Desorption
Matthew Marcinkowski Group Meeting
June 27, 2016
Adsorption and Desorption
Eads
Eads
Eads
Eads
Heater T Controller
1. Gases are adsorbed onto the
cooled sample.
2. Pressure in chamber recovers. N2(l)
𝑑Ө(𝑇𝑠 ) 𝑉 𝑑𝑃 𝑆𝑃
= +
𝑑𝑡 𝐴𝑘𝐵 𝑇𝑔 𝑑𝑡 𝑉
CONSTANT
m=0
m=1
m=2
Ha - 0.01 ML Pt/Cu(111)
C2H4
m/z 27
−𝐸𝑑
𝑑Ө 𝐴 𝑚
𝑅𝑑 = − = Ө 𝑒 𝑅𝑇
𝑑𝑇 β
𝑅𝑑 𝐴 𝐸𝑑 1
ln =ln −
Ѳ𝑚 β 𝑅 𝑇
(7X7)
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
me
Methanol on Cu(111)
• Complete Analysis
• Redhead Analysis
−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
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.
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.
•T is at a maximum Tp when:
•T is at a maximum Tp when:
•T is at a maximum Tp when:
= 𝑅𝑇
𝐴𝑇𝑝 𝐸𝑑
𝐸𝑑 𝑝 ln − ln
β 𝑅𝑇𝑝
Redhead Analysis
= 𝑅𝑇
𝐴𝑇𝑝 𝐸𝑑
𝐸𝑑 𝑝 ln − ln
β 𝑅𝑇𝑝
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.
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
DCOOH on Ni(110)
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.
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
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