
plotted, and a trend line was added with an intercept of 0. The
absolute values were calculated according to the following equation:
DOI: 10.1021/acssuschemeng.5b01069
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ACS Sustainable Chemistry & Engineering
Figure 2. (a) HRTEM image of EDA-CDs. (b) UV−vis spectrum and the PL emission spectrum of EDA-CDs aqueous solution. (c) UV−vis spectra
of DPPH ethanol solution upon the addition of EDA-CDs solution. (d) ESR spectrum of EDA-CDs.
⎛ GradX ⎞⎛ ηX2 ⎞
ΦX = ΦST⎜ ⎟⎜⎜ 2 ⎟⎟
⎝ GradST ⎠⎝ ηST ⎠
where the subscripts ST and X represent the standard sample and test
samples, respectively, Φ is the fluorescence quantum yield, Grad is the
gradient from the plot of the integrated fluorescence intensity vs UV−
vis absorbance, and η is the refractive index of the solvent.
The radical inhibition activity of EDA-CDs was determined using
DPPH free radical assay with certain alteration involving L-ascorbic
acid as a standard sample according to the previous studies.17,23 The
DPPH solution in ethanol and EDA-CDs aqueous solution were
freshly prepared with concentration of 0.05 mg/mL. The radical
scavenging activity was measured by monitoring the decline of
absorption peak of DPPH at 517 nm in UV−vis spectra with
incremental amounts of EDA-CDs solution. The radical inhibition
activity was calculated as follows:
⎡ A − Ai ⎤
inhibition = ⎢1 − m ⎥ −NH2 groups and amide carbonyl groups are detected on the
⎣ A0 ⎦
Where Am is the absorbance of the DPPH solution (2 mL) with
diluted EDA-CDs solution (1 mL) at various concentrations (ranged
from 0 to 0.05 mg/mL, concentration step: 0.005 mg/mL), Ai is the
absorbance of corresponding diluted EDA-CDs solution (1 mL) with
the addition of 2 mL ethanol, A0 is the absorbance of DPPH solution
(2 mL) with the addition of 1 mL distilled water. All the reaction
mixtures were left in dark place for 40 min then receiving UV−vis test.
■ RESULTS AND DISCUSSION
The overall synthetic process is illustrated in Figure 1. CA, as a
typical renewable resource, was used as the carbon source and
EDA was used as a surface passivation agent to fabricate CDs
with peripheral amine groups. Furthermore, a series of amine
molecules, including urea, BDA, and TEA were utilized as
passivation agents to achieve the rational design of CDs with a
tunable photoluminescent QY and nitrogen content.24,25
Notably, all of the CDs were synthesized via the microwave-
assisted method, which is fast, high-yielding, cost-effective, and
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sustainable. More importantly, the EDA-CDs has been
demonstrated to have low or even no toxicity toward cells.24
The HRTEM image (Figure 2a) clearly shows that the as-
prepared EDA-CDs are narrowly distributed and essentially
amorphous, with diameters of 2.5−3.5 nm. The UV−vis spectra
of EDA-CDs show an absorption at approximately 240 nm,
which is attributable to the π−π* transition, and a typical peak
at approximately 340−360 nm, which is characteristic of
graphite structure.23 Meanwhile, the aqueous solution of EDA-
CDs exhibited bright blue fluorescence under excitation at 360
nm (Figure 2b). Detailed PL study of EDA-CDs with vary
excitation wavelengths ranging from 300 to 420 nm were
carried out (Figure S1). The excitation-independent-emission
phenomenon of EDA-CDs is detected, which also indicates
relatively uniform size and structure of EDA-CDs are achieved.
Moreover, as confirmed by FTIR and XPS, a large amount of
surface of the resultant EDA-CDs (Figure S2 and S3). These
results, which are consistent with those of a previous study,24
indicate that EDA-CDs were successfully prepared. As a well-
known test for the evaluation of the radical scavenging ability of
compounds, DPPH radical assay with certain alterations was
performed to estimate the radical scavenging ability of the
EDA-CDs.17,26 After the addition of EDA-CDs aqueous
solution, the purple DPPH solution turned yellow and the
absorbance peaks at 517 nm in the UV−vis spectrum
apparently decreased in intensity (Figure 2c). The radical
inhibition calculated according to the previous studies17
revealed that the corresponding radical scavenging ability of
EDA-CDs was distinctly higher than that of L-ascorbic acid (a
standard radical scavenger), which indicated the resultant EDA-
CDs were highly efficient radical scavengers (Figure S4). The
ESR spectra of EDA-CDs showed a Lorentzian shaped signal at
g-value ∼ 2.001 (Figure 2d), which indicated a singly occupied
orbital in ground-state carbon nanodots.27,28 This indicated that
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Figure 3. (a) DSC of all SBR compounds without curatives after the purge gas was switching from nitrogen to oxygen at 180 °C (OIT is measured
by tangent method as shown). (b) ESR spectra of SBR/1.5 phr EDA-CDs before and after in situ thermo-aging. (c) Evolution of the FTIR spectrum
for SBR/1.5 phr EDA-CDs during aging. (d) Relative intensity of the CO peak vs the aging time. (e) Evolution of the XPS spectrum for SBR/1.5
phr EDA-CDs during aging. (f) The O/C molar ratio vs the aging time.
EDA-CDs could serve as electron acceptors to stabilize and
scavenge reactive radicals during reaction.
To achieve a homogeneous dispersion of nanocarbons, such
as graphene, in elastomers, previous studies generally utilized
solution blending method, which requires a sophisticated
process or massive volumes of solvents. However, because the
aromatic skeleton of CDs is similar to that of aromatic amine
antioxidants, CDs are miscible with dienic elastomer. Hence, all
of the CDs were mixed into SBR via traditional two-roll milling,
a common rubber processing procedure.
To evaluate the antioxidative efficiency of EDA-CDs, OIT of
the SBR/EDA-CDs was measured by DSC analysis at 180 °C
(Figure 3a). As expected, the addition of EDA-CDs
considerably prolonged the OIT of the SBR compounds
(Figure S5). In comparison with 4010NA, a well-known
antioxidant for its balanced performance of antiaging in tire
industry, an equivalent amount of EDA-CDs performed
unexpected talent in preventing thermo-oxidative aging,
prolonging the OIT to 17 min. A key factor in inhibiting the
thermo-oxidation is to capture and stabilize the radicals as soon
as possible. To identify the capacity of the radical scavenging
activity of the antioxidant in the SBR composite, ESR
measurement was carried out during in situ thermo-oxidative
aging. All SBR composites exhibited a broad singlet with a g-
value ∼ 2.004 which was typical for free radicals (g-value ∼ 2.0)
(Figures 3b and S6). In general, it is inclined to generate alkyl
and allyl radicals due to the high reactivity of α-hydrogen in the
oxidation process of SBR matrix.29 However, the ESR signals of
such radicals will show a multiplet with hyperfine splitting so
that can be ruled out in this system.30,31 However, it has been
reported that the allyl radicals in SBR tended to transform into
polyenyl radicals with a g-value ∼ 2.004 under thermal
condition.32−34 Hence, it is reasonable to believe that some
polyenyl radicals have contributions to the ESR signals in SBR
composites. Moreover, the formation of peroxy radicals is
another inevitable section during the oxidation process of
polymer. The typical ESR signal of the peroxy radical has been
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Research Article
verified as a broad asymmetric singlet due to the orbital of the
unpaired electron being confined among two oxygen
atoms.35−37 The g-values of peroxy radicals are always higher
than 2.003 because coupling with heavier oxygen atoms
increases the spin−orbit coupling of the electron on peroxy
radicals.30,38 According to this, we suggest that contributions
from peroxy radicals to the singlet in SBR composites should be
taken into account too. After in situ thermo-oxidative aging, the
intensity of the signal for blank SBR increased acutely which
revealed a sharp growth of radical concentration inside blank
SBR matrix during in situ aging (Figure S6a). The addition of
4010NA reduced the intensity of the singlet of radicals
compared to that for the blank SBR but it was still not
satisfied (Figure S6b). For the SBR/1.5 phr EDA-CDs, the
intensity and shape of this singlet were almost unaltered after
aging, which meant the radical concentration was not
substantially altered, indicating the superior inhibition effect
on the reactive radicals of EDA-CDs (Figure 3b). Furthermore,
the carbonyl index and oxygen/carbon molar ratio (O/C) were
measured by FTIR and XPS, respectively. As shown in Figure
3c, the change of the intensity of the peaks associated with the
carbonyl groups (CO) and CC double bonds were
significantly inhibited, which reveals that the oxidation reaction
was effectively delayed by incorporating EDA-CDs. Taking the
bending vibration peak of the stable aromatic C−H bond at
760 cm−1 as the internal standard peak, we calculated the
relative CO and CC peak intensities for all SBR
composites vs the aging time, as shown in Figure 3d and
Figure S7, respectively. With increasing aging time, the SBR/
1.5 phr EDA-CDs exhibited a weakest increase of the relative
peak intensity of CO because the degradation rate of CC
was remarkably slowed in comparison to those of blank SBR
and SBR/1.5 phr 4010NA (Figure S7c). In addition, the
intensity of the O 1s peak centered at about 530 eV in the XPS
spectrum of SBR/1.5 phr EDA-CDs (Figure 3e) shows the
smallest increase after aging (up to 16 days) compared to those
of the blank SBR and the SBR/1.5 phr 4010NA (Figure S8).
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Figure 4. (a) EAB vs aging time. (b) Cross-link density vs aging time. (c) Evolution of temperature-dependent tan δ curves for SBR/1.5 phr EDA-
CDs during aging. (d) Relative tan δ peak values vs aging time.

Figure 5. (a) EAB retention for the SBR/amine-passivated CDs with increasing aging time. (b) PL QY of amine-passivated CDs. (d) Interplay
among the PL QY of amine-passivated CDs, increase in the O/C molar ratio and EAB retention of SBR/amine-passivated CDs (after 6 days of
aging). (d) Schematic of the thermo-antioxidative mechanism of amine-passivated CDs.

The corresponding O/C molar ratio for all of the SBR
composites also confirmed that the increase of the O/C ratio of
the SBR/1.5 phr EDA-CDs was the lowest (Figure 3f). This
remarkable reduction in the O/C molar ratio is attributed to
the superior antioxidant activity of the EDA-CDs, which inhibit
the oxidation process of the SBR matrix by capturing and
scavenging reactive radicals.
Because the addition of EDA-CDs prominently inhibits the
oxidation of the SBR matrix, which generates a significant
difference within the composite, evaluating the effects of EDA-
CDs on the mechanical properties of SBR during thermo-
oxidative aging is still important. In both cases, the aging
process led to a reduction in stretchability (elongation at break,
251
EAB) and an increase in cross-link density (Figure 4a, b), due
to the recombination of reactive radicals generated from
aging.39 The retention of EAB of the blank SBR drastically
decreased to only 20% after aging for 16 days (Figure S9a).
Although the incorporation of 1.5 phr 4010NA resulted in
significant improvement of the EAB after aging, the final
retention of EAB was still only 30%. Surprisingly, in the case of
SBR/1.5 phr EDA-CDs, the final retention of EAB was up to
42% and the corresponding EAB was approximately 50% higher
than that of SBR/1.5 phr 4010NA, which suggests that EDA-
CDs are a more efficient antioxidant than 4010NA. Moreover,
incremental incorporation of EDA-CDs led to consistent
improvement in the retention of EAB after aging but did not
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deteriorate the tensile strength (TS) of the composites (Figure
S9). Dynamic mechanical analysis was performed to obtain
more detailed information about the effects of different
antioxidants on the chain relaxation. After thermo-oxidative
aging, the peak value of the loss tangent (tan δ) for blank SBR
exhibited a substantial decrease (Figure S10a), which contrasts
sharply with the slight reduction of that of the SBR/1.5 EDA-
CDs (Figure 4c). The addition EDA-CDs generated minimal
variations in the relative peak value of tan δ (Figure 4d) and in
the shift of temperature of the tan δ peak (ΔTg) (Figure S10).
In general, reactive radicals are considered to dominate the
cross-linked reaction in the whole process of the aging of
SBR.39 Hence, the remarkable preservation of the static and
dynamic mechanical properties of SBR/1.5 phr EDA-CDs
demonstrates that the thermo-antioxidant activity of the EDA-
CDs is definitely superior to that of 4010NA because of the
outstanding ability of the EDA-CDs to capture and stabilize the
radicals.
On the basis of the combined aforementioned evidence, the
EDA-CDs are reasonably believed to exhibit superior thermo-
antioxidant activity for dienic elastomers because of their
prominent radical scavenging capability. Although the diame-
ters of the EDA-CDs are only 2−3 nm, their particulate nature
could prevent them from blooming during long-term storage,
which is a challenging issue for many organic antioxidants
(Figure S11). In addition, by incorporating EDA-CDs with NR
through a similar process, we have demonstrated that EDA-
CDs are a superior antioxidant to NR on the basis of the
retention of EAB and TS of the NR/EDA-CDs composites
after aging (Figure S12). However, the mechanism of the
superior thermo-antioxidant activity of the EDA-CDs was
unclear until now. By utilizing amine molecules as passivation
agents, the surface of the EDA-CDs contains abundant −NH2
groups, which may serve as proton donors to terminate reactive
radicals, similar to the function of p-phenylenediamine.40
Hence, we fabricated four types of amines-passivated CDs by
using different amines with various nitrogen contents as surface
passivation agents (Figure 1). By incorporating four amines-
passivated CDs with SBR, we verified the antioxidant activity of
different amine-passivated CDs on the basis of the static
mechanical properties of the corresponding composites after
aging. As shown in Figure 5a, the retentions of EAB at various
aging times (the corresponding EAB are shown in Figure S13)
are generally degressive with decreasing N content of the CDs
(Table S1). This result confirms the previous speculation that
the amount of peripheral amine groups is one of the major
factors affecting the antioxidant activity of CDs. Curiously, the
N contents of the EDA-CDs and UREA-CDs were
approximately the same; however, the retentions of EAB for
the corresponding composites after aging apparently differed.
Notably, the amines serve as not only passivation agents but
also N-doping precursors. Doped N atoms disturb the intrinsic
regularity of the CDs, resulting in a highly defected structure
with a mass of energy traps in the intrinsic carbon core which
can also stabilize the reactive radicals. These traps and the
surface passivated −NH2 groups both contribute to the PL
property of CDs.24,41 Figure S14 shows the integrated PL
intensity of all CDs vs the absorbance, while the calculated PL
QYs of all CDs are shown in Figure 5b and the corresponding
numerical values are listed in Table S1. By correlating the
retention of EAB at various aging times and the PL QY of
different CDs, we speculate that the PL QY of CDs can act as
the specific indicator of the antioxidant activity of CDs. In order
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Research Article
to further demonstrate our proposal, the O/C molar ratios and
retentions of EAB for the SBR/CDs composites after aging for
6 days are calculated and listed in Table S2. Obviously, the
increase of O/C molar ratio for SBR/CDs composites is
inversely proportional to the PL QY of CDs while the
corresponding retentions of SBR/CDs composites go the
opposite way as shown in Figure 5c (The separated figures can
be found in Figure S15). This result is reasonable because the
PL performance of amine-passivated CDs is also determined by
surface passivated groups and intrinsic energy traps,24,41 both of
which can capture and stabilize reactive radicals to prevent the
oxidation of the SBR matrix. A schematic mechanism of amine-
passivated CDs as superior antioxidants is given in Figure 5d.
This confirms our above proposal that the PL QY of CDs can
act as the sensitive and specific indicator of their antioxidant
activity because they have similar influencing factors.
In summary, we have utilized a facile, sustainable, cost-
effective, microwave-assisted pyrolysis method to synthesize
amine-passivated CDs and, for the first time, to incorporate the
sustainable CDs with dienic elastomers as novel antioxidants via
the commonest two-roll milling process. The resultant amine-
passivated CDs exhibited superior thermo-antioxidant activity
to suppress the oxidation process of dienic elastomers, as
evidenced by the higher retention of the static and dynamic
mechanical performances of the SBR composites compared to
those of the commercial antioxidant 4010NA. By controlling
the nitrogen content and PL QY of amine-passivated CDs with
various amine passivation agents, we achieved tunable
antioxidative capability for the resultant CDs. We attribute
the superior antioxidant activity of the amine-passivated CDs to
their prominent reactive radical scavenging activity, which could
be rationally controlled by the PL QY of the CDs. The present
work provides new insight into the green and generic design of
highly aging-resistant polymers with CDs and into under-
standing antiaging performance through the PL properties of
CDs.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.5b01069.
Abbreviation list, PL emission spectra, FTIR spectra and
high-resolution C 1s and N 1s spectra of EDA-CDs;
Comparison of the radical scavenging activity of EDA-
CDs and L-ascorbic acid; DSC analysis of SBR/EDA-
CDs compounds, ESR and DMA spectra of blank SBR
and SBR/4010NA composites, FTIR and XPS spectra of
all rubber composites, mechanical properties of SBR/
EDA-CDs and NR/EDA-CDs, and PL QY and elemental
analysis of CDs (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: psbcguo@scut.edu.cn. Tel.: +86 20 87113374. Fax:
+86 20 22236688.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by National Basic Research Program
of China (2015CB654703), National Natural Science Founda-
DOI: 10.1021/acssuschemeng.5b01069
ACS Sustainable Chem. Eng. 2016, 4, 247−254
ACS Sustainable Chemistry & Engineering
tion of China (Nos. 51222301, 51473050 and 51333003),
Fundamental Research Funds for the Central Universities
(Nos. 2015PT003 and 2015ZM011) and Natural Science
Foundation of Guangdong Province (2014A030310435 and
2014A030311051).
■
REFERENCES
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254 DOI: 10.1021/acssuschemeng.5b01069

ACS Sustainable Chem. Eng. 2016, 4, 247−254