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Baker
DOI: 10.1002/anie.200906623
Nanotechnology
Angewandte
Chemie
6726 www.angewandte.org 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2010, 49, 6726 – 6744
Carbon Nanodots
Angewandte
Chemie
Similar to its popular older cousins the fullerene, the carbon nano- From the Contents
tube, and graphene, the latest form of nanocarbon, the carbon
1. Introduction 6727
nanodot, is inspiring intensive research efforts in its own right. These
surface-passivated carbonaceous quantum dots, so-called C-dots, 2. Synthetic Methods 6729
combine several favorable attributes of traditional semiconductor-
based quantum dots (namely, size- and wavelength-dependent lumi- 3. Physical and Chemical
nescence emission, resistance to photobleaching, ease of bioconju- Properties 6734
gation) without incurring the burden of intrinsic toxicity or elemental 4. Applications 6740
scarcity and without the need for stringent, intricate, tedious, costly, or
inefficient preparation steps. C-dots can be produced inexpensively 5. Graphene-Derived Luminescent
and on a large scale (frequently using a one-step pathway and Carbons 6741
potentially from biomass waste-derived sources) by many approaches,
6. Summary and Outlook 6743
ranging from simple candle burning to in situ dehydration reactions to
laser ablation methods. In this Review, we summarize recent advances
in the synthesis and characterization of C-dots. We also speculate on
their future and discuss potential developments for their use in energy
conversion/storage, bioimaging, drug delivery, sensors, diagnostics,
and composites.
1. Introduction
Carbon nanodots (C-dots) constitute a fascinating class of Ironically, C-dots were discovered serendipitously by
recently discovered nanocarbons that comprise discrete, researchers purifying single-walled carbon nanotubes
quasispherical nanoparticles with sizes below 10 nm.[1–23] (SWCNTs) fabricated by arc-discharge methods.[1] When
Typically displaying size and excitation wavelength (lex) processing a suspension of these SWCNTs by gel electro-
dependent photoluminescence (PL) behavior, C-dots are phoresis, much to these researchers surprise, the suspension
attracting considerable attention as nascent quantum dots, separated into three distinct classes of nanomaterials, includ-
particularly for applications in which the size, cost, and ing a fast-moving band of highly luminescent material. They
biocompatibility of the label are critical. Advances in this area further found that this carbonaceous material could be
are appearing frequently, with a number of significant break- fractionated into a number of components with size-depen-
throughs taking place within the last couple years. Several of dent fluorescent properties. While certainly not the SWCNTs
the seminal advances made to date are illustrated in Figure 1. they were looking for, the researchers went on to analyze the
Typically, C-dots contain many carboxylic acid moieties at basic properties of this then-unknown fluorescent nanomate-
their surface, thus imparting them with excellent water rial, with the astute assertion that they “promise to be
solubility and the suitability for subsequent functionalization interesting nanomaterials in their own right”.[1] Since their
with various organic, polymeric, inorganic, or biological initial discovery, these materials have come to be known as
species (Figure 2). Their well-defined, nearly isotropic carbon dots or carbon nanodots, and have been studied and
shapes together with their ultrafine dimensions, tunable fabricated by numerous research groups hoping to glean a
surface functionalities, and the sheer variety of simple, fast, better understanding into the origins of their photophysical
and cheap synthetic routes available provide an encouraging behavior, achieve better synthetic routes, and develop novel
technological platform for C-dot emitters as alternatives to applications for these emergent nanomaterials.
other nanocarbons (fullerenes, nanodiamonds, carbon nano- Another carbon-based nanomaterial similar in size and
tubes) in a host of applications. Most notable, however, is surface functionality to the C-dot is the nanodiamond, which
their potential as replacements for toxic metal-based quan- has been recently reviewed.[30–33] For clarification purposes,
tum dots (QDs) currently in use. As a consequence of the one should take care in distinguishing these two types of
health concerns and the known environmental and biological
hazards of QDs, C-dots are at the center of significant
research efforts to develop low-toxicity, eco-friendly alter- [*] Dr. S. N. Baker, Dr. G. A. Baker
Oak Ridge National Laboratory
natives that have the desirable performance characteristics of
1 Bethel Valley Road, Oak Ridge, TN 37831-6201 (USA)
QDs. C-dots have already demonstrated their viability in a Fax: (+ 1) 865-574-6080
variety of applications since they display PL properties E-mail: sb3@ornl.gov
reminiscent of those of QDs[24–26] and surface-oxidized Si bakerga1@ornl.gov
nanocrystals.[27–29] Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.200906623.
Angew. Chem. Int. Ed. 2010, 49, 6726 – 6744 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 6727
Reviews S. N. Baker and G. A. Baker
Figure 1. Timeline showing recent activity regarding C-dots in the literature. Reproduced from Refs. [1, 2, 7, 9, 12, 17, 18, 20].
Sheila Baker was born in the US in 1974. Gary Baker studied chemistry at SUNY
She obtained her BS in Chemistry in 1997 Oswego followed by the University at Buffalo
at Georgia Southern University, , and then where he earned a PhD in 2001 in the
her PhD in 2002 (F. V. Bright) at the group of professor Frank V. Bright. After
University at Buffalo. After a postdoctoral completing Director’s and Frederick Reines
stay at Los Alamos National Laboratory Postdoctoral Fellowships at Los Alamos
(T. M. McCleskey) and a one-year stint at a National Laboratory, he joined the research
biotech start-up, she joined Oak Ridge staff at Oak Ridge National Laboratory as a
National Laboratory in 2008. Her primary Wigner Fellow in 2005. His research interests
research interests include sub- and supercrit- focus on solar cells, ionic liquids, and smart
ical fluids, designer ionic liquids, magnetic nanomaterials. He recently received a Presi-
and morphologically unique nanostructures, dential Early Career Award for Scientists and
and materials for next-generation photovol- Engineers (PECASE) in 2008.
taics, batteries, and supercapacitors.
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Carbon Nanodots
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erties, with some discussion of preliminary toxicological baking, curing, and annealing under an argon flow.[12] A Q-
evaluation. Their application as labels for bioimaging is the switched Nd:YAG laser (1064 nm, 10 Hz) was then used to
topic of Section 4. Section 5 provides an account of the recent ablate the carbon target in a flow of argon gas carrying water
observation of PL in graphene-based materials. It is our aim vapor at 900 8C and 75 kPa. The sample was then heated at
that the synthesis of this knowledge will offer valuable insight reflux in 2.6 m HNO3 for up to 12 h to produce C-dots ranging
but, moreover, we hope to inspire research into the origins of from 3 to 10 nm in size. At this point, the C-dots were surface
the unique properties of this emergent class of nanocarbons passivated by polymeric agents such as diamine-terminated
and to encourage their exploration in a multitude of exciting poly(ethylene glycol) (PEG1500N)[12] or poly(propionyl-
areas, ranging from medical diagnostics to catalysis and ethylenimine-co-ethylenimine) (PPEI-EI, with an EI fraction
photovoltaics. of ca. 20 %)[4] and then purified by dialysis against water,
followed by a centrifugation step to yield purified C-dots in
the supernatant liquid.[11] A slightly modified version of this
2. Synthetic Methods procedure using 13C powder and more rigorous control
resulted in 13C-enriched C-dots 4–5 nm in diameter which
Approaches for synthesizing C-dots can be generally exhibited a PL quantum yield (QY) of up to 20 % with
classified into two main groups: top-down and bottom-up excitation at 440 nm.[16]
methods. Top-down methods consist of arc discharge,[1] laser A single-step procedure that integrated synthesis and
ablation,[4–6, 11, 12, 14–16] and electrochemical oxidation,[8, 17–19] passivation was reported by Hu et al. (Scheme 1).[6] In this
where the C-dots are formed or “broken off” from a larger approach, a pulsed Nd:YAG laser was used to irradiate
carbon structure. Bottom-up approaches consist, for example,
of combustion/thermal,[2, 3, 7, 10, 13] supported synthetic,[2, 9] or
microwave methods[20] during which the C-dots are formed
from molecular precursors. Typically, their surfaces are
oxidized by nitric acid (HNO3) and further purified by using
centrifugation, dialysis, electrophoresis, or another separation
technique. Scheme 1. One-step synthesis of C-dots in PEG200N solvent. Repro-
duced from Ref. [6] with permission.
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Reviews S. N. Baker and G. A. Baker
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Carbon Nanodots
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or a glass plate atop a burning candle. The collected soot was by using this approach. This important point is further
then mixed with 5 m HNO3 and refluxed for 12 h to oxidize discussed in Section 3.
particle surfaces. After cooling, the formed C-dots (< 2 nm) This candle-burning approach was also followed by Ray
were collected by centrifugation or dialysis and further et al. [10] The candle soot was similarly collected and refluxed
subjected to polyacrylamide gel electrophoresis (PAGE) with 5 m HNO3 for 12 h. It was found that refluxing for under
fractionation. Similar to the observations of Xu et al.,[1] the 12 h gave a lower C-dot yield, while refluxing for longer
C-dot electrophoretic mobilities were correlated with the PL periods resulted in no appreciable gain in yield. The particles
emission color, with faster moving C-dots emitting at shorter suspended in solution were then precipitated by adding
wavelengths (Figure 4). The C-dots were found to be roughly acetone and centrifuging at 14 000 rpm for 10 minutes. Size
separation was then performed in a water/ethanol/chloroform
solvent mixture combined with high-speed, stepwise centri-
fugation. Supernatant was collected at spinning speeds of
4000, 5000, 6000, and 8000–16 000 rpm, in each case starting
with the supernatant collected from the previous step. The
supernatant obtained with centrifugation at 8000 rpm, for
which precipitate was no longer observed, contained C-dots
with particle sizes in the 2–6 nm range. Precipitates at lower
centrifugation speeds contained large carbon nanoparticles of
201–350 nm in size. The 2–6 nm C-dots were found to be
graphitic in nature, according to lattice spacings in HRTEM
images, and exhibited high PL quantum yields in comparison
with the larger particles found. XPS compositional analysis,
while insensitive to hydrogen, revealed the presence of C, O,
and N at 59, 37, and 4 atom %, respectively.
In a further study, Chen and co-workers purified C-dots
from the combustion soot of natural gas.[13] By inverting a
glass beaker above the flame of a natural gas burner, they
were able to collect around 100 mg of soot, which was then
refluxed in 5 m HNO3 for 12 h, followed by centrifugation and
dialysis to afford purified C-dots of (4.8 0.6) nm diameter.
The as-purified C-dots (no gel electrophoresis was performed
in this case) exhibited PL, again without the need for surface
passivation, with a lex maximum of 310 nm and an emission
wavelength (lem) maximum of 420 nm. No experiments were
Figure 4. Optical characterization of PAGE separated C-dots produced conducted to determine if the emission characteristics showed
from candle soot. Optical images illuminated under white (top) and
a lex dependence as was noted for other C-dots. HRTEM
UV light (312 nm; center). Bottom: Fluorescence emission spectra (lex
at 315 nm) of the corresponding C-dot solutions. The maximum
measurements revealed lattice spacings of 0.208 nm,
emission wavelengths are indicated above the spectra. Reproduced 0.334 nm, 0.194 nm, and 0.186 nm, which is consistent with
from Ref. [7] with permission. the (102), (006), (104), and (105) diffraction planes of sp2
graphitic carbon (Figure 5). 13C NMR and FTIR measure-
ments also revealed the presence of sp2 carbon and carbox-
1 nm in height by using AFM, however, no additional ylic/carbonyl moieties, thus leading the authors to conclude
measurements were used to further elucidate their size and that the C-dots most likely consist of a nanocrystalline core
morphology. From 13C NMR measurements, three types of featuring graphitic sp2 carbon atoms and a surface function-
carbon signals were observed: external C=C bonds, internal alized with carboxylic/carbonyl moieties. Interestingly, in
C=C bonds, and C=O bonds. Importantly, no evidence for sp3- contrast to C-dots made from candle combustion, no N (as
hybridized carbon was found. The make-up of the purified C- determined from XPS data) was found to be present in these
dots (36.8 % C, 5.9 % H, 9.6 % N, 44.7 % O) was vastly C-dots.
different from that of the raw candle soot (91.7 % C, 1.8 % H, Giannelis and co-workers used a one-step thermal
1.8 % N, 4.4 % O), with the significantly higher oxygen decomposition of low-temperature-melting molecular pre-
content due in part to the presence of surface carbonyl groups. cursors to form surface-passivated C-dots that were either
The solubility of the C-dots was determined to be about hydrophilic or organophilic in nature.[3] This process is highly
30 mg mL 1 in water, 18 mg mL 1 in methanol, 20 mg mL 1 in attractive in that it directly leads to surface-passivated C-dots
dimethylformamide (DMF), and 41 mg mL 1 in dimethylsulf- with precisely engineered surface properties and, by careful
oxide. The PL of the C-dots was both lex- and pH-dependent, selection of the carbon source and surface modifier, better
with peak emissions in the 415–615 nm range and increased control over the geometry and physical properties of the C-
broadening of the bands at longer wavelengths (Figure 4). dots is possible. In this study, C-dots were produced by
Interestingly, no external surface passivation agent, as employing two different routes, both yielding monodispersed
required for other approaches, was needed for PL to occur C-dots with sizes less than 10 nm. In the first route, an
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Carbon Nanodots
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dots produced lex-dependent broadband PL emission with lem showed a diffraction peak corresponding to 3.4 (d002).
maxima ranging from 400 to 580 nm. Elemental analysis showed O-rich C-dots comprised of
Following a different approach, Giannelis and co-workers 57.0 % C, 7.5 % H, 8.5 % N, and 27.0 % O (wt %).
produced C-dots using NaY zeolites as supports.[2] The NaY
zeolite was first ion-exchanged with 2,4-diaminophenol
dihydrochloride followed by thermal oxidation at 300 8C in 2.3. C-Dot Nanocomposites
air for 2 h. It was found that ion exchange took place mostly at
the surface of the zeolite as opposed to the interior, thereby In the study by Sun et al., hybrid C-dots made by laser
resulting in C-dots decorating the surface of the zeolite after ablation of graphite were subsequently doped or coated with
oxidation. The zeolitic material was then etched away by ZnO or ZnS.[11] The C-dots were first refluxed in 2.6 m HNO3
hydrofluoric acid to leave behind 4–6 nm sized C-dots that for 12 h followed by extensive dialysis against large volumes
exhibited PL properties similar to those reported by using a of water and centrifugation (1000g for 5 min) to remove any
nonsupported formation route.[3] large particles. The supernatant was retained and the water
evaporated to leave behind the oxidized C-dots. The 4–5 nm
2.2.3. Synthesis with Microwaves and in Aqueous Solution particles were then dispersed in DMF. To make ZnO/C-dots,
zinc acetate was added to the C-dot dispersion under vigorous
A facile microwave pyrolysis approach to synthesize C- stirring followed by the dropwise addition of NaOH. The
dots was carried out by combining PEG200 and a saccharide ZnO/C-dots were then recovered through centrifugation,
(for example, glucose, fructose) in water to form a transparent repeatedly washed with water, and dried at 60 8C in a vacuum
solution, followed by heating in a 500 W microwave oven for oven before final annealing at 200 8C for 2 h. ZnS/C-dots were
2–10 min (Scheme 4).[20] The solution changed from colorless similarly obtained by adding zinc acetate to a DMF dispersion
of the C-dots followed by the slow addition of Na2S solution,
centrifugation, and extensive washing of the ZnS/C-dot
precipitate with water. Thermogravimetric analysis revealed
the C/ZnO and C/ZnS molar ratios to be 20:1 and 13:1,
respectively. ZnO and ZnS were found to incompletely coat
the C-dot surface, thus leaving intact patches rich in
carboxylic acid moieties which could then be functionalized
Scheme 4. Microwave approach to C-dot synthesis. Reproduced from
by reaction with PEG1500N. Interestingly, the Zn-based coat-
Ref. [20] with permission. ings afforded higher emission quantum yields than the
uncoated C-dots, however, in both cases PEG1500N passivation
was requisite for PL to occur.
to tan to dark brown over the time course of the reaction. The Metal/C-dot nanocomposites were made by Tian et al. by
recovered C-dots exhibited sizes and PL properties related to reducing metal salts in the presence of C-dots generated from
the duration of the microwave heating. Longer heating times the oxidative etching of natural gas soot.[13] The metal ions,
result in the C-dots enlarging slightly and emitting at longer most likely bound to the peripheral carboxylic moieties by an
wavelengths. For example, the average C-dot diameters were ion-exchange process, were reduced to zero-valent metal
(2.75 0.45) nm and (3.65 0.6) nm for heating times of 5 upon addition of ascorbic acid and evolved into metal
and 10 minutes, respectively. When PEG was omitted, a nanostructures. The resulting nanostructures were water
similar color change was observed during microwave heating, soluble and, unlike the case of ZnO and ZnS[11] mentioned
but it is noteworthy that the nonpassivated particles expressed above, were far larger than the original C-dot: growing from
weak and irregular PL. 5 nm to 16–20 nm in size (Figure 6). Instead of the metal
Most recently, Peng and Travas-Sejdic described a simple coating the C-dot, here the C-dots decorated the outside of
route to C-dots by using carbohydrates in aqueous solution.[23] the metal nanostructure. The metal particles appear to form
The carbohydrates were first dehydrated using concentrated chainlike structures embedded in a carbon matrix, thus
sulfuric acid to produce large carbonaceous materials. These supporting the hypothesis that the deposition of the metal
materials were then ruptured into C-dots by refluxing in 2 m nanoparticles was initiated from the C-dot surface.
HNO3. After cooling, the solution was neutralized by Na2CO3
solution and most of the water removed under vacuum. The
C-dots were then dialyzed extensively to remove excess salts. 2.4. Surface Functionalization
The nonpassivated C-dots were 5 nm in size and exhibited a
weak PL. The FTIR spectra revealed bands at 1572 cm 1 and C-dots separated from SWCNTs produced by arc-dis-
1375 cm 1, which were ascribed to C=C bond stretching and charge methods showed carbonyl functionalities at their
C H vibrations, respectively. The C-dots were surface- surface, as evidenced by FTIR.[1] Other studies, including
passivated by treatment with 4,7,10-trioxa-1,13-tridecanedi- those of C-dots produced electrochemically from graphite[18]
amine (TTDDA), ethylenediamine, oleylamine, or PEG1500N or by the chemical oxidation of candle soot,[10] showed similar
at 120 8C for 72 h under N2. TEM analysis revealed a results, with C-dots sporting COOH groups at their surface, as
crystalline structure consisting of a lattice spacing close to strongly evidenced by characteristic IR absorptions for ~n(C=
that of turbostratic carbons. Concurrent XRD experiments O) around 1580 cm 1 and 1630 cm 1. Indeed, acid oxidative
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Reviews S. N. Baker and G. A. Baker
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Carbon Nanodots
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Reviews S. N. Baker and G. A. Baker
Figure 10. Absorbance and luminescence spectra with increasingly excited at 365 nm.[19] These C-dots also showed lex-dependent
longer excitation wavelengths (in 20 nm increments starting from 400)
emission but, interestingly, no additional passivation step was
of 5 nm PPEI-EI C-dots in aqueous solution formed from laser ablation
methods. Reprinted from Ref. [12] with permission.
required here for PL to occur. At this time, it is unclear why
this would be the case or whether TBA+ ions might serve as
passivating agents. Yet another report on electrochemical C-
dot synthesis did not comment on whether the PL showed lex
dependence, but further surface passivation was not required
for PL to occur in this case either.[18]
Similarly, C-dots produced from the oxidation of candle
soot contained an abundance of carbonyl groups at their
surface and required no further functionalization for PL to
occur.[7, 10] Although their excitation spectra differed little,
their PL emission spectra were strongly linked to their
electrophoretic mobilities (Figure 4). At this time, it is not
entirely clear whether size or surface charge effects were most
responsible for the observed C-dot mobilities. The PL spectra
have a broad color range, with peak intensity wavelengths
ranging from 415–615 nm. The FWHM broadens as the
Figure 11. Aqueous solution of C-dots passivated with PEG1500N emission red-shifts, perhaps because of incomplete size
A) excited at 400 nm and photographed through band-pass filters of separation.
different wavelengths as indicated, and B) excited at the indicated
An SiO2-supported route to 1.5–2 nm C-dots required
wavelengths and photographed directly. Reprinted from Ref. [12] with
permission.
surface passivation for PL to occur, with the PL showing
marked lex dependence.[9] When produced by microwave
synthesis of saccharides in PEG200, the resulting 3 nm C-dots
Another laser ablation method produced similar results in also exhibited lex dependence.[20] These C-dots gave broad
terms of surface passivation being required for PL to occur.[6] emission, with an emission maximum at 425 nm when excited
In this study, PL occurred when C-dots formed directly in the at 330 nm. The PEG200 was essential for PL to occur here as
presence of PEG200N were excited at 420 nm. However, no PL well, but some COOH functionality was still retained at the
occurred when C-dots were formed in water and only methyl C-dot surface, as evident by FTIR analysis.
and few carboxylic moieties were present on the surface. Only C-dots (7 nm) made from the one-step thermal decom-
minimal PL resulted even after oxidation in perchloric acid to position of ammonium salts or 4-aminoantipyrine compounds
produce many more carboxylic moieties at the surface. Only showed emission that depended very strongly on the lex.[2, 3] In
by subsequent passivation by incubation in PEG200N were fact, those C-dots made from the carbonization of 2-(2-
these C-dots capable of producing strong PL emission. The lex aminoethoxy)ethanol citrate salt[3] or 11-aminoundecanoate
and lem maxima were red-shifted upon increasing the MW of citrate salt[2] are among those emitting the most red-shifted
the PEG used. The use of two different C-dot starting PL of any covered in this Review (Figure 13, for example).
materials, graphite and carbon black, produced no notable For C-dots produced electrochemically in water-rich ILs,
changes in the final C-dot properties. However, for this the resulting 8–10 nm particles were oxidized at the surface
fabrication method, no studies were done to determine if the and had a lem maximum at 364 nm when excited at 260 nm.
C-dot emission was dependent upon lex. However, when the water content was very low (< 10 %), the
C-dots (2.8 0.5 nm) prepared by electrochemical oxida- 2–4 nm C-dots produced were found to be functionalized by
tion of MWCNTs, exhibit blue PL centered at 410 nm when the IL and had higher quantum yields (2.8–5.2 %) than the
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Figure 13. Absorption and normalized PL spectra at different excitation Figure 14. UV absorption and PL of C-dots electrochemically exfoliated
wavelengths of hydrophilic C-dots made from thermal decomposition using IL electrolytes containing different water contents. The emission
of 2-(2-aminoethoxy)ethanol citrate salt. Reproduced from Ref. [3] with spectra were excited using 260 nm light: a) 10 wt % water(blue curve);
permission. b) 60 wt % water(black curve); c) 90 wt % water (pink curve). A blue
shift of the emission is apparent with higher wt % of water in the
electrolyte. Reproduced from Ref. [8] with permission.
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tively. These values are beyond the upper limit for such enhanced the ECL (ET2 route in Figure 19) in the cathodic
quenching processes in solution, thus suggesting the high potential range and produced a stable and sensitive (as no
efficiency of the underlying electron-transfer process as well other co-reactants tested elicited an ECL enhancement) ECL
as static quenching effects. Once static quenching effects are response, thus suggesting the application of C-dots for ECL
taken into account, these quenching rate constants are still at sensing.[18]
the diffusion-controlled limit for dynamical quenching, thus As ECL is mainly characterized by surface-state tran-
proving that C-dots can act as very efficient electron donors. sitions in nanoparticles (whereas in nanoparticles, PL is more
Additionally, C-dots can serve as strong electron accept- reminiscent of the core state), comparison between the ECL
ors, and can quench the luminescence of known electron and the PL of nanoparticles is an excellent way to investigate
donors such as N,N-diethylaniline (0.88 V versus NHE) the presence of surface traps.[40–42] When excited at 330 nm,
highly efficiently. This behavior is solvent-dependent and is the PL emission of the C-dot was centered at 455 nm, while
more efficient in polar solvents, which is indicative of an the ECL emission was centered at 535 nm.[18] This substantial
electron transfer quenching mechanism. red-shift indicates that the emitting states are different,
thereby signifying the presence of surface traps with incom-
3.2.4. Electrochemical Luminescence plete passivation. If the particle were more completely
passivated, the ECL profile would resemble the PL spectrum,
Since semiconductor nanocrystals are well known to as seen in the case of CdSe/ZnSe core/shell nanoparticles.[41]
exhibit electrochemiluminescence (ECL),[38, 39] it comes as Further support for this notion is provided by the persistence
no surprise that C-dots have aroused interest for ECL of the red-edge tail in the PL emission spectrum for many C-
studies.[18, 20] The ECL emission of C-dots (ca. 2.0 nm) pro- dots, which indicates emission from incompletely-passivated
duced from the electrochemical oxidation of graphite was surface traps (see Figures 10 and 12–14).[40–42] The C-dot
observed as the potential was cycled between + 1.8 and particles in these ECL studies contain COOH groups at their
1.5 V (Figure 18).[18] surfaces, as shown by FTIR results.[18]
On the basis of ECL evidence implying the presence of
surface trap states, coupled with the pervasive size and lex
dependency of C-dot PL, we postulate that C-dots feature
core band gaps that are dependent on the size, with the most
intense PL attributable to the direct recombination of
electron-holes whereas the less intense bands (those further
red-shifted) may be assigned to surface-state traps and
phonon-assisted recombination similar to observations in Si
nanocrystals.[42] Experiments aimed at investigating the
effects of different surface capping agents on the ECL of C-
dots would prove invaluable for elucidating the effects of
Figure 18. ECL responses a) with and b) without C-dots at a Pt surface passivation on surface traps. It would also be
electrode in 0.1 m phosphate buffer solution (pH 7.0) with a scan rate interesting to determine whether the ECL of C-dots is size-
of 0.1 Vs 1. Reproduced from Ref. [18] with permission.
independent, as is the case for Si nanocrystals.[42]
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notion is consistent with the observed pH-switchable PL, variety of synthetic techniques, including methods that
during which the GQDs emit strongly under alkaline employ inexpensive renewable resources such as lignocellu-
conditions but are almost completely quenched in acidic losic biomass wastes (for example, corn stover, switchgrass,
media. used cooking oil) as starting materials.
In all of the examples cited in this Section, graphene Not surprisingly, given their low cost, ready scalability,
materials were produced either by micromechanical cleavage excellent chemical stability, biocompatibility/nontoxicity, col-
or exfoliation of graphite by following a modified Hummers loidal stability, and resilience of PL in vivo, C-dots have
method. In an intriguing departure from these approaches, shown primary potential in optical imaging and related
Giannelis and co-workers prepared a layered carbonaceous biomedical applications. In this regard, they share some of
material containing both heteroatoms and fixed ammonium the attractive traits of groups of uniform materials based on
groups simply by pyrolysis of the molecular precursor bis(2- organic salts (GUMBOS)[55, 56] and fluorescent thiolate-
chloroethyl)amine hydrochloride at 260 8C in open air.[54] capped gold nanoclusters[57] as prospective alternatives to
Although the exact structure remains an open question, this Q-dots labels in biologically motivated experiments. How-
material can essentially be regarded as a carbonaceous ever, the recent report demonstrating the capacity for photo-
analogue of conventional layered inorganic materials such induced electron-transfer behavior in C-dots[14] means they
as smectic clays or layered double hydroxides. These layered may additionally hold compelling potential in battery tech-
carbons behave similarly to laponite, a well-known phyllo- nology as well as in photovoltaic devices, possibly as potential
morphic aluminosilicate, are colloidally stable in water, light-harvesting units. Additionally, the ability to easily
possesses ion-exchange properties, and share many character- introduce versatile functionality at the C-dot surface by
istics of GO. Indeed, the layered carbons present PL behavior rational conjugation chemistry allows them to be fine-tuned
quite similar to that observed in C-dots, including lex- in ways beyond influencing optoelectronic properties, includ-
dependent emission spectra and a high quantum yield of ing the modulation of solubility in desired solvent systems and
11 %. the suitability for coupling with various surfaces (bulk,
As remains the case for C-dots, the detailed mechanism nanoscale, or biological). By suitable doping, chemical
and chemical species responsible for PL in graphene deriv- manipulation, or as essential components of nanocomposites,
atives awaits further understanding. Throughout these stud- they may open the door to a host of unforeseen applications
ies, some interesting questions arise such as whether energy ranging from contrast agents for magnetic resonance imaging
relaxation and spectral diffusion in GO-type materials are (MRI) and magnetic data storage applications to battery
altered by aggregation and interlayer coupling and whether electrodes. Ultimately, once a deeper understanding of their
significant inhomogeneity of the oxidation profile exists fundamental properties is achieved, one can even envision C-
within the GO plane. It also becomes apparent that while dot-based systems in organic light-emitting diodes (OLEDs),
absolute values for the emissive quantum yields and an separation membranes, displays and backlights, drug delivery,
appreciation for inner filter effects will illuminate these and advanced cancer/photodynamic therapy. Only time will
questions, the accurate measurement of these quantities is tell, but the future of these emergent nanolights positively
problematic for ensembles of heterogeneous nanomaterials. appears bright.
These facts notwithstanding, taken together, the early results
cited here suggest that GO may become a promising platform This work was sponsored by the Division of Chemical
that paves the way toward interesting biomedical labeling and Sciences, Office of Basic Energy Sciences, U.S. Department
optoelectronics applications. An outstanding challenge in this of Energy under Contract DE-AC05-00OR22725 with Oak
regard is the ability to engineer desired molecular sp2 Ridge National Laboratory, managed and operated by UT-
topologies while controlling their organization and fraction Battelle, LLC.
in graphene. Advances along these lines are a near-certainty
in the not-too-distant future. Received: November 24, 2009
Published online: August 4, 2010
Angew. Chem. Int. Ed. 2010, 49, 6726 – 6744 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 6743
Reviews S. N. Baker and G. A. Baker
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