Surface science I

The catalytic properties of a surface are determined by its composition and structure on the
atomic scale. Hence, it is not sufficient to know that a surface consists of a metal and a
promoter – perhaps iron and potassium – but it is essential to know the exact structure of the
iron surface, including any defects and steps, as well as the exact location of the promoter
atoms. Thus, from a fundamental point of view, the ultimate goal of catalyst characterization
should be to examine the surface atom by atom, and under reaction conditions.
There are three levels of research in catalysis:

 The macroscopic level is the world of reaction engineering, test reactors and catalyst
beds. Questions concerning the catalyst deal with such aspects as activity per unit
volume, mechanical strength, and whether it should be used in the form of extrudates,
spheres, or loose powders.
 The mesoscopic level comprises kinetic studies, activity per unit surface area,and the
relationship between the composition and structure of a catalyst versusits catalytic
behavior. Much of the characterization studies belong to this category.
 The microscopic level is that of fundamental studies, and deals with the details of
adsorption on surfaces, reaction mechanisms, theoretical modeling, and surface
science.
Surfaces
As we remember from other lectures, surfaces are important for the reactivity of the catalyst.
More open surfaces are more reactive. Different surfaces provide also different adsorption
sites, like shown in the figure below.

UHV in Surface Science experiments

Ultra high vacuum is required for most surface science experiments for two principal
reasons :

1. To enable atomically clean surfaces to be prepared for study, and such surfaces to be
maintained in a contamination-free state for the duration of the experiment.
 2. To permit the use of low energy electron and ion-based experimental techniques
without undue interference from gas phase scattering.

Photo-electron spectroscopies
 UPS: uses UV light (less energetic); light is not energetic enough to expell electrons
from core levels.
 XPS: uses X-Ray light (more energetic); possible to eject electrons from core levels.

UPS: ultraviolet photoelectron spectroscopy

The kinetic energy of the photoelectrons is E=hv-I, where I is the ionization energy of the
material in analysis. He discharge lamps are used as source of UV light, which is not energetic
enough to go into core levels, hence photoemission is limited to valence electrons.
It is useful for: probing in metals, molecules and in adsorbed species.

In figure, a UPS spectrum for a d-metal is shown. First of all, the Fermi level is the zero of the
spectrum. As soon as we shine UV light, electrons in the valence band with very low binding
energy are expelled from the material and detected. At higher binding energy, the most
intense peak comes from secondary electrons. Secondary electrons are electrons which are
inelastically scattered by the material, meaning that they lost some energy while travelling
through the solid. The shape of the secondary electrons peak is dependent on the structure
and composition of the surface.
UPS gives also a simple way to calculate the work function of a material, by measuring the
width of the bands, like shown in Figure.

XPS: X-ray photoelectron spectroscopy

With XPS, we use a X-ray source which can expell electrons from the core level. From the
kinetic energy of the ejected electrons, we can measure the binding energy (B.E.). This is
element and chemical state specific, hence XPS is a useful tool to identify elements and
oxidation states. X-Ray source can be Al-Kα at 1486 eV.

A typical XPS peak is shown above. Usually peaks are identified by j=l+s, where l is 0,1,2,3
(s,p,d,f) and s is the spin number (+1/2 or -1/2).
A technique becomes surface-sensitive if the radiation or particles to be detected travel no
more than a few atomic distances through the solid.
XPS is surface sensitive, meaning that the probing depth is limited at the first few atomic
layers. That is why XPS is mostly used to study surfaces of catalysts.
Chemical specificity
 Binding energies are element specific, but also chemical
state specific. As we can see from the picture, going from
Pt(0) to Pt(4), there is a shift towards higher binding
energy. The reason is that there are less electrons in
Pt(IV), which feel of course a higher attraction to the
nucleus.
XPS peaks also depend on the chemical environment. As
we can see from the picture below, C peak will change
accordingly to the electronegativity of his neighbours.
Highest binding energy is found for the C1s, where C is
bonded to F (most electronegative).

Spin orbit splitting

As said before, peaks are identified by j. The ratio between peaks is given by the multiplicity
(2j+1).
Real time XPS
Photoelectrons do not far very long in a gas. The attenuation of the intensity can be tolerated
only if the mean free path is in the order of magnitude of a few millimeters. One way to deal
with the attenuation, is by using highly intense X-rays from a syncrothron. Using a syncrothron
enables us also to study XPS in real time, which can give very important information, for
example about adsorption dynamics.
An example is shown in the figure below, where CO adsorption on Rh(111) is studied in real
time. What happens is that first CO adsorption is seen in a peak O 1s at 531.5 eV, then it goes
to 530 eV. The reason behind this is in the geometry of adsorption. When CO adsorbs linearly
on top, we have a peak at 531.5 eV, when it adsorbs on a hollow, it shifts to 530 eV. Hence,
we can determine from these experiments that CO adsorbs mostly linearly on top at room
temperature or higher, while at low temperature hollow adsorption is preferred. At first,
though, adsorption starts on-top. At higher surface coverage, due to CO molecules repulsions,
hollow sites are obtained.
Auger spectroscopy
Auger spectroscopy uses a source of 1-10 keV to create holes in the core levels. These holes
are filled by electrons in higher levels, and they liberate the corresponding energy both as X-
ray or as Auger electrons (expelled). The energy of the Auger electrons is element specific.
Usually Auger peaks are small and mostly covered by secondary electron peaks. That is why,
to improve the visibility of such peaks, they are usually shown in derivative mode.
The energy of an Auger transition is given by:

Temperature programmed desorption / reaction (TPD, TPR)

Information on the influence of promoters (i.e. Vanadium) can be obtained with TPR, where
a reaction takes place in a specific range of temperature. TPD examines the desorption of
gases from single crystals or polycrystalline foils into vacuum. From the desorption,
information about the reaction kinetics can be obtain, that is why it’s extremely useful.

A temperature controller heats up tantalum wires. Temperature is checked by a

thermocouple. A mass spectrometer (quadrupole) is used to analyze desorbed species.
Pumping capacity has to be enough to prevent readsorption.
In the case there is no readsorption, the rate of desorption can be written as:
Here we analyze three different plots, corresponding to zeroth, first and second order
desorption kinetics. CO has a first order kinetic: first the desorption happens always in the
same temperature range, then after a certain initial coverage, an additional peak appears,
meaning that CO populates new sites and a faster desorption route opens up at lower
temperature.
In the desorption of N2, being it a second order kinetics, we observe a decrease in the
temperature associated to the peak, as predicted by the rate of desorption. Finally, zeroth
order Ag desorption is studied. Here, when coverage is high there is an additional peak. That
is the desorption of a second layer of Ag (Ag-Ag bond is weaker, so it desorbs at lower T).
TOF-SIMS (Time of Flight, Secondary ion mass spectrometry)
SIMS is a very popular technique to analyze surface. It consists in using a primary ion beam
(Ar+) to sputter atoms and ions from the surface of a sample. This is combined with a
quadrupole mass spectrometer, or for higher sensitivity with a TOF mass spectrometer.
Three operational modes are available: surface spectroscopy, surface imaging and depth
profiling. A possible application is for analysis of zeolites. It gives concentration of Al+, Si+,
etc.
Vibrational spectroscopies
Currently, several forms of infrared spectroscopy are in general use, as illustrated in the
figure. The most common form of the technique is transmission infrared spectroscopy, in
which the sample consists typically of 10 to 100 mg of catalyst, cm2 pressed into a self-
supporting disk of approximately 1 and a few tenths of a millimeter thickness.
IR techniques are also good because we can study catalysts in situ, even if it is a technical
problem to realize windows that resist at high temperatures and pressures.

Reflection absorption infrared spectroscopy (RAIRS)

RAIRS is used to analyze absorption spectra of gases adsorbed on surfaces (single crystal or
polycrystalline foils). In RAIRS, the infrared beam enters at very low angles (parallel to
surface). Only the component perpendicular to surface can be absorbed by molecules which
have a perpendicular dipole moment. This is a strict selection rule for RAIRS.
RAIRS can be used to analyze CO adsorption, for example. CO prefers to adsorb on two-fold
sites on Pd. When there is NO, though, CO molecules shift to top sites. With RAIRS, we can
follow this shift, like shown in the following figure.

SFG / PM-RAIRS: higher pressure [sum frequency generation; polarization modulation

RAIRS]
SFG probes adsorbates both in real time and in situ. It is a complicated technique which let us
study catalytic surfaces in working conditions. Two beams of different frequency (IR + green
light) focus on the surface of the sample. Process happens only at interface (1 nm thickness),
hence there is no influence from gas or bulk catalyst.
PM-RAIRS uses polarization modulation to remove the influence of gas particles. p-polarized
signal is from surface + gas, s-polarized signal is only from gas. The difference between the
two signals gives information about the surface.
These two techniques can be used at higher pressure, without need for vacuum.
Electron energy loss spectroscopy (EELS)
In EELS (also HREELS), electrons with low energy fall on the surface of catalyst, providing
energy for molecular vibrations of adsorbed species or lattice vibrations. Scattered electrons
are measured, so to understand how much electrons lost in vibrations. Experiments need
ultra-high vacuum, because electrons are involved.
E = E0 – hv
where E0 is the energy of the electrons and v is the frequency of the excited vibration.
IR and Raman spectroscopy are limited to vibrations where dipole moment or polarizability
changes. EELS instead works with any vibration. There are two main processes involved in this
technique: dipole scattering and impact scattering.

Dipole scattering refers to electrons which excite only vibrations in which the dipole moment
is normal to the surface (just like RAIRS). The outgoing electrons, again like in RAIRS, travel in
the specular direction. Impact scattering, instead, refers to collisions between electrons and
the surface. These electrons travel in all directions (wide range of angles). The important thing
about impact scattering is that now all vibrations can be excited, and not only the IR and
Raman active.

CO adsorption on Rh(111) can be studied via HREELS. First spectrum is Rh surface. EELS can
be used to understand if the surface is clean, because presence of C and O on the surface
would result in peaks between 300 and 600 cm-1. Increasing the CO coverage, we get a peak
at approx. 2000 cm-1 and one at 470. These vibrations are associated to CO internal stretch
and metal-molecule bond. Last spectrum shows full coverage of CO. Here, not only we see
the peak at 2000 cm-1 (linear adsorption), but also another one at 1860 cm -1 (threefold
adsorption).