SEMESTER II EXAMINATIONS

2018/19

CHEM 40870 / CHEM 40770

Nanomaterials Chemistry
Nanochemistry (Taught MSc)

Professor Howe

Professor Redmond

Associate Professor Brougham

Associate Professor Quinn*

Time Allowed: 2 Hours

Instructions for Candidates

Answer ALL Questions

The assignment of marks to a question, and to the parts of that question, is indicated in
parentheses.

Please use a separate answer book provided for each question.

No loose rough work sheets are to be used. The rough work for each question should be
included in the answer book for that question.

Instructions for Invigilators

The use of electronic calculators (non programmable) is permitted.

Graph paper should be provided.
Provide each student with two answer booklets.

Page 1 of 6
Attempt Question 1 and 2.

1. Answer two parts from (a) to (c).

(a) A sample of 10 nm spherical Au NPs has been contaminated with either semiconducting
single-walled carbon nanotubes, 30 nm gold nanorods, 50 nm spherical AuNPs or graphene
oxide. You have access to spectroscopic techniques but no access to microscopy. Suggest
measurements that could be performed to check for the presence of each contaminant? (15)
Your answer should detail:
(i) The position of the spectroscopic features.
(ii) The optical phenomenon which gives to the observed spectroscopic feature.

Evaporation of a 100 mL sample of the purified Au NPs yielded 7.5 mg of Au.

(iii) Calculate the concentration of the purified NPs given the density of gold is 19.32 g cm−3.
(iv) Comment on the difference in the total surface area of the NPs in the 100 mL compared
to the surface area of a single bulk particle of mass 7.5 mg. (10)

(b) Microscopy is a powerful technique to image NP interactions with cells. Tungsten disulfide
nanoparticles can act as contrast agents for CT imaging of tumours due to the strong X-ray
attenuation of elemental W. Below are images recorded for cells exposed to WS2 NPs.

(i) Identify the technique and the collection modes used to record images A and B. (3)
(ii) Describe the electron scattering processes that give rise to the differences observed
between the images and the instrument configuration to allow the detection. In the case
of image A describe what gives rise to the differences observed regions 1 and 2. (8)
(iii) Describe three mechanisms of NP cellular uptake. (4)
(iv) Describe two other applications of NPs for cell studies and the specific advantage posed
by the use of NPs. (5)
(v) Describe two optical methods that allow the detection of NPs in cells. In your answer you
should provide details of the nature of the light being detected and provide examples of
NPs that can be imaged in this way. (5)

Question continues over page…

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(c) Inorganic quantum dot materials exhibit excellent size dependent properties.
(i) Summarise with the aid of suitable sketches the difference in the electronic structure
between molecules, QDs and bulk semiconductor materials. (5)
(ii) Using appropriate sketches, describe the processes that may occur when a photon of
light is absorbed by a QD. (5)

A researcher has been sent the emission spectra recorded for two CdSe QD samples, which
show emission at 480 nm for sample 1 and 600 nm for sample 2.
(iii) Calculate the energy of the emitted light in units of eV and kJ mol−1. (5)
(iv) Using the equation below describing the change in energy for a QD with radius r
estimate the size of the QDs in each sample. (8)

1 eV = 1.6022  10−19 J
NA = 6.022  1023 mol−1
c = 2.998  108 m s−1
me = 9.10938 × 10−31 kg
Egap for CdSe = 1.74 eV
h = Planck’s constant 6.626 × 10−34 J s
For CdSe: me* = 0.13 me and mh* = 0.45 me

(v) TEM analysis revealed that sample 1 was significantly less monodisperse than sample
2. How would this be expected to manifest in the spectra. (2)

Question 2 is on the following page…

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2. Answer two parts from (a) to (c).

(a) The critical nucleation radius for a given material can be predicted using the following
relation:
2𝛾
𝑟𝑐 =−
𝐺𝑣

Where  is the surface free energy and Gv the Gibbs energy per unit volume of the solid. For
copper  = 0.200 J.m-2 and Gv = -1.77x109 J.m-3. In an experiment monodisperse 20 nm
spherical Cu nanoparticles are prepared by thermal decomposition of 2 mmol of copper(II)
acetate in the presence of an excess of dodecanethiol (DDT, C12H25SH) and other reagents.
The footprint of DDT on copper is c. 0.24 nm2, and the density of bulk copper is 8.96 g/cm³.

(i) Calculate the critical nucleation radius for Cu nanoparticles. (1)

(ii) Calculate the number of nanoparticles after the reaction (assuming 100% yield) and
use this value to estimate the mimimum %yield of the nucleation step (the fraction of
monomer transformed into nuclei during the burst). Comment on the implications of
this value (10)
(iii) Calculate the number copper atoms per unit surface area of the nanoparticles. Use
the value obtained to discuss the limiting factors for binding dodecanethiol on copper.
(8)
(iv) Discuss all of the assumptions made in these calculations. (6)

(b) For nanoparticles synthesised by thermal decomposition methods in non-aqueous solvents

long chain alkyl ligands, e.g. oleic acid or dodecanethiol, play an important role in stabilising
the nanoparticles in suspension both during and after their formation.
Describe in detail the role of ligands in either;
(i) the formation of non-aqueous NP suspensions during nanoparticle formation (by
thermal decomposition), and in particular the effect of the ligand to precursor mole
ratio (at fixed precursor concentration) on determining particle size in terms of the la
Mer mechanism. (25)
Or;
(ii) providing colloidal stability. In particular describe their key contributions to the overall
inter-particle interaction potential. (25)

Question continues over page…

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(c) Oleic acid stabilised cubic magnetic iron oxide (Fe3O4) nanoparticles were synthesised by a
thermal decomposition method. A typical TEM micrograph recorded for a sample of the dried
heptane suspension is shown below. The dynamic light scattering correlogram G(t) which
was recorded for the heptane suspension is also provided. The DLS instrument was setup to
detect at 90o using red light at 633 nm, hence for heptane q = 1.87x10-7 m-1.

(i) Comment on the form of the correlogram (annotate a sketch of G(t) it in your
answerbook). (5)
(ii) Estimate the average TEM size, dTEM, from the micrograph and the correlation time,
c, from the correlogram. (5)
(iii) Use the relation given in Eqn 1 to determine the particle diffusion coefficient, Dt. (5)
1
𝐷𝑡 = Eqn 1
𝑞 2 𝜏𝑐
(iv) Use the Stokes-Einstein relationship, Eqn 2, to determine the average hydrodynamic
size, dhyd; (5)
𝑘𝐵 𝑇
𝑑ℎ𝑦𝑑 = Eqn 2
3𝜋𝜂𝐷𝑡
where kB = 1.380x10-23 JK-1, T is the temperature, and the viscosity of heptane,  =
3.74x10-4 Pa s (at 25 oC).
(v) Comment on the nature of the values for size obtained from the two techniques and
what these suggest about the suspension. (5)

oOo

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 Periodic Table of the Elements

1 2 Group (new notation) 13 14 15 16 17 18

I II Group (old notation) III IV V VI VII VIII

1 N Atomic number 2
Hydrogen Name Name Helium
H El Symbol He
1.0079 Mass Atomic mass 4.0026
3 4 5 6 7 8 9 10
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Li Be B C N O F Ne
6.941 9.0122 10.811 12.0112 14.0067 15.9994 18.9984 20.18
11 12 13 14 15 16 17 18
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Na Mg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar
22.989 24.305 26.9815 28.086 30.9738 32.066 35.453 39.948
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.0983 40.08 44.956 47.87 50.942 51.996 54.938 55.847 58.933 58.69 63.546 65.39 69.723 72.61 74.922 78.96 79.904 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.468 87.62 88.905 91.224 92.906 95.94 98 101.07 102.905 106.42 107.868 112.411 114.82 118.71 121.75 127.60 126.904 131.29
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.905 137.34 138.91 178.49 180.948 183.85 186.207 190.2 192.22 195.09 196.967 200.59 204.38 207.19 208.98 209 210 222
87 88 89 104 105 106 107 108 109
Francium Radium Actinium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium
Fr Ra Ac Rf Db Sg Bh Hs Mt
223 226 227 261 262 266 264 269 268

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Cerium Praesodymium NeodymiumPromethium Samarium Europium Gadoloinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.12 140.907 144.24 144.913 150.35 151.96 157.25 158.925 162.50 164.93 167.26 168.934 173.04 174.97
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Thorium Proactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.038 231.036 238.03 237.048 244.064 243 247 247 242.058 254 257.095 258.10 259.101 260.105

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