REVIEW
Recent Advances in Graphitic Carbon Nitride-BasedChemiluminescence, Cataluminescenceand Electrochemiluminescence
Hongjie Song1 • Lichun Zhang1 • Yingying Su2 • Yi Lv1,2
Received: 30 July 2017 / Accepted: 10 August 2017 / Published online: 18 September 2017
� The Nonferrous Metals Society of China and Springer Nature Singapore Pte Ltd. 2017
Abstract Graphitic carbon nitride (g-C3N4) has attracted
considerable attention due to its special structure and
properties, such as its good chemical and thermal stability
under ambient conditions, low cost and non-toxicity, and
facile synthesis. Recently, g-C3N4-based sensors have been
demonstrated to be of high interests in the areas of sensing
due to the unique optical, electronic and catalytic proper-
ties of g-C3N4. This review focuses on the most salient
advances in luminescent sensors based on g-C3N4,
chemiluminescence, cataluminescence and electrochemi-
luminescence methods are discussed. This review provides
valuable information for researchers of related areas and
thus may inspire the development of more practical and
effective approaches for designing two-dimensional (2D)
nanomaterial-assisted luminescent sensors.
Keywords Graphitic carbon nitride (g-C3N4) �Chemiluminescence (CL) � Cataluminescence (CTL) �Electrochemiluminescence (ECL) � Sensors
1 Introduction
Graphitic carbon nitrides (g-C3N4) are a class of two-di-
mensional (2D) polymeric materials consisting exclusively
of covalently linked, sp2-hybridized carbon and nitrogen
atoms. The research works focused on carbon nitride
oligomers and polymers could be traced back to the 1830s,
when Berzelius and Liebig reported the general formula
(C3N3H)n and coined the notation ‘‘melon’’, respectively
[1, 2]. Since 1989, works have been inspired due to a
theoretical prediction proposed by Liu and Cohen that the
b-polymorph C3N4 would have extremely high hardness
values [3]. In 1993, Chen and co-authors synthesized C3N4
thin films via dc magnetron sputtering of a graphite target
on Si(100) and polycrystalline Zr substrates under a pure
nitrogen ambience and studied the structure of C3N4 with
analytical electron microscopy and Raman spectroscopy
[4]. Three years later, according to first-principle calcula-
tions of the relative stability, structure, and physical
properties of carbon nitride polymorphs, Teter and Hemley
[5] predicted a-C3N4, b-C3N4, cubic-C3N4 and pseudo-
cubic-C3N4 exhibit high hardness approaching that of
diamond, they also speculated that graphitic-C3N4 has
preferable stability at ambient atmosphere. This break-
through report inspired more and more research interests of
scientists towards graphitic carbon nitride.
The g-C3N4 possesses a graphite-like stacked 2D
structure, which could be regarded as a nitrogen heteroa-
tom-substituted graphite framework consisting of p-con-
jugated graphitic planes formed via sp2 hybridization of
carbon and nitrogen atoms. The layer distance in g-C3N4 is
of 0.326 nm, 3% more dense than that of in crystalline
graphite (0.335 nm).This smaller interlayer distance can be
explained by altering the localization of electrons and
strengthening the binding between layers due to nitrogen
heteroatom substitution [6]. There are two types of g-C3N4
structural polymorphs, which can be obtained by proper
selection of precursors and condensation methods. The first
one (Fig. 1a) comprises the condensed s-triazine units (ring
of C3N3) with a periodic array of single-carbon vacancies.
The second one (Fig. 1b) is composed of the condensed tri-
& Yi Lv
1 College of Chemistry, Sichuan University,
Chengdu 610064, Sichuan, China
2 Analytical and Testing Center, Sichuan University,
Chengdu 610064, Sichuan, China
123
J. Anal. Test. (2017) 1:274–290
https://doi.org/10.1007/s41664-017-0024-6
s-triazine (tri-ring of C6N7) subunits connected through
planar tertiary amino groups, which has larger periodic
vacancies in the lattice. The density functional theory
(DFT) calculations further indicate that the g-C3N4 net-
works composed of the melon-based segments (the second
type structure) are thermodynamically more stable than the
melamine-based arrangements (the first type structure)
because the tri-s-triazine unit is energetically more
stable than s-triazine [7, 8]. Therefore, it is widely accepted
that the tri-s-triazine nucleus is the basic unit for the for-
mation of the g-C3N4 network.
In general, the g-C3N4 are synthesized by polymeriza-
tion of abundant nitrogen-rich and oxygen-free compound
precursors containing pre-bonded C–N core structures
(triazine and heptazine derivatives) through various ther-
mal treatments, such as physical vapor deposition (PVD)
[9], chemical vapor deposition (CVD) [10], solvothermal
method [11] and solid-state reaction [11]. Cyanamide [12],
dicyandiamide [13], melamine [14], urea [15], thiourea
[16], guanidinium chloride [17] and guanidine thiocyanate
[18] were usually used as precursors for the preparation of
g-C3N4 through polymerization. However, the obtained
materials are usually bulk g-C3N4, which are difficult to
directly use in many fields due to the poor dispersity and
ordinary properties. In the last few years, plenty of
researchers tried to prepare various g-C3N4 with abundant
micro/nanostructures and morphologies, which are availed
for enhancing the dispersity and properties of g-C3N4. For
example, ultrathin g-C3N4 nanosheets prepared by exfoli-
ating bulk g-C3N4 materials [19–21] were negatively
charged, and could be well dispersed in water. The exfo-
liation methods mainly include thermal oxidation exfolia-
tion, ultrasonic exfoliation and chemical exfoliation. Meso-
g-C3N4 materials exhibit higher specific surface area (up to
830 m2 g-1) and larger porosity (up to 1.25 cm3 g-1);
larger numbers of active sites present on the surface and
higher size or shape selectivity result in enhanced perfor-
mance. Soft-templating (self-assembly) [22, 23] and hard-
templating (nanocasting) [24] methods are most important
pathways for the preparation of meso-g-C3N4. Some
groups tried to synthesize g-C3N4 with smaller sizes,
known as g-C3N4 quantum dots (QDs). The g-C3N4 QDs
could be synthesized through ‘‘top-down’’ methods
[25, 26], namely cutting bulk g-C3N4 by hydrothermal
treatment, chemical oxidation, or chemical oxidation
combined with hydrothermal/solvothermal treatment. Also
the g-C3N4 could be synthesized by ‘‘bottom-up’’ methods,
namely thermally treating some special organic precursors
[27, 28]. The obtained g-C3N4 QDs usually exhibit excel-
lent luminescent properties. In brief, synthetic routes,
condensation temperatures, and the compositions and
morphologies of precursor are important factors to deter-
mine the attained structure and morphology, which
strongly relate to its properties and applications of g-C3N4.
Furthermore, tremendous attempts were made to explore
new strategies for g-C3N4 surface modifications and func-
tionalities, through which various particular
micro/nanoarchitectures, such as 3D hierarchical bulks, 2D
nanosheets, 2D films, 1D nanorods, 1D nanotubes, 1D
nanowires, and 0D quantum dots came into being.
Graphitic carbon nitride was demonstrated to be the
most stable allotrope under ambient conditions in the C3N4
family. Thermal gravimetric analysis (TGA) indicates that
the thermal decomposition and vaporization of the frag-
ments have started at more than 600 �C [29]. In addition to
the outstanding thermal stability, g-C3N4 also shows
excellent chemical stability due to the strong covalent C–N
bonds between carbon and nitrogen in the graphene-like
planar structure, as well as the van der Waals forces in each
layer. This material was found to remain stable in some
organic solvents, acidic and alkaline environments. The
stability demonstrates g-C3N4 can be used as sensing
materials for fabrication chemosensors with excellent
reproducibility. The heptazine ring structure and the high
condensation degree enable g-C3N4 to possess an appealing
electronic structure combined with a medium band gap
(2.7 eV), indicating stable physicochemical properties and
high catalytic activities of g-C3N4. The various
Fig. 1 a s-Triazine and b tri-s-
triazine as unit structures of
g-C3N4. Reproduced with
permission [6]
J. Anal. Test. (2017) 1:274–290 275
123
applications of g-C3N4 as photocatalysts [30–32] and
electrocatalysts [21, 33] have already attracted tremendous
attention. Its merit of being metal free has always been
linked with graphitic carbon nitride from the very begin-
ning. The constitution elements for g-C3N4 are just C, N,
and usually residual hydrogen in defects and for surface
termination. The metal-free constitution of g-C3N4 renders
the materials nontoxic and biocompatible for some bio-
logical applications [34–36]. Graphitic carbon nitride
shows the typical absorption pattern of an organic semi-
conductor with a pronounced band gap at about 420 nm,
thus making the material slightly yellow. The unique
photoluminescence (PL) properties of carbon nitride
materials was observed as early as about 15 years ago
[37–39], then there were many reports focused on the PL
behaviors and mechanisms of g-C3N4 with one or two
photons’ excited emission peak from visible light region to
near infrared. The long-persistent luminescence (also
called long-lasting afterglow) of g-C3N4 is another inter-
esting phenomenon which shows favorable application in
imaging detection and real-time monitoring in bioanalysis
[40]. In the last few years, the electrochemiluminescence
(ECL) behavior of graphite-like carbon nitride was inves-
tigated, and the cathodic and anodic ECL emissions were
observed, respectively. The structure and properties dis-
cussed above demonstrates that g-C3N4 can be promising
sensing materials in luminescent sensors. Now that sig-
nificant advances have been made on g-C3N4-based lumi-
nescence analysis in recent years, comprehensive review
on this subject is necessary to accelerate further develop-
ments in this exciting research domain. This review article
places special emphasis on g-C3N4-based CL, CTL and
ECL sensors, the topic of g-C3N4-based photolumines-
cence sensors have been excluded since they were
addressed in excellent previous reviews [41–43].
2 Chemiluminescence
The process of transforming chemical energy into light
emission [44], a phenomenon known as chemilumines-
cence (CL), has been an attractive topic of intensive
research since 1920s [45, 46], in view of its fundamental
mechanistic significance and the diversity of practical
applications [47–54]. CL-based chemosensors show supe-
rior sensitivity which is ascribed to the avoidance of the
noise caused by light scattering and feature simpler setup
with lower background emissions in comparison with
photoluminescence-sensing systems [55, 56]. Compared to
traditional liquid-phase CL mostly based on molecular and
ion systems, nanometer (nm)-sized particle (NP)-based CL
systems improve the sensitivity and the stability, mainly
resulting from the large surface area and special structure
of nanomaterials; therefore, there were plenty of reports
about NP-participated CL reactions [57–62] during which
NPs were used as catalysts, reductants, luminophors or
energy acceptors. Although other carbon nanostructures
(graphene, graphene oxide, fullerenes, carbon nanodots,
carbon nanotube, carbon nanospheres) have gained quite a
lot of attentions in developing CL-based analytical meth-
ods and applications in CL systems [63], the investigation
of CL behavior of g-C3N4 with different co-reactants or
g-C3N4-assisted CL systems for developing g-C3N4-based
luminescent sensors is still in its infancy, only several
published reports involve this topic.
2.1 Graphitic Carbon Nitride as Luminophor in CL
Systems
Similar to carbon nanodots and graphene quantum dots,
graphitic carbon nitride quantum dots can also be used as
luminophor to produce CL emission in specific systems. As
shown in Fig. 2, the CL property and CL reaction of gra-
phitic carbon nitride quantum dots (g-CNQDs) were first
investigated by Lv’s group [64]. Water-soluble and uni-
form g-CNQDs with strong fluorescence were prepared via
the facile one-step microwave treatment of guanidine
hydrochloride and EDTA; EDTA was chosen as the cap-
ping and stabilizing agent to control the size of the product
effectively, owing to its rich carboxyl and amino motifs.
Strong chemiluminescence emission was observed when
NaClO was injected into the prepared g-CNQDs, the CL
phenomenon was ascribed to the radiative recombination
of oxidant-injected holes and electrons in the g-CNQDs
and the simultaneous generation of O2 from some reactive
oxygen species on the surface of g-CNQDs, which were
able to transfer energy to g-CNQDs and thus further
enhance the CL emission. Then a flow injection analysis
CL method for highly sensitive and selective measurement
of free chlorine in water samples was established based on
the CL reaction of g-CNQD–NaClO system.
Fig. 2 Schematic illustration for microwave-assisted prepared
g-CNQDs and the CL mechanism of the g-CNQD–NaClO system.
Reprinted with permission [64]
276 J. Anal. Test. (2017) 1:274–290
123
Similarly, Fan et al. [65] proposed a facile, green and
economical synthesis route towards highly fluorescent
g-CNQDs via one-step solid-phase pyrolyzing melamine
and EDTA at low temperature. The obtained g-CNQDs
exhibit exceptional fluorescent properties with high quantum
yield and can produce strong CL when coexisting with K3-
[Fe(CN)6] in alkaline condition. The CL mechanism of the
g-CNQD–K3[Fe(CN)6] system was also explained by the
radiative recombination of oxidant-injected holes and elec-
trons of the g-CNQDs. The K3[Fe(CN)6] as an oxidant could
serve as the hole injector and convert g-CNQDs to
g-CNQDs�?, thus increased the injected holes in the
g-CNQDs and accelerated the electron–hole annihilation,
which resulted in energy release in the form of CL emission.
DA, as an important catecholamine neurotransmitter
responsible for message transfer in the central nervous sys-
tem, could inhibit the CL intensity of g-CNQD–K3[Fe(CN)6]
system dramatically, due to the competition reaction
between DA and g-CNQDs with K3[Fe(CN)6]. According to
this phenomenon, a flow injection analysis CL method for
determination of DA was established, and the designed
method was evaluated by determination of the recovery of
the spiked DA in serum from three volunteers. The results
demonstrated the g-CNQD-based CL method was efficient
in practice application. Abdolmohammad-Zadeh et al. also
reported the CL phenomenon of g-CNQD–K3[Fe(CN)6]
system [66], based on the diminishing effect of Hg(II) ion on
the g-CNQD–K3[Fe(CN)6] CL system; a simple and sensi-
tive chemosensor was constructed for Hg(II) ion detection in
aqueous solutions. Afterwards, Fan and co-authors observed
a dramatically enhanced chemiluminescence (CL) in Ce(IV)
and sulfite system in the presence of graphitic carbon nitride
quantum dots (g-CNQDs) [67]. Iodine, as an essential
micronutrient for normal human, could obviously inhibit the
CL emission of g-CNQD–Ce(IV)–SO32- system due to the
competitive reaction between I- with Ce(IV); therefore, a
flow injection analysis CL method for detecting I- in urine
samples was proposed. The mechanism of g-CNQD-en-
hanced Ce(IV)–SO32- CL system was described (Fig. 3),
they discussed the reaction process in detail. In acid medium,
�HSO3 was formed by the reaction (R) between HSO3- and
Ce(IV) (R1), then two �HSO3 radicals combined to produce
S2O62- (R2), which was unstable in solution, then converted
to sulfate and excited state SO2* (R3). When SO2
* returned to
its ground state, weak CL was generated (R4). Then with the
addition of g-CNQDs into the solution, on the one hand,
Ce(IV) could act as the hole injector and convert g-CNQDs
to g-CNQDs�? (R5), and the electron donated from �HSO3 to
g-CNQDs produced g-CNQDs�- (R6). Finally, the electron–
hole annihilation in g-CNQDs�? and g-CNQDs�- resulted in
excited state g-CNQDs (g-CNQDs*) (R7), which was
unstable and converted to g-CNQDs by releasing energy to
generate light (R9). On the other hand, a chemiluminescence
resonance energy transfer (CRET) might occur between
SO2* (donors) and g-CNQDs (acceptors) (R8), since the
wide emission spectra range of SO2* (450–600 nm) over-
lapped the absorption spectra of the g-CNQDs. Then reaction
(R9) occurred and luminescence at 475 nm was emitted.
Ce IVð Þ þ HSO�3 ! �HSO3 þ Ce IIIð Þ ðR1Þ
2 � HSO3 ! S2O2�6 þ 2Hþ ðR2Þ
S2O2�6 ! SO2�
4 þ SO2� ðR3Þ
SO2� ! SO2 þ hm 450�600 nmð Þ ðR4Þ
Ce IVð Þ þ g-CNQDs ! Ce IIIð Þ þ g-CNQDs�þ ðR5Þ
�HSO3 þ g-CNQDs ! SO3 þ Hþ þ g-CNQDs�� ðR6Þ
g-CNQDs �þ þ g-CNQDs�� ! g-CNQDs� ðR7ÞSO2
� þ g-CNQDs� ! g-CNQDs� þ SO2 ðR8Þg-CNQDs� ! g-CNQDs þ ht 475 nmð Þ ðR9Þ
2.2 Graphitic Carbon Nitride as Catalyst in CL
Systems
Besides luminophor, g-C3N4 could be used as novel
signal enhancers with their unique redox catalytic
properties to catalyze CL reactions, under proper con-
ditions, providing amplified CL emission. Yu and co-
authors reported that g-C3N4 nanosheets could enhance
the chemiluminescence of luminol and hydrogen perox-
ide (H2O2) system [68], g-C3N4 nanosheets catalyzed the
decomposition of H2O2 to form reactive hydroxyl radi-
cal, which further reacted with luminol and H2O2 anion,
generating a light emission. Moreover, 2,4,6-trinitro-
toluene (TNT) was observed to inhibit the CL effec-
tively, then a sensitive and selective CL-sensing
approach was successfully developed for the detection of
TNT, the linearity ranged from 1 pM to 1 nM with a
Fig. 3 Schematic illustration of the CL mechanism of g-CNQD–
Ce(IV)–SO32- system. Reprinted with permission [63]
J. Anal. Test. (2017) 1:274–290 277
123
detection limit of 0.75 pM. Willner’s group prepared
Cu2?-functionalized carbon nitride nanoparticles (Cu2?–
g-C3N4 NPs), which exhibited catalytic properties
mimicking HRP catalytic activities [69], the hybrid
heterogeneous catalysts can catalyze the generation of
chemiluminescence in the system of luminol–H2O2 and
dopamine–H2O2. The surface functionalities associated
with g-C3N4 and their catalytic activities provide a
means to apply these particles for the development of
different sensors and as catalysts for other oxidation
processes.
Interestingly, Lin’s group observed a novel chemilumi-
nescence phenomenon when g-C3N4 nanosheet suspension
was mixed with NaHSO3 solution [70], and the intensity of
CL could be obviously enhanced by some metal ions
(Cu2?, Fe3? or Mn2?), which was distinctly different from
the phenomenon that Cu2? ions can quench the fluores-
cence of g-C3N4 nanosheets as reported before. To illu-
minate the CL mechanism, electron spin resonance (ESR)
spectra and the effects of radical scavengers (nitro-blue
tetrazolium chloride, NaN3, thiourea and ascorbic acid) on
CL intensity were investigated. As shown in Fig. 4, they
speculated that the g-C3N4 nanosheets could catalyze the
dissolved oxygen to an oxide of NaHSO3 which generate
the intermediate �SO3-, which self-quenched to generate
the excited state SO2 (SO2*). SO2
* returned to the ground
state to emit light. The g-C3N4 nanosheets could absorb
metal ions on their surface, leading to the collision prob-
ability of �SO3- to increase rapidly, which caused the
increase in CL intensity.
3 Cataluminescence
In 1976, Breysse et al. observed the chemiluminescence
emission during the catalytic oxidation of carbon monoxide
on thoria ThO2, and named it as cataluminescence (CTL)
[71]. Research works about CTL in early stage mainly
concentrated on adsorption and the intermediate state of
catalytic process [72–76] without involving gas detection.
In 1990s, Nakagawa and coworkers observed intense CTL
emission during the catalytic oxidation of ethanol or ace-
tone vapor on a heated aluminum oxide powder [77–80].
Then they have observed CTL emission during the cat-
alytic oxidation of various organic vapors: ethanol, buta-
nol, acetone, xylene, n-butyric acid, and the fragrance
substances of linalool, cital, limonene, and a-pinene [81].
Because of this, they developed a series of CTL-based
sensor and established a complete theory about CTL-
sensing system. Compared to traditional CL-based sensors
which usually suffers the deficiencies of short lifetime and
signal drift due to the irreversible consumption of CL
reagents, the CTL-based sensors have long lifetime and
experiment data reliability because the catalytic reaction of
gases on a solid catalyst proceeds without changes in the
solid. Therefore, CTL-based sensors have broad applica-
tion prospects. In the twenty-first century, nanometer (nm)-
sized materials have attracted a great deal of attention due
to their fascinating properties and potential applications in
nanotechnology. The distinct physical properties such as
quantum size effects, high surface energy and the large
surface area makes nanometer (nm)-sized materials have
strong catalytic properties for redox reactions, which are
usually determined by their size distribution, shapes and
structure. Zhang and coworkers proposed nanosized TiO2
as the sensing material to detect ethanol and acetone [82],
which was considered as a pioneering work for the com-
bination of nanomaterials and CTL-based chemosensors.
Since then, CTL-based chemosensors with the adoption of
various nanocatalysts have been intensively researched by
many academic groups such as Zhang’s [83–86], Cao’s
[87–89], Lu’s [90–93], Li’s [94, 95], Lv’s [96–101] and so
on. Due to the high chemical stability, specific structure
and composition as well as the catalytic, electronic and
optical properties, g-C3N4 can provide greater versatility in
carrying out gas adsorption, selective catalytic and sensing
processes; therefore, g-C3N4-based materials may provide
new opportunities to develop new CTL-sensing materials.
Recently, some g-C3N4-based CTL sensors were
designed and investigated by Lv’s group. Zeng et al. pre-
pared a-Fe2O3/g-C3N4 composites by refluxing a mixture of
g-C3N4 suspension and FeCl3 solution in boiling water, the
composites were explored as good catalysts for the oxidation
of H2S [102]. During the oxidation of H2S on the surface ofFig. 4 Schematic illustration of the CL mechanism in the g-C3N4
nanosheet–Mn?–NaHSO3 system. Reprinted with permission [70]
278 J. Anal. Test. (2017) 1:274–290
123
a-Fe2O3/g-C3N4 composites, strong CTL emission would
generate with fast response and short recovery time
approximatively 0.1 and 0.6 s, respectively, based on which
a highly sensitive H2S gas sensor was developed. It can be
concluded from the experimental results that the introduc-
tion of g-C3N4 into the composite played a key role in
enhancing CTL-sensing performance for H2S and reducing
the CTL reaction temperature. Dielectric barrier discharge
(DBD), refers to a kind of gas discharge in which strong non-
equilibrium plasma at atmospheric pressure and at a mod-
erate gas temperature is generated between two separated
electrodes covered with dielectric barriers [103], was chosen
as an assisted approach for synthesizing g-C3N4–Mn3O4
composites for the first time by Hu and co-authors, the
obtained g-C3N4–Mn3O4 composites possessed rapid,
stable, highly selective and sensitive cataluminescent
response to gaseous H2S [104]. The principle of the DBD
plasma-assisted fabrication of g-C3N4–Mn3O4 composites
was illustrated as Fig. 5a, the mixture of g-C3N4–Mn2?,
which from the dried resultant of g-C3N4 powder after
adsorption equilibrium of Mn(II) on the layers, treated in the
DBD reactor with the cold plasma was initiated under an AC
input voltage of 45 V, using air (100 mL min-1) as working
gas. Mn2? was anchored by the functional groups of the bulk
g-C3N4 to form g-C3N4–Mn2? complexes through
physisorption, electrostatic binding, coordination effect or
charge transfer interactions, which acts as nucleation center
for subsequent metal oxide anchoring [105]. The highly
active oxygen-containing species produced in the plasma
would react with the absorbed Mn2? to form Mn3O4 modi-
fying on the g-C3N4 surface. Interestingly, apart from pro-
viding oxidizing species, the plasma etching process induced
by reactive species also proceeds in DBD treatment, giving
rise to the fragmentation of bulk g-C3N4 into smaller parti-
cles with enlarged surface area and pore volume. Then the
obtained g-C3N4–Mn3O4 composites were used as a superior
CTL catalyst for H2S gas sensor (Fig. 5b). Later, Li et al.
reported a highly sensitive CTL gas sensor for 2-butanone
based on g-C3N4 sheets decorated with CuO nanoparticles,
which were synthesized via a simple and facile ultrasound-
assisted calcining route [106]. The CuO nanoparticles evenly
dispersed on the g-C3N4 sheets, which not only effectively
reduced the stacking of g-C3N4 sheets but prevented the
agglomeration of CuO nanoparticles, giving rise to excellent
catalytic activity of g-C3N4/CuO in CTL reaction and highly
efficient analytical performance for 2-butanone senor.
4 Electrochemiluminescence
Electrochemiluminescence (also called electrogenerated
chemiluminescence) is one kind of CL emission triggered by
electrochemical processes whereby species generated at
electrodes undergo high-energy electron transfer reactions to
form excited states that emit light [107]. Due to the unique
advantages such as rapidity, high sensitivity, and simplified
optical setup, the ECL analytical methods have gained plenty
of attentions after the first detailed ECL studies reported by
Hercules and Bard et al. in the mid-1960s [108–110]. As an
optical analytical technique, ECL does not require the use of
any external light source. Thus, the attendant problems of
scattered light and luminescent impurities are absent, which
leads to low optical background noise and high sensitivity for
analysis [111]. Therefore, ECL has been widely used in
various sensors or probes for metal ions, anions, explosives,
toxic food additives, biomolecules, and so on. Nanomaterials
with smaller sizes, diversity shapes, specific structures and
unique properties have played an increasingly important role
in the development of ECL sensors [112–115]. In the recent
years, g-C3N4 has been extensively used in ECL-sensing
systems due to the excellent electroconductive and catalytic
characteristics and enormous specific surface area for the
immobilization of various kinds of molecules; S2O82- is the
most widely used as the co-reactant to react with g-C3N4 to
emit light. Here in this review, we mainly discuss most of the
salient achievements in g-C3N4-based ECL sensors.
4.1 Pure g-C3N4-Based ECL Sensors
In 2012, Cheng et al. and coworkers for the first time
investigated the ECL behavior of g-C3N4 on carbon paste
electrode [116, 117], cathodic ECL and anodic ECL,
respectively. It was found that the g-C3N4 modified carbon
paste electrode produced a very weak ECL emission neg-
ative potential and the ECL signal could be greatly
enhanced by K2S2O8. Furthermore, the ECL spectrum of
the g-C3N4/S2O82- system was measured and the spec-
trogram displays a maximum emission peak at ca. 470 nm,
which matches well with the PL spectrum of g-C3N4,
suggesting that the same excited states are formed in both
Fig. 5 a Schematic illustration of the DBD plasma-assisted fabrica-
tion of g-C3N4–Mn3O4 composite; b schema of CTL reaction cell and
simulation of CTL reaction process on the surface of g-C3N4–Mn3O4
composite. Reprinted with permission [106]
J. Anal. Test. (2017) 1:274–290 279
123
the electroexcitation and photoexcitation processes. Then
possible ECL reaction mechanisms are proposed (shown in
Fig. 6): electro-reduced g-C3N4 (g-C3N4�-) formed by the
injected electron from the electrode could react with
S2O82- to produce an excited state which subsequently
decays back to its ground state, emitting strong lumines-
cence. Based on the phenomenon that ECL intensity is
efficiently quenched by trace amounts of Cu2?, they fab-
ricated an ECL sensor with high selectivity for detection of
trace Cu2? in nanomolar concentration. The anodic ECL
behavior of g-C3N4 was studied using triethanolamine as a
co-reactant; an ECL sensor based on quench mechanism
was designed for sensitive detection of rutin showing a
linear response in the range of 0.20–45.0 lM and a low
detection limit of 0.14 lM.
In the same year, Chi’s group also reported the ECL
property of g-C3N4, they prepared highly water-dispersible
g-C3N4 nanoflake particles (g-C3N4 NFPs) with a height of
5–35 nm and a lateral dimension of 40–220 nm from bulk
g-C3N4 materials by chemical oxidation [118]. The
obtained g-C3N4 NFPs on a glassy carbon electrode exhibit
strong non-surface state ECL activity in the presence of
reductive-oxidative co-reactants, including dissolved oxy-
gen (O2), hydrogen peroxide (H2O2) and peroxydisulfate
(S2O82-) and give rise to blue light emission (435 nm),
which is the same as the wavelength of PL, suggesting that
identical excited states are generated. They proposed that
the ECL reactions may involve four processes, i.e., electron
injection, hole donor production, hole injection, and elec-
tron–hole annihilation producing ECL emission (Fig. 7).
The energy of the electron on GCE is raised with the
cathodic polarization of potential, and is high enough to be
injected into the conducting bands (CB) of g-C3N4 NFPs
(R1); meanwhile, hole donors (i.e., free radicals) are pro-
duced from the reductive–oxidative co-reactants, such as
dissolved O2, H2O2 and S2O82- (R2–R4), then the holes
are subsequently injected into the valence bands (VB) of
g-C3N4 NFPs by the interaction of the free radicals (�OH or
SO4�-) produced in R2–R4 with g-C3N4 NFPs (R5–R6),
finally, the electrons injected in the conducting band
annihilates with the holes in the valence band to form the
excited state of the g-C3N4 NFPs, generating ECL emission
when the excited state converts to their ground states (R7).
Likewise, the ECL emissions of g-C3N4 nanosheets
(CNNS) with co-reactant (triethylamine, dissolved O2 and
H2O2) were observed by Ju’s group [119, 120]. Based on
the annihilation between the oxidation product of dopa-
mine (DA�?) and triethylamine (Et3N�) radical, a quench-
ing-based ECL senor was established for sensitive and
specific detection of dopamine ranging from 1.0 to 100 nM
with a detection limit of 96 pM. The adsorption of hemin-
labeled ssDNA on CNNS leads to in situ consumption of
Fig. 6 Schematic illustration of ECL emission of g-C3N4-modified carbon paste electrode. Reprinted with permission [116]
Fig. 7 Proposed ECL reaction mechanism for g-C3N4 NFP–co-
reactant systems. Reprinted with permission [118]
280 J. Anal. Test. (2017) 1:274–290
123
dissolved oxygen via hemin-mediated electrocatalytic
reduction, thus decreases the formation of H2O2 and
quenches the ECL emission of CNNS, then the recog-
nization of hemin-labeled ssDNA to target DNA results in
the departure of hemin-labeled hybridization product from
the CNNS modified electrode, thus inhibits the annihilation
of co-reactant and recovers the ECL emission, based on
which they designed an ECL sensor for target DNA
(Fig. 8). The proposed ECL sensor shows a wide detection
range over 6 orders of magnitude and wondrously high
sensitivity with a detection limit down to 2.0 fM, mean-
while it exhibits good performance with excellent selec-
tivity, high reliability, and acceptable fabrication
reproducibility.
Sun’s group developed a novel one-step strategy for rapid
high-yield synthesis of g-C3N4 nanosheets by pyrolyzing a
melamine–KBH4 mixture under Ar, the ECL behaviors of
g-C3N4/S2O82- system and the quench effect of metal ions
on this ECL system were investigated in detail, and then
g-C3N4-based ECL sensor for Cu2? was constructed [121].
Furthermore, Chi’s group found pyrophosphate anion (PPi)
could chelate with Cu2? with a strong affinity and release
Cu2? from the Cu2?/g-C3N4 reaction system [122], resulting
in the ECL recovery. Therefore, a highly sensitive ECL
sensor for PPi was proposed and has been used to detect PPi
in the synovial fluid. Lu’s group reported the strong and
stable ECL emission of g-CNQDs generated in the presence
of co-reactant (S2O82-) [123]. The ECL signal of g-CNQDs
was quenched by the mechanism of resonance energy
transfer (RET) between donor g-CNQDs and receptor ribo-
flavin (RF), which was used to design a simple ECL sensor
for RF.
Intriguingly, Zhou et al. demonstrate that the ECL
properties of carbon nitride nanosheets (CNNS) with tun-
able chemical structures were significantly modulated
[124]. As a result, addition of different metal ions would
result in distinct changes for different CNNS in quenching
of ECL because of inner filter effect/electron transfer and
enhancement of ECL due to catalytic effect. On the basis of
this, adopting various CNNS as signal probe, highly
selective ECL sensors for rapid detecting multiple metal
ions such as Cu2?, Ni2?, and Cd2? were successfully
developed without any labeling and masking reagents
(Fig. 9).
4.2 Enhanced g-C3N4-Based ECL Sensors
Similar to graphene, g-C3N4 nanosheets could be easily
modified and hybridized by molecules and nanomaterials
via various strategies such as covalent bonding, electro-
static adsorption, p–p stacking interactions and so on,
which is of increasing requirement for enhancing the ECL
behavior of g-C3N4 and developing more sensitive ECL
sensors. In the last few years, many research groups have
made some interesting works on this topic. To date, several
macromolecules and nanomaterials, such as nanoparticles
(AuNPs), Au-nanoflowers (AuNFs), Ag nanoparticles
(AgNPs), graphene oxide (GO), reduced graphene oxide
(RGO) and graphene, were used to hybridize with g-C3N4Fig. 8 Schematic illustration of CNNS-based ECL sensor for DNA.
Reprinted with permission [120]
Fig. 9 ECL emission spectra of
different CNNS and ECL-
sensing response to metal ions.
Reprinted with permission [124]
J. Anal. Test. (2017) 1:274–290 281
123
for further enhancement of electron transfer ability and
target-carrying ability, resulting in improvement of
g-C3N4-based ECL sensors.
In 2013, Wei’s group fabricated a carboxylated g-C3N4
and graphene (g-C3N4–G) nanocomposite-based ECL
immunosensor for the detection of SCCA [125]. The
g-C3N4–G was prepared via the electrostatic adsorption
between positively charged poly(diallyldimethylammo-
nium chloride) (PDDA) and negatively charged carboxy-
lated g-C3N4 and graphene. Carboxylated g-C3N4, as the
luminophore, exhibits high water dispersibility which adds
benefit to the stability of immunosensor. Antibody of
squamous cell carcinoma (anti-SCC) was covalently bon-
ded to the carboxylated g-C3N4 through the formation of
the amide bond between the –COOH groups of carboxy-
lated g-C3N4 and –NH2 groups of anti-SCC. The results
indicated that excellent conductivity of graphene facilitated
the ECL reaction, generating enhanced ECL response.
Soon they reported another ECL immunosensor for
Nuclear Matrix Protein 22 (NMP 22) using g-C3N4 com-
bined with AuNPs as signal probe [126]. With AgNPs as
the signal amplification element, ECL immunosensor for
carcinoembryonic antigen (CEA) was constructed by the
quenching mechanism of ferrocene (Fc) [127]. In sandwich
immunoassay format, CEA primary antibody (Ab1) was
immobilized on Ag@g-C3N4. The ECL intensity decreased
with the increasing CEA concentration for the conjugation
of more Fc-labeled antibody, which caused much more
strong quenching effect on g-C3N4. Similarly, an enhanced
ECL biosensor for IgG was reported [128], pristine g-C3N4
nanosheets were simply incorporated into the nanoporous
gold matrix and the enhanced sensing performance is
achieved by a ‘‘space effect’’, this three-dimensional (3D)
porous matrix is favorable for electron conduction and the
immobilization of both luminophors and biological recog-
nition elements.
From 2014, Chi’s group developed a series of prominent
research works about the multi-functionalization of g-C3N4
and its application in ECL biosensors and immunosensors.
A CEA ECL immunosensor was constructed using g-C3N4
nanosheets (g-C3N4 NSs) hybridized with AuNPs [129].
The AuNP-functionalized g-C3N4 NS nanohybrids (Au–g-
C3N4) exhibited strong and stable cathodic ECL activity
due to the important roles of AuNPs in trapping and storing
the electrons from the conduction band of g-C3N4 NSs, as
well as preventing high-energy electron-induced passiva-
tion of g-C3N4 NSs. The designed ECL immunosensor has
a sensitive response to CEA in a linear range of
0.02–80 ng mL-1 with a detection limit of 6.8 pg mL-1.
As illustrated in Fig. 10, Au–g-C3N4, as the excellent ECL
emitter, was combined with a polyelectrolyte to develop a
solid-state stimuli–response-based ECL sensor for bisphe-
nol A (BPA) [130]. In detail, an overlayer of polyelec-
trolyte thin films containing DNA aptamers assembled on
top of Au–g-C3N4 film was used as a gate to greatly control
the diffusion of S2O82-, which was the co-reactant to
trigger ECL (Fig. 10a). In the presence of target, the con-
formation of the aptamer would be changed due to the
binding between the target and the aptamer. As a result, the
permeability of the polyelectrolyte–aptamer film was
increased, leading to ECL enhancement (Fig. 10b). In view
of the wide range of applications of aptamers, the proposed
approach can be used for many other small molecule
assays. The similar method was used to design ECL sen-
sors for proteases and nucleases [131]. For this kind of
ECL sensors, high sensitivity could be achieved by (1) the
turn-on assay that shows higher sensitivity and a lower
chance of a false-positive signal as compared to the turn-
off assay; (2) preconcentration of targets via proper
Fig. 10 Schematic principle of
the ECL aptasensor with a
target-responsive permeability
gate. Reprinted with permission
[130]
282 J. Anal. Test. (2017) 1:274–290
123
selection of the outermost layer of polyelectrolyte multi-
layered film. They also chose reduced graphene oxide
(RGO) to hybridize g-C3N4 NSs, fabricating an ultrasen-
sitive sensor for folic acid [132]. RGO significantly
improves the stability of g-C3N4 NSs and lowers its ECL
onset potential. In addition, g-C3N4 nanosheets embedded
with C3N4 QD nanocomposites (C3N4 QD@CNNS) pre-
pared by simple oxidation with hydrogen peroxide and UV
light irradiation was used to design a signal-on aptasensor
for platelet-derived growth factor [133]. The nanocom-
posite exhibits more stable and stronger ECL behavior
compared with CNNS. Zhu et al. reported the similar
finding of strong ECL emission from the C3N4 QD@CNNS
nanocomposite using S2O82- as the co-reactant. The ECL
intensity of this system obviously decreased in the presence
of nitrites, based on which the ECL sensor for nitrites was
successfully developed [134].
Yuan’s group also designed many significant g-C3N4
nanocomposite-based ECL sensors since 2014. Gold nano-
flower hybridized with g-C3N4 and polyaniline (AuNF@g-
C3N4–PANI) was reported by Lu et al. for the first time to
fabricate an enhanced ECL sensor towards dopamine [135].
AuNFs could enormously enhance the ECL intensity of
g-C3N4 and PANI was beneficial for the coating of AuNFs.
Later, they designed a signal-on-sensitive ECL biosensor for
organophosphate pesticides (OPs) based on carboxylated
graphitic carbon nitride-poly(ethylenimine) (C-g-C3N4–
PEI) composite and acetylcholinesterase (AChE) [136]; the
C-g-C3N4–PEI prepared through covalent bonding between
the –COOH of C-g-C3N4 and the –NH2 of PEI exhibited
significantly enhanced ECL efficiency and stability. S2O82-
as the co-reactant of C-g-C3N4–PEI could be consumed by
thiocholine, produced by the hydrolysis of AChE. Since OPs
are one of the AChE inhibitors, the consumption of coreac-
tant decreased with the increasing concentration of OPs, thus
enhancing ECL signal. Chen and co-authors fabricated a
signal-on ECL biosensor for detecting concanavalin A (Con
A) [137] with phenoxy dextran–graphite-like carbon nitride
(DexP–g-C3N4) as signal probe and linking to the binding
sites of Con A through a specific carbohydrate–Con A
interaction, three-dimensional graphene–AuNP (3D-GR–
AuNP) nanocomposites were used as matrix for high loading
of glucose oxidase (GOx), resulting in an enhancement of
ECL. Based on the dual molecular specific recognition of
oxyethyl groups to diol and carboxyl to amine groups, signal-
on ECL sensors for dopamine and glucose were constructed
utilizing g-C3N4 nanosheet/3,4,9,10-perylenetetracar-
boxylic acid hybrids (g-C3N4–PTCA), synthesized via p–pstacking between g-C3N4 nanosheets and PTCA, as a signal
probe [138, 139]. Similarly, a highly sensitive ECL sensor
[140] based on a dual molecular recognition strategy and the
quenching effect of polyaniline (PANI) was designed to
detect DA in the concentration range of 0.10 pM–5.0 nM,
with a detection limit of 0.033 pM. Furthermore, they also
found C60 could enhance the ECL emission of g-C3N4/
S2O82- system due to its improvement in the electron and
charge transfer, and then a C60–g-C3N4-based ECL sensor
for melamine with a wide linear range of 5.0 9 10-13–
2.7 9 10-11 M and 2.7 9 10-11–1.9 9 10-8 M, the detec-
tion limit was 1.3 9 10-13 M. The similar ECL sensor for
ConA was also reported using Ag-doped graphitic carbon
nitride nanosheet (Ag-g-C3N4) as signal probe [141].
Guo’s group developed an ECL immunosensor for tumor
marker carbohydrate antigen 125 based on multifunctional-
ized g-C3N4 coated on the one-off-screen-printed carbon
electrodes (SPCEs) [142], the multifunctionalized g-C3N4
was prepared with amino-coated Fe3O4 nanoparticles and
CA125 antibody (anti-CA125) chemically bound to the
surface of carboxylated g-C3N4 simultaneously, this
assembly promoted the electron transfer between g-C3N4
and the electrode resulting in greatly enhanced ECL inten-
sity. Likewise, they reported a novel ‘‘in-electrode’’-type
ECL immunosensor for the sensitive detection of squamous
cell carcinoma antigen (SCCA) which was constructed using
nano-Fe3O4@GO and AuNPs/g-C3N4 [143].
Xia et al. adopted graphene oxide (GO) and graphene (G) to
enhance the cathodic ECL signal of g-C3N4 (*3.8 and 4.7
times) with dissolved O2, the ultrasensitive g-C3N4/GO-based
ECL sensor for Cu2? and pentachlorophenol was designed,
respectively, due to the quenching mechanism [144, 145].
Furthermore, the ECL onset potential of g-C3N4/GO or
g-C3N4/G was more positive than that of g-C3N4. It was
proposed that GO and G could decrease the potential barrier of
the g-C3N4 reduction and accelerate electron transfer between
the electrode and g-C3N4. Zheng and co-authors reported an
ECL immunosensor for alpha-fetoprotein (AFP) using AuNP-
modified g-C3N4 NSs [146]. They explained the ECL of
g-C3N4/S2O82- system was greatly enhanced due to the fact
that AuNPs can promote electron transfer and electrocatalytic
reduction of S2O82- to produce large amounts of hole donor.
In additions, other ECL sensors with g-C3N4-nanomaterial
composites as emitter were discussed in Sect. 4.3 because
they involved in the new strategy of dual-signaling probe.
The researches on macromolecule-functionalized
g-C3N4-based ECL sensors also had good progress. For
example, polystyrene microsphere-enhanced ECL sensor to
galactosyltransferase (Gal T) activity was reported by Xie
et al. [147]. Chen et al. developed the molecularly imprinted
polypyrrole-modified g-C3N4 nanosheet as a cathodic ECL
emitter with S2O82- as co-reactant, exhibiting a stable and
significantly amplified ECL signal [148]. Then an ECL
sensor for perfluorooctanoic acid (PFOA) was constructed
on the basis of the quenching effect of PFOA on ECL signal,
due to the redox reaction between the electrogenerated
strong oxidants produced from the reduction of S2O82-. Lin
et al. designed a stereo-selective ECL sensor for specific
J. Anal. Test. (2017) 1:274–290 283
123
recognition of penicillamine (Pen) enantiomers using
hemoglobin (Hb), as chiral selector, and gold-nanoparticle-
functionalized g-C3N4 nanosheet composite modified glassy
carbon electrodes as sensing unit [149].
4.3 Dual-Signaling ECL Sensors Related to g-C3N4
ECL sensor with dual-signaling responses is a novel kind of
sensing system in this domain. Chen’s group developed some
prominent sensing methods related to g-C3N4-based ECL. Xu
and co-authors built a novel ratiometric ECL cell sensor for
the first time with g-C3N4 and Ag–poly-amidoamine
(PAMAM)–luminol nanocomposites served as reductive–
oxidative and oxidative–reductive ECL emitters, respectively
[150]. In detail, DNA probe-functionalized Ag–PAMAM–
luminol NCs would hybridize with aptamers modified onto
magnetic beads. In the presence of HL-60 cells, the aptamer
would conjugate with the target cell and release Ag–
PAMAM–luminol NCs. After magnetic separation, released
Ag–PAMAM–luminol NCs would hybridize with capture
DNA on g-C3N4 nanosheets. ECL from g-C3N4 nanosheets
coated on ITO electrode at -1.25 V (vs SCE) could be
quenched by Ag–PAMAM–luminol NCs due to the resonance
energy transfer (RET) from g-C3N4 nanosheets to AgNPs.
Meanwhile, Ag–PAMAM–luminol brought the ECL signal of
luminol at ?0.45 V (vs SCE). Thus, the concentration of HL-
60 cancer cells could be quantified by both the quenching of
ECL from g-C3N4 nanosheets and the enhancement of ECL
from luminol. According to the resonance energy transfer
between A–g-C3N4 hybrid and Ru(bpy)32?, Xu et al. also
designed ECL ratiometric biosensors for sensitively detection
of microRNA (Fig. 11) [151]. Au–g-C3N4 exhibited strong
and stable ECL emissions with emission peak centered at
460 nm, which can stimulate the emission of Ru(bpy)32? at the
wavelength of 620 nm, producing ECL resonance energy
transfer with high efficiency. Thus, based on the ECL signals
quenching at 460 nm and increasing at 620 nm, a dual-
wavelength ratiometric ECL-RET-sensing system was
designed. Through duplex-specific nuclease magnification
strategy, the concentration of miRNA-21 in a wide range from
1.0 fM to 1.0 nM can be accurately quantified through mea-
suring the ratio of ECL460 nm/ECL620 nm, holding potential
capability in the detection of nucleic acids via dual-wave-
length ECL ratiometry. Shortly after, the same strategy was
also used in design a spatial-resolved ECL ratiometic sensor
based on a closed biopolar electrode (BPE) is reported for the
highly sensitive detection of prostate-specific antigen (PSA)
[152]. Au–g-C3N4 as one ECL emitter (dissolved O2 as the co-
reactant) was first coated on the cathode of BPE, while the
anode of the BPE served for calibration via another ECL
substance, Ru(bpy)32?.
He et al. also fabricated a dual-signaling-responsive
ECL biosensor for synchronous detection of cancer cells
and their surface N-glycan using Ru(phen)32? and Con
A-conjugated gold-nanoparticle-modified g-C3N4 (Con
A@Au-C3N4) as the ECL probe at positive and negative
potentials, respectively [153]. Guo’s group fabricated a
novel potential-resolved ‘‘in-electrode’’-type ECL
immunosensor based on two different types of luminant
Ru–NH2 and AuNPs/g-C3N4 to realize simultaneous
detection of dual targets (CA125 and SCCA) [154].
Fig. 11 Schematic illustration
of the dual-wavelength
ratiometric ECL-RET biosensor
configuration strategy.
Reprinted with permission [151]
284 J. Anal. Test. (2017) 1:274–290
123
Shang et al. proposed a different strategy for dual-sig-
naling-responsive ECL sensor [155], in which the dual-ECL
signals could be actuated by different ECL reactions merely
from graphite-phase polymeric carbon nitride (GPPCN)
nanosheets at anodic and cathodic potentials with tri-
ethanolamine and S2O82- as co-reactants, respectively.
Interestingly, the different metal ions exhibited distinct
quenching/enhancement of the ECL signal at different dri-
ven potentials, presumably ascribed to the diversity of
energy-level matches between the metal ions and GPPCN
nanosheets and catalytic interactions of the intermediate
species in ECL reactions. Therefore, without any labeling
and masking reagents, the accuracy and reliability of
GPPCN-based sensors toward metal ions were largely
improved.
4.4 Graphitic Carbon Nitride-Amplified ECL
Sensors
Due to the superior catalytic properties, g-C3N4 also results
in ECL signal amplification of other luminophors [156],
which provides another chance to design highly sensitive
ECL sensors. Chen and co-authors reported the catalytic
effect of g-C3N4–hemin on the luminol–H2O2 ECL system,
and then designed an ECL biosensor based on g-C3N4–
hemin nanocomposites and hollow gold nanoparticles for
the detection of lactate. Deng et al. prepared a highly
efficient biomimetic catalyst with ultrathin c C3N4
nanosheet-supported cobalt(II) proto-porphyrin IX (CoP-
PIX) [157]. The periodical pyridinicnitrogen units in C3N4
backbone could serve as electron donors for great affinity
with Co2? in PPIX. Using biotinylated molecular beacon as
the capture probe, a sensitive ECL DNA assay was
developed via the electroreduction of H2O2 as the co-re-
actant after the hairpin was unfolded by the target
(Fig. 12), exhibiting linearity from 1.0 fM to 0.1 nM and a
detection limit of 0.37 fM.
5 Conclusion and Future Perspectives
In summary, g-C3N4, as a class of emerging nanomaterials,
has attracted significant attentions due to the specific planar
structure and unique characteristics. Combining g-C3N4
with CL, CTL and ECL analytical methods, scientists
designed various interesting sensors for metal ions, anion,
gases, biomolecules and so on. Those sensors have wide
application prospect in environmental monitoring, food
analysis and clinical diagnosis. Although considerable
progress has been achieved, the studies in this field are still
at the primary stage and further systematic investigations
are needed.
First, the study of g-C3N4 in CL analysis is still in the
early stages. More research works are required to exploit
new CL system including adopting g-C3N4 with various
micro/nanoarchitectures in CL sensors and reveal the exact
CL mechanisms of g-C3N4, thus to boost their sensing
applications. Due to properties such as facile and cheap
production, high biocompatibility, ease of conjugation to
biomolecules, the coupling of g-C3N4 CL detection sys-
tems with immunoassay and image analysis will gain
increasing concern and popularity in bioanalysis. Various
amplification strategies or techniques will play an impor-
tant part in improving the sensitivity of g-C3N4-based CL
sensors.
Second, as a multifunctional metal-free catalyst, g-C3N4
shows increasing significance in heterogeneous catalysis.
However, the development of g-C3N4-based CTL sensors
is still in its infancy. The g-C3N4-based sensing materials
need to extended, the g-C3N4 with 3D hierarchical bulks
and 2D nanosheets or film structures can be decorated,
functionalized and hybridized with various kinds of novel
materials, which provide greater versatility in carrying out
gas adsorption, selective catalytic and sensing processes.
The theoretical inquiry about the CTL emission mechanism
of gas molecule on g-C3N4 will be beneficial for designing
high-efficiency CTL sensors.
Third, despite the ECL behaviours of g-C3N4 and related
signal-amplifying techniques investigated intensively,
g-C3N4-based ECL sensors remain an underappreciated
and underutilized analytical method. Efforts made to
optimize this method should be continued. Synthetic
approaches, modification and signal-amplifying strategies
will be continuously improved to obtain superior g-C3N4-
based ECL systems. Seeking the novel co-reactants,
Fig. 12 Schematic illustration of the preparation of CoPPIX@C3N4
for ultrasensitive DNA detection via the consumption of co-reactant.
Reprinted with permission [157]
J. Anal. Test. (2017) 1:274–290 285
123
nanocarriers and electrocatalyst, to develop new ECL
system is a persistent research hotspot for ECL sensors.
There is still tremendous space for development of g-C3N4-
based ECL-sensing strategies, such as ECL-RET, ECL
images, multi-dimensional ECL sensor array and so on.
Acknowledgements Authors gratefully acknowledge financial sup-
port for this project from the National Natural Science Foundation of
China [nos. 21405107 and 21375089].
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