Lancaster

Write balanced equations and calculate gravimetric

capacities of ammonia borane (maximum hydrogen
release) and V0.85Ti0.1Fe0.05H2 with respect to the release
of hydrogen?
Relative Atomic Masses H:1.0 B:10.8 N:14.0 Ti:47.9
V:50.9 Fe:55.8

Lancaster
Write
balanced equations and calculate gravimetric capacities

of ammonia borane (maximum hydrogen release) and

V0.85Ti0.1Fe0.05H2 with respect to the release of hydrogen?
Relative Atomic Masses H:1.0 B:10.8 N:14.0 Ti:47.9 V:50.9 Fe:55.8
H3NBH3 BN + 3H2

V0.85Ti0.1Fe0.05H2 V0.5Ti0.1Fe0.05 + H2

wt% = 6 / (6+10.8+14.0)
= 19.5

= 3.78

wt% = 2 / (43.27+4.79+2.79+2)

Lancaster
Compare ammonia borane and V0.85Ti0.1Fe0.05H2 as
hydrogen storage materials.

Lancaster
Compare ammonia borane and V0.85Ti0.1Fe0.05H2 as hydrogen
storage materials.
ammonia borane V0.85Ti0.1Fe0.05H2
- v. high wt%

- v. low wt%

- Impractical in real life - good thermodynamics and

(need catalyst) reversibility
- Irreversible due to polymer - no change in topology for
formation

hydrogen release / uptake

Lancaster
Discuss covalent organic frameworks as a hydrogen
storage material.

Lancaster
Discuss covalent organic frameworks as a hydrogen
storage material.
Very high surface area and contains no metals (very light)
Topology does not change during hydrogen uptake / release
Hydrogen binding very weak requires low temperatures
and high pressures (thermodynamics bad)
Functional groups can be added to promote interactions
with hydrogen

Wright
Discuss how the following compound acts as a
biomimeticmodel for the active site in [FeFe]hydrogenase enzymes.

Replace
{4Fe4S}
for one
electron
source.
Redox
couple of
ferrocene*
similar to
{4Fe4S}

NH difficult to synthesise so
use NR instead.
Use of N(H/R) gives full activity
in Apo protein whereas O, CH2
gives no activity

Carbonyls present but in

slightly different
position.
Contains 2Fe2S

DPPV rigid and

cannot bridge two
centres.
Allyl phosphines
electron donating
like cyanide.
In biology CN
stabilised by
protein, but in real
life reacts with

Wright
Compare solid state WOC Co-OEC with respect to
photosystem II OEC

Wright
Compare solid state WOC Co-OEC with respect to
photosystem II OEC
Co-OEC
PS II OEC
CoO lattice
Co(II) Co(III)
Co(II) dissociates from solid support
With no overpotential Co(II) does not
oxidise
Potential bias needed to oxidise Co(II) to
Co(III)
Catalyst will begin to degrade
Can be repaired by adding inorganic
phosphate Pi which binds Co(III) back to
solid support

MnO lattice
Mn(III) Mn(IV)
Uses light to expel H+ and e- as
a source of an overpotential
TOF = 100 400 s-1
Mn surrounded by acetates
etc to prevent catalyst being
attacked by reactive species
(ie oxygen)

Wildgoose
A hydrogen fuel cell has been constructed and
approximations of the performance can be analysed by a
linear approximation of an IV curve.
The gradient magnitude of the IV curve is 20 mV mA-1
Calculate the current and power when the cell is
operated at 0.8 V and maximum power of the fuel cell.

Wildgoose
A hydrogen fuel cell has been constructed and
approximations of the performance can be analysed by a
linear approximation of an IV curve.
The gradient magnitude of the IV curve is 20 mV mA-1
Calculate the current and power when the cell is
operated at 0.8 V and maximum power of the fuel cell.
i = (VOC Vcell) / k = (1.2 0.8) / 20 = 0.02 A
W = (Vcell(VOC - Vcell)) / k = 0.016 W
2

Wildgoose
Describe the main requirement for a polymer electrolyte
membrane (PEM)? How does Nafion fullfill this? What are
the disadvantages of Nafion as a PEM?

Describe
the main requirement for a polymer electrolyte membrane (PEM)? How does

Nafion fullfill this? What are the disadvantages of Nafion as a PEM?

-Needs to conduct protons / electrons WHILST being resistant to highly acidic media.
-Nafion is fluorinated to prevent -CH bond radical attack
Hydrophillic sulphonated side chains conduct protons
-(-F2C=CF2-)- hydrophobic backbone gives mechanical support
Needs to be wet as water molecules essential for fast proton transport
-Complex and environmentally unfriendly synthesis
Expensive
Proton conductivity declines as water content decreases
In DMFC methanol can permeate membrane
Chemically degrades over time as highly acidic and constant flow of ionic current
Fragile to pressure and thermal build ups
Contributes to voltage loss
Can inbed in PTFE for higher mechanical strength

Fielden
Sketch an electronic energy level diagram of a Tandem
cell using n-type TiO2 and p-type NiO (You do not need to
know what n-type and p-type means so please do not ask
they are just names).
What are the advantages and disadvantages of a tandem
cell in comparison to a DSSC?

Fielden
Sketch an electronic energy level diagram of a Tandem
cell using n-type TiO2 and p-type NiO

Fielden
What are the advantages and disadvantages of a tandem cell in comparison
to a DSSC?
Increased spectral coverage (dyes with complementary absorption profiles)
Increased photovoltage (VOC)this is now the difference in energy between the CB
of TiO2, and VB of NiO (or other p-SC)
Tandem efficiency > 15%
Best tandem cells are ca. 4% efficient worse than regular DSSC. The limit is the
p-type photocathode
Hole injection fast to NiO (~10-12 s) but recombination also fast (~10-9 s)injection
only 103 times faster than recombination (10 8 times faster in TiO2 n-DSSC)
Hole transport through NiO slow: >100 x slower than electron transport through TiO 2

Fielden
What are the requirements for a dye? What are the
requirements for the solvent? Give an example of each.

What are the requirements for a dye? What are the requirements for the solvent? Give an example
of each.
Dye (Ru(pby)3)
Cover full vis / near IR with high extinction coefficient
Strong binding to semiconductor (via CO 2H or PO3H2)
Excited states (S1 / T1) higher in energy than semiconductor CB edge
Oxidised state (S0) lower in energy than redox electrolyte couple
Not aggregate on semiconductor surface
Photo- Chemically- Electrically- Thermally- Stable
Solvent (MeCN)
Chemically stable and low volatility
Low viscosity (minimise charge transport problems)
Good solvent for redox mediator and additives
Poor solvent for dye and semiconductor
Does not react with dye and semiconductor
Can be sealed into unit

Yimin
What are the differences between a microemulsion and
a miniemulsion?
What is otswald ripening?

Yimin
What are the differences between a microemulsion and a miniemulsion?
Microemulsion (<100 nm)
Mixtures of oil / water / surfactant that are clear, isotropic, and thermodynamically stable
Miniemulsion (100-1000 nm)
Thermodynamically unstable (phases eventually separate), not necessarily clear
(scatters light to appear milky), and not necessarily isotropic due to larger particle sizes.
What is otswald ripening?
Phenomenon in solid / liquid solutions which describes evolution of an inhomogeneous
structure over time. When a phase precipitates, energetic factors causes larger
precipitates to grow drawing material from smaller particulates which shrink

Yimin
Explain the electronic differences between zigzag and
armchair CNTs

Yimin
Explain the electronic differences between zigzag and armchair
CNTs
Armchair
Metallic
p-orbitals orientated perpendicular to one another so direct
overlap is possible
Zigzag
Semiconductor
p-orbitals twisted so overlap is hindered

Round
Give an expression for the relationship between the real
radii of sample defect, tip, and detected distance of
sample defect in AFM (probe sample convolution).
If the detected distance is 100nm, what is the real radius
of the sample defect if the radius of the tip is 50nm?

Round
Give an expression for the relationship between the real radii of
sample defect, tip, and detected distance of sample defect in AFM
(probe sample convolution).
L = (4Rr)1/2
If the detected distance is 100nm, what is the real radius of the
sample defect if the radius of the tip is 52nm?
100 = (4 x 52 x r)1/2 r = 48 nm

Round
Name the three main classes of inorganic solid
nanoparticles. Give a brief description of each with an
application.

Round
Name the three main classes of inorganic solid nanoparticles. Give a brief description
of each with an application.
Magnetic
Magnetic elements with magnetic properties
MRI / Hyperthermia therapy
Gold
Surface plasmon resonance
Biosensors (pregnany tests) / Redox / Fluorescence etc
Quantum Dots
Core II VI elements ie CdSe with ZnS shell broad excitation and sharp emis
Photodynamic therapy / FRET based biosensors