Utilization of graphitic carbon nitride in dispersed media

Utilization of sunlight for energy harvesting has been foreseen as sustainable replacement for fossil fuels, which would also eliminate side effects arising from fossil fuel consumption such as drastic increase of CO2 in Earth atmosphere. Semiconductor materials can be implemented for energy harvesting, and design of ideal energy harvesting devices relies on effective semiconductor with low recombination rate, ease of processing, stability over long period, non-toxicity and synthesis from abundant sources. Aforementioned criteria have attracted broad interest for graphitic carbon nitride (g-CN) materials, metal-free semiconductor which can be synthesized from low cost and abundant precursors. Furthermore, physical properties such as band gap, surface area and absorption can be tuned. g-CN was investigated as heterogeneous catalyst, with diversified applications from water splitting to CO2 reduction and organic coupling reactions. However, low dispersibility of g-CN in water and organic solvents was an obstacle for future improvements. Tissue engineering aims to mimic natural tissues mechanically and biologically, so that synthetic materials can replace natural ones in future. Hydrogels are crosslinked networks with high water content, therefore are prime candidates for tissue engineering. However, the first requirement is synthesis of hydrogels with mechanical properties that are matching to natural tissues. Among different approaches for reinforcement, nanocomposite reinforcement is highly promising. This thesis aims to investigate aqueous and organic dispersions of g-CN materials. Aqueous g-CN dispersions were utilized for visible light induced hydrogel synthesis, where g-CN acts as reinforcer and photoinitiator. Varieties of methodologies were presented for enhancing g-CN dispersibility, from co-solvent method to prepolymer formation, and it was shown that hydrogels with diversified mechanical properties (from skin-like to cartilage-like) are accessible via g-CN utilization. One pot photografting method was introduced for functionalization of g-CN surface which provides functional groups towards enhanced dispersibility in aqueous and organic media. Grafting vinyl thiazole groups yields stable additive-free organodispersions of g-CN which are electrostatically stabilized with increased photophysical properties. Colloidal stability of organic systems provides transparent g-CN coatings and printing g-CN from commercial inkjet printers. Overall, application of g-CN in dispersed media is highly promising, and variety of materials can be accessible via utilization of g-CN and visible light with simple chemicals and synthetic conditions. g-CN in dispersed media will bridge emerging research areas from tissue engineering to energy harvesting in near future.Sonnenlicht kann fossile Brennstoffe in der Energieerzeugung ersetzen und ermöglicht neben der Nutzung einer nachhaltigen Ressource dabei auch die deutliche Reduktion der Umweltbelastung in der Energieerzeugung. Die Verfügbarkeit geeigneter Energiegewinnungstechnologien hängt entscheidend von der Verfügbarkeit geeigneter Superkondensatoren (SC) ab. Ideale SC sollten sich in diesem Zusammenhang durch eine geringe Rekombinationsrate, gute Verarbeitbarkeit, Langzeitstabilität, Ungiftigkeit und die Verfügbarkeit aus nachhaltigen Ressourcen auszeichnen. Graphitisches Kohlenstoffnitrid (graphitic carbon nitride – g-CN), ein metall-freier Halbleiter, der aus nachhaltigen und in großer Menge verfügbaren Ausgangsstoffen hergestellt werden kann, ist als Material für dieses Eigenschaftsprofil hervorragend geeignet. Darüber hinaus können die Eigenschaften dieses Materials (innere Oberfläche, Bandlücke, Lichtabsorption) eingestellt werden. Daraus ergibt sich ein großes Forschungsinteresse z.B. im Bereich heterogener Katalyse, wie in der Kohlenstoffdioxidreduktion, elektrolytischen Wasserspaltung und verschiedener organischer Kupplungsreaktionen. Unglücklicherweise ist die schlechte Dispergierbarkeit von g-CN in organischen Lösungsmitteln und Wasser ein wesentlicher Hinderungsgrund für die erfolgreiche Nutzbarmachung dieser hervorragenden Eigenschaften. Das Design von Materialien, die biologisches Gewebe in seinen mechanischen und biologischen Eigenschaften nachahmen und ersetzen können, ist das Ziel der Gewebekonstruktion (Tissue Engineering – TE). Hydrogele, also Netzwerke mit hohem Wassergehalt, gelten als die vielversprechendsten Materialen in diesem Forschungsfeld. Die Herstellung von Hydrogelen, die biologischem Gewebe in seinen mechanischen Eigenschaften ähnelt gilt allerdings als äußerst schwierig und erfordert die Stabilisierung der Netzwerke. Besonders der Einsatz von Nanoverbundstrukturen (nanocomposites) erscheint in diesem Zusammenhang vielversprechend. Die vorliegende Arbeit beschäftigt sich mit der Untersuchung von g-CN in sowohl wässrigen, als auch organischen Dispersionen. Im Zuge dessen werden wässrige Dispersionen für die Synthese von Hydrogelen, bei der g-CN sowohl als Photoinitiator für die durch sichtbares Licht ausgelöste Vernetzung, als auch als Strukturverstärker fungiert. Zur Verbesserung der Dispergierbarkeit des g CN werden vielseitige Ansätze präsentiert, welche von der Verwendung von Co-Lösungsmitteln bis zur Präpolymerbildung reichen. Durch die aufgezeigten Ansätze können Hydrogele mit unterschiedlichen mechanischen Eigenschaften hergestellt werden (hautartig bis knorpelig). Darüber hinaus wird eine Ein-Topf Synthese für die Oberflächenfunktionalisierung vorgestellt, durch die die Dispergierbarkeit von g-CN in organischen und wässrigen Medien verbessert werden kann. Beispielsweise erlaubt die Oberflächenfunktionalisierung mit Vinylthiazol die Herstellung von kolloidal dispergiertem g-CN mit verbesserten photophysikalischen Eigenschaften ohne zusätzliche Additive und eröffnet damit die Möglichkeit transparenter g-CN Beschichtungen und ermöglicht die Druckbarkeit von g-CN aus handelsüblichen Tintenstrahldruckern. Die Anwendung von g-CN in dispergierten Medien ist vielversprechend, da eine große Zahl sehr vielfältiger Materialien durch die Kombination von g-CN mit sichtbarem Licht aus günstigen, nachhaltigen Ressourcen verfügbar ist. Daher ist zu erwarten, dass g-CN in dispergierten Medien verschiedene im Entstehen begriffene Forschungsfelder von TE bis zur Energiegewinnung überspannen wird

A biomimetic nanofluidic diode based on surface-modified polymeric carbon nitride nanotubes

A controllable ion transport including ion selectivity and ion rectification across nanochannels or porous membranes is of great importance because of potential applications ranging from biosensing to energy conversion. Here, a nanofluidic ion diode was realized by modifying carbon nitride nanotubes with different molecules yielding an asymmetric surface charge that allows for ion rectification. With the advantages of low-cost, thermal and mechanical robustness, and simple fabrication process, carbon nitride nanotubes with ion rectification have the potential to be used in salinity-gradient energy conversion and ion sensor systems

Photoinduced post-modification of graphitic carbon nitride-embedded hydrogels : synthesis of 'hydrophobic hydrogels' and pore substructuring

Hydrogels are a special class of crosslinked hydrophilic polymers with a high water content through their porous structures. Post-modifications of hydrogels propose an attractive platform so that a variety of fresh functions, which are not arising from initial monomers, could be accessible on a parental network. Photoinduced post-modification of hydrogels by embedding semiconductor nanosheets would be of high interest and novelty. Here, a metal-free semiconductor graphitic carbon nitride (g-CN)-embedded hydrogel as an initial network was synthesized via redox-couple initiation under dark conditions. Post-photomodification of so-formed hydrogel, thanks to the photoactivity of the embedded g-CN nanosheets, was exemplified in two scenarios. The synthesis of ‘hydrophobic hydrogel’ is reported and its application in delayed cation delivery was investigated. Furthermore, pores of the initial hydrogel were modified by the formation of a secondary polymer network. Such a facile and straightforward synthetic protocol to manufacture functional soft materials will be of high interest in near future by the means of catalysis and agricultural delivery

Colloidal tornadoes in a vial under gravitational sedimentation

Collective motion in living matter is highly intriguing but can also be observed in charged colloidal systems. Collective motion observed in colloidal systems requires extensive material synthesis, external stimuli, and advanced characterization methods that might be highly costly to be employed for teaching. Besides that, colloidal systems can inherently possess dynamic movements. Generally, colloidal sedimentation is pictured as a linear movement, but under certain conditions autonomously activated sedimentation can be attained. In this demonstration, a simple formation of colloidal tornadoes will be explored by gravitational force as the sole stimulus. This demonstration is ideal for the general public for colloid chemistry learning, and these findings can be coupled to colloidal stability lectures

On the photopolymerization of mevalonic lactone methacrylate : exposing the potential of an overlooked monomer

Functional polymers remain at the core of polymer science in the second century of macromolecular material research. Lactones are known as monomers for ring-opening polymerizations; however, polymers containing lactone rings as pendant groups are rare. In this study, we revive an overlooked monomer, mevalonic lactone methacrylate, by demonstrating its radical polymerization, reporting the properties of the polymer product, and providing information on the thermal, UV, and hydrolytic stabilities of both the monomer and polymer. Controlled polymerization (via RAFT) provides synthetic precision and active terminal groups; thus, the formation of a simple block copolymer based on the aforementioned polymer is presented. The pendant ring accepts nucleophilic attacks, so the initially hydrophobic polymer can be altered to make it hydrophilic via reactions with nucleophiles in just seconds. Thus, the polymer film provides responsive surface formation

Oxidative photopolymerization of 3,4-ethylenedioxythiophene (EDOT) via graphitic carbon nitride : a modular toolbox for attaining PEDOT

Conductive polymers found key applications ranging from optoelectronics and OLEDs to conductive composite materials. The synthesis of conductive polymers from monomers such as thiophene derivatives, pyrroles and aniline mainly relies on oxidative polymerization, and the processing of so-formed (insoluble) polymers is a major issue that needs to be addressed. In the present work, oxidative photopolymerization of 3,4-ethylenedioxythiophene (EDOT) by visible light employing the metal-free semiconductor graphitic carbon nitride (g-CN) is presented. Two main reaction pathways based on g-CN content will be described, and the formation of processable oligo-EDOT will be demonstrated

Differential dose contributions on total dose distribution of 125I brachytherapy source

AbstractThis work provides an improvement of the approach using Monte Carlo simulation for the Amersham Model 6711 125I brachytherapy seed source, which is well known by many theoretical and experimental studies. The source which has simple geometry was researched with respect to criteria of AAPM Tg-43 Report. The approach offered by this study involves determination of differential dose contributions that come from virtual partitions of a massive radioactive element of the studied source to a total dose at analytical calculation point. Some brachytherapy seeds contain multi-radioactive elements so the dose at any point is a total of separate doses from each element. It is momentous to know well the angular and radial dose distributions around the source that is located in cancerous tissue for clinical treatments. Interior geometry of a source is effective on dose characteristics of a distribution. Dose information of inner geometrical structure of a brachytherapy source cannot be acquired by experimental methods because of limits of physical material and geometry in the healthy tissue, so Monte Carlo simulation is a required approach of the study. EGSnrc Monte Carlo simulation software was used. In the design of a simulation, the radioactive source was divided into 10 rings, partitioned but not separate from each other. All differential sources were simulated for dose calculation, and the shape of dose distribution was determined comparatively distribution of a single-complete source. In this work anisotropy function was examined also mathematically

Upgrading poly(styrene-co-divinylbenzene) beads : incorporation of organomodified metal-free semiconductor graphitic carbon nitride through suspension photopolymerization to generate photoactive resins

The inclusion of the metal free semiconductor graphitic carbon nitride (g-CN) into polymer systems brings a variety of new options, for instance as a heterogeneous photoredox polymer initiator. In this context, we present here the decoration of the inner surface of poly(styrene-co-divinylbenzene) beads with organomodified g-CN via one pot suspension photopolymerization. The resulting beads are varied by changing reaction parameters, such as, crosslinking ratio, presence of porogens, and mechanical agitation. The photocatalytic activity of so-formed beads was tested by aqueous rhodamine B dye photodegradation experiments. Additionally, dye adsorption/desorption properties were examined in aqueous as well as in organic solvents. Photoinduced surface modification with vinylsulfonic acid and 4-vinyl pyridine is introduced. Overall, metal-free semiconductor g-CN donates photoactivity to polymer networks that can be employed for dye photodegradation and acid–base catalyst transformation through facile photoinduced surface modifications

Carbon nitride-coated transparent glass vials as photoinitiators for radical polymerization

Benign polymerization routes offer new perspectives in current polymer technology. Especially for automated or continuous flow synthesis of polymers, new devices and principles have to be considered by the means of minimizing addition or separation sequences as well as the type of a polymer initiation. Near-UV and visible light-induced polymerization utilizing metal-free semiconductor polymeric carbon nitride (pCN) as heterogeneous photocatalyst was a first step into this direction. Moving from heterogeneous powder catalysis (which still requests catalyst separation) to surface photocatalysis via coating glass tubes or vials with pCN thin films is presented. Performance and effectivity of those photoactive reactors are proven by free radical photopolymerization of variety of monomers. Reusability of vials is demonstrated via reversible addition-fragmentation chain-transfer polymerization-assisted block copolymer synthesis. This strategy eliminates the necessity of adding or removing initiators, works at room temperature, and offers a platform for cheap and effective polymer synthesis at the age of automated synthesis

Visible-light induced emulsion photopolymerization with carbon nitride as stabilizer and photoinitiator

Photopolymerization is a common method in the synthesis of polymers with various applications. Herein, a simple and effective route for surfactant-free emulsion photopolymerization (EPP) under visible light irradiation is described. Therein, graphitic carbon nitride (g-CN) was utilized as an stabilizer and a photoinitiator at the same time. As such, g-CN provides the starting point for polymer chain growth and particle formation. Notably, the as-prepared polymer latexes are directly crosslinked by g-CN, and the existence of g-CN is confirmed inside of the particle, as well as outside, where it forms relatively stable latexes. Moreover, surface functionalized g-CN was utilized to tailor the g-CN/monomer interactions for improved particle formation. g-CN quantum dots with enhanced photoluminescence properties were introduced in EPP as well, providing polymer latexes with enhanced photoluminescence. The obtained polymer nanoparticles might be promising candidates for bioimaging applications