Universitat Politècnica de Catalunya

Engineering Physics
Bachelor’s Thesis

Photocatalytic water splitting over Au/TiO2

nanoclusters
s

Author: Supervisors:
Maria Miró Jordi Llorca
Lluís Soler

inte

January 2018


Contents

Acknowledgements ...................................................................................... iii

Abstract ....................................................................................................... iv

1 Introduction ............................................................................................... 1
1.1 Current energetic model ..................................................................................1
1.2 Tendency towards decarbonization .................................................................3
1.3 Hydrogen .........................................................................................................4
1.4 H2 production ..................................................................................................6
1.5 Aims of this work ............................................................................................8
2 Theoretical background ............................................................................. 9
2.1 Photocatalytic H2 production ..........................................................................9
2.1.1 Principles of photocatalytic H2O splitting ................................................. 10
2.1.2 Strategies to improve performance ............................................................ 12
2.1.3 Photocatalytic production of H2 from EtOH and H2O mixtures over
Au/TiO2 nanoclusters ........................................................................................... 13
2.2 Au nanoclusters ............................................................................................ 14
2.2.1 Stability of thiolate protected gold nanoclusters ....................................... 14
2.2.2 Nanoscale gold catalysis ............................................................................ 15
3 Experimental section ............................................................................... 16
3.1 Photocatalyst preparation and deposition..................................................... 17
3.2 Experimental set-up ...................................................................................... 19
3.3 Evaluation parameters .................................................................................. 21
4 Results & discussion ................................................................................ 23
4.1 Photocatalyst characterization ...................................................................... 23
4.2 Photocatalytic tests ...................................................................................... 27
4.2.1 Au nanoclusters ......................................................................................... 27
5 Conclusions & further work..................................................................... 33

A Photocatalyst preparation calculations (1%Au25/TiO2) .......................... 34

B Table of sizes of the nanoparticles PG, PT and PM .............................. 36

C Surface area exposed over catalyst loading ............................................. 37

List of Figures ............................................................................................. 38

List of Tables .............................................................................................. 39

References ................................................................................................... 40

ii
Acknowledgements

I would like to express my honest gratitude to Dr. Jordi Llorca Piqué and Dr. Lluís Soler
Turu for giving me the opportunity to work in such promising project and for their
expert advice, extraordinary support, supervision, and for taking the time to mentor me.

I am also grateful to the people at Institut de Tècniques Energètiques for being so lovely
and engaging people, always willing to help. I am especially thankful for the support,
encouragement, and guidance of Dr. Albert Casanovas.

Lastly, I must express my heartfelt gratitude to my family and my friends for their
unfailing support throughout these four years of study. This accomplishment would not
have been possible without them.

Thank you.

iii
Abstract

Developing a source of energy which is storable, clean, continuous and renewable is

required to meet global energy demand and avoid the possible consequences of the
climate change which may be irreversible. Hydrogen is an advantageous fuel for being
abundant, having high energy yield, environmentally friendly and high storage
capability.

Most methods for producing hydrogen from water are cost-prohibitive or require large
amounts of energy, but recent studies of water splitting with the help of a photocatalyst
and a renewable source of energy as UV light have gained interest. The most common
photocatalyst used is TiO2 loaded with noble metal nanoparticles.

The major aim of this work is to improve the performance of these photocatalysts by
using Au clusters anchored on TiO2 in order to increase the surface/volume ratio of Au
exposed. Three types of nanoclusters are going to be studied: Au20, Au25, and Au144 and
the results will be compared to conventional Au nanoparticles, which have a larger
particle size.

Hydrogen production has been evaluated under dynamic conditions at room temperature
and ambient pressure in a photocatalytic reactor equipped with an emitting UV light
source. Gaseous water and ethanol mixtures have been the reactants together with a gas
carrier of argon (Ar).

iv
Chapter 1

Introduction

1.1 Current energetic model

Humankind has been burning biomass since antiquity. After all, humans were the first
to discover how to make a fire and use it in his favor. Humans have made good use of
the Earth’s resources until the arrival of the industrial revolution, which coincided with
the harnessing of coal, a new energy source more efficient than wood. Energy
consumption has been experimenting a constant increase ever since.

Since then, there have been discoveries of other energy sources, such as oil and natural
gas. Together with coal, they dominate the energy consumption of the world. Figure 1.1
shows the world’s energy consumption by supply source expressed in million tonnes of
oil equivalent, Mtoe. It can be seen how, in the last 50 years, there has been an increase
of more than 300% of the world energy consumption: from less than 4000 Mtoe in 1965
to more than 12000 Mtoe in 2016. This has become in a system based essentially on the
combustion of fossil fuels and only 10% comes from the use of clean energy sources, like
geothermal, solar, wind and hydroelectricity [1].
14000
World consumption (Mtoe)

12000
10000
8000
6000
4000
2000
0
1965 1971 1977 1983 1989 1995 2001 2007 2013

Oil Natural gas Nuclear energy Hydroelectricity Renewables Coal

Figure 1.1: World energy consumption from 1965 to 2016. Adapted from BP [1].

1
The use of hydrocarbons as energy sources has resulted in an increase of the carbon
dioxide (CO2) in the atmosphere due to the emissions that cause the burning of fossil
fuels. Figure 1.2. shows the evolution of CO2 concentration in the atmosphere in parts
per million, ppm. It can be seen that has small wiggles in a range from approx. 200ppm
to 300ppm, but lately this concentration has taken off to more than 400ppm [2]. Ancient
air bubbles trapped in ice are the ones that allow one to step back in time and see what
Earth's atmosphere was like in the distant past. And from there it is possible to know
that levels of CO2 in the atmosphere are higher than they have been at any time in the
past 400,000 years. As shown in Figure 1.2, during ice ages, CO2 levels were around 200
ppm, and during the warmer interglacial periods, they hovered around 280 ppm. In
2013, CO2 levels exceeded 400 ppm for the first time in documented history.
concentration (ppm)

400
CO2 atmosphere

300

200

100
-800 -600 -400 -200 0
Thousand years before present (kyr)
Figure 1.2: Evolution of the CO2 concentration in the atmosphere in ppm. Adapted from [2].

This recent relentless rise in CO2 exhibits a remarkably consistent relationship with
fossil-fuel burning. Along with the increasing concentrations of CO2 and other
Greenhouse Gases (GHG), the surface of the Earth has been getting warmer since 1970
[3]. For the last 10,000 years, the Earth’s temperature has been fairly steady, fluctuating
by only about one degree Celsius. Little wiggles were caused by the sun getting brighter
or dimmer, or caused by volcanoes exploding and blocking the sun with dust for a couple
years, but nowadays temperature is 1°C higher than the average from the 10,000 years
before now [4].

Today may be the threshold of a new geologic era, which some term the Anthropocene,
an epoch dating from the commencement of significant human impact on the Earth,
where the climate is very different to the one our ancestors knew, but this term is still
yet to be approved by the International Commission on Stratigraphy (ICS).

Climate change has an anthropogenic origin, and the United Nations Environment
Programme (UNEP) established in 1988 the International Panel on Climate Change
(IPCC), to provide the world with a clear scientific view on the current state of
knowledge in climate change and its potential environmental and socio-economic
impacts. Climate change is now one of the major issues to solve because of its possible
consequences, such as irreversible loss of Arctic sea ice, now declining at a rate of 13.2%
per decade, loss of species, endanger global food supplies, cause disruptive mass

2
migrations, extreme heat, storms, sea level rise, ocean warming and acidification, and
other unpredictable consequences [5].

IPCC and the Group of Eight (G8) have warned that the global average temperature
should not exceed in 2°C the pre-industrial level. The 2015 Paris Agreement is aiming
to keep the global temperature increase well below 2°C, and hopefully limit it to 1.5°C,
which is not an easy outcome because we are already locked into at least another 0.5°C
of warming [6]. But if humanity wishes to preserve a planet similar to that on which
civilization developed and to which life on Earth is adapted, scientists suggest that
CO2 will need to be reduced from its current 400 ppm to at most 350 ppm, always below
450ppm.

Nevertheless, reversing this trend is in people’s hands. The way to reduce climate change
and preserve the Earth is to stop burning fossil fuels and quickly achieve a transition to
100% renewable energy, to lessen world consumption, and to improve the efficiency in
the methods of using energy. Global emissions of GHGs must follow a reduction path
that reaches zero from 2060 to 2080 in order to limit global warming and match the
Paris Agreement [7]. The timing and speed of emission reductions may differ between
countries, as a consequence of the principle of “common but differentiated
responsibilities” and between sectors due to the differing availability and cost of
technologies. However, it is clear that all sectors in all countries must aim for deep
decarbonization with the goal of reaching zero emissions. However, there is a huge
disconnect between policy ambitions and technology readiness, and industrial uptake.
This is mainly due to the lack of a business model: costs are immediate, but the
benefits are long term.

In conclusion, from the review of the current energy scenario, one can deduce that in the
21st-century mankind cannot apply the same energetic recipe as in the 20th century.
With all the information, it is clear that the availability of energy is compatible with
respecting the environment, and hence a sustainable social and economic development.

1.2 Tendency towards decarbonization

An outstanding fact that emerges from energy studies during the past two decades is
that, for the last 200 years, the world has progressively pursued a path of
decarbonization, a decreasing relative reliance on carbon. Wood, which relied most
heavily on carbon, was the first and most used fuel until mid 19th century. Wood is
made of much cellulose and some lignin. Both are structures with high carbon content.
Wood effectively burns about ten carbon for each hydrogen atom. By 1800 or so, in
England and other early loci of industry, high population density and the slow but steady
increase in energy use per capita raised the density of energy consumption. Wood and
hay, the prevalent energy resources rapidly became bulky and inconvenient to transport
and store. Hence, the need of another energy source with more density of energy, coal.
Coal approaches parity with one or two C’s per H, depending on the variety. Later, in
3
the beginning of the 20th century, started a demand for liquid fuels, easier to transport,
store and quantify, like oil. Oil is lighter yet, with more or less two H’s per C. Oil
defeated coal by 1950 as the world’s leading energy source.

There still had to take care of issues, like transfer between cans, which brings out a
fundamental point. The strongly preferred configuration for very dense spatial
consumption of energy is a grid that can be fed and bled continuously at variable rates.
There is a more successful grid, gas. Here is when methane appears, or most commonly
known as natural gas. A molecule of methane is just an atom of carbon surrounded by
atoms of hydrogen forming CH4. Natural gas is distributed through an efficient system
of pipes, right to each residence. It can be easily purified, permitting complete
combustion. Nowadays, natural gas is the third source of energy used worldwide [8].

The next natural step towards decarbonization, as shown in Figure 1.3., is to use
hydrogen combustion as an energy source. Hydrogen is a gas with zero emissions besides
water when combusted. Because carbon becomes soot or the feared greenhouse gas CO2,
and hydrogen becomes only water when combusted, carbon appears a bad element, and
hydrogen a good one. So, decarbonization is not only a fact but an advantageous fact.

H H
H C C H
C C C C
H C C C C H H H H H H H H H H H

C C C C H C C C C C C C C C H H C H H H
H C C C C H H H H H H H H H H H
C C C C
H C C H
H H

H:C=0.5:1 H:C=2:1 H:C=4:1 H:C=∞

Coal Oil Methane Hydrogen

Figure 1.3: Atomic hydrogen/carbon ratio of different fuels. Adapted from [8].

Therefore, developing a source of energy which is storable, clean, continuous and

renewable, is required to meet global energy demand. Hydrogen is an advantageous fuel
for being: (1) abundant from various sustainable sources (biomass or water); (2) having
high energy yield; (3) environmentally friendly and (4) high storage capability.
Consequently, it is considered as an ideal fitting alternative source of energy for fossil
fuels.

1.3 Hydrogen

Hydrogen is the most abundant gas in the universe and the simplest and smallest
element, consisting of one proton and one electron. Hydrogen constitutes 93% of our
universe, therefore being the most abundant element, and it is the tenth most abundant
4
element in the Earth’s crust [9]. However, due to its reactivity, under normal conditions
on Earth hydrogen is not found in its pure molecular form, H2, a colorless, odorless,
nontoxic gas. It is always combined with other elements, it is found in all fossil fuels, all
organic matter, and water.

Hydrogen can be used as an alternative energy source for fuel cells. It is not a primary
energy source, but an energy vector, as electricity or gasoline. Therefore, it transports
or stores the chemical energy contained in its H-H bonds, which can be released or
processed as required. The energy content of H2 is very high: 141.6 MJ/kg (39.3
kWh/kg), compared with 44.4 MJ/kg (3.12 kWh/kg) of gasoline [10].

When hydrogen reacts with oxygen from the air, the resulting products are only water
and heat (see equation 1.1). Also, nitrogen oxides can be formed due to the high
temperatures reached during combustion, when we use air as an O2 source [11].

1
H 2 (g) + O2 (g) ⎯⎯
→ H 2 O(l) + 2 8 6 kJ·mol-1 (1.1)
2
If one compares hydrogen to another gas fuel, like methane, it should be done using
volumetric higher heating value (HHV), which is the heat of formation, because it reflects
the true energy content of the fuel based on the energy conservation principle.

Parameter Dimensions Hydrogen Methane

3
Density at NTP kg/m 0.09 0.72
Gravimetric HHV MJ/kg 142.0 55.6
Volumetric HHV MJ/m3 12.7 40.0
Table 1.1: Comparison of different parameters between hydrogen and methane at normal conditions of 1
bar and 25°C (NTP). Adapted from [12].

Table 1.1. shows how hydrogen is 8 times lighter than methane and the difference
between energy carrier options. Despite the fact that hydrogen gas has a gravimetric
higher heating value (HHV) 2.5 times that of methane, at any pressure, hydrogen gas
clearly carries less energy per volume than methane [12].

In contrast to combustion, the oxidation of hydrogen in a fuel cell provides direct

electricity as well as heat and water but does not generate harmful nitrogen oxides. The
efficiency of fuel cells can reach fabulous values up to 90%, which is 3-4 times higher
than that of most combustion engines. Clearly, the combination of hydrogen and fuel
cells constitute one of the most desirable technologies to manage energy in the future
[12].

Like oil and natural gas, hydrogen can be transported via pipeline or shipped in
containers. Hydrogen benefits the environment because it replaces older, dirtier fuels,
thus reducing greenhouse gas emissions and improving air quality, and it can contribute
to economic growth through job development, investment opportunities, and the
creation of a sustainable, secure energy supply. But while infrastructures exist for

5
methane and oil, hydrogen gas requires a totally new distribution network, which is an
essential factor to take into account if hydrogen is to be the new energy source.

In 1972, the electrochemist John Brockis first used the concept of “Hydrogen Economy”
as the ultimate solution for energy and environment, a new energy system where
hydrogen would replace fossil fuels [10]. Without question, technology for a hydrogen
economy exists or can be developed. In fact, enormous amounts of hydrogen are
generated, handled, transported and used in the chemical industry today. But this
hydrogen is a chemical substance, not an energy commodity.

But to achieve an economy based on H2, that feeds the homes, industries, trades, and
transports, requires its production, distribution, storage and exploiting it in economic
ways. These ways must be equal or more competitive than the ones used today with
fossil fuels. It should be mentioned that most problems of creating an infrastructure for
the complete hydrogen operation as an energy carrier, have been identified and have
obtained considerable progress; furthermore, they are not completely new, because
hydrogen is a gas commonly used in the industry.

One of the principal problems for the establishment of this new economy is hydrogen
storage. As shown before, hydrogen’s energy density per volume unit is very small (12.8
MJ/m3). Thus, it is usually stored usually under high pressure or liquefied, with
associated risks. While these two techniques have almost reached their physical limits,
there is still potential for development in the field of solid materials such as metal
hydrides.

Hydrogen can be utilized to store clean energy that is produced both from traditional
fuels using carbon capture and storage technology and from renewable energy sources.
Stored as hydrogen or one of its compounds, this clean energy can be moved to where it
is needed. As an energy carrier, hydrogen holds the potential to dramatically transform
the ways in which we use energy. And, because hydrogen can be stored and transported
to where it is needed, it may be used in combination with fuel cells to provide energy in
locations not served by the electric power grid and, for stationary applications that
require very reliable sources of electricity, such as the information technology industry
and medical applications. Most importantly, because hydrogen can be produced from a
variety of energy sources found in most countries, it holds the potential for reducing
dependence on imported energy. When produced with clean technologies, it can
dramatically reduce the emission of carbon dioxide, an important greenhouse gas.

1.4 H2 production

Because hydrogen does not exist in a natural state it must be manufactured in an energy-
intensive process. The energy needed to produce hydrogen can be obtained from many
sources, including traditional fossil fuels, nuclear energy, and renewable energy sources.
Today, the most common method to produce hydrogen is to employ steam to separate

6
it from carbon found in petroleum and natural gas. Hydrogen can also be produced by
using electricity to separate it from oxygen in water through a process known as
electrolysis. The electricity for the electrolysis process can be produced from a variety of
energy sources such as fossil fuels, nuclear energy, and renewable energy sources such as
wind power, hydroelectricity, biomass, geothermal, and solar energy. Other less
developed and applied methods include thermo and biochemical processes [13].

Hydrogen from fossil fuels

Hydrogen can be produced from most fossil fuels. Since carbon dioxide is produced as a
by-product, the CO2 should be captured to ensure a zero-emission process. Because
hydrogen here is obtained by a non-renewable source of energy it can be called as well
non-renewable H2.

The production of hydrogen from fossil fuels can be done by a catalytic process termed
steam reforming from natural gas or coal. All of the used processes generate carbon
monoxide, CO, which later is converted to CO2 and H2.

Hydrogen from biomass

In biomass conversion processes, a hydrogen-containing gas is normally produced in a

manner similar to the gasification of coal. Currently, the pathways followed are steam
gasification, entrained flow gasification, and more advanced concepts such as gasification
in supercritical water, application of thermochemical cycles, or the conversion of
intermediates (e.g. ethanol, bio-oil or torrified wood). However, no commercial plants
exist to produce hydrogen from biomass.

Hydrogen from water splitting

It was 1800 when English chemist Nicholson discovered water splitting. He discovered
that when leads from a battery are placed in water, the water breaks up into hydrogen
and oxygen bubbles, which collect separately at the submerged ends of the wires. This
process is called electrolysis (see equation 1.2.).
1
H 2O + electricity ⎯⎯
→ H 2 + O2 (1.2.)
2
Electrolysis needs electricity to work, so depending on the energy source used to get that
electricity, is going to be non-renewable or renewable H2.

Other methods of hydrogen production are:

- Photo-electrolysis (photolysis): a photovoltaic system coupled to electrolyzers is

in charge of getting the solar energy needed for the reaction. The system offers
some flexibility, as the output can be electricity from photovoltaic cells or
hydrogen from the electrolyzer. Renewable H2.

7
 - Photo-biological production (biophotolysis): Photo-synthesis of algae organisms
is used for hydrogen production. The hydrogen obtained has not only not emitted
any GHG but has captured CO2 that has been converted to O2 and energy for
the algae.
- High-temperature decomposition: High-temperature splitting of water occurs at
about 3000°C. At this temperature, 10% of the water is decomposed and the
remaining 90% can be recycled [14]. Non-renewable H2.
- Thermo-chemical water splitting: conversion of water into hydrogen and oxygen
by a series of thermally driven chemical reactions. Thermo-chemical water-
splitting cycles have been known for the past 35 years. They were extensively
studied in the late 1970s and 1980s, but have been of little interest in the past
10 years. While there is no question about the technical feasibility and the
potential for high efficiency, cycles with proven low cost and high efficiency have
yet to be developed commercially.
- Photocatalytic water splitting: water splitting with the help of a catalyst and a
renewable source of energy as UV light of the sun. A problem that accompanies
catalysts is that the best ones to obtain hydrogen from water requires the use of
expensive precious metals, such as platinum, and are therefore not competitive
with current approaches to energy production.

1.5 Aims of this work

The main objective of this work is the hydrogen generation for energy purposes from
mixtures containing water and ethanol by means of a photocatalytic process in a reactor.

To achieve this general goal, five main objectives were defined as follows:

1. Preparation and characterization of an effective catalyst of gold nanoclusters

deposited over a substrate of titanium dioxide (TiO2).
2. Deposition of the catalyst onto the surface of a cellulose paper.
3. Preparation of the needed set-up for the reactor in order to achieve the desired
reaction.
4. Study of the photocatalytic reaction in terms of hydrogen production under
ultraviolet light by means of gas chromatography.
5. Comparison between different parameters that influence hydrogen production
and optimization of the catalyst.

8
Chapter 2

Theoretical background

This chapter is focused on presenting the theoretical concepts involved in this work,
which are principally the photocatalytic hydrogen production and the strategies to
enhance its performance.

2.1 Photocatalytic H2 production

As it has already been discussed in the previous chapter, the conversion of solar radiation
into hydrogen could overcome the fundamental discrepancies among solar energy supply
and human energy demands, offering the advantages of being transportable as well as
storable for extended periods of time. Photocatalytic water splitting using sunlight is a
promising technology capable of providing high energy yield without pollutant
byproducts.

Photocatalytic water splitting is an artificial photosynthesis process used for the

dissociation of water into its constituent parts, hydrogen (H2) and oxygen (O2), using
either artificial or natural light. Theoretically, only solar energy (photons), water, and
a photocatalyst are needed. Photosynthesis has been for many years a fascinating source
of inspiration for the development of model systems able to achieve efficient light-to-
chemical energetic transduction. This field of research, called “artificial photosynthesis”,
is currently the subject of intense interest, driven by the aim of converting solar energy
into carbon-free fuel hydrogen.

Being unlimited, renewable and free, solar energy is capable of producing electricity or
heat without the requirements of having turbines and maintenance. The energy usage of
one year could be provided by half an hour of solar irradiation on the Earth surface.
However, sunlight is an intermittent source of energy which limits the amount of solar
radiation due to its dependence on geographical position, day, time, and season. Another
disadvantage of solar energy is its low density per unit of Earth surface.

9
Water splitting using solar light follows the reaction shown in equation 2.1. The energy
needed is shown in equation 2.2:

1
H 2O ⎯sunlig
⎯⎯⎯⎯ → H2 + O (2.1)
ht
2 2
ΔG0 = 2 3 7 kJ · mol-1 = 2 .4 6 eV per molecule (2.2)

The standard Gibbs free energy change greater than 2.46 eV per molecule is equivalent
to the energy of photons with wavelengths in the range between 1010 and 500 nm.
However, pure water does not absorb solar radiation in that range, and therefore water
splitting is only possible in the presence of a photo-semiconductor which can absorb solar
energy and then use it to split the molecule in an indirect way, acting as a catalyst.

Fujishima and Honda first reported in 1972 hydrogen generation via splitting of water
using photocatalysts based on n-type TiO2. TiO2 was a promising photo-anode for UV
light-driven photocatalytic water splitting, which has been widely studied in many
photocatalytic reactions due to its chemical stability, low cost, environmentally friendly
nature, and tunable electronic energy band gap. However, TiO2 materials suffer from
two major drawbacks. One is the fast charge carrier recombination, which results in the
release of unproductive energy. Another one is the inability to harvest visible light since
TiO2 can only be excited by UV light due to its wide band gap of 3-3.2 eV which only
covers 4% of the solar spectrum, whereas 49% lies in the visible spectrum [15]. Therefore,
the low quantum efficiency (hydrogen yield per number of incident photons) limits the
TiO2 application for large scale. In consequence, research is being carried in the field of
materials science and engineering to improve and provide better semiconductor catalysts.

2.1.1 Principles of photocatalytic H2O splitting

The photocatalytic process is based on electron-hole pairs (e–/h+) that are generated in
semiconductors. Semiconductors have non-overlapping valence bands and conduction
bands with a band gap in between that of insulators and conductors. When sufficient
photochemical energy is applied, electrons will be excited into the conduction band,
leaving electron holes in the valence band and excess electrons in the conduction band.
These electron-hole pairs play key roles in the redox reactions of water splitting.
Electrons are responsible for reducing protons to hydrogen molecules, and oxygen anions
will be oxidized by the holes as shown in Figure 2.1.

10
 H2
+
H

- CB
UV light

recombination

+ VB

H2 O
TiO2
O2
Figure 2.1: Sketch of electron-hole generation by UV light radiation on TiO2.

The reaction is first initiated by photon absorption, which generates numerous electron-
hole pairs with sufficient potentials. Once the electron-hole pairs are generated, these
charge carriers need to move to the surface of the catalysts and react with surface active
sites. Finally, the photogenerated electrons reduce water to form hydrogen, and the holes
oxidize water molecules to give oxygen [16]. The major challenge in this step is the
recombination of electrons and holes [17].

The ability of photogenerated charge carriers to split water depends on the relative
positions of the VB and CB energy levels with respect to hydrogen and oxygen evolution
potentials. Therefore, the bottom of the CB must be located at a more negative potential
than the reduction potential of H+/H2 (0 V vs. normal hydrogen electrode (NHE)),
whereas the top of the VB has to be more positive than the oxidation potential of
H2O/O2 (1.23 V vs. NHE). In consequence, only if the photon energy is superior to 1.23
eV water-splitting reaction is theoretically viable. Nevertheless, in practice and due to
energy losses (transport of e−/h+, kinetic losses, e−/h+ recombination), the theoretical
value of 1.23 eV increases to 2.0 – 2.2 eV [18].

Several semiconductor materials fulfill the first condition, such as TiO2, KTaO3, SrTiO3,
ZnS, CdS, and SiC. However, some of them, like CdS, though with an interesting Eg (2.4
eV), are not stable in aqueous media, being susceptible to photo-corrosion when
dispersed in water. Titanium dioxide remains one of the most promising materials due
to its nontoxicity, high photostability, chemical inertness, and environmentally friendly
nature. Another advantage of TiO2 is its low cost, owing to the abundance of Ti (0.44%
of Earth’s crust). With worldwide reserves in excess of 600 million tons, the annual
production of Ti metal is approximately 90000 tons and the annual production of TiO2
is around 4.3 million tons. Among the different polymorphs, anatase holds a slower e−/h+

11
recombination, being more active than rutile. TiO2 major disadvantage is its large Eg
(3.2 eV for anatase), only activated by photons in the UVA region [19].

2.1.2 Strategies to improve performance

Various parameters affect the photocatalytic activity of an inorganic photoconductor

including surface chemistry, surface and junction defects, crystallinity, doping and deep
traps, band edge positions, particle size, and morphology. There are several ways to
improve TiO2 or others photocatalysts performance in hydrogen production. Current
research is mainly dedicated to two fronts: the development of a new TiO2 photocatalyst
by extending the absorption of the wavelength range into the visible light region, as well
as improving charge separation in order to avoid e−/h+ recombination.

To extend the spectral response to the visible light region, suitable modification methods
must be made, like doping, making heterojunctions with other semiconductors or metals,
and structural changes. In this work, the modification method used was to make
heterojunctions with a metal. In a metal-semiconductor heterojunction structure, noble
metals, such as Au, Pt, Pd, Ru, have been reported to trap photogenerated electrons
due to their significant role as electron sinks. Among noble metals, Au has been studied
as the preferred co-catalyst for photocatalytic hydrogen production due to its high
affinity towards photo-generated electrons, high resistance to oxidation, less activity
towards the side reactions of hydrogen production, and the existence of surface plasmon
resonance.

H2 Au nanocluster

- CB
UV light
- Ef

+
H

+ VB

H2 O
TiO2
O2

Figure 2.2: Sketch of electron-hole generation by UV light radiation on Au/TiO2 heterojunction.

The Fermi level (Ef) of gold nanoclusters lies slightly lower than the Ef from TiO2. This
way, photo-excited electrons find energetically favorable to migrate from TiO2 to surface
Au nanoclusters, until both Fermi levels are aligned with each other, as one can see in
Figure 2.2. The resulting Schottky barrier formed at the interface between TiO2 and Au

12
nanoclusters acts as an electron trap, providing an effective charge separation and
therefore inhibiting e–/h+ recombination. Also, Au nanoclusters present an absorption
band around 560 nm, corresponding to the surface plasmon band [20].

Finally, there is another method to avoid e–/h+ recombination, consisting in adding

reducing reagents, such as alcohols or carboxylic acids, into the water. This way,
photogenerated holes irreversibly oxidize the organic molecule that will act as a sacrificial
donor, preventing e–/h+ recombination and the H2 + O2 back reaction. These reagents
are called hole scavengers and reactions with a presence of this kind of reagents show a
much higher H2 production than those using only pure water as a reactive. The most
promising hole scavenger is ethanol. Ethanol offers numerous advantages among other
fuels: (1) it can be produced from renewable sources, (2) it has a relatively high hydrogen
content per unit volume in the liquid phase and a high hydrogen-to-carbon ratio
(H/C=3), (3) it is non-toxic, (4) it can be transported, stored and handled safely and
easily and (5) it is already available in the distribution networks of some countries.
Ethanol can be produced renewably from the fermentation of a large variety of sources,
mainly corn, sugarcane, and starch. But other non-edible sources, which do not compete
with food, such as cellulose, wood, agricultural and forest residues can also be used as a
source of bioethanol; these lignocellulosic increase the availability of raw materials and
reduce the production costs of bioethanol.

2.1.3 Photocatalytic production of H2 from EtOH and H2O

mixtures over Au/TiO2 nanoclusters

When a mixture of EtOH and H2O is made in order to produce H2 two reactions take
place. The multistep reaction pathway of the photoreaction of ethanol is presented below
in equation 2.3, indicating that the amount of H2 released is related to the amount of
acetaldehyde (CH3CHO) formed, which partly decomposes to CH4 and CO.

CH 3CH 2OH ⎯⎯
→ H 2 + CH 3CHO (2.3)

Ethoxide formation:
CH 3 CH 2 OH + Ti 4s + -O2s - ⎯⎯
→ CH 3 CH 2 O - Ti 4s + + OH(a) (2.3a)
Electron excitation:
TiO2 ⎯UVA
⎯⎯ → e - + h+ (2.3b)
First electron injection:
CH 3 CH 2 O - Ti 4s + + h + + Os ⎯⎯
→ CH 3 CH·OTi 4s + + OH a (2.3c)
Second electron injection:
CH 3CH·OTi 4s + + h + ⎯⎯
→ CH 3CHO(g) + Ti 4s + (2.3d)
Hydrogen reduction:
2 OH(a) + 2 e - ⎯Au nanoclusters
⎯⎯⎯⎯ → 2 O2s - + H 2 (2.3e)

(a): adsorbed; (g): gas; (s): surface

13
In step (a), ethanol is dissociatively adsorbed, forming an ethoxide and a hydrogen ion,
in the form of surface hydroxyl. Step (b) involves the excitation under UVA radiation
of VB TiO2 electrons to the CB, leaving an h+ behind. Reactions (c) and (d) happen
almost simultaneously, with the generation of a radical after the first electron injection,
releasing the second hydrogen ion, and the second electron injection, with the production
of acetaldehyde (CH3CHO). Finally, in reaction (e) the two remaining electrons in the
surface of the Au NP reduce the two hydrogen ions, yielding to the production of one
hydrogen molecule (H2) [21].

2.2 Au nanoclusters

A metal cluster is composed of a number of metal atoms grouped close together which
can have direct metal-metal bonding interactions or interactions through a bridging
ligand, but which are not necessarily held together by these interactions. Recently,
thiolate ligands have been used for the synthesis of gold clusters with high nuclearity.
Nanoparticles have all three external dimensions in the size range from 1 nm to 100 nm
as stablished by the British Standards. The two fields of clusters and nanoparticles have
merged closer together in recent years. Ultra-small gold nanoparticles (<2 nm) in the
quantum size regime can now be obtained with atomic precision. These ultra-small
nanoparticles are often called nanoclusters to distinguish them from regular
nanoparticles. The field of nanotechnology allows higher functionality and also reduces
both resource and energy requirements.

2.2.1 Stability of thiolate protected gold nanoclusters

Thiolate-protected gold clusters (Aun(SR)m) are nanomaterials that have received

significant attention as new functional nanomaterials because they exhibit size-specific
physical and chemical properties that are not seen in bulk gold. Thiolate ligands protect
gold nanoclusters from aggregation by providing electrostatic and steric barriers. The
relatively strong organothiolate-gold bond, which is partially covalent in nature, makes
it difficult to dissociate ligands from the nanocluster surface [22].

Gold nanoclusters with certain sizes possess superior stabilities due to geometric and
electronic reasons. Generally, the thiolate protected gold nanocluster comprises a
symmetric Au core, which is well-protected by a chain-like structure on the surface,
formed by thiolate ligands and gold ad-atoms. These clusters show size-specific physical
and chemical properties, such as photoluminescence, catalytic activity, and redox
behavior, that are not observed in the case of bulk gold. Furthermore, it is possible to
determine the geometrical structures of these clusters. For these reasons, applications
are expected to be found in various field, such as water-splitting photocatalytic materials.
Recent studies have demonstrated that the use of smaller co-catalyst particles result in
higher photocatalytic activity [20].

14
 2.2.2 Nanoscale gold catalysis

Gold nanoparticles (AuNPs) are typically of the size of 1 to 100 nm and have been used
as catalysts for the efficient production of useful compounds since Haruta reported the
high catalytic activity of metal oxides supported AuNPs in various reactions in 1989
[23]. Gold possesses a rich organometallic and coordination chemistry but has been
originally considered to be inert for catalytic application. Notwithstanding, AuNPs are
attractive for the catalysis by offering high surface-to-volume ratio and tunable electronic
and structural properties (including size, morphology, and even composition) to improve
the catalytic activity and selectivity.

The well-defined structure is crucial for the understanding of the gold nanoparticle
catalytic behavior regarding the size effect and active site. The atomic precise structure
(precise size, exact gold number, and well-defined surface) of gold nanocluster makes it
a promising candidate to study its catalytic behavior at atomic level and correlate the
catalytic activity with the cluster structures. Compared to conventional nanoparticles,
gold nanocluster adopts unique geometric and electronic structures. Gold nanoparticles
typically adopt an FCC structure, while gold nanoclusters have a different way of atom
packing. For example, an icosahedral gold core of most extensively studied nanocluster,
Au25, has been revealed by X-ray crystallography [23]. The ultra-small size of Au
nanocluster (1-2 nm) induces strong size-dependent electron energy quantization,
whereas metallic gold nanoparticles or bulk gold possess a continuous conduction band.
Gold nanoparticle shows sintering or structure change under certain reaction conditions.
The important factor for the catalytic application of gold nanoclusters is to balance the
nanocluster stability and activity.

15
Chapter 3

Experimental section

The first chapter presented the current energetic model, its advantages, and
disadvantages and exposed some of the issues that humankind has to try to overcome
the next years and the importance to solve them. In the second chapter, the theoretical
background of hydrogen production by means of photocatalytic water splitting was
explained. In this third chapter, the experimental work developed in the laboratory is
going to be presented.

Hydrogen production has been evaluated by means of a photocatalytic reaction carried

out over a photocatalyst deposited on a cellulose paper inside a photoreactor equipped
with an emitting UV light source. Gaseous water and ethanol mixtures have been the
reactants together with a gas carrier of argon (Ar).

Two different types of Au/TiO2 photocatalyst have been prepared and tested based on
Au nanoclusters and nanoparticles. The work is mainly focused on size effect of the Au
nanoclusters, but the performance of conventional Au is also evaluated for comparison.
Three different sizes of Au nanoclusters are going to be studied: Au20, Au25, and Au144.

Additionally, several parameters influence the hydrogen production. Basically, they are
the catalyst loading and the thermal pretreatment. The results of the influence of these
parameters are going to be presented in the fourth chapter of this work.

In the following pages, one can find a complete description regarding the preparation,
characterization, and deposition of the photocatalysts as well as the development and
assembling of the experimental set-up. Finally, the evaluation of the photocatalytic
performance will be presented.

16
3.1 Photocatalyst preparation and deposition

Preformed thiolate-protected Au20, Au25, and Au144 nanoclusters were delivered from the
Institute of Materials Chemistry (IMC) at Vienna University of Technology (TU Wien)
and are represented in Figure 3.1. The respective formulas of the nanoclusters are the
following: Au20(SCH2CH2Ph)16, Au25(SCH2CH2Ph)18 and Au144(SCH2CH2Ph)60. These
nanoclusters are soluble in toluene and not soluble in alcohols.

a) b) c)
Figure 3.1: (a) Detail of the core structure of Au20. Color labels: golden and yellow, Au. (b) Depiction of
gold and sulfur atoms, showing six orthogonal “staples” surrounding the Au13 core. Color labels: orange, Au;
green, sulfur. (c) Structure of the icosahedral Au144(SR)60 cluster. The grand core is covered in “staples”.
Color labels: orange, Au; yellow, S; black, C; white, H. The phenil groups have been left out for clarity
[24][25][26].

The first step towards preparing the catalyst is purifying the sample as received to
remove all the impurities. To do so, methanol is added to the vial and then ultra-
sonicated. As our complex is not soluble in methanol, the Au nanoclusters will remain
solid while impurities will dilute. Methanol is later removed using a micropipette leaving
just particles of interest in the vial. After the methanol purification, the sample is dried
in an oven at 50°C for 45 minutes and the amount of Au nanoclusters weighted after
transferring them in toluene into a second vial, which is sealed with parafilm and stored
in a fridge. Knowing the grams of complex and the volume of toluene concentration can
be calculated (see appendix A).

The loading of the Au nanoclusters was chosen to be of Au content of 1 wt.% with

respect to TiO2. The reason for choosing this Au content is that in previous studies the
effect of gold loading was analyzed and it was found that the maximum photogenerated
H2 rates were obtained at about 1wt.% Au/TiO2 [28]. For higher Au content, H2
photoproduction diminished, suggesting that an excess of Au is detrimental for hole
scavenging by ethanol on TiO2. Au loading is going to be studied in this work for loadings
lower than 1%.

The next step in the preparation of the catalyst is the impregnation of TiO2 with the
suspension of Au nanoclusters previously prepared. 100 mg of catalyst are going to be
prepared. The TiO2 corresponds to TiO2 P90. The method to impregnate the Au

17
nanoclusters on TiO2 is called incipient wetness impregnation and consists on the
deposition of a given volume of the suspension of the Au nanoclusters in toluene similar
to the pore volume of the TiO2 support. The impregnated TiO2 is dried in the oven at
50°C during 2 hours; The drying temperature will be studied further on this study.
Calcination is not desired to preserve the nanoclusters. Finally, the sample is grinded by
means of an agate mortar to avoid possible agglomerations and assure homogeneity of
the catalyst.

Catalyst deposition

To conduct the photocatalytic study, a previously weighted amount of Au/TiO2 is

dispersed in ethanol and ultra-sonicated to homogenize and deagglomerate the mixture.
The resultant suspension is poured onto a circular porous cellulose membrane of diameter
1.8 cm, which corresponds to the inner diameter of the tubular glass reactor. The
cellulose porous membrane was a laboratory filter paper from Albet, pore size 35-40 µm,
80 g·m-2, thickness 0.18 mm. The impregnated membrane is dried in an oven at 50°C.
Figure 3.2 shows the followed procedure.

Figure 3.2: Schematic drawing of the methodology used for the photocatalyst deposition.

The notation that is going to be used further on is 1%Au25/TiO2 for a 1% concentration

of Au25 nanoclusters on TiO2.

Three types of nanoparticles were delivered from Institut de Ciència de Materials de

Barcelona (CSIC). The difference between them was the molecule used to attach the
AuNPs to the TiO2 surface, which are shown in Figure 3.3. The AuNPs were given at
2%, 4% and 8% concentration, varying the size of the particle, which are shown in
Appendix B.
O O O

HS HS

OH OH HS OH

PG PT PM
Figure 3.3: Different ligand to TiO2. The notation used (PG, PT, and PM) is the one given from Institut
de Ciència de Materials de Barcelona (CSIC).

18
3.2 Experimental set-up

The photocatalytic tests were performed at room temperature and atmospheric pressure
in a tubular glass photoreactor inside a fume hood.

Reactants are transported to the tubular glass photoreactor with an argon stream
bubbled through a Drechsel bottle containing a liquid mixture of ethanol/water. The
concentration of the liquid mixture was calculated to obtain a gaseous reactant mixture
of EtOH:H2O=1:9 (molar basis), which was directly introduced in the reactor. In order
to get the desired molar concentration, the liquid mixture contained 87.5 mL of water
for every 12.5 mL of EtOH. Ethanol was chosen as sacrificial agent in the photocatalytic
experiments because of its renewable character and its widespread use. Argon was used
as a carrier gas because is heavier than other inert gases (N2, He, …) and is more effective
to purge the photoreactor.

-1
The gas hourly space velocity was ca. 26000 h , which means a residence time or contact
time between the reactants and the photocatalyst only 0.14 s. The UV-light source (from
SACOPA, S.A.U.) consisted of four LEDs at 365±5 nm and a synthetic quartz glass
cylindrical lens that transmits the light at 81.7 mW/cm2 to the photocatalyst. The
impregnated cellulose membrane was placed between the glass tubes of the photoreactor,
with the side that contains the photocatalyst facing towards the UV-light source. The
reactor tubes and the impregnated membrane were sealed using an O-ring, parafilm and
a clamp. The photoreactor was connected to a GC (micro gas chromatograph Agilent
490), for a complete analysis of the photoreaction products, which were monitored on-
line every 4 minutes. Figure 3.4 shows a photograph of the experimental set-up and a
close-up look at the configuration inside the tubular gas photoreactor. In Figure 3.5 one
can see a schematic drawing of the experimental set-up.

Figure 3.4: Photocatalytic experiment. (A) Experimental photoreactor. (B) Scheme of the central part of
the photoreactor. Extracted from [27].

19
Ar

Gas mass flow controller

Gas chromatograph
Sample

EtOH:H 2O=1:9

Drechsel bottle UV-Light

Figure 3.5: Schematic set-up of the photocatalytic experiment inside the fume hood.

From left to right, one can
provide Ar flux; a Drechsel
facing the sample and a
concentrations of different
chromatograph is collected
distinguish the following elements: a mass flow controller to
bottle containing H2O and EtOH mixture; a UV-light source
gas chromatograph, responsible for the analysis of the
gases, connected to a computer, where the data from the
and processed.

Gas chromatograph

In gas chromatography, the components of the sample being analyzed move at velocities
that are influenced by the degree of interaction of each constituent with the stationary
phase which coats the column. The substances having the greater interaction with the
stationary phase are retarded and consequently separate from those with lower
interaction. As the components elute from the column they can be quantified by a
detector.

The instrument used in this work is equipped with three different columns, MS 5Å, Plot
U and Stabilaw columns, and each one of them is connected to a thermal conductivity
detector, which relies on the thermal conductivity of matter passing around a tungsten-
rhenium filament with a current traveling through it. The difference in thermal
conductivity between the sample components in the carrier gas and the reference flux of
the carrier gas alone produces a voltage signal proportional to this difference, which in
turn is proportional to the concentration of the sample components. The result is a
voltage signal with respect to time, with the peaks corresponding to different compounds,
such as H2, O2, N2, CO, EtOH, CH3CHO, etc. According to their molecular weight and
polarity, the analysis is performed in separate columns. The integration of every peak
gives the relative concentration (%x) of each compound if the instrument has been
previously calibrated.

Finally, by means of the software provided by the same company, one can analyze on-
line and off-line the obtained chromatograms. All the upcoming discussion of the results

20
from different analysis will be based on the information provided by the gas
chromatograph.

3.3 Evaluation parameters

Data analysis will be carried out studying four parameters that will give the necessary
information to compare catalysts and come to a conclusion on performance.

H2 production

From gas chromatography, the H2 concentration is obtained. To know the H2 production

rate a conversion factor is needed and will be calculated from Equation 3.1.
%H 1
rH = 2
·Q· (3.1)
2
100 2 9 8 · 0 .0 8 2
where %H2 is the relative concentration of hydrogen and Q is the gas flow, expressed in
mL/h. The last part of the equation is a conversion factor from mL/h to mmol/h. In
this way, rH2 is expressed in mmol/h. This parameter will be widely used in the following
presentation and discussion of the results, as it quantifies the hydrogen production rate,
which is the main goal of this work.

Photoactivity

This parameter will allow to evaluate the role of the photocatalyst in hydrogen
production. Photoactivity k measures the H2 production rate with respect to catalyst
loading, as it can be seen in Equation 3.2.
rH
k= 2
(3.2)
m
Where rH2 is the hydrogen production rate in mmol/h and m is the amount of catalyst,
expressed in mg. In this way, the H2 production is normalized with respect to the amount
of photocatalyst in the cellulose paper. It is a useful parameter to compare photocatalyst
performance between different catalysts.

Apparent quantum efficiency

This parameter will be of use in evaluating the efficiency of the reactor configuration in
photonics terms. That is, if incident photons effectively yield hydrogen molecules,
through the steps previously discussed (absorption by TiO2 and generation of an e—/h+
pair, e— migration to the surface of the Au nanoparticle and e— transference to H+ to

21
produce molecular H2). It is assumed that two photons are required to liberate one
hydrogen molecule, as two electrons are needed. The apparent quantum efficiency (AQE)
will be calculated from Equation 3.3.
2 rH
AQE = 2
·100 (3.3)
Nλ
where rH is the hydrogen production rate in mol/h and N corresponds to the overall
2

number of photons irradiated by the LEDs plate, expressed in mol/h. N can be calculated
as follows. First of all, by means of the Einstein relation one can calculate the energy
corresponding to 1 photon, as in Equation 3.4, for a wavelength of 365 nm.
c
E = h·ν = h· = 5 .4 4 ·1 0 -9 J / photon (3.4)
λ
Then, N can be calculated from Equation 3.5.
mW 1 J / s 1 photon 1 mol 1 0 6 µmol 6 0 s
N λ = I rad · Areacm 2
· · · · · (3.5)
cm 2 1 0 3 mW 5 .4 4 ·1 0 -9 J N A photon 1 mol 1 min

where Irad is the incident radiation and Area the one illuminated by the LEDs, being the
result expressed in units of µmol photon/h.

Efficiency

The light-to-chemical energy conversion efficiency (η) is calculated from Equation 3.6.

rH ·ΔH 2
η= 2
·100 (3.6)
I ra d ·Area
where ΔH2 is the heating value of hydrogen, being 285.8 kJ/mol.

22
Chapter 4

Results & discussion

Chapter 3 was dedicated to the description of the experimental set-up. Chapter 4 will
be dedicated to analyze the results obtained in such experiments and to compare the
performance between the different catalysts tested.

4.1 Photocatalyst characterization

Ultraviolet-visible spectroscopy (UV-Vis) was used to characterize the catalysts

containing Au nanoparticles and X-Ray photoelectron spectroscopy (XPS) was used to
characterize the catalysts prepared with the Au nanoclusters.

UV-vis spectroscopy

The UV-Vis absorbance spectrum was collected with a Shimadzu UV3600 UV-Vis-NIR
spectrometer equipped with an integrating sphere. First of all, a blank analysis with
barium sulphate (BaSO4) was carried out in order to calibrate the instrument, by setting
the reference for zero absorbance. Afterwards, the samples were analyzed, in the range
from 800 nm to 290 nm, with a step of 1 nm. Figure 4.1 shows the obtained spectra.

23
 290 390 490 590 690 790
Wavelength (nm)

Au/TiO2
Au/TiO2 Non impregnated cellulose membrane

Figure 4.1: In blue, there is the UV-Vis spectrum of the cellulose membrane impregnated with the catalyst
and without impregnation in red.

The first comment is for the high absorbance showed by the photocatalyst for
wavelengths shorter than 400 nm. That is, when entering into the UVA region,
absorbance increases significantly, which is in concordance with the presence of the
polymorphs of TiO2 present in the sample. Anatase (~80%), with a band gap energy of
3.2 eV, can absorb photons with 𝜆 < 386 nm, while rutile (~20%), with Eg = 3.0 eV, can
absorb photons with 𝜆 < 412 nm. Therefore, a sudden increase in the absorbance starting
at ≈ 400 nm is as expected.

Secondly, in the central part of the spectrum one can see a peak in absorbance around
560 – 570 nm for the Au/TiO2 catalyst containing Au nanoparticles. This broad peak
corresponds to the localized surface plasmon resonance (LSPR) of Au nanoparticles
supported on TiO2 [29]. In this way, the existence of the LSPR peak for the blue spectrum
and the absence of the peak for the red spectrum corroborates the presence of Au NPs
in the photocatalyst.

X-Ray photoelectron spectroscopy

The motivation of using X-Ray photoelectron spectroscopy (XPS) is to determine

whether Au nanoclusters experience any change in its configuration before and after the
reaction of photoproduction of hydrogen. Other information we can get from XPS is the
concentration of Au with respect to TiO2 and if there is any contamination in the sample.
The chosen technique to do so is XPS because it is really a useful technique for catalyst
characterization since X-Rays have a penetration of just some nanometers in the sample.
In this way, only the surface is studied, which is the part of the catalyst in contact with
the reactants. The results will show the composition of the surface.

24
The detector inside the XPS is able to determine the kinetic energy (KE) of the electron
and from that information it is able to know the binding energy of such electron
subtracting it from the initial kinetic energy from the X-Ray source (see Equation 4.1).

BE = h·ν - KE - φ (4.1)

XPS analysis was performed on a SPECS system equipped with a Phoibos 150 MCD-9
detector. XPS can work with two different X-Ray sources: magnesium (Mg) and
aluminum (Al). The first source emits photons at E = 1253.6 eV and the latter at E =
1486.6 eV. Both sources have different outcomes in the spectrum. Experiments are being
carried out under high vacuum (10-8 bar). Resulting spectra is shown in Figure 4.2.

O 1s Ti 2p Au 4f

800 700 600 500 400 300 200 100 0

Binding energy (eV)

Figure 4.2: XPS spectrum for the 1%Au25/TiO2 photocatalyst.

In the XPS spectrum are marked the three elements of interest for this experiment.
There is an unmarked peak at 290 eV approx. corresponding to adventitious carbon.
The Au peak is less intense due to the little concentration on the catalyst (1%).

A second run of the XPS is done at high resolution in the range of interest where O, Ti
and Au appear. In Figure 4.3 one can see the high-resolution Au 4f XPS spectrum for
Au25/TiO2.

25
 80 81 82 83 84 85 86 87 88 89 90
Binding energy (eV)
CPS Au 4f Au4f5/2
Au 4f5/2 AuAu 4f7/2
4f7/2

Figure 4.3: XPS spectrum for 1%Au25/TiO2.

With the help of the software the signal is deconvoluted and integrated respect to the
baseline (not shown in the figure). The two peaks correspond to two electron orbitals,
4f5/2 and 4f7/2. Accurate positions and % concentration of the three elements are shown
in table 4.1:

Name Position (eV) %At Conc

O 1s 530.0 43.5
O 1s 531.3 11.5
Ti 2p3/2 458.7 22.4
Ti 2p1/2 464.5 22.3
Au 4f7/2 83.4 0.12
Au 4f5/2 86.9 0.14
Table 4.1: Results of the position of the peaks and % concentration of each element.

Comparing to the theoretical value of Au 4f7/2 = 84.00 eV and Au 4f5/2 = 88 eV it is

conclusive that it is Au in our sample. Adding up the percentages, the final concentration
of Au respect to TiO2 is of 0.25%, which is lower compared to the 1% of the bulk. This
may indicate either that some of the Au nanoclusters are not available at the surface or
are partly aggregated as shown in Figure 4.4:
e-
X-Ray

TiO2

Au nanocluster
Figure 4.4: Photocatalyst surface sketch.

26
A second experiment with the XPS is done with the sample after the photocatalytic
reaction, but no significant changes are seen. Table 4.2 and 4.3 show the results from
before and after UV-light exposition.

Results before UV-light exposition Au 4f7/2 Au 4f5/2 Ratio

Position 83.7 87.2 0.96
Full width half maximum (FWHM) 1.57 1.75 0.90
Table 4.2: Results before UV-light exposition. Ratio is the division between the first column and the
second column.

Results after UV-light exposition Au 4f7/2 Au 4f5/2 Ratio

Position 83.4 86.9 0.96
Full width half maximum (FWHM) 1.65 1.86 0.89
Table 4.3: Results after UV-light exposition. Ratio is the division between the first column and the second
column.

4.2 Photocatalytic tests

As stated in the introduction, two types of Au entities are going to be used for the
photocatalytic tests. On one side Au nanoclusters of different size anchored onto TiO2,
and on the other side, TiO2 decorated with Au nanoparticles.

Gold nanoclusters supported on TiO2 are going to be studied under the influence of
catalyst loading, Au concentration in the catalyst and drying temperature. A stability
test will also be conducted.

Hydrogen production in photocatalysts containing gold nanoclusters and gold

nanoparticles will be compared in order to infer on the role of the entity size.

4.2.1 Au nanoclusters

For the first experiments, 1%Au25/TiO2 is used. The reason for choosing this Au content
is that, as already commented, in previous studies the effect of gold loading was analyzed
and it was found that the maximum photogenerated H2 rates were obtained at about
1wt.% Au/TiO2 for nanoparticles. For higher Au content, H2 photoproduction
diminished, suggesting that an excess of Au is detrimental for hole scavenging by ethanol
on TiO2.

Influence of photocatalyst loading

A study with different catalyst loading was carried out and the results are shown in
Figure 4.5.

27
 140 140

120 120

100 100

k (mmol/h·g)
(mmol/h)

80 80

60 60

40 40

20 20

0 0
0 0.5 1 1.5 2 2.5 3 3.5 4
Catalyst loading (mg)
Total production Relative production

Figure 4.5: Influence of catalyst loading in H2 production.

For this experiment, 6 different loading values were studied: 1.5, 2, 2.5, 3, 3.5 and 4 mg.
Lower values were not attempted due to the difficulty of manipulation of the sample.

The results are represented by two different values, the total H2 production (shown in
blue) and the normalized production with respect to the catalyst loading (in red).

The relative production is maintained constant until 2.5 mg and then the H2 relative
production decreases. Then 2.5 mg is chosen as the optimal catalyst loading for the next
experiments for a proper balance of catalyst handling and hydrogen production.

Influence of temperature drying

Different drying temperatures were used to see if there is any change in the configuration
of the clusters that induced a better or worse efficiency of the reaction. A study with
different drying temperature was carried out and the results are shown in Figure 4.6. It
is clear that the higher the temperature the lower the hydrogen production. This is
explained in terms of agglomeration phenomena. Therefore, 50 degrees are chosen as the
drying temperature from now to avoid any damage to the sample.

28
 50

40

(mmol/h)
30

20

10

0
50 100
Temperature of drying (℃)

Figure 4.6: Influence of drying temperature of the catalyst in H2 production.

Influence of Au concentration

The next parameter studied is the gold concentration in TiO2. Up until now, 1%
concentration was used because other studies carried out with conventional Au
nanoparticles showed the best results; nevertheless, Au nanoclusters have not been
studied previously, so the influence of their concentration on TiO2 is explored here. The
effect of Au concentration was checked on photocatalysts containing 0.25%, 0.5% and
1% Au concentrations. The results are shown in Figure 4.7.

50 8
Normalized production (mmol/h·gcat·µgAu )

40 6.4
k (mmol/h·g)

30 4.8

20 3.2

10 1.6

0 0
0.25 0.50 0.75 1.00
Au mass concentration in TiO2 (%)

Relative production Normalized production

Figure 4.7: Influence of Au concentration with respect to mass of TiO2 in H2 production.

29
In this graphic, the relative H2 production respect to catalyst loading increases with the
Au concentration. However, the relative H2 production with respect to gold loading
decreases. Therefore, the best Au% value is 0.25%.

Influence of Au nanocluster size

The purpose of this section is to see if there is a role for gold surface exposition in the
reaction. For this experiment, the Au loading used was of 0.5%.

If one takes as spheres the three Au nanoclusters and suppose that 100% of the surface
is exposed to the reaction, then it is possible to calculate the total surface area per gram
of catalyst as shown in table 4.4.

Cluster Radii (nm) Surface area (nm2) Surface area/catalyst loading (m2/g)
Au20 0.5 3.14 2.40
Au25 0.55 3.80 2.32
Au144 0.85 9.08 0.96
Table 4.4: Required data to calculate the surface of Au exposed.

Surface area exposed over catalyst loading is calculated in the Annex C.

The comparison of the H2 production rates vs. the surface area of Au exposed is shown
in Figure 4.8. It is clear that there is an important decrease in hydrogen production for
the catalyst with Au144 nanoclusters.
3 45

2.5 37.5

2 30
k (mmol/h·g)
(m2/g)

1.5 22.5

1 15

0.5 7.5

0 0
Au20
Au20 Au
Au25 Au
Au144
144
25

Au surface on the photocatalyst

Hydrogen rate production

Figure 4.8: Influence of Au surface exposition in H2 production.

To corroborate the effect of the surface area of Au exposed, an additional experiment

was carried out with the Au144 nanoclusters on TiO2 changing the Au concentration to

30
attain a surface of Au exposed similar to those exhibited by the photocatalysts
containing Au20 and Au25 nanoclusters. The new concentration needed is calculated (see
equation 4.2).
0 .5 % wt. mass
2 .3 2 4 4 m 2 / g· = 1 .2 1 % wt. mass (4.2)
0 .9 6 3 8 m 2 / g
The results are given in Figure 4.9:

3 45

2.5 37.5

2 30

k (mmol/h·g)
(m2/g)

1.5 22.5

1 15

0.5 7.5

0 0
Au20
Au20 Au25
Au 25 Au144 1.21%
1.21%Au 144

Au surface on the photocatalyst

Hydrogen rate production

Figure 4.9: Influence of Au surface exposition in H2 production.

Now the photoproduction of H2 is similar in all samples, demonstrating that surface area
of Au definitely has a role in hydrogen production. Obviously, the use of Au144 is of no
interest because of its poor ratio surface/mass, that is, the Au atoms located inside the
Au nanoclusters do not play any role and causes the photocatalyst to be more expensive
(more Au is needed when compared to catalysts with Au20 and Au25 nanoclusters).

Stability study of the catalyst

Two different samples of Au25 nanoclusters from Vienna University, one from 2016 and
one from 2017 were compared to check for stability. Additional, two Au25/TiO2 catalysts
with 1Au% prepared in 2016 and 2017 were also compared. The results are provided in
Figure 4.10.

31
 40

35

30

25
k (mmol/h·g)

20

15

10

0
Impregnated Dissolved
1%Au25/TiOfrom
1%Au25/TiO2 2 from 2017
2017 1%Au25/TiOfrom
1%Au25/TiO2 2 from 2016
2016

Figure 4.10: Stability of 1%Au25/TiO2 photocatalyst over a year.

It is observed that after 1 year there is a slight deactivation of both the sample prepared
in 2017 from 2016 nanoclusters and the sample already containing the nanoclusters
prepared in 2016. Then, it is concluded that the nanoclusters show a good stability
although a minor deactivation occurs over time.

Influence of particle size

For this second part of the photocatalytic tests Au nanoclusters and Au nanoparticles
supported over TiO2 are compared. The results are shown in Figure 4.11. It is clear that
the smaller the particle, the better results in hydrogen production.

3.5
3
Normalized production
(mmol/h·gcat·µgAu)

2.5
2
1.5
1
0.5
0
0 2 4 6 8 10
Particle size (nm)

Nanoclusters Nanoparticles

Figure 4.11: Influence of Au particle size in H2 production.

32
Chapter 5

Conclusions & further work

The main objective of this work was to prepare and characterize an effective
photocatalyst of gold nanoclusters deposited over a substrate of titanium dioxide to
carry out water splitting for hydrogen production. The successful photocatalytic reaction
in terms of H2 production was studied under different influencing parameters and
optimized.

The obtained results with Au20/TiO2, Au25/TiO2, and Au144/TiO2 showed higher H2
production rates than the photocatalysts containing conventional Au nanoparticles. The
surface exposition study carried out suggested strong dependency of surface/volume ratio
of gold in H2 production. Smaller particles with higher surface/volume ratio showed
higher H2 production than larger particles. The best photoactivity for hydrogen
generation was recorded over Au25 larger and Au20 supported on TiO2.

The study of the gold nanoclusters loading on TiO2 showed optimum results for 0.25%.
Compared to the 1% loading for gold nanoparticles, this reduces the material cost of the
photocatalyst made from nanoclusters.

Photocatalysts with Au nanoclusters also showed great stability over a year, preserving
up to 90% of its photocatalytic activity, an important feature for practical application.

Further work may be aimed towards the study of other Au nanoclusters or bandgap
engineering to reduce electron-hole recombination, and the scalability of the
photocatalyst.

33
Appendix A

Photocatalyst preparation
calculations (1%Au25/TiO2)

When the purified sample is already dried and cooled at room temperature, the vial with
the sample is weighted and total weight was 11,4472 mg. In order to know how many
grams of nanoclusters there are inside the first vial, it is needed to transfer all the sample
to a second vial of known weight. The used substance for the transferring is going to be
toluene because nanoclusters are soluble in it.

Because of the high volatility of toluene vial is going to be closed at the moment of the
weighting. That is the reason why the second vial is weighted with the cap. Empty vial
with cap weights 11,993 g.

Using a micropipette 4mL of toluene are added to the first vial and once the sample is
completely dissolved are transferred to the second vial. The second vial is rapidly closed
and weighted, and total weight is now 15,3462 g. Once weighted, the vial is protected
with parafilm, which is impermeable to liquids and gases, and kept in a fridge to reduce
to the maximum toluene evaporation and preserve the concentration of Au inside for
future uses.

In parallel, the first vial, now empty, is cleaned and weighted again. Weight of the empty
vial is of 11,4442 g. Total grams of complex can be now calculated:

11,4472 g - 11,4442 g = 0,0030 g

Knowing the grams of complex and the volume of toluene, its concentration can be
calculated:

1 mol Au 2 5 (SCH2 CH2 Ph)1-18 2 5 Au moles 1 9 7 8 g Au

0 .0 0 3 0 g complex · · · = 0 .0 0 2 0 g Au
7 3 9 1 g complex 1 mol Au 2 5 1 Au mol
2 mg Au mg Au
= 0 .5 concentration
4 mL toluene mL toluene
34
The catalyst was chosen to be of Au content of 1 wt.% with respect to TiO2, that is, of
every 100 g of catalyst, 1 g is Au.

Next step in the preparation of the catalyst is TiO2 impregnation with the solution
previously prepared. 100 mg of catalyst are going to be prepared, for which there will be
needed 99 mg of TiO2 and 1 mg of Au. Impregnated TiO2 is dried at the oven at 50°C
during 2 hours. Finally, it is grinded by means of an agate mortar to avoid possible
agglomerations and assure homogeneity of the catalyst.

After deposition, photocatalysts look like Figure A.1.

Figure A.1: Photography of an impregnated photocatalyst ready for the experiment.

35
Appendix B

Table of sizes of the nanoparticles

PG, PT and PM

Table B.1 shows the sizes in nm given from Institut de Ciència de Materials de
Barcelona (CSIC) of the Au nanoparticles.

% wt Au/TiO2 PG size (nm) PT size (nm) PM size (nm)

2% 8.6 <1.5 <1.5
3.9% 3.6 3.5 3.4
7.9% - 4.5 4.7
Table B.1: Sizes of AuNPs in nm.

36
Appendix C

Surface area exposed over catalyst

loading

Some calculation is needed in order to convert Au nanoclusters concentration in % to

surface of Au exposed in m2/g of photocatalyst. For the Au20 nanocluster see equations
C.1, C.2, and C.3.

mg Au 2 0 atoms 1 9 6 .9 6 6 5 g Au 1 mg
= · · = 6 .5 4 ·1 0 -1 8 mg Au / nanocluster (C.1)
nanocluster nanocluster 6 .0 2 ·1 0 2 3 atoms 1 0 -3 g

surface area
= 4 πr 2 = 4 π · 0 .5 2 = 3 .1 4 1 6 nm 2 / nanocluster (C.2)
nanocluster

surface area 3 .1 4 1 6 ·1 0 -1 8 m 2 1 mg 0 .5 g Au
= · -3 = 2 .4 0 1 2 m 2 / g (C.3)
catalyst loading 6 .5 4 ·1 0 mg Au 1 0 g 1 0 0 g catalyst
-1 8

For the Au25 and Au144 is needed to change the number of atoms per cluster and the
radium of the nanocluster.

37
List of Figures

1.1 World energy consumption from 1965 to 2016 .........................................................1

1.2 Evolution of the CO2 concentration in the atmosphere in ppm ................................2
1.3 Atomic hydrogen/carbon ratio of different fuels .......................................................4

2.1 Sketch of electron-hole generation by UV light radiation. ...................................... 11

2.2 Sketch of electron-hole generation by UV light radiation on Au/TiO2 ................... 12

3.1 Detail of the core structure of Au20, Au25, and Au144 ............................................... 17
3.2 Schematic drawing of the methodology used for the photocatalyst deposition ....... 18
3.3 Different ligand to TiO2 .......................................................................................... 18
3.4 Photocatalytic experiment ...................................................................................... 19
3.5 Schematic set-up of the photocatalytic experiment inside the fume hood .............. 20

4.1 UV-Vis spectrum of the photocatalyst .................................................................... 24

4.2 XPS spectrum for the Au25/TiO2 photocatalyst...................................................... 25
4.3 XPS spectrum for the Au25/TiO2 ............................................................................ 26
4.4 Photocatalyst surface sketch ................................................................................... 26
4.5 Influence of catalyst loading in H2 production ........................................................ 28
4.6 Influence of drying temperature of the catalyst in H2 production ........................... 29
4.7 Influence of Au concentration with respect to mass of TiO2 in H2 production ....... 29
4.8 Influence of Au surface exposition in H2 production ............................................... 30
4.9 Influence of Au surface exposition in H2 production ............................................... 31
4.10 Stability of 1%Au25/TiO2 photocatalyst over a year ............................................. 32
4.11 Influence of Au particle size in H2 production ....................................................... 32

A.1 Photography of an impregnated photocatalyst ready for the experiment .............. 35

38
List of Tables

1.1 Comparison of different parameters between hydrogen and methane .......................5

4.1 XPS results of the position of the peaks and % concentration of each element. ..... 26
4.2 Results before UV-light exposition ......................................................................... 27
4.3 Results after UV-light exposition ............................................................................ 27
4.4 Required data to calculate the surface of Au exposed ............................................ 30

B.1 Sizes of AuNPs in nm ............................................................................................ 36

39
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