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Recent progress in carbon quantum dots: synthesis,

properties and applications in photocatalysis
Cite this: J. Mater. Chem. A, 2017, 5,
3717
Ru Wang,a Kang-Qiang Lu,ab Zi-Rong Tang*a and Yi-Jun Xuab

Received 6th October 2016
Accepted 2nd January 2017
DOI: 10.1039/c6ta08660h
www.rsc.org/MaterialsA
Carbon quantum dots (CQDs) as a rising star of carbon nanomaterials, by virtue of their unique
physicochemical, optical and electronic properties, have displayed tremendous momentum in numerous
fields such as biosensing, bioimaging, drug delivery, optoelectronics, photovoltaics and photocatalysis. In
particular, the rich optical and electronic properties of CQDs including efficient light harvesting, tunable
photoluminescence (PL), extraordinary up-converted photoluminescence (UCPL) and outstanding
photoinduced electron transfer have attracted considerable interest in different photocatalytic
applications for the sake of full utilization of the solar spectrum. This review aims to demonstrate the
recent progress in the synthesis, properties and photocatalytic applications of CQDs, particularly
highlighting the fundamental multifaceted roles of CQDs in photoredox processes. Furthermore, we
discuss the challenges and future direction of CQD-based materials in this booming research field, with
a perspective toward the ultimate achievement of highly efficient and long-term stable CQD-based
photocatalysts.

from traditional semiconductor quantum dots or other carbon

1. Introduction
Carbon quantum dots (CQDs), also called carbon dots (CDs or
C-dots) or carbon nanodots (CNDs),1 are a novel class of carbon
nanomaterials with prominent uorescence composed of
discrete, quasi-spherical carbon nanoparticles with ultrane
sizes below 10 nm. Remarkably, CQDs integrate the unique
optical properties of quantum dots with the prominent elec-
tronic properties of carbon materials, making them distinctive
a
College of Chemistry, Fuzhou University, New Campus, Fuzhou, 350108, P. R. China.
E-mail: zrtang@fzu.edu.cn; Fax: +86 591 22866126; Tel: +86 591 22866126
b
State Key Laboratory of Photocatalysis on Energy and Environment, College of
Chemistry, Fuzhou University, Fuzhou, 350002, P. R. China. Fax: +86 591
83779326; Tel: +86 591 83779326
nanomaterials (e.g., graphene and carbon nanotubes).2 Their
discovery should be traced back to a 2004 report on the
components of uorescent nanoparticles derived from single-
wall carbon nanotubes (SWNTs).3 Till 2006, these uorescent
carbon nanoparticles received their name “carbon quantum
dots” from Sun et al.4 who proposed a synthesis route to
produce CQDs with much enhanced uorescence emission via
surface passivation. From then on, there have been extensive
and increasing investigations on CQDs in different elds
including biosensing,5,6 bioimaging,7–9 drug delivery,10,11 pho-
tocatalysis,12–15 photovoltaic devices16,17 and optoelectronics.18–21
CQDs are commonly described in terms of a carbogenic core
with surface functional groups. Most CQDs consist of an

Ru Wang is now pursuing her Kang-Qiang Lu is now pursuing

Master degree under the super- his Ph.D. degree under the
vision of Associate Professor Zi- supervision of Prof. Yi-Jun Xu at
Rong Tang at the College of the State Key Laboratory of
Chemistry, Fuzhou University, Photocatalysis on Energy and
P. R. China. Her current Environment, College of Chem-
research interests include istry, Fuzhou University, P. R.
carbon-based composite mate- China. His research interest
rials synthesis and their func- focuses on the synthesis of
tional applications in carbon-based materials, espe-
heterogeneous photocatalysis. cially graphene-based composite
nanomaterials for applications
in heterogeneous photocatalysis.

This journal is © The Royal Society of Chemistry 2017 J. Mater. Chem. A, 2017, 5, 3717–3734 | 3717

Journal of Materials Chemistry A
amorphous to a nanocrystalline core with predominantly sp2
carbon, the lattice spacings of which are consistent with
graphitic or turbostratic carbon.22–24 Simultaneously, CQDs are
typically terminated by oxygenic moieties (with a content of
5–50 wt%) on their surface,22–24 which impart high solubility in
aqueous solutions and provide potential for further function-
alization compared to other carbon nanomaterials. Broadly,
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graphene quantum dots (GQDs) which share similar structures
with CQDs can be regarded as one kind of CQDs, although they
usually possess better crystallinity than their cousins.25 Due to
the aforementioned specic structures, CQDs unfold distinct
properties such as effective absorbance of solar light, tunable
photoluminescence (PL), infrared-responsive up-converted
photoluminescence (UCPL) and unique photoinduced electron
transfer. By selecting specic synthesis routes, the surface states
of the CQDs could be modied to achieve tunable light emis-
sion, which renders them efficient for different purposes in
optical science research. In particular, besides normal or down-
converted PL, CQDs are also found to possess excellent UCPL,
which is known to be an optical phenomenon whereby the
uorescence emission wavelength is shorter than the used
excitation wavelength.26,27 This unique feature enables the
potential design of high-performance CQD-based photocatalyst
systems for efficient utilization of the full spectrum of sunlight.
Furthermore, it has been reported that PL of CQDs can be
quenched efficiently by either electron donor or electron
acceptor molecules in solution, which indicates that photoex-
cited CQDs are able to show excellent electron transfer
properties.28
Considering the compelling optical and electronic properties
of CQDs, it is not surprising to see the entry of CQDs into the
eld of photocatalysis. As is known, the photocatalytic process
involves the generation of charge carriers, i.e., electrons and
holes induced by light. However, many of the present photo-
catalytic systems suffer from low usage of sunlight and high
recombination rate of the photoinduced charge carriers, which
seriously limit the overall quantum efficiency and practical
applications of photocatalysis.29–31 Therefore, due to the unique
PL behavior, UCPL emission and photoinduced electron
Zi-Rong Tang is an associate
professor now working at the
College of Chemistry, Fuzhou
University, P. R. China. Her
current research interests
primarily focus on the fabrica-
tion of one dimensional semi-
conductor-based and carbon-
based composite materials and
their multifunctional applica-
tions in heterogeneous photo-
catalysis and thermocatalysis.
3718 | J. Mater. Chem. A, 2017, 5, 3717–3734
View Article Online
Review
transfer properties, CQDs are potentially considered to be an
efficient component in the construction of high-performance
photocatalysts. CQDs can not only act as an electron mediator,
but also as a photosensitizer, a spectral converter or a sole
photocatalyst in photocatalytic processes.
Although some review articles on CQDs have been published
with emphasis on their synthesis approaches, properties,
surface engineering and applications in biomedicine and
energy conversion,1,25,32–40 there are few dedicated reviews
focusing on the diverse applications of CQDs in photocatalysis,
especially on their specic and multifaceted roles in photo-
catalytic redox processes. Hence, it is essential to compile
a general review from the widely dispersed literature in this
important research area to provide collective enriched infor-
mation and spark enlightened ideas in this eld toward prac-
tical applications. Herein, we introduce the recent development
in the synthesis routes, structures and properties (mainly
optical and electronic properties) of CQDs in Section 2–4,
respectively, which is closely related to their roles in light-driven
photocatalytic processes. In Section 5, we focus on the funda-
mental roles of CQDs in photocatalytic systems. Finally, some
unsettled issues and potential opportunities in this promising
eld are proposed in Section 6, which we hope will contribute to
shaping the development road of CQD-based photocatalysts.
2. Synthesis
Xu et al. rst discovered uorescent CQDs accidentally when
they were purifying single-walled carbon nanotubes (SWCNTs)
from arc-discharged soot.3 Since then, a variety of synthesis
routes have been developed for the preparation of CQDs. Most
of the studies pursue facile, cost-effective, size-controllable and
large scale methods to synthesize CQDs that possess advanced
functions with different compositions and structures. Along the
direction of size development of the implemented materials,
the fabrication of CQDs can generally be classied into two
kinds of approaches, “top-down” and “bottom-up” (Fig. 1). Top-
down approaches synthesize CQDs from macroscopic carbon
structures, such as graphite, activated carbon and carbon
Yi-Jun Xu is a full professor
working at the State Key Labo-
ratory of Photocatalysis on
Energy and Environment,
College of Chemistry, Fuzhou
University, P. R. China. He is
a Fellow of Royal Society of
Chemistry (FRSC) and his
research interest focuses on the
assembly and applications of
composite materials, such as
graphene-based semiconductor
composites, core–shell compos-
ites and metal-based nanostructured materials, in heterogeneous
photocatalysis.
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Fig. 1Schematic illustration of CQD preparation via “top-down” and

“bottom-up” approaches.

nanotubes by treatments like arc-discharge,3 laser abla-

tion,4,23,41–44 electrochemical oxidation,45–51 chemical oxida-
tion,52–54 and ultrasonic synthesis.55–58 Bottom-up approaches
fabricate CQDs from molecular precursors such as citric acid,
sucrose and glucose through microwave synthesis,59–62 thermal
decomposition,18,63,64 hydrothermal treatment,65–70 template-
based routes,71–73 and plasma treatment.74 Here, we will intro-
duce some representative preparation methods for CQDs in
detail and compare their merits and demerits in Table 1.
2.1 Top-down approaches
2.1.1 Laser ablation. More recently, laser ablation has been
used for CQD preparation widely, since it can be used to prepare
a variety of nanostructures, leading to easy morphology
control.4,23,41–44 Sun et al. prepared CQDs by laser ablation of
graphite under an argon ow in the presence of water vapor.4
Subsequently, Hu et al. found that the size control of CQDs can
be realized by tuning the laser pulse width (Fig. 2A–C), which
can have impacts on the nucleation and growth of CQDs.44 The
interaction between the laser beams and the graphite akes
Fig. 2 (A–C) Typical HRTEM images of a sample produced from laser
pulse widths of 0.3, 0.9 and 1.5 ms, respectively. (D) Schematic of the
mechanism of size control of CQDs obtained upon laser ablation. C1
and C2 correspond to the cases of short and long laser pulse widths,
respectively. Reprinted with permission from ref. 44. Copyright 2011
Springer.
produces an instant local high-temperature and high-pressure
vapor/plasma plume at the interface of the graphite ake and
the surrounding liquid medium (Fig. 2D-step 1). Due to the
connement of the liquid, a bubble is formed at the laser focus,
and quickly expands up to a maximum radius. Aer a laser
pulse width nishes, the bubble starts to shrink due to the
pressure of the surrounding liquid, leading to the cooling of its
inner region and thus to the formation of clusters or nuclei
(Fig. 2D-step 2). Bubbles with different cluster densities can be
formed when the laser pulse width is changed, further
producing CQDs with different sizes (Fig. 2D-step 3).

Table 1 Comparison of the merits and demerits of a representative CQD preparation

Methods Merits Demerits Ref.

Top-down Laser ablation
Electrochemical oxidation
Chemical oxidation
Ultrasonic treatment
Bottom-up Microwave synthesis
Thermal decomposition
Hydrothermal treatment
Controllable morphology and size Complicated operation, high cost 4, 23 and 41–44
High purity, high yield, controllable size, Complicated operation 45–51
good reproducibility
Easy operation, large scale production, Non-uniform size distribution 52–54
no elaborate equipment
Easy operation Instrumental wastage, high 55–58
energy cost
Short reaction time, uniform size High energy cost 59–62
distribution, easy size control
Easy operation, solvent-free, low cost, Non-uniform size distribution 18 and 63–64
large scale production
High quantum efficiency, low cost, Low yield 65–70
non-toxicity

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2.1.2 Electrochemical oxidation. Electrochemical oxidation
is the most common method to obtain CQDs with the advan-
tages of high purity, low cost, high yield, easy manipulation of
size and good reproducibility.45–51 Zhou et al. rst demonstrated
the electrochemical synthesis of CQDs from multiwalled carbon
nanotubes (MWCNTs).46 Additionally, Kang et al. reported an
alkali-assisted electrochemical method to prepare size-control-
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lable CQDs with benign optical and electronic properties.47 The
judicious cutting via electrochemical oxidation of a graphite
honeycomb layer into ultrasmall particles can lead to tiny
fragments of graphite, which can offer a direct strategy to
prepare high-quality CQDs. Using graphite rods as both the
anode and cathode, and NaOH/EtOH as the electrolyte, they
prepared CQDs under different current intensities of 10–200
mA cm
2 with different sizes (as shown in Fig. 3A–G). Moreover,
the results of control experiments using acids (e.g., H2SO4/
EtOH) as the electrolytes indicate that an alkaline environment
is the key factor for the formation of CQDs in this electro-
chemical oxidation process. Recently, Liu et al. also produced
CQDs with high crystallinity from the electrochemical oxidation
of a graphite electrode in alkaline alcohols (Fig. 3H).50 Inter-
estingly, the as-prepared CQD dispersion is colorless but the
dispersion will gradually change to bright yellow when kept at
room temperature, which can be attributed to oxygenation of
surface species over time. It is also proved that applied poten-
tials and pH have signicant effects on the generation of CQDs.
2.1.3 Chemical oxidation. Chemical oxidation is an effec-
tive and convenient approach for large scale production and
requires no complicated devices.52–54 Qiao et al. presented
a facile approach to produce CQDs with excitation-wavelength
(lex) dependent PL which can be carried out on a large scale.54
They use three typical activated carbons including coal activated
carbon (CAC), wood activated carbon (WAC) and coconut acti-
vated carbon (CNAC) as carbon sources with HNO3 etching. A
passivation process is then carried out via amine-terminated
Fig. 3 (A) TEM image of CQDs with diameters less than 4 nm. (B–G)
HRTEM images of typical CQDs with different diameters (scale bar:
2 nm). Reprinted with permission from ref. 47. Copyright 2010 John
Wiley and Sons. (H) Schematic illustration of CQD generation via
electrochemical oxidation. Reprinted with permission from ref. 50.
Copyright 2016 Royal Society of Chemistry.
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compounds such as 4,7,10-trioxa-1,13-tridecanediamine
(TTDDA). Fig. 4A shows the preparation procedure of CQDs. The
TEM images (Fig. 4B–D) indicate that the as-prepared CQDs are
amorphous as no discernible lattice structures are observed.
Additionally, these three kinds of CQDs are well dispersed and
have similar size distribution in the range of 2–6 nm.
2.1.4 Ultrasonic synthesis. It is acknowledged that ultra-
sound can generate alternant low-pressure and high-pressure
waves in liquid, resulting in the formation and collapse of small
vacuum bubbles. These cavitations cause high-speed impinging
liquid jets, deagglomeration and strong hydrodynamic shear
forces.55–58 Thus, the energy of ultrasonic waves can cut
macroscopic carbon materials into nanoscale CQDs. Kang
et al.57 synthesized water-soluble CQDs from activated carbon by
a one-step hydrogen peroxide (H2O2)-assisted ultrasonic treat-
ment. The CQD solution is very stable without nanoparticle
precipitation for 6 months. Park et al. reported a large-scale
“green solution” for the synthesis of CQDs using waste food as
carbon sources under ultrasound treatment at room tempera-
ture.56 The HRTEM image and AFM image of the obtained CQDs
reveal that the nanoparticles have a uniform spherical shape
with an average size of 4.6 nm.56
2.2 Bottom-up approaches
2.2.1 Microwave synthesis. Microwave is a type of electro-
magnetic wave with a large wavelength range of 1 mm to 1 m,
which can provide intensive energy to break off the chemical
bonds of a substrate. Therefore, the microwave method can
effectively shorten the reaction time and provide simultaneous,
homogeneous heating, which leads to uniform size distribution
of quantum dots.59–62 Zhu et al. rstly reported an economical
and facile microwave pyrolysis approach to synthesize CQDs
with bright, stable luminescence and excellent water dispersion
only for several minutes.60 In this synthesis, different amounts
of polyethylene glycol (PEG-200) and saccharide are added to
distilled water to form a transparent solution. The solution is
then heated in a 500 W microwave oven for 2–10 minutes. With
increasing reaction time, the solution changes from colorless to
Fig. 4 (A) Preparation procedure of CQDs. TEM images of 4,7,10-
trioxa-1,13-tridecanediamine (TTDDA)-passivated CQDs derived from
coal activated carbon (CAC) (B), wood activated carbon (WAC) (C), and
coconut activated carbon (CNAC) (D). The inset histograms are the
size distributions of the CQDs measured by TEM. Reprinted with
permission from ref. 54. Copyright 2010 Royal Society of Chemistry.
This journal is © The Royal Society of Chemistry 2017

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yellow, and nally to dark brown, which implies the formation
of CQDs. Later, Tang et al. prepared glucose-derived water-
soluble crystalline GQDs with controlled size by a facile
microwave-assisted hydrothermal (MAH) method that
combines both the advantages of hydrothermal and microwave
techniques (Fig. 5A).61 The monodispersion properties of the
GQDs could be attributed to the rapid, simultaneous, homo-
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geneous heating of the solvent (H2O) and glucose by microwave
irradiation, which provides uniform nucleation and growth of
the GQDs. The size of the GQDs can be increased from 1.65 to
21 nm by simply prolonging the microwave heating time from 1
to 9 min, respectively (Fig. 5B–D).
2.2.2 Thermal decomposition. Thermal decomposition has
been used to synthesize different semiconductor and magnetic
nanomaterials previously. Recent studies have shown that
external heat can contribute to the dehydration and carbon-
ization of organics and turn them into CQDs. This method
offers advantages of easy operation, solvent-free approach, wide
precursor tolerance, short reaction time, low cost and scalable
production.18,62,63 Ma et al. synthesized N-doped GQDs with
graphene-like structures by the direct carbonization of ethylene
diamine tetraacetic acid (EDTA) heated in a sand bath at
260–280  C.18 This study proposed the growth mechanism of
GQDs as shown in Fig. 6. The species produced during EDTA
decarboxylation might gradually fuse together to give graphite-
like structures under the solid-state reaction conditions, which
is supported by the fact that the N-containing compounds can
be converted into various graphitic carbon nitrides at much
higher pyrolysis temperatures. Martindale et al. prepared CQDs
with a high yield of 45% by the straightforward pyrolysis of citric
acid at 180  C for 40 h.64 The resultant CQDs have an average
size of 6.8  2.3 nm with a relatively broad size distribution.
2.2.3 Hydrothermal treatment. Hydrothermal carboniza-
tion is a low cost, environmentally friendly and nontoxic route
Fig. 5 (A) Preparation of GQDs by a microwave-assisted hydrothermal
(MAH) method. The HRTEM images of the GQDs prepared for 1 min
(B), 5 min (C) and 9 min (D) microwave heating, respectively. The
average size is 1.65 nm, 3.39 nm and 21 nm, respectively. Reprinted
with permission from ref. 61. Copyright 2012 American Chemical
Society.
This journal is © The Royal Society of Chemistry 2017
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Journal of Materials Chemistry A
Fig. 6 Schematic illustration of the reaction process for the prepa-
ration of GQDs derived from EDTA and their graphene-like structures.
Reprinted with permission from ref. 18. Copyright 2015 Royal Society
of Chemistry.
to produce novel carbon-based materials from saccharides,
organic acids, juice or waste peels.65–70 Generally, a solution of
organic precursor is sealed and reacted in a hydrothermal
reactor at high temperature and high pressure. Mehta et al.
reported a single-step hydrothermal approach for the prepara-
tion of highly uorescent CQDs by using sugarcane juice as
a rich carbon source.68 The reaction mixture of sugarcane juice
and ethanol is heated at constant temperature (120  C) for 3 h
until a dark brown solution is formed. Aer further extraction
and centrifugation, highly blue uorescent CQDs with uniform
size of 3.0 nm are obtained. Bourlinos et al. produced surface
functionalized CQDs with visible uorescence stimulated by
a wide range of excitation wavelengths via hydrothermal treat-
ment of ammonium citrate or 4-aminoantipyrine at 300  C for
2 h.75 The as-prepared CQDs are monodispersed with sizes less
than 10 nm and they are effectively dispersible in various
solvents depending on the nature of the passivation agent.
Zhang et al. established a green one-step hydrothermal route to
prepare CQDs by using L-ascorbic acid as a carbon source at
180  C for 4 h.67 The water-soluble CQD solutions are very stable
for at least six months at room temperature with stable uo-
rescence, which do not change over a wide pH range and even in
solvents with strong ionic strengths.
3. Structures
3.1 Chemical structures of CQDs
CQDs are commonly described in terms of a carbogenic core
consisting of amorphous and crystalline parts with surface
functional groups. Noticeably, despite the fact that many
researchers demonstrated the existence of a crystalline sp2
carbon section,47,76 CQDs possess poorer crystallinity, namely
with more defects than GQDs which usually have graphene
lattices inside the dots, resembling the crystalline structure of
single or few layered graphene. Interestingly, though CQDs and
GQDs have different core structures, both of them are termi-
nated with oxygen related functional groups. From this view,
GQDs can be usually considered as one kind of CQDs.25
Many structural models of the CQD core have been sug-
gested, such as the following: diamond-like structure,77
graphite/graphite oxide structure,75,78,79 amorphous carbon
structure.6,42,80 CQDs passivated by polyethylene glycol
(PEG200N) via laser ablation share the same selected area elec-
tron diffraction (SAED) pattern, corresponding to the planes of
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Journal of Materials Chemistry A
the diamond structure (Fig. 7A).77 The high-resolution trans-
mission electron microscopy (HRTEM) image shows variable
lattice spacings within 0.2–0.23 nm (Fig. 7B). Bao et al. reported
a lattice spacing of ca. 0.325 nm for CQDs obtained by electro-
chemical etching of carbon bers, which corresponds to the
(002) facet of graphite (Fig. 7C).79 The corresponding X-ray
photoelectron spectroscopy (XPS) spectrum shows a peak
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centered at 284.5 eV, assigned to graphitic sp2 carbons (Fig. 7D).
Zhu et al. prepared highly photoluminescent CQDs by a hydro-
thermal method, which are observed to be amorphous carbon
particles without any lattices (Fig. 7E).6 The X-ray diffraction
(XRD) pattern of the CQDs (Fig. 7F) also displays a broad peak
centered at 25 (0.34 nm), which is also attributed to highly
disordered carbon atoms.
Over the past few decades, fairly comprehensive research has
been conducted on CQD surface functional groups. Liu et al.
reported multicolor uorescent CQDs obtained from the
combustion soot of candles by means of an oxidative acid
treatment, which can introduce –OH and –COOH groups to the
CQD surfaces.81 Elemental analysis shows that the chemical
composition of these CQDs (36.8% C; 5.9% H; 9.6% N; 44.7% O)
is vastly different from that of raw candle soot (91.7% C; 1.8% H;
Fig. 7 (A) TEM image of the PEG200N passivated CQDs and direct
photograph of the sample under a 365 nm UV lamp (the inset is the
SAED pattern of the CQDs); (B) HRTEM image of the PEG200N
passivated CQDs. Reprinted with permission from ref. 77. Copyright
2009 Royal Society of Chemistry. (C) HRTEM images and (D) XPS
spectra of CQDs@0.5 V. Reprinted with permission from ref. 79.
Copyright 2011 John Wiley and Sons. (E) HRTEM image and (F) XRD
pattern of the CQDs. Reprinted with permission from ref. 6. Copyright
2013 John Wiley and Sons.
3722 | J. Mater. Chem. A, 2017, 5, 3717–3734
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Review
1.8% N; 4.4% O), having a signicantly higher oxygen content,
partly due to the presence of carbonyl groups. Fourier transform
infrared (FTIR) spectroscopy of CQDs reveals the presence of
carboxylic functional groups on their surface. For GQDs
prepared using the microwave assisted method (MAH),61 the
stretching vibrations of C–O bonds (1027 and 1076 cm
1) and
stretching vibrations of O–H moieties (around 1360 cm
1 and
2927 cm
1, respectively) are detected in the FTIR spectra
(Fig. 8A). In addition, the surface components of this kind of
GQDs determined by XPS are in good agreement with FTIR
results (Fig. 8B).
3.2 Electronic structures of CQDs
Many research groups proposed that the electronic structures of
CQDs can be illustrated by molecular orbital (MO)
theory.34,47,53,80,82 In most cases, CQDs exhibit n / p* and p /
p* transitions due to their easily accessible transition energies.
The p-states of CQDs can be ascribed to aromatic sp2-hybrid-
ized carbons in their core. Lee et al. have demonstrated that the
energy gap between p-states decreases gradually as the number
of aromatic rings increases, just as in the case of p-conjugation
in organic molecules.47,82 The n-states of CQDs can be ascribed
to functional groups containing electron lone pairs, such as
carbonyls, amines, amides, and thiols. If the functional groups
with electron lone pairs are bonded to aromatic sp2-hybridized
carbons, electron transitions from the n-states of the functional
groups to the p*-states of the aromatic rings (n / p*) can
happen.
3.3 Defects of CQDs
As mentioned above, most CQDs prepared by different
approaches possess a certain amount of defects. For example,
the CQDs produced electrochemically from graphite clearly
show the characteristics of both disordered carbon and sp2
carbon.83 As shown in Fig. 9A, besides the protrudent peak at
26 corresponding to the (002) planes of graphite, two new
Fig. 8 (A) FTIR spectra of the source glucose and the CQDs prepared
under different conditions. All the CQDs prepared under different
conditions show similar infrared absorption peaks. (B) The C1s XPS
spectrum of the CQDs. Reprinted with permission from ref. 61.
Copyright 2012 American Chemical Society.
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Review
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Fig. 9 (A) XRD patterns, (B) Raman spectra (lex ¼ 633 nm), (C) C1s XPS
spectra and (D) FTIR spectra of graphite and CQDs. Reprinted with
permission from ref. 83. Copyright 2012 Royal Society of Chemistry.
peaks emerged at 22.59 (signed with +) and 18.20 , which refer
to the amorphous carbon and (103) planes (belonging to
hexagonal carbon) in the XRD pattern of CQDs. A detailed
comparison of the XRD patterns of the CQD samples reveals
that the electrochemical oxidation process leads to weak,
broadened graphite peaks compared to pristine graphite
samples. The decrease in the peak intensity indicates the
transformation of crystalline graphite into amorphous carbon,
and the partial conversion of sp2-hybridized C]C in the
aromatic ring into sp3-hybridized C]C in the CQDs. Addi-
tionally, as shown in the Raman spectra (Fig. 9B), the CQDs
display a noticeably increased ID/IG ratios aer electrochemical
oxidation of graphite. This indicates that some structural
defects appear in the CQDs during the graphite oxidation, such
as oxygenated groups (C–O, C]O, O–C]O) in the sp2 carbon
site which result in the vacant lattice sites and sp3 carbon. The
Fig. 10 Aqueous solution of the polyethylene glycol PEG1500N-
attached CQDs (A) excited at 400 nm and photographed through
bandpass filters of different wavelengths as indicated, and (B) excited
at the indicated wavelengths and photographed directly. (C) Absor-
bance (ABS) and luminescence emission spectra (with progressively
longer excitation wavelengths from 400 nm on the left in 20 nm
increment) of propionylethyleneimine-co-ethyleneimine (PPEI-EI)
CQDs in an aqueous solution. The emission spectral intensities are
normalized to quantum yields (inset: normalized to spectral peaks).
Reprinted with permission from ref. 4. Copyright 2006 American
Chemical Society.
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Journal of Materials Chemistry A
XPS spectra and FTIR spectra (Fig. 9C and D) indicate that the
oxygen functional groups are formed through electrochemical
oxidation, and the sp2-hybridized C]C in the aromatic rings in
graphite are partially decomposed into oxygen functional
groups in the CQDs.
It has been reported by some research groups that surface
defects, which can be created through surface functionalization
and doping, may serve as capture centers for excitons, thus
giving rise to surface-state-related PL.13,79,84 The detailed exam-
ples will be discussed in Section 4.5.
4. Properties
4.1 Optical absorption
CQDs typically show obvious optical absorption in the UV
region (260–320 nm), with a tail extending to the visible range
(Fig. 10C and 11). For example, CQDs produced from the elec-
trochemical oxidation of multiwalled carbon nanotubes
(MWCNTs) show an absorption band at 270 nm, with a narrow
full width at half maximum (FWHM) of 50 nm.46 In addition,
recent studies have shown that the absorbance of CQDs can be
red-shied aer specic surface modication.77,85,86 For
instance, the absorption wavelength of the CQDs passivated by
TTDDA is increased in the 350 to 550 nm range, thus inducing
increased intensity of emission in this region.85 CQDs obtained
aer the treatment of PEG-200 and NaOH clearly show a distinct
absorbance peak centered at 262 nm.86
4.2 Photoluminescence (PL)
In recent years, there has been a rapid expansion of research into
the PL of CQDs, which is one of the most fascinating features of
CQDs and has been utilized in the area of photocatalysis. PL
emission follows the Stokes type emission; namely, the PL
emission wavelength is longer than the excitation wavelength.
Fig. 11 Absorption curves (Abs) and PL emission spectra under exci-
tation with different wavelengths of light (see the inset legends) of four
typical samples exhibiting blue (A), green (B), yellow (C), and red
fluorescence (D). Reprinted with permission from ref. 90. Copyright
2016 American Chemical Society.
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There have been many literature reports on the observation of PL

emissions in CQDs, which have been assigned to various
origins.22,87,88 A closer examination on the spectroscopic features
of the emissions and the associated structural characteristics in
the underlying materials suggests that most of the observed PL
emissions could be classied roughly into two categories. One is
due to bandgap transitions corresponding to conjugated
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p-domains, and the other with more complex origins that are
associated with defects in the graphene structures. The two
categories may be interconnected in many cases, as the creation
or induction of the p-domains is oen based on the exploitation
or manipulation of defects in graphene sheets.89
A large number of studies discussed the relationship
between the PL emission and the excitation-wavelength (lex) of
the CQDs. Sun et al. reported that uorescent CQDs modied
with polyethylene glycol (PEG1500N) or propionylethyleneimine-
Fig. 12 (A) Optical images of typically sized CQDs illuminated under
co-ethyleneimine (PPEI-EI) display obvious lex-dependent
white (left; daylight lamp) and UV light (right; 365 nm). (B) PL spectra of
emission (Fig. 10).4 This phenomenon was also conrmed typical sized CQDs: the red, black, green and blue lines are the PL
subsequently by Bourlinos and co-workers,75 in which CQDs spectra for blue-, green-, yellow- and red-emission of CQDs,
fabricated via one-step thermal treatment of 4-aminoantipyrine respectively. (C) Relationship between the CQD size and the PL
show lex-dependent PL emission from 525 to 660 nm with properties. (D) HOMO–LUMO gap dependence on the size of the
graphene fragments. Reprinted with permission from ref. 47. Copy-
excitation wavelength from 425 to 625 nm. However, CQDs
right 2010 John Wiley and Sons.
hydrothermally synthesized from urea and separated via silica
column chromatography by Ding et al. show only one peak in
the PL excitation spectrum, only one peak in the excitation-
feature. UCPL emission is in contrast to the normal photo-
independent PL emission spectrum, and similar mono-
luminescence (PL) wherein the emission wavelength has lower
exponential uorescence lifetimes.90 Fig. 11 displays their
energy than the excitation wavelength, that is, the emission
absorption curves (Abs) and PL emission spectra (Em) under
wavelength is shorter than the excitation wavelength.91 Cao et al.
excitation with different wavelengths of light.
rst observed that the CQDs produced via laser ablation exhibit
Besides the excitation wavelength, PL emission of CQDs is
strong luminescence with two-photon excitation in the near-
also discussed based on manipulation of their size. Kang et al.
infrared (800 nm),41 thereby suggesting that the CQDs possess
reported a one-step alkali-assisted electrochemical synthesis of
UCPL properties. Later, other groups also found UCPL emis-
CQDs with sizes of 1.2–3.8 nm.47 Fig. 12A shows optical images
sions from CQDs prepared by drastically different synthesis
of CQDs with four typical sizes, illuminated under white
routes.92–94 For instance, Kang et al. found that CQDs, which are
(daylight lamp) and UV light (365 nm). The bright blue, green,
directly prepared from glucose by a one-step alkali or acid
yellow, and red PL of CQDs is strong enough to be easily seen
assisted ultrasonic treatment, possess UCPL properties in
with the naked eyes. Fig. 12B shows the corresponding emission
addition to their normal PL emission.94 Fig. 13A shows the PL
spectra; the red, black, green, and blue lines are the PL spectra
spectra of these CQDs excited by long-wavelength light (from
for blue-, green-, yellow- and red-emitting CQDs, respectively. A
700 to 1000 nm) with the up-converted emissions located in the
detailed study uncovered that the PL properties vary sharply as
range from 450 to 750 nm. However, there are doubts about the
the CQD size increases (Fig. 12C). Fig. 12D shows the depen-
UCPL in some related reports.95,96 In some cases, a mono-
dence of highest occupied molecular orbital–lowest unoccupied
chromatic light from a uorescent spectrophotometer (xenon
molecular orbital (HOMO–LUMO) gap on the size of the gra-
lamp as the light source) is used without lters added. Hence,
phene fragments. First, as the size of the fragment increases,
routine PL occurs by second-order diffraction of the light of
the HOMO–LUMO gap decreases gradually. Furthermore, the
wavelength l/2 (which always coexists with the excitation light
gap energy in the visible spectral range can be obtained from
of wavelength l), and this has been misunderstood as
the graphene fragments with the sizes of 14–22 Å, which agrees
UCPL.58,97–99 Nonetheless, certain CQDs do have UCPL proper-
well with the visible light emission of CQDs with diameters of
ties only observable with a femtosecond pulse laser and their
less than 3 nm. However, Hola et al. found that the CQDs
UCPL emissions are related to the power density (Fig. 13B).100
derived from different alkyl gallates with different sizes display
Although UCPL properties have been observed and
similar steady-state PL spectra, implying that the PL emission of
researched for a couple of years, the mechanism of this unique
the CQDs is size-independent.78
character is not fully understood. Cao et al. rst proposed a two-
photon mechanism to elucidate UCPL emission.41 Later, Gong
4.3 Up-converted photoluminescence (UCPL) et al. and Jiang et al. further supported this hypothesis.101–103
Gong et al. prepared nitrogen-doped graphene quantum dots
In addition to conventional PL emission, it has also been shown
(N-GQDs) as efficient two-photon uorescent probes for cellular
in recent studies that certain CQDs have UCPL emission

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Fig. 13 (A) UCPL spectra of CQDs under excitation using different
wavelengths. Reprinted with permission from ref. 94. Copyright 2011
Elsevier. (B) UCPL spectra of GQDs under excitation of a femtosecond
pulsed laser at 800 nm. Reprinted with permission from ref. 100.
Copyright 2013 John Wiley and Sons. (C) Two-photon-induced fluo-
rescence (TPF) spectrum under 800 nm femtosecond laser excitation
and one-photon-induced fluorescence (OPF) spectrum under the
maximum excitation wavelength (390 nm) of the N-GQD solution.
Inset: two-photon fluorescence image of solid N-GQDs (scale bar:
10 mm); (D) fluorescence mechanism of N-GQDs. Reprinted with
permission from ref. 102. Copyright 2013 American Chemical Society.
(E) UCPL properties of GQDs; (F) schematic illustration of various
typical electronic transition processes of GQDs. Normal PL mecha-
nisms in small size (a) and large size (b) GQDs; UCPL mechanisms in
large size (c) and small size (d) GQDs. Reprinted with permission from
ref. 104. Copyright 2011 Royal Society of Chemistry.
and deep-tissue imaging.102 They prepared the N-GQD via
a hydrothermal method using graphene oxide (GO) as the
carbon source and dimethylformamide as the nitrogen source.
Fig. 13C shows two-photon-induced uorescence (TPF) spec-
trum under 800 nm femtosecond laser excitation and one-
photon-induced uorescence (OPF) spectrum under the
maximum excitation wavelength (390 nm) of the N-GQD solu-
tion. For the obtained TPF spectrum, the maximum emission
wavelength is indistinguishable with that of the OPF spectrum
of N-GQD, but with much narrower bandwidth. The inset of
Fig. 13C is the TPF image of the dried N-GQD samples obtained
on a two-photon microscope. Fig. 13D illustrates the uores-
cence mechanism of N-GQD. The strong orbital interaction
between dimethylamido and p-conjugated system of N-GQD
raises the primary HOMO (blue dashed line) to a higher energy
orbital such as HOMO (black solid line), resulting in a decrease
in bandgap and red-shi of uorescence emission. However,
Shen et al. argued that the multi-photon excitation is inade-
quate to account for the UCPL emission properties of GQDs.104
They fabricated GQDs by the hydrazine hydrate reduction of
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graphene oxide (GO) with their surface passivated by poly-
ethylene glycol (PEG). In view of the practically constant energy
difference of 1.1 eV between the excitation light and emission
light (Fig. 13E), they established an energy level structural
model for the UCPL properties as shown in Fig. 13F. They
postulated that the UCPL emission originates from the relaxa-
tion of electrons from a higher energy state of the p orbital
(LUMO) to the s orbital since some electrons would inevitably
transit to the LUMO when a large number of low energy photons
excite the electrons in the p orbital. In addition, the electrons in
the s orbital can also be excited, but they only emit conven-
tional down-conversion light.
4.4 Photoinduced electron transfer properties
Sun et al. rst proposed that CQDs can be quenched efficiently
by either electron acceptors or electron donors in solution, that
is, photoinduced CQDs are both excellent electron donors and
electron acceptors.28 Although this photoinduced electron
transfer feature of CQDs has been widely reported recently,
direct evidence and essence of the photoinduced charge sepa-
ration in CQDs have not been accomplished. Some indirect
experimental proof was obtained through certain redox
processes. For instance, Kang et al. conrmed this property
through photoluminescence decay studies of CQDs with the
known electron acceptor 2,4-dinitrotoluene (
0.9 V vs. NHE)
and electron donor N,N-diethylaniline (DEA, 0.88 V vs. NHE)
(Fig. 14A and B).105
The substantial photoinduced electron transfer properties of
CQDs open up new opportunities for their potential uses in
Fig. 14 Luminescence decays (485 nm excitation, monitored with
a 550 nm narrow bandpass filter) of the CQDs with (A) 2,4-dini-
trotoluene and (B) N,N-diethylaniline (DEA). Insets: Stern–Volmer plots
for the quenching of luminescence quantum yields (485 nm excita-
tion) of the CQDs by (A) 2,4-dinitrotoluene and (B) DEA. Reprinted with
permission from ref. 105. Copyright 2012 Royal Society of Chemistry.
(C) Transient photocurrent response for pure BiOBr and the 3 wt%
CQDs/BiOBr composite; (D) electrochemical impedance spectra of
BiOBr and the 3 wt% CQDs/BiOBr composite. Reprinted with
permission from ref. 106. Copyright 2016 Elsevier.
J. Mater. Chem. A, 2017, 5, 3717–3734 | 3725

Journal of Materials Chemistry A
redox processes like light energy conversion and related appli-
cations. Xia et al. reported that CQDs in composite photo-
catalysts can efficiently trap photogenerated electrons from
semiconductors, leading to enhanced separation efficiency of
photoinduced electrons and holes (Fig. 14C and D).106
Furthermore, it was demonstrated that photoexcited CQDs have
redox active nature which results in the reduction of metal ions
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in an aqueous solution.107,108 Specically, the irradiation of CQD
solution with a noble metal (silver, gold, or platinum) salt
results in the formation and deposition of the noble metal on
the surface of CQDs. Because the noble metal has high electron
affinity, it takes electrons from the attached CQDs, again dis-
rupting the radiative recombination, to result in the observed
extremely efficient static quenching of uorescence
emissions.109
4.5 Tailoring the properties of CQDs
Surface functionalization with various molecules such as
organic or inorganic molecules and polymers is an effective way
of tailoring the properties of CQDs by controlling their surface
states. Hola et al. reported the synthesis of alkyl chain passiv-
ated CQDs with controlled size and surface functionalization.
The alkyl chains on the CQD surface are readily converted to
carboxylate groups via mild base (NaOH) hydrolysis and
induced red-shied emission (from 402 to 440 nm) due to
COO
surface states (Fig. 15).78 Kwon et al. conducted the
introduction of new surface states using organic molecules.
Surface functionalization with para-substituted anilines
endowed CQDs with new energy levels, exhibiting long-wave-
length (up to 650 nm) PL of very narrow spectral widths with
high quantum yields of ca. 20%.80 Ding et al. reported an
approach to controlling the CQD surface via silica column
chromatography separation.90 The observed red-shi in their
emission peaks from 440 to 625 nm was ascribed to a gradual
reduction in their bandgap with the increasing incorporation of
oxygen species into their surface structures.
Recently, another effective way, doping has been evidenced
to tune the properties of CQDs by changing their electronic
structures. Dai et al. produced nitrogen-doped GQDs (N-GQDs)
via a facile hydrothermal treatment of graphene oxide (GO),
using ammonium hydroxide as the nitrogen source.110 The
Raman spectra in Fig. 16A demonstrate the intrinsic charac-
teristics of sp2 carbon with disorder. Therefore, the N dopants
Fig. 15 Schematic representation of the PL mechanism for LG27 and
LG27O (treated by NaOH). Reprinted with permission from ref. 78.
Copyright 2014 Elsevier.
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Fig. 16 (A) Raman spectra of (a) pristine graphene oxide (GOs) and
N-GQDs fabricated with (b) 1.9, (c) 3.7, (d) 5.6, and (e) 7.4 mol L
1 of
NH4OH. (B) Schematic illustration of the structure of the N-GQDs. The
red, dashed circles highlight three substituted N atoms. Reprinted with
permission from ref. 110. Copyright 2018 John Wiley and Sons.
as heteroatoms inevitably induce the increased La ((ID/IG)
1) and
Ld ((ID/IG)
1/2) by disrupting the conjugated sp2 cluster and
accelerating point-like defect density through generating
disordered structures. The possible structure of the N-GQDs is
proposed as shown in Fig. 16B. However, excessive N dopants
could lead to PL quenching, possibly due to the deactivated
zigzag-edge sites and effective energy transfer between N
dopants and graphene.111 The N-GQDs are further found to be
suitable as photocurrent conversion materials due to benign
energy matching with anatase nanobers, the ultrafast electron
injection at their interface, and efficient electron transfer.
Besides nitrogen doping, Sarkar et al. proved that phosphorus
doping with NaH2PO4 solution could tune the uorescence
emission of the CQDs and enhance their PL intensity as well as
quantum yields.112 In addition, Qu et al. reported the synthesis
of S,N-doped GQDs by microwave-assisted thermal decompo-
sition of citric acid as a carbon source and urea as the nitrogen
and sulfur dopant.70 Compared with N-doped GQDs, the S,N-
doped GQDs show prominent absorption in the region of 550–
595 nm, which leads to better photocatalytic activity
accordingly.
5. Applications in photocatalysis
CQDs can show potential in photocatalysis applications
because of the features as follows. Primarily, CQDs show
superiority in water solubility, chemical stability and low
toxicity to other common photocatalysts (e.g., ZnO, TiO2, CdS).
In addition, CQDs exhibit excellent and tunable optical prop-
erties of absorbance and PL aer specic surface modication.
In particular, UCPL of CQDs, known to be an optical phenom-
enon wherein materials emit shorter wavelength light than the
excitation source, can considerably extend the sunlight
absorption of wide bandgap semiconductors into the visible
region and even the near infrared region. Moreover, photoin-
duced CQDs are both excellent electron donors and acceptors,
resulting in efficient separation of electrons and holes. There-
fore, CQDs can serve as a versatile component in photocatalyst
design, such as electron mediators, photosensitizers, spectral
converter and sole photocatalyst. Actually, these multiple effects
occur simultaneously in many cases. In this section, we
summarize the fundamental multifaceted roles and diverse
applications of CQDs in CQD-based photocatalyst systems.
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5.1 Electron mediators
Photocatalytic activity is strongly dependent on the transport
and separation efficiencies of photo-generated electrons and
holes in the photocatalysts. However, free charge carriers
(electrons and holes) can be trapped or scattered by various
kinds of random defects, resulting in increased recombination
probability.113,114 Therefore, promoting the separation of pho-
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togenerated electrons and holes will facilitate the photocatalytic
process. It has been demonstrated that carbon nanostructures
have a large electron-storage capacity;115 thus, the photoexcited
electrons from semiconductors or other kinds of photocatalysts
can be shuttled in the conducting network of CQDs, retarding
the recombination of photogenerated carriers at the junction
interface. In fact, CQDs with their ease of synthesis and low
toxicity have attracted considerable interest in serving as elec-
tron mediators.65,105,116–119 For example, Kang et al. fabricated
a Fe2O3/CQDs composite, and CQDs can improve photocatalytic
performance of Fe2O3 for the degradation of toxic gases (gas-
phase benzene and methanol) under visible light.117 The elec-
tron–hole pairs react with the adsorbed oxidants/reductants
(usually O2 and OH
) to produce active oxygen radicals
(e.g., $O2
and $OH), with very strong oxidation capability,
which subsequently cause the degradation of toxic gases. In this
process, CQDs act as an electron reservoir to trap electrons
emitted from Fe2O3 particles under visible light irradiation,
thus hindering the recombination of electron–hole pairs in
Fe2O3/CQDs (Fig. 17A). Fig. 17B shows the degradation rates of
benzene over Fe2O3 particles and Fe2O3/CQDs, respectively.
Aer visible light irradiation for 24 h, the degradation efficiency
of benzene is found to be about 37% over Fe2O3 particles, while
Fig. 17 (A) Schematic model for the photocatalytic process of the
Fe2O3/CQD composite under visible light. Photocatalytic degradation
of (B) gas-phase benzene, and (C) gas-phase methanol over Fe2O3
nanoparticles and Fe2O3/CQDs. Reprinted with permission from ref.
117. Copyright 2011 Royal Society of Chemistry.
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80% conversion is achieved over the composite photocatalyst
under identical reaction conditions. Furthermore, Fig. 17C
indicates that the Fe2O3/CQD composite exhibits much higher
activity for the gas-phase methanol degradation than Fe2O3
particles.
Subsequently, the authors conrmed that the electron
transfer properties of CQDs can enhance the stability of semi-
conductor photocatalysts besides their catalytic perfor-
mances.105 As shown in Fig. 18A, the complete degradation of
methyl orange (MO) takes about 25 min for CQDs/Ag3PO4, while
it takes about 55 min for Ag3PO4. Fig. 18B indicates that
CQDs/Ag3PO4 photocatalysts are stable enough during the
recycling experiments without exhibiting any signicant loss of
photocatalytic activity. In this process, CQDs can act as both
electron acceptors and donors, in which the electrons can be
easily transferred to the surface of Ag3PO4 and Ag/Ag3PO4, and
the redundant electrons on Ag3PO4 and Ag/Ag3PO4 can also be
transferred to CQDs (Fig. 18C). Thus, CQDs can effectively
protect the Ag3PO4 from dissolution and photocorrosion, thus
enhancing their photostability.
Recently, Di et al. further proved the electron transfer prop-
erties of CQDs in their recent work on the CQDs/Bi2MoO6
composite.118 As shown in Fig. 19A, the photocatalytic activity of
the hybrid material is signicantly improved for the degrada-
tion of ciprooxacin (CIP) compared with pure Bi2MoO6. The
noticeable improvement of photocurrent response (Fig. 19B)
reveals that the photogenerated electrons in the conduction
band (CB) of Bi2MoO6 are transferred to CQDs, which can
enhance the separation of the photogenerated charge carriers,
Fig. 18 (A) Photocatalytic activities of Ag3PO4, Ag/Ag3PO4, CQDs/
Ag3PO4 and CQDs/Ag/Ag3PO4 for MO degradation under visible light.
(B) The repeated bleaching of methyl orange (MO) over CQDs/Ag3PO4
photocatalysts under visible light. (C) Schematic model for the
important roles of CQDs in the high photocatalytic activity and good
stability of CQDs/Ag3PO4. Reprinted with permission from ref. 105.
Copyright 2013 Royal Society of Chemistry.
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Fig. 19 (A) Photocatalytic degradation of ciprofloxacin (CIP) in the

presence of pure Bi2MoO6 and CQDs/Bi2MoO6 materials and
photolysis of CIP under visible light irradiation. (B) Transient photo-
current responses for the pure Bi2MoO6 and 2 wt% CQDs/Bi2MoO6
materials. (C) Schematic of the separation and transfer of photo- Fig. 20 (A) Aqueous soluble PEG-functionalized carbon nanoparticles
generated charges in CQDs/Bi2MoO6 combined with the possible before (left, fluorescent) and after (right, photocatalytic for CO2
reaction mechanism of the photocatalytic procedure. Reprinted with reduction in aqueous solution) coating with a metal. Reprinted with
permission from ref. 118. Copyright 2015 Royal Society of Chemistry. permission from ref. 120. Copyright 2012 American Chemical Society.
(B) Schematic illustration of the photocatalytic H2 production mech-
anism over CQDs/P25 under ultraviolet-visible (UV-vis) and visible light
(l > 450 nm) irradiation. Reprinted with permission from ref. 121.
and consequently improve the photocatalytic activity. Fig. 19C Copyright 2014 Royal Society of Chemistry.
illustrates the photocatalytic mechanism diagram of degrada-
tion of CIP over CQDs/Bi2MoO6. As shown in the schematic,
CQDs not only play a crucial role in inhibiting the recombina- irradiation, the photocatalytic H2 evolution rate of CQDs/P25
tion of photogenerated electron–hole pairs but also act as with an optimal mass ratio is 9.1 mmol h
1 (4 times higher
photocatalytic reaction centers of O2 to O2
. than that of pure P25). Different from pure P25, CQDs/P25 also
exhibited efficient visible-light-driven photocatalytic H2
5.2 Photosensitizers production activity. Under visible light (l > 450 nm) irradiation,
the CQDs act as a photosensitizer, like organic dyes, to sensitize
Apart from performing as an electron mediator, CQDs display
P25 into a visible light responsive “dyade” structure (the newly
PL and UCPL rendering them as promising photosensitizers in
formed chemical bond Ti–O–C), in which the photoinduced
photocatalytic systems.16,64,66,70,120,121 Meanwhile, CQDs show
electrons transfer from the excited CQDs to P25 via electronic
remarkable merits on multiple aspects compared to other
coupling between the LUMO orbitals of CQDs and the
photosensitizers. Firstly, CQDs are typically terminated by
conduction band states of TiO2, and then react with protons for
carboxylic acid groups at their surface, which impart high
H2 production. The possible mechanism of the photocatalytic
solubility in aqueous solutions and provide potential for further
H2 evolution over CQDs/P25 is visualized in Fig. 20B.
functionalization. Besides, unlike graphene materials122,123 and
Recently, Martindale and co-workers reported a photo-
organic dyes,124–126 CQDs can be cost-effectively synthesized on
catalytic H2 production system using CQDs as a photosensitizer
a large scale via environmentally friendly methods. Further-
in combination with a molecular Ni catalyst (NiP, nickel bis-
more, because of their low-toxicity, CQDs could be adopted to
(diphosphine) complex).64 This work demonstrated the poten-
replace toxic CdS/CdSe quantum dots.127 Sun et al. presented
tial use of CQDs in photocatalytic schemes, whereby they can
that CQDs aer being surface functionalized with polyethylene
absorb UV and visible light and directly transfer photoexcited
glycol (PEG) can act as photosensitizer in Au(Pt)–CQDs system
electrons to solution-based molecular electron acceptors and
for photocatalytic reduction of CO2.120 As revealed in Fig. 20A,
catalysts. Maximum activity with respect to CQDs of 398 mmol
CQDs harvest visible photons which subsequently generate
H2 (gCQDs)
1 h
1 optimized for NiP is achieved through
charge carriers on their surface to drive the photocatalytic
parameter optimization under full solar spectrum light irradi-
process efficiently. Furthermore, the aqueous solubility of the
ation at 1 sun intensity. Remarkably, as shown in Fig. 21B, in
catalysts enables such a photoreduction process under more
the absence of any of the components of the system – CQDs
desirable homogeneous reaction conditions.
(light absorber), NiP (catalyst), or EDTA (electron donor) – H2
Yu et al. prepared a CQDs/P25 composite with efficient
evolution does not occur. Accordingly, it is proposed that the
photocatalytic H2 evolution activity via a facile one-step hydro-
CQDs serve as an excellent photosensitizer in the following
thermal strategy.121 Under ultraviolet-visible (UV-vis) light

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Fig. 21 (A) Schematic illustration of solar H2 production using the
hybrid CQDs–NiP system. (B) Optimized H2 generation using CQDs
(10 mg) and NiP (10 nmol) in aqueous EDTA solution (0.1 M, pH 6)
under 1 sun irradiation in the absence (l > 300 nm) and presence of
a 400 nm UV filter. Control experiments without EDTA, CQDs, NiP, as
well as with heterogeneous catalyst precursors, NiCl2 (30 nmol) and
K2PtCl4 (128 nmol, 0.5 wt%), are also shown. (C) Photocatalytic H2
generation using CQDs (10 mg) and NiP (10 nmol) in aqueous EDTA
solution under 1 sun full solar spectrum irradiation. Activity is recov-
ered upon each readdition of the catalyst, NiP (10 nmol), but not upon
readdition of CQDs (10 mg). Reprinted with permission from ref. 64.
Copyright 2015 American Chemical Society.
process (Fig. 21A): the CQDs are excited under solar irradiation
rstly and then the photogenerated electrons transfer to the
NiP, which enables the excitation of NiP. Simultaneously, the
photoinduced CQDs are quenched by the electron donor EDTA
to inhibit the recombination of photogenerated carriers.
Subsequently, the excited electrons from NiP lead to the
reduction of aqueous protons. Additionally, the stability of the
system is evaluated through readdition of fresh CQDs and NiP
aer each 6 h of irradiation (as shown in Fig. 21C). Reactivation
is observed upon each readdition of NiP, and a repeating
pattern of resumed activity followed by gradual decay of the
catalyst occurs. Conversely, if the same quantity of fresh CQDs
(10 mg) is readded to the inactive solution following 6 h of
irradiation, H2 production does not resume. This result
conrms that the CQDs show good photostability and the NiP is
the limiting factor for the stability in this system.
5.3 Spectral converters
Many conventional photocatalysts are wide-bandgap semi-
conductors (e.g., TiO2, ZnO) that can only be excited by UV light.
This greatly limits their wide practical applications because the
UV light only accounts for 4% of the total solar power.128
Generally, narrow-bandgap semiconductors like CdS and CdSe
are employed to couple with conventional TiO2-based photo-
catalyst systems to utilize the full spectrum of sunlight.
However, they are restricted in practical applications because of
This journal is © The Royal Society of Chemistry 2017
View Article Online
Journal of Materials Chemistry A
their toxicity and instability. To extend the light absorption
range from the UV to the visible light region, more robust
approaches are desirable. CQDs are employed as a spectral
converter in CQD-based composite photocatalysts, taking
advantages of their UCPL properties.57,83,129–132 Kang et al.83
designed a CQDs/TiO2 photocatalyst system, which exhibits
higher photocatalytic activity than bare CQDs, TiO2 and P25
toward the photo-degradation of methylene blue (MB) under
visible light (Fig. 22A) and higher transient photocurrents than
P25 (Fig. 22B). The possible photocatalytic mechanism over
CQDs/TiO2 is proposed in Fig. 22C. First of all, hybridization of
CQDs with TiO2 extends the light response of TiO2 into the
visible range of the solar spectrum, due to the electronic
coupling between the p states of graphite-essential CQDs and
the conduction band states of TiO2.115,133 Such electronic
coupling will induce a smaller nano-hybrid bandgap compared
to bare TiO2, or new carbon energy levels in the TiO2 bandgap
also bring about smaller bandgap energy and a red-shi.
Additionally, the UCPL properties of CQDs will convert longer
wavelength light into shorter wavelength emission. Conse-
quently, light with a wider range of wavelengths, from UV to
visible, can be used by the TiO2/CQDs. Then, O2 adsorbed on
the surface of the CQDs can capture photogenerated electrons
and form O2
, and oxidize MB directly on the surface.
A recent study by Pan et al. reported the preparation of
a CQDs/TiO2 nanotube composite for the photo-degradation of
rhodamine B (RhB) under visible light (l > 420 nm).129 The
results demonstrate that the CQDs/TiO2 nanotube composite
Fig. 22 (A) Comparison of the visible light-driven photocatalytic
activity of pure TiO2, CQDs, TiO2/CQDs and P25 for photo-degrada-
tion of methylene blue (MB). (B) Transient photocurrents of the as-
prepared TiO2/CQDs and P25 irradiated with wavelength larger than
510 nm. (C) Proposed formation mechanism of the dyadic structure
with charge transfer-type orbital hybridizations at the surface of TiO2
and CQDs. Reprinted with permission from ref. 83. Copyright 2012
Royal Society of Chemistry.
J. Mater. Chem. A, 2017, 5, 3717–3734 | 3729
 View Article Online

Journal of Materials Chemistry A Review

shows signicantly higher photocatalytic activity than pure TiO2

nanotubes. This improved visible light photo-activity can be
ascribed to the UCPL properties of CQDs. As shown in the UCPL
spectra (Fig. 23A), the CQDs/TiO2 nanotube composite exhibits
UCPL emissions with excitation wavelengths ranging from 550
to 850 nm, while the blank TiO2 cannot be excited, which
implies that CQDs act as a spectral converter in the composite
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system. However, it is obvious that the UCPL of CQDs is not fully

utilized by TiO2 especially with the excitation wavelength of
600 nm. Fig. 23B shows a schematic diagram of the photo-
catalytic process for the CQDs/TiO2 nanotube composite under
visible light. TiO2 can be bandgap photoexcited to generate
electron–hole pairs by wavelengths less than or equal to 380 nm.
In the CQDs/TiO2 composite system, CQDs can convert a frac-
tion of visible light into a shorter wavelength, which then excites
TiO2 to generate electron–hole pairs.

5.4 Sole photocatalyst

The abovementioned photocatalytic applications of CQDs are
all in conjunction with other inorganic materials, while it has
been found that CQDs can also directly act as photocatalysts

Fig. 24 (A) The photocatalytic mechanism of CQDs with oxygen-

containing surface groups. Reprinted with permission from ref. 53.
Copyright 2009 John Wiley and Sons. (B) The selective oxidation
process of benzyl alcohol to benzaldehyde in the presence of CQDs
under NIR light irradiation. Reprinted with permission from ref. 135.
Copyright 2013 Royal Society of Chemistry.

alone.53,134–136 Hu et al. have proposed the mechanism of CQDs

Fig. 23 (A) UCPL spectra of blank-TiO2 and the CQDs/TiO2 composite
under visible/near infrared excitation. (B) Schematic diagram of the
photocatalytic mechanism for the CQDs/TiO2 nanotube composite
under visible light irradiation. Reprinted with permission from ref. 129.
Copyright 2014 Royal Society of Chemistry.
as a sole photocatalyst and highlighted that surface oxygenated
functional groups are the signicant factor affecting the pho-
tocatalytic activities of CQDs.53 As shown in Fig. 24A, the pho-
tocatalytic mechanism of CQDs is proposed. Carbonyl and
carboxylic acid groups can induce the high upward band
bending, which will reduce the recombination of electron–hole
pairs. In contrast, hydroxyl groups can only bring about low
upward band bending, which hardly prevents the electron–hole
pairs from surface recombination.
Kang et al. synthesized CQDs with sizes of 1–4 nm through
an alkali-assisted electrochemical method, for the selective
oxidation of benzyl alcohol to benzaldehyde with high conver-
sion (92%) and selectivity (100%) in the presence of H2O2 under
near infrared (NIR) light irradiation.135 Fig. 24B shows the
mechanism of photocatalytic oxidation of benzyl alcohol to
benzaldehyde by CQDs under NIR light. H2O2 molecules
previously adsorbed on CQDs are decomposed into active
oxygen species (HO$), which have strong oxidation ability and
are able to oxidize benzyl alcohol to benzaldehyde or benzoic
acid. Additionally, a p–p interaction exists between CQDs and
benzyl alcohol or benzaldehyde, facilitating the adsorption of
benzyl alcohol and benzaldehyde on the surface of CQDs. With
NIR light irradiation, the photoinduced electron transfer ability
of CQDs can protect benzaldehyde produced in the rst step

3730 | J. Mater. Chem. A, 2017, 5, 3717–3734 This journal is © The Royal Society of Chemistry 2017

Review
from further oxidation by the photo-electron reductive envi-
ronment, which yields high selectivity (100%) to benzaldehyde.
6. Conclusion and outlook
Since the discovery of CQDs in 2004, there has been extensive
research on the synthesis, modications, properties, and
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applications of CQDs because of their unique and tunable
physicochemical, optical and electronic properties. It is
heartening to witness the diversion of research interest in
CQDs away from traditional elds such as bioimaging, bio-
sensing and drug delivery, to other energy storage and
conversion related elds such as articial photocatalysis. As
such, we have attempted to give a general review of the recent
advances in CQDs, focusing on their synthesis, properties and
multiple roles in photocatalytic applications. To date, various
facile, cost-effective, size-controllable and large scale methods
have been developed for the preparation of CQDs with
different compositions and structures. Accordingly, CQDs
unfold effective absorbance of solar light, tunable PL, unique
UCPL and unique photoinduced electron transfer properties.
In particular, CQDs are able to play multifaceted roles in
photocatalysis, such as electron mediators, photosensitizers,
spectral converter and sole photocatalyst.
Although signicant advancement has been made in this
area over the past decade, there are still many issues worthy of
further investigation as follows:
(1) The defects of CQDs have a signicant inuence on their
optical and electronic properties. However, approaches and
techniques that are capable of precisely manipulating the
amount of defects in CQDs are still unavailable. Thus, more
efforts should be devoted to the well-dened and atom-precise
structural synthesis of CQDs.
(2) So far, there have been large amounts of research on the
modication of CQDs. However, simple and controllable func-
tionalization and doping of CQDs are still crucial issues, which
could open the doors for better PL control and higher efficiency
in many applications.
(3) Theoretical and experimental studies are further expected
to understand the mechanisms of CQD-associated properties.
For instance, convincing explanation is still absent for the UCPL
mechanism of CQDs. Therefore, more efforts on inferring the
transfer route of photogenerated electrons in the process of
UCPL are desired to make it possible to fully use this specic
property.
(4) Most of the CQDs used in photocatalysis display strong
absorption in UV region, indicating a limited light-harvesting
ability. It is worth fabricating specic CQDs through hetero-
atom doping or surface modication to enable them to be
excited in the visible or even NIR region. This will benet the
intelligent design of heterogeneous photocatalysts with efficient
utilization of the solar spectrum.
(5) There are few studies on the photostability of CQD-based
nanocomposites, representing one main challenge for this type
of photocatalyst development. For instance, the oxygenic
groups on the surface of CQDs can signicantly affect their
photocatalytic activity. However, these oxygenic functional
This journal is © The Royal Society of Chemistry 2017
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Journal of Materials Chemistry A
groups will be reduced during the photocatalytic process, which
accordingly raises a signicant concern on the issue of photo-
stability of CQD-based photocatalysts. Thus, it will be a core
task to develop a stable CQD-based photocatalytic system for
their future practical applications.
Despite the fact that some issues associated with CQDs are
still up in the air, numerous stimulating challenges and
opportunities still await us to explore the immense potential of
CQDs in diverse technological applications in the near future. It
is hoped that this review could afford enriched information on
the versatile functions of CQDs for the rational design of pho-
tocatalysts, with a view to improving their burgeoning devel-
opments toward the ultimate achievement of highly efficient
and long-term stable CQD-based photocatalysts.
Acknowledgements
The support from the Key Project of National Natural Science
Foundation of China (U1463204), the National Natural Science
Foundation of China (20903023 and 21173045), the Award
Program for Minjiang Scholar Professorship, the Natural
Science Foundation of Fujian Province for Distinguished Young
Investigator Grant (2012J06003), the Independent Research
Project of State Key Laboratory of Photocatalysis on Energy and
Environment (No. 2014A05), the rst Program of Fujian Prov-
ince for Top Creative Young Talents, and the Program for
Returned High-Level Overseas Chinese Scholars of Fujian
province is kindly acknowledged.
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