Temperature Programmed

Desorption
Matthew Marcinkowski Group Meeting
June 27, 2016
 Adsorption and Desorption

Eads

Eads

Non-activated, non-dissociative adsorption Activated, dissociative process.

 Adsorption and Desorption

Eads

Eads

Non-activated, non-dissociative adsorption Activated, dissociative adsorption.

 Temperature Programmed Desorption (TPD)
Experimental Setup

Heater T Controller
1. Gases are adsorbed onto the
cooled sample.
2. Pressure in chamber recovers. N2(l)

3. Rotate sample to face mass

spectrometer. UHV Thermocouple
4. Apply linear heating rate to
sample.
5. A plot showing partial Precision Mass
pressure of gas species vs. leak valve Spectrometer
temperature is obtained.
 What Does TPD do for us?

Gives us information about:

1. Rate of desorption
2. Kinetic order of desorption
3. Number of adsorption
sites/packing structures
4. Sticking probabilities/Surface
Coverage
5. Energy of desorption
6. Surface reactions
 TPD Gives us the Rate of Desorption

𝑑Ө(𝑇𝑠 ) 𝑉 𝑑𝑃 𝑆𝑃
= +
𝑑𝑡 𝐴𝑘𝐵 𝑇𝑔 𝑑𝑡 𝑉
CONSTANT

• Ө is the surface coverage

• dӨ/dt is the desorption rate per unit area
• Ts is the sample temperature
•
•
V is the chamber volume
A is the adsorbent area
𝑑𝑃 𝑆𝑃
• Kb is the Boltzmann constant ≪
• Tg is the gas phase temperature 𝑑𝑡 𝑉
• P is the pressure increase over the background
• S is the pumping speed of the chamber

D. A. King, Surf. Sci., 47, 384-402 (1975).

 What Does TPD do for us?

Gives us information about:

1. Rate of desorptiona
2. Kinetic order of desorption
3. Number of adsorption
sites/packing structures
4. Sticking probabilities/Surface
coverage
5. Energy of desorption
6. Surface reactions
 TPD Theory
• Typically TPDs are run with a linear heating ramp.
T= Temperature
β= Heating rate
t= Time
• The rate of desorption can be written as follows.
Ө=Surface coverage
kd= Desorption rate
constant
m= desorption order

• Applying a linear heating ramp where

• Gives the equation

 TPD Theory
• Typically TPDs are run with a linear heating ramp.
T= Temperature
β= Heating rate
t= Time
• The rate of desorption can be written as follows.
Ө=Surface coverage
kd= Desorption rate
constant
m= desorption order

• Applying a linear heating ramp where

• Gives the equation

 TPD Theory
• Typically TPDs are run with a linear heating ramp.
T= Temperature
β= Heating rate
t= Time
• The rate of desorption can be written as follows.
Ө=Surface coverage
kd= Desorption rate
constant
m= desorption order

• Applying a linear heating ramp.

• Gives the equation

 TPD Theory
• Typically TPDs are run with a linear heating ramp.
T= Temperature
β= Heating rate
t= Time
• The rate of desorption can be written as follows.
Ө=Surface coverage
kd= Desorption rate
constant
m= desorption order

• Applying a linear heating ramp where

• Gives the equation

 TPD Theory
• Typically TPDs are run with a linear heating ramp.
T= Temperature
β= Heating rate
t= Time
• The rate of desorption can be written as follows.
Ө=Surface coverage
kd= Desorption rate
constant
m= desorption order

• Applying a linear heating ramp where

• Gives the equation

 TPD Theory

• Desorption is an activated process that obeys the Ahrrenius equation.

A= Pre-exponential factor
Ed= Activation energy for desorption
R= Ideal gas constant

• Plugging in kd from the Arrhenius equation gives the Polyani

Wigner equation.
 TPD Theory

• Adsorption is an activated process that obeys the Ahrrenius equation.

A= Pre-exponential factor
Ed= Activation energy for desorption
R= Ideal gas constant

• Plugging in kd from the Arrhenius equation gives the Polyani

Wigner equation.
 TPD Theory

• Adsorption is an activated process that obeys the Ahrrenius equation.

A= Pre-exponential factor
Ed= Activation energy for desorption
R= Ideal gas constant

• Plugging in kd from the Arrhenius equation gives the Polanyi-Wigner

equation.

Attard and Barnes. Surfaces. 1998

Why is there a peak maximum?
 TPD Theory

• TPD peaks are a convolution of surface coverage and rate of desorption.

• A point of maximum desorption (TP) occurs because although kd increases
exponentially with T surface coverage drops as T increases.
 TPD Peak orders

What happens when we change m?

 Zero Order

m=0

•Shifts to higher temperature with increasing coverage.

•Exhibits a shared leading edge.
•Shift is due to intermolecular interactions.
•Seen in multilayer desorption.
 First Order

m=1

• Desorption temperature is independent of coverage.

• Asymmetric peaks with an ascending leading edge.
• Occurs when a molecule adsorbs and then desorbs without
dissociating.

Ranke, Wolfgang “Thermal Analysis-TDS” Lecture. Fritz- Haber Institut

 Second Order

m=2

• Symmetric peak with shared trailing edge shifts to a lower

temperature with increasing coverage.
• Occurs when molecule adsorbs and in doing so dissociates on
the surface, and then desorbs.
• At higher coverage, probability of recombination is greater.
Ranke, Wolfgang “Thermal Analysis-TDS” Lecture. Fritz- Haber Institut
 Rate Limiting Step Determines Order
4.5 L CH3I
Cu(111) CH4
m/z 16

Ha - 0.01 ML Pt/Cu(111)
C2H4
m/z 27

Lin, J.-L. et al. J. Phys. Chem. 97 9713-9718 (1993)

Lin, J.-L. et al. J. Vac. Sci. Technol. A 10 2202-2209 (1991)
How Do We Accurately Determine Order?
Fits for simulated first order desorption
spectra

−𝐸𝑑
𝑑Ө 𝐴 𝑚
𝑅𝑑 = − = Ө 𝑒 𝑅𝑇
𝑑𝑇 β

𝑅𝑑 𝐴 𝐸𝑑 1
ln =ln −
Ѳ𝑚 β 𝑅 𝑇

de Jong A. M. Surf. Sci. 233, 355-365 (1990)

 What Does TPD do for us?

Gives us information about:

1. Rate of desorptiona
2. Kinetic order of desorptiona
3. Number of adsorption
sites/packing structures
4. Sticking probabilities/Surface
coverage
5. Energy of desorption
6. Surface reactions
 Packing Structure/Sites
Terrace Peaks
(4X4)
(√3 × √3)

(7X7)

Saturation dose of CO on Cu(111)

Steps m/z=28
 Packing Structure/Sites
Terrace Peaks TPD is saturation dose of CO on 1% Pd/Cu(111)
(4X4)
(√3 × √3)

(7X7)

Steps
Pd sites m/z=28

M. D. Marcinkowski Nat. Mater., 12, 523-528 (2013).

 What Does TPD do for us?

Gives us information about:

1. Rate of desorptiona
2. Kinetic order of desorptiona
3. Number of adsorption a
sites/packing structures
4. Sticking probabilities/Surface
coverage
5. Energy of desorption
6. Surface reactions
 Surface Coverage
𝐴𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑇𝑃𝐷 𝑐𝑢𝑟𝑣𝑒 𝑓𝑜𝑟 𝑢𝑘𝑛𝑜𝑤𝑛 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒
Ө= 𝐴𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑇𝑃𝐷 𝑐𝑢𝑟𝑣𝑒 𝑓𝑜𝑟 𝑘𝑛𝑜𝑤𝑛 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒
∗ 𝑘𝑛𝑜𝑤𝑛 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒

If the mass spec ionized all adsorbates area

under the curve would be equal to coverage,
but realistically it is only proportional to
coverage.

M
me
Methanol on Cu(111)

M. B. Boucher ACS Nano, 7, 6181-6187 (2013).

 What Does TPD do for us?

Gives us information about:

1. Rate of desorptiona
2. Kinetic order of desorptiona
3. Number of adsorption a
sites/packing structures
4. Sticking probabilities/Surface
coverage a
5. Energy of desorption
6. Surface reactions
 How do we find the Energy of Desorption?

• Complete Analysis

• Leading Edge Analysis

• Redhead Analysis

• Vary Heating Rate

−𝐸𝑑
𝑑Ө 𝐴 𝑚
𝑅𝑑 = − = Ө 𝑒 𝑅𝑇 Polanyi-Wigner
𝑑𝑇 β
 Complete Analysis
−𝐸𝑑
𝑑Ө 𝐴 𝑚
𝑅𝑑 = − = Ө 𝑒 𝑅𝑇 Polanyi-Wigner
𝑑𝑇 β

𝐴Ө𝑚 𝐸𝑑 1
ln(𝑅𝑑 )=ln − Natural log of Polanyi-Wigner
β 𝑅 𝑇

If we plot ln(Rd) vs. 1/T then the slope is related to Ed and the intercept is related to A

D. A. King, Surf. Sci., 47, 384-402 (1975).

 Complete Analysis
−𝐸𝑑
𝑑Ө 𝐴 𝑚
𝑅𝑑 = − = Ө 𝑒 𝑅𝑇 Polanyi Wigner
𝑑𝑇 β

𝐴Ө𝑚 𝐸𝑑 1
ln(𝑅𝑑 )=ln − Natural log of Polanyi Wigner
β 𝑅 𝑇

If we plot ln(Rd) vs. 1/T then the slope is related to Ed and the intercept is related to A.

The expression is a function of coverage so it helps to fix the coverage.

D. A. King, Surf. Sci., 47, 384-402 (1975).

 Complete Analysis
𝐴Ө𝑚 𝐸𝑑 1
ln(𝑅𝑑 )=ln −
β 𝑅 𝑇

A and Ed both depend on the coverage. This method takes a long time but gives accurate
results. Ranke, Wolfgang “Thermal Analysis-TDS” Lecture. Fritz- Haber Institut
 Leading Edge Analysis
𝐴Ө𝑚 𝐸𝑑 1
ln(𝑅𝑑 )=ln − Natural log of Polyani-Wigner
β 𝑅 𝑇
• Using one curve plot the rate of desorption vs. 1/T for the leading
edge of the TPD.

• At the leading edge coverage changes very little so an Arrhenius

plot can be obtained.

• Signal to noise at the leading edge must

H2O from Cu(111) be very good for this method to work
m/z=18 well.
 Redhead Analysis
• Polanyi-Wigner.

•T is at a maximum Tp when:

• Using this derivative relationship the Polanyi-Wigner can be

used to relate Tp, β, and Ed.

P. A. Redhead, Vacuum, 12, 203-211 (1962).

 Redhead Analysis
• Polanyi-Wigner.

•T is at a maximum Tp when:

• Using this derivative relationship the Polanyi-Wigner can be

used to relate Tp, β, and Ed.

P. A. Redhead, Vacuum, 12, 203-211 (1962).

 Redhead Analysis
• Polanyi-Wigner.

•T is at a maximum Tp when:

• Using this derivative relationship the Polanyi-Wigner can be

used to relate Tp, β, and Ed.

P. A. Redhead, Vacuum, 12, 203-211 (1962).

 Redhead Analysis
• For 1st order desorption there is a special case.
−𝐸𝑑
𝐸𝑑 𝐴 𝑅𝑇𝑝
= 𝑒
𝑅𝑇𝑝2 β
• Rearrange.
−𝐸𝑑
𝐸𝑑 𝐴𝑇𝑝 𝑅𝑇𝑝
= 𝑒
𝑅𝑇𝑝 β

• Take natural log and solve for Ed.

𝐸𝑑 𝐴𝑇𝑝 𝐸𝑑
ln =ln −
𝑅𝑇𝑝 β 𝑅𝑇𝑝

= 𝑅𝑇
𝐴𝑇𝑝 𝐸𝑑
𝐸𝑑 𝑝 ln − ln
β 𝑅𝑇𝑝
Redhead Analysis

= 𝑅𝑇
𝐴𝑇𝑝 𝐸𝑑
𝐸𝑑 𝑝 ln − ln
β 𝑅𝑇𝑝

The second natural log is relatively small and for first

order desorption Ed is related linearly to Tp as shown
in the graph on the left. Therefore an estimate of its
value can be made.

P. A. Redhead, Vacuum, 12, 203-211 (1962).

 Redhead Analysis
𝐴𝑇𝑝
𝐸𝑑 = 𝑅𝑇𝑝 𝑙𝑛 − 3.46
β
• Special case for first order desorption.
• Useful for obtaining and estimate of Ed for first order peaks with
just a single TPD spectra.
• Assumes Ed and A are coverage independent.
• Typically assumes a value of A of 1013 s-1.
• Error in Ed can be huge due to all these assumptions.

Note confusion in literature. Value is listed as either 3.64 or 3.46. Original paper states 3.64
but 3.46 makes more sense based on the graph it presents.

P. A. Redhead, Vacuum, 12, 203-211 (1962).

 Vary Heating Rate
• Start with general Redhead equation.

• For first order:

−𝐸𝑑
𝐸𝑑 𝐴 𝑅𝑇𝑝
= 𝑒
𝑅𝑇𝑝2 β

• Take natural log and rearrange.

β −𝐸𝑑 𝐴𝑅
ln 2 = +ln
𝑇𝑝 𝑅𝑇𝑝 𝐸𝑑

• Plotting β/Tp2 vs 1/Tp gives a plot where Ed can be calculated from the
slope and A can be calculated from the intercept.
 Vary Heating Rate
• For second order:
−𝐸𝑑
𝐸𝑑 2𝐴Ө 𝑇𝑝 𝑅𝑇𝑝
= 𝑒
𝑅𝑇𝑝2 β

• Since for second order peaks are symmetrical the coverage at Tp is half
the initial coverage. Therefore:
−𝐸𝑑
𝐸𝑑 𝐴Ө0 𝑅𝑇𝑝
= 𝑒
𝑅𝑇𝑝2 β

• Take natural log and rearrange.

β −𝐸𝑑 𝐴𝑅Ө0
ln 2 = +ln
𝑇𝑝 𝑅𝑇𝑝 𝐸𝑑

Falconer and Madix, Surf. Sci., 48, 393-405 (1975).

 Vary Heating Rate

DCOOH on Ni(110)

Falconer and Madix, Surf. Sci., 48, 393-405 (1975).

Effectiveness of Methods

Falconer-Madix = Heating Rate Variation

(Dashed lines use the method we discussed)

Habenschaden-Kueppers = Leading Edge

de Jong A. M. Surf. Sci. 233, 355-365 (1990)

 What Does TPD do for us?

Gives us information about:

1. Rate of desorptiona
2. Kinetic order of desorptiona
3. Number of adsorption a
sites/packing structures
4. Sticking probabilities/Surface
coverage a
5. Energy of desorptiona
6. Surface reactions
 Temperature Programmed Reaction (TPR)
Hydrogenation

m/z=2

m/z=2
m/z=28

m/z=106 m/z=26
m/z=104

Expose the surface to hydrogen and styrene and get ethylbenzene. Expose the surface to
acetylene and hydrogen and get ethene.

G. Kyriakou, Science, 335, 1209-1212 (2012).

 Temperature Programmed Reaction (TPR)
Dehydrogenation

D S
T

m/z=2
HCOOH CO2+H2
HCOOH(g)HCOO(a) + H(a) S
H(a) ½ H2(g)
HCOO(a)  CO2(g) + ½ H2(g)
T m/z=44
m/z=29

Expose the surface to HCOOH and get CO2 and H2.

 What Does TPD do for us?

Gives us information about:

1. Rate of desorptiona
2. Kinetic order of desorptiona
3. Number of adsorption a
sites/packing structures
4. Sticking probabilities/Surface
coverage a
5. Energy of desorptiona
6. Surface reactionsa
 Disadvantages of TPD
• Destructive technique.
• No way to see what is on the surface just what comes off.
• Cannot identify binding sites, packing structures, or absolute
coverage by itself.
• Data treatment can be complex and it is easy to make mistakes
when applying the different methods.
• Temperatures of reactions are hard to determine (If desorption
rate limited).
• Cross talk between masses can make spectra difficult to
determine.

Questions?
Making Publication Quality Spectra
• Background subtract spectra using the “Peaks and Baseline” tool in the “Analysis”
tab in origin
• Integrate the area under the TPD trace using “Integrate” under “Gadgets” tab
– Relative area equal to relative coverage
• When comparing area/coverage of different molecules account for ionization cross
section (analogous to relative probability of ionization)
– NIST database, T = 70 eV, divide area over cross section
– In cases where the molecule fragments into many masses also account for this factor (i.e. you may
only be monitoring half of the molecules that got ionized)
– In cases of monitoring high masses be aware that the signal is lower, but this has yet to be quantified
• Smooth if necessary
– Savitzky-Golay smoothing in Origin found under “Signal Processing” or take derivative with derivative
order = 0 (or average multiple curves if it’s a saturation trace)
– Oscillation in heating rate will make spectra bumpy!
• Format and export plots – refer to file on the N Drive in General -> How To ->
Making Origin Figures