Chemical Physics Letters 641 (2015) 29–32

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Chemical Physics Letters

journal homepage: www.elsevier.com/locate/cplett

Graphene quantum dots/Au hybrid nanoparticles as electrocatalyst

for hydrogen evolution reaction
Peihui Luo a,∗ , Linqin Jiang a,b , Weilong Zhang a , Xiangfeng Guan a,b
a
College of Electronics and Information Science, Fujian Jiangxia University, Fuzhou 350108, People’s Republic of China
b
Institute of Advanced Photovoltaics, Fujian Jiangxia University, Fuzhou 350108, People’s Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: Graphene quantum dots/Au hybrid nanoparticles (denoted as GQDs–Au) were prepared by heating
Received 17 May 2015 HAuCl4 with GQDs, and they showed higher electrocatalytic activity for hydrogen evolution reaction
In final form 19 October 2015 than that of pure Au nanoparticles.
Available online 24 October 2015
© 2015 Elsevier B.V. All rights reserved.

1. Introduction hybrid nanoparticles (denoted as GQDs–Au) according to our

Graphene quantum dots (GQDs) recently discovered are a new
class of quantum dots emitters with near graphene structure
and sizes usually below 10 nm [1–3]. Due to quantum confine-
ment and edge effects, GQDs possess a discrete bandgap and
unique photoluminescence (PL) properties. In addition, they have
low-toxicity, chemical inertness, biocompatibility and no photo-
bleaching properties, facilitating their applications in many fields,
including photoelectronics and catalysis, etc. [1–11]. To achieve
the full potential of GQDs, GQDs-based nanocomposites have been
fabricated, which could integrate properties of GQDs and func-
tional components for many specific applications. For example, the
hybrids of GQDs with optical active oxides [7,12–14], polymers
[15] and graphene [16] showed applications in photoelectronics,
supercapacitor and sensing fields, respectively. Recently, several
nanocomposites based on GQDs with noble metals such as Au,
Ag, Pt and Pd were also prepared [17–21]. Especially for GQDs/Pt
nanocomposites [21], it exhibited markedly enhanced electro-
catalytic activity in oxygen reduction reactions, in comparison
with commercial Pt/C catalysts. GQDs contain many carboxylic
and hydroxyl groups at their surface, imparting them with excel-
lent water solubility and inducing many structural defects, which
improving the electrocatalytic performance of the composites. Pt
is widely used as the electrocatalyst, but its high cost largely lim-
its the commercialization. In comparison, the cost of Au is lower
than Pt, and Au nanoparticles supported on metal oxides exhibit
high catalytic activity, inspiring numerous scientists for explor-
ing nanoscale Au catalysis [22,23]. In order to further explore
electrocatalytic properties of GQDs, we synthesized GQDs/Au
method reported previously [24]. The obtained GQDs–Au formed a
Au@GQDs core–shell nanostructure with an average diameter of
15.6 nm, and showed much higher electrocatalytic activity than
pure Au nanoparticles for hydrogen evolution reaction (HER).
2. Experimental
2.1. Synthesis of GQDs–Au
The GQDs–Au were prepared according to our method reported
previously [24]. Typically, 0.5 mL aqueous solution of HAuCl4
(0.83 mg/mL) was added to 30 mL aqueous suspension of GQDs
(0.03 mg/mL). The mixed solution was kept at 60 ◦ C for 80 min
to yield a stable pink suspension of GQDs–Au. The diameter of
GQDs–Au composite nanoparticles was measured to be 15.6 nm.
2.2. Electrocatalytic HER
All the electrochemical measurements were performed on a CHI
440 potentiostat under computer control. A glassy carbon elec-
trode (diameter = 3 mm) with a catalyst loading of 0.17 mg/cm2 was
used as the working electrode and a graphite rod was used as the
counter electrode. The electrolyte was a 0.5 M aqueous solution of
H2 SO4 . All the potentials were referred to a saturated calomel elec-
trode (SCE). They were further calibrated with respect to reversible
hydrogen electrode (RHE). The calibrations were simply performed
according to the formula: ERHE = ESCE + 0.273 V [25].
3. Results and discussion

Figure 1 shows the synthesis procedure of GQDs–Au. GQDs–Au

∗ Corresponding author. were synthesized by simply heating GQDs with HAuCl4 (see Section
E-mail address: luopeihui1986@aliyun.com (P. Luo). 2). The mechanism for reducing Au nanoparticles was proposed

http://dx.doi.org/10.1016/j.cplett.2015.10.042
0009-2614/© 2015 Elsevier B.V. All rights reserved.
30 P. Luo et al. / Chemical Physics Letters 641 (2015) 29–32
Figure 1. Schematic illustration of the strategy for the GQDs–Au preparation.
to be Galvanic displacement and redox reaction by the relative
potential difference, similar to the reduction of metal ions under
heating in the presence of reduced graphene oxide [26–28]. GQDs,
which contain various oxygenated groups, were equivalent to small
graphene oxide sheets. Oxygenated groups functioned as nuclea-
tion sites, and aromatic conjugated domains on GQDs acted as
an electron-donating source to reduce Au3+ ions. Meanwhile, the
GQDs also functioned as stabilizing agents, and encapsulated naked
Au nanoparticles and prevented their aggregation. Eventually, the
GQDs–Au with core–shell structure were formed. The residual
oxygenated groups of the GQDs coatings made the composite
nanoparticles could be stably dispersed in water [24].
In this letter, GQDs were obtained via electrooxidation of
graphite rods [24]. They reveal the average size of 3.1 ± 0.6 nm
(Figure 2(a)), and fine crystalline patterns with a lattice
Figure 2. TEM images of GQDs (a) and GQDs–Au (c); HRTEM images of double GQDs (b) and single GQDs–Au (d).
spacing of 0.238 nm, corresponding to the (1 0 0) facet of
graphite (Figure 2(b)). The heights of typical GQDs mea-
sured by AFM were around 0.7 nm and 1.4 nm, equivalent to
single-layer and double-layer graphene sheets, respectively (see
Figure S1 in the Supporting material) [29]. TEM image shown in
Figure 2(c) indicates the synthetic GQDs–Au were nearly spherical
in shape with an average diameter of 15.6 ± 1.7 nm. HRTEM image
of single composite nanoparticle clearly shows the high-contrast
lattice fringes assigned to Au (2 0 0) and (1 1 1) planes inside, and
the low-contrast lattice fringes of graphite (1 0 0) facets on the
periphery (Figure 2(d)). And the size of graphite crystalline region
in Figure 2(d) was similar to that of GQDs in Figure 2(a) and (b). The
SAED pattern (see Figure S2 in the Supporting material) of GQDs–Au
also displays the diffraction rings assigned to Au and graphite lat-
tice planes, respectively. It suggests the formation of GQDs coated
Au nanostructure. However, the intact GQDs shell layer of single
nanoparticle in Figure 2(d) was not observed obviously, probably
due to that an ultra-thin carbon film was used as the substrate for
taking out this image [21]. The HRTEM image of single nanoparticle
on a carbon nanotube grid clearly shows a low-contrast halo ring
associated with aggregated GQDs wrapping around a high-contrast
Au core (see Figure S3 in the Supporting material). This observation
further reflects our prepared GQDs–Au with a core–shell structure.
The GQDs–Au can be stably dispersed in water for several weeks.
Although GQDs–Au with average diameters smaller that 15.6 nm
can be obtained by decreasing the concentration of HAuCl4 in the
 P. Luo et al. / Chemical Physics Letters 641 (2015) 29–32 31

Figure 3. UV–visible absorption spectra (a) and fluorescence spectra excited at 330 nm. (b) of GQDs and GQDs–Au dispersed in water. Insets of (a) are photographs of GQDs
and GQDs–Au aqueous dispersions under daylight.

reaction system, they were tested to be unstable and easy to form catalyst is about 0.13 V lower than that of the latter, indicating
large aggregates. Improvement for stability of GQDs–Au of smaller a much higher electrocatalytic activity. The improved electro-
sizes is in progress. catalysis performance of the GQDs–Au nanoparticles is mainly
The UV–visible spectra of GQDs and GQDs–Au dispersions are attributed to the strong chemical coupling/interactions between
shown in Figure 3(a). The spectrum of GQDs–Au has a plasmon their both components, which afforded a strong GQDs coating layer
absorption peak associated with Au nanoparticles at 528 nm, while at Au surface and prevented Au nanoparticles aggregation together.
that of GQDs does not show any peaks in the range of 300–650 nm.
As a result, the aqueous dispersions of GQDs and GQDs–Au are
yellowish and pink under daylight, respectively. The fluorescence
intensity of GQDs–Au dispersion is much weaker than that of GQDs
dispersion (Figure 3(b)). This phenomenon can be explained by the
photoinduced electron transfer from GQDs shells to Au cores and
the aggregation of GQDs [24]. And the emission peak of GQDs–Au
shows a little blue-shift compared to that for pure GQDs. This
phenomenon was relevant to oxygenated groups at GQDs surface.
Because GQDs acted as a reducing agent in synthesis of GQDs–Au,
and part of their oxygenated groups were further oxidized by Au3+
ions upon heating and removed from the reaction system. A lower
degree of surface oxidation of GQDs in GQDs–Au produces less
surface defects, resulting in blue-shift of emission [29].
Hydrogen has been recognized as a clean energy carrier [30,31],
and it can be produced by electrolysis of water [32]. Platinum (Pt)
has been tested to be the most effective catalyst for the electro-
chemical HER because of its low overpotential () [33]. But the
high cost and scarcity of Pt have limited its widespread com-
mercialization. Therefore, it is important to explore highly active
HER catalysts based on more abundant materials at lower costs.
We investigated the electrocatalytic activity of our GQDs–Au for
HER by coating them on a glassy carbon (GC) electrode. The
experiments were carried out in a 0.5 M H2 SO4 solution using a
typical three-electrode cell (Section 2). The polarization curve of
the GC electrode modified with GQDs–Au (sizes = 15.6 ± 1.7 nm)
shows a small overpotential of 0.14 V for HER, while that of a Pt
electrode is close to zero (Figure 4(a)). In comparison, the GC elec-
trode coated by pure Au nanoparticles with the same sizes (see
Experimental section in the Supporting material) exhibits a higher
overpotential of 0.27 V, and GQDs have a negligible HER activity
(Figure 4(a)). The linear portions of the polarization curves were
fit to the Tafel equation ( = b log j + a, where j is current den-
sity and b is Tafel slope) [33], yielding Tafel slopes of about 30,
78, 75, 140 mV/decade for Pt, GQDs–Au, Au and GQDs, respec-
Figure 4. Polarization curves (a) obtained with several catalysts as indicated and
tively (Figure 4(b)). Although the Tafel slopes of GQDs–Au and Au
corresponding Tafel plots (b) recorded on glassy carbon electrodes with a catalyst
nanoparticles are almost the same, the overpotential of the former loading 0.17 mg/cm2 for each electrode.
32 P. Luo et al. / Chemical Physics Letters 641 (2015) 29–32

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the online version, at doi:10.1016/j.cplett.2015.10.042.