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

lvy@scu.edu.cn

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].

References

1. Liebig J. Uber einige stickstoff-verbindungen. Eur J Organic

Chem. 1834;10(1):1–47.

2. Gmelin L. Ueber einige Verbindungen des Melon’s. Eur J

Organic Chem. 1835;15(3):252–8.

3. Liu AY, Cohen ML. Prediction of new low compressibility

solids. Science. 1989;245(4920):841–2.

4. Chen MY, Li D, Lin X, Dravid VP, Chung YW, Wong MS,

Sproul WD. Analytical electron-microscopy and raman-spec-

troscopy studies of carbon nitride thin-films. J Vac Sci Technol

A. 1993;11(3):521–4.

5. Teter DM, Hemley RJ. Low-compressibility carbon nitrides.

Science. 1996;271(5245):53–5.

6. Thomas A, Fischer A, Goettmann F, Antonietti M, Mueller J-O,

Schloegl R, Carlsson JM. Graphitic carbon nitride materials:

variation of structure and morphology and their use as metal-

free catalysts. J Mater Chem. 2008;18(41):4893–908.

7. Kroke E, Schwarz M, Horath-Bordon E, Kroll P, Noll B, Nor-

man AD. Tri-s-triazine derivatives. Part i. From trichloro-tri-s-

triazine to graphitic C3N4 structures. New J Chem.

2002;26(5):508–12.

8. Zheng WX, Wong NB, Liang XQ, Long XP, Tian AM. Theo-

retical prediction of properties of triazidotri-s-triazine and its

azido-tetrazole isomerism. J Phys Chem A. 2004;108(5):840–7.

9. Gago R, Jimenez I, Caceres D, Agullo-Rueda F, Sajavaara T,

Albella JM, Climent-Font A, Vergara I, Raisanen J, Rauhala E.

Hardening mechanisms in graphitic carbon nitride films grown

with N2/Ar ion assistance. Chem Mater. 2001;13(1):129–35.

10. Wang Y, Wang F, Zuo Y, Zhang X, Cui LF. Simple synthesis of

ordered cubic mesoporous graphitic carbon nitride by chemical

vapor deposition method using melamine. Mater Lett.

2014;136:271–3.

11. Lu D, Fang P, Wu W, Ding J, Jiang L, Zhao X, Li C, Yang M, Li

Y, Wang D. Solvothermal-assisted synthesis of self-assembling

TiO2 nanorods on large graphitic carbon nitride sheets with their

anti-recombination in the photocatalytic removal of Cr(VI) and

Rhodamine B under visible light irradiation. Nanoscale.

2017;9(9):3231–45.

12. Yu Q, Guo S, Li X, Zhang M. One-step fabrication and high

photocatalytic activity of porous graphitic carbon nitride/-

graphene oxide hybrid by direct polymerization of cyanamide

without templates. Russ J Phys Chem A. 2014;88(10):1643–9.

13. Yu Q, Li X, Zhang M. One-step fabrication and high photo-

catalytic activity of porous graphitic carbon nitride synthesised

via direct polymerisation of dicyandiamide without templates.

Micro Nano Lett. 2014;9(1):1–5.

14. Li X, Zhang J, Shen L, Ma Y, Lei W, Cui Q, Zou G. Preparation

and characterization of graphitic carbon nitride through pyrol-

ysis of melamine. Appl Phys a-Mater Sci Process.

2009;94(2):387–92.

15. Liu J, Zhang T, Wang Z, Dawson G, Chen W. Simple pyrolysis

of urea into graphitic carbon nitride with recyclable adsorption

and photocatalytic activity. J Mater Chem.

2011;21(38):14398–401.

16. Dong F, Sun Y, Wu L, Fu M, Wu Z. Facile transformation of

low cost thiourea into nitrogen-rich graphitic carbon nitride

nanocatalyst with high visible light photocatalytic performance.

Catal Sci Technol. 2012;2(7):1332–5.

17. Huang Z, Li F, Chen B, Yuan G. Nanosheets of graphitic carbon

nitride as metal-free environmental photocatalysts. Catal Sci

Technol. 2014;4(12):4258–64.

18. Long B, Lin J, Wang X. Thermally-induced desulfurization and

conversion of guanidine thiocyanate into graphitic carbon

nitride catalysts for hydrogen photosynthesis. J Mater Chem A.

2014;2(9):2942–51.

19. Tian J, Liu Q, Asiri AM, Al-Youbi AO, Sun X. Ultrathin gra-

phitic carbon nitride nanosheet: a highly efficient fluorosensor

for rapid, ultrasensitive detection of Cu2?. Anal Chem.

2013;85(11):5595–9.

20. Tian J, Liu Q, Ge C, Xing Z, Asiri AM, Al-Youbi AO, Sun X.

Ultrathin graphitic carbon nitride nanosheets: a low-cost, green,

and highly efficient electrocatalyst toward the reduction of

hydrogen peroxide and its glucose biosensing application.

Nanoscale. 2013;5(19):8921–4.

21. Tian J, Liu Q, Asiri AM, Alamry KA, Sun X. Ultrathin graphitic

C3N4 nanosheets/graphene composites: efficient organic elec-

trocatalyst for oxygen evolution reaction. Chemsuschem.

2014;7(8):2125–30.

22. Yan H. Soft-templating synthesis of mesoporous graphitic car-

bon nitride with enhanced photocatalytic H2 evolution under

visible light. Chem Commun. 2012;48(28):3430–2.

23. Yang Z, Zhang Y, Schnepp Z. Soft and hard templating of

graphitic carbon nitride. J Mater Chem A. 2015;3(27):14081–92.

24. Xie RL, Zong ZM, Liu FJ, Wang YG, Yan HL, Wei ZH,

Mayyas M, Wei X-Y. Nitrogen-doped porous carbon foams

prepared from mesophase pitch through graphitic carbon nitride

nanosheet templates. RSC Adv. 2015;5(57):45718–24.

25. Song Z, Lin T, Lin L, Lin S, Fu F, Wang X, Guo L. Invisible

security ink based on water-soluble graphitic carbon nitride

quantum dots. Angew Chemie-Int Ed. 2016;55(8):2773–7.

26. Zhan Y, Liu Z, Liu Q, Huang D, Wei Y, Hu Y, Lian X, Hu C. A

facile and one-pot synthesis of fluorescent graphitic carbon

nitride quantum dots for bio-imaging applications. New J Chem.

2017;41(10):3930–8.

27. Li H, Shao FQ, Huang H, Feng JJ, Wang AJ. Eco-friendly and

rapid microwave synthesis of green fluorescent graphitic carbon

nitride quantum dots for vitro bioimaging. Sens Actuators B

Chem. 2016;226:506–11.

28. Barman S, Sadhukhan M. Facile bulk production of highly blue

fluorescent graphitic carbon nitride quantum dots and their

application as highly selective and sensitive sensors for the

detection of mercuric and iodide ions in aqueous media. J Mater

Chem. 2012;22(41):21832–7.

29. Liu L, Ma D, Zheng H, Li X, Cheng M, Bao X. Synthesis and

characterization of microporous carbon nitride. Microporous

Mesoporous Mater. 2008;110(2–3):216–22.

30. Chen X, Jun YS, Takanabe K, Maeda K, Domen K, Fu X,

Antonietti M, Wang X. Ordered mesoporous SBA-15 type

graphitic carbon nitride: a semiconductor host structure for

photocatalytic hydrogen evolution with visible light. Chem

Mater. 2009;21(18):4093–5.

31. Maeda K, Wang X, Nishihara Y, Lu D, Antonietti M, Domen K.

Photocatalytic activities of graphitic carbon nitride powder for

water reduction and oxidation under visible light. J Phys Chem

C. 2009;113(12):4940–7.

32. Zhu J, Wei Y, Chen W, Zhao Z, Thomas A. Graphitic carbon

nitride as a metal-free catalyst for no decomposition. Chem

Commun. 2010;46(37):6965–7.

286 J. Anal. Test. (2017) 1:274–290

123

33. Tian J, Ning R, Liu Q, Asiri AM, Al-Youbi AO, Sun X. Three-

dimensional porous supramolecular architecture from ultrathin

g-C3N4 nanosheets and reduced graphene oxide: solution self-

assembly construction and application as a highly efficient

metal-free electrocatalyst for oxygen reduction reaction. ACS

Appl Mater Interfaces. 2014;6(2):1011–7.

34. Ayan-Varela M, Villar-Rodil S, Paredes JI, Munuera JM, Pagan

A, Lozano-Perez AA, Cenis JL, Martinez-Aonso A, Tascon

JMD. Investigating the dispersion behavior in solvents, bio-

compatibility, and use as support for highly efficient metal

catalysts of exfoliated graphitic carbon nitride. ACS Appl Mater

Interfaces. 2015;7(43):24032–45.

35. Ma TY, Tang Y, Dai S, Qiao SZ. Proton-functionalized two-

dimensional graphitic carbon nitride nanosheet: an excellent

metal-/label-free biosensing platform. Small.

2014;10(12):2382–9.

36. Tian J, Liu Q, Asiri AM, Qusti AH, Al-Youbi AO, Sun X.

Ultrathin graphitic carbon nitride nanosheets: a novel peroxidase

mimetic, fe doping-mediated catalytic performance enhance-

ment and application to rapid, highly sensitive optical detection

of glucose. Nanoscale. 2013;5(23):11604–9.

37. Zhang M, Nakayama Y, Harada S. Photoluminescence of

hydrogenated amorphous carbon nitride films after ultraviolet

light irradiation and thermal annealing. J Appl Phys.

1999;86(9):4971–7.

38. Miller DR, Wang JJ, Gillan EG. Rapid, facile synthesis of

nitrogen-rich carbon nitride powders. J Mater Chem.

2002;12(8):2463–9.

39. Wang JJ, Miller DR, Gillan EG. Photoluminescent carbon

nitride films grown by vapor transport of carbon nitride pow-

ders. Chem Commun. 2002;19:2258–9.

40. Tang Y, Song H, Su Y, Lv Y. Turn-on persistent luminescence

probe based on graphitic carbon nitride for imaging detection of

biothiols in biological fluids. Anal Chem.

2013;85(24):11876–84.

41. Liu J, Wang H, Antonietti M. Graphitic carbon nitride ‘‘reloa-

ded’’: emerging applications beyond (photo)catalysis. Chem

Soc Rev. 2016;45(8):2308–26.

42. Dong Y, Wang Q, Wu H, Chen Y, Lu C-H, Chi Y, Yang H-H.

Graphitic carbon nitride materials: sensing, imaging and ther-

apy. Small. 2016;12(39):5376–93.

43. Zhu C, Du D, Lin Y. Graphene-like 2D nanomaterial-based

biointerfaces for biosensing applications. Biosens Bioelectron.

2017;89:43–55.

44. Adam W, Kazakov DV, Kazakov VP. Singlet-oxygen chemi-

luminescence in peroxide reactions. Chem Rev.

2005;105(9):3371–87.

45. Petrikaln A. The chemi-luminescence and the energy conver-

sions in the oxidation of phosphorous. Z Angew Phys.

1924;22:119–26.

46. Rideal EK. Chemiluminescence. Nature. 1929;123:417–9.

47. Lin Z, Xue W, Chen H, Lin J-M. Peroxynitrous-acid-induced

chemiluminescence of fluorescent carbon dots for nitrite sens-

ing. Anal Chem. 2011;83(21):8245–51.

48. Liu J, Chen H, Lin Z, Lin J-M. Preparation of surface imprinting

polymer capped Mn-doped ZnS quantum dots and their appli-

cation for chemiluminescence detection of 4-nitrophenol in tap

water. Anal Chem. 2010;82(17):7380–6.

49. Huang YM, Zhang C, Zhang XR, Zhang ZJ. Chemilumines-

cence of sulfite based on auto-oxidation sensitized by Rho-

damine 6G. Anal Chim Acta. 1999;391(1):95–100.

50. Lan D, Li B, Zhang Z. Chemiluminescence flow biosensor for

glucose based on gold nano particle-enhanced activities of

glucose oxidase and horseradish peroxidase. Biosens Bioelec-

tron. 2008;24(4):934–8.

51. Dodeigne C, Thunus L, Lejeune R. Chemiluminescence as a

diagnostic tool. A review. Talanta. 2000;51(3):415–39.

52. Pavlov V, Xiao Y, Gill R, Dishon A, Kotler M, Willner I.

Amplified chemiluminescence surface detection of DNA and

telomerase activity using catalytic nucleic acid labels. Anal

Chem. 2004;76(7):2152–6.

53. Yakovleva J, Davidsson R, Lobanova A, Bengtsson M, Eremin

SA, Laurell T, Emneus J. Microfluidic enzyme immunoassay

using silicon microchip with immobilized antibodies and

chemiluminescence detection. Anal Chem.

2002;74(13):2994–3004.

54. Zhang ZF, Cui H, Lai CZ, Liu LJ. Gold nanoparticle-catalyzed

luminol chemiluminescence and its analytical applications. Anal

Chem. 2005;77(10):3324–9.

55. Aboul-Enein HY, Stefan RI, van Staden JF, Zhang XR, Garcia-

Campana AM, Baeyens WRG. Recent developments and

applications of chemiluminescence sensors. Crit Rev Anal

Chem. 2000;30(4):271–89.

56. Zhang ZY, Zhang SC, Zhang XR. Recent developments and

applications of chemiluminescence sensors. Anal Chim Acta.

2005;541(1–2):37–47.

57. Bi S, Yan Y, Yang X, Zhang S. Gold nanolabels for new

enhanced chemiluminescence immunoassay of alpha-fetoprotein

based on magnetic beads. Chem A Eur J. 2009;15(18):4704–9.

58. Haghighi B, Bozorgzadeh S. Flow injection chemiluminescence

determination of isoniazid using luminol and silver nanoparti-

cles. Microchem J. 2010;95(2):192–7.

59. Huang X, Ren J. Nanomaterial-based chemiluminescence reso-

nance energy transfer: a strategy to develop new analytical

methods. TRAC Trends Anal Chem. 2012;40:77–89.

60. Li Q, Zhang L, Li J, Lu C. Nanomaterial-amplified chemilu-

minescence systems and their applications in bioassays. TRAC

Trends Anal Chem. 2011;30(2):401–13.

61. Su Y, Lv Y. Graphene and graphene oxides: recent advances in

chemiluminescence and electrochemiluminescence. RSC Adv.

2014;4(55):29324–39.

62. Su Y, Xie Y, Hou X, Lv Y. Recent advances in analytical

applications of nanomaterials in liquid-phase chemilumines-

cence. Appl Spectrosc Rev. 2014;49(3):201–32.

63. Iranifam M. Analytical applications of chemiluminescence

systems assisted by carbon nanostructures. TRAC Trends Anal

Chem. 2016;80:387–415.

64. Tang Y, Su Y, Yang N, Zhang L, Lv Y. Carbon nitride quantum

dots: a novel chemiluminescence system for selective detection

of free chlorine in water. Anal Chem. 2014;86(9):4528–35.

65. Fan X, Feng Y, Su Y, Zhang L, Lv Y. A green solid-phase

method for preparation of carbon nitride quantum dots and their

applications in chemiluminescent dopamine sensing. RSC Adv.

2015;5(68):55158–64.

66. Abdolmohammad-Zadeh H, Rahimpour E. A novel chemosen-

sor based on graphitic carbon nitride quantum dots and potas-

sium ferricyanide chemiluminescence system for Hg(II) ion

detection. Sens Actuators B Chem. 2016;225:258–66.

67. Fan XQ, Su YY, Deng DY, Lv Y. Carbon nitride quantum dot-

based chemiluminescence resonance energy transfer for iodide

ion sensing. RSC Adv. 2016;6(80):76890–6.

68. Yu H, He Y, Li W, Duan T. Graphitic carbon nitride nanosheets-

enhanced chemiluminescence of luminol for sensitive detection

of 2,4,6-trinitrotoluene. Sens Actuators B Chem.

2015;220:516–21.

69. Vazquez-Gonzalez M, Liao W-C, Gazelles R, Wang S, Yu X,

Gutkin V, Willner I. Mimicking horseradish peroxidase func-

tions using Cu2?-modified carbon nitride nanoparticles or Cu2?-

modified carbon dots as heterogeneous catalysts. ACS Nano.

2017;11(3):3247–53.

J. Anal. Test. (2017) 1:274–290 287

123

70. Zheng Y, Dou X, Li H, Lin J-M. Bisulfite induced chemilumi-

nescence of g-C3N4 nanosheets and enhanced by metal ions.

Nanoscale. 2016;8(9):4933–7.

71. Breysse M, Claudel B, Faure L, Guenin M, Williams RJJ,

Wolkenstein T. Chemiluminescence during catalysis of carbon-

monoxide oxidation on a thoria surface. J Catal.

1976;45(2):137–44.

72. Tang F, Guo CA, Chen J, Zhang X, Zhang S, Wang X. Cata-

luminescence-based sensors: Principle, instrument and applica-

tion. Luminescence. 2015;30(7):919–39.

73. Aras VM, Breysse M, Claudel B, Faure L, Guenin M. Chemi-

luminescence during catalysis. 2. Luminescent transitions of

some rare-earth activators embedded in catalyst lattice. J Chem

Soc Faraday Trans I. 1977;73:1039–47.

74. Breysse M, Claudel B, Faure L, Guenin M. Temperature-pro-

grammed desorption and photo-luminescence studies of tho-

rium-dioxide surface-states. J Colloid Interface Sci.

1979;70(1):201–7.

75. Klodel B, Breiss M, For L, Genin M. Luminescence phenomena

on the semiconductor surface-model of electron-energy levels of

semiconductor catalysts. Zh Fiz Khim. 1978;52(12):3080–6.

76. Breysse M, Claudel B, Faure L, Guenin M. Role of surface and

bulk impurities in the adsorbo-luminescence and photo-lumi-

nescence of thorium-dioxide. J Lumin. 1979;18-9:402–6.

77. Utsunomiya K, Nakagawa M, Tomiyama T, Yamamoto I,

Matsuura Y, Chikamori S, Wada T, Yamashita N, Yamashita Y.

Discrimination and determination of gases utilizing adsorption

luminescence. Sens Actuators B Chem. 1993;11(1–3):441–5.

78. Nakagawa M. A new chemiluminescence-based sensor for dis-

criminating and determining constituents in mixed gases. Sens

Actuators B Chem. 1995;29(1–3):94–100.

79. Nakagawa M, Kawabata S, Nishiyama K, Utsunomiya K,

Yamamoto I, Wada T, Yamashita Y, Yamashita N. Analytical

detection system of mixed odor vapors using chemilumines-

cence-based gas sensor. Sens Actuators B Chem.

1996;34(1–3):334–8.

80. Nakagawa M, Yamamoto I, Yamashita N. Detection of organic

molecules dissolved in water using a gamma-al2o3 chemilu-

minescence-based sensor. Anal Sci. 1998;14(1):209–14.

81. Nakagawa M, Yamashita N, Cataluminescence-based gas sen-

sors. In: Frontiers in chemical sensors. Springer series on

chemical sensors and biosensors, vol 3. Berlin: Springer; 2005.

p. 93–132.

82. Zhu YF, Shi JJ, Zhang ZY, Zhang C, Zhang XR. Development

of a gas sensor utilizing chemiluminescence on nanosized tita-

nium dioxide. Anal Chem. 2002;74(1):120–4.

83. Sun ZY, Yuan HQ, Liu ZM, Han BX, Zhang XR. A highly

efficient chemical sensor material for H2S: a-Fe2O3 nanotubes

fabricated using carbon nanotube templates. Adv Mater.

2005;17(24):2993–7.

84. Na N, Zhang S, Wang S, Zhang X. A catalytic nanomaterial-

based optical chemo-sensor array. J Am Chem Soc.

2006;128(45):14420–1.

85. Almasian MR, Na N, Wen F, Zhang S, Zhang X. Development

of a plasma-assisted cataluminescence system for benzene,

toluene, ethylbenzene, and xylenes analysis. Anal Chem.

2010;82(9):3457–9.

86. Wu Y, Zhang S, Na N, Wang X, Zhang X. A novel gaseous ester

sensor utilizing chemiluminescence on nano-sized sio2. Sens

Actuators B Chem. 2007;126(2):461–6.

87. Wu CC, Cao X, Wen Q, Wang Z, Gao Q, Zhu H. A vinyl acetate

sensor based on cataluminescence on mgo nanoparticles.

Talanta. 2009;79(5):1223–7.

88. Zhang R, Cao X, Liu Y, Chang X. A new method for identifying

compounds by luminescent response profiles on a catalumines-

cence based sensor. Anal Chem. 2011;83(23):8975–83.

89. Zhang R, Cao X, Liu Y, Chang X. Development of a simple

cataluminescence sensor system for detecting and discriminating

volatile organic compounds at different concentrations. Anal

Chem. 2013;85(8):3802–6.

90. Li Z, Xi W, Lu C. Hydrotalcite-supported gold nanoparticle

catalysts as a low temperature cataluminescence sensing plat-

form. Sens Actuators B Chem. 2015;219:354–60.

91. Roda A, Cui H, Lu C. Highlights of analytical chemical lumi-

nescence and cataluminescence. Anal Bioanal Chem.

2016;408(30):8727–9.

92. Wang S, Yuan Z, Zhang L, Lin Y, Lu C. Recent advances in

cataluminescence-based optical sensing systems. Analyst.

2017;142(9):1415–28.

93. Zhang L, Chen Y, He N, Lu C. Acetone cataluminescence as an

indicator for evaluation of heterogeneous base catalysts in bio-

diesel production. Anal Chem. 2014;86(1):870–5.

94. Zhang R, Hu Y, Li G. Development of a cyclic system for

chemiluminescence detection. Anal Chem. 2014;86(12):6080–7.

95. Zhang R, Huang W, Li G, Hu Y. Noninvasive strategy based on

real-time in vivo cataluminescence monitoring for clinical

breath analysis. Anal Chem. 2017;89(6):3353–61.

96. Song H, Zhang L, He C, Qu Y, Tian Y, Lv Y. Graphene sheets

decorated with SnO2 nanoparticles: in situ synthesis and highly

efficient materials for cataluminescence gas sensors. J Mater

Chem. 2011;21(16):5972–7.

97. Xu H, Li Q, Zhang L, Zeng B, Deng D, Lv Y. Transient cata-

luminescence on flowerlike MgO for discrimination and detec-

tion of volatile organic compounds. Anal Chem.

2016;88(16):8137–44.

98. Zhang L, Hou X, Liu M, Lv Y, Hou X. Controllable synthesis of

Y2O3 microstructures for application in cataluminescence gas

sensing. Chem A Eur J. 2011;17(25):7105–11.

99. Zhang L, Hu J, Lv Y, Hou X. Recent progress in chemilumi-

nescence for gas analysis. Appl Spectrosc Rev.

2010;45(6):474–89.

100. Zhang L, Song H, Su Y, Lv Y. Advances in nanomaterial-as-

sisted cataluminescence and its sensing applications. TRAC

Trends Anal Chem. 2015;67:107–27.

101. Zhang L, Zhou Q, Liu Z, Hou X, Li Y, Lv Y. Novel Mn3O4

micro-octahedra: promising cataluminescence sensing material

for acetone. Chem Mater. 2009;21(21):5066–71.

102. Zeng B, Zhang L, Wan X, Song H, Lv Y. Fabrication of a-

Fe2O3/g-C3N4 composites for cataluminescence sensing of h2s.

Sens Actuators B Chem. 2015;211:370–6.

103. Meyer C, Mueller S, Gurevich EL, Franzke J. Dielectric barrier

discharges in analytical chemistry. Analyst.

2011;136(12):2427–40.

104. Hu Y, Li L, Zhang L, Lv Y. Dielectric barrier discharge plasma-

assisted fabrication of g-C3N4-Mn3O4 composite for high-per-

formance cataluminescence H2S gas sensor. Sens Actuators B

Chem. 2017;239:1177–84.

105. Li X-H, Antonietti M. Metal nanoparticles at mesoporous

N-doped carbons and carbon nitrides: functional Mott-Schottky

heterojunctions for catalysis. Chem Soc Rev.

2013;42(16):6593–604.

106. Li L, Hu Y, Deng D, Song H, Lv Y. Highly sensitive catalu-

minescence gas sensors for 2-butanone based on g-C3N4 sheets

decorated with CuO nanoparticles. Anal Bioanal Chem.

2016;408(30):8831–41.

107. Miao W. Electrogenerated chemiluminescence and its biorelated

applications. Chem Rev. 2008;108(7):2506–53.

108. Hercules DM. Chemiluminescence resulting from electrochem-

ically generated species. Science. 1964;145(363):808–9.

109. Visco RE, Chandross EA. Electroluminescence in solutions of

aromatic hydrocarbons. J Am Chem Soc. 1964;86(23):5350–1.

288 J. Anal. Test. (2017) 1:274–290

123

110. Santhana KS, Bard AJ. Chemiluminescence of electrogenerated

9,10-diphenylanthracene anion radical. J Am Chem Soc.

1965;87(1):139–40.

111. Wu P, Hou X, Xu J-J, Chen H-Y. Electrochemically generated

versus photoexcited luminescence from semiconductor nano-

materials: bridging the valley between two worlds. Chem Rev.

2014;114(21):11027–59.

112. Chu C, Li M, Ge S, Ge L, Yu J, Yan M, Song X, Li L, Han B, Li

J. ‘‘Sugarcoated haws on a stick’’-like mwnts-fe3o4-c coaxial

nanomaterial: synthesis, characterization and application in

electrochemiluminescence immunoassays. Biosens Bioelectron.

2013;47:68–74.

113. Hu L, Xu G. Applications and trends in electrochemilumines-

cence. Chem Soc Rev. 2010;39(8):3275–304.

114. Li J, Guo S, Wang E. Recent advances in new luminescent

nanomaterials for electrochemiluminescence sensors. RSC Adv.

2012;2(9):3579–86.

115. Zhang Y, Lu F, Yan Z, Wu D, Ma H, Du B, Wei Q. Electro-

chemiluminescence immunosensing strategy based on the use of

Au@Ag nanorods as a peroxidase mimic and NH4CoPO4 as a

supercapacitive supporter: application to the determination of

carcinoembryonic antigen. Microchim Acta.

2015;182(7–8):1421–9.

116. Cheng C, Huang Y, Tian X, Zheng B, Li Y, Yuan H, Xiao D,

Xie S, Choi MMF. Electrogenerated chemiluminescence

behavior of graphite-like carbon nitride and its application in

selective sensing Cu2?. Anal Chem. 2012;84(11):4754–9.

117. Cheng C, Huang Y, Wang J, Zheng B, Yuan H, Xiao D. Anodic

electrogenerated chemiluminescence behavior of graphite-like

carbon nitride and its sensing for rutin. Anal Chem.

2013;85(5):2601–5.

118. Chen L, Huang D, Ren S, Dong T, Chi Y, Chen G. Preparation

of graphite-like carbon nitride nanoflake film with strong fluo-

rescent and electrochemiluminescent activity. Nanoscale.

2013;5(1):225–30.

119. Liu Y, Wang Q, Lei J, Hao Q, Wang W, Ju H. Anodic elec-

trochemiluminescence of graphitic-phase C3N4 nanosheets for

sensitive biosensing. Talanta. 2014;122:130–4.

120. Feng Y, Wang Q, Lei J, Ju H. Electrochemiluminescent DNA

sensing using carbon nitride nanosheets as emitter for loading of

hemin labeled single-stranded DNA. Biosens Bioelectron.

2015;73:7–12.

121. Cheng N, Jiang P, Liu Q, Tian J, Asiri AM, Sun X. Graphitic

carbon nitride nanosheets: one-step, high-yield synthesis and

application for Cu2? detection. Analyst. 2014;139(20):5065–8.

122. Xu H, Zhu X, Dong Y, Wu H, Chen Y, Chi Y. Highly sensitive

electrochemiluminescent sensing platform based on graphite

carbon nitride nanosheets for detection of pyrophosphate ion in

the synovial fluid. Sens Actuators B Chem. 2016;236:8–15.

123. Wang H, Ma Q, Wang Y, Wang C, Qin D, Shan D, Chen J, Lu

X. Resonance energy transfer based electrochemiluminescence

and fluorescence sensing of riboflavin using graphitic carbon

nitride quantum dots. Anal Chim Acta. 2017;973:34–42.

124. Zhou Z, Shang Q, Shen Y, Zhang L, Zhang Y, Lv Y, Li Y, Liu

S, Zhang Y. Chemically modulated carbon nitride nanosheets

for highly selective electrochemiluminescent detection of mul-

tiple metal-ions. Anal Chem. 2016;88(11):6004–10.

125. Li X, Zhang X, Ma H, Wu D, Zhang Y, Du B, Wei Q. Cathodic

electrochemiluminescence immunosensor based on nanocom-

posites of semiconductor carboxylated g-C3N4 and graphene for

the ultrasensitive detection of squamous cell carcinoma antigen.

Biosens Bioelectron. 2014;55:330–6.

126. Han T, Li X, Li Y, Cao W, Du B, Wei Q. Gold nanoparticles

enhanced electrochemiluminescence of graphite-like carbon

nitride for the detection of nuclear matrix protein 22. Sens

Actuators B Chem. 2014;205:176–83.

127. Li X, Guo Z, Li J, Zhang Y, Ma H, Pang X, Du B, Wei Q.

Quenched electrochemiluminescence of Ag nanoparticles func-

tionalized g-C3N4 by ferrocene for highly sensitive

immunosensing. Anal Chim Acta. 2015;854:40–6.

128. Li X, Ma H, Zhang Y, Wu D, Lv X, Du B, Wei Q. Enhanced

sensing performance of supported graphitic carbon nitride

nanosheets and the fabrication of electrochemiluminescent

biosensors for IgG. Analyst. 2015;140(24):8172–6.

129. Chen L, Zeng X, Si P, Chen Y, Chi Y, Kim D-H, Chen G. Gold

nanoparticle-graphite-like C3N4 nanosheet nanohybrids used for

electrochemiluminescent immunosensor. Anal Chem.

2014;86(9):4188–95.

130. Chen L, Zeng X, Ferhan AR, Chi Y, Kim D-H, Chen G. Signal-

on electrochemiluminescent aptasensors based on target con-

trolled permeable films. Chem Commun. 2015;51(6):1035–8.

131. Chen L, Zeng X, Dandapat A, Chi Y, Kim D. Installing logic

gates in permeability controllable polyelectrolyte-carbon nitride

films for detecting proteases and nucleases. Anal Chem.

2015;87(17):8851–7.

132. Zhou C, Chen Y, Shang P, Chi Y. Strong electrochemilumi-

nescent interactions between carbon nitride nanosheet-reduced

graphene oxide nanohybrids and folic acid, and ultrasensitive

sensing for folic acid. Analyst. 2016;141(11):3379–88.

133. Xu H, Liang S, Zhu X, Wu X, Dong Y, Wu H, Zhang W, Chi Y.

Enhanced electrogenerated chemiluminescence behavior of

C3N4 QDs@ C3N4 nanosheet and its signal-on aptasensing for

platelet derived growth factor. Biosens Bioelectron.

2017;92:695–701.

134. Zhu X, Kou F, Xu H, Yang G. A rapid and sensitive electro-

chemiluminescent sensor for nitrites based on C3N4 quantum

dots on C3N4 nanosheets. RSC Adv. 2016;6(107):105331–7.

135. Lu Q, Zhang J, Liu X, Wu Y, Yuan R, Chen S. Enhanced

electrochemiluminescence sensor for detecting dopamine based

on gold nanoflower@graphitic carbon nitride polymer nanosh-

eet-polyaniline hybrids. Analyst. 2014;139(24):6556–62.

136. Wang B, Zhong X, Chai Y, Yuan R. Ultrasensitive electro-

chemiluminescence biosensor for organophosphate pesticides

detection based on carboxylated graphitic carbon nitride-

poly(ethylenimine) and acetylcholinesterase. Electrochim Acta.

2017;224:194–200.

137. Ou X, Tan X, Liu X, Lu Q, Chen S, Wei S. A signal-on elec-

trochemiluminescence biosensor for detecting con a using phe-

noxy dextran-graphite-like carbon nitride as signal probe.

Biosens Bioelectron. 2015;70:89–97.

138. Fu X, Feng J, Tan X, Lu Q, Yuan R, Chen S. Electrochemilu-

minescence sensor for dopamine with a dual molecular recog-

nition strategy based on graphite-like carbon nitride nanosheets/

3,4,9,10-perylenetetracarboxylic acid hybrids. RSC Adv.

2015;5(53):42698–704.

139. Fan Y, Tan X, Liu X, Ou X, Chen S, Wei S. A novel non-

enzymatic electrochemiluminescence sensor for the detection of

glucose based on the competitive reaction between glucose and

phenoxy dextran for concanavalin a binding sites. Electrochim

Acta. 2015;180:471–8.

140. Zuo F, Jin L, Fu X, Zhang H, Yuan R, Chen S. An electro-

chemiluminescent sensor for dopamine detection based on a

dual-molecule recognition strategy and polyaniline quenching.

Sens Actuators B Chem. 2017;244:282–9.

141. Fan Y, Tan X, Ou X, Lu Q, Chen S, Wei S. A novel ‘‘on-off’’

electrochemiluminescence sensor for the detection of con-

canavalin a based on ag-doped g-C3N4. Electrochim Acta.

2016;202:90–9.

142. Wu L, Sha Y, Li W, Wang S, Guo Z, Zhou J, Su X, Jiang X.

One-step preparation of disposable multi-functionalized g-C3N4

based electrochemiluminescence immunosensor for the detec-

tion of CA125. Sens Actuators B Chem. 2016;226:62–8.

J. Anal. Test. (2017) 1:274–290 289

123

143. Wu L, Hu Y, Sha Y, Li W, Yan T, Wang S, Li X, Guo Z, Zhou

J, Su X. An ‘‘in-electrode’’-type immunosensing strategy for the

detection of squamous cell carcinoma antigen based on elec-

trochemiluminescent Au NPs/C3N4 nanocomposites. Talanta.

2016;160:247–55.

144. Xia B, Chu M, Wang S, Wang W, Yang S, Liu C, Luo S.

Graphene oxide amplified electrochemiluminescence of gra-

phitic carbon nitride and its application in ultrasensitive sensing

for Cu2?. Anal Chim Acta. 2015;891:113–9.

145. Xia B, Yuan Q, Chu M, Wang S, Gao R, Yang S, Liu C, Luo S.

Directly one-step electrochemical synthesis of graphitic carbon

nitride/graphene hybrid and its application in ultrasensitive

electrochemiluminescence sensing of pentachlorophenol. Sens

Actuators B Chem. 2016;228:565–72.

146. Zheng X, Hua X, Qiao X, Xia F, Tian D, Zhou C. Simple and

signal-off electrochemiluminescence immunosensor for alpha

fetoprotein based on gold nanoparticle-modified graphite-like

carbon nitride nanosheet nanohybrids. RSC Adv.

2016;6(26):21308–16.

147. Xie S, Wang F, Wu Z, Joshi L, Liu Y. A sensitive electrogen-

erated chemiluminescence biosensor for galactosyltransferase

activity analysis based on a graphitic carbon nitride nanosheet

interface and polystyrene microsphere-enhanced responses. RSC

Adv. 2016;6(39):32804–10.

148. Chen S, Li A, Zhang L, Gong J. Molecularly imprinted ultrathin

graphitic carbon nitride nanosheets-based electrochemilumi-

nescence sensing probe for sensitive detection of perfluorooc-

tanoic acid. Anal Chim Acta. 2015;896:68–77.

149. Lin X, Zhu S, Wang Q, Xia Q, Ran P, Fu Y. Chiral recognition

of penicillamine enantiomers using hemoglobin and gold

nanoparticles functionalized graphite-like carbon nitride

nanosheets via electrochemiluminescence. Colloids Surf B

Biointerfaces. 2016;148:371–6.

150. Wang Y-Z, Hao N, Feng Q-M, Shi H-W, Xu J-J, Chen H-Y. A

ratiometric electrochemiluminescence detection for cancer cells

using g-C3N4 nanosheets and Ag-PAMAM-luminol nanocom-

posites. Biosens Bioelectron. 2016;77:76–82.

151. Feng Q-M, Shen Y-Z, Li M-X, Zhang Z-L, Zhao W, Xu J-J,

Chen H-Y. Dual-wavelength electrochemiluminescence

ratiometry based on resonance energy transfer between au

nanoparticles functionalized g-C3N4 nanosheet and Ru(bpy)32?

for microrna detection. Anal Chem. 2016;88(1):937–44.

152. Wang Y-Z, Zhao W, Dai P-P, Lu H-J, Xu J-J, Pan J, Chen H-Y.

Spatial-resolved electrochemiluminescence ratiometry based on

bipolar electrode for bioanalysis. Biosens Bioelectron.

2016;86:683–9.

153. He Y, Li J, Liu Y. Reusable and dual-potential responses elec-

trogenerated chemiluminescence biosensor for synchronously

cytosensing and dynamic cell surface N-glycan evaluation. Anal

Chem. 2015;87(19):9777–85.

154. Guo Z, Wu L, Hu Y, Wang S, Li X. Potential-resolved ‘‘in-elec-

trode’’ type electrochemiluminescence immunoassay based on

functionalized g-C3N4 nanosheet and Ru-NH2 for simultaneous

determination of dual targets. Biosens Bioelectron. 2017;95:27–33.

155. Shang Q, Zhou Z, Shen Y, Zhang Y, Li Y, Liu S, Zhang Y.

Potential-modulated electrochemiluminescence of carbon nitride

nanosheets for dual-signal sensing of metal ions. ACS Appl

Mater Interfaces. 2015;7(42):23672–8.

156. Chen H, Tan X, Zhang J, Lu Q, Ou X, Ruo Y, Chen S. An

electrogenerated chemiluminescent biosensor based on a

g-C3N4-hemin nanocomposite and hollow gold nanoparticles for

the detection of lactate. RSC Adv. 2014;4(106):61759–66.

157. Deng S, Yuan P, Ji X, Shan D, Zhang X. Carbon nitride

nanosheet-supported porphyrin: a new biomimetic catalyst for

highly efficient bioanalysis. ACS Appl Mater Interfaces.

2015;7(1):543–52.

290 J. Anal. Test. (2017) 1:274–290

123