1. Temperature Programmed Desorption
Matthew Marcinkowski Group Meeting
June 27, 2016

2. Adsorption and Desorption
Eads
Eads
Non-activated, non-dissociative adsorption
Activated, dissociative process.

3. Adsorption and Desorption
Eads
Eads
Non-activated, non-dissociative adsorption
Activated, dissociative adsorption.

4. Temperature Programmed Desorption (TPD) Experimental Setup
Heater
T Controller
Gases are adsorbed onto the cooled sample.
Pressure in chamber recovers.
Rotate sample to face mass spectrometer.
Apply linear heating rate to sample.
A plot showing partial pressure of gas species vs. temperature is obtained.
N2(l)
UHV
Thermocouple
Mass Spectrometer
Precision leak valve
Turbo molecular pump

5. What Does TPD do for us? Gives us information about:
Rate of desorption
Kinetic order of desorption
Number of adsorption sites/packing structures
Sticking probabilities/Surface Coverage
Energy of desorption
Surface reactions

6. TPD Gives us the Rate of Desorption
𝑑Ө( 𝑇 𝑠 ) 𝑑𝑡 = 𝑉 𝐴 𝑘 𝐵 𝑇 𝑔 𝑑𝑃 𝑑𝑡 + 𝑆𝑃 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
Kb is the Boltzmann constant
Tg is the gas phase temperature
P is the pressure increase over the background
S is the pumping speed of the chamber
𝑑𝑃 𝑑𝑡 ≪ 𝑆𝑃 𝑉
D. A. King, Surf. Sci., 47, (1975).

7. What Does TPD do for us? Gives us information about:
Rate of desorption
Kinetic order of desorption
Number of adsorption sites/packing structures
Sticking probabilities/Surface coverage
Energy of desorption
Surface reactions a

8. 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.
Applying a linear heating ramp where
Gives the equation
Ө=Surface coverage
kd= Desorption rate constant
m= desorption order

9. 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.
Applying a linear heating ramp where
Gives the equation
Ө=Surface coverage
kd= Desorption rate constant
m= desorption order

10. 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.
Applying a linear heating ramp.
Gives the equation
Ө=Surface coverage
kd= Desorption rate constant
m= desorption order

11. 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.
Applying a linear heating ramp where
Gives the equation
Ө=Surface coverage
kd= Desorption rate constant
m= desorption order

12. 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.
Applying a linear heating ramp where
Gives the equation
Ө=Surface coverage
kd= Desorption rate constant
m= desorption order

13. 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.

14. 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.

15. 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

16. Why is there a peak maximum?

17. 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.

18. TPD Peak orders
What happens when we change m?

19. 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.

20. 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

21. 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

22. Rate Limiting Step Determines Order
4.5 L CH3I
CH4
Cu(111)
m/z 16
Ha ML Pt/Cu(111)
C2H4
m/z 27
Lin, J.-L. et al. J. Phys. Chem (1993)
Lin, J.-L. et al. J. Vac. Sci. Technol. A (1991)

23. How Do We Accurately Determine Order?
Fits for simulated first order desorption spectra
𝑅 𝑑 =− 𝑑Ө 𝑑𝑇 = 𝐴 β Ө 𝑚 𝑒 −𝐸 𝑑 𝑅𝑇
ln 𝑅 𝑑 Ѳ 𝑚 =ln 𝐴 β − 𝐸 𝑑 𝑅 1 𝑇
de Jong A. M. Surf. Sci. 233, (1990)

24. What Does TPD do for us? Gives us information about:
Rate of desorption
Kinetic order of desorption
Number of adsorption sites/packing structures
Sticking probabilities/Surface coverage
Energy of desorption
Surface reactions a a

25. Packing Structure/Sites
Terrace Peaks
(4X4)
(√3 × √3)
(7X7)
Saturation dose of CO on Cu(111)
Steps
m/z=28

26. 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, (2013).

27. What Does TPD do for us? Gives us information about:
Rate of desorption
Kinetic order of desorption
Number of adsorption sites/packing structures
Sticking probabilities/Surface coverage
Energy of desorption
Surface reactions a a a

28. Surface Coverage Methanol on Cu(111)
Ө= 𝐴𝑟𝑒𝑎 𝑢𝑛𝑑𝑒𝑟 𝑇𝑃𝐷 𝑐𝑢𝑟𝑣𝑒 𝑓𝑜𝑟 𝑢𝑘𝑛𝑜𝑤𝑛 𝑐𝑜𝑣𝑒𝑟𝑎𝑔𝑒 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, (2013).

29. What Does TPD do for us? Gives us information about:
Rate of desorption
Kinetic order of desorption
Number of adsorption sites/packing structures
Sticking probabilities/Surface coverage
Energy of desorption
Surface reactions a a a a

30. How do we find the Energy of Desorption?
Complete Analysis
Leading Edge Analysis
Redhead Analysis
Vary Heating Rate
𝑅 𝑑 =− 𝑑Ө 𝑑𝑇 = 𝐴 β Ө 𝑚 𝑒 −𝐸 𝑑 𝑅𝑇
Polanyi-Wigner

31. Complete Analysis 𝑅 𝑑 =− 𝑑Ө 𝑑𝑇 = 𝐴 β Ө 𝑚 𝑒 −𝐸 𝑑 𝑅𝑇
𝑅 𝑑 =− 𝑑Ө 𝑑𝑇 = 𝐴 β Ө 𝑚 𝑒 −𝐸 𝑑 𝑅𝑇
Polanyi-Wigner
ln⁡(𝑅 𝑑 )=ln 𝐴 Ө 𝑚 β − 𝐸 𝑑 𝑅 1 𝑇
Natural log of Polanyi-Wigner
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, (1975).

32. Complete Analysis 𝑅 𝑑 =− 𝑑Ө 𝑑𝑇 = 𝐴 β Ө 𝑚 𝑒 −𝐸 𝑑 𝑅𝑇
𝑅 𝑑 =− 𝑑Ө 𝑑𝑇 = 𝐴 β Ө 𝑚 𝑒 −𝐸 𝑑 𝑅𝑇
Polanyi Wigner
ln⁡(𝑅 𝑑 )=ln 𝐴 Ө 𝑚 β − 𝐸 𝑑 𝑅 1 𝑇
Natural log of Polanyi Wigner
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, (1975).

33. Complete Analysis ln⁡(𝑅 𝑑 )=ln 𝐴 Ө 𝑚 β − 𝐸 𝑑 𝑅 1 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

34. Leading Edge Analysis ln⁡(𝑅 𝑑 )=ln 𝐴 Ө 𝑚 β − 𝐸 𝑑 𝑅 1 𝑇
Natural log of Polyani-Wigner
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 be very good for this method to work well.
H2O from Cu(111)
m/z=18

35. 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, (1962).

36. 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, (1962).

37. 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, (1962).

38. Redhead Analysis 𝐸 𝑑 𝑅 𝑇𝑝 2 = 𝐴 β 𝑒 − 𝐸 𝑑 𝑅 𝑇 𝑝
For 1st order desorption there is a special case.
Rearrange.
Take natural log and solve for Ed.
𝐸 𝑑 𝑅 𝑇𝑝 2 = 𝐴 β 𝑒 − 𝐸 𝑑 𝑅 𝑇 𝑝
𝐸 𝑑 𝑅 𝑇 𝑝 = 𝐴 𝑇 𝑝 β 𝑒 − 𝐸 𝑑 𝑅 𝑇 𝑝
ln 𝐸 𝑑 𝑅 𝑇 𝑝 =ln 𝐴 𝑇 𝑝 β − 𝐸 𝑑 𝑅 𝑇 𝑝
𝐸 𝑑 = 𝑅 𝑇 𝑝 ln 𝐴 𝑇 𝑝 β −ln 𝐸 𝑑 𝑅 𝑇 𝑝

39. Redhead Analysis 𝐸 𝑑 = 𝑅 𝑇 𝑝 ln 𝐴 𝑇 𝑝 β −ln 𝐸 𝑑 𝑅 𝑇 𝑝
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, (1962).

40. Redhead Analysis 𝐸 𝑑 = 𝑅𝑇 𝑝 𝑙𝑛 𝐴 𝑇 𝑝 β −3.46
𝐸 𝑑 = 𝑅𝑇 𝑝 𝑙𝑛 𝐴 𝑇 𝑝 β −3.46
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 Original paper states 3.64 but 3.46 makes more sense based on the graph it presents.
P. A. Redhead, Vacuum, 12, (1962).

41. Vary Heating Rate 𝐸 𝑑 𝑅 𝑇𝑝 2 = 𝐴 β 𝑒 − 𝐸 𝑑 𝑅 𝑇 𝑝
Start with general Redhead equation.
For first order:
Take natural log and rearrange.
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.
𝐸 𝑑 𝑅 𝑇𝑝 2 = 𝐴 β 𝑒 − 𝐸 𝑑 𝑅 𝑇 𝑝
ln β 𝑇𝑝 = −𝐸 𝑑 𝑅 𝑇 𝑝 +ln 𝐴𝑅 𝐸 𝑑

42. Vary Heating Rate 𝐸 𝑑 𝑅 𝑇𝑝 2 = 2𝐴Ө 𝑇 𝑝 β 𝑒 − 𝐸 𝑑 𝑅 𝑇 𝑝
For second order:
Since for second order peaks are symmetrical the coverage at Tp is half the initial coverage. Therefore:
Take natural log and rearrange.
𝐸 𝑑 𝑅 𝑇𝑝 2 = 2𝐴Ө 𝑇 𝑝 β 𝑒 − 𝐸 𝑑 𝑅 𝑇 𝑝
𝐸 𝑑 𝑅 𝑇𝑝 2 = 𝐴 Ө 0 β 𝑒 − 𝐸 𝑑 𝑅 𝑇 𝑝
ln β 𝑇𝑝 = − 𝐸 𝑑 𝑅 𝑇 𝑝 +ln 𝐴𝑅 Ө 0 𝐸 𝑑
Falconer and Madix, Surf. Sci., 48, (1975).

43. Vary Heating Rate DCOOH on Ni(110)
Falconer and Madix, Surf. Sci., 48, (1975).

44. 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, (1990)

45. What Does TPD do for us? Gives us information about:
Rate of desorption
Kinetic order of desorption
Number of adsorption sites/packing structures
Sticking probabilities/Surface coverage
Energy of desorption
Surface reactions a a a a a

46. 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, (2012).

47. Temperature Programmed Reaction (TPR)
Dehydrogenation D S T
m/z=2
HCOOH CO2+H2
HCOOH(g)HCOO(a) + H(a)
H(a) ½ H2(g)
HCOO(a)  CO2(g) + ½ H2(g) S T
m/z=44
m/z=29
Expose the surface to HCOOH and get CO2 and H2.

48. What Does TPD do for us? Gives us information about:
Rate of desorption
Kinetic order of desorption
Number of adsorption sites/packing structures
Sticking probabilities/Surface coverage
Energy of desorption
Surface reactions a a a a a a

49. Disadvantages of TPD Questions? 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?

50. 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