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Applied Mechanics and Materials Vols.

556-562 (2014) pp 77-80

© (2014) Trans Tech Publications, Switzerland

Carbon Dots for Detection of Metal Ions

Jing Yu1, a, Menglu Wu2,b,Na Song1,c, LiningYang1,d, Jianrong Chen1,e
College of Geography and Environmental Sciences, Zhejiang Normal University,Jinhua Zhejiang
Chuyang Honors College, Zhejiang Normal University,Jinhua Zhejiang 321004,China

Keywords: Carbon dots; Nano-materials; Preparation; Fluorescent; the detection of metal ions

Abstract. Carbon dots are novel fluorescent nano-materials which have easy to preparation. They
have good stability, low toxicity, environment-friendly and are widely used in biological imaging,
biomedical, and biochemical analysis, metal reduction, fluorescence probe and optoelectronic
devices. This paper summarized several new methods for the detection of metal ions with carbon dots.

In the past 20 years, quantum dots as new semiconductor nano-materials were widely used in the
field of life science and environmental detection because of its good optical properties and
biocompatibility which have caused many scholars’ interests. But the synthesis methods of common
semiconductor quantum dots, such as CdSe, CdS, are complex, and they are also expensive. What’s
more, the toxicity of semiconductor quantum dots is very serious, and they will affect the environment
and animals’ health. It is necessary and essential to develop cheap, low toxicity and simple synthetic
Carbon dots were found in recent years which have high fluorescent, they are zero dimension
materials which have three dimensions within the nanoscale. Carbon dots not only have the traditional
semiconductor quantum dots like excellent optical performance, but also have low toxicity, good
chemical stability, good biological compatibility and the advantages of simple synthetic. Compared
with the traditional fluorescent materials, carbon dots as a novel fluorescent nano-material have more
superior performance. So carbon dots have important application value in biological imaging,
optoelectronic devices, biological sensors, fluorescent probe biological detection, medical diagnosis,
metal cation and anion analysis and catalytic fields [1-3].

Carbon quantum dots used in the detection of metal ions

With the improvement of people’s living, people have a higher requirement to the environments.
In recent years, a number of environmental issues caused by high concentration of metal ions attracted
people's attention. So the analysis of metal ions plays a more and more important role. The traditional
methods for detection of metal ions are mainly contain atomic absorption spectrometry (AAS),
inductively coupled plasma atomic emission spectrometry (ICP-AES), ultraviolet spectrophotometry
(UV), anodic stripping voltammetry (ASV). But the traditional detection methods are often
complicated to operate, susceptible to interference and the equipment is expensive, so simple and fast
technologies are necessary to make the detection of metal ions.
Carbon dots have the advantages of non-toxic, strong fluorescence, biocompatibility, stability,
economical, make them become widely used as potential materials. Studies have found that carbon
dots and surface-modified carbon dots have specific response to certain metal ions even has a linear
relationship. So they can be used for the qualitative or quantitative detection of certain metal ions.
78 Mechatronics Engineering, Computing and Information Technology

Detection of Hg2 +
Lu et al. [4] obtained carbon dots by hydrothermal synthesis which using low cost wastes of
pomelo peelasa carbon source. And explore the use of such carbon dots as probes for a fluorescent
Hg2 + detection application based on Hg-induced fluorescence quenching of carbon dots. This sensing
system exhibits excellent Hg2 + sensitivity and selectivity toward Hg2+, and a detection limit as low as
0.23 nM is achieved. The practical use of this system for Hg2+ determination in lake water samples is
also demonstrated successfully. Wu et al. [5] prepared carbon dots utilizing the rhizome of the plant
Giant Knotweed Rhizome, a traditional Chinese medicine, as a carbon source via hydrothermal
method is developed for the first time with a quantum yield of approximately 11.5%. It has been
successfully applied as a novel probe for the detection of Hg2 +. This method has been successfully
applied to the river Hg2 + quantitative detection and the detection limit was 8.2 nmol / L.
Cao et al. [6] found a novel nanohybrid ratiometric fluorescence probe that comprised of carbon
dots and hydrophilic CdSe@ZnS quantum dots has been developed by simply mixing the
blue-emission C-dots with red-emission carboxylmethyldithiocarbamate modified CdSe@ZnS QDs
(GDTC-QDs). The nanohybrid ratiometric fluorescence probe exhibits dual emissions at 436 nm and
629 nm under a single excitation wavelength. Due to the strong chelating ability of GDTC on the
surface of QDs to mercuric ion, the fluorescence of the GDTC-QDs in the nanohybrid system could
be selectively quenched in the presence of Hg2 + while the fluorescence of the C-dots remained
constant, resulting in an obviously distinguish-able fluorescence color evolution (from red to blue) of
the nanohybrid system. The detection limit of this method was found to be as low as 0.1 M.
Furthermore, the recovery for Hg2 + in real samples including tap water and lake water by this method
was satisfying, suggesting its potential application for Hg2 + sensing.

Cu2+ detection
Dong et al. [7] explored polyamine-functionalized carbon dots (CDs) with high fluorescence
quantum yield (42.5%) have been synthesized by the low temperature (<200C) carbonization of citric
acid with branched polyethylenimine (BPEI) in one simple step. The obtained BPEI–CDs are
spherical graphite nanocrystals (average 6.2 nm in size) capped with abundant BPEI at their surfaces
which can capture Cu2+. And the fluorescence of BPEI-CDs significantly inhibited by Cu2+.
Zhao et al. [8] reported a facile strategy for producing highly luminescent, surface-different
nitrogen-doped carbon dots by using different ionic liquids. The surface-different C-Dots show
different selectivity for Cu2+ and Fe3+. For example, ionic liquid [BMIM] [Br] as the precursors for
producing carbon dots without other modification could detect for Cu2+, and other ions such as Ni2+,
Cu2+, Ca2+, Mg2+, Al3+, Pb2+ , Ag+, Cd2+, Co2+, Fe3+ are no respondings.
Gonc'alves et al. [9] used laser etching method to obtain carbon dots which modified with
PEG200 and N-acetyl-l-cysteine (NAC). The fluorescence intensity of the carbon dots is quenched by
the presence of Hg2 + and Cu2+ ions. Because of non-toxic, bio-compatibility, they could be used for
the detection of Hg2 + and Cu2+ in vivo.

Fe3 + detection
Zhu et al. [10] achieved the high fluorescence carbon dots by hydrothermal method with the
fluorescence quantum yield of about 80%. The carbon dots obtained had response to Fe3+. Because
the Fe3+ could react with the phenolic and hydroxyl groups on the surface of carbon dots which cause
the fluorescence quenching. As the low toxicity and biocompatibility, they could be used for detecting
Fe3+ in vivo.
Zhao et al. [8] used the ionic liquid [BMIM] [BF4] as the precursors for producing carbon dots
without other modification could selectively detect Fe3+ while the other ions unresponsive.
Qu et al. [11] synthesized carbon dots by microwave method. The carbon dots solution showed
two different π-π * transition band at 455 and 520 nm that made they had two (blue and green)
Applied Mechanics and Materials Vols. 556-562 79

fluorescence bands. The two fluorescence bands of the carbon dots were attributed to different surface
states that may produce different fluorescent signal responses to external physical or chemical stimuli.
The ratio of blue fluorescence and green fluorescence would change with the adding of Fe3+. And this
could be used for detecting the concentration of Fe3+.

Other metal ions detection

Chang et al. [12] prepared luminescence carbon dots by refluxing the combustion soot of kerosene
in nitric acid whose fluorescence is higher than the unmodified carbon dots. And they were stable at
pH 4.0–7.0. Because the thiourea modified carbon dots, there are lots of functional groups such as
-OH, -COOH, and-NO2 which enhances the adsorption and deposition between metal and carbon
dots. They found carbon dots almost have no response to K+,Na+,Mg2+,Co2+,Al3+,Cr3+, while
Ni2+,Sr2+,Cd2+,Mn2+,Cu2+, Ca2+ and Fe3+ have more obvious response.
Liu et al. [13] synthesized carbon dots with candle soot through hydrothermal reaction in sodium
hydroxide aqueous solution whose surface covered with a lot of hydroxyls. The fluorescence of the
hydroxyls-coated CDs could be selectively quenched by metal ions such as Cr3+, Al3+ and Fe3+, which
is because these metals can easily combine with the hydroxyl groups on the surface of carbon dots.
But this detection method is vulnerable for the influence of interfering ions, so to remove interference
ions before the detection is needed.

Carbon dots as a highly promising nanomaterial have generated much excitement. The advantages
of non-toxic, strong fluorescence, biocompatibility, stability, economical, make them become widely
used as potential materials. But nowadays the reported carbon dots because of complicated synthesis
method and their surface modification studies are also quite limited their application. If we can find a
more simple and green routes synthetic to synthesis, as well as the unique features of the surface
modification then they will have a broader application space in the metal ion detection.

This research was supported by National Natural Science Foundation of China (No.21275131),
and Zhejiang Environmental Protection Bureau (No. 2013A025) and Project of Zhejiang Emerging
Artists Talent (2014R40403)

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