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A minireview on doped carbon dots for

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Cite this: DOI: 10.1039/d0nr03163a

photocatalytic and electrocatalytic applications
Zhengting Zhang, a,b,c Guiyun Yi, *a,b,c Peng Li, a,b,c Xiuxiu Zhang,a,b,c
Haiyang Fan,a,b,c Yulong Zhang,a,b,c Xiaodong Wanga,b,c and Chuanxiang Zhanga,b,c

Received 22nd April 2020,
Accepted 8th June 2020
DOI: 10.1039/d0nr03163a
rsc.li/nanoscale
To date, carbon dots (CDs) or carbon quantum dots (CQDs), considered as alternatives to conventional
fluorescent materials such as organic dyes and semiconductor quantum dots (QDs), have drawn signifi-
cant attention from relevant researchers due to their superior properties, including nontoxicity, biocom-
patibility, low cost and facile synthesis, and high photoluminescence. In particular, doping heteroatoms
with CDs can not only dramatically enhance the fluorescence but also greatly improve the electronic
structure and doped CDs have been successfully applied in various technological fields. Herein, this mini-
review summarizes recent advances on the synthesis and optical properties of doped CDs and their
promising applications for photocatalysis and electrocatalysis. Finally, some challenging issues as well as
future perspectives of this exciting material are discussed.

Introduction have been made in the synthesis, properties, characterization

methods, and applications of CDs, as can be seen from a
In comparison with conventional fluorescent materials such as number of review articles.25–28 On the other hand, in order to
organic dyes and semiconductor quantum dots (QDs), carbon improve the fluorescence properties of CDs, a doping strategy
dots (CDs) have already attracted increasing research attention has been introduced and a desirable as well as unexpected
in terms of their fascinating properties including low toxicity, effect like a highly improved electronic structure is achieved.
biocompatibility, water solubility, and ease of surface modifi- Recently, reviews concerning properties, synthesis, characteriz-
cation or functionalization. In 2004, Xu et al.1 discovered CDs ation, and various technological applications of doped CDs
for the first time, which were impurities during the purifi- have been published.29–32 However, a focused review of doped
cation process of single-walled nanotubes. These CDs are zero- CDs for promising catalytic applications still remains unavail-
dimensional carbon materials with sizes below 10 nm, which able in the literature. As a result, in this minireview, we first
are usually quasi-spherical particles. As clearly shown in Fig. 1, briefly review the already-reported synthesis approaches and
numerous scientific literature studies related to CDs have been fluorescence properties of doped CDs originating from various
increasingly published since 2005. The increased research
interest in such carbon-based materials may be attributed to a
number of congenital advantages of CDs, such as abundant in
source, facile and low-cost synthesis procedure, and superior
photoluminescence. Additionally, the fluorescent CDs are of
great chemical stability, inert from the colloidal solution, and
highly resistant to photobleaching, and are widely utilized for
bioimaging,2–7 biosensing,8–12 catalysis,13–19 energy
20,21 22–24
research and other applications. Among the various
excellent properties of CDs, the luminescence property has
been considered as the most fascinating property and much
effort has been devoted to it, despite the incongruity of the
photoluminescence mechanism. To date, great achievements

a
College of Chemistry and Chemical Engineering, Henan Polytechnic University,
Jiaozuo 454003, China. E-mail: ygyun@hpu.edu.cn
b
Collaborative Innovation Center of Coal Work Safety, Jiaozuo 454003, China Fig. 1 The number of published literature studies according to the
c
Henan Key Laboratory of Coal Green Conversion, Jiaozuo 454003, China Google scholar search (keyword “carbon dots”).

This journal is © The Royal Society of Chemistry 2020 Nanoscale


Minireview
carbon-rich sources. Then, recent representative articles in
regard to the photocatalytic and electrocatalytic applications of
doped CDs are reviewed and discussed in detail. Eventually,
we will offer several future perspectives and stress the signifi-
cance of doped CDs employed for promising catalytic
applications.
Synthesis of doped CDs and their
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properties
Similar to those of CDs, approaches to synthesis of doped CDs
were numerous, which could also be classified into “top-
down” and “bottom-up” strategies. The “top-down” strategies,
including acidic oxidation,33 hydrothermal or solvothermal
treatment,34,35 an electrochemical method,17 laser ablation,36
microwave irradiation37and ultrasonication,38 denote the syn-
thesis of doped CDs by cleaving or breaking down large-sized
carbon-based materials by means of physical, chemical, and
electrochemical methods. The detailed doping procedure of
CDs is achieved usually when the heteroatoms have already
been successfully doped in the carbon-based materials before
the “top-down” process or during the process. In contrast, the
“bottom-up” strategies, consisting of hydrothermal or solvo-
thermal synthesis39,40 and a microwave method,41 refer to
pyrolysis or self-assembly of small-sized organic molecules
containing various heteroatoms as the starting precursors to
construct more complicated systems by mutual interactions
between the precursors. Among these various synthetic
methods, the hydrothermal method has been considered as
one of the most appropriate choices when synthesizing doped
CDs considering its advantages such as simple and low-cost
synthesis, controllable variables, and large-scale synthesis. In
this method, a carbon-rich composite such as graphene,
sugars and organic molecules in a tightly closed reactor
should be heated to initiate the carbonization process.
In order to obtain doped CDs with desirable sizes, reac-
tants, reaction conditions, additives and surfactants should be
controlled. Fluorescent CDs can be synthesized from glucose,
graphene, citric acid, etc.,42–44 while the highly luminescent
doped CDs synthesized by the hydrothermal method can be
obtained from milk, lignin, ethanolamine, bee pollen, etc.45–49
Lu et al.25 have recently reported a review related to biomass-
derived CDs and their fascinating applications, which shows
the priority of biomass sources through hydrothermal treat-
ment. So far, the majority of the published literature studies
related to CDs report the synthesis of blue emitting CDs with
excitation-dependent emission spectra. Nevertheless, the peak
of the emission spectra can be tuned by doping of CDs with
various heteroatoms (including metal ions) such as nitrogen,
sulfur, phosphorus, boron, zinc ions, etc. In addition, unex-
pected properties can be possessed by codoping CDs with two
or more heteroatoms, as reported in many recently reported
works.2,5,50–53 Most significantly, doping of CDs can also lead
to luminescence enhancement and improvement of electronic
structures, further widening their practical applications. For
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Fig. 2 (a) UV-vis absorption spectrum of the as-prepared CDs with two
peaks located at 234 nm and 332 nm and the photoluminescence (PL)
spectrum with maximum excitation and emission wavelength at 363 nm
and 460 nm, respectively. Inset: photograph of CDs-6 taken under UV
irradiation at 365 nm. Emission spectra of (b) CDs-1, (c) CDs-3, and (d)
CDs-6 obtained at different excitation wavelengths. Inset: the normal-
ized emission spectra. Reprinted with permission from ref. 54. Copyright
2016 Royal Society of Chemistry.
example, a series of luminescent nitrogen-doped CDs with
blue emission were successfully synthesized by adjusting reac-
tion conditions in hydrothermal route, as shown in Fig. 2, and
were potentially utilized for sensing, bioimaging, and
catalysis.54
Two typical absorption peaks of the as-prepared CDs (CDs-1
to CDs-6 with different contents of nitrogen) are located at
234 nm and 332 nm, respectively, confirming the superior
optical properties (Fig. 2a). The 234 nm absorption band con-
sists of the π → π transition of CvC, while the band at 332 nm
may be ascribed to the n → π* transition of surface functional
groups. Moreover, the maximum excitation wavelength at
363 nm is in accordance with the UV-vis absorption peak
located at 332 nm and the maximum emission wavelength at
460 nm is obtained. In addition, CDs-1 and CDs-3 exhibit exci-
tation-dependent emission (EDE), while CDs-6 shows exci-
tation-independent emission (EIE), which proves that surface
passivation by incorporating nitrogen into the CDs can cause
the transfer from EDE to EIE. The exact origin of fluorescence
in CDs and doped CDs is not clearly clarified yet, thus, there
exist various mechanism interpretations in the literature. For
example, Zhu et al.26 reviewed four typical photoluminescence
mechanisms, which were confirmed by relevant experimental
data and reasonable analysis. The origin of fluorescence is
ascribed to the quantum confinement effect or conjugated
π-domains determined by the carbon core, the surface state
determined by hybridization of the carbon backbone and con-
nected groups, the molecule state solely determined by the
fluorescent molecules on the surface, and the crosslink-
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enhanced emission (CEE) effect mainly employed to explain
the fluorescence of polymer quantum dots (PDs).
Recently, Sarkar and coworkers55 investigated the origin of
red fluorescence in nitrogen-doped CDs and discovered that
the red luminescence originates from graphitic nitrogen
centers and oxygen containing functional groups. In this work,
the presence of graphitic nitrogen centers induces red-shift in
the absorption spectra of CDs, which may be attributed to the
electron-doping effect reducing the magnitude of the elec-
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tronic gap. Additionally, different emission centers and traps
can be created with the doping of different heteroatoms with
CDs. As a consequence, the emission spectra can be tuned
from blue to red. Therefore, the competition and synergy of
the emission centers, traps, and surface states mainly accounts
for the difference between emission spectra of doped CDs. In
addition, Zheng et al.56 reported the aggregation-induced
emission (AIE) of CDs with concentration-modulated fluo-
rescence, which accounts for the continuous redshift of fluo-
rescence with an increase in concentration. This novel emis-
sion mechanism for CDs gives researchers great inspiration to
elucidate the original and enhanced fluorescence of doped
carbon dots. Nevertheless, the exact photoluminescence
mechanism of doped CDs is still an open debate needing
further investigation and breakthrough progress is expected in
the near future. On the other hand, the fascinating optical pro-
perties of doped CDs have already been employed for numer-
ous technological applications.57–60 Hence, the practical utiliz-
ation of doped CDs for photoelectrocatalysis will be discussed
in detail in the following section.
Doped CDs for photocatalytic
applications
In recent years, much effort has been devoted to doping CDs
with other materials or heteroatoms, and the as-composited
CDs can be employed for both photocatalytic and electro-
catalytic applications. It is unique fluorescence behavior and
photoelectron transfer properties of doped CDs that make
them a promising candidate for high-performance photo-
catalyst. Doping with heteroatoms or metals will decrease the
surface function and adjust the band gaps of CDs, rendering
the electron transfer among reactions more convenient, thus,
the doped CDs possess a certain catalytic performance.
Recently, a great deal of literature studies related to photocatal-
tic applications of doped CDs are published, including photo-
degradation, photooxidation, and photoreduction.61–63
Incorporating heteroatom-doped CDs into certain nano-
materials for photodegradating large organic molecules has
attracted increasing attention from researchers and numerous
literature studies have been published, including, 4-nitro-
phenol (4-NP), 1,4-dihydropyridine (1,4-DHP), dichlorophenol,
rhodamine B (RhB), methylene blue (MB), etc.14,64–68
For example, Han and coworkers65 recently reported a
simple route for incorporating nitrogen-doped CDs into meso-
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Fig. 3 In situ incorporation of CDs into amorphous and mesoporous
NiB nanospheres is schematically illustrated. Reprinted with permission
from ref. 65. Copyright 2018 Elsevier.
porous and amorphous hybrids and photocatalytic activities of
the as-prepared doped CDs for degrading nitrobenzene deriva-
tives using the visible light were impressive. Fig. 3 demon-
strates the specific process of in situ incorporation of CDs into
NiB nanospheres, as mainly achieved by mutual electrostatic
interactions. In this experiment, CDs@NiB (S1) and NiB (S2)
are prepared for further comparison. Cyclic voltammetry,
photocurrent, and zeta potential of S1 and S2 were measured,
as shown in Fig. 4. It turns out that the conduction band
minimum (CBM) of S1 (−1.2 V) becomes more negative com-
pared to that of S2 (−1.0 V) and such band alignment drives
the motion of charge carriers as well as the transfer of photo-
generated electrons from S1 to 4-NP, thus improving the
photocatalytic activity. Furthermore, S1 is positively charged,
while S2 is more negative than 4-NP (reactant) and obviously,
S1 tends to absorb 4-NP more easily compared to S2. As a con-
sequence, all the tested data provide strong evidence for the
higher performance of S1 for photodegradation of 4-NP. In
addition, Tang et al.69 prepared novel nitrogen-doped CD
modified CuBi2O4 photocatalyst by a simple hydrothermal
approach, which was applied to photocatalytic water splitting
for H2 evolution. Sonkar and coworkers15 synthesized red-emit-
ting zinc doped CDs employed for the photoreduction of Cr(VI)
to Cr(III) under sunlight irradiation and the recyclability of the
as-prepared CDs can reach seven cycles. Works associated with
doped CDs employed for photocatalytic CO2 conversion were
also reported.70 A nitrogen-doped carbon quantum dot (CQD)/
Cu2O heterostructure with a protruding structure was syn-
thesized and found to offer highly efficient photocatalytic con-
version of CO2 to methanol under solar-light irradiation.71 The
photocatalyst exhibited excellent stability during the conver-
sion process, which was attributed to the photo-induced elec-
tron transfer properties of the doped CQDs. As a result, the
promising contribution of doped CDs to photocatalysis has
been confirmed.
Some potential reaction mechanisms were offered by rele-
vant researchers. Habibi-Yangjeh et al.66 proposed that doped
CDs were used as the electron mediator, which could work as
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Doped CDs for electrocatalytic

applications
Similar to photocatalytic applications of doped carbon dots,
the specific electronic structure can also be directly or
indirectly utilized for electrocatalytic applications. Here, we
introduce some currently published literature studies related
to electrocatalytic applications of doped CDs. Zhu et al.74 con-
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ceived a facile yet effective route for synthesizing nitrogen-

doped CDs by soy milk and the as-prepared doped CDs not
only exhibited superior fluorescence properties but also pos-
sessed excellent electrocatalytic activity to the oxygen reduction
reaction. Gao and coworkers75 developed a novel strategy using
willow leaves to fabricate CDs by the hydrothermal method. In
this work, strong blue luminescence under UV light irradiation
is observed and the light-yellow suspension (SP1) can also be
directly utilized as a fluorescent ink. Furthermore, the
obtained solid product (SP2) after being pyrolyzed possesses
great electrocatalytic performance when employed for the
oxygen reduction reaction (ORR). In addition, the excellent
stability of this catalyst outweighs that of the commercial Pt/C
catalyst. Fig. 5a shows cyclic voltammograms (CVs) of bare
glassy carbon (1), SP2 (2), and Pt/C (3) electrodes in N2-and O2-
saturated 0.1 M KOH solutions, respectively, while Fig. 5b exhi-
bits the linear sweep voltammograms (LSVs) of the SP2 elec-
trode for the ORR in the O2-saturated 0.1 M KOH solutions
Fig. 4 (a) Cathodic scan and (b) anodic scan for determining the con-
duction band minimum (CBM) and the valence band maximum (VBM) of
S1 and S2, respectively; (c) EIS Nyquist plots of S1 and S2; (d) transient
photocurrent responses of S1 and S2; (e) energy level diagrams of S1
and S2 along with the potential for the 4-NP degradation reaction; (f )
Zeta potential measurement of S1, S2, 4-NP and 4-AP, respectively.
Reprinted with permission from ref. 65. Copyright 2018 Elsevier.

electron acceptors or electron donors between AgCl and

g-C3N4. The photogenerated electrons can be rapidly trans-
ferred to AgCl in the presence of doped CDs, leaving the holes
on g-C3N4. Moreover, a Z-scheme NCD/Ag3PO4/g-C3N4 with
excellent photocatalytic activity was prepared.72 A possible
reaction mechanism was proposed: first, NCDs (nitrogen-
doped CDs) enhanced the light absorption ability due to their
up-conversion PL properties, leading to exciting g-C3N4 and
Ag3PO4 to form more charge carriers; second, due to the excel-
lent electron conductivity of NCDs, it could serve as the charge
transmission bridge between g-C3N4 and Ag3PO4, accelerating
the combination of electrons on the conduction band (CB) of
Fig. 5 (a) Cyclic voltammograms (CVs) of the bare glassy carbon (1),
Ag3PO4 and holes on the valence band (VB) of g-C3N4; finally,
SP2 (2), and Pt/C (3) electrodes in N2- and O2-saturated 0.1 M KOH at a
NCDs allowed electrons easily to transfer to the surface of scan rate of 10 mV s−1; (b) linear sweep voltammograms (LSVs) for the
g-C3N4 and Ag3PO4, further improving the separation of elec- ORR on the sp2 electrode in an O2-saturated 0.1 M KOH solution at a
tron–hole pairs. Most importantly, doped CDs can adjust the scan rate of 10 mV s−1 and a series of rotation rates from 400 to 2025
band gap of the catalyst making the reactant easier to react as rpm; (c) HER polarization curves for the Ru@CDs, CDs, Ru powder, com-
mercial Ru/C and commercial Pt/C; (d) durability measurement of
well as improving the activity, as reviewed by Yang’s group.73
Ru@CDs in 1 M KOH before and after 10 000 cycles. Reprinted with per-
However, clear reaction mechanism of doped CDs is still mission from ref. 75. Copyright 2014 Royal Society of Chemistry.
under investigation and breakthrough progress is expected in Reprinted with permission from ref. 76. Copyright 2018 Wiley-VCH
the near future. Verlag GmbH & Co. KGaA, Weinheim.

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with rotation rates ranging from 400 to 2025 r min−1. Such
linear sweep voltammograms were then employed for the
highly efficient oxygen reduction reaction, confirming the out-
standing catalytic activity of SP2. In addition, Li et al.76 suc-
cessfully synthesized a novel nanoparticle electrocatalyst com-
posited by ruthenium and doped CDs (Ru@CDs) and the as-
prepared composite was used for the hydrogen evolution reac-
tion (HER). It was found that the high electrocatalytic perform-
ance of Ru@CDs outweighs that of any already-reported metal
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or nonmetal materials for the HER. Meanwhile, the catalytic
durability of this novel catalyst outweighs that of Pt/C catalyst
under alkaline conditions. As clearly exhibited in Fig. 5c and
d, the superiority of this catalyst can be confirmed by the HER
polarization curves of Ru@CDs, CDs, Ru powder, Ru/C, and
Pt/C, and a durability measurement in 1 M KOH after 10 000
cycles.
A doping strategy has always been considered as a promis-
ing method for improving the properties of various functional
materials and doped CDs can also bring us infinite possibili-
ties. As demonstrated by several recent-reported works, the
improved electron transfer properties of doped CDs have
already been utilized for many other electrocatalytic
fields.18,19,77–79 However, same as photocatalytic applications,
no clear working mechanism of doped CDs is obtained and
much effort still needs to be devoted to make a breakthrough
in the near future.
Summary and future outlook
In this minireview, recent advances on photocatalytic and
electrocatalytic applications of doped CDs are overviewed and
discussed in detail, allowing us to take a closer look at doped
CDs. Doping CDs with various heteroatoms will not only
enhance the fluorescence but also greatly change the energy
band structure, which should be responsible for the excellent
catalytic performance of doped CDs. The synthesis of doped
CDs can be facile, low cost, green and highly efficient due to
numerous carbon-rich sources and large-scale preparation of
doped CDs at the gram-scale has become a reality. However,
some fundamental issues, including the photoluminescence
(PL) mechanism, the exact role of doped heteroatoms or ions,
and their location at CDs are still not resolved and under
investigation. Therefore, to better understand and control
various outstanding properties of doped CDs, these issues
should be addressed in the near future. On the other hand,
much progress has already been made both in the mechanism
explanation, property adjustment and technological appli-
cations. For example, one can design and tailor the surface
groups of CDs by a facile yet effective strategy developed by Hu
et al.80 Similar to an inner electronic field that facilitates the
separation of electron–hole pairs and carrier migration, the
coexistence of the O atom and the Cl atom on the surface
caused both upward and downward energy band bending
leading to excellent photocatalytic activity. In addition,
different doped atoms exert different impacts on the electron
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transfer properties of CDs. For instance, phosphorus (n-type
dopant) accelerates the electron transfer from CDs to phthalo-
cyanine, while boron ( p-type dopant) slows down the electron
transfer process and generates a simultaneous hole transfer
process.50 As a result, in order to improve the photocatalytic
and electrocatalytic efficiency of CD-based catalysts, one can
design the surface group and manipulate the dopant, such as
codoping of two or more heteroatoms. Aside from photo-
catalytic and electrocatalytic applications, doped CDs may be
potentially utilized for many other catalytic reactions.
Generally, published literature studies concerning the superior
fluorescence of doped CDs employed for sensing and bio-
imaging applications far outweigh those related to tunability
of electron transfer properties utilized for photocatalytic and
electrocatalytic applications, which are mainly attributed to
the incomplete understanding of doped CDs. However, we
strongly believe that the number of studies on catalytic appli-
cations of doped CDs will dramatically grow in the near future.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (51974110 and U1803114), the
Fundamental Research Funds for the Universities of Henan
Province (NSFRF180313), the Education Department Science
Foundation of Henan Province (19A440002 and 19A530002),
the Key Scientific and Technological Project of Henan Province
(202102210183) and the Young Key Teacher Training
Foundation of Henan Province’s Universities (2017GGJS052).
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