Microporous materials have received much attention and offer new opportunities in electrochemistry because of their interesting properties. Compared with the corresponding nonporous materials, the highly porous structure may facilitate internal mass transport process, provide accessibility to binding sites and provide size selectivity. A new class of microporous materials, polymers of intrinsic microporosity (PIMs) emerged about ten years ago. They combine the microporosity generated from the rigid and contorted backbones and the processibility of linear molecular polymers, which make them particularly attractive for the applications in gas storage, membrane separations and also in electrochemistry. PIM-EA-TB containing ethanoanthracene (EA) and Tröger’s base (TB) is one of the most interesting PIMs and has a high BET surface area around 1000 m2 g-1. Most of the work in this thesis are based on PIM-EA-TB. Results chapters focus on catalysis in PIM films, ion flux in free-standing PIM membranes and carbonization of PIM-EA-TB. Electrochemical oxidation of glucose is important due to the practical applications in glucose sensing and in biological fuel cells. However, the practical application of many catalysts is limited by the poisoning by interferences such as proteins and chloride. Here, PIM-EA-TB was spin-coated onto the surface of supported gold nanoparticles to protect the catalysts from poisoning. It was demonstrated that the PIM-EA-TB film would not negatively affect the catalytic performance of gold nanoparticles for glucose oxidation. Also, it provided effective protection against protein poisoning because of its rigid backbone and rigid molecular structure preventing protein access. Chloride poisoning was reduced but not surpressed. In addition to nanoparticle catalysts, water-insoluble molecular catalysts were investigated. PIM-EA-TB was used as a rigid host for model catalyst, tetraphenylporphyrin (FeTPP). FeTPP was immobilised in the PIM-EA-TB film and then deposited on the electrode to create a high density heterogenised catalysts. Different compositions of PIM and FeTPP and different scanrates were investigated to reveal the catalytic mechanism. The PIM hosted FeTPP catalysts showed facile electron transfer and effective electrocatalytic reduction of oxygen and peroxide. The 4-(3-phenyl-propyl)-pyridine was applied to the PIM-FeTPP film to give an organogel in 12 order to investigate the liquid-liquid interface. The PIM immobilisation method could offer a new opportunity to the immobilisation of a wide range of the molecular catalysts. The understanding of transport processes in PIM-EA-TB membranes is important for the development of further applications in the electrochemistry. Different types of anions were investigated to see the anion uptake and charge transport in PIM-EA-TB films. Three cases were investigated, including the oxidation of ferrocene, the reduction of protons and the transport of anions and protons in the PIM-EA-TB thick films. In all three cases, the diameter and hydrophobicity of anions are important in the competing effects. The pKa of PIM-EA-TB was determined and novel ionic diode effects were observed. Nanofluidic devices are used to regulate the flow of ions to one preferential direction and they have great importance because of the similarity to biological ion channels and the application in biochemical fields. PIMs were explored to the possibility to establish an artificial ion channel with the gate function. A thin film preparative method was introduced to produce thin free-standing polymer films. The 300 nm PIM-EA-TB films supported on a poly-ethylene-terephthalate (PET) film with a 20 m diameter microhole exhibited ionic diode behaviour. Only when the cation and anion had different mobility, the current rectification effects were observed. Different pH values of the electrolyte were also investigated and resulted in a gradual change in rectification effects. Porous carbon materials have wide applications in different fields such as gas separation, water purification, catalyst supports, and fuel cells. One of the common methods to produce the porous carbon is the carbonization of polymers. However, the challenge is that it is difficult to control the pore size and pore distribution. PIM-EA-TB was carbonized at 500 °C in vacuum to produce a novel type of microporous carbon. The microporosity and morphology of the PIM precursor remained after carbonization. The new material exhibited relatively low electrical conductivity and low activity in the electrochemical oxygen reduction. The capacitance of the new carbon material was investigated and found to vary with pH depending on the protonation status of micropores. 13 Finally, the carbonized PIM films were used to control the formation of platinum nanoparticles. Platinum nanoparticles are important catalysts in many areas but may suffer from high costs and lack of reproducibility. Therefore, it is important to reduce the amount of platinum, increase the utilization of platinum as well as control the particle size. The carbonized PIM films still have the microporosity and offer an ideal substrate for platinum nanoparticles. The platinum nanoparticles were formed at the same time with the carbonization of PIM, which helped to control the size of platinum nanoparticles. Compared with bare platinum, the platinum nanoparticles produced by PIM-EA-TB showed a high electrochemically active surface area and good catalytic performances for oxygen reduction, methanol oxidation and glucose oxidation. Much less platinum (1μg per cm2) was needed to achieve the same catalytic performance compared to the bulk platinum.

Since 2016 there are world-wide more mobile phone contracts than people on the planet, and in all these devices critical raw materials (CRMs) are incorporated.[1] For instance, commonly used silicon-based transistors are limited in their chemical modularity. Inorganic materials for solar cells and photocatalysis suffer from critical raw elements content, low apparent quantum efficiencies and photodegradation. Hence, considerable research interest in recent years is focused on development of new high-performance devices for optical and electronic applications that avoid CRMs entirely. To address all these problems materials chemists are exploring for new pathways towards making more sustainable and reliable materials. In that respect, porous organic π- conjugated polymers (POPs) are among the most promising candidates and have gained tremendous attention in materials research over the last decade, especially in the fields of photocatalysis, opto- and electrochemical sensorics, and microelectronics. Synthetic diversity, chemical and physical stability, as well as comparatively low production costs and scalability enable POPs to overcome the drawbacks of inorganic materials. Moreover, the absence of rare earth elements in the purely organic structure of POPs makes these materials more environmentally...

Porous materials (e.g. zeolites, activated carbon, etc.) have found various applications in industry, such as the use as sorbents, catalyst supports and membranes for separation processes. Recently, much attention has been focused on synthesizing porous polymer materials. A vast amount of tailor-made polymeric systems with tunable properties has been investigated. Very often, however, the starting substances for these polymers are of petrochemical origin, and the processes are all in all not sustainable. Moreover, the new polymers have challenged existing characterizing methodologies. These have to be further developed to address the upcoming demands of the novel materials. Some standard techniques for the analysis of porous substances like nitrogen sorption at 77 K do not seem to be sufficient to answer all arising questions about the microstructure of such materials. In this thesis, microporous polymers from an abundant natural resource, betulin, will be presented. Betulin is a large-scale byproduct of the wood industry, and its content in birch bark can reach 30 wt.%. Based on its rigid structure, polymer networks with intrinsic microporosity could be synthesized and characterized. Apart from standard nitrogen and carbon dioxide sorption at 77 K and 273 K, respectively, gas sorption has been examined not only with various gases (hydrogen and argon) but also at various temperatures. Additional techniques such as X-ray scattering and xenon NMR have been utilized to enable insight into the microporous structure of the material. Starting from insoluble polymer networks with promising gas selectivities, soluble polyesters have been synthesized and processed to a cast film. Such materials are feasible for membrane applications in gas separation. Betulin as a starting compound for polyester synthesis has aided to prepare, and for the first time to thoroughly analyse a microporous polyester with respect to its pores and microstructure. It was established that nitrogen adsorption at 87 K can be a better method to solve the microstructure of the material. In addition to that, other betulin-based polymers such as polyurethanes and polyethylene glycol bioconjugates are presented. Altogether, it has been shown that as an abundant natural resource betulin is a suitable and cheap starting compound for some polymers with various potential applications. / Das Bestreben, ölbasierte Produkte durch nachwachsende Rohstoffe zu ersetzen, hat dazu geführt, dass in immer größerer Zahl günstige, reichlich vorhandene Naturstoffe als Ausgangsstoffe für chemische Synthesen untersucht werden. In dieser Arbeit werden Polymere auf Basis von Betulin, einem aus Birkenrinde extrahierten Naturstoff, vorgestellt. Betulin ist zu 30 Gewichtsprozent in Birkenrinde enthalten. Da Betulin ein Nebenprodukt der Holzindustrie ist, ist es kostengünstig und sein Einsatz als Ausgangsstoff äußerst lukrativ. Die ersten Berichte über Betulin-basierte Polymere sind in den 1980er Jahren in Russland und Finnland erschienen, in den Ländern mit großen natürlichen Vorkommen an Birken. Betulin wurde in dieser Arbeit verwendet, um sogenannte mikroporöse Polymere herzustellen. Dies sind Stoffe mit Poren von molekularer Dimension. Mikroporöse Materialien sind wegen ihrer potentiellen Anwendung als Katalysatorträger und Gasseparationsmembranen hochinteressant. Die Klasse mikroporöser Polymere wurde durch die Synthese von unlöslichen Betulin-basierten Polyesternetzwerken erweitert. Außerdem gelang es, lösliche Polyester in Form dünner Filme herzustellen. Diese zeigten vielversprechende Ergebnisse in der Trennung von Stickstoff und Kohlendioxid und weisen somit Potential für die Nutzung als Membran auf. Dies könnte z. B. für Kohlendioxid-Reduzierung in Postcombustion-Verfahren interessant sein. Überdies wurde gezeigt, dass Stickstoffadsorption bei 77 K nicht ohne weiteres als Standardmethode für die Analyse von mikroporösen Materialien geeignet ist und dass die mikroporösen Materialien ferner durch Stickstoffadsorption bei 87 K und andere Gassorptionsmethoden bei verschiedenen Temperaturen zu charakterisieren sind. Diese Arbeit trägt zum besseren Verständnis mikroporöser Polymere bei.

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Das Ziel der Arbeit war die Kombination von 1,3,5-Triethynylbenzen (TEB)-basierten konjugierten mikroporösen Polymeren (CMPs) mit den unterschiedlichen Materialien Silica, Chitosan und Silizium um Hybridmaterialien herzustellen. Als Grundprämisse galt dabei die anwendungsorientierte Verbesserung der Eigenschaften, wobei sich an den literaturbekannten Hauptanwendungen von CMPs – als Adsorber oder als Photokatalysator – orientiert wurde. Die Optimierung von Hybridmaterialien erfordert drei Grundvoraussetzungen: Genaue Kenntnisse der CMPs, dasselbe Verständnis von den Eigenschaften der zu kombinierenden Materialien und die Möglichkeit der umfassenden Charakterisierung. Nur unter diesen Voraussetzungen lassen sich die kollektiven und die aus der Kombination entstehenden Eigenschaften des Hybridmaterials definiert einstellen. Die erste Studie ist der Grundvoraussetzung, der Struktur-Eigenschaftsbeziehung in CMPs, gewidmet. Dabei wurden neuartige CMPs auf Basis von TEB gekuppelt mit Dibromophenanthren-diol Monomeren hergestellt (Polymer TEB-Phenanthren =PTPh). Diese Monomere wurden über die Diolgruppe mit Methyl-(OMe), Trimethylsilyl- (TMS) oder Tertbutyldimethylsilyl (TBDMS) funktionalisiert, wodurch eine homologe Reihe mit steigendem sterischen Anspruch und variierender Polarität entstand. Diese Monomere wurden jeweils mit TEB zu CMPs umgesetzt, um den Einfluss der Sterik auf die CMP Eigenschaften zu analysieren. Über dynamische Kontaktwinkelmessung wurde ermittelt, dass mit Ausnahme von PTPh-TMS, alle PTPh-CMPs mit Kontaktwinkeln zwischen 136° und 148° stark hydrophob sind. Für PTPh-TBDMS ergab sich eine weitere ungewöhnliche Eigenschaft: entgegen den klassischen CMP-Eigenschaften, war es in hydrophoben Lösungsmitteln löslich. Aus Kernspinresonanzspektroskopie (NMR), dynamischen Lichtstreuungs- (DLS) und Transmissionselektronenmikroskop- (TEM) Messungen ging hervor, dass es in Form gequollener, stärker vernetzter Nanopartikel vorliegt, die von weniger vernetztem, quasi-linearem Polymer kolloidal stabilisiert werden. Für potentielle Anwendungen in der Sensortechnik ist dabei relevant, dass dieses PTPh-TBDMS bei einer Anregung mit Licht von 400 nm fluoreszierende Eigenschaften aufweist. Die zweite Studie befasst sich mit dem ersten Hybridmaterial aus mesoporösen Silica-Mikrosphären (40 – 70 µm Durchmesser) ummantelt mit CMPs zur Adsorption organischer Schadstoffe. Während die CMPs in ihren Funktionalitäten genau auf die zu adsorbierende Substanz eingestellt werden können, verbessern die SiO2 Partikel die Dispergierbarkeit und die technische Handhabung der ansonsten schwierig abzutrennenden CMPs. In der ersten Teilstudie wurde das literaturbekannte CMP aus Dibromopyrimidin und TEB (CMP = Polymer TEB Pyrimidin = PTP) für die Ummantelung verwendet. Die in der Synthese eingesetzte Menge an SiO2 beeinflusst die Adsorption des Diclofenacs (DCF), eines weitverbreiteten Pharmazeutikums, welches als Modelladsorptiv verwendet wurde. Die ermittelten maximalen Beladungskapazitäten zeigen ein Maximum bei 3.0 g Silica auf die Standardmenge CMP. Das Silica selbst adsorbiert DCF in vernachlässigbaren Mengen, weshalb die CMP-spezifische Kapazität aus dem tatsächlich im Material enthaltenen CMP-Massenanteil (Thermogravimetrische Analyse (TGA) -Bestimmung) berechnet wurde. Hier ergibt sich für das Maximum bei 3.0 g Silica eine maximale Beladung von 422 mg DCF pro Gramm CMP, welche mit den besten bekannten Adsorbern konkurrieren kann. In der zweiten Teilstudie wurde das Prinzip der Silicasphären-Ummantelung auf andere CMPs aus jeweils TEB und Dibromonaphtalen, Dibromoanilin und Dibromopyridin übertragen. Es konnte gezeigt werden, dass die Monomerpolarität starken Einfluss auf den Erfolg der Ummantelung hat: Nur bei gleicher Polarität von Monomer und Silicaoberfläche war eine Beschichtung möglich. Mittels Präfunktionalisierung des Silicas war eine Ummantelung auch für die hydrophoberen Monomere möglich. Diese Beschichtungen wurden mit Fourier-Transformations-Infrarotspektroskopie (FTIR), Festkörper-NMR, REM, REM-EDX, TGA und TEM analysiert. Im Anschluss wurde erneut die DCF-Adsorption untersucht, wobei das Dibromoanilin basierte CMP@SiO2 die höchste CMP-spezifische DCF-Adsorptionskapazität mit 228 mg/g lieferte. Ein anderes Hybridmaterial, bestehend aus den in der ersten Studie entwickelten CMPs eingebettet in das biobasierte Polymer Chitosan, wird in der dritten Studie thematisiert. Das Ziel war, analog zu den vorhergehenden Studien, eine bessere Verteilung und Zugänglichkeit der CMPs für Adsorptive bei gleichzeitiger Retention in definierten Strukturen zur Vereinfachung der Handhabung. Chitosan als biobasiertes und biokompatibles Polymer ist vergleichsweise nachhaltig, ermöglicht medizinische Applikationen und ist gut über die Aminogruppe funktionalisierbar. Daher wurde die Aminofunktionalität mit Hexanoylchlorid umgesetzt, um eine hydrophobe Hexanoylgruppe in das Chitosan einzuführen. Das modifizierte Hexanoyl Chitosan (H-chitosan) wurde auf verschiedene Weise analysiert, wobei besonders die Änderung der rheologischen Eigenschaften aufgrund der Unterbrechung der Wasserstoffbrückenbindung zwischen den Chitosanketten durch die hydrophobe Modifizierung bedeutend waren. Anschließend wurden sowohl das reine Chitosan als auch das H-chitosan verwendet, um CMP@Chitosan Gel-Beads herzustellen. Da das CMP das teurere Material ist, wurde es im Massenverhältnis von 1:4 eingesetzt, wobei über REM und REM-EDX nachgewiesen wurde, dass die CMPs großflächig in den Chitosanmatrizen verteilt sind. Beim Trocknen wurde beobachtet, dass die luftgetrockneten Beads zu kompakten Strukturen kollabieren, während die vakuumgetrockneten Beads die gequollene Form beibehalten. Dies wirkt sich auf die Quellung der trockenen Beads im wässrigen Adsorptionsmedium aus, wobei die luftgetrockneten Beads nur geringfügig und die vakuumgetrockneten Beads deutlich stärker quellen. Dabei quellen die H-chitosan Beads generell besser, was auf die gehinderte Zusammenlagerung der Chitosanketten durch die hydrophobe Gruppe zurückgeführt wurde. Mittels Batchversuchen wurde die Adsorption von DCF bei einer niedrigen Konzentration von 1 mg/L und einer hohen Konzentration von 300 mg/L untersucht, wobei sich die vakuumgetrockneten Beads als effektiver erwiesen. Die Hybridmaterialbeads adsorbierten mehr DCF als sowohl die reinen Chitosan- bzw. H-chitosan Beads als auch die reinen CMPs. Die CMP@H-chitosan Beads adsorbierten aufgrund der verbesserten Quellung die höchsten Mengen an DCF. Die CMP-spezifische Adsorption wurde durch die Einbindung und Verteilung in den Chitosanmatrizen deutlich gesteigert, während gleichzeitig die Handhabbarkeit erleichtert wurde, da die Beads mittels eines Siebes aus der Adsorptionslösung abgetrennt werden können. Die letzte Studie ist auf Silizium-Nanopartikel (SiNPs)@CMP-Hybridmaterialien zur Anwendung als Photokatalysator in der solaren Wasserstoffgenerierung (HER) ausgerichtet. In diesem Prozess wird solare Energie direkt genutzt, um aus Wasser Wasserstoff herzustellen. Die für CMP-typischen geringen HER-Raten sollen durch die, von der AG Dasog (Dalhousie Universität, Halifax, Kanada) hergestellten, SiNPs angehoben werden. Mittels FTIR Spektroskopie wurde bestätigt, dass diese CMPs auch im Beisein der SiNPs gebildet wurden. Über TGA wurde der Massenanteil der SiNPs in den jeweiligen Hybridmaterialien bestimmt, welcher von 4 wt% bis 22 wt% variiert und vor allem vom eingesetzten Monomer abhängt. REM-EDX Analysen zeigten eine lösungsmittelunabhängige, flächendeckende Verteilung der SiNPs in den jeweiligen CMPs. Die Einbindung der SiNPs, analysiert über DLS und TEM Messungen, ergab in einem Fall eine vollständige Einbindung, in einem anderen Fall eine schlechte Einbindung und in allen übrigen Fällen partielle Einbindung. Diese partielle Einbindung, bei der Teile der SiNPs nicht mit CMP bedeckt sind, erwies sich als vorteilhaft in den Wasserstoffgenerierungsversuchen. Bei diesen SiNP@CMP Hybridmaterialien waren die HER Raten gegenüber den reinen CMPs deutlich gesteigert, wobei das beste Material 32 µmol/g*h Wasserstoff produzierte. Dieses Material wurde durch Dotierung mit H2PtCl4 weiter optimiert und in Zyklisierungsstudien eingesetzt. Während die Langzeitstabilität sich als optimierungsbedürftig erwies, war die Dotierung erfolgreich und steigerte die HER Rate auf 42 µmol/g*h. Im Rahmen dieser Arbeit wurden CMPs mit je einem Vertreter der anorganischen Isolatoren, der biobasierten Polymere und der anorganischen Halbleiter kombiniert. Die grundlegende Unterschiedlichkeit dieser Materialien zeigt, dass der Kombinationsvielfalt nur wenige Limitationen gesetzt sind. Die anwendungsbezogenen Machbarkeitsstudien zeigen die daraus erwachsenden Vorteile auf. Dabei befindet sich die Erforschung der CMP-Hybridmaterialien noch in ihren Anfängen, enthält jedoch bereits vielversprechende Strategien und Ansätze zur Lösung gesellschaftlich relevanter Problemstellungen.:Abstract V Kurzfassung VIII Abbreviations XI Symbols XII List of publications XIII List of figures XVI List of schemes XVIII List of tables XIX 1. Introduction 1 2. Theoretical background 4 2.1. Synthesis and properties of conjugated microporous polymers (CMPs) 4 2.1.1. Conjugated microporous polymers - a new class of materials 4 2.1.2. Synthesis of CMPs 5 2.1.3. Properties of CMPs 8 2.2. Fundamentals of adsorption and application of CMPs as adsorbers 11 2.2.1. Basic adsorption models 12 2.2.2. CMPs as adsorbers 16 2.3. Fundamentals and application of CMPs for hydrogen evolution 19 2.3.1. Physicochemical fundamentals of photocatalysis 19 2.3.2. Reaction and conditions of solar-driven hydrogen evolution 22 2.3.3. CMPs for solar-driven hydrogen evolution 24 2.4. Hybrid materials based on CMPs 26 2.4.1. CMPs combined with nanoparticulate systems 26 2.4.2. Macroscale CMP-based hybrid materials 30 2.5. Fundamentals of instrumental analysis 31 2.5.1. Fourier transform infrared spectroscopy 31 2.5.2. Nuclear magnetic resonance 34 2.5.3. Gas sorption analysis 37 3. Results and discussion 41 3.1. Synthesis and characterization of conjugated microporous polymers 41 3.1.1. Dibromophenanthrene-based monomers 42 3.1.2. CMPs of the basic monomers 43 3.1.3. CMPs of the functionalized monomers 46 3.1.4. Properties of the PTPh-CMPs 48 3.1.5. PTPh-TBDMS - a special case 50 3.2. CMP@Silica microspheres 52 3.2.1. Conjugated Microporous Polymer Hybrid Microparticles for Enhanced Applicability in Silica-boosted Diclofenac Adsorption 53 3.2.2. Polarity and Functionality Tailored Conjugated Microporous Polymer Coatings on Silica Microspheres for Enhanced Pollutant Adsorption 71 3.3. CMP@Chitosan 86 3.3.1. A Complementary and Revised View on the N-Acylation of Chitosan with Hexanoyl Chloride 88 3.3.2. CMP@Chitosan synthesis and characterization 106 3.3.3. Diclofenac adsorption of CMP@Chitosan beads 110 3.4. Silicon nanoparticles@CMPs 115 3.4.1. New materials for solar-driven hydrogen evolution 115 3.4.2. Synthesis and characterization of selected SiNP@CMP hybrid materials 116 3.4.3. Distribution and incorporation of SiNPs in the CMP matrices 121 3.4.4. Hydrogen evolution reaction 124 4. Experimental section 128 4.1. Synthesis 128 4.1.1. Synthesis of the CMPs 129 4.1.2. Synthesis of dibromo-phenanthrene based monomers 129 4.1.3. Synthesis of CMP@Chitosan beads 131 4.1.4. Synthesis of the SiNP@CMP hybrid materials 132 4.2. Characterization and application-related studies 133 4.2.1. Characterization of the PTPh-monomers and CMPs 133 4.2.2. Characterization of the CMP@Chitosan beads 133 4.2.3. Characterization of the SiNP@CMP 134 5. Conclusion and outlook 135 6. References 141 7. Appendix 151 Danksagung / The thesis aimed to combine 1,3,5-triethynylbenzene (TEB)-based conjugated microporous polymers (CMPs) with the different materials silica, chitosan, and silicon to produce hybrid materials. The basic premise was an application-oriented improvement of properties, guided by the main applications of CMPs known from the literature - as adsorbers or as photocatalysts. Optimization of hybrid materials requires three basic prerequisites: Precise knowledge of the CMPs, the same understanding of the properties of the materials to be combined, and the possibility of comprehensive characterization. Only under these conditions the collective properties and those resulting from the combination of the hybrid material can be adjusted in a defined way. The first study is devoted to the basic premise, the structure-property relationship in CMPs. Here, novel CMPs based on TEB coupled with dibromo phenanthrene-diol monomers were prepared (polymer TEB-phenanthrene =PTPh). These monomers were functionalized with methyl-(OMe), trimethylsilyl- (TMS), or tertbutyldimethylsilyl (TBDMS) via the diol group, resulting in a homologous series with increasing steric demand and varying polarity. These monomers were each coupled with TEB to form CMPs in order to analyze the influence of steric demand on the CMP properties. Via dynamic contact angle measurement, it was determined that except PTPh-TMS, all PTPh-CMPs are highly hydrophobic with contact angles between 136° and 148°. For PTPh-TBDMS, another unusual property emerged: Contrary to the classical CMP properties, it was soluble in hydrophobic solvents. From nuclear magnetic resonance (NMR), dynamic light scattering (DLS), and transmission electron microscopy (TEM) measurements, it was found to consist of swollen, more cross-linked nanoparticles colloidally stabilized by less cross-linked quasi-linear polymer. Further, PTPh-TBDMS exhibits fluorescent properties when excited with light at 400 nm, which is of relevance to potential applications in sensor technology. The second study deals with the first hybrid material consisting of mesoporous silica microspheres (40 – 70 µm diameter) coated with CMPs for the adsorption of organic pollutants. While the functionalities of the CMPs can be precisely adjusted to interact with the pollutant, the SiO2 particles improve dispersibility and technical handling of the CMP that is otherwise difficult to recover. The first sub-study used the literature-known CMP of dibromo pyrimidine and TEB (CMP = polymer TEB pyrimidine = PTP) for the coating. From scanning electron microscopy (SEM) images, it can be seen that the PTP grows on the SiO2 spheres in the form of hemispheres. The amount of SiO2 used in the synthesis affects the adsorption of diclofenac (DCF), a widely applied pharmaceutical used as a model adsorptive. The maximum loading capacities determined show a maximum at 3.0 g of silica to the standard amount of CMP. The silica itself adsorbs DCF in negligible amounts, which is why the CMP-specific capacity was calculated from the CMP mass fraction actually contained in the material (thermogravimetric analysis -TGA determination). Here, the maximum loading at 3.0 g silica is 422 mg DCF per gram CMP, which is competitive with the best-known adsorbents. In the second sub-study, the principle of silica sphere coating was transferred to other CMPs from TEB and dibromo naphthalene, dibromo aniline, and dibromo pyridine, respectively. It was shown that the monomer polarity has a strong influence on the success of the coating: The coating was only possible if the monomer and the silica surface featured the same polarity. Through pre-functionalization of the silica, the coating was also made possible for the more hydrophobic monomers. Fourier transform infrared spectroscopy (FTIR), solid-state NMR, SEM, SEM-EDX, TGA, and TEM were used to analyze these coatings. DCF adsorption was then investigated, with the dibromo aniline-based CMP@SiO2 providing the highest CMP-specific DCF adsorption capacity of 228 mg/g. Another hybrid material, consisting of the CMPs developed in the first study embedded in the biobased polymer chitosan, is investigated in the third chapter. The goal, analogous to the previous studies, was to improve the distribution and accessibility of the CMPs for adsorptives while retaining them in defined structures for ease of handling. As a biobased and biocompatible polymer, chitosan is comparatively sustainable, enables medical applications, and is well-functionalizable via the amino group. Therefore, the amino functionality was converted with hexanoyl chloride to introduce a hydrophobic hexanoyl group into the chitosan. The modified hexanoyl chitosan (H-chitosan) was analyzed in several ways. The change in rheological properties due to the disruption of hydrogen bonding between the chitosan chains by the hydrophobic modification was particularly significant. Subsequently, the pure chitosan and the H-chitosan were used to prepare CMP@Chitosan gel beads. Since the CMP is the more expensive material, it was used in a mass ratio of 1:4. It was verified via SEM and SEM-EDX that the CMPs were distributed over a large area in the chitosan matrices. Upon drying, it was observed that the air-dried beads collapsed into compact structures, while the vacuum-dried beads retained the swollen shape. This affects the swelling of the dry beads in the aqueous adsorption medium, with the air-dried beads swelling only slightly and the vacuum-dried beads swelling significantly stronger. In general, the H-chitosan beads swell better, which was attributed to the hydrophobic group's hindered assembly of the chitosan chains. Batch experiments were used to investigate the adsorption of DCF at a low concentration of 1 mg/L and a high concentration of 300 mg/L, in which the vacuum-dried beads were found to be more effective. The hybrid material beads adsorbed more DCF than pure chitosan or H-chitosan beads and the pure CMPs. The CMP@H-chitosan beads adsorbed the highest amounts of DCF due to improved swelling. Overall, the CMP-specific adsorption was significantly enhanced by incorporation and distribution in the chitosan matrices. At the same time, handling was facilitated because the beads can be separated from the adsorption solution using a sieve and do not need to be centrifuged like the CMPs. The final study is focused on silicon nanoparticles (SiNPs)@CMP hybrid materials for use as photocatalysts in solar-driven hydrogen evolution reaction (HER). In this process, solar energy is directly used to produce hydrogen from water. The low HER rates typical for CMPs are to be raised by the SiNPs produced by the Dasog group (Dalhousie University, Halifax, Canada). In turn, the SiNPs are to be protected from oxidative influences by the CMPs. For this purpose, the CMPs known from the literature and investigated in the previous studies were used. By FTIR, it was confirmed that all CMPs were also formed in the presence of the SiNPs. Via TGA, the mass fraction of SiNPs in the respective hybrid materials was determined, which varied from 4 wt% to 22 wt% and depended mainly on the monomer used. SEM-EDX analyses showed a solvent-independent, areal distribution of SiNPs in the respective CMPs. The incorporation of the SiNPs analyzed via DLS and TEM measurements showed complete incorporation in one case, poor incorporation in another, and partial incorporation in all other cases. This partial incorporation, where parts of the SiNPs are not covered with CMP, proved beneficial in the hydrogen evolution experiments. For these SiNP@CMP hybrid materials, the HER rates were significantly increased compared to the pure CMPs, with the best material producing 32 µmol/g*h of hydrogen. This material was further optimized by doping with H2PtCl4 and used in cyclization studies. While long-term stability proved to require more optimization, doping was successful as it increased the HER rate to 42 µmol/g*h. In this work, CMPs were combined with one representative of inorganic insulators, biobased polymers, and inorganic semiconductors. The fundamental difference between these materials shows that there are few limitations set to the variety of combinations. The application-related feasibility studies showed the advantages that arise from this. Although research into CMP hybrid materials is still in its infancy, it already holds promising strategies and approaches for solving socially relevant problems.:Abstract V Kurzfassung VIII Abbreviations XI Symbols XII List of publications XIII List of figures XVI List of schemes XVIII List of tables XIX 1. Introduction 1 2. Theoretical background 4 2.1. Synthesis and properties of conjugated microporous polymers (CMPs) 4 2.1.1. Conjugated microporous polymers - a new class of materials 4 2.1.2. Synthesis of CMPs 5 2.1.3. Properties of CMPs 8 2.2. Fundamentals of adsorption and application of CMPs as adsorbers 11 2.2.1. Basic adsorption models 12 2.2.2. CMPs as adsorbers 16 2.3. Fundamentals and application of CMPs for hydrogen evolution 19 2.3.1. Physicochemical fundamentals of photocatalysis 19 2.3.2. Reaction and conditions of solar-driven hydrogen evolution 22 2.3.3. CMPs for solar-driven hydrogen evolution 24 2.4. Hybrid materials based on CMPs 26 2.4.1. CMPs combined with nanoparticulate systems 26 2.4.2. Macroscale CMP-based hybrid materials 30 2.5. Fundamentals of instrumental analysis 31 2.5.1. Fourier transform infrared spectroscopy 31 2.5.2. Nuclear magnetic resonance 34 2.5.3. Gas sorption analysis 37 3. Results and discussion 41 3.1. Synthesis and characterization of conjugated microporous polymers 41 3.1.1. Dibromophenanthrene-based monomers 42 3.1.2. CMPs of the basic monomers 43 3.1.3. CMPs of the functionalized monomers 46 3.1.4. Properties of the PTPh-CMPs 48 3.1.5. PTPh-TBDMS - a special case 50 3.2. CMP@Silica microspheres 52 3.2.1. Conjugated Microporous Polymer Hybrid Microparticles for Enhanced Applicability in Silica-boosted Diclofenac Adsorption 53 3.2.2. Polarity and Functionality Tailored Conjugated Microporous Polymer Coatings on Silica Microspheres for Enhanced Pollutant Adsorption 71 3.3. CMP@Chitosan 86 3.3.1. A Complementary and Revised View on the N-Acylation of Chitosan with Hexanoyl Chloride 88 3.3.2. CMP@Chitosan synthesis and characterization 106 3.3.3. Diclofenac adsorption of CMP@Chitosan beads 110 3.4. Silicon nanoparticles@CMPs 115 3.4.1. New materials for solar-driven hydrogen evolution 115 3.4.2. Synthesis and characterization of selected SiNP@CMP hybrid materials 116 3.4.3. Distribution and incorporation of SiNPs in the CMP matrices 121 3.4.4. Hydrogen evolution reaction 124 4. Experimental section 128 4.1. Synthesis 128 4.1.1. Synthesis of the CMPs 129 4.1.2. Synthesis of dibromo-phenanthrene based monomers 129 4.1.3. Synthesis of CMP@Chitosan beads 131 4.1.4. Synthesis of the SiNP@CMP hybrid materials 132 4.2. Characterization and application-related studies 133 4.2.1. Characterization of the PTPh-monomers and CMPs 133 4.2.2. Characterization of the CMP@Chitosan beads 133 4.2.3. Characterization of the SiNP@CMP 134 5. Conclusion and outlook 135 6. References 141 7. Appendix 151 Danksagung

A bifunctional imidazolium linker was used for the production of highly crosslinked element organic frameworks by Suzuki-coupling with tetrafunctional boronic acids. The resulting porous materials are good heterogeneous organocatalysts in the N-heterocyclic carbene-catalyzed conjugated umpolung of α,β-unsaturated cinnamaldehyde. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

A bifunctional imidazolium linker was used for the production of highly crosslinked element organic frameworks by Suzuki-coupling with tetrafunctional boronic acids. The resulting porous materials are good heterogeneous organocatalysts in the N-heterocyclic carbene-catalyzed conjugated umpolung of α,β-unsaturated cinnamaldehyde. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

4 ABSTRACT The synthesis has been described yielding a new type of rigid conjugated polymer networks which possess a high content of permanent micropores and macropores and exhibit high surface areas up to 1469 m2/g. The networks have been prepared via chain-growth coordination polymerization catalysed with insertion catalysts based on Rh complexes. This polymerization has been newly applied to bifunctional acetylenic monomers of diethynylarene type (1,4-diethynylbenzene, 1,3-diethynylbenzene and 4,4'-diethynylbiphenyl). The covalent structure of the networks consists of the polyacetylene main chains densely connected by arylene struts. The W and Mo metathesis catalysts have been revealed as inefficient for the synthesis of these networks. The increase in the polymerization temperature and time has been shown to affect positively the content and the diameter (up to 22 nm) of the mesopores in the networks. A mechanism has been proposed that explains the mesopores formation as a result of mutual knitting of small particles of the microporous polymer. The application of emulsion polymerization technique allowed to prepare texturally hierarchical polyacetylene networks possessing interconnected open macropores (diameter up to 4,8 μm) the walls of which exhibited micro/mesoporous texture. It was demonstrated...