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Bridging the material and pressure gaps in catalysis studies by Au-TiO_1tn2-Ru model catalysts and UHV attached high pressure cell [Elektronische Ressource] / Zhong Zhao

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154 pages
Bridging the Material and Pressure Gaps in Catalysis Studies By Au/TiO /Ru Model Catalysts and UHV attached 2High Pressure Cell Universität Ulm Abteilung Oberflächenchemie und Katalyse Dissertation zur Erlangung des Doktorgrades Dr. rer. nat der Fakultät für Naturwissenschaften Zhong Zhao (Ulm) 2006 1. Gutachter: Prof. Dr. Rolf Jürgen Behm 2. Gutachter: apl. Prof. Dr. Hans Gerd Boyen 3. PD. Dr. Hubert Rauscher 道冲,而用之或不盈。 渊兮,似万物之宗; 湛兮,似或存。吾不知谁之子, 象帝之先。 ------------老子 the way is a limitless vessel; used by the self, it is not filled by the world; it cannot be cut, knotted, dimmed or stilled; its depths are hidden, ubiquitous and eternal; I don't know where it comes from; it comes before nature. ------------Lao tzi Contents i Contents List of publications 1 Introduction and motivation…………………………………….………...1 1.1 Planar model catalysts…………………………………………….………....…2 1.
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Bridging the Material and Pressure Gaps
in Catalysis Studies

By

Au/TiO /Ru Model Catalysts and UHV attached 2
High Pressure Cell



Universität Ulm
Abteilung Oberflächenchemie und Katalyse




Dissertation
zur Erlangung des Doktorgrades Dr. rer. nat
der Fakultät für Naturwissenschaften





Zhong Zhao

(Ulm)

2006






























































































1. Gutachter: Prof. Dr. Rolf Jürgen Behm
2. Gutachter: apl. Prof. Dr. Hans Gerd Boyen
3. PD. Dr. Hubert Rauscher
































































道冲,而用之或不盈。
渊兮,似万物之宗;
湛兮,似或存。吾不知谁之子,
象帝之先。



------------老子






the way is a limitless vessel;
used by the self, it is not filled by the world;
it cannot be cut, knotted, dimmed or stilled;
its depths are hidden, ubiquitous and eternal;
I don't know where it comes from;
it comes before nature.




------------Lao tzi


























Contents i







Contents


List of publications

1 Introduction and motivation…………………………………….………...1
1.1 Planar model catalysts…………………………………………….………....…2
1.2 Bridging the material and pressure gaps in catalysis studies…….……....….3
1.2.1 Bridge the material gap……………………………………………….….……..3
1.2.2 Bridge the pressure gap..………………………….…………………..…...……..5

2 Experimental.………………………………………………………….……8
2.1 STM chamber.…………………………………………………………….….…9
2.2 TPD chamber.……………………………………………………….…………13
2.3 High pressure cell………………………………………………………..…….15
2.3.1 The set up of the high pressure cell.……………………………………………….15
2.3.2 Gas handling system………………………………….…………………………..21
2.3.3 Test of the high pressure cell system…………………………………….………..........24
2.3.4 Conclusions.………………………………………………………………………..…..27
2.4 Surface science approaches in UHV………………………………………….28
2.4.1 Scanning tunneling microscopy……………………………………………...…28
2.4.2 X-ray photoelectron spectroscopy and Auger electron spectroscopy ………….32
2.4.3 Temperature-programmed Desorption ……………………………………........36

3 Preparation and characterization of titania thin film on Ru(0001) …..40
3.1 Introduction……………………………………………………………….…...41
3.1.1 Bulk of TiO .………………………………………………………………...….42 2Contents ii
3.1.2 Surface of the rutile TiO ……………………………………………….……...43 2
3.1.3 Growth of oxide thin films……………………………………………………...46
3.2 Experimental results and discussion…………………………………………50
3.2.1 TiO ultrathin film (<2 ML)……………………………………………………52 x
3.2.1.1 Morphology and structure of ultrathin TiO films……………………………………...52 x
3.2.1.2 Chemical composition of the TiO films………………………….57 x
3.2.1.3 Thermal stability of the ultrathin TiO films………………………………………...…60 x
3.2.2 Growth mode of the thin TiO films and thermal stability of the TiO x x
films up to 10 ML………………………………………………………………69
3.3 Conclusions…………………………………………………………………….82

4 Au supported on TiO thin film studied by STM, XPS and CO-TPD...83 2
4.1 Introduction…………………………………………………………………….84
4.2 Au supported on TiO studied by STM and XPS……………………………85 2
4.2.1 Previous studies…………………………………………………………………85
4.2.2 Experimental results and discussion…………………………………………….87
4.3 CO-TPD studies of Au/TiO …………………………………………………..96 2
4.3.1 Previous studies of CO adsorption on TiO surfaces……………………………96 2
4.3.2 Experimental results and discussion…………………………………………….97
4.4 Conclusions……………………………………………………………………108

5 Kinetic measurement of CO oxidation in high pressure cell………….109
5.1 Introduction…………………………………………………………………...110
5.2 Previous studies of CO oxidation on Au/TiO ……………………………...112 2
5.3 Experimental results and discussion………………………………………...115
5.4 Conclusions……………………………………………………………………120

6 Summary and outlook…………………………………………………...121



Bibliography………………………………………………………………….124
Acknowledgements…………………………………………………………..139 Contents iii
Curriculum Vitae…………………………………………………………….141











































List of publications i







List of publications



1 A. Männig, Z. Zhao, D. Rosenthal, K. Christmann, H. Hoster, H. Rauscher and R.J.
Behm, “Structure and growth of ultrathin titanium oxide films on Ru(0001)”, Surf. Sci.
576 (2005) 29.

2 Z. Zhao, T. Diemant, T. Häring, H. Rauscher and R.J. Behm, “Small-volume, UHV
compatible high-pressure reaction cell for combined kinetic and in-situ IR spectroscopic
measurements on planar model catalysts”, Rev. Sci. Instrum.76, 123903 (2005)

3 Z. Zhao, T. Diemant, D. Rosenthal, K. Christmann, J. Bansmann, H. Rauscher and R. J.
Behm, “Au/TiO /Ru(0001) model catalysts and their interaction with CO”, Surf. Sci., 600 2
(2006) 4992.

4 Z. Zhao, J. Bansmann, H. Rauscher and R.J. Behm, “Titania thin films on Ru(0001)
studied by STM and XPS”, to be published.

5 T. Diemant, Z. Zhao, J. Bansmann, H. Rauscher, R.J. Behm, “Kinetic and IR study on the
CO oxidation by planar Au/TiO model catalysts under realistic conditions”, to be published. 2

6 T. Diemmann, H. Rauscher, R.J. Behm, “Interaction of CO with
Au/TiO model catalysts at elevated pressure”, to be published. 2

7 T. Diemant B. Schumacher, D. Hansgen, Z. Zhao, H. Rauscher, R.J. Behm, “Bridging the
material gap and pressure in catalysis studies”, to be published


Conference contributions:

1 Z. Zhao, A. Männig, D. Rosenthal, J. Oswald, S.L.M. Schröder , K. Christmann , H.
Rauscher, and R.J. Behm, “Structure and thermal stability of thick TiO films and x
Au/TiO on Ru(0001)”, Spring-Meeting of the German Physical Society, March, 2003 in x
Dresden, Germany.

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