Mitul Patel 1

Glass colouring using Gold Nanoparticles

Mitul Patel
Collaborators: Andrew Slator, Kerri Loughney
BSc (Hons) Applied Physics, St. Mary's University, Twickenham London
Group Centred Problem Based Learning Unit, APH4005 Environmental Physics and Nanotechnology

The aim of this project was to make colloidal gold nanoparticles using three methods and deduce which
method was the best. As size and shape plays a key role at nano scale, by determining the colour of the
nanoparticles we were able to determine their size. We found that method A was the best one. The diameter of
the gold nanoparticles was determined by means of two routes. The size of gold nanoparticles produced by
method A was determined to be 36nm by route (I) and 25nm by route (II), whereas method C produced
nanoparticles of 19nm in diameter. The report also explains how the spectrophotometer was used in our
experiment and various other applications of nanotechnology, gold nanoparticles such as in energy,
materials etc.

Introduction
Nanotechnology is basically the manipulation of atoms and
molecules. The prefix nano means billionth of a meter i.e.
10
-9
m. Nanotechnology is a new area of research. Although
nanotechnology has been around since 4
th
century, it has
only been active since 1857
[1]
. Romans were the first
nanotechnologists to have made red stained glass by mixing
gold chloride to molten glass thus creating tiny gold spheres,
which absorbed and reflected light producing a rich ruby
colour. One of the application of the use of gold and silver
nanoparticles is shown in figure 1; stained glass which was
created in 1235 and is currently based at Chartres Cathedral
in France
[2]
. At the time they did not know about
nanoparticles and how different colours were produced, but
now we know about the properties of gold nanoparticles due
to cutting edge research in this area.


Figure 1. Shows the image of stained glass produced in 1235 by using gold
and silver colloidal.

Apart from stained glasses, gold nanoparticles
and nanotechnology have many other applications
ranging from energy and materials to medicine. In
energy one of the potential impacts of nanotechnology
is to provide clean energy and renewable energy sources
with greater efficiency. Lithium-ion batteries and
nanostructured solar cells were invented, these are
much more efficient
[3]
. Lithium-ion batteries are
nontoxic, less flammable, and lighter and last longer
than the batteries we use today. Nanostructured solar
cells are used to convert sunlight into energy efficiently
and they are flexible, cheaper and easy to install. Also
new type of wires are developed using carbon
nanotubes
[3]
. As nanomaterials are very strong and have
high conductivity therefore they could be used to have
higher tension in the electric grid and thus reduce the
transmission power loss
[4]
.
Materials: nanomaterials are very strong and
lighter therefore they can be used for aircrafts and
vehicles. Nanomaterials could also be used to build
space elevators

due to its high tensile strength
[4]
.
Building space elevator could reduce significantly the
amount of rocket fuel required and also could reduce the
cost of reaching higher orbit and traveling in space
[4]
.
Gold nanoparticles are also used in organic
photovoltaic, sensory probes, therapeutic agents, carriers
for drug delivery in biological and medical applications,
electronic conductors and catalysis.
To understand gold nanoparticles, it is very
important to understand the properties of gold at macro
scale. Gold is an interesting element. It is the most
malleable and ductile metal as it can be beaten into very
thin sheets of material. One of the properties of gold is the
colour of the particles. The colour of gold is purely
metallic yellow at macro scale but it can be altered into
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various other colours by alloying gold with metals. It is
also a good conductor of heat and electricity as the
conduction electrons are free to move around
[5][6]
.
These properties of gold particles start to change at nano
scale in comparison to the macro scale. Gold at nano
scale can have several colours for instance red, blue,
orange or green. Not just gold but also silver is an
interesting metal because it behaves differently at nano
scale, too. Silver particles are grey at macro scale but at
nano scale their colour varies from yellow, red or blue
depending on their size. The changing in colour is not
only due to the size of the particles but it is also related to
the way the material interacts with light at nano scale
[6]
.
The colour change arises from a phenomenon
called Surface Plasmon resonance (SPR)
[6][7]
. SPR is the
vibration of electrons in the conduction band due to its
interaction with light. The frequency of the light matches the
frequency at which the electrons oscillate therefore giving
rise to resonance. SPR causes the absorption and scattering
intensities of gold nanoparticles to be much higher than
identically sized non-plasmonic nanoparticles. Depending
upon the size of the particles, the particles produce different
colours. For example gold nanoparticles of the size of 30nm
produces an absorption of 450nm (i.e. blue-green) whilst red
light of 700nm is reflected therefore red colour of gold
nanoparticles is produced. As the particle size increases, the
wavelength of SPR causes the absorption spectrum to shift
in to longer wavelength. As the particles continue to
increase, the light shifts toward longer wavelength as shown
in figures.2 and 3
[8]
.

Figure 2. This absorption spectrum demonstrates the characteristic
absorptions of colloidal gold. As the diameter of the nanoparticles
increases, the wavelength of the radiation absorbed also increases leading
a difference in the colour of the solutions
[8]
.


Figure 3. This graphs shows how the diameter of the gold nanoparticles
increases exponentially with increase in wavelength.

The surface plasmon resonance can be altered by varying
the size or shape of the nanoparticles, leading to particles
with tailored optical properties for different applications.
This SPR phenomenon is also seen when excess salt is
added to the gold solution. The surface charge of the gold
nanoparticles becomes neutral, causing nanoparticles to
aggregate. As a result, the gold nanoparticles colour changes
from red to blue. In order to minimize aggregation, the
versatile surface chemistry of gold nanoparticles allows
them to be coated with polymers and small molecules
[8][9]
.
This surface modification enables gold nanoparticles to be
used extensively in chemical, biological, engineering, and
medical applications

.
In our experiments we aim to produce gold
nanoparticles by suspending gold particles into an aqueous
solution. We used the absorption spectrum to determine the
size of gold nanoparticles by two different routes:
(I) Using the resonant wavelength from the absorption
spectrum like the one in figure.2 and substituting the
resonant wavelength into equation 1
(II) Using the resonant wavelength and determine the size
directly from the figure.3.


The above equation can be re-arranged to determine d and
rearrangement is given in equation (1)
(1)
The only parameter measured in our experiment was
as the rest other parameters were provided to us in the
0
20
40
60
80
100
120
140
160
180
500 600 700 800
d
i
a
m
e
t
e
r
/
n
m

peak wavelength/nm
Mitul Patel 3

protocol by the demonstrator. The values of those
parameters are as follows
= 512nm, L
1
= 6.53 and L
2
= 0.0216
Experimental Method

Gold nanoparticles were produced using three different
methods. The best method was then selected for
spectrophotometer analysis to determine the size of the gold
nanoparticles. All the three methods are described below.

Method A- Sodium citrate + Heating/Stirring
0.5g of Sodium citrate was weighted accurately precise to
0.001g and then was dissolved in 50mL of deionised water.
40mL of the gold solution was measured out and was poured
into the 100mL beaker. The beaker containing the gold
solution was then placed on the hot plate for heating the
solution to boiling point while stirring it with a magnetic
stirrer. When the gold solution began to boil, 4mL of sodium
citrate was added to it and the solution was further allowed
to boil for 20 to 25 minutes. As the solution was boiling, any
colour change in the solution was observed and noted. Once
the red colour was obtained the hot plate was turned off and
the solution was allowed to cool down to room temperature
for about 30 minutes.

Method B- using Sodium Citrate +UV irradiation at room
temperature
40mL of the gold solution was measured out and was poured
into a 100mL beaker. 4mL of the sodium citrate solution
was added to gold solution and the solution was stirred using
a magnetic stirrer. The solution was stirred until sodium
citrate was completely mixed with the gold solution. The
solution was then exposed to UV lamp for 1 minute after
which any colour change was observed and noted. As there
was no colour change, the solution was placed back in the
lamp until any colour change was observed.

Method C- Ascorbic at room temperature
0.3g of Ascorbic was accurately weighted precise to 0.001g
and then was dissolved in 100mL of deionised water. 50mL
of the gold solution was measured out and was poured into
100mL beaker. The gold solution was placed on to the hot
plate and stirred using a magnetic stirrer. While stirring, 2ml
of ascorbic acid solution was added and any colour change
was observed and noted.

A 2-3mL sample was placed in a spectrophotometer in order
to measure the absorbance spectrum of each of the solutions.
Once the absorbance spectrum was obtained, the size of the
gold nanoparticles was determined by route (I) and route
(II).
Spectrophotomer:
A spectrophotometer is designed to analyse the visible
spectrum. It is a technique used to measure the concentration
of the solute in the solution by measuring how much light is
absorbed by the solution in a cuvette. The visible spectrum
is part of the electromagnetic spectrum which consists of
radio waves microwaves, infrared, ultraviolet, X rays and
gamma rays as shown in the figure.4

Figure 4. Electromagnetic spectrum. The visible spectrum is highlighted.
In brief, a spectrophotometer measures the intensity of light
that is transmitted through the sample. The principle of
operation of spectrophotometer is shown in figure 5.
In spectrophotometers the light sources emits light in all
range of wavelength (i.e. white light) and these light is
transmitted through prism which then splits the white light
into its component wavelength as shown in figure 5. This
light is then directed towards the solution in cuvette (sample
compartment). The sample absorbs certain wavelength of
light and transmits other wavelength of light. The
transmitted light through the sample hits the phototube, and
it converts the photons into electrical signal which can be
read out.

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Figue 5. Shows the schematic view of the spectrophotometer

Results and discussion

Of all three methods, the solution of method A and method
C are presented in figures 6 - 9. No results of method B are
presented as the solution precipitated out quickly. The
detailed results obtained for method A and B are shown in
appendix.

Method A results:

The pictures of gold nanoparticles produced by method A is
shown in figures 6 and 7. Method A was by far the best
method to produce gold nanoparticles as the solution did not
precipitate quickly and the solution was red as expected. The
sample was analysed further i.e. was placed in the
spectrophotometer and the spectrum was measured. The
graph of absorption spectrum against wavelength was
plotted which is shown in figure 8. The graph was used to
determine the size of gold nanoparticles by using route (I)
and route (II). The diameter of the gold nanoparticles
determined by route (I) was 36nm and by route (II) was
25nm.


Figure 6. Gold nanoparticles of method A under preparation.


Figure 7. Gold nanoparticles produced by Method A which was considered
to be the best method by far. The solution produced was red.


Figure 8. Shows the absorption spectrum of the gold nanoparticles
produced at 100
o
C by method A.

Method C results:

The pictures of gold nanoparticles by method C are shown
in figure 9 where a step of the preparation of the solution is
displayed. In figure 10, the final product is displayed. It can
be seen clearly, by comparing the two figures that the
solution precipitated. Therefore, we decided that this was
not the best method to produce gold nanoparticles. A 2-3mL
sample was placed in the spectrophotometer, and the
absorbance was measured. Finally, graph of absorption
spectrum against wavelength was plotted which is shown in
figure 11, to determine the size of gold nanoparticles. The
diameter of the gold nanoparticles determined by route (I)
was 19nm.



480 300 320 340 360
0
0.1
0.2
0.3
0.4
0.3
0.6
0.7
WavelengLh/nm
A
b
s
o
r
b
a
n
c
e
/

absorbance vs wavelength
Mitul Patel 5

Figure 9. Gold nanoparticles produced by Method C while still under
preparation. The colour of the colloidal solution is ruby red.


Figure 10. Gold nanoparticles produced using Method C precipitated
quickly to pink.


Figure 11. Shows the absorption spectrum of the gold nanoparticles
produced by method C.
As can be seen from the experimental procedure, method A
and method B had the same amount of sodium citrate
dissolved in the same amount of gold stock solution. The
citrate basically act as a reducing agent (reducing agent is an
element or compound that loses electron in a redox chemical
reaction) and as a stabiliser. The citrate anions electrostatic
repulsion keeps the nanoparticles separated and so prevents
the nanoparticles from aggregating. Reducing the amount of
citrate causes the nanoparticles to aggregate, to a point at
which they precipitate. Therefore the solution turns into
black. This could have been one of the reason why, the
solution of method B precipitated into black over time.
Temperature also have a strong influence on the size of gold
nanoparticles. Generally, the greater the energy and
concentration of the reducing agent, the smaller the resultant
gold particles in the suspension; reducing the temperature
shifts the size and quality of gold nanoparticles towards
larger diameter. In method A, the solution was boiled to
100
o
C so greater energy was supplied to the nanoparticles to
form resultant gold particles of size 25nm. Whereas in
method B, the solution was exposed to UV lamp and as the
solution turned black over out, this could mean that the UV
could not provide sufficient energy for smaller particles to
form. As a result, we had to expose the solution to UV lamp
for much longer period than we were suggested in the
protocol that was provided to us and so method B was not
analysed further.
In Method C, the solution was only stirred so it had the
lowest activation energy. This method did produce red
solution, but the solution quickly formed a precipitate. At
the instant when the solution was produced it was red, then
the solution formed dark purple precipitate, and at last
solution formed dirty blue/brown precipitate. The size of
gold nanoparticle of method C was determined to be 19nm.

Conclusion

Method A was found to be the best method so far to produce
gold nanoparticles. The size of gold nanoparticles produced
by method A was 36nm by route (I) and 25nm by route (II).
Method C was the second best method to produce gold
nanoparticles and the size of these particles was determined
to be 19nm by route (I).
The experimental method of B and C could be improved
further by using a much more efficient UV lamp which
could provide higher activation energy. Also the equation
used in our experiments was not the right equation, as it can
only be applied to particle size greater than 10-15nm. The
red colour gold nanoparticles are usually size of 10nm as
can be seen in figure 1. Using the right equation could lead
to the precise value of gold nanoparticles. Therefore, I
conclude that the route (II) was the best method to determine
the size of gold nanoparticles, as the value provided by that
method was fairly precise than route (I).

References

[1] Nanotechnology timeline, http://www.nano.gov/timeline
[2] Stained glass, http://en.wikipedia.org/wiki/Stained_glass
[3] Ramsden, J. (2011). Nanotechnology. Oxford ,Waltham,
MA: William Andrew/Elsevier.
[4] Takeichi, N. (2012). Geostationary station keeping
control of a space elevator during initial cable deployment.
Acta Astronautica, 70(0), 85-89.
[5] Heiligtag, F. J., & Niederberger, M. (2013). The
fascinating world of nanoparticle research. Materials Today,
16(78), 262-271.
[6] Philippe Colomban. (2009). The use of metal
nanoparticles to produce yellow, red and iridescent colour,
from bronze age to present times in lustre pottery and glass:
Solid state chemistry, spectroscopy and nanostructure.
Journal of Nano Research, 8, 109. doi:10.4028.
[7] Susie Eustis and Mostafa A. El-Sayed (2005). Why gold
nanoparticles are more precious than pretty gold: Nobel
metal surface plasmon resonance and its enhancement of the
radiative and nonradiative properties of nanocrystals of
different shapes. doi: 10.1039/B514191E
[8] Gold Nanoparticles: Optical Properties,
http://nanocomposix.com/pages/gold-nanoparticles-optical-
properties
490 300 310 320 330
-0.2
-0.13
-0.1
-0.03
0
0.03
0.1
0.13
0.2
0.23
wavelengLh/nm
a
b
s
o
r
b
a
n
c
e
/

absorbance vs wavelength
Mitul Patel 6

[9] J. Kimling, M. Maier, B. Okenve, V. Kotaidis, H. Ballot,
and A. Plech (2006). Turkevich Method for Gold
Nanoparticle Synthesis Revisited.


Appendix
The results obtained using the spectrophotometer are given
in table 1 and table 2 below.
Wavelength
nm
Absorbance
%
Absorbance +
calibration value
500 -0.152 0
501 -0.152 0
502 -0.152 0
503 -0.152 0
504 -0.152 0
505 -0.152 0
506 -0.143 0.009
507 -0.129 0.023
508 -0.11 0.042
509 -0.049 0.103
510 0.037 0.189
511 0.143 0.295
512 0.211 0.363
513 0.287 0.439
514 0.404 0.556
515 0.475 0.627
516 0.456 0.608
517 0.44 0.592
518 0.409 0.561
519 0.386 0.538
520 0.365 0.517
521 0.344 0.496
522 0.323 0.475
523 0.303 0.455
524 0.281 0.433
525 0.266 0.418
526 0.249 0.401
527 0.236 0.388
528 0.221 0.373
529 0.207 0.359
530 0.195 0.347
531 0.183 0.335
532 0.175 0.327
533 0.16 0.312
534 0.151 0.303
535 0.136 0.288
536 0.124 0.276
537 0.111 0.263
538 0.095 0.247
539 0.079 0.231
540 0.064 0.216
541 0.048 0.2
542 0.031 0.183
543 0.011 0.163
544 -0.01 0.142
545 -0.034 0.118
546 -0.058 0.094
547 -0.082 0.07
548 -0.108 0.044
549 -0.139 0.013
550 -0.152 0
Table 1. Shows the data of method A obtained using the spectrophotometer.
wavelengLh/nm absorbance
497 -0.134
498 -0.134
499 -0.107
300 -0.043
301 0.087
302 0.178
303 0.169
304 0.133
303 0.09
306 0.068
307 0.03
308 0.031
309 0.014
310 -0.007
311 -0.026
312 -0.044
313 -0.06
314 -0.07
313 -0.08
316 -0.089
317 -0.089
318 -0.1
319 -0.106
320 -0.111
321 -0.117
322 -0.124
323 -0.128
324 -0.13
323 -0.132
326 -0.133
327 -0.134
328 -0.134
329 -0.134
Table 2. Shows the data of method C when the experiment was repeated
for the second time obtained using the spectrophotometer.
Mitul Patel 7