OPEN Formation mechanism and optimization

SUBJECT AREAS:
of highly luminescent N-doped graphene
PHOTOCATALYSIS
NANOPARTICLES
quantum dots
Dan Qu1,3, Min Zheng1, Ligong Zhang1, Haifeng Zhao1, Zhigang Xie2, Xiabin Jing2, Raid E. Haddad4,
Received Hongyou Fan4,5 & Zaicheng Sun1
15 April 2014
Accepted 1
State Key Laboratory of Luminescence and Applications, Changchun Institute of Optics, Fine Mechanics and Physics, Changchun
27 May 2014 130033, Jilin, P. R. China, 2State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry,
Changchun 130022, Jilin, P. R. China, 3University of Chinese Academy of Science, Beijing 100000, P. R. China, 4Center for Micro-
Published Engineering and Materials, Department of Chemical and Nuclear Engineering, University of New Mexico, Albuquerque, NM
18 June 2014 87106, United State, 5Sandia National Laboratories, Advanced Materials Laboratory, Albuquerque, NM 87106, United State.

Correspondence and Photoluminescent graphene quantum dots (GQDs) have received enormous attention because of their
unique chemical, electronic and optical properties. Here a series of GQDs were synthesized under
requests for materials
hydrothermal processes in order to investigate the formation process and optical properties of N-doped
should be addressed to GQDs. Citric acid (CA) was used as a carbon precursor and self-assembled into sheet structure in a basic
H.Y.F. (hfan@sandia. condition and formed N-free GQD graphite framework through intermolecular dehydrolysis reaction.
gov) or Z.C.S. (sunzc@ N-doped GQDs were prepared using a series of N-containing bases such as urea. Detailed structural and
ciomp.ac.cn) property studies demonstrated the formation mechanism of N-doped GQDs for tunable optical emissions.
Hydrothermal conditions promote formation of amide between –NH2 and –COOH with the presence of
amine in the reaction. The intramoleculur dehydrolysis between neighbour amide and COOH groups led to
formation of pyrrolic N in the graphene framework. Further, the pyrrolic N transformed to graphite N
under hydrothermal conditions. N-doping results in a great improvement of PL quantum yield (QY) of
GQDs. By optimized reaction conditions, the highest PL QY (94%) of N-doped GQDs was obtained using
CA as a carbon source and ethylene diamine as a N source. The obtained N-doped GQDs exhibit an
excitation-independent blue emission with single exponential lifetime decay.

P
hotoluminescent carbon or graphene quantum dots (GQDs) have received enormous attention because of
their unique chemical, electronic and optical properties1–4. They also show good biocompatibility, low
cytotoxicity, excellent water solubility and stable photoluminescence. These unique chemical and physical
properties make them a great promising material for applications in photocatalyst, energy conversion, sensor, and
bioimaging5–17. Various approaches have been developed to fabricate GQDs including ‘‘top–down’’ and ‘‘bottom–
up’’ methods. The ‘‘top–down’’ methods refer to carving bulk carbon materials into nanoparticles by using
physical or chemical approaches, such as acid oxidation3,18, electrochemical7,13, hydrothermal11,19,20, etc.
Compared with top-down routes, the bottom-up routes have obvious advantages in adjusting the composition
and physical properties of GQDs by the careful selection of diversified organic precursors and carbonization
conditions. Li and co-workers have made great effort to synthesize GQDs via stepwise solution chemistry based
on oxidative condensation reactions8,21. Liu et al. prepared multicolor photoluminescent GQDs with uniform
morphology by using hexa-peri-hexabenzocoronene as the carbon source through a pyrolysis and exfoliation
process12. Loh et al. reported the synthesis of a series of well-defined GQDs on a ruthenium surface using C60
molecules as a precursor22. Besides the conjugated precursors used in above studies, some non-conjugate organic
precursors have also shown great potential for the preparation of GQDs via thermal pyrolysis or carbonization.
Tang et al. reported a facile microwave-assisted hydrothermal route for the synthesis of GQDs using glucose as
the sole carbon source23. The size of GQDs can be tuned from 1.65 to 21 nm by simply prolonging the reaction
time from 1 min to 9 min. The obtained GQDs showed size-independent photoluminescence (PL). Dong et al.
prepared the blue luminescent GQDs through tuning the extent of carbonization of citric acid (CA)24,25. The
resulting GQDs are nanosheets with 15 nm in width and 0.5–2.0 nm in thickness. The GQDs showed 9.0% of
photoluminescent quantum yield (QY), and excitation-independent emission activity. Despite of previous
efforts, the QY of GQDs has been relatively low. GQDs with high QY are highly desired for practical applications.

SCIENTIFIC REPORTS | 4 : 5294 | DOI: 10.1038/srep05294 1

 www.nature.com/scientificreports

Figure 1 | Characterizations of GQDs-NaOH. (A) Representative TEM images of GQDs- NaOH. Inset panels show the HR-TEM image (left) and
size (diameter) distribution (right). (B) SPM height image of the graphene nanoparticles. Line through some of the GQDs-NaOH shows the height
profile. (C) UV-Vis spectrum (dash curve) and photoluminescence spectra (solid curves) of the graphene nanoparticles. (D) X-ray photoelectron
spectroscopy (XPS) full scan survey and the high-resolution C1s spectra are shown in inset.

Doping and/or surface passivation are effective methods to change resulted GQDs showed excitation independent and single exponen-
the electronic density of bulk semiconductor materials and to tune tial decay.
their optical and electrical properties. Through passivation and/or
doping, GQDs have shown improved PL3,26–30. Herein, we synthe- Results
sized N-doped GQDs and investigated the N-doping process of Formation of graphene core materials using NaOH (GQDs-
GQDs and their corresponding optical properties through a series NaOH). No GQDs were formed when pure CA was used in
of experiments. CA was used as the carbon source and different hydrothermal reactions without using bases (e.g., NaOH, amines).
amines were used as the N source. We first synthesized GQD core NaOH was added as a base into the reaction solutions followed by
materials by using NaOH as dopants. Under basic reaction con- adjusting the solution pH to 8. After hydrothermal reaction, a light
dition, the CA molecules self-assembled into sheet structure followed yellow solution with blue emission under UV light was obtained,
by condensation reactions through intermolecular dehydroxylation, which is the same as the GQDs prepared from sodium citrate.
forming nanocrystalline GQDs. The final GQDs have unreacted Transmission electron microscopy (TEM) images of the resulting
functional groups such as carboxyl and hydroxyl groups on particle GQDs-NaOH (Figure 1A) show that these GQDs are uniform in
surface. At this point, the obtained GQDs show relative low QY of size ranging from 1.8 to 3.8 nm in diameter. High resolution TEM
,10%, excitation-independent PL, and single exponential lifetime. (HR-TEM) (Figure 1A inset) clearly shows the lattice fringes
We then replaced NaOH with different amines to synthesize N- measured to be 0.24 nm, which corresponds to the (1120) crystal
doped GQDs. We discovered that N atom enters GQDs by forming phase of graphite18,31. Some GQDs particles also showed the lattice
pyrrolic structure through intramolecular dehydroxylation between fringe of 0.35 nm, which attributes to the (002) crystal phase of
neighbor carboxyl groups. Pyrrolic N is gradually transferred into graphite. Scanning probe microscopy (SPM) images (Figure 1B)
quaternary N in the graphene with increasing the reaction time. The further confirm the uniformity of the GQDs. The SPM height
extent of doping effectively improves the optical properties of GQDs, profile in Fig 1B inset revealed that a typical topographic height of
especially QY of N-doped GQDs. We investigated the influence of the GQDs ranges from 0.5 to 2.0 nm. This suggests that these GQDs
the types of amines, such as primary, secondary and ternary amines. consist of 1–5 graphene layers. As shown in the UV-Vis spectrum in
The primary amine resulted in a high doping degree and the N- Figure 1C, the GQDs show two absorption bands at 270 nm and
doped exhibited the highest QY among the three types of amines. 350 nm. A strong blue emission at 450 nm was observed under
When ethylene diamine (EDA) was used as the dopant, N-doped excitation of 340 nm–400 nm. This photoluminescent emission
GQDs showed a QY of 94%, which is the highest QY reported to our band did not shift with the change of excitation wavelength. The
knowledge. Besides the investigation on three types of amines, we calculated QY is ,22%. X-ray photoelectron spectroscopy (XPS)
also optimized the reaction conditions of CA and EDA reaction measurement was performed to determine the GQD composition.
including carbon sources, reaction time, and reaction temperature The full scan XPS spectrum of GQDs-NaOH was shown in
in order to obtain high PL QY of the N-doped GQDs. Overall, the Figure 1D. C1s, Na auger and O1s signals were observed at 284,

SCIENTIFIC REPORTS | 4 : 5294 | DOI: 10.1038/srep05294 2

 www.nature.com/scientificreports

Figure 2 | Representative TEM images of GQDs-U samples prepared at (A) 4 hours, (B) 6 hours, 8 hours, and (C) 24 hours. The corresponding HR-
TEM images and particle size distribution are shown as left and right insets, respectively.

399 and 530 eV, respectively. No N peak was observed in full scan previous reports32. These absorption bands are related to pRp*
XPS survey. That confirms GQDs-NaOH does not contain N and n Rp* transition of C5C and C5O bond in the GQDs. All
element. The element analysis result also showed no N element GQDs-U samples show excitation-independent and narrow
was detected. These results disclose that the as-obtained GQDs- photoluminescent emission band at 450 nm and full width at half
NaOH are N free GQDs in this case. The high-resolution C1s XPS maximum is ,65 nm, which suggests both the size and the surface
spectrum can be fitted into three Gaussian peaks at 284.5, 285.9, and state of these GQDs should be uniform24. Besides, the lifetimes (t,
288.4 eV, which attribute to sp2 C (C-C, C5C), sp3 C (C-O) and Supplementary Figure S1, S3) of GQDs-U samples are 8 ns, which is
oxidized C (C5O), respectively. Based on above results, we can single exponential decay. This suggests that the origin of PL is one
conclude that the GQDs were formed through dehydrolysis single species.
process between CA molecules that is promoted by the weak basic Figure 3 and Supplementary Figure S1B showed the XPS results of
environment due to the formation of citrate salt. GQDs-U-n samples. N signal can be barely seen in the GQDs-U-2
sample. In high-resolution N1s XPS of GQDs-U-2, there is a weak N
N-doping processes of GQDs using urea (GQDs-U). To prepare 1s signal at 400.0 eV, which is close to the pyrrolic N. These results
high luminescent N-doped GQDs, urea was chosen because it could indicate that the graphene framework has formed at this stage, but
be used as both a base and the N source for N-doping processes. A only trace amount of N can enter the graphene framework. In full
series of samples were prepared at different reaction time (samples scan XPS spectra of GQDs-U-4,24 (column A in Figure 3), the N
are denoted as GQDs-U-n, n is reaction time). Figure 2 and peak intensity turned stronger and stronger with extended reaction
Supplementary Figure S1 showed the TEM images of GQDs-U-n time. The peak intensity ratios of N1s/C1s (RN/C) were calculated
samples at different reaction times from 2 to 24 hours. The overall from full survey XPS spectra. The RN/C increased from 0.22 to 0.48
size of GQDs–U increases as the reaction time increases. The average (Supplementary Figure S4). This indicates that N doping degree of
sizes of GQDs-U-n are 2.45 6 0.26, 2.58 6 0.34, 4.3 6 0.7, 5.26 6 GQDs increases with reaction time. The high-resolution C1s XPS
0.78 and 7.11 6 1.06 nm in diameter for the samples prepared at spectra were shown in column B of Figure 3. The spectra can be fitted
from 2, 4, 6, 8 and 24 hours, respectively. The related HR-TEM into 3 Gaussian peaks at 284.5, 286.1, 288.6 eV, which correspond to
images showed that all the GQDs-U exhibited highly crystalline the sp2 carbon (C-C/C5C) in graphene, the sp3 carbon (C-O and C-
graphite nature. The measured lattice fringe distance is 0.24 nm, N), and the C5O in carboxyl group. The relative intensity ratio of sp3
which corresponds to the (1120) crystal phase of graphite. The and sp2 increases with the increasing of reaction time because more N
UV-Vis and PL spectra are showed in Supplementary Figure S1 atoms enter the graphene structure. High-resolution N1s XPS spec-
and S2 in Supplementary Information. There are two clear tra were shown in column C of Figure 3. The high-resolution N1s
absorption bands at 234 nm and 340 nm, which is close to XPS peak of GQDs-U-2 appeared at 400 eV, which contributed from

SCIENTIFIC REPORTS | 4 : 5294 | DOI: 10.1038/srep05294 3

 www.nature.com/scientificreports

Figure 3 | XPS spectra of GQDs-U-4, GQDs-U-6, GQDs-U-8 and GQDs-U-24. Column A is the full scan survey, column B is the high-resolution C1s
XPS spectra, and column C is the high-resolution N1s XPS spectra.

the pyrrolic N. The spectrum can be fitted with 2 Gaussian peaks at of the sp3 C. This is consistent with the fact that the relative amount of
399.8 and 401.5 eV that correspond to the pyrrolic N and graphite N, graphite N in the GQDs-U increases with the reaction time. Element
respectively25,33. Existence of Pyrrolic N indicates that N bonds with analysis results also show the same trend that the amount of N
C in 5 member-ring structures that are formed from dehydrolysis increases with the reaction time (Supplementary Table S1), indi-
between the neighbor carboxyl and amide groups (Figure 4). cating that the extent of N-doping increases with the reaction time.
Graphite N originates from the N atoms that are bonded with 3 Supplementary Figure S5 showed the FTIR spectra of N-doped
neighbor C atoms. With the increase of reaction time, more and GQDs-U prepared at different reaction time. There is a shoulder
more N atoms enter the graphene layer, which leads to the increase peak at 1712 cm21 that can be assigned to the carboxyl acid groups

Figure 4 | Possible formation process of N-doped GQDs.

SCIENTIFIC REPORTS | 4 : 5294 | DOI: 10.1038/srep05294 4

 www.nature.com/scientificreports

Table 1 | PL QY and life time of all GQDs samples (-COOH). Along with the reaction, this peak disappears, suggesting
the consumption of –COOH groups due to the dehydrolysis. In
Sample PL QY (%) tave (ns) addition, two new shoulder peaks at 1700 and 1642 cm21 gradually
GQDs-NaOH 22 7 show up with the increase of reaction time. These new peaks con-
GQDs-U-2 58 8 tribute to formation of amide in the N-doped GQDs. The absolute PL
GQDs-U-4 78 8 QY increases from 58% to 81% with increasing reaction time from 2
GQDs-U-6 80 8 to 24 hours (Table 1).
GQDs-U-8 81 8
GQDs-U-24 82 8 The influence of the types of amines on QY. GQDs were
GQDs-HMTA 20 10 synthesized using different kinds of amine such as tertiary,
GQDs-DEA 30 7
secondary, and primary amine (mono and diamine) in order to
GQDs-EA 36 6
GQDs-EDA 94 14 investigate the effect of the types of amines. The GQDs-HMTA,
GQDs-G 6 7 GQDs-DEA, GQDs-EA and GQDs-EDA are used to denote the
GQDs-TRIS 16 6 GQDs that were prepared using hexamethylene tetraamine
(HMTA), diethylene amine (DEA), ethanol amine (EA), and
tave: average lifetime.
ethylene diamine (EDA), respectively. Figure 5A–C showed TEM
images of GQDs-HMTA, GQDs-DEA, and GQDs-EA. TEM
images showed these three GQDs are monodispersed with a

Figure 5 | Representative TEM images (A–C), SPM images (D–F) and XPS spectra (G–I) of GQDs-HMTA, GQDs-DEA and GQDs-EA. Left and right
insets are the corresponding HR-TEM images and particles size distribution in A–C. The height profiles in D–F are inserted along the line cut. High
resolution C 1s and N1s spectra are inserted in the full scan survey in G–I.

SCIENTIFIC REPORTS | 4 : 5294 | DOI: 10.1038/srep05294 5

 www.nature.com/scientificreports

Figure 6 | Characterizations of GQDs-EDA. (A) Representative TEM images of GQDs-EDA. Insets: HR-TEM image (left) and particles size (diameter)
distribution (right). (B) SPM height image of GQDs-EDA. (C) UV-Vis spectrum (black dash curve) and photoluminescence spectra. (D) XPS full
scan survey. Inset: high-resolution C 1s and N1s XPS spectra.

uniform diameter of 3.39 6 0.69 nm, 4.53 6 0.27 nm, 5.13 6 O 1s peak at ,532 eV. No significant N 1s peak at 401 eV was
0.47 nm, respectively. HR-TEM images confirmed that GQDs- observed for GQDs-HMTA. Even high-resolution N 1s spectrum
HMTA showed a lattice fringe with 0.24 nm, which corresponds also shows a relative weak signal. Element analysis results show that
to the (1120) crystal phase of graphite. The corresponding SPM the GQDs-HMTA contains C 43.62%, H 6.28% and N 0.89%, sug-
height image revealed a typical topographic height of 1–2.0 nm gesting the trace amount of N. Evidences from FTIR spectrum of
(Figure 5D–E), indicating that most of the GQDs consist of ca. 1–5 GQDs-HMTA (Supplementary Figure S9) further confirm this. The
graphene layers12,31. Raman spectrum (Supplementary Figure S6) peak at 1714 cm21 is attributed to the vibration of C5O in -COOH.
was employed to further characterize the microstructure of GQDs- There is no peak appear at ,1670 cm21, which indicates there exists
HMTA. GQDs-HMTA shows a disordered (D) band at 1359 cm21, no amide group in the GQDs-HMTA sample. The XPS, element
related to the presence of sp3 defects, and the crystalline (G) band at analysis, and FTIR results indicate the GQDs-HMTA is also N free
1578 cm21, related to in-plane vibration of sp2 carbon. The ratio of GQDs like GQDs-NaOH. Comparing with that of GQDs-HMTA,
the intensities (ID/IG) of these characteristic bands can be used to XPS results of GQDs-DEA and GQDs-EA exhibit relatively high N
correlate the structural properties of the carbon. The value of ID/IG is amount in the samples. The RN/C of GQDs-DEA and GQDs-EA are
0.9 for GQDs-HMTA, meaning that the as-prepared GQDs-HMTA 0.31 and 0.37. It obviously primary amine have highest doping degree
have highly crystalline nature, which is consistence with the TEM among three types amine. The PL QY was improved from 20% to
results. The optical properties of GQDs-HMTA, GQDs-DEA and 30% and 36% for the samples of GQDs-DEA and EA, respectively.
GQDs-EA are shown in Supplementary Figure S7. All GQDs Based on the XPS results, primary amine is the best dopant for the N
exhibit a shoulder band at 235 nm and a clear absorption band doped GQDs among these three types of amines.
,340 nm, which is close to GQDs-U. The PL spectra show all Although the PL QY of GQDs-EA show the highest PL QY among
GQDs have an emission at 450 nm that is excitation-independent. the primary, secondary and tertiary amine, the GQDs-U series sam-
This further suggests that both the size and the surface state of these ples show much higher PL QY comparing with the GQDs-EA. We
GQDs are uniform. The measured lifetime of GQDs-HMTA, -DEA, increased the amount of EA, no significant improvement of PL QY
and -EA are 10, 7 and 6 ns, respectively, showing single exponential was obtained. (Supplementary Table 1) Since urea could be treated as
decay (Supplementary Figure S8). a diamine that gives us a hint that diamine may be a better dopant
Although these three GQDs samples have close structures and than monoamine. Then we chose ethylene diamine (EDA) as a dop-
similar optical properties, they have different PL QY of 20%, 30% ant for preparing N doped GQDs. TEM images of GQDs-EDA, as
and 36% for GQDs-HMTA, GQDs-DEA and GQDs-EA, respect- shown in Figure 6A, reveal that the GQDs-EDA are uniform and
ively. From XPS studies of these GQDs, we found that the QY differ- have a diameter of 2.30 6 0.31 nm. The HR-TEM images exhibit
ences might be caused by the different extent of N-doping within clear lattice fringe of 0.24 nm, which discloses that the GQDs-EDA
these three samples. The full scan XPS spectra of GQDs-HMTA, also have a graphite nature. AFM image of GQDs-EDA (Figure 6B)
GQDs-DEA, and GQDs-EA are shown in Figure 5G–I. The full scan discloses the sheet structure, which is about ,1 nm in thickness.
XPS of GQDs-HMTA shows a predominant C 1s peak at 284 eV and UV-Vis spectrum of GQDs-EDA exhibits 2 clear absorption bands

SCIENTIFIC REPORTS | 4 : 5294 | DOI: 10.1038/srep05294 6

 www.nature.com/scientificreports

Table 2 | PL QY of GQDs-EDA prepared at different reaction is. From above results, the N doped GQDs are hardly obtained from
conditions tertiary amine as dopant because it has no active N-H. As a dopant,
primary amine is better than secondary amine; diamine is a better
Sample 1h 4h 8h 24 h dopant than monoamine.
140uC 68 79 72 65
160uC 88 94 90 76 The influence of reaction time and temperature on QY. We
180uC 77 82 78 69 optimized the reaction conditions such as reaction temperature,
200uC 65 76 72 61 reaction time, and the ratio of reactant for preparation of high
quality GQDs using CA and EDA. Table 2 shows the PL QY of N-
doped GQDs obtained from CA and EDA under different reaction
at 235 and 340 nm, which are the same as GQDs-U. A strong and conditions. The reaction temperature and time show a parabolic
bright blue emission at 450 nm that is excitation-independent emis- trend. The optimum reaction temperature and time are 160uC and
sion, was observed in the PL spectrum. GQDs-EDA exhibits a much 4 hours, respectively. The molar ratio of CA and EDA was changed
longer lifetime of 14 ns that is almost double longer than GQDs-U. from 151 to 157, the PL QY of all the GQDs are above 80%
The full scan XPS spectrum (Figure 6D) shows three signals at 284, (Supplementary Table S2). The optimum ratio of CA and EDA is
399 and 521 eV that are attributed to C 1s, N1s, and O1s respectively. 153, the PL QY of GQDs reaches 94%.
The RN/C is 0.59, which is higher than any other N doped GQDs in
this report. High-resolution C 1s spectrum revealed that there exist The influence of carbon source on the PL QY. We synthesized
three types of C including sp2 C (C5C), sp3 C (C-C, C-N, and C-O), GQDs using other carbon sources such as glucose and TRIS under
and oxidized C (C5O). Two types of N, pyrrolic N and graphite N the same hydrothermal route. Figure 7 shows the TEM images of
are shown in the high-resolution N 1s spectrum. These results indi- GQDs prepared from glucose (GQDs-G) and TRIS (GQDs-TRIS) as
cate that the extent of doping of GQDs-EDA increases from mono- carbon source. The graphite lattice fringes also are observed in the
amine to diamine. Due to the higher doping degree, the PL QY of HR-TEM images. Different optical properties are observed. The
GQDs-EDA also exhibits very high PL QY of 94%, which is the GQDs-G exhibits two absorption bands at 300 nm and 350 nm in
highest PL QY of GQDs to our knowledge. Comparing with the UV-Vis spectrum. There is a relative broad emission band at
GQDs, N doping introduces a new surface state labeled as the N- 445 nm under excitation of 360 nm. The emission band shifts to
state25,34. Electrons trapped by the N-state are able to facilitate a high 510 nm when excitation wavelength changes to 420 nm. The
yield of radiative recombination and depress non-radiative recom- lifetime (Supplementary Figure S10) is not a single exponential
bination. The density of N-state strongly affects the PL QY of GQDs. decay anymore. It can be fitted as double exponential decay, where
The higher N doping degree is in GQDs, the higher density of N-state t1 is 7.9 ns (64.5%) and t2 is 1.8 ns (25.5%) (the numbers in

Figure 7 | Characterizations of GQDs-G and GQDs-T. (A) Representative TEM images of GQDs-G. Inset: HR-TEM and particle size distribution.
(B) Representative TEM images of GQDs-T. Inset: HR-TEM and particle size distribution. (C) UV-Vis spectra (dash line) and PL spectra (solid lines) of
GQDs-G and (D) GQDs-TRIS.

SCIENTIFIC REPORTS | 4 : 5294 | DOI: 10.1038/srep05294 7

 www.nature.com/scientificreports

parentheses are the percentages of each lifetime). GQDs-TRIS also Synthesis of N-doped GQDs-EDA. 0.21 g (1 mmol) CA and 0.18 g (3 mmol) EDA
were dissolved into 5 mL water, and stirred to form a clear solution. Then the solution
exhibits an excitation-dependent PL emission and double was transferred into a 20 mL Teflon lined stainless autoclave. The sealed autoclave
exponential lifetime decay (tave 5 6 ns). Both GQDs-G and was heated to 160uC in an electric oven and kept for additional 4 hours. The final
GQDs-T show relative low PL QY of 6% and 16%, respectively. product was collected by adding ethanol into the solution and centrifuged at
From above results, citric acid is a better carbon source in the 5000 rpm for 5 min. The solid can be easily re-dispersed into water.
preparation of GQDs through hydrothermal routes.
Synthesis of N-doped GQDs-DEA. 0.21 g (1 mmol) CA and 0.21 g (3 mmol) DEA
were dissolved into 5 mL water, and stirred to form a clear solution. Then the solution
Discussion was transferred into a 20 mL Teflon lined stainless autoclave. The sealed autoclave
was heated to 160uC in an electric oven and kept for additional 4 hours. The final
Based on above results and understandings, we believe that the forma- product was collected by adding ethanol into the solution and centrifuged at
tion of N-doped GQDs involve two steps (Figure 4). At first, the amine 5000 rpm for 5 min. The solid can be easily re-dispersed into water.
works as a base to facilitate the dehydrolysis reaction. CA molecules
self-assemble into sheet structure and dehydrolyze to form graphene Synthesis of N-doped GQDs-EA. 0.21 g (1 mmol) CA and 0.18 g (3 mmol) EA were
framework with ,2 nm in diameter24,32. During this process, amide dissolved into 5 mL water, and stirred to form a clear solution. Then the solution was
transferred into a 20 mL Teflon lined stainless autoclave. The sealed autoclave was
molecules are formed between CA and amine. Then the amides react heated to 160uC in an electric oven and kept for additional 4 hours. The final product
with neighbor carboxylic groups and form pyrrolic N through the was collected by adding ethanol into the solution and centrifuged at 5000 rpm for
second step of intramolecular dehydrolysis. No other type of N state 5 min. The solid can be easily re-dispersed into water.
was observed in the XPS, which proves that N atoms enter graphene
Characterization. Fourier Transform Infrared (FT-IR) spectra of GQDs were
framework through the intramolecular dehydrolysis between amide recorded as KBr pellets with a Bruker Vertex 70 spectrometer from 4000–500 cm21.
and -COOH. Once the pyrrolic N is formed, the PL QY exhibits a Fluorescence emission spectra were recorded on an LS-55 fluorophotometer. UV-Vis
significant improvement. Comparing with N free GQDs (GQDs- absorption spectra were conducted on a Shimadzu UV-2450 spectrophotometer. HR-
NaOH), the PL QY of N-doped GQDs increases to 58% for sample TEM images and fast Fourier transform (FFT) spot diagrams were recorded with FEI-
TECNAI G2 transmission electron microscope operating at 200 kV. X-Ray
GQDs-U-2 with only two hours reaction and trace amount N doped photoelectron spectra were obtained on a Thermo Scientific ESCALAB 250
GQDs. GQDs continue to grow with more N doped into the graphene Multitechnique Surface Analysis with Al Ka X-ray monochromator, pass energy
framework along with the reaction. The PL QY of resulting GQDs 20 eV. Raman spectra were recorded on Jobin Yvon Horiba LAB-RAM Infinity with
increases to 78% for GQDs-U-4 sample in which part of N is trans- 325 nm laser beam. Absolute quantum yield were obtained in a calibrated integrating
ferred into graphite N as the reaction undergoing since the ratio of sphere on Edinburgh FLS920 spectrometer. Lifetime experiments were obtained on
Edinburgh TSCPS FL 920. Atomic Force Microscope (AFM) images were recorded
graphite N/pyrrolic N increases. These results are consistent with the with Bruker multi-mode 8.
C1s XPS results as the relative amount of sp3 C increases with the
reaction due to graphite N bonded with C in sp3 form.
1. Ritter, K. A. & Lyding, J. W. The Influence of Edge Structure on the Electronic
Properties of Graphene Quantum Dots and Nanoribbons. Nat. Mater. 8, 235–242
Conclusions (2009).
We designed and synthesized a series of GQDs in order to investigate 2. Baker, S. N. & Baker, G. A. Luminescent Carbon Nanodots: Emergent Nanolights.
Angew. Chem. Int. Ed. 49, 6726–6744 (2010).
the N-doping process through a hydrothermal route. CA was chosen as 3. Shen, J., Zhu, Y., Yang, X. & Li, C. Graphene Quantum Dots: Emergent Nanolights
carbon source because it easily forms graphene framework through for Bioimaging, Sensors, Catalysis and Photovoltaic Devices. Chem. Commun. 48,
intermolecular dehydrolysis. The N enters the graphene framework 3686–3699 (2012).
through intramolecular dehydrolysis and form pyrrolic structure. The 4. Li, L.-S. & Yan, X. Colloidal Graphene Quantum Dots. J. Phys. Chem. Lett. 1,
2572–2576 (2010).
pyrrolic N can transform to graphite N in the hydrothermal condition. 5. Li, L., Wu, G., Yang, G., Peng, J., Zhao, J. & Zhu, J.-J. Focusing on Luminescent
By changing different types of amine, high PL QY GQDs (94%) can be Graphene Quantum Dots: Current Status and Future Perspectives. Nanoscale 5,
prepared by using CA as carbon source and EDA as N source. 4015–4039 (2013).
Comparing with other carbon source such as glucose and TRIS, CA 6. Cao, L., Meziani, M. J., Sahu, S. & Sun, Y.-P. Photoluminescence Properties of
is the best precursor for preparation of very high luminescent GQDs. Graphene versus Other Carbon Nanomaterials. Acc. Chem. Res. 46, 171–180
(2012).
7. Li, H. et al. Water-Soluble Fluorescent Carbon Quantum Dots and Photocatalyst
Methods Design. Angew. Chem. Int. Ed. 49, 4430–4434 (2010).
8. Yan, X., Cui, X., Li, B. & Li, L.-S. Large, Solution-Processable Graphene Quantum
Materials. All chemicals are commercial available and analysis pure grade without
Dots as Light Absorbers for Photovoltaics. Nano Lett. 10, 1869–1873 (2010).
further purification. Citric acid monohydrate, D-(1)-glucose, tris(hydroxymethyl)
9. Jin, S. H., Kim, D. H., Jun, G. H., Hong, S. H. & Jeon, S. Tuning the
aminomethane, NaOH, urea, hexamethylenetetramine, diethylamine, ethanolamine,
Photoluminescence of Graphene Quantum Dots through the Charge Transfer
ethylenediamine were purchased from Beijing Chemicals or Aladdin Chemicals.
Effect of Functional Groups. ACS Nano 7, 1239–1245 (2012).
10. Gupta, V., Chaudhary, N., Srivastava, R., Sharma, G. D., Bhardwaj, R. & Chand, S.
Synthesis of GQDs-NaOH. 0.21 g (1 mmol) CA and 0.12 g (3 mmol) NaOH were Luminscent Graphene Quantum Dots for Organic Photovoltaic Devices. J. Am.
dissolved into 5 mL water, and stirred to form a clear solution. Then the solution was Chem. Soc. 133, 9960–9963 (2011).
transferred into a 20 mL Teflon lined stainless autoclave. The sealed autoclave was 11. Zhu, S. et al. Strongly Green-Photoluminescent Graphene Quantum Dots for
heated to 160uC in an electric oven and kept for additional 4 hours. The final product Bioimaging Applications. Chem. Commun. 47, 6858–6860 (2011).
was collected by adding ethanol into the solution and centrifuged at 5000 rpm for 12. Liu, R., Wu, D., Feng, X. & Muellen, K. Bottom-Up Fabrication of
5 min. The solid can be easily re-dispersed into water. The obtained samples are Photoluminescent Graphene Quantum Dots with Uniform Morphology. J. Am.
denoted as GQDs-xxx, where xxx stands for NaOH or amine abbreviation, for Chem. Soc. 133, 15221–15223 (2011).
example this sample was denoted as GQDs-NaOH. 13. Li, Y. et al. An Electrochemical Avenue to Green-Luminescent Graphene
Quantum Dots as Potential Electron-Acceptors for Photovoltaics. Adv. Mater. 23,
Synthesis of N-doped GQDs-U. 0.21 g (1 mmol) CA and 0.18 g (3 mmol) urea were 776–780 (2011).
dissolved into 5 mL water, and stirred to form a clear solution. Then the solution was 14. Wang, Y., Shao, Y., Matson, D. W., Li, J. & Lin, Y. Nitrogen-Doped Graphene and
transferred into a 20 mL Teflon lined stainless autoclave. The sealed autoclave was Its Application in Electrochemical Biosensing. ACS Nano 4, 1790–1798 (2010).
heated to 160uC in an electric oven and kept for additional 4 hours. The final product 15. Cao, L. et al. Carbon Nanoparticles as Visible-Light Photocatalysts for Efficient
was collected by adding ethanol into the solution and centrifuged at 5000 rpm for CO2 Conversion and Beyond. J. Am. Chem. Soc. 133, 4754–4757 (2011).
5 min. The solid can be easily re-dispersed into water. 16. Ding, C., Zhu, A. & Tian, Y. Functional Surface Engineering of C-Dots for
Fluorescent Biosensing and in Vivo Bioimaging. Acc. Chem. Res. 47, 20–30
Synthesis of N-doped GQDs- HMTA. 0.21 g (1 mmol) CA and 0.42 g (3 mmol) (2014).
HMTA were dissolved into 5 mL water, and stirred to form a clear solution. Then the 17. Zheng, M. et al. Integrating Oxaliplatin with Highly Luminescent Carbon Dots:
solution was transferred into a 20 mL Teflon lined stainless autoclave. The sealed An Unprecedented Theranostic Agent for Personalized Medicine. Adv. Mater. 26,
autoclave was heated to 160uC in an electric oven and kept for additional 4 hours. The DOI: 10.1002/adma.201306192 (2014).
final product was collected by adding ethanol into the solution and centrifuged at 18. Peng, J. et al. Graphene Quantum Dots Derived from Carbon Fibers. Nano Lett.
5000 rpm for 5 min. The solid can be easily re-dispersed into water. 12, 844–849 (2012).

SCIENTIFIC REPORTS | 4 : 5294 | DOI: 10.1038/srep05294 8

 www.nature.com/scientificreports

19. Zhu, S. et al. Highly Photoluminescent Carbon Dots for Multicolor Patterning, 34. Cushing, S. K., Li, M., Huang, F. & Wu, N. Origin of Strong Excitation
Sensors, and Bioimaging. Angew. Chem. Int. Ed. 52, 3953–3957 (2013). Wavelength Dependent Fluorescence of Graphene Oxide. ACS Nano 8,
20. Pan, D., Zhang, J., Li, Z. & Wu, M. Hydrothermal Route for Cutting Graphene 1002–1013 (2013).
Sheets into Blue-Luminescent Graphene Quantum Dots. Adv. Mater. 22, 734–738
(2010).
21. Yan, X., Cui, X. & Li, L.-S. Synthesis of Large, Stable Colloidal Graphene Quantum
Dots with Tunable Size. J. Am. Chem. Soc. 132, 5944–5945 (2010). Acknowledgments
22. Lu, J., Yeo, P. S. E., Gan, C. K., Wu, P. & Loh, K. P. Transforming C60 Molecules The project was supported by Open Research Fund of State Key Laboratory of Polymer
into Graphene Quantum Dots. Nat. Nano. 6, 247–252 (2011). Physics and Chemistry. The financial support from the National Natural Science
23. Tang, L. et al. Deep Ultraviolet Photoluminescence of Water-Soluble Self- Foundation of China (No. 21201159, 61176016), Z. S. thanks the support of the ‘‘Hundred
Passivated Graphene Quantum Dots. ACS Nano 6, 5102–5110 (2012). Talent Program’’ of CAS, and Innovation and Entrepreneurship Program of Jilin. Science
24. Dong, Y. et al. Blue Luminescent Graphene Quantum Dots and Graphene Oxide and technology department of Jilin (No. 20121801) Z. X. thanks the support of CIAC
Prepared by Tuning the Carbonization Degree of Citric Acid. Carbon 50, start-up fund. Sandia is a multiprogram laboratory operated by Sandia Corporation, a
4738–4743 (2012). wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of
25. Dong, Y. et al. Carbon-Based Dots Co-doped with Nitrogen and Sulfur for High Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000.
Quantum Yield and Excitation-Independent Emission. Angew. Chem. Int. Ed. 52,
7800–7804 (2013).
26. Li, Y. et al. Nitrogen-Doped Graphene Quantum Dots with Oxygen-Rich Author contributions
Functional Groups. J. Am. Chem. Soc. 134, 15–18 (2012). D.Q., M.Z. and Z.S. design and study of experiments and research. L.Z. and H.Z.
27. Qu, S., Wang, X., Lu, Q., Liu, X. & Wang, L. A Biocompatible Fluorescent Ink contributed to the electron microscopy results, Z.X. and X.J. contributed to the lifetime of
Based on Water-Soluble Luminescent Carbon Nanodots. Angew. Chem. Int. Ed. GQDs. R.H. and H.F. contributed to the discussion of all the data. All authors reviewed the
51, 12215–12218 (2012). manuscript.
28. Li, X., Zhang, S., Kulinich, S. A., Liu, Y. & Zeng, H. Engineering surface states of
carbon dots to achieve controllable luminescence for solid-luminescent
composites and sensitive Be21 detection. Sci. Rep. 4, 4976 (2014). Additional information
29. Du, F., Zeng, F., Ming, Y. & Wu, S. Carbon Dots-Based Fluorescent Probes Supplementary information accompanies this paper at http://www.nature.com/
for Sensitive and Selective Detection of Iodide. Microchim. Acta 180, 453–460 scientificreports
(2013). Competing financial interests: The authors declare no competing financial interests.
30. Wang, F., Pang, S., Wang, L., Li, Q., Kreiter, M. & Liu, C.-Y. One-Step Synthesis of
Highly Luminescent Carbon Dots in Noncoordinating Solvents. Chem. Mater. 22, How to cite this article: Qu, D. et al. Formation mechanism and optimization of highly
4528–4530 (2010). luminescent N-doped graphene quantum dots. Sci. Rep. 4, 5294; DOI:10.1038/srep05294
31. Zhu, S. et al. Surface Chemistry Routes to Modulate the Photoluminescence of (2014).
Graphene Quantum Dots: From Fluorescence Mechanism to Up-Conversion
Bioimaging Applications. Adv. Funct. Mater. 22, 4732–4740 (2012). This work is licensed under a Creative Commons Attribution-NonCommercial-
32. Qu, D. et al. Highly Luminescent S, N Co-doped Graphene Quantum Dots with NoDerivs 4.0 International License. The images or other third party material in
Broad Visible Absorption Bands for Visible Light Photocatalysts. Nanoscale 5, this article are included in the article’s Creative Commons license, unless indicated
12272–12277 (2013). otherwise in the credit line; if the material is not included under the Creative
33. Ding, W. et al. Space-Confinement-Induced Synthesis of Pyridinic- and Pyrrolic- Commons license, users will need to obtain permission from the license holder
Nitrogen-Doped Graphene for the Catalysis of Oxygen Reduction. Angew. Chem. in order to reproduce the material. To view a copy of this license, visit http://
Int. Ed. 52, 11755–11759 (2013). creativecommons.org/licenses/by-nc-nd/4.0/

SCIENTIFIC REPORTS | 4 : 5294 | DOI: 10.1038/srep05294 9

 DOI: 10.1038/srep07998

SUBJECT AREAS: CORRIGENDUM: Formation mechanism and optimization of highly luminescent

NANOPARTICLES N-doped graphene quantum dots
PHOTOCATALYSIS
Dan Qu, Min Zheng, Ligong Zhang, Haifeng Zhao, Zhigang Xie, Xiabin Jing, Raid E. Haddad,
Hongyou Fan & Zaicheng Sun
SCIENTIFIC REPORTS:
4 : 5294 This Article contains an error in figure 5. Data from figure 1b is duplicated in figure 5e.
DOI: 10.1038/srep05294 The correct figure 5 appears below as figure 1.
(2014)

Published:
18 June 2014
Updated:
16 January 2015

SCIENTIFIC REPORTS | 5 : 7998 | DOI: 10.1038/srep07998 1

 www.nature.com/scientificreports

Figure 1 |

SCIENTIFIC REPORTS | 5 : 7998 | DOI: 10.1038/srep07998 2