Max Planck Institute für Kolloid und Grenzflächenforschung Abteilung für Kollide; Prof. M. Antonietti Mesoporous organosilica materials with amine functions: surface characteristics and chirality Dissertation zur Erlangung des akademischen Grades "doctor rerum naturalium" (Dr. rer. nat.) in der Wissenschaftsdisziplin "Chemie" eingereicht an der Mathematisch-Naturwissenschaftlichen Fakultät der Universität Potsdam von Rebecca Voß Potsdam, den 23.03.2005 Table of Contents 1 Introduction and motivation 2 2 Introduction to PMO materials and the sol-gel process 5 2.1 History of PMO materials 5 2.2 Formation of mesoporous materials by the surfactant–templated sol-gel method 7 3 Analytical methods 11 3.1 Adsorption behavior of PMO materials 11 3.2 Isothermal titration calorimetry 17 4 MO materials produced from silsesquioxane surfactant precursors 21 4.1 Introduction 21 4.2 Non-chiral “all-in-one” method 23 4.3 MOs for chiral separation 35 4.4 Long chain amine precursors for mesoporous materials: A MO with non-glassy walls 58 5 Surface properties of the pore walls of MO materials with different organic groups 73 5.1 Introduction 73 5.2 The influence of different organic groups on the hydrophilicity in MO materials 76 5.3 The influence of the surfactant on a series of MO materials prepared from different precursors 81 5.4 The influence of mixing two precursors on the hydrophilicity of a MO as well as the influence of the “all-in-one” method compared to usual templating 83 5.5 Conclusion 91 6 Summary and future work 93 7 Appendices 97 7.1 Instruments 97 7.2 Chemicals used 98 7.3 Abbreviations 98 8 Literature 100 1 Introduction and motivation 1 Introduction and motivation By taking into consideration the adverse effects of pollution on the global weather and on the health of human beings, chemistry, as an applied science, is compelled to find solutions for the reduction and cleansing of wastes. As a materials chemist one way to pursue this objective is to find materials having a high surface area and a tailorable functionalization. These materials could then be used as catalysts in industrial processes increasing the energy to product ratio, or they could be employed as filters to clean water or air through adsorption of heavy metals from waste water or of volatile organic compounds from the air, as well as membranes for fuel cells or electrolytes or electrodes for solid state batteries. These materials should be harmless to the environment by themselves, synthesizable under green chemistry conditions and usable in multiple cycles. One class of materials that might combine these qualities are mesoporous silicas. These materials have been found in 1992 by Kresge and coworkers[1] using the self-assembly of templating surfactants to micelles combined in a sol-gel process with silica precursors. The sol-gel process, a condensation reaction between silanol groups to from siloxane bridges, was at that point already well known and used to form xero- or aero-gels with unconnected and unordered micropores as well as the ordered microporous zeolites. These materials are prepared in an aqueous or ethanolic solution with the help of acid or base as a catalyst. The structure-inducing molecules can then be extracted with the help of a solvent like ethanol or thermally by calcination. There are two general methods used for the condensation of silica precursors: the first is working in a dilute solution of all the components (micellation route) while the second employs the lyotropic phase of the surfactant in a more concentrated sol (nanocasting). 2 Introduction and motivation The behavior of these mesoporous materials can now be influenced through different factors. First of all the templates used can be changed to give different pore structures. This method has been widely employed to give pore sizes in a wide range between 2 nm and 500 nm, employing amphiphilic molecules as well as polymers[2-6] and colloids.[7-9] A second way to influence the properties is to use different precursors in the synthesis. Instead of using only the chemically inert silica, organic groups can be incorporated into the pore walls to change the physical and chemical properties of the material. This has been done by different groups leading to materials with simple alkyl functions as well as complicated metal complexes.[10-13] However, there have only been few chiral mesoporous organosilica materials and to our knowledge none of them showed separation. So the incorporation of chirality into mesoporous organosilica and the separation of racemates on these solids will be one topic of this work. Especially precursors with two siloxyl groups bridged by a chiral organic function will be considered here. One factor that has not received much consideration in the field of mesoporous materials is that a lot of the functional groups which can be incorporated into the silica framework are hidden in the walls and therefore not accessible for any interaction or reaction. In this work we devise a new approach that ensures that the organic function tailored for catalysis and adsorption will be on the pore surface of the material. We use two precursors in a way that while one of them is functionalizing the surface of the pores, the other is creating the skeleton of the structure by forming the pore walls. In this way the bulk properties of the material can be made independent of the surface properties and vice versa. This would allow an unprecedented degree of control on the physical and chemical properties of such class of mesoporous materials. The mesoporous materials could also find applications in separation science[14-19] and in environmental remediation.[20, 21] In this context, the properties of organically modified 3 Introduction and motivation mesoporous silicas towards water will be tested. Water is used in many applications and industrial processes and effective materials for waste water clean-up have to be found. Organosilica materials with high surface areas could be used for this task, since with the right modification they are able to bind metal ions or other pollutants from this waste water.[22, 23] Also our atmosphere is becoming more polluted and needs to be protected. In this case it is not metal ions but gaseous organic molecules that are in need to be removed from air. Since the atmosphere contains water vapor in combination with organic molecules, their interaction has to be considered in any separation scheme.[24] The first step in this thesis work is to get an idea about the behavior of pure water towards different mesoporous organosilica (MO) materials. 4 Introduction to PMO materials and the sol-gel process 2 Introduction to PMO materials and the sol-gel process 2.1 History of PMO materials In the last decade, a of lot interest has been put into the synthesis of well defined porous materials, because of their potential applications in catalysis,[25-32] separation science[14-19] and environmental remediation.[20, 21] Porous materials can be classified by size, network forming material and degree of order. A material will be called microporous if the pores are smaller than 2 nm, macroporous if they are over 50 nm and mesoporous for all the sizes in between. In this work mesoporous materials with a silica framework will be considered in more detail. One of the methods to synthesize these materials is to use a surfactant-templated sol- gel system, which was reported for the first time by Kresge and coworkers in 1992,[33] who discovered surfactant-assembled silica mesostructures. Unfortunately pure silica materials are not that interesting chemically, and different synthetic methods have been examined to create materials with chemical functionality. One way is to anchor a functional group on the surface of the pores in a post synthesis procedure. After the removal of the surfactant the silica surface contains a certain amount of hydroxyl groups, which can function as chemical tethering sites for a wide range of organic molecules with interesting functionality. The disadvantages of this approach are that the organic groups are dangling into the pore void and therefore blocking off space and sometimes even clogging the entire pore. Also not every silanol is modified creating a none uniform distribution of grafted organics. Nevertheless, amine functions,[34-37] ephedrine,[38, 39] and organometallic complexes[40] have been introduced into mesoporous silica materials by this method. 5 Introduction to PMO materials and the sol-gel process Another way is to change the framework itself by introducing organic groups in the precursor. This can be done by using molecules containing R’-Si-(OR) during the 3 condensation.[41-45] This has been successful for alkyl, aryl, thiol, amine and other side chains as well as metal and chiral complexes.[22, 41-48] However, only about 25% of the modified precursor could be used in the synthesis without causing collapses of the framework. Another potential disadvantage of this method is the uneven distribution of organic groups on the surface. This problems may be exacerbated by microphase separation, which leads to some parts of the material containing more of the function than the others.[49] In 1999 three different research groups independently introduced organically bridge- bounded precursors for the synthesis of mesoporous hybrid organic-inorganic silica compounds.[50-55] This method enabled materials to be made exclusively from organically modified precursors, leading to a uniform distribution of organic functionality in the solid. These materials have been labeled “periodic mesoporous organosilica” (PMO). Some of the organic groups included into PMOs are alkyl bridges like ethene and methene, double bond containing molecules like ethylene, phenylene, benzene and derivatives thereof, also heteroatoms functionalities like ferrocene, thiophene, 4-phenyl ether and 4-phenyl sulfide and amines.[50-53, 55-60] The incorporation of organic groups inside the channel walls of silica-based materials leads to the possibility to fine tune the chemical, physical and mechanical properties of the compound through synthetic chemistry. And, compared to the methods described above, the groups do not take space from the pores and pure organic precursor can be condensed without compromising the mechanical stability of the material as well as its short and long range order. 6 Introduction to PMO materials and the sol-gel process 2.2 Formation of mesoporous materials by the surfactant–templated sol-gel method For a standard synthesis of PMO materials non-covalently bound templates are used, including molecules, supramolecular arrays, polymers[2-6] and colloids.[7-9] When dissolved in solution these species can template small inorganic precursors via electrostatic, van de Waals, and hydrogen bonding interactions to form nanostructured materials with tailorable pore shapes and sizes. Surfactant templates consist of bi-functional molecules with a hydrophilic head group and a hydrophobic tail. As a result of their amphiphilic nature, surfactants can self-assemble into supramolecular arrays. These molecules exist as monomers when the solution is dilute, but when their concentration exceeds a certain minimum (the so-called “critical micellar concentration” cmc) the monomers organize spontaneously, forming aggregates of colloidal dimensions, the micelles. The formation of micelles in aqueous media is generally seen as a compromise between the tendency for the hydrophobic groups to avoid the energetically unfavorable contacts with water and the desire for the polar parts to maintain contact with the aqueous environment. Depending on the size ratio between the hydrophobic chain and the head group of a surfactant different superstructures can be formed (Figure 2-1). Figure 2-1: Supramolecular structures for surfactants. A = sphere, B = cylinder, C = planar bilayer, D = reverse micelle, E = bicontinous phase, F = liposomes.[61] 7 Introduction to PMO materials and the sol-gel process Since these supramolecular structures are in thermodynamic equilibrium they are often called “phases”, and a phase diagram can be constructed for each surfactant-solvent system. These phase diagrams allow prediction of the shape of the micelles depending on the thermodynamic conditions, involved in the system under consideration. For example, cetyltrimethylammonium bromide (CTAB) in water will form spherical micelles above the cmc in which the hydrophilic head group forms the outer surface and the hydrophobic tails point towards the center. Figure 2-2: Schematic phase diagram for CTAB in water.[62] As the concentration of the surfactant increases, the spherical micelles can coalesce to form cylindrical micelles (cmc2). Further increasing the surfactant concentration leads to liquid-crystalline (LC) phases. The rod like micelles aggregate and form hexagonal close packed LC arrays. A further increase of the surfactant concentration can produce cubic bicontinuous LC phases and even leads to LC lamellar phases. At very high concentrations, in 8