SCIENCE CHINA

Chemistry
Science China Press and Springer-Verlag Berlin Heidelberg 2012 chem.scichina.com www.springerlink.com

*Corresponding author (email: chengzhi@swu.edu.cn)
ARTICLES doi: 10.1007/s11426-012-4494-0


July 2012 Vol.55 No.1: 16

Light scattering investigations on mercury ion induced
amalgamation of gold nanoparticles in aqueous medium
QI WenJing
1
, WANG Yi
1
, WANG Jian
1
& HUANG ChengZhi
1,2*

1
Education Ministry Key Laboratory on Luminescence Real-Time Analysis; College of Chemistry and Chemical Engineering, Southwest
University, Chongqing 400715, China
2
College of Pharmaceutical Sciences, Southwest University, Chongqing 400715, China
Received August 18, 2011; accepted December 1, 2011

With the aids of SEM, XPS measurements, localized plasmon resonance light scattering (PRLS) spectrometry and light scat-
tering imaging, investigations on the amalgamation process of both cetyltrimethylammonium bromide (CTAB) and cit-
rate-coated gold nanoparticles (AuNPs) in the presence of Hg
2+
showed that the Au-Hg amalgam process of gold nanoparticles
is surface coating dependent in aqueous medium, and the scattering light color change of AuNPs under a dark-field microscope
is blue-shifted from red-orange into yellow-orange or even yellow. The former one involves the reduction of Hg
2+
to Hg
0
spe-
cies and adsorption of Hg
0
on the surfaces of AuNPs, while the later one indicates the shape-evolution of AuNPs.
PRLS, light scattering imaging, amalgamation process, gold nanoparticels (AuNPs), Hg
2+




1 Introduction
Amalgamation is one of the oldest methods of extracting
gold from its ores in mining industry. In order to liberate the
gold particles from the gangue, mill operators must get the
gold and the mercury into intimate contact with each other
to form amalgam that is a solution of gold in mercury or an
alloy of gold and mercury [1]. Although numerous investi-
gations have been made on the high affinity of mercury and
gold, the physical and/or chemical characteristics that make
the formation of amalgamation are not clearly understood
even up to now [2, 3]. In such case, efforts to investigate the
formation of amalgamation process have to be made such as
by bubbling with pure argon prior to irradiation [3], directly
exposing the gold to mercury [4, 59]

or undergoing an elec-
tro-deposition process using gold electrodes [2, 7, 1012].
Metal nanoparticles (NPs), owing to the occurrence of
plasmon resonance in the case that the electron in the metal
NPs oscillates at the same frequency as that of the incident
electromagnetic wave, display very unique features includ-
ing localized plasmon resonance absorption (PRA) and res-
onance light scattering (PRLS) depending on their size,
shape and surrounding medium [1316]. With the develop-
ment of nanosciences, on the other hand, bimetallic nano-
particles have shown high promise owing to their unique
physical properties [15]. So, it easily occurs to us to inves-
tigate the formation of Au-Hg amalgam on the basis of the
localized PRA and PRLS features.
With the aids of SEM, XPS measurements and dark-field
light scattering imaging, we noticed that only CTAB-coated
AuNPs can directly form Au-Hg amalgam with Hg
2+
by the
reductant L-AA, which has existed excessively in the
AuNPs aqueous solution and there is no need of special
addition of some other reductants. While citrated-coated
AuNPs can indirectly form Au-Hg amalgam with Hg
2+
after
the special addition of reductant NaBH
4
. Both of the amal-
gamation can show an obvious blue shift in PRA spectra
and greatly enhance PRLS signals in the presence of Hg
2+
,
accompanied by shape-evolution with the color changing
from red to yellow via orange. It indicates that the amalga-
2 Qi WJ, et al. Sci China Chem July (2011) Vol.54 No.7
mation process of gold nanoparticles is surface-coating de-
pendent, suggesting that it is necessary to add some reduct-
ants such as L-AA if extracting gold from the gangue by
using mercury.
2 Experimental
2.1 Materials
All reagents were prepared by dissolving their commercial
products in doubly distilled water (18.2 M). Sodium bo-
rohydride (NaBH
4
) and L-ascorbic acid (L-AA) were com-
mercially obtained from Huanwei Fine Chemical Co., Ltd.
(Tianjin, China) and Chuandong Chemical Group Co., Ltd.
(Chongqing, China), respectively. Cetyltrimethylammonium
bromide (CTAB) and Hydrogen tetrachloroaurate (III) tet-
rahydrate (HAuCl
4
4H
2
O) were purchased from Sinopharm
Group Chemical Regent Co., Ltd. (Shanghai, China). HgCl
2
was purchased from the Shanghai Chemical reagent Co.,
Ltd. (Shanghai, China). BR buffer was used to control the
acidity.
2.2 Apparatus
PRLS signals and plasmon resonance absorption (PRA)
spectra were measured with an F-4500 fluorescence spec-
trophotometer (Hitachi Ltd., Tokyo, Japan) and a Hitachi
U-3010 spectrophotometer (Tokyo, Japan), respectively. A
Hitachi S-4800 scanning electron microscope (SEM, Tokyo,
Japan) was used to record the morphology of AuNPs. The
light scattering imaging of AuNPs was made with an
Olympus BX51 inverted microscope, coupled with a tung-
sten lamp and a highly numerical dark-field condenser
(U-DCW, 1.21.4, Tokyo, Japan). X-ray photoelectron
spectroscopy (XPS) analysis was carried out on an
ESCRLRB250X (America) cispectrometer with a standard
Al K source (1486.6 eV). An S-10A digital pH meter
(Xiaoshan Scientific Instruments Plant, Zhejiang, China)
was used to measure the pH-values of the solutions. An
MVS-1 vortex mixer (Beide Scientific Instrumental Ltd.,
Beijing, China) was employed to mix the solutions.
2.3 Methods
Citrated-coated AuNPs were prepared by means of citrate
reduction of HAuCl
4
[17], and CTAB-coated AuNPs were
prepared by seed-mediated method with two-step proce-
dures [15, 18]. Gold seeds were firstly prepared by reducing
HAuCl
4
4H
2
O with ice-cold NaBH
4
, and then were added
into a growth solution containing HAuCl
4
4H
2
O, L-AA and
CTAB. The mixed solution was finally left undisturbed for
24 h in water bath to prevent CTAB from crystallization
throughout the procedure. The prepared AuNPs are about
25 nm in diameter, and positively charged due to the ad-
sorption of the positively charged surfactant (CTAB) on the
surface of AuNPs.
0.3 mL CTAB-coated AuNPs (8.3 10
5
M), 0.20 mL
BR buffer (pH 8.0), and an appropriate volume of HgCl
2

working solution were added into a 1.5-mL plastic vial, then
diluted to 1.0 mL with doubly distilled water (18.2 M).
After vortex-mixed and placed for 10 min in a 55 C water
bath, the mixture was transferred to PRLS and PRA meas-
urements.
The samples for SEM imaging and XPS analysis were
prepared as the above process, followed by centrifuging at
12000 r/min for 10 min at 25 C to separate AuNPs from
excessive CTAB. Then the precipitate was re-dispersed in
distilled water, and drops of 5 L of the re-dispersed solu-
tion were respectively pipetted onto the aluminum foils for
SEM imaging and XPS analysis. Optical light scattering
imaging was made only after these drops got dried in the air.
Optical light scattering imaging was performed on the
Olympus BX51 inverted microscope.
3 Results and discussion
3.1 Morphological change of CTAB-coated AuNPs in
the presence of Hg
2+
Scheme 1 shows the general procedure of the extraction of
gold particles from the gangue by using the mercury, during
which the formation of Au-Hg amalgam, shown as follows,
involves the reduction of Hg
2+
to Hg
0
species and adsorp-
tion on the surfaces of AuNPs. Figure 1 displays the PRA
spectral change owing to the addition of Hg
2+
into the
CTAB-coated AuNPs suspension, which could be visually
observed from red to green yellow via orange, as shown in
the inserted picture. Characteristic PRA bands of AuNPs at
524 nm typically get blue-shifted with increasing mercury
content. This systematic blue shift of PRA spectra, namely,
the plasmon mode on the surface of the AuNPs has occurred,
indicating that the morphological change of CTAB-coated
AuNPs has taken place [3, 6].
Corresponding to the PRA shifts, enhanced PRLS signals
of AuNPs could be observed with the aids of a common
spectrofluorometer. As shown in Figure 2, the characteristic
PRLS spectra of CTAB-coated AuNPs are located at 560
nm. With the addition of Hg
2+
, the PRLS spectra at 560 nm
get enhanced, accompanied by the emergence of 350 nm
light scattering signal. If a large amount of Hg
2+
is added, it
overlaps the 560 nm band, indicating that the features of
AuNPs have totally changed [14, 1920].
The gradual evolution of PRLS spectra in Figure 2 is
identical to the change of the shape and size of AuNPs. As
shown in Figure 3, CTAB-coated AuNPs are mostly highly
uniform spheres with the diameter about 25 nm and have
smooth surface (Figure 3(A)). With the addition of Hg
2+
,
coalescence of two particles takes place (red arrow in Fig-
ure 3(B)), and the rod-shaped particles are newly formed.
Qi WJ, et al. Sci China Chem June (2011) Vol.54 No.6 3

Scheme 1 Schematic diagrams illustrating gold placers formation and extraction process, as well as Au-Hg amalgamation process and the corresponding
dark-field scattering images in which the reduction of Hg
2+
into Hg
0
was induced by the existing residue of L-ascorbic acid which was applied to the prepara-
tion of AuNPs.

Figure 1 Characteristic PRA spectra of AuNPs with the addition of Hg
2+
.
c
HgCl2
for curves from 1 to 11 (M): 0, 2.0, 4.0, 6.0, 8.0, 10.0, 15.0, 20.0,
40.0, 60.0, 80.0; c
AuNPs
, 8.3 10
5
M; BR buffer, 0.01 M; pH, 8.0; 55 C,
10 min. The inserted picture displays the color change with the addition of
Hg
2+
. The change of wavelengths (, nm) has a relationship with Hg
2+

concentration (c, M) in the range of 2.020.0 M with the correlation
coefficient (r) of 0.977.
With increasing Hg
2+
concentration, the amount of rod-
shaped dimers largely increases. With further addition of
Hg
2+
, coalescence of three or several particles takes place,
resulting in erose morphologies of AuNPs (Figure 3(C)). If
the content of Hg
2+
gets up to 100.0 M, mostly spherical
AuNPs disappear and are instead by the erose stone-shaped
morphologies (Figure 3(D)). This formation process of
Au-Hg amalgam yields scattering light color change of
AuNPs under a dark-field microscope since scattering light
is blue-shifted from red-orange into yellow-orange or even
yellow (Figure 3(EH)), which, as shown by the new XPS
measurements, is due to the increase of dielectric constant

Figure 2 Characteristic PRLS spectra of AuNPs with the addition of
Hg
2+
. c
HgCl2
for curves from 1 to 11 (M): 0, 2.0, 4.0, 6.0, 8.0, 10.0, 15.0,
20.0, 40.0, 60.0, 80.0; other conditions are the same as those in Figure 1.
The inserted picture displays the linear relationship.
of the medium re-sulting from the formation of Hg
0
from
Hg
2+
.
Anyway, the size of AuNPs is apt to enlarge during the
amalgamation process, accompanied by the change from the
initial sphere particles into stone-shaped large particles. All
the measurements of PRA, PRLS spectra, SEM, and dark-
field scattering images are identical, fully illuminating that
amalgamation action between Hg and AuNPs occurs indeed.
3.2 Mechanism of amalgamation process
In order to confirm the amalgamation action between Hg
and AuNPs, we further investigated the species states of
both gold and Hg elements. XPS assay of Hg and AuNPs
4 Qi WJ, et al. Sci China Chem July (2011) Vol.54 No.7

Figure 3 SEM (AD) and dark-field scattering images (EH) of AuNPs
in different content of Hg
2+
. Coalescence of two particles in rod-shaped and
three or several particles in erose stone-shaped morphologies takes place as
indicated with red arrow. The content of Hg
2+
(M) from A to D is 0, 40.0,
60.0, 100.0. Other conditions are the same as above.
(Figure 4) shows that mercury (Hg
0
) and gold (Au
0
)

are
characterized by the double 4f photoelectron emissions oc-
curring at 100 and 104, 88 and 84 eV, respectively [6, 7].

They are ascribed to the function of mercury depositing on
the surface of AuNPs. Just owing to the deposition of Hg
0
,
it consequently changes the refractive index of the medium
in AuNPs and Hg
0
mixture [2123]. Based on the XPS as-
say, we can conclude that there must have some residues of


Figure 4 XPS analysis of Au-Hg amalgam.
the reductant L-ascorbic acid which reduced Hg
2+
into Hg
0

during the synthesis of CTAB-coated AuNPs.
Different from the CTAB-coated AuNPs, citrated-coated
AuNPs display different features. PRA spectral measure-
ments show that citrated-coated AuNPs get aggregated and
the solution color changes from red to blue, while
CTAB-coated AuNPs can form Au-Hg amalgam with color
change from red to orange. This obviously different proper-
ty can be easily observed by the naked eyes. However, the
addition of reductant ascorbic acid lead citrated-coated
AuNPs to form Au-Hg amalgam indirectly, similar to the
change of CTAB-coated AuNPs, supposedly ascribing it to
that ascorbic acid has relatively stronger reduction than
trisodium citrate (Figure 5).
Besides, SEM images show that Hg
2+
can only lead to
the aggregation of citrated-coated AuNPs without mor-
phology change (Figure 6(B)). While after the addition of
reductant such as ascorbic acid, Hg
2+
can be reduced into
Hg
0
,

leading to the formation of Au-Hg amalgam and ac-
companied by some large erose particles (Figure 6(C)). In
addition, dark-field scattering images also display that the
color of scattering light is blue-shifted only in the sample
with the presence of both reducing agent ascorbic acid and
Hg
2+
(Figure 6(F)).
With respect to the gold extraction process, some alkali
and alkaline-earth metals usually prevent to get the mercury
and gold together. So we investigated the effect of other
metallic ions such as Mg(II), Ca(II), Ba(II) on the amal-
gamation action. We noticed that other metallic ions did not
show the similar amalgamation process to the CTAB-coated
AuNPs, confirming that the high affinity between Hg and
Au (Figure 7).
4 Conclusions
We identified that AuNPs underwent an amalgamation pro-
cess from spheric NPs into erose stone-shaped NPs, which


Figure 5 PRA spectra of citrated-coated AuNPs before and after the
addition of Hg
2+
. Curve A, control (citrated-coated AuNPs); curve B, the
aggregation in the presence of Hg
2+
; curve C, the amalgamation in the
presence of Hg
2+
and reductant L-AA. The concentrations of citrat-
ed-coated AuNPs, Hg
2+
and ascorbic acid are 3.3 10
-4
M, 6.0 10
-5
M,
and 2.0 10
-5
M, respectively.
Qi WJ, et al. Sci China Chem June (2011) Vol.54 No.6 5

Figure 6 SEM and dark-field scattering images of citrated-coated AuNPs
before and after the addition of Hg
2+
. (A, D) Control (citrated-coated
AuNPs); (B, E) the aggregation in the presence of Hg
2+
; (C, F) the amal-
gamation in the presence of Hg
2+
and reductant ascorbic acid. The concen-
trations of citrated-coated AuNPs, Hg
2+
and ascorbic acid are 3.3 10
-4
M,
6.0 10
-5
M, and 2.0 10
-5
M, respectively.

Figure 7 Effect of other metal ions on the amalgamation of AuNPs. The
concentration of all metal ions is 6.0 10
5
M. Other conditions keep the
same as above.
might supply some useful information for extracting gold
particles from the gangue by using the mercury. This is a
new report about the one-step formation of Au-Hg amalgam
reduced Hg
2+
into Hg
0
by ascorbic acid, investigated by
SEM and XPS measurements. Owing to the absorption of
Hg
0
on AuNPs, the effective dielectric constant of the me-
dium has changed and correspondingly leads to PRA and
PRLS properties of AuNPs regularly changes. Therefore, it
is not only a general study on the optical property of Au-Hg
amalgam, but also can open up new applications of Au-Hg
NPs for the determination of Hg
2+
. Also, this is the first time
to report the dark-field scattering imaging of Au-Hg amal-
gam, and its unique light scattering property maybe can
open up a new window for the study on the Au-Hg amal-
gamation and also the bimetallic nanoparticles.
This work was supported by the National Natural Science Foundation of
China (21035005) and Postgraduate Science and Technology Innovation
Program of Southwest China University (2009004).
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