Spectrum of Emerging Sciences, 2 (1) 2022, 66-77
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Spectrum of Emerging
Sciences
Journal homepage: https://esciencesspectrum.com
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Carbon Quantum Dot and Application: A Review
Bhupendra Kande1, Prachi
Parmar1*
1Shri Shankaracharya Professional
University, Bhilai 490020 Chhattisgarh, India.
*Corresponding Author:
E-mail Address: bhupandrak277@gmail.com
Article
available online at: https://esciencesspectrum.com/AbstractView.aspx?PID=2022-1-2-3
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ARTICLE INFO
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ABSTRACT
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Original
Research Article
Received:
25 June 2022
Accepted:
20 July 2022
DOI
10.55878/SES2021-1-2-2
KEYWORDS
Carbon quantum dots, fluorescence, surface Passivation,
doping, sensing, bioimaging, nanomedicine, photocatalysis, electrocatalysis.
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Non-toxic,
fluorescent
carbon nanoparticles or carbon quantum dots or carbon dots, a brand new
category of carbon material, had high interest due to its optical and
fluorescence properties with advantages of eco-friendly, low coast and simple
way of synthesis. Their physical – chemical properties also depend to on functionalization
and surface passivation. From the discovery of non – toxic caron nano
materials, CQDs had numerous applications in different areas like sensing,
biological sensing, vivo and vitro imaging, nano drug, drug carrier, drug
delivery, energy, food industry, agriculture, photocatalysis and
electrocatalysis etc. Here, we described here, the methods of synthesis and functionalization
of carbon quantum dots, properties and applications with future prospects.
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Introduction
Carbon
nanomaterials had extensive studied and received great attention since the
discovery of Buckminster fullerene [1]. Carbon
dots (CDs) consist, graphene, carbon quantum dots (CQDs), carbon nanotubes
(CNTs), carbon nano onions (CNOs) and now it’s a new, important fluorescent
carbon nanomaterial with below than 10 nm in size. These carbon nano materials
had strong luminescent property and highly soluble in aqueous medium [2]. An
experiment designed to understand the procedure of the preparation of long
chain carbon moieties interstellar space, took the place of fullerene. The
characterization of carbon nanotubes (CNTs) was made after this [3]. After a year of the discovery of
CNT, another member of carbon family, carbon nano onion (CNO) or carbon quantum
dot (CQD) was discovered [4], an ideal member of the carbon
allotropes, which made up of concentric graphitic shells [5]. It was first synthesized and
obtained by Iijima in 1980 [6], in vacuum deposited amorphous
carbon films by high resolution TEM (Fig. 1). After discovery CNO, Ugarte
observed a transformation of CNT to CNO [4]. CNO had a quasi-spherical onion
like structure composed of concentric graphitic layers with an inner core,
which either hollow or encapsulated with metal. Because of the ideal structure,
potential applications of CNO for lubricants [7, 8], magnetic storage materials [9], devices [10] and electrochemical capacitors [11]. Carbon
quantum dots (CQDs) had amorphous sp2-conjugated nanocrystalline
core with sp2/sp3 hybridization and consist highly
abundant oxygen groups (like carboxyl, hydroxyl, aldehyde etc) on the surface [12], which consider those nano materials as water soluble
CQDs (Fig. 2). They had wonderful electron donor-acceptor induced
photoluminescence and fluorescence properties. Due to photoluminescence
property, critical to re-size and change the surface chemical groups of carbon
dots [13]. Doping with other elements also used to increase
their properties [14]. Carbon quantum dots or carbon dots, consider as next
generation material in nanomaterial technology which had unique optical and
electronic properties.
In comparison of other quantum dot semiconductors,
organic agents, and other fluorescent sensors, carbon quantum dots (CQD) had
very interesting properties like unique emissions with various fluorescence
excitation, chemical compositions, cheap and simple synthesis,
functionalization of surface and modification, photo-chemical stability [2], which proved CQDs or CDs could be apply in different
technical, medical applications. Carbon dots easily played favourable roles in
applications due to their simple and cheap synthesis, easily water soluble and
biocompatible [15-18]. Those fluorescent carbon nano materials attract the interest of
researchers due to their wide variety of applications like bioimaging,
bioanalysis, sensor, drug delivery, photocatalysis, optoelectronics, electrocatalysis,
fuel cell and many more [19].
Many fluorescent quantum dots like graphene quantum
dots (GQDs) [20-24], polymer dots (PDs) [25, 26], carbon nanotube (CNT) dots [27, 28], nano diamonds (NDs) [29-33], and CQDs synthesised previously. According to
density of states (DOS), quantum dots had distinct materials with compact atoms.
When the size of QD particles decreased upto below the size, bandgap energy
increased. Because of electron-hole radiative recombination, effect of quantum-confinement
did not relevant to carbon dots. Carbon quantum dots consist small size with high
surface defects. Size-dependent optical properties because of various surface
defect and surface to volume ratio [34].
Here, we described the synthesis, characterization and properties of carbon
quantum dots with their application in various areas.
Fig.1. Spherical particles of graphitic carbon nano-onions found in the
amorphous carbon films, (a – d). (scale bar 2 nm) [6]
Fig.2. Structure of carbon quantum dots (CQDs) [35].
2. Synthesis of nano carbon quantum dots (CQDs):
Carbon
quantum dots (CQDs), serendipitously determined in the process of single wall carbon nano tubes
(SWCNTs) purification [36].
Suspension of SWCNTs on gel electrophoresis, differentiated into three
important classes of materials, included a fast moving band of high fluorescent
material which showed size dependent
fluorescent properties. It was first
discovery of carbon nanoparticles or carbon dots. CDs contain contained lower
amount of carbon with high oxygenated groups, also called carbogenic nanodots [17].
Baker et al. described different synthesis process and properties of
carbon nanoparticles. Synthesis
of CDs divided into two classes of methods; top-down and bottom-up. Top down
method included synthesis of nanoparticles from large carbon structure. And other
hand, in bottom-up method CDs prepared by molecular precursor.
2.1
Top-down methods:
Firstly,
fluorescence nano materials CDs stable graphene sheets, carbon fibres, CNTs,
CNOs, carbon soots etc, classified as following methods:
(i) Arc-discharge
method: Bottini et al. [37]
used electric arc technology to synthesized luminescence CDs through pristine
CNTs and oxidized (with nitric acid) CNTs.
(ii)
Laser ablation method: Sun's et al. [38]
synthesized CDs via Q-switched Nd : YAG laser ablation at 900 °C and 75 kPa, by
graphite and cement mixture hot pressing. Carbon dot’s surface were passivated
via diamine-terminated oligomeric PEG1500N with passing acid; which
attached with organic moieties on the surface of CDs obtained (Fig. 3a).
(iii)
Hydrothermal cutting method: Pan et al. [39]
synthesized CDs via hydrothermal method,
in it cutting graphene sheets into 10 nm sized functionalized graphene quantum
dots. These functionalized GQDs exhibited blue fluorescence which induced
through edge effect.
(iv)
Chemical oxidation method: Zhou et al. [40]
reported that carboxylic group attached onto carbon nano materials or GQDs
surface, synthesized through oxidation reaction under UV irradiation, in between
graphene oxide (GO) and Fenton reagent (Fe2+/Fe3+/H2O2).
(v)
Electrochemical oxidation method: Zhou et al.
described [41],
synthesis of CD through multiwall carbon
nanotubes which fabricated by electrochemical oxidation method (Fig. 3b).
Fig.3. Schematic view of synthesis of (a) fluorescent
carbon nano dots (CDs) via laser ablation and attached with PEG on the surface [38];
(b) GCDs synthesized by exfoliation in ionic liquid [42].
TEM image of graphene quantum dots and illumination the aq. Solution of carbon
dots by UV lamp.
Fig. 4. Schematic view of bottom-up synthesis of
carbon dots with different temperature and relationship between different
products [43].
2.2 Bottom – up methods:
CDs were developed by bottom – up methods by
self-assembling molecular precursors, which used to control and well-defined
properties of molecular weights, particle sizes, morphologies, and optical. Oxygenated,
carboxy(-COOH) and hydroxyl (-OH) groups, used as carbon precursors and amine, amido
groups used as nitrogen precursors. The fluorescence colour and quantum yield
dependent upon ratio of carbon and nitrogen precursors. According to different
synthesis methods, bottom-up classified into
following categories.
(i) Thermal decomposition: Wang et al. [44] reported, fluorescent, amorphous CDs
prepared by coordinating solvent. It attached via methoxy silyl groups which exhibited
high quantum yield 47% and 0.9 nm diameter.
(ii) Combustion: Vinci et
al. [45] described a low-cost process synthesis of carbon nano
particles based on soots and it also obtained from combustion of paraffin oil.
(iii) Hydrothermal synthesis: Yang et al. described the amino attached fluorescent
CDs obtained from chitosan via hydrothermal
carbonization [46].
(iv) Microwave synthesis: Liu et al. described the preparation of carbon
dots through mechanism of one-step microwave assisted and polyethyleneimine attached
onto surface of carbon materials [47] (Fig. 4).
(v) Supported synthesis: Bourlinos et al. described, carbon dots (CDs)
obtained from ion-exchanged NaY zeolite via thermal oxidation and as resultant spherical
carbon nano dots or particles attached onto the zeolite surfaces [48].
3. Properties of Carbon Dots (CDs)
3.1 Structures
Carbon dots had graphitic in-plane lattice spacing
0.18–0.24 nm and 0.32 nm spaces of interlayer (Fig. 5a). CDs varied on raw
materials and synthetic method and
composed of carbon crystalline cores similar to sp2 carbon
and amorphous clusters (Fig. 5b) [49-51]. The crystallinity degree of carbon dots lesser than graphene
quantum dots, and some CDs had diamond like
sp3 hybridisation of carbon [52]. According to Raman spectroscopy, two peaks observed around
1350 and 1600 cm−1, indicate disorder of sp2 carbon and
crystalline graphitic carbon, respectively [51, 53]. At framework of carbon, different functional groups
attached onto the surface of CDs via surface passivation or functionalization.
It protect the surface of CDs and enhance their luminance property .
3.2
Fluorescence
The origin of photoluminescence emission of
carbon nanoparticles had centre of interest. Depending upon the experimental and
theoretical results three factors responsible for the origin of PL emission, as
follows: (1) the presence of triplet ground state of carbene (σ1π1)
at zigzag sites [39, 54]; (2)
Fig. 5. (a) HR TEM images of carbon dots (CDs);
(b) schematic view of carbon dots with sp2 carbon [53].
the presence of triplet ground state of carbene
(σ1π1) at zigzag sites [39, 54]; (2) the presence of localized finite – sized sp2
clusters within sp3 matrix, lead to confinement of π – electrons.
Radiative recombination of electron – hole pairs in sp2 clusters,
rise the PL emission [54-56]; (3) Surface passivation of carbon moiety by organic
molecules or by hydrophilic groups which introduced by covalent
functionalization or by oxidation reaction respectively. In presence of oxygenated
functional groups, suggested for observed PL emission from carbon nanoparticles
[38, 57], as like surface – oxidized silicon nanocrystal [58]. the oxygen containing functional groups can
passivate the surface by extended hydrogen bonding [59, 60].
Presently, mechanism of photoluminescence
property for CDs/CQDs, received much attention and interest for applications in
different fields. Regarding photoluminescence property of CDs, there many
theories had proposed, like nanoscale dependence, dependence of excitation
wavelength and dependence of surface group. Li's group [61] reported a electrochemical synthesis CDs within
1.2–3.8 nm size range and resultant size-dependent photoluminescence carbon
nanoparticles; small size nano carbon dots (1.2 nm) get emitted under UV light
(350–450 nm), medium-size carbon dots (1.5–3 nm) get emission spectra at 400–
700 nm wavelength and large size carbon dots (3.8 nm) get emission spectra at NIR
range. Bao group [62] reported the size of CDs observed through
electrochemical methods with various potential and at constant excitation
wavelength and decreasing size of CDs the emission spectra showed red-shift [61]. Here, the degree of surface oxidation, CDs had
essential and much important in photo-luminescence properties. Red
fluorescent carbon dots had higher potential, exhibited high oxygenated surface
states. Thus, red shift of emission peak responsible for surface states.
In chemical processes, the surface of carbon dots,
modified through attached oxygenated functional groups and the
photoluminescence property depend on it, which cause of higher quantum yield
with high emission spectra observed
respectively. At high surface oxidation degree, increase the surface
defects and red shift emission observed. Ding et al. [63] described,
the preparation of carbon dots via hydrothermal process with their PL property,
which showed a relation in between the surface of CDs, with degree of oxidation.
Zheng et al. [64]
synthesized, the green colour fluorescence carbon dots
Fig. 6. Schematic view of photoluminescence (a)
CQDs; (b) carbon nano dots as fluorescent nanodots [65].
through graphite via oxidation reaction with nitric
acid. After reduction of CDs with NaBH4, blue colour emission
observed. Due to reduction of CDs, quantum yield changed from 2% -24% and
emission spectra also observed from 520 nm to 450 nm.
Thus, the fluorescence property of CDs, depend upon
quantum confinement effects; i.e., the size of CDs decrease, the energy gap
between the valence shell and conduction band enhanced and the emission spectra
also decreased. According to previous studies, the fluorescence of carbon dots
didn’t cause of single factor but it raised because of combine of various
causes like size, surface passivation, functional groups, and heteroatoms [62].
According to Fig. 6, PL emission of carbon
quantum dots occur when trap states present in the bandgap [65]. The PL properties of CDs or CQDs attracted interest
due to their applications like fluorescent imaging, nanocarriers drug delivery
and controlled release method, analytes detection, biosensors,
optical/electrochemical sensors, light- emitting diodes, energy conversion and
storage, electro and photocatalysis [66].
3.3 Surface Passivation and Doping
Pristine carbon dots, called as undoped carbon dots. After the initial
synthesis, it had exposed carbon and oxygen sites [53]. Burlinos et al. reported, the
functionalization of CDs through one-step pyrolysis, which had thermal
decomposition process, citric acid mix with different amines. In it, citrate
provided the carbon core, whereas the amines were attached as functional groups
on the CDs [67]. Yang group described a method for
large-scale synthesis of heavy metal-doped fluorescence CDs [68]. Hetero-atom (N, S, or Se) based doped CQDs
obtained through one-step hydrothermal reduction and in situ doping treatment.
Heavy metal-doped CQDs had 1 - 6 nm size
with their photoluminescence property at various emission wavelength which
depended on electro-negativity of heteroatom (Fig. 7). Thus, N- and S doped
carbon dots were highly sensitive for detection of Cu2+ and Hg2+, respectively [68].
Pristine graphene material had zero-band gap
which important for optoelectronic properties including their fluorescence
properties [69]. Chemical functionalization of graphene changed the
band gap and it shifts at their Fermi level [70]. If graphene doped with more electronegative elements
like nitrogen, a blue shift emission observed, on the other hand if it
Fig. 7. Relation between electronegativity of
heteroatoms and emission wavelength (λem) of doped carbon dots [68].
Fig. 8. Schematic view of microwave bottom-up
method for synthesis of green-GQDs and blue-GQDs [71].
doped with less electronegative elements
like sulfur, a red shift fluorescence
observed [68]. In general, after attachment of oxygenated groups
like epoxy, hydroxyl functional groups, on surface of sp2-hybridized
carbon material, wide bandgap observed. N-doped carbon dots (N-CDs) prepared
with organic molecules like hydrazine, urea, hexamethylenetetramine, diethyl
amine, ethanolamine, and ethylenediamine, which increased electron density and
reduced the work function of the CDs, cause of blue shift emission. Umrao group
described a sequential bottom up method to synthesized blue and green
fluorescent GQDs; g-GQDs and b-GQDs (Fig. 8) [71]. Green fluorescent of g-GQDs formed at initial stage
and final product was blue fluorescent b-GQDs, observed respectively. It showed
only one emission peak at 433 nm. Thus, two-step microwave irradiation method decreased
size of graphene quantum dots.
4. Application:
4.1 Chemical sensing
Among many application fields of carbon quantum dots,
chemical sensing one of the interesting use. Heavy metal detection like Hg2+
utmost important due to harmful effect at environment and human health. Due to non-toxic,
water soluble, high photo and chemical stability property, carbon quantum dots
used for chemical sensing.
Firstly, CQDs used as chemical sensor for specific
detection of Hg2+ in aq. solutions [72-77]
and live cells [78].
Goncalves et al. described about the emissions of CQDs for detection of
Hg2+ [79, 80].
Yan et al. described, Hg2+–CQD composite use to detect Hg2+
ion within live cells [78].
They synthesized two types of CQDs; (CQD-1) with 1,2-ethyldiamine and
(CQD-2)N-(b-aminoethyl)-g-aminopropyl which had high quantum yield upto 65.5
and 55.4%, respectively and also describe the
quenching of CQD-1 and CQD-2 through Hg2+ (Fig. 9).
Furthermore, carbon nano materials used as highly sensitive fluorescence moiety
for sensing of minute amount of Hg2+ in both aqueous medium and
living cell. Some fluorescence were quenched but after adding strong chelating
agent like EDTA, it could be recovered, which proved those CQDs had reversible
fluorescent moieties [78].
Similarly, other elements like Cu2+ [81],
Fe3+ [82],
Pb2+ [83],
Cr(VI) [84]
and Ag+ [85]
also detected by carbon quantum dots.
Along with the sensing of metal ions, CQDs also able
to detect pH [85, 86],
C2O42- [87],
PO43- [88],
CN- [89],
F- [90],
S2- [91],
ClO- [92],
I- [93]
and NO2 gas [94].
Moreover, small organic molecules like ascorbic acid [84];
and 4-nitrophenol [95],
quercetin, 2,4-dinitrophenol and 2-amino-3,4,8-trimethyl-3H-imidazo [4,5 f] quinoxaline
[96]
also sensed by CQDs via fluorescence spectra. CQDs exhibited good
chemi-luminescence [97]
and electrochemiluminescence [98]
property. thus, many groups developed for chemi-luminescent sensing for NO2-
[99]
and Co2+ [100]
and electro chemi-luminescent assays for minute amount of penn-POM/CNO hybrid composite, detected toxic metanil
yellow food colour upto 3.83 nmol ml-1 (Fig. 10) [102].
Fig. 9. Comparison of UV-visible (black) and fluorescence
spectra of (a) CQD-1 and (b) CQD-2 in absence (blue) and presence (red) of Hg2+
in aq. solution; fluorescence spectra of (c) CQD-1 and (d) CQD-2 in aqueous
solution with presence of 20 mM concentration of different metal ions at 360 nm
wavelength [78].
Fig. 10. Fluorescence change of various concentration
of metanil yellow food colour in presence of constant 3.43 x 10-6
mol ml-1 aq. solution of the Ln-POM/CNO nanocomposite [102].
4.2 Bioimaging
CQDs/CDs were chemically and photochemically stable
including had interesting optical properties as well as environmentally
friendly. Thus, CQDs used in biological
systems with vivo and vitro system [103].
Central core of carbon were non-toxic but because of surface passivating
on surface CQDs showed cytotoxicity also
[104].
After using CQDs, did not observed
any abnormality in harvested organs [105].
In bio sensing, different amount of CQDs used for treating cell viability. At
1.8 mg ml-1 concentration of CQDs cell viability greater than 95%.
This showed that CQDs were highly biocompatible than other semiconductor
quantum dots [106].
Organic dye composite with CQDs were highly effective luminescent
moiety for H2S. With FRET method, in the presence of minute amount
of H2S, blue to green fluorescence observed [107].
Previously described that H2S able to penetrate cell membrane by
diffusion process [108].
Here, fluorescence microscope used for observation property of CQDs with organic
dye composite and it also changed physiology of H2S in living cells.
According to Fig. 11, the fluorescence images of HeLa and L929 cells, incubated
with composite of CQDs before and after treated with H2S. The
intracellular fluorescence of organic dye composite with CQD stained cells and
exposed to H2S within 30min at 37 °C, green fluorescence observed,
which showed organic dye composite with CQDs had fluorescence for sense
different level of H2S in live cells [107].
It was well known, CQDs able to exhibited
multicolour emissions, which were used as labelling agents and also allowed chemists
to use different excitation and emission wavelengths [109]. According to Fig. 12, the emissions property of CQDs
were clearly visible [110]. At various wavelengths light were emitted with excitation
of different wavelengths. HepG2 cells incubated with 4,7,10-trioxa-1,
13-tridecanediamine-passivated CQDs, which showed multicolour
Fig. 11. Emission images of live cells which
treated with organic dye composite with CQDs, before (A, D) and after
incubating (B, E), in presence of 100 mM H2S (C, F) [107]
Fig. 12. (a) Absorption and fluorescence emission spectra
of carbon quantum dots at various excitation wavelength; fluorescent images of
MCF-10A cells which treated with CQDs and excite on (b) at UV, (c) at blue and
(d) at green light [110].
emissions after excitation at various
wavelengths [111]. Synthesis of CQDs from juice of sugar cane showed various emissions, at various
excitation wavelength and also observed different colour fluorescence images in
bacterial and yeast cells [103]. Ray and co -worker described that surface
passivation not necessary for high emission, which necessary for cell imaging [112]. Here, CQDs synthesized from thermal combustion of
soots with acid treatment and also translocate Ehrlich ascites carcinoma cells [112].
Sarkar et al. reported fluorescence images of
life-cycle of Drosophila malenogaster of
through CQDs [59].
4.3 Biosensing
Carbon quantum dots also used in biosensing for
antibodies and gene-recovery fragments. CQDs specially
used as
Fig. 13. Schematic view of nucleic acid LFA (NALFA) [113].
fluorescent labels for immunoassays. According to
Posthuma-Trumpie and co-workers [113],
CQDs use as lateral flow and microarray immunoassays. It were cheap in coast
but more stable and more sensitive thus used as fluorescent labels. CQDs were
highly sensitive as fluorescence moiety in lateral flow assays (LFAs) [114].
Carbon quantum dots also showed sensitivity upto picomolar range [115].
Nucleic acid LFA (Fig. 13), differentiate as the biosensing labels on amplicons
which identified their unique antibodies respectively and emission signals also
observed. CQDs also used as fluorescent moiety for identify small bio molecules
like anti-bacterial, anti-viral moieties, including combat those bacterial and
viral diseases [116].
4.4
Nanomedicine
Carbon quantum dots had great attraction in the field
of nanomedicine because of its non-toxic nature [117].
it was demonstrated by toxicity experiments in mice. Where it injected through
CQDs in vain, which observed upto four weeks and resultant after four weeks, internal
organs and their functions did not affected, respectively. CQDs had
bio-comparability property which supported to prothrombin time assays in
plasma. Thus, it showed that CQDs did not lead for blood coagulation [110].
Bechet et al. demonstrate the application of CQDs
in photodynamic therapy. It were clinical treatment usually used in tumours [118].
In tumour tissue, it used as photosensitizers, with a specific wavelength, and
also generate singlet oxygen species which cause of cell death. Carbon quantum
dots had inhibition effect on MCF-7 and MDA-MB-231 cancer cells (Fig. 14) [110].
CQDs also generate reactive oxygen species (ROS) which make it an ideal photosensitizers
[116, 119],
including also able to combat highly infectious bacterial and viral strains in
presence of light and air to cure dangerous diseases such as New
Delhi metallo-betalactamase-1 (NDM-1) producing Enterobacteriaceae (Fig. 15) [116]
and novel corona virus. Besides that, CQDs also used as nano drug carriers and
fluorescent tracers, which able to regulate release of drugs. Sarkar et al.
described carbon nano material or CQDs as nanocarrier for alzimer via pH
dependent the “open and close” target system [120].
Fig. 14. Fluorescence images of mice with tumour [76].
Fig. 15. Under visible
light, rGO activity on Enterobacter sp.: in presence of air (a) absence of rGO,
(b) with presence rGO, (a and b); in argon (c) absence of rGO and (d) presence of rGO, (c and d) [116].
Fig. 16. Under visible light, demonstration of catalytic
mechanism of TiO2 – CQD nanocomposites [61].
4.5 Photocatalysis
Now present days, photocatalytic methods get high
interest as green alternatives in organic synthesis [121-125].
The very famous and important photocatalyst TiO2 which use for removing
of organic pollutants and also used in water splitting and generation of H2
[125].
Due to bandgap of TiO2 exist in UV region (3.0–3.2 eV) and TiO2
used only less than 5% of sunlight. Nanocomposite of CQDs-TiO2 used
the full spectrum of sunlight that increased efficiency, in this experiment
methylene blue (MB) used as ideal compound (Fig. 16). Li et al. reported
that under visible light, CQDs-TiO2 nanocomposites, degraded complete
MB (50 mg mL-1) within 25 min as photocatalyst, where only MB
degraded upto 5% by TiO2 [61].
4.6 Electrocatalysis
These days, production of
energy for example fuel cells and fuel production, oxygen reduction reaction
(ORR) and oxygen
evolution reaction (OER) attracts
interest by scientists. Electrocatalysts generally used to increase kinetic
activity of ORR. Unfortunately, platinum-based electrocatalysts which were high
in cost, forced scientists to find out replacement of platinum, or
non-platinum-based electrocatalysts for better efficiency of electrocatalytic than
platinum-based electrocatalysts. Small sized CQDs, which had good electrical
conductivity and stability, made it ideal electrocatalytic materials for ORR.
Previously, doped nitrogen atoms with carbon nano materials play an important
role to enhanced their electrocatalytic activities toward ORR [126]. Li and co-workers [127] described, the synthesis of N-CQDs with
oxygenated functional groups through electrochemical methods, electrocatalytically
active. Potential of ORR was -0.16 V (vs. Ag/AgCl), which resemble to electrocatalysts
of commercial platinum-based (Fig. 17).
Later, similar observations
get by Yan group [128] and Liu group [129] with nitrogen doped CQDs, which prepared by same
methods. In comparison between absence of CQDs and nitrogen doped CQDs
(N-CQDs), enhanced electrocatalytic property of nitrogen doped CQDs were related
with nitrogen doping effect in presence of methanol. The observed
electrocatalytic activity were responsible for nitrogen with graphene [130]. Zhu et al. described CQDs and its electrocatalytic
activity, which synthesized by natural biomass – soy milk [131]. It had similarity with N-CQDs for obtained oxygen
and enhanced electrochemical reduction reaction.
Fig. 17. Spectra of cyclic voltammetry of (a) nitrogen
doped CQD/graphene; (b) commercial Pt/C on GC electrode at N2-saturated
0.1 M KOH, O2-saturated 0.1 M KOH and O2-saturated 3 M CH3OH
solutions [127].
Fig. 18. Demonstration of Gram plants after 10 days, (a) plants
grown (v-1 to v-5) treated with non-toxic wsCNTs; without treated blank (v-6)
(b) after 10 days, plant growth measurements of gram plants (b-1, b-2) without
wsCNTs, (b-3, b-4) treated with 200 μL wsCNTs and (b-5) treated with 100 μL of
wsCNTs respectively [132].
4.7 Agriculture
Water soluble CQDs,
take a very important part in field of agriculture, where supply of
water difficult and the supply of water crucial which requires maximum conservation. Sarkar and group [132] developed
wsCNTs from mustard oil and described, the effect of water soluble CNTs in plant
growth of gram seeds (Cicer arietinum) with or without conventional
fertilizers. It had short life cycle and their vascular bundles arranged in
rings. Continuously
used non - toxic wsCNTs enhance the growth rate of plant. Firstly, plant seeds
were grown without CNTs in 5.0 ml distilled water. Then, 100 μL wsCNT used in 5.0 ml distilled
water; next, 200μL of wsCNT used in 5.0
ml double distilled water. Monitored the whole system upto 10 days in comparison
of root length, shoot length, number of
roots and uptake of water by gram plants. Results showed the enhancement in
plant growth (Fig. 18) [132] .
5.
Conclusion
Since from the discovery of
carbon nano materials had numerous, cheap and efficient way to prepare
fluorescent CQDs. The defects of CQDs played an important role in fluorescence
emissions at excitation of different wavelength. The physicochemical properties
of fluorescent CQDs, developed highly sensitive sensing property with their
chemical stability. CQDs take an important part in analytical and biological
science. Applications of CQDs in the field of sensing and bioimaging increased
the sensitivity and selectivity. CQDs, an ideal nano material for biomedicine
for their use in imaging and nanomedicine. The non - toxic and chemically
stable CQDs had great advantages for vivo biomedical applications. It also had
ability to develop new diagnostics, therapeutics and preventives which can be
use in diagnose and treat cancer and other serious diseases. CQDs also
used in drug delivery which more
prominent than nano spheres made by biodegradable polymers [133]. CQDs able to generate ROS, which could be combat
harmful and dangerous bacterial and viral strains like NDM-1 producing Enterobacteriaceae and corona virus. It also used in photocatalytic and
electrocatalytic applications including fuel cell, hydrogen evolution, water
splitting etc. CQDs also used in food industry for adulteration of toxic food
colours at nano level. It also helpful in agriculture for increase plant
growth.
Although, carbon quantum
dots already proved the it take a very impotent part in nanotechnology for
development of assays, sensors, bioimaging agents, drug carriers, phototherapy,
photocatalysis and electrocatalysis, agriculture, food industry, combat pathogens,
water treatment etc. it also take part in the area of bioimaging and
biomedical. Thus, CQDs recognised by researchers as materials science,
synthetic chemistry, drug delivery, nanomedicine and clean energy. Research on
cheap and non-toxic CQDs also proved as ideal implement and bioinformatics for
diagnosis, prevention and treatment of dangerous diseases like cancer,
Alzheimer, diabetes etc pathogenic diseases NDM -1, corona etc, which did not
have any cure; including energy storage and conversion, food industry.
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