Facile route for synthesis and controlled growth of SURMOFs on functionalized organic surfaces [Elektronische Ressource] / vorgelegt von Hui Wang

Facile Route for Synthesis and
Controlled Growth of SURMOFs
on Functionalized Organic
Surfaces





Dissertation
zur Erlangung des Grades eines Doktors
der Naturwissenschaften der Fakultä t fü r Chemie
der Ruhr-Universitä t Bochum

Vorgelegt von
Hui Wang
aus China

Bochum 2010 Facile Route for Synthesis and
Controlled Growth of SURMOFs
on Functionalized Organic
Surfaces







Referees: Prof. Dr. Christof Wö ll
Prof. Dr. Roland A. Fischer

Day of Defense: 17 September 2010 Die vorliegende Arbeit wurde im Zeitraum von Mai 2007 bis August
2010 am Lehrstuhl fü r Physikalische Chemie I der Fakultä t fü r Chemie
der Ruhr-Universitä t Bochum unter Anleitung von Herrn Prof. Dr.
Christof Wö ll angefertigt.









Dedicated
To
My Loving Parents
&
Supportive Husband












Table of Contents

TABLE OF CONTENTS ..................................................................................................... 1
CHAPTER I .......................................................... 4
INTRODUCTION ................................................................................ 4
1.1 METAL ORGANIC FRAMEWORKS (MOFS) ....... 4
1.1.1 Introduction .......................................................................................................... 4
1.1.2 Applications ......... 7
1.1.3 Thin Films of MOFs ........................................................................................... 10
1.2 LAYER-BY-LAYER METHOD (LBL) ................ 11
1.3 SELF-ASSEMBLED MONOLAYERS (SAMS) ..................................................................... 12
1.4 MICRO CONTACT PRINTING (µCP) ............... 14
1.5 MOTIVATION ................................................................................................ 15
CHAPTER II ...................... 18
METHODS FOR THE CHARACTERIZATION OF SURMOF THIN FILMS ............ 18
2.1 INFRARED REFLECTION ADSORPTION SPECTROSCOPY (IRRAS) .................................... 18
2.1.1 Theory of Infrared Adsorption ....................................... 18
2.1.2 INFRARED REFLECTION ABSORPTION SPECTROSCOPY ............................................... 19
2.2 X-RAY DIFFRACTION (XRD) ........................................................ 21
2.2.1 X-ray sources ..................................................................... 21
2.2.2 Bragg’s Law ....................................... 22
2.2.3 Thin Film Diffraction ......................................................... 23
2.3 SURFACE PLASMON RESONANCE (SPR) SPECTROSCOPY ............... 25
2.4 ATOMIC FORCE MICROSCOPY (AFM) .......................................................................... 27
2.4.1 Feedback operation ............................................................ 28
2.4.2 Tapping Mode .... 29
CHAPTER III ..................................................................................................................... 30
EXPERIMENTAL .............. 30
1
3.1 CHEMICALS ................................................................................................................. 30
3.2 PREPARATION OF GOLD (AU) SUBSTRATES ... 31
3.3 FUNCTIONALIZATION OF AU SUBSTRATES WITH SAMS .................. 32
3.4 PATTERNING AU SUBSTRATE USING µCP METHOD ........................................................ 32
3.5 GROWTH OF SURFACE MOUNTED MOFS (SURMOFS) ON FUNCTIONALIZED SURFACES BY
USING LAYER-BY-LAYER (LBL) METHOD ........................................................................... 33
3.6 CHARACTERIZATION TECHNIQUES ............... 34
3.6.1 IRRAS ................................................. 34
3.6.2 SPR ..................................................................................... 35
3.6.3 XRD .................... 35
3.6.4 AFM ................................................... 35
3.6.4.1 AFM scratching experiments ....................................................................... 36
CHAPTER IV ..................... 37
GROWTH OF CU BTC ·H O SURMOFS ON FUNCTIONALIZED ORGANIC 3 2 2 X
SURFACES ........................................................................................................................ 37
4.1 INTRODUCTION ........... 37
4.2 EXPERIMENTAL ........................................................................................................... 40
4.3 CHARACTERIZATION OF HKUST-1 SURMOF THIN FILMS ............ 40
4.3.1 Growth of H btc ligand without metal ions on functionalized organic surfaces 40 3
4.3.2 Growth of H btc framework with the presence of metal ions on functionalized 3
organic surfaces .......................................................................................................... 41
4.3.2.1 IRRAS .......... 41
4.3.2.2 SPR .............. 48
4.3.2.3 XRD ............................................................................................................. 49
4.3.3 Study of growth mechanism of SURMOFs using SPR technique ....................... 51
4.3.4 Topographic Characterization of HKUST-1 thin films ...... 58
4.2.4.1 Laterally patterned samples ........................................................................ 58
4.2.4.2 Non-patterned samples ................ 62
CHAPTER V ....................................................................................................................... 64
GROWTH OF LBMOFS ON FUNCTIONALIZED ORGANIC SURFACES ............... 64
5.1 INTRODUCTION ........................................................................................................... 64
2
5.2 EXPERIMENTAL ........................................................................................................... 69
5.3 CHARACTERIZATION OF 2D LBMOFS THIN FILMS ........................ 70
5.3.1 IRRAS ................. 70
5.3.3 XRD .................................................................................................................... 74
5.4 CHARACTERIZATION OF 3D LBMOFS THIN FILMS ........................ 80
5.4.1 Growth of dabco pillared 3D LBMOFs on functionalized organic surfaces ..... 80
5.4.2 [Zn(bdc)(bipy) ] (MOF-508) on the pyridine terminated SAM surface – 0.5
Controlling interpenetration in MOFs by using LBL method ..................................... 87
CHAPTER VI ..................................................................................................................... 96
CONCLUSION ................... 96
LIST OF FIGURES ......................................................................................................... 100
REFERENCE ................... 107

3
Chapter I
Introduction


1.1 Metal Organic Frameworks (MOFs)
1.1.1 Introduction
The synthesis of new materials has been long considered as the most essential element in
advancing technology, however, the discovery of new solid-state materials with
outstanding properties such as high porosity has mostly been serendipitous, using methods
[1]referred to by critics as “shake and bake”, “mix and wait” and “heat and beat” . With the
[2]emergence of a new class of porous solids ca. twenty years ago , a logical and seemingly
simple way which is to link together molecular building blocks exhibiting the desired
[3]property, have been introduced . As a new domain of research, an explosion of papers
exhibits the more and more attention for this hybrid porous solid. Along the enormous
development of this family, many mew vocabularies were generated. In the first hybrid
[4-7]open frameworks , coordination polymers was generated to label these solids due to the
inorganic part which contained either isolated polyhedral or small cluster contained, like
in coordination chemistry. However, very soon, with the use of the inorganic parts with
large dimensionality for these hybrid solids, solids with the structure of chains (1D), layers
(2D), and even inorganic frameworks (3D) were synthesized, a more general term Metal-
[8]Organic Frameworks (MOFs) was then introduced with some derived acronyms, for
instance IRMOF (for Isoreticular MOFs), MMOFs (for microporous MOFs), PCP (for
porous coordination polymers) etc to identify some specificities of the corresponding
[9]series . Currently, the present contribution of hybrid solids is placed in their similarities
with the other families such as zeolite, their advantages, their potentialities and the
unprecedented properties they sometimes exhibit.
4
As defined by Gé rard Fé rey in the article [9], hybrid porous solids result from the reaction
between organic and inorganic species in order to build up three-dimensional frameworks
whose skeleton contains both organic and inorganic moieties only linked by strong bonds,
at variance to supramolecular chemistry. Similarly, O. M. Yaghi has also given a visual
description for these new porous solids with a definition of “molecular scaffold”: “To
produce a robust porous material one could envision constructing the equivalent of a
„molecular scaffold‟ by connecting rigid rod-li