Chemical Engineering Journal 417 (2021) 129125

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Chemical Engineering Journal

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Methods, principles and applications of optical detection of metal ios

Xiangfu Wang a, c, *, Chengqian Shen a, Chengfeng Zhou a, c, Yanyan Bu a, b, *, Xiaohong Yan a, c
a
College of Electronic and Optical Engineering & College of Microelectronics, Nanjing University of Posts and Telecommunications, Nanjing 210023, China
b
College of Science, Nanjing University of Posts and Telecommunications, Nanjing 210046, China
c
Key Laboratory of Radio Frequency and Micro-Nano Electronics of Jiangsu Province, Nanjing, 201146 Jiangsu, China

A R T I C L E I N F O A B S T R A C T

Keywords: Heavy metal elements were widely used in alloy manufacturing, medical treatment, food additive, military in­
Optical detection dustry and other fields, which were harmful to human body. Optical detection was a non-contact nondestructive
Metal ions detection method, which had the advantages of high selectivity, high sensitivity and low cost, and had important
Detection principles and methods
applications and prospects in environmental monitoring and biological science. In this paper, the optical
Wide applications
detection methods, detection principles and detection methods of 12 kinds of metal ions (Ag+, Al3+, Cd2+, Co2+,
Cr3+, Cu2+, Fe2+, Fe3+,Hg2+,Pb2+, Pd2+,Zn2+) were reviewed. Fluorescence, colorimetry and spectral change
were the main detection methods. Fluorescence detection methods mainly included fluorescence quenching,
fluorescence enhancement and fluorescence spectrum changes; The colorimetric method included the change of
color and the change of ultraviolet absorption spectrum; The spectral changes mainly included circular di­
chroism, phosphorescence and surface enhanced Raman scattering, etc. Photoinduced electron transfer, intra­
molecular charge transfer and fluorescence resonance energy transfer were the primary principles of optical
detection. The application prospect and main challenges of optical detection were discussed.

1. Introduction
With the continuous development of industrial production and
manufacturing industry, the pollution of heavy metal ions is more and
more serious. The waste liquid containing heavy metal ions, which is
discharged into the environment, pollutes the soil and water sources,
and then affects crops, animals and plants, and eventually accumulates
in the human body, resulting in serious diseases [1–4]. For example, the
toxicity of aluminum ions is not only harmful to some animals and crops
[5,6], but also causes severe damage to the central nervous system of the
human body, leading to serious diseases such as encephalopathy and
Alzheimer’s disease [7,8]. Copper ions, which are widely used in in­
dustry, can also cause neurological diseases such as Parkinson’s disease
and Wilson’s disease in the human body [9,10]. Mercury ions, for
example, are highly toxic and do extremely serious harm to human
health and the environment [11,12]. Therefore, sensitive and efficient
detection of heavy metal ions in food, clinical medicine and environ­
ment is particularly important.
In order to detect heavy metal ions, over the past few decades, a
variety of detection methods came into being. Some detection tech­
niques, such as atomic absorption spectrometry [13], electrochemical
sensor [14], X-ray fluorescence [15], optical way [16] and so on, had
made remarkable progress and achievements. Among them, compared
with other methods, the optical method had the unique advantages of
high selectivity, high sensitivity, low cost and simple operation mode
[17]. Optical sensors for the detection of various heavy metal ions had
been developed rapidly. The optical methods for detecting metal ions
mainly fall into the following categories: (1) Fluorescence method
[18,19]. The metal ions are selectively detected by fluorescence
enhancement, quenching or variation in fluorescence spectrum. (2)
Colorimetry [20,21]. The metal ions are selectively detected by colori­
metric change or changes in the ultraviolet absorption spectrum. (3)
Other methods [22,23]. Including surface enhanced Raman scattering
spectroscopy and circular dichroism spectroscopy, all of them can be
used for selective detection of metal ions.
In this review, 12 common optical detection methods of metal ions,
including their principles and phenomena, were reviewed (metal ions:
Ag+, Al3+, Cd2+, Co2+, Cr3+, Cu2+, Fe2+, Fe3+,Hg2+,Pb2+, Pd2+,Zn2+).
Firstly, the main optical detection principles of PET (photo-induced
electron transfer), ICT (intramolecular charge transfer), FRET (fluores­
cence resonance energy transfer) and so on were introduced. Then, the
representative detection methods of each metal ion were described

* Corresponding authors.
E-mail addresses: xfwang@njupt.edu.cn (X. Wang), buyy@njupt.edu.cn (Y. Bu).

https://doi.org/10.1016/j.cej.2021.129125
Received 10 November 2020; Received in revised form 19 February 2021; Accepted 20 February 2021
Available online 12 March 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
X. Wang et al.
systematically, including the detection principle and experimental
phenomena. Finally, the application prospect and main challenges of
optical detection were discussed.
2. Fundamental principles of optical detection
The main optical detection methods for heavy metal ions are fluo­
rescence detection and colorimetric detection. In addition, the changes
of fluorescence emission spectrum or ultraviolet absorption spectrum,
phosphorescence quenching and circular dichroism spectrum are also
effective methods for optical detection of heavy metal ions. Based on the
principles of photoinduced electron transfer, intramolecular charge
transfer and fluorescence resonance energy transfer, many new metal
ion sensors with high selectivity had been designed and great progress
had been made too.
2.1. Photo-induced electron transfer mechanism (PET)
In the fluorescence detection of various metal ions, the fluorescence
sensors based on the principle of photo-induced electron transfer (PET)
are the most common [24–26]. When excited by light, the electron
transfer occurred between the electron donor and the electron acceptor,
resulting in the fluorescence weakening or even quenching of the fluo­
rophore. After the analyte was combined with the sensor, the PET effect
was suppressed and the fluorescence emission of the fluorophore was
restored [27]. As shown in Fig. 1(a), when the highest occupied mo­
lecular orbital (HOMO) of the receptor was between the energy of the
two orbitals of the fluorescent group, the receptor with the ability of
electron donation can transfer the electrons in the HOMO into the
HOMO, vacated by the fluorescent group due to electron excitation, so
that the electrons excited by light cannot directly jump back to the
original ground state orbital to emit fluorescence, resulting in fluores­
cence quenching of the fluorescent group. When the lowest unoccupied
molecule orbital (LUMO) of the receptor was between the energy of the
two orbitals of the fluorophore, after the fluorescent group was excited
by light, one of the electrons in the HOMO jumped to the LUMO, and
Fig. 1. (a) Schematic diagram of front-line orbit PET theory; (b) The schematic diagram of the fluorescence sensor model and the detection based on PET mechanism.
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Chemical Engineering Journal 417 (2021) 129125
then transfered to the empty LUMO of the receptor, and finally returned
to the HOMO of the fluorophore. The excited electrons returned to the
ground state in a non-radiative way, resulting in fluorescence quench­
ing. A typical PET sensing system was consisted of a receptor containing
an electron donor, which was connected to the fluorophore through the
spacer group. Under the excitation of light, the process of PET between
the receptor and the fluorophore occurred, which quenched the fluo­
rescence. When the receptor bound to the analyte, the PET process be­
tween the receptor and the fluorophore was inhibited, thus restoring the
fluorescence, as shown in Fig. 1(b). Sensors based on the principle of
photoinduced electron transfer (PET) can detect metal ions efficiently
and sensitively [28,29].
2.2. Intermolecular charge transfer (ICT)
A typical fluorescence sensor based on the principle of intra­
molecular charge transfer (ICT) had both an electron-pushing group
(electron donor) and an electron-absorbing group (electron acceptor)
connected to the fluorescent group. Under the excitation of light, the
charge of the electron donor transfered to the electron acceptor, as
shown in Fig. 2(a) [30,31]. And the electron-pushing group or the
electron-absorbing group itself contained the recognition group. When
detecting metal cations (electron-deficient groups), there were two sit­
uations: one was the combination of metal ions with electron-pushing
groups, so that the arc-pair electrons originally transferred to the con­
jugated system were used to form coordination bonds with cations,
which weakened the intramolecular charge transfer, resulting in the
blue shift of fluorescence spectrum; The other was the combination of
metal ions with electron-absorbing groups, which enhanced the intra­
molecular charge transfer and led to the red shift of fluorescence spec­
trum, as shown in Fig. 2(b). Sensors based on the mechanism of
intramolecular charge transfer (ICT) mechanism had been widely used
in the detection of metal ions [32,33].
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 2. (a) Schematic diagram of charge transfer between electron donor and electron acceptor; (b) Schematic diagram of the detection principle based on intra­
molecular charge transfer.

2.3. Fluorescence resonance energy transfer (FRET)
Fluorescence resonance energy transfer system (FRET) meant that a
fluorescence system contained two different fluorescent groups, one as
an energy donor (D), and the other as an energy acceptor (A). When the
excitation wavelength of donor D was used to excite the fluorescence
system, the non-radiative energy transfer from D to A might occur
[34,35]. If the fluorescence quantum yield of receptor A was zero, the
fluorescence of the system was extinguished after energy transfer, and if
the receptor was also a fluorescence emitter, it showed the fluorescence
of the receptor. The generation of FRET needed certain conditions.
There were mainly: (1) the distance between the energy donor and the
acceptor must be close enough; (2) there was a certain overlap between
the emission spectrum of the energy donor and the absorption spectrum
of the energy acceptor; (3) the donor and the acceptor must be arranged
in an appropriate way. As shown in Fig. 3, only if these conditions were
met will an effective FRET be achieved. The fluorescence sensor based
on FRET bound to the analyte by bonding groups, thus changing the
distance between D and A, arrangement and other factors. If the addition
of analyte kept these factors in the appropriate range, energy donor D
would transfer energy to energy receptor A by non-radiative means, and
receptor A would show specific fluorescence changes; If the addition of
analyte did not make these factors meet the requirements of FRET
occurrence, then FRET would be inhibited, with the fluorescence

Fig. 3. (a) Distance condition generated by FRET; (b) The spectral conditions generated by FRET.

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X. Wang et al.
emission of D, as shown in Fig. 4 [36–38].
2.4. Detection method based on nanoparticles/quantum dots
Some nanoparticles (NPs) and their functional states (such as silver
nanoparticles, gold nanoparticles, etc) had attracted much attention
because of their unique electronic, photonic and catalytic properties
[39,40]. And it had been used in many important applications in the
detection of metal ions, as fluorescent and colorimetric sensors to detect
metal ions. Similarly, some quantum dots and their functional states
(such as carbon quantum dots, graphene quantum dots, etc.) had the
characteristics of good stability, good solubility, good biocompatibility
and low cytotoxicity, so they were widely used in the detection of metal
ions [41–43]. There are three main principles of detection: (1) The
binding or reaction of nanoparticles or quantum dots with metal ions, as
shown in Fig. 5(a). For example, specific metal bonds were formed be­
tween metal nanoparticles and metal ions, which generally changed the
optical properties of the whole system. Redox reactions of metal ions
might also occur; (2) The binding or reaction of ligands or modifiers on
the surface of nanoparticles/quantum dots with metal ions, as shown in
Fig. 5(b); and (3) Metal ions induced the aggregation of nanoparticles or
quantum dots, as shown in Fig. 5(c) [44–47].
Fig. 4. Detection Mechanism of fluorescence Sensor based on FRET.
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Chemical Engineering Journal 417 (2021) 129125
2.5. Detection method based on rhodamine and its derivatives
The detection principle of metal ion sensors based on rhodamine and
its derivatives was based on the fluorescence characteristics of rhoda­
mine. This property of Rhodamine was related to the open loop and
closed loop of the five-membrance in its structure [48]. As shown in
Fig. 6(a), the left picture showed the open-loop rhodamine structure,
showing strong fluorescence; the right picture showed the closed-loop
rhodamine structure, with the fluorescence disappearing. The open-
loop and closed-loop states of rhodamine can be converted to each
other under certain conditions. Metal ions induced the transformation of
the spirolactam structure of rhodamine into ring-opening structure
(ring-opening), resulting in different fluorescent and colorimetric
changes. Different rhodamine derivatives were designed and synthe­
sized in different ways, which showed uniquely fluorescent changes or
colorimetric response in the presence of different metal ions, so as to
achieve the purpose of detecting metal ions, as shown in Fig. 6(b)
[49–51].
X. Wang et al.
Fig. 5. (a) Metal ions bind to nanoparticles or quantum dots; (b) Metal ions bind to ligands on the surface of nanoparticles or quantum dots; (c) Metal ions induce the
aggregation of nanoparticles or quantum dots.
3. Optically detected metal ions
3.1. Optical detection of Ag+
Silver ions had many applications in the electrical, photographic and
medical industries, which resulted in large amounts of silver ions being
released into the environment each year. Excessive silver ions will not
only cause cell poisoning and inactivation of sulfhydryl enzymes and
other effects on human body, but also caused pollution to the environ­
ment. In order to detect silver ions, Kumar designed and prepared a
novel Ag+ fluorescence chemical sensor [52] based on thio-calixarene,
as shown in Fig. 7(a). And the detection principle was that the binding
of silver ion and thio-calixarene receptor will change the receptor from
the original excimer emission to monomer emission, so that the fluo­
rescence emission spectrum was quenched at 470 nm and enhanced at
377 nm, as shown in Fig. 7(b). Zhang reported a fluorescent sensor based
on cytidine-stabilized gold nanoclusters (Au NCs) [53], which can
quickly and sensitively identify Ag+. As shown in Fig. 7(c), the combi­
nation of the sensor and Ag+ resulted in a unique fluorescence turn-on
phenomenon, which may be related to the formation of Au-Ag metal
bond. It can be observed from Fig. 7(d) that the prepared gold nano­
clusters emitted weak green fluorescence under ultraviolet (365 nm)
irradiation, while AuAg NCs emitted strong yellow fluorescence after the
addition of silver ions, and the emission intensity increased monoto­
nously with the increase of Ag+ concentration. Shi designed and syn­
thesized a fluorescence Schiff base derivative (M1) with simple structure
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Chemical Engineering Journal 417 (2021) 129125
containing hydrazine thioamide [54]. The interaction between M1 and
Ag+ produced the photo-induced electron-transfer (PET) effect, as
shown in Fig. 7(e). By studying the optical response of M1 to common
metal ions, it can be seen that silver ion had a unique partial quenching
and red-shift effect on the fluorescence spectrum of M1, as shown in
Fig. 7(f).
In addition to some compounds that can be used as fluorescent
probes to detect silver ions, some quantum dots are also very suitable as
fluorescent probes due to their better stability and high biocompati­
bility. Gao reported a simple method for the preparation of fluorescent
carbon quantum dots [55], as shown in Fig. 8(a). After the addition of
silver ions, the fluorescence intensity of carbon quantum dots signifi­
cantly increased and showed a linear relationship with the concentra­
tion of Ag+, as shown in Fig. 8(b). This was attributed to the reduction of
silver ions to Ag clusters on the surface of carbon quantum dots. Bian
had prepared and reported a sulfur-doped graphene quantum dot (S-
GQD) for Ag+ detection [56], as shown in Fig. 8(c). Due to the syner­
gistic effect of S and O functional groups on S-GQDS, S-GQDS was highly
selective to Ag+. It can be seen from Fig. 8(d) that the addition of silver
ions can effectively quench the fluorescence of S-GQD. With the increase
of Ag+ concentration, the fluorescence intensity of S-GQDs decreased
gradually. Based on a synthetic amine-terminated graphene quantum
dot (Am-GQDs), Suryawanshi developed a fluorescence sensor for silver
ion detection [57]. The fluorescence of Am-GQDs was quenched by the
addition of Ag+, and then regenerated after the addition of L-cysteine, as
shown in Fig. 8(f), and only the combination of Ag+ and L-cysteine could
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 6. (a) Schematic diagram of the transition of open-loop and closed-loop states of five-membered rings in rhodamine structure; (b) Schematic diagram of
rhodamine and its derivatives for detecting metal ions.

cause the process of fluorescence turn-off and re-opening. The principle (G4.ds (C–C)) [61]. After the addition of Ag+, C-Ag+-C base pairs were
was that L-cysteine groups had a strong affinity for Ag+ ions. The formed to enhance the DNA activity of G4.ds (C–C), as shown in Fig. 10
addition of L-cysteine can release Ag+ attached to Am-GQD, causing the (c). With the increase of Ag+ concentration, the absorption intensity of
fluorescence to turn on, as shown in Fig. 8(e). the system gradually increased, and the DNA enzyme activity of G4.ds
Besides fluorescence detection, colorimetric method can detect silver (C–C) also gradually increased, as shown in Fig. 10(d).
ions quickly and intuitively. Chang reported a fast and sensitive Ag+
colorimetric sensor based on the activity of gold nanocluster peroxidase
3.2. Optical detection of Al3+
stabilized by bovine serum albumin (BSA @ AuNCs) [58]. BSA@AuNCs
has peroxidase activity and can catalyze the oxidation of 3,3′ ,5,5′ -tet­
As the most abundant metal element in the earth’s crust, aluminum is
ramethylbenzidine (TMB) by H2O2. However, after adding Ag+,
widely used in medicine, automobile manufacturing, food additives,
BSA@AuNCs enzyme activity was significantly inhibited, making the
alloy appliances and other fields. This makes aluminum ions easily
reaction impossible, as shown in Fig. 9(a). This was due to the strong Ag-
exposed to the environment, which does great harm to the environment
Au interaction. Fig. 9(b) showed three scenarios: without BSA@AuNCs,
and human health. Excessive aluminum ions in the body can cause a
there was no reaction between TMB and H2O2 (curve A); BSA@AuNCs
number of serious diseases, such as osteoporosis, encephalopathy and
catalyzed the oxidation of TMB by H2O2 to produce strong colored
Alzheimer’s disease. In order to detect aluminum ions, Jiang designed
products (curve B); BSA@AuNCs could hardly catalyze the chromogenic
and synthesized a novel fluorescence sensor based on 8-hydroxyquino­
reaction between TMB and H2O2 (curve C) after adding Ag+. Hung re­
line formaldehyde Schiff base [62]. The combination of the sensor and
ported a new detection method based on mercaptans and gold nano­
Al3+ effectively suppressed the PET phenomenon of Schiff base and
particles, which can detect Ag+ quickly and efficiently [59]. In the 2-
quinoline nitrogen atoms, thus significantly enhancing the fluorescence
mercaptoethanol/Au NPs system, the presence of Ag+ leaded to the
intensity of the sensor, as shown in Fig. 11(a). Fig. 11(b) showed that the
significant aggregation of gold nanoparticles, which was attributed to
fluorescence intensity of the sensor increased with the addition of Al3+.
the deposition of silver ions on the surface of gold nanoparticles, as
Xu reported a newly synthesized three-dimensional lanthanide-organic
shown in Fig. 9(c). At the same time, the addition of Ag+ caused the red
framework {[Eu (BTB) (phen)]⋅ 4.5DMF⋅2H2O}n for the detection and
shift of the UV–vis absorption spectrum, as shown in Fig. 9(d).
recovery of aluminum ions [63], and its schematic diagram was shown
In addition to the fluorescence spectrum and colorimetric changes,
in Fig. 11(c). In the ethanol solution of the framework sample, the
the changes of optical absorption spectrum and emission band caused by
luminescence intensity was measured after adding different metal ions.
some substances and metal ions can also be used to detect silver ions.
As shown in Fig. 11(d), aluminum ions had an obvious quenching effect
Based on the redshift of the emission wavelength of CdTe Quantum dots
on it, which may be attributed to the energy consumption caused by the
(QDs) wrapped in TGA, Wang designed and reported a new method for
collision interaction between the framework and free aluminum ions,
detecting Ag+ [60], as shown in Fig. 10(a). It can be seen from Fig. 10
resulting in the decrease of luminous intensity. Gui reported a novel
(b), as the concentration of silver ions added to CdTe QDs solution
fluorescence-turned-on chemical sensor 2 (4-(1,2,2-triphenylethyl)
increased, the fluorescence emission peak gradually strengthened and
phenoxy) acetic acid (TPE-COOH) for the detection of aluminum ions
moved to a longer wavelength. The illustration showed a good linear
[64]. When Al3+ was added to the solution of the sensor, the fluores­
relationship between emission wavelength redshift (Y) and silver ion
cence intensity was enhanced and there was blue fluorescence visible to
concentration. Li reported a method for the detection of silver ions based
the naked eye. This was due to the aggregation of TPE-COOH induced by
on the enzyme activity changes of quadruplex/ duplex DNA structure
aluminum ions, resulting in significant fluorescence emission, as shown

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X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 7. (a) Schematic diagram of detecting Ag+ with thiacalixarene; (b) Fluorescence spectra of the sensor upon different additions of Ag+(0–300 equiv.); (c)
Schematic diagram of detecting Ag+ with the Au NCs; (d) Fluorescence spectra of Au NCs in the presence of different concentration Ag+; (e) The interaction
mechanisms of M1 with Ag+; (f) Fluorescence spectra of M1 upon the addition of various metal ions. Reproduced from Ref. [52–54] with permission of American
Chemical Society and Elsevier.

in Fig. 11(e). Fig. 11(f) showed that the fluorescence of 470 nm emission
gradually increased with the increase of concentration of Al3+. And the
sensor had been successfully applied to the detection of aluminum ions
in living cells.
In addition to fluorescence enhancement and quenching, aluminum
ions can also be effectively detected by the change of fluorescence
spectrum. Zou successfully designed a fluorescence sensor based on
fluorescent carbon nanodots (CNDs) [65]. Fig. 12(a) showed the binding
principle of CNDs and Al3+, the mechanism of which was the fluores­
cence resonance energy transfer (FRET) between them. With the in­
crease of Al3+ concentration, the fluorescence spectra of carbon
nanoparticles changed, and the intensity increased, as shown in Fig. 12
(b). Yang reported a rhodamine-benzothiazole fluorescent probe (P)
based on the mechanism of fluorescence resonance energy transfer
(FRET), which can effectively detect aluminum ions [66]. The reaction
diagram was shown in Fig. 12(c). The addition of Al3+ caused the energy
transfer from benzothiazole to rodanbenzenyl group. As the concentra­
tion of Al3+ increased, the fluorescence of the probe increased at 586 nm
and decreased at 535 nm, as shown in Fig. 12(d).
In addition to fluorescence detection of Al3+, colorimetry can be used
to quickly and intuitively detect aluminum ions. Xue reported a new
type of Al3+ colorimetric probe: MMT-AUNP probe was formed by
modifying 5-mercaptomethyl tetrazole (MMT) as chelating ligand to the
surface of gold nanoparticles (AuNPs) [67]. The addition of Al3+
induced the aggregation of MMT-AuNPs, resulting in color changes, as
shown in Fig. 13(a). When titrated with different concentrations of
aluminum ions, the absorption spectrum of the probe decreased at 520
nm and produced a new absorption peak at 620 nm, as shown in Fig. 13
(b), and the color of the solution changed from red to dark blue. Borase
reported a new synthetic Schiff base receptor (E)-1-(4-((4-(dieth­
ylamino) − 2-hydroxybenzylidene) amino) phenyl) − 3, 4-diphenyl − 1H-
pyrrole-2, 5-dione (BASB) which was used as colorimetry sensor for
selective detection of aluminum ions [68]. As shown in Fig. 13(c), the
color of BASB changed from colorless to yellow in the presence of Al3+,
which was attributed to the formation of the BASB⋅Al3+ complex. Fig. 13
(d) showed that with the continuous addition of aluminum ions, the
absorption spectrum of the receptor solution decreased at 373 nm and a
new absorption peak appeared at 425 nm.
3.3. Optical detection of Cd2+
Cadmium is an important metal element, which is widely used in
metallurgy, electroplating, chemical fertilizer, military and other in­
dustrial and agricultural fields. Therefore, it is easy to flow into the
environment, causing serious harm to the environment and human be­
ings. It can cause damage to human bones, kidneys and nervous system,
and even cause cancer. In order to detect cadmium ions, Ye reported a
proportional fluorescence probe based on 6-substituted quinoline Zn2+
complex (HQZn) [69]. Fig. 14(a) showed a schematic diagram of the
interaction between HQZn and Cd2+. The fluorescent color changed
from green to yellow. With the constant addition of Cd2+ to methanol
solution of HQZn, the fluorescence spectrum was redshifted, and the
intensity decreased at 485 nm and increased at 560 nm, as shown in
Fig. 14(b). The reaction principle was that Zn2+ in HQZn was replaced

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X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 8. (a) Schematic representation of the formation of C-dots. (b) Fluorescent emission spectra of the C-dots with the addition of different concentrations of Ag+. (c)
Schematic illustration for the detection of Ag+ by S-GQDs; (d) Fluorescence spectra of S-GQDs with the addition of different concentration of Ag+; (e) Schematic
illustration for the detection of Ag+ by Am-GQDs; (f) The selectivity of Am-GQDs for different metal ions. Reproduced from Ref. [55–57] with permission of The
Royal Society of Chemistry and ELSEVIER.

Fig. 9. (a) Schematic diagram of detect­

ing Ag+ with BSA@AuNCs; (b) UV–vis
absorption spectra of (a) TMB + H2O2,
(b) TMB + H2O2 + BSA@AuNCs, (c)
TMB + H2O2 + BSA@AuNCs + Ag+; (c)
Schematic diagram of sensing mecha­
nism of the 2-mercaptoethanol/Au NPs
system for the detection for Ag+; (d)
UV–vis absorbance spectra of (a) Au NPs,
(b) Au NPs and 2- mercaptoethanol, (c)
Au NPs, 2- mercaptoethanol, and Ag+,
(d) Au NPs, 2- mercaptoethanol, and
Pb2+, and (e) Au NPs, 2- mercaptoetha­
nol, and Cu2+. Reproduced from
Ref. [58,59] with permission of ELSEV­
IER and American Chemical Society.

8
X. Wang et al.
Fig. 10. (a) The process of reaction between Ag+ and the CdTe QDs; (b) Fluorescence spectra of the CdTe QDs with the addition of different concentrations of Ag+;
(c) Schematic diagram of detecting Ag+ with G4.ds (C–C); (d) UV–vis absorption spectrum of G4.ds (C–C) upon adding different concentration of Ag+. Reproduced
from Ref. [60,61] with permission of Springer and Wiley.
by Cd2+. Li reported a fluorescence sensor for embedding triethylene
glycol triazole bonded silica nanospheres into CdSe quantum dots
(CdSe@SiO2-TGT) [70]. The added sulfite anions interacted with the
amino group on CDSE@siO2-TGT in electrons, which caused the
photoinduced electron transfer (PET) process that ultimately leaded to
fluorescence quenching. The addition of Cd2+ then inhibited the PET
process, resulting in the recovery and significant enhancement of the
fluorescence, as shown in Fig. 14(c). After adding different metal ions to
the solution of the sensor, only Cd2+ significantly enhanced the fluo­
rescence of the solution, as shown in Fig. 14(d).
In addition to the fluorescent method, the colorimetric method can
detect metal ions more quickly and sensitively. Zhang reported a newly
synthesized graphite-like nitride-doped carbon quantum dot coated gold
nanoparticles (Au@g-CNQDs) and used for colorimetric detection of
Cd2+ [71]. The addition of Cd2+ caused the aggregation of Au@g-
CNQDs and changed the color of the solution from wine red to blue-
purple, as shown in Fig. 15(a). After adding different concentrations
of Cd2+ to the Au@g-CNQDs solution, the ratio of absorbance at 650 nm
to that at 520 nm gradually increased, and the solution showed corre­
sponding color changes, as shown in Fig. 15(b). Liu reported a porphyrin
functionalized cotton fiber (CPT), which successfully detected and
adsorbed cadmium ions [72]. Fig. 15(c) showed the preparation process
of CPT and its reaction principle with Cd2+. Cotton fiber was selected as
adsorbent substrate, and 5,10,15,20-tetrakis(1-methy-4-pyridinio)
porphyrin tetra (p-toluenesulfonate) (TMPyP) was selected as the
color indicator of cadmium ions and fixed on the surface of cotton fiber.
The color change of CPT after adsorption of cadmium ions was caused by
charge transfer from metal to ligand.A cadmium ion bound to four ni­
trogen atoms on the TMPyP porphyrin ring, causing the plane structure
of the TMPyP molecule to deviate. It can be seen from Fig. 15(d) that the
absorbance of CPT sample increased linearly and the color changed from
brown to dark green after adsorbing different initial concentrations of
Cd2+.
In addition to fluorescence and colorimetric methods, Cd2+ can be
effectively detected by absorption spectra and surface-enhanced Raman
scattering spectra. Yin reported a new type of sensor based on surface-
enhanced Raman scattering ((SERS)), in which the SERS-active
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Chemical Engineering Journal 417 (2021) 129125
nanoparticles were composed of gold nanoparticles and a layer of Cd2+
chelating polymer brush coating [73]. The addition of Cd2+ resulted in
the aggregation of particles, which turned on SERS signal, as shown in
Fig. 16(a). Fig. 16(b) showed the change of surface-enhanced Raman
scattering spectra after adding different metal ions, in which the addi­
tion of cadmium ions significantly enhanced the intensity of SERS. Yin
reported a nanocomposite material MoS2@TMPyP, consisting of mo­
lybdenum disulfide (MoS2) nanosheets and 5, 10, 15, 20-Tetrakis (1-
methyl-4-pyridinio) porphyrintetra(p-toluenesulfonate) (TMPyP), for
the detection and removal of Cd2+ [74]. The complexation rate of Cd2+
with MOS2@TMPyP was higher than that of Cd2+ and TMPyP. MoS2
increased the chance of contact between Cd2+ and TMPyP, thus accel­
erating their complexation, as shown in Fig. 16(c). With the continuous
addition of Cd2+, the absorption spectrum of MoS2@TMPyP changed
uniquely, as shown in Fig. 16(d).
3.4. Optical detection of Co2+
Cobalt is a kind of trace element which has certain benign biological
effects on human body and microorganisms. It is essential in the process
of metabolism, red blood cell production and protein synthesis. How­
ever, excessive cobalt can cause serious harm to the human body, such as
diarrhea, anemia, heart disease, lung disease and vasodilation and other
health problems. Some industrial production processes caused cobalt
pollution in the environment and threaten human health, so it is
necessary to detect cobalt in the environment quickly and effectively.
Mohamed reported a water-soluble CdS quantum dot (MPA-CdS QDS)
modified with mercaptopropionic acid (MPA) as stabilizer, and Co2+
was detected successfully by fluorescence quenching mechanism [75].
Fig. 17(a) showed the process of complex formation between MPA-CdS
quantum dots and Co2+ through electrostatic interaction. The addition
of Co2+ to QDs solution caused a sharp quenching of the fluorescence
intensity of the whole solution, and the intensity gradually decreased
with the concentration of Co2+ increasing, as shown in Fig. 17(b). The
reason of quenching was the formation of MPA-CO2 + complex. Zeng
reported a novel polycrystalline rare earth complex prepared by acety­
lacetone (ACAC) tuning method as a sensor for detecting Co2+ [76]. The
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 11. (a) The binding mechanism of Al3+ and sensor; (b) Fluorescence spectra of the sensor with the continuous addition of Al3+; (c) Schematic diagram of
synthetic skeleton capturing Al3+; (d) Luminescence intensity of the framework sample in the presence of different metal ions; (e) Schematic diagram of detecting
Al3+ with the sensor; (f) Fluorescence spectra of the sensor upon addition of different amounts of Al3+. Reproduced from Ref. [62–64] with permission of Elsevier and
American Chemical Society.

Fig. 12. (a) The schematic illustration of detecting Al3+ with CNDs; (b) Fluorescence spectra of the CNDs in the presence of various amounts of Al3+ (0–80 μM); (c)
Schematic diagram of detecting Al3+ with the probe; (d) Fluorescence spectra of the probe upon addition of different amounts of Al3+. Reproduced from Ref. [65,66]
with permission of Elsevier.

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X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 13. (a) The synthetic route of the probe and the schematic illustration of detecting Al3+ with the probe; (b) Absorbance spectra of the probe in the presence of
various amounts of Al3+; (c) Schematic diagram of BASB and Al3+; (d) Absorption spectral of BASB with successive addition of Al3+. Reproduced from Ref. [67,68]
with permission of Elsevier.

Fig. 14. (a) Schematic diagram of Cd2+ detection by HQZn; (b) Fluorescence spectra of HQZn solution after adding different concentrations of Cd2+(0–1.2 equiv); (c)
The schematic diagram of sensor detecting Cd2+; (d) Fluorescence spectra of the sensor with different metal ions added. Reproduced from Ref. [69,70] with
permission of Elsevier and The Royal Society of Chemistry.

addition of Co2+ had a significant quenching effect on the luminescence
of the sensor, which was attributed to the unique external electron
configuration of Co2+ that induced the dissociation of the poly­
crystalline rare earth complexes, as shown in Fig. 17(c). As shown in
Fig. 17(d), in the presence of different metal ions (representing blank,
Al3+, K+, Ca2+, Hg2+, Ba2+, Ni2+, Na+, Cd2+, Fe3+, Zn2+, Pb2+, Mn2+,
Mg2+, Cu2+, Cr3+ and Co2+ respectively from inside to the front), only
Co2+ had obvious quenching effect on the sensor.
Compared with fluorescence method, colorimetric method can
detect cobalt ions visually and quickly without complicated instruments.
Zhang reported an etching method of gold nanorods (GNRs) based on
Fenton-like reaction and applied it to colorimetric detection of cobalt
ions [77]. Due to the Fenton-like reaction initiated by Co2+, H2O2 was
decomposed to produce a large amount of superoxide anion free radicals
(O.-2), which caused GNRs to be oxidized, resulting in a color change from
green to red, as shown in Fig. 18(a). With the concentration of cobalt
ions increasing, the ultraviolet extinction spectral peak of GNRs
decreased and moved towards the shortwave direction, as shown in

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X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 15. (a) Schematic diagram of the combination of Au@g-CNQDs and Cd2+; (b) The effect of different Cd2+ concentrations on the absorption ratio of A650/A520
and the corresponding color change; (c) Synthesis of CPT and its combination with Cd2+; (d) Absorbance and color changes corresponding to the adsorption of
different concentrations of cadmium ions by CPT. Reproduced from Ref. [71,72] with permission of Elsevier.

Fig. 16. (a) Reaction principle of SERS active nanoparticles with Cd2+; (b) The surface-enhanced Raman spectra of nanoparticles after adding different metal ions;
(c) Schematic diagram of MoS2@TMPyP synthesis and complexation with Cd2+; (d) Time-dependent UV–vis absorption spectra of MoS2@TMPyP and Cd2+.
Reproduced from Ref. [73,74] with permission of American Chemical Society.

Fig. 18(b). Maity reported a novel colorimetric sensor for Co2+ based on yellow to dark pink, as shown in Fig. 18(c). With the addition of Co2+,
coumarin coupled thiocarbanohydrazone [78]. The sensor reacted with the absorption band of the sensor red-shifted from 470 nm to 510 nm,
Co2+ to form a complex, resulting in a significant color change from and the color of the solution changed from yellow to dark pink, as shown

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X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 17. (a) The complex formed by MPA-CdS QDs and Co2+; (b) Fluorescence spectra of MPA-CdS QDs with the concentration of Co2+ increasing; (c) Possible
mechanism of luminescence quenching when the sensor sensing Co2+; (d) The 3D luminescence spectra of the sensor react with different metal ions. Reproduced from
Ref. [75,76] with permission of Elsevier.

Fig. 18. (a) The schematic diagram of etching GNRs by Co2+-induced Fenton-like reaction; (b) Ultraviolet extinction spectra of GNRs in the presence of different
concentrations of Cobalt ions; (c) Schematic diagram of sensor detecting Co2+; (d) The ultraviolet absorption spectrum of the sensor after gradually adding Co2+
(0.0–3.0 μ M) to aqueous solution. Reproduced from Ref. [77,78] with permission of American Chemical Society.

in Fig. 18(d).
Apart from the methods above, cobalt ions can also be detected by
changes such as ultraviolet absorption spectra. Shaabani reported a bis
(azophenol) calixarene derivative and studied its optical response to
various metal ions [79]. It was found that there was a significant change
in the absorption spectrum after combining with Co2+. Fig. 19(a)
showed that calixarene derivatives combined with Co2+ at a ratio of 1:1
to form the complex. When Co2+ was added to the DMSO solution of the
calixarene, the UV–vis absorption band at 518 nm and 317 nm increased
with the concentration of Co2+ increasing, as shown in Fig. 19(b).
Sharma reported a new synthetic imine-connected receptor-coated ZnO
sensor with organic receptor (containing imine bond) as the capping

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X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 19. (a) Schematic diagram of the combination of calixarene and Co2+; (b) Changes of UV–vis spectra after adding Co2+ to the DMSO solution of calixarene; (c)
Schematic diagram of imine bond modified ZnO crystal; (d) Left: Changes in the fluorescence spectrum of the sensor in the presence of different concentrations of
Co2+(0–50 nM);Right: Schematic diagram of the relationship between the ratio fluorescence intensity (I353/I445) and the concentration of Co2+. Reproduced from
Ref. [79,80] with permission of Elsevier and American Chemical Society.

agent for the recognition of Co2+ [80]. Fig. 19(c) showed a diagram of
imine receptor modified ZnO crystals, which can be used to detect nano-
moles of Co2+. This was due to the imine attachment of the sensor which
provided additional binding sites for the recognition of metal ions. When
salt solution of Co2+ was gradually added to the HEPES buffered DMSO/
H2O (8:2, v/v) containing the sensor, the fluorescence intensity of the
solution was quenched at 445 nm and increased at 353 nm. And the ratio
of fluorescence intensity at these two points was linearly related to the
concentration of cobalt ion, as shown in Fig. 19(d).
3.5. Optical detection of Cr3+
Trivalent chromium (Cr3+) is one of the essential trace elements for
human and other mammals, which plays an important role in the
metabolism of fat, nucleic acid and protein in vivo. Chromium is also
widely used in electroplating, metal processing, leather production and
other industrial and agricultural fields, so it is easy to cause chromium
pollution in the environment. Lack of chromium can lead to cardiovas­
cular disease, diabetes and even neurological diseases. Therefore, it is

Fig. 20. (a) The mechanism for the detection of Cr3+ using the probe; (b) Fluorescence spectra of the probe with different concentrations of Cr3+; (c) Schematic
illustration for the detection of Cr3+ using CdSe QDs; (d) Fluorescence intensity of the QDs in the presence of different metal ions. Reproduced from Ref. [81,82] with
permission of Elsevier.

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X. Wang et al.
necessary to detect Cr3+ in the environment. Liu reported a novel fluo­
rescent probe based on rhodamine-urea methacrylate, which can be
used for sensitive detection of Cr3+ [81]. Due to the molecular recog­
nition of the urea part of the probe by Cr3+ and the accompanied
spirocycle-open reaction, the combination of Cr3+ with the probe
resulted in significant fluorescence enhancement, as shown in Fig. 20(a).
In the CH3CN-H2O (90/10, v/v, pH 7.0) solution containing the probe,
the fluorescence intensity of the probe at 580 nm increased significantly
with the increase of the concentration of Cr3+ (0–100 equivalent), as
shown in Fig. 20(b). Sung reported a fluorescent probe based on the
water-soluble CdSe quantum dots immobilized on the tip of an optical
fiber in a sol–gel matrix for the detection of Cr3+ [82]. In the presence of
Cr3+, the electron transfer reaction on the surface trap of CdSe QDs was
formed rapidly, resulting in fluorescence quenching, which may be
related to the paramagnetism of Cr3+, as shown in Fig. 20(c). In the
solution of CdSe QDs, the effect of different metal ions on the fluores­
cence intensity of QDs was studied. It was found that only Cr3+ could
significantly quench the fluorescence intensity of QDs, as shown in
Fig. 20(d).
The colorimetric sensor based on gold nanoparticles (AuNPs) has
high sensitivity to Cr3+. Shellaiah reported a sensor based on bare gold
nanoparticles prepared by borohydride reduction method, which can
effectively detect Cr3+ [83]. As can be seen from Fig. 21(a), the addition
of Cr3+ caused the aggregation of AuNPs, and the color of the solution
changed rapidly from red to blue. Fig. 21(b) showed the color changes of
AuNPs toward 0–2.5 μM of Cr3+ with respect to time(0–60 min). In the
aqueous solution of AuNPs, with the increase of Cr3+ concentration, the
absorption peak of AuNPs at 520 nm decreased gradually, while a new
absorption peak appeared at 654 nm, and its intensity increased grad­
ually, as shown in Fig. 21(c). With the increase of Cr3+ concentration
(0.3–3 μm), the absorbance ratio (A654/A520) of AuNPs at 654 nm and
520 nm presented a linear relationship with the concentration of Cr3+,
and the limit of detection (LOD) for Cr3+ was 13.42 nM, as shown in
Fig. 21(D).
Fig. 21. (a) Schematic diagram for the detection of Cr3+ using AuNPs; (b) Colorimetric changes of AuNPs toward 0–2.5 μM of Cr3+ with respect to time (0–60 min);
(c) Absorption spectra of the AuNPs in the presence of different concentrations of Cr3+; (d) The absorbance ratio (A654/A520) of the AuNPs in the presence of different
concentrations of Cr3+. Reproduced from Ref. [83] with permission of Elsevier.
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Chemical Engineering Journal 417 (2021) 129125
3.6. Optical detection of Cu2+
Copper is one of the indispensable trace elements in the human body,
and it plays an important role in many physiological processes in the
human body, such as serving as a catalytic factor of various enzymes,
participating in metabolism and so on. Excessive copper in organisms
can cause anemia, liver disease, Alzheimer’s disease, Menkes syndrome
and other serious diseases. Due to the wide application of copper in
industrial and agricultural fields, such as alloy manufacturing, battery
wire, chemical fertilizer manufacturing and so on, it is easy to cause
pollution, which requires a rapid and efficient method for the detection
of copper ions. Tian reported a fluorescence sensor based on ultrathin
graphitic carbon nitride (g-C3N4) nanosheets [84]. The sensing mecha­
nism is that the redox potential of Cu2+ is between the valence band (VB)
and the conduction band (CB) of g-C3N4. After the addition of Cu2+, it
occurred the photoinduced electron transfer (PET) effect with the con­
duction band, thus quenching the fluorescence of the sensor, as shown in
Fig. 22(a). With the increase of Cu2+ concentration, the fluorescence
intensity of g-C3N4 nanosheets decreased significantly, as shown in
Fig. 22(b). Suganya reported a new type of fluorescence sensor based on
thiophene Schiff base, which detected copper ions in aqueous solution
by fluorescence enhancement effect [85]. As shown in Fig. 22(c), the
binding of Schiff base receptor to Cu2+ inhibited the original photoin­
duced electron transfer mechanism and enabled fluorescence to be
turned on. With the continuous addition of Cu2+, the fluorescence of the
receptor at 430 nm gradually increased, as shown in Fig. 22(d).
Colorimetric method also provides a convenient and efficient way to
detect Cu2+. Wang reported a rhodamine-based fluorescent chemical
sensor synthesized by the condensation reaction of 5-hydroxymethylfur­
fural and rhodamine B hydrazide, which recognized Cu2+ by obvious
colorimetric phenomenon [86]. As shown in Fig. 23(a), the color of the
solution changed from colorless to pink after the sensor was combined
with Cu2+, which was attributed to the addition of Cu2+ inducing the
ring opening of rhodamine spiro lactam. By adding Cu2+ to the Tris-HCl
buffer solution of the sensor and observing the change of the absorption
spectrum, it can be seen that the intensity of the absorption spectrum
increased linearly with the increase of the Cu2+ concentration (0 ~ 5 μ
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 22. (a) Sensing mechanism of g-C3N4 nanosheet and Cu2+; (b) The PL spectra of g-C3N4 nanosheets in the presence of different Cu2+ concentrations; (c)
Schematic diagram of binding mechanism of thiophene Schiff base receptors to Cu2+; (d) Fluorescence emission spectra of Schiff base receptors with the continuous
addition of Cu2+(0–0.8 eq). Reproduced from Ref. [84,85] with permission of American Chemical Society and Elsevier.

Fig. 23. (a) The mechanism of sensor detecting Cu2+; (b) The absorption spectra of the solution after the reaction of the sensor with different concentrations of Cu2+;
(c) The complex structure of probe and Cu2+; (d) Top: the color change after the probe reacted with different metal ions; Bottom: Changes in the absorption spectra of
the probe combined with different metal ions. Reproduced from Ref. [86,87] with permission of Elsevier.

M), as shown in Fig. 23(b). Ye reported a successfully developed
colorimetric probe based on rhodamine B and 5-ferrocenyl-1,3,4-thia­
diazole [87]. The probe reacted with Cu2+ to form a complex with a
stoichiometric ratio of 1:1, as shown in Fig. 23(c). By studying the ab­
sorption response of the probe to various metal ions in EtOH /HEPES
(8:2, V/V, pH7.2) solution, it was found that only the addition of Cu2+
caused a color transition from colorless to pink, and a strong absorption
band centered at 554 nm was formed in the absorption spectrum, which
was attributed to the the ring opening of rhodamine spironolactam
induced by Cu2+. As the concentration of Cu2+ increased, the absorbance
at 554 nm gradually increased, as shown in Fig. 23(d).
In addition to the above methods, Cu2+ can also be effectively
detected by specific changes in absorption spectrum or fluorescence
spectrum. Zong reported a probe based on fluorescent silica nano­
particles, which can be used for rapid and effective detection of Cu2+
[88]. Fig. 24(a) clearly showed the binding mode of the probe and Cu2+.
Polyethylenimine (PEI) was covalently grafted onto the surface of dye-
doped silica nanoparticles by hyperbranched surface polymerization,

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X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 24. (a) Schematic diagram of detecting Cu2+ with nanoprobe; (b) After adding different concentrations of Cu2+(from top to the bottom:0–4000 × 10-8M) , the
fluorescence spectra of the probe; (c) The coordination mode of Cu2+ and sensor; (d) Changes in absorption spectrum of sensor upon adding different concentration of
Cu2+. Reproduced from Ref. [88,89] with permission of American Chemical Society and Elsevier.

and then the fluorescence dye rhodamine B isothiocyanate (RBITC) was
covalently connected through the reaction of primary amine groups on
PEI with thiocyanate on RBITC molecules. Moreover, PEI as a strong
complexing agent of Cu2+ can selectively detect Cu2+.With the increase
of Cu2+ concentration, the fluorescence intensity of the nanoprobe at
580 nm gradually decreased, as shown in Fig. 24(b). Hu reported a
sensor based on hydrazine, which was successfully applied to the
colorimetric detection of Cu2+ [89]. Fig. 24(c) expressly showed the
coordination mode and deprotonation mechanism between the sensor
and Cu2+. The possible mechanism was Cu2+ induced deprotonation of
the receptor. After adding different concentrations of Cu2+ to the THF/
water(9:1, v/v) containing HEPES buffer (10 mM, pH = 7.0), with the
concentration of Cu2+ increasing, the intensity of the absorption spec­
trum at 336 nm gradually decreased, while a new absorption band
appeared at 502 nm and gradually enhanced, as shown in Fig. 24(d).
3.7. Optical detection of Fe2+
Iron is the most abundant transition metal element in organisms.
Fe2+ ions and Fe3+ ions play an important role in many physiological

Fig. 25. (a) Schematic diagram of Fe2+ detection with QDs; (b) In the presence of H2O2, the changes in fluorescence spectra of GSH-CdTe QDs with the increase of
Fe2+ (0–1 μ M) concentration; (c) Schematic diagram of the combination of sensor and Fe2+; (d) The changes in fluorescence spectra of the sensor with the con­
centration of Fe2+ increasing. Reproduced from Ref. [90,91] with permission of American Chemical Society and Elsevier.

17
X. Wang et al.
processes, such as the transport and storage of oxygen, metabolism and
so on. The imbalance of iron concentration can lead to serious diseases
such as anemia, hepatitis, Parkinson’s disease and nervous system
damage. Iron also plays an important role in industry, medicine and
biology, so it is necessary to develop convenient and effective methods
for the detection of iron ions. Wu reported a new glutathione modified
CdTe quantum dot (GSH-CdTe QDs) which can detect Fe2+ by fluores­
cence quenching effect [90]. Fe2+ reacted with H2O2 to produce hy­
droxyl radicals with oxidizing nature, which made the electrons transfer
from the traps of quantum dots to hydroxyl radicals to induce fluores­
cence quenching, as shown in Fig. 25(a). As can be seen from Fig. 25(b),
with the continuous addition of Fe2+, the fluorescence intensity of QDs
significantly decreased. Based on the mechanism of fluorescence reso­
nance energy transfer, Kumar successfully connected rhodamine with
dimethylaminocinnamaldehyde to form a new fluorescence sensor [91].
Fe2+ bound to the rhodamine spirolactam ring of the sensor and opened
it to amide form, thus enhancing the intramolecular FRET, as shown in
Fig. 25(c). With the concentration of Fe2+ increasing, the fluorescent
intensity of the sensor decreased gradually at 470 nm, while a new peak
was generated at 582 nm and enhanced continuously, as shown in
Fig. 25(d).
Compared with fluorescent method, colorimetric method is also an
effective and rapid method for the detection of Fe2+. Ondigo reported a
novel colorimetric probe for the detection of Fe2+, which was synthe­
sized by functionalized poly (vinylbenzyl chloride) (PVBC) nanofibers
using 2-(2′ -pyridine) imidazole (PIMH) as the ligand [92]. Fig. 26(a)
showed the binding mode of the probe and Fe2+, accompanied by a
significant color shift from yellow to red. Fig. 26(b) studied the UV
absorption spectrum of the mixed solution of the probe and Fe2+. With
the increase of Fe2+ concentration, the light absorption intensity at 484
nm increased gradually, as shown in Figure (b). This was due to the spin
crossover (SCO) effect from high spin Fe2+ to low spin Fe2+ when Fe2+
interacted with PIMH. Zhang reported a new sensor based on phenyl­
ene–acetylene, which can detect Fe2+ through obvious colorimetric
phenomena [93]. Fig. 26(c) showed the bonding modes of the sensor
with Fe2+, Cd2+ and Zn2+, respectively. Among them, it recognized Fe2+
by colorimetric phenomenon and detected Cd2+ and Zn2+ by different
fluorescence colors. After adding Fe2+ to the EtOH-H2O (1/1, v/v) so­
lution of the sensor, the absorption spectrum of the solution produced a
Fig. 26. (a) Schematic diagram of the probe for the detection of Fe2+; (b) Absorption spectral changes of PIMH solution with the concentrations of Fe2+ increasing;
(c) The combination modes of the sensor with Fe2+, Cd2+ and Zn2+; (d) Left: UV–vis spectrum of the sensor with the concentration of Fe2+ (0–1.5 eq.) increasing ;
Right: The relationship curve between the intensity of the absorption spectrum of the sensor at 573 nm and the concentration of Fe2+. Reproduced from Ref. [92,93]
with permission of Elsevier.
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Chemical Engineering Journal 417 (2021) 129125
new absorption peak at 573 nm accompanied by a significant color
change from colorless to fuchsia. This was due to the N-metal coordi­
nation effect caused by the addition of Fe2+. Moreover, as the concen­
tration of Fe2+ gradually increased, the light absorption intensity at 573
nm increased linearly, as shown in Fig. 26(d). This was attributed to the
N-metal coordination effect.
In addition to the fluorescence effect and colorimetric change, the
change of phosphorescence spectrum can also effectively detect Fe2+.
Jin reported a method for detecting Fe2+ based on phosphor 3-mercap­
topropionic acid (MPA) coated with manganese doped ZnS quantum
dots (MP-Mn: ZnS quantum dots)-Fenton hybrid system [94]. Due to the
hydroxyl radical produced by the Fenton reaction of Fe2+ with H2O2, the
phosphorescence of MPA-Mn: ZnS QDs was quenched, as shown in
Fig. 27(a). With the continuous addition of Fe2+, the phosphorescence of
MPA-Mn: ZnS QDs was quenched, and the intensity decreased gradually,
as shown in Fig. 27(b). Fig. 27(c) showed that the phosphor intensity of
quantum dots linearly increased with the concentration of Fe2+
increasing.
3.8. Optical detection of Fe3+
Iron plays many important roles in the body, such as oxygen meta­
bolism, DNA synthesis, enzymatic assistance and so on. Lack or excess of
iron can lead to serious diseases such as anemia, low immune function,
organ damage, and cancer. Moreover, the trivalent form of iron is
indispensable to living system. Its deficiency and excess can cause
neurological diseases, diabetes, hepatitis and various cancers. In view of
the importance of iron, it is necessary to develop efficient, rapid and
sensitive detection methods to detect iron ions in the environment and
cells. Ananthanarayanan reported a high-efficiency green electro­
chemical method that can obtain BMIM+ -functionalized graphene
quantum dots (GQDs) from 3D graphene, which can detect Fe3+ by
fluorescence quenching mechanism [95]. In this method, GQDs were
obtained by electrochemically incising 3D graphene using room tem­
perature ionic liquid (1-butyl-3-methylimidazoliumhexafl-uor­
ophosphate (BMIMPF6) in acetonitrile) as the electrolyte, and then Fe3+
was added to make GQDs accumulate, which caused fluorescence
quenching, as shown in Fig. 28(a). With the concentration of Fe3+
increasing, the fluorescence of GQDs was quenched gradually, as shown
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 27. (a) Schematic diagram of Fe2+ detection with MPA-Mn: ZnS QDs; (b) The effect of concentration of Fe2+ on the phosphor spectra of QDs in the presence of
0.5 μM H2O2; (c) Schematic diagram of the relationship between the ratio of phosphorescence intensity and the concentration of Fe2+. Reproduced from Ref. [94]
with permission of the Royal Society of Chemistry.

Fig. 28. (a) Schematic diagram of the synthesis of GQD from 3D-graphene and detection mechanism of Fe3+; (b) Fluorescence emission spectra of GQDs in the
presence of different concentrations of Fe3+; (c) Schematic diagram of Fe3+ detection with the sensor; (d) Left: fluorescence emission spectrum of the sensor with the
concentration of Fe3+ (1–700 eq.) increasing ; Right: The relationship curve between the emission intensity and the concentration of Fe3+. Reproduced from
Ref. [95,96] with permission of Wiley and American Chemical Society.

in Fig. 28(b). Sui reported a novel fluorescence sensor synthesized by
using boron-dipyrromethene (BODIPY) as a fluorophore and 1, 10-diaz-
18-corown-6 based cryptand as the recognition element of Fe3+, which
detected Fe3 + through fluorescence enhancement mechanism [96].
After the combination of the sensor and Fe3+, the PET process from the
cryptand to the BODIPY fluorophore was suppressed, thus the fluores­
cence emission was significantly enhanced, as shown in Fig. 28(c). When
1–700 equivalent of Fe3+ was continuously added to the H2O-CH3CN
(9:1 v/v) solution of the sensor, the fluorescence intensity of the sensor
gradually increased, and within the range of 0–200 equivalent, the

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X. Wang et al.
emission intensity was linearly related to the concentration of Fe3+.
After that, the strength increased slowly and finally tended to be stable,
as shown in Fig. 28(d).
Compared with the fluorescence method, the colorimetric method is
more direct and effective, and the cost is lower. Narayanaswamy re­
ported a novel aldazine ligand (8-hydroxyjulolidinal-azine (JA)) syn­
thesized by simple condensation reaction of 8-hydroxyjulolidinal and
hydrazine, which can be used as a colorimetric sensor for detection of
Fe3+ [97]. After JA was combined with Fe3+, the color changed from
light yellow to purple, as shown in Fig. 29(a). The principle of recog­
nition was based on the twisted plane intramolecular charge transfer.
Fe3+ was continuously added to the acetonitrile solution of the ligand
JA, and the absorption band of JA at 445 nm gradually red-shifted to
575 nm, as shown in Fig. 29(b). Wang reported a novel fluorescent probe
based on the reaction of ethylenediamine with N-stabilization rhoda­
mine [98]. The addition of Fe3+ caused an obvious color change from
colorless to red, which was attributed to the opening of spirolactam ring
caused by the combination of Fe3+ and probe, as shown in Fig. 29(c). In
the aqueous solution of the probe, the absorbance of the probe at 562 nm
was significantly enhanced with the increase of the concentration of
Fe3+, as shown in Fig. 29(d).
In addition to the above methods, some specific spectral changes can
be used to detect Fe3+ sensitively and efficiently. Saleem reported a
novel Schiff base derivative synthesized by the reaction of 4-amino-3-(2-
fluorobenzyl)-1H-1,2,4-triazole-5 (4H)-thione 5 with thiophene-2-
carbaldehyde under microwave irradiation as a highly efficient fluo­
rescence probe for the detection of Fe3+ [99]. Fig. 30(a) showed the
chelating mechanism and reversibility of the probe with Fe3+ in the
presence of excess potassium cyanide. By titrating the solution of the
probe with Fe3+, it was found that the continuous addition of Fe3+
caused the decrease of the absorption intensity at 253 nm and 293 nm,
and a new absorption signal appeared at 357 nm. With the increase of
the concentration of Fe3+, the absorption intensity gradually increased,
as shown in Fig. 30(b). As the concentration of Fe3+ increased, the
fluorescence intensity of the probe at 478 nm gradually quenched, as
shown in Fig. 30(c). These phenomena were attributed to the confor­
mational change of the structure caused by the combination of Fe3+ and
probe.
Fig. 29. (a) The coordination mode of JA and Fe3+; (b) Absorption Spectra of JA upon the addition of Fe3+ (0–25 μ M); (c) Possible sensing mechanism of the sensor
with Fe3+; (d) UV–vis absorption spectra of sensor in the presence of different concentrations of Fe3+. Reproduced from Ref. [97,98] with permission of Elsevier.
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Chemical Engineering Journal 417 (2021) 129125
3.9. Optical detection of Hg2+
Mercury is one of the most toxic heavy metal elements, which is
seriously harmful to the environment and human health. Mercury
pollution mainly comes from chemical manufacturing, coal and other
fossil fuel combustion and volcanic eruption. Mercury poisoning can
cause damage to the brain, kidney, nervous system and other organs,
leading to serious diseases such as cardiomyopathy and cancer. There­
fore, it is necessary to develop methods that can effectively detect
mercury ions in water and food. Fan reported a new chemical sensor
(SQ-1) based on squaraine dye, which can detect and identify Hg2+
through fluorescence quenching mechanism [100]. Hg2+ complexed
with SQ-1, which destroyed the donor–acceptor-donor (D-A-D) charge
transfer and caused the quenching of the fluorescence signal, as shown
in Fig. 31(a). When Hg2+ (0–110 μ M) was gradually added to the
ethanol aqueous solution of SQ-1, the fluorescence intensity of SQ-1 was
gradually quenched with the increase of Hg2+ concentration, as shown
in Fig. 31(b). Wanichacheva reported a novel fluorescent chemical
sensor based on the connection of fluorescein to two rhodamine B flu­
orophores via hydrazide moieties, and successfully realized the effective
detection of Hg2+ [101]. The binding of the sensor and Hg2+ led to the
formation of spirolactam ring-opening complexes of fluorescein and
rhodamine B, and the fluorescence signal of the sensor at the 575 nm
was enhanced by the FRET process from fluorescein to rhodamine B, as
shown in Fig. 31(c). In the dichloromethane solution of the sensor, the
fluorescence intensity of the sensor at 575 nm was significantly
enhanced with the concentration of Hg2+ increasing, as shown in Fig. 31
(d). Huang reported a time-gated fluorescence resonance energy transfer
(TGFRET) sensing technique based on manganese-doped quantum dots
and gold nanoparticles [102]. The quantum dots and gold nanoparticles
were functionalized by two single-stranded DNA respectively. When
Hg2+ was added to the solution containing quantum dots and gold
nanoparticles, it combined with two thymine (T) bases to form stable T-
Hg2+-T base pairs, which initiated the DNA hybridization. As a result,
the energy of the quantum dots was transferred to the gold nano­
particles, and the fluorescence intensity of the solution was significantly
reduced, as shown in Fig. 31(e). In the solution of quantum dots and gold
nanoparticles, the time-gated fluorescence emission intensity of the
X. Wang et al.
Fig. 30. (a) The chelating mode of probe and Fe3+; (b) UV–visible absorption spectra of the probe with the increasing concentration of Fe3+(0–10 eq) in methanol/
water (8:2, v/v) at pH 7; (c) Fluorescence spectra of the probe in the presence of different concentrations of Fe3+. Reproduced from Ref. [99] with permission
of Elsevier.
solution decreased with the increase of Hg2+ concentration, and this
change can be observed at very low mercury ion concentration, as
shown in Fig. 31(f).
Compared with the fluorescence method, the colorimetric method
has the advantages of simple operation and low cost. Nidya reported a
novel cysteine-modified silver nanoparticles probe for colorimetric
detection of Hg2+ [103]. As shown in Fig. 32(a), the cysteine-modified
silver nanoparticle probe complexed with Hg2+ in a specific way to
form a silver amalgam, while other metal ions did not. With the
continuous addition of Hg2+, the color of cys-Ag sol gradually changed
from honey brown to transparent, and the absorption peak was
quenched, as shown in Fig. 32(b). However, other metal ions did not
cause obvious color changes. Farhadi reported a colorimetric sensor
based on biologically green synthesized silver nanoparticles (Ag NPs) for
the detection of Hg2+ [104]. As shown in Fig. 32(c), redox reaction was
occurred between the added Hg2+ and Ag NPs, which gradually changed
the color of solution from yellowish brown to colorless. In the solution of
Ag NPs, the absorption peak of Ag NPs at 408 nm decreased with the
increase of Hg2+ concentration, as shown in Fig. 32(d).
Hg2+ can also be effectively detected by specific changes in the cir­
cular dichroism or absorption spectrum. Nan reported a new type of
noble metal–organic hybrid chiral complex nanoparticles with high
optical activity, named chiral Ag-L-cysteine complex nanoparticles,
which can be used as probes for the detection of Hg2+ [105]. After Hg2+
replaced the Ag+ in chiral Ag-L-cysteine complex nanoparticles through
displacement reaction, the achiral structure was formed, resulting in the
change of circular dichroism (CD), as shown in Fig. 33(a). With the in­
crease of Hg2+ concentration, the intensity of CD spectrum of probe
colloid at 254 nm decreased gradually, as shown in Fig. 33(b). Li re­
ported a new method for the detection of Hg2+ by nucleic acid-treated
AuNPs mixtures [106]. In the stable mixture of AuNPs and nucleic
acid, Hg2+ was combined with nucleic acid to form a hairpin complex,
and AuNPs aggregation was induced, as shown in Fig. 33(c). The curve
(a)-(f) in Fig. 33(d) corresponded to the absorption spectrum of nucleic
acid/AuNPs mixture in the presence of different concentrations of Hg2+
(a-f: 0–5 × 10-6M). With the concentration of Hg2+ increasing, the
corresponding redshift band increased gradually.
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Chemical Engineering Journal 417 (2021) 129125
3.10. Optical detection of Pb2+
Pb2+ is one of the most toxic heavy metal ions. Lead poisoning can
cause serious harm to human brain, nervous system, kidney and other
organs, resulting in muscle paralysis, neurosis, brain edema and other
diseases. In particular, it does great harm to the brain development of
children. Lead pollution can be caused by paint, petroleum industry and
alloy manufacturing, so it is necessary to develop a rapid and effective
method for the detection of Pb2+. Zhang reported a novel fluorescence
sensor which was constructed using C-PS2.M− DNA− templated silver
nanoclusters (Ag NCs) [107]. The DNA template was composed of two
segments: one was the Ag-NCs nucleation segment located at both ends
of the DNA template, and the other was the aptamer segment of the Pb2+
located in the middle of the DNA template. The addition of Pb2+ induced
the conformational change of Pb2+ aptamer in the template, which made
DNA-Ag NCs bind tightly, thus greatly enhanced the fluorescence in­
tensity of Ag NCs, as shown in Fig. 34(a). With the increase of Pb2+
concentration, the fluorescence intensity of C-PS2.M− DNA− Ag NCs
gradually increased, as shown in Fig. 34(b). Yao reported a sensitive and
effective method to detect Pb2+ using the fluorescence quenching
characteristics of single-walled carbon nanotubes (SWCNT) and its
ability to bind single-stranded DNA (ssDNA) [108]. As shown in Fig. 34
(c), the substrate (blue) labeled by Cy3 was hybridized with 8-17DNA­
zyme (green) to generate dsDNA, which was not easy to be adsorbed
on the surface of SWCNT, thus presenting high fluorescence. Then the
addition of Pb2+ catalyzed DNAzyme to divide the fluorescence-labeled
substrate into two halves, and the released single-chain products were
adsorbed on SWCNT, resulting in complete fluorescence quenching.
With the increase of Pb2+ concentration (1 nm ~ 10 μm), the pyrolysis
yield of substrate increased and fluorescence intensity decreased, as
shown in Fig. 34(d).
Colorimetric method can detect Pb2+ quickly and effectively with the
advantages of low cost and simple operation. Chai reported a colori­
metric probe based on glutathione functionalized gold nanoparticles
(GSH-GNPs) for rapid and sensitive detection of Pb2+ [109]. The Pb2+ in
aqueous solution was captured by glutathione, resulting in the aggre­
gation of GNPs, which changed the color of solution from red to blue, as
shown in Fig. 35(a). With the increase of Pb2+ concentration, the ab­
sorption spectrum of GSH-GNPS gradually redshifted, as shown in
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 31. (a) Schematic diagram of complexation between SQ-1 and Hg2+; (b) Fluorescence spectra of SQ-1 under different concentrations of Hg2+; (c) Schematic
diagram of Hg2+ detection with the sensor; (d) Fluorescence spectra of the sensor under different concentrations of Hg2+;(e) Schematic description of TGFRET sensing
of Hg2+; (f) Time-gated Fluorescence spectra of the solution after the addition of various concentrations of Hg2+. Reproduced from Ref. [100–102] with permission of
Elsevier and American Chemical Society.

Fig. 35(b). The illustration in Fig. 35(b) showed a linear relationship
between the absorbance ratio (A700/520) and the concentration of
Pb2+. Wang designed and reported a novel Pb2+ sensor based on poly­
diacetylene (PDA). The main part of the sensor was a novel conjugated
polymer (Poly-PDA-L) synthesized by derivation of the monomers 1-
(1,4,7,10,13-pentaoxa-16-aza-cyclooctadec-16-yl)-pentacosa-10,12-
diynamide (PCDA-L) and 10,12-pentacosadiynoic acid (PCDA) [110].
The combination of the head group (1-aza-18-crown-6-ether) of PCDA-L
with Pb2+ released the strain energy applied on the alkyl side chains
produced during the polymerization, resulting in changes in the color
and optical properties of the solution, as shown in Fig. 35(c). In the
HEPES buffer of poly-PDA-L (10 mM,pH = 7.4), with the increase of
Pb2+ concentration, the color of the solution changed from blue to
purple, while the absorption intensity at 640 nm decreased gradually
and the absorption intensity at 540 nm increased gradually, as shown in
Fig. 35(d).
In addition to common fluorescence methods and colorimetric
methods, Pb2+ can also be effectively and sensitively detected by
changes in surface enhanced Raman scattering and phosphorescence
spectra. Chen reported a novel room-temperature phosphorescent (RTP)
sensor based on glutathione-capped manganese doped ZnS quantum
dots (GSH-Mn-ZnS), which can be used for simple and effective detec­
tion of Pb2+ [111]. The addition of Pb2+ effectively quenched the room
temperature phosphorescence of GSH-Mn-ZnS QDs, which was attrib­
uted to the strong binding of Pb2+ to the surface of glutathione coating,
as shown in Fig. 36(a). The RTP intensity of QDs was proportionally
quenched with the increase of Pb2+ concentration, in the Tris-HCl buffer
containing GSH-Mn-ZnS QDs, as shown in Fig. 36(b). Frost designed and
reported a novel sensor for the detection of Pb2+ based on surface-
enhanced Raman spectroscopy (SERS) of citrate functionalized gold
nanoparticles (AuNPs) [112]. Due to the high affinity of citric acid to
heavy metals, citrate molecules interacted with Pb2+ through carboxyl
and hydroxyl groups, which caused the aggregation of AuNPs, thus
changing its surface enhanced Raman spectra, as shown in Fig. 36(c). As
the concentration of Pb2+ increased, the intensity of each band in SERS
spectrum changed specifically, as shown in Fig. 36(d).
3.11. Optical detection of Pd2+
Palladium is an important excessive metal, which plays an important
role in experiments and industrial fields, such as petroleum fuel in­
dustry, automobile industry, chemical products manufacturing, jewelry
manufacturing and so on. As a result, a lot of palladium pollutants have
been released into the environment. Pd2+ can compound with biological
macromolecules such as DNA and protein, resulting in DNA degrada­
tion, allergic reactions and cytotoxicity and other serious harm.

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X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 32. (a) Schematic diagram of complexation between cys-Ag and Hg2+; (b) Top: color photography of cys-Ag colloidal solution under the action of different metal
ions; Bottom: Absorption spectra of cys-Ag colloidal solution under the action of different metal ions; (c) Possible mechanism and schematic illustration of Hg2+
detected by Ag NPs; (d) UV–vis absorption spectra of Ag NPs colloidal solution upon the addition of Hg2+ (0–100 μM). Reproduced from Ref. [103,104] with
permission of Elsevier.

Fig. 33. (a) The schematic diagram of detecting Hg2+ with CD probe; (b) CD spectral change with the concentration of Hg2+; (c) Schematic diagram of complexation
between nucleic acid/AuNPs mixture and Hg2+; (d) The absorption spectra of nucleic acid /AuNPs system in the presence of Hg2+ at different concentrations.
Reproduced from Ref. [105,106] with permission of Wiley and The Royal Society of Chemistry.

23
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 34. (a) Schematic diagram of the sensing

method for the detection of Pb2+ by using the
sensor; (b) Changes of fluorescence emission
spectra of C-PS2.M− DNA− Ag NCs upon the addi­
tion of Pb2+ in different concentrations; (c) Sche­
matic diagram using the Cy3 (red dot)-labeled
substrate (blue), 8–17DNAzyme (green), and
SWCNT-COOH for Pb2+ detection; (d) The changes
of cutting yield and fluorescence intensity respec­
tively with the concentration of Pb2+ increasing.
Reproduced from Ref. [107,108] with permission
of Elsevier and The Royal Society of Chemistry.

Fig. 35. (a) Schematic diagram for the detection of Pb2+ using GSH-GNPs; (b) UV–vis absorption spectra of GSH-GNPs after the addition of different concentrations
of Pb2+(0–50 µM); (c) The binding of polymer with Pb2+; (d) Vis absorption spectra of poly -PDA-L after the addition of different concentrations of Pb2+(0–6 µM).
Reproduced from Ref. [109,110] with permission of American Chemical Society and Elsevier.

24
X. Wang et al.
Fig. 36. (a) Schematic diagram for the detection of Pb2+ using GSH-Mn-ZnS QDs; (b) Phosphorescence spectra of GSH-Mn-ZNS QDs with different concentrations of
Pb2+; (c) Schematic diagram for the detection of Pb2+ using citrate functionalized gold nanoparticles; (d) SERS spectra of AuNPs at different concentrations of Pb2+.
Reproduced from Ref. [111,112] with permission of Elsevier.
Therefore, it is particularly important to study and design an efficient
and sensitive method for the detection of Pd2 + . Tang reported a novel
fluorescent probe based on the newly developed 2-(2-hydroxyphenyl)
quinazoline-4 (3H)-one derived enaminone for the detection of Pd2+
[113]. The probe was combined with Pd2+ at a stoichiometric ratio of
1:1, and the fluorescence of the probe was quenched due to the para­
magnetism of Pd2+, as shown in Fig. 37(a). In the PBS buffer (10 mM, pH
7.4) of the probe, the fluorescence intensity of the solution at 538 nm
decreased with the increase of the concentration of Pd2+ (0–1.5 equiv.),
as shown in Fig. 37(b). Chen reported a novel fluorescent probe syn­
thesized by 1H-benzimidazole-2-ethanamine and a rhodamine B moiety
[114]. After the probe was combined with Pd2+, the spiro lactam ring of
rhodamine was opened into the acyclic xanthene form and generated
strong fluorescence, as shown in Fig. 37(c). The fluorescence intensity of
the probe at 569 nm increased linearly with the gradual increase of Pd2+
concentration (0–60 μM), in EtOH/H2O (1:1, v/v) containing the probe,
as shown in Fig. 37(d). Liu reported a novel fluorescent probe based on
surfactant micelle (Triton X-100) coated with 2-phenyl-3-(prop2-yny­
loxy)-4H-chromen-4-one (PPC), which can efficiently detect Pd2+
[115]. Under the action of Pd2+, PPC was degraded to 3-hydroxy-2-
phenyl-4 h-chromen-4-one (HPC), and the fluorescence was enhanced.
However, water molecules in pure water quenched this fluorescence,
while hydrophobic nuclei in Triton X-100 micelles prevented the influ­
ence of water molecules on fluorescence, thus enhancing fluorescence,
as shown in Fig. 37(e). In pure water containing the probe, the fluo­
rescence intensity of the probe at 526 nm gradually increased with the
concentration of Pd2+ (0–60 μM) increasing, as shown in Fig. 37(f).
Compared with fluorescence method, colorimetric method can also
identify Pd2+ effectively. Yang reported a novel colorimetric sensor
based on rhodamine [116]. The combination of the sensor and Pd2+
induced the ring-opening of rhodamine spiro lactam, resulting in
25
Chemical Engineering Journal 417 (2021) 129125
significant color change and fluorescence enhancement, as shown in
Fig. 38(a). In the methanol/PBS (1:1, v/v, pH 7.4) solution of the sensor,
only Pd2+ caused a significant color change after different metal ions
were added. And the absorption intensity of the sensor at 555 nm
increased significantly with the increase of Pd2+ concentration, as
shown in Fig. 38(b). Li designed and reported a new rhodamine-based
propargyl ether derivative (L), as a sensor for the detection of Pd2+
[117]. After the complexation of L and Pd2+, the color of the solution
changed from yellow to pink, which was attributed to the depro­
pargylation of the hydroxyl groups mediated by Pd2+, as shown in
Fig. 38(c). In the CH3CN-H2O containing L, with the increase of Pd2+
concentration, the absorption intensity of L at 394 nm gradually shifted
to 432 nm, and a new absorption peak appeared at 558 nm, which was
gradually enhanced, as shown in Fig. 38(d).
In addition, when some sensors and probes detect Pd2+, there are
fluorescence changes and colorimetric changes at the same time. Li re­
ported a ratio fluorescent probe (RN3) based on 7-substituted coumarin
and rhodamine B to detect Pd2+ by FRET mechanism [118]. As shown in
Fig. 39(a), RN3 emitted green fluorescence in the absence of Pd2+. And
the addition of Pd2+ induced the ring opening of spiro lactam rhodamine
B, which emitted red fluorescence due to FRET process. The absorption
intensity of RN3 in the range of 530–600 nm gradually increased with
the increase of Pd2+ concentration, accompanied by color change, in
methanol–water solution (1:99, v/v, 50 mM, PBS buffer, pH = 7.4)
containing RN3, as shown in Fig. 39(b). With the continuous addition of
Pd2+, the intensity of RN3 at 515 nm gradually weakened, while a new
peak appeared at 575 nm and increased continuously, in methanol–­
water solution (1:99, v/v, 50 mM, PBS buffer, pH = 7.4) containing RN3,
as shown in Fig. 39(c).
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 37. (a) Schematic diagram for the detection of Pd2+ using the probe; (b) Changes of fluorescence spectra of the probe upon the addition of Pd2+ in different
concentrations; (c) Schematic diagram of the complexation of the probe and Pd2+; (d) Fluorescence spectra of the probe after the addition of different concentrations
of Pd2+; (e) Schematic diagram for the detection of Pd2+ using the Triton X-100 coated with PPC; (f) Fluorescence spectra of the probe with different concentrations
of Pd2+. Reproduced from Ref. [113–115] with permission of Elsevier.

3.12. Optical detection of Zn2+ derivative 3-hydroxy-N’-((3 hydroxy-5-(hydroxymethyl)-2-

Zinc is the second richest transition metal element in human body
which plays a very important role in various biological processes of
human body, such as enzyme catalysis, gene expression, nerve signal
transmission and so on. The imbalance of Zn2+ in the body can lead to
serious health problems such as Parkinson’s disease, Alzheimer’s dis­
ease, brain loss, epilepsy and cancer. Due to the extensive application of
Zn in the medical field, automobile hardware electroplating and other
industrial fields, zinc pollution in the natural environment has been
caused. Therefore, it is urgent to design and develop efficient and sen­
sitive sensor for the detection of Zn2+. Dong reported a new Schiff base
oxime sensor (H2L) 1- (2-hydroxy-3 - (2-hydroxybenzylidene) amino)
phenyl) ethenone methyl oxime based on condensation reaction, which
has a high selectivity to Zn2+ [119]. H2L exhibited weak fluorescence
due to its intramolecular photo-induced electron transfer (PET) effect,
but when combined with Zn2+, the intramolecular PET effect was
inhibited, resulting in greatly enhanced fluorescence, as shown in
Fig. 40(a). In the Tris-HCl buffer (MeOH/H2O = 9:1, v/v, pH 7.2)
containing H2L, with the increase of Zn2+ concentration, the fluores­
cence intensity of H2L gradually increased and blue shifted by 14 nm, as
shown in Fig. 40(b). Anand reported a novel vitamin B6 cofactor
methylpyridin-4-yl) methylene)-2-naphthohydrazide (NPY) synthe­
sized by one-pot condensation reaction of pyridoxal with 3-hydroxy-2-
naphthoichydrazide, as a fluorescence probe for the detection of Zn2+
[120]. As shown in Fig. 40(c), NPY combined with Zn2+ through the
imine-N, pyridoxal-OH and carbonyl-O of naphthyl units to form a
complex, which caused the change of fluorescence color. With the
concentration of Zn2+ increasing, the emission intensity of NPY at 530
nm decreased gradually, and a new blue shift band appeared at 475 nm
with gradually increased intensity, as shown in Fig. 40(d).
In addition to fluorescence method, colorimetry can recognize Zn2+
by intuitive color changes. Vidya reported a fluorescein dye containing
imidazole synthesized by the condensation of imidazole carboxaldehyde
with fluorescein hydrazide in methanol, which was used as a colori­
metric probe for the detection of Zn2+ [121]. The combination of the
probe and Zn2+ transformed the spiro lactam ring into an open amide
form, resulting in a significant color change from colorless to greenish
yellow, as shown in Fig. 41(a). In the aqueous DMSO (DMSO/H2O =
1:9) containing the probe, after adding various metal ions, only the
addition of Zn2+ made the probe produce a new absorption band at 505
nm, and the absorption band at 335 nm had a small red shift, as shown in
Fig. 41(b). Lee reported a new type of chemical sensor (Rh6G-Cin) based

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X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 38. (a) The binding mechanism of sensor and Pd2+; (b) Top: The color change of the solution after the sensor reacted with various metal ions (Pd2+ on the far
left); Bottom: The UV–vis absorption spectrum of the sensor with the concentration of Pd2+ increasing; (c) Schematic diagram for the detection of Pd2+ using L; (d)
The absorption spectra of L upon gradual addition of Pd2+(0–5 equiv.). Reproduced from Ref. [116,117] with permission of Elsevier.

Fig. 39. (a) The sensing mechanism of RN3 for Pd2+ detection; (b) UV–Vis spectra of RN3 upon the addition of Pd2+ (0–1.2 equiv.); (c) Fluorescence spectra of RN3
upon addition of Pd2+ (0–1.2 equiv.). Reproduced from Ref. [118] with permission of Elsevier.

27
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

Fig. 40. (a) Schematic diagram for the detection of Zn2+ using the H2L; (b) Fluorescence spectra of H2L with different concentrations of Zn2+; (c) Schematic diagram
for the detection of Zn2+ using the NPY; (d) Fluorescence spectra of NPY with successive incremental addition of Zn2+. Reproduced from Ref. [119,120] with
permission of Elsevier and The Royal Society of Chemistry.

Fig. 41. (a) The mechanism for Zn2+ sensing by the probe; (b) Absorption spectral changes of the probe upon addition of various cations; (c) The synthesis of Rh6G-
Cin and the binding mechanism of Rh6G-Cin-Zn2+ complex; (d) Absorption spectral of Rh6G-Cin with different concentrations of Zn2+. Reproduced from
Ref. [121,122] with permission of Wiley and American Scientific Publishers.

28
X. Wang et al.
Fig. 42. (a) Schematic diagram of the synthesis of UCNPs assembled by chromatin group and its response to Zn2+; (b)Left: The absorption spectral of PAA-UCNPs, 1-
PAA-UCNPs, and 1-PAA-UCNP with Zn2+; Right: The UCL spectral of PAA-UCNPs, 1-PAA-UCNPs, and 1-PAA-UCNP with Zn2+; (c) The UCL spectra of 1-PAA-UCNPs
with different concentrations of Zn2+ (0–0.09 mM). Reproduced from Ref. [123] with permission of American Chemical Society.
on rhodamine, which can effectively detect Zn2+ [122]. Fig. 41(c)
showed the synthesis route of the sensor Rh6G-Cin. It combined with
Zn2+ to form a complex [Rh6G-Cin-Zn2+], resulting in the color of so­
lution changing from colorless to pink, which was attributed to the ring
opening of rhodamine spiro lactam induced by the addition of Zn2+. In
the CH3CN solution of Rh6G-Cin, with the increase of Zn2+ concentra­
tion, a new absorption band was appeared in the absorption spectrum of
Rh6G-Cin at 557 nm, and its intensity gradually increased, as shown in
Fig. 41(d).
Moreover, some special sensors can also realize the effective detec­
tion of Zn2+. Peng reported a novel fluorescent probe synthesized by
assembling lanthanide-doped upconversion nanoparticles (UCNPs) with
chromophores [123]. As shown in Fig. 42(a), NaYF4: Yb/Tm@NaYF4
with blue upconversion luminescence (UCL) was selected as the
upconversion nanocrystals. After UCNPs was modified with polyacrylic
acid (PAA) and compound 1 (abbreviated as 1-PAA-UCNPs), the original
UCL was quenched. In the presence of Zn2+, the UCL signal was restored
due to the coordination between Zn2+ and compound 1. In the presence
of Zn2+, the absorbance of 1-PAA-UCNPs was significantly blue shifted
from 475 nm to 360 nm due to the coordination of Zn2+ with compound
1, resulting in the recovery of UCL signal, as shown in Fig. 42(b). In the
solution of 1-PAA-UCNPs (1 mg/mL), with the continuous addition of
Zn2+, the UCL intensity at 475 nm gradually increased, as shown in
Fig. 42(c).
4. Conclusion and challenges
The optical detection methods of Ag+, Al3+, Cd2+, Co2+, Cr3+, Cu2+,
Fe2+, Fe3+, Hg2+, Pb2+, Pd2+, Zn2+ were reviewed in detail here. The
principles of optical detection were mainly based on photoinduced
electron transfer, intramolecular charge transfer, fluorescence
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Chemical Engineering Journal 417 (2021) 129125
resonance energy transfer, as well as the quantum dots and nano­
particles with specific optical properties, and the optical properties of
rhodamine and its derivatives. The main optical detection methods for
each ion were summarized. Different metal ions were selectively
detected by fluorescence, colorimetric and other spectral changes.
The principle and methods of detection were summarized. The
fluorescence sensor based on PET, ICT and FRET interacted with
different metal ions to cause the fluorescence change of the whole sys­
tem, which was specifically manifested as fluorescence quenching,
fluorescence enhancement or specific change of fluorescence spectrum.
The probe based on quantum dots and nanoparticles can selectively
detect metal ions by interacting with metal ions and causing fluores­
cence or colorimetric changes by itself or surface complexes. The sensor
based on rhodamine and its derivatives can detect metal ions by fluo­
rescence, colorimetric and other spectral changes due to the optical
properties of rhodamine. In fluorescence detection, with the change of
ion concentration, the fluorescence intensity was gradually enhanced or
quenched. In colorimetric detection, the system had significant color
changes in the presence of different ion concentrations. In other spectral
detection, the spectra showed specific changes with the increase of
metal ion concentration.
Up to now, metal ion sensors based on optical methods had been used
in many applications. Such as the detection of heavy metal ions in
environment, water quality and food; Tracking and detection of metal
ions in biological cells; Imaging and detection in the field of biomedi­
cine, etc. There is no doubt that it has a good development prospect and
its application scope will be more and more extensive. At the same time,
it also faces the challenge of how to realize the detection of various
metal ions more effectively, and how to realize the detection in cells and
living bodies better. On the other hand, it will be the development di­
rection in the future to study the mechanism of new detection methods
X. Wang et al. Chemical Engineering Journal 417 (2021) 129125

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2336–2342.

Xiangfu Wang received his PhD degree from Nanjing Univer­

sity of Aeronautics and Astronautics, in 2012. From 2012 to
present, he works as an associate professor in the Nanjing
University of Posts and Telecommunications, China. His current
research concentrates on optoelectronic devices, and sensors
and photoluminescence of rare-earth ions doped nano-
materials and transparent glass ceramics.
Xiaohong Yan received his PhD degree from Institute of Solid
State Physics, Chinese Academy of Science, in 1997. From 2010
to present, he works as a professor in the College of Electronic
Science and Engineering at Nanjing University of Posts and
Telecommunications. His current research concentrates on
transport and manipulation of quantum system and new energy
materials.

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