Characterization of Catalysts

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 X-ray Photoelectron Spectroscopy (XPS)
Principle
• Surface of the specimen is irradiated by X-ray with the energy of hν
• Mono-energetic photon knocks out the electron from atoms in the surface region.
Photons with higher energy hν penetrate deeper into the surface of the sample.
• Electrons emitted by photons from lower energy X-rays originates from inner
atomic energy levels and were bound to atomic nuclei with the binding energy E b.
• Electrons emitted in this manner are referred to as photoelectrons.

An example of a photoelectron
emitted due an incident photon

The binding energy is the energy required to break a nucleus into its constituent protons and neutrons
 Theory

• XPS spectra is obtained by irradiating a material with a beam of X-rays while

simultaneously measuring the kinetic energy and number of electrons that
escape from the top 0 to 10 nm of the material being analyzed.
• So in this particular technique we are utilizing x-ray to excite a particular
material, then generate photoelectrons and eventually get a spectrum to finally,
evolve with the chemical analysis.
• It is also called electron spectroscopy, because electron which is emitted as the
photoelectron, that is being captured for the chemical analysis of a particular
material.
• We can analyze its elemental composition, chemical formula, empirical formula
and chemical or electronic state of the elements.
• So, we can easily determine the overall nature of a particular element and its
electronic state
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• XPS detects all elements except Hydrogen and Helium.
• Detection limits for most of the elements (on a modern instrument) are in
the parts per thousand range.
• Detection limits of parts per million (ppm) are possible but require
special conditions: concentration at the top surface or very long collection
time (overnight).

Why Ultra High Vacuum

• Remove adsorbed gases from the sample.
• Eliminate adsorption of contaminants on the sample.
• Prevent high voltage breakdown.
• Increase the mean free path for electrons, ions and photons.
• Electron counting detectors in XPS instruments are typically one meter
away from the material irradiated with X-rays.
• This long path length for detection requires low pressures.
 Einstein’s Photoelectric Equation
• An electron, which is negatively charged, is attracted to the nucleus of an atom
because of the positive charge that is there.
• The amount of energy that is required to be given to the electron to pull it away from
this attractive (Coulombic) force is called the binding energy.
• Sometimes binding energy is also called a work function

• Ephoton denotes the energy of the incident photon, which is equal to h𝜈

• Φ denotes the threshold energy of the metal surface
• Ekinetic denotes the kinetic energy of the photoelectron, which is equal to ½m ev2 (me =
mass of electron = 9.1 X 10-31 kg)

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 Features of XPS
• A typical XPS spectrum is a plot of the number of electrons detected
(sometimes per unit time) (Y-axis, ordinate) versus the binding energy of the
electrons detected (X-axis, abscissa).
• Each element produces a characteristic set of XPS peaks at characteristic
binding energy values that directly identify each element that exists in or on the
surface of the material.
• The number of detected electrons in each of the characteristic peaks is directly
related to the amount of element within the XPS sampling volume.
• Signals detected from analytes at the surface much stronger than the signals
detected from analytes deeper below the sample surface.
• 1–20 minutes for a broad survey scan that measures the amount of all
detectable elements.
• 1–15 minutes for high resolution scan that reveal chemical state differences
• 1–4 hours for a depth profile that measures 4–5 elements.
• The minimum analysis area ranges from 10 to 200 micrometres.

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Quantification of XPS

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 Powder X-ray Diffraction
• X-ray diffraction (XRD) is an characterization technique followed for
determining the crystal structure of materials.
• It detects crystalline materials having crystal domains greater than 3-5 nm.
It is used to characterize bulk crystal structure, particle size and chemical
phase composition.
• X-ray is a form of electromagnetic radiation have wavelength of from
0.01-0.7 nm.
• The spacings between lattice planes in the crystal are comparable to X-
rays.
• When an incident beam of X-rays interacts with the target atom, X-ray
photons are scattered in different directions.
• Scattering is elastic when there is no change in energy between the
incident photon and the scattered photon.
• In inelastic scattering the scattered photon loses energy.
• These scattered waves may super impose.
• Diffraction from different planes of atoms produces a diffraction
pattern, which contains information about the atomic arrangement
within the crystal.
• The X-ray beams incident on a crystalline solid will be diffracted by
the crystallographic planes.
• Bragg's law for diffraction. It is given as sinθ=nλ/2d; where n = an
integer λ = wave length of the radiation d = spacing between two
planes or layers θ = diffraction peak at a specific angle.
• The spacing between diffracting planes of the atoms determines the
peak positions. The peak intensity is determined by the atoms are in the
diffracting plane.
Bragg's Law refers to the simple equation
nλ   = 2d sinθ
The rays of the incident beam are always in phase
and parallel up to the point at which the top beam
strikes the top layer at atom z.
The second beam continues to the next layer where
it is scattered by atom B.
The second beam must travel the extra distance
AB + BC if the two beams are to continue
traveling adjacent and parallel.
This extra distance must be an integral (n) multiple of the wavelength (λ) for the
phases of the two beams to be the same: nλ  = AB +BC eq. (1)

Recognizing d as the hypotenuse of the right triangle Abz,

we can use trigonometry to relate d and to the distance (AB + BC).
The distance AB is opposite so, AB = d sinθ eq. (2)

Because AB = BC eq. (1) becomes, nλ  = 2AB eq. (3)

Substituting eq. (2) in eq. (3) we have,                                      

nλ   = 2d sinθ
 4000

3000

Intensity
2000

1000

10 20 30 40 50 60 70 80

Angle (2)

Amorphous Pattern Crystalline Pattern

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Thank You

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