TY - THES A1 - Hussein, Mahmoud T1 - Solvent engineering for highly-efficient tin perovskite solar cells T1 - Lösungsmitteltechnik für hocheffiziente Zinn-Perowskit-Solarzellen N2 - Global warming, driven primarily by the excessive emission of greenhouse gases such as carbon dioxide into the atmosphere, has led to severe and detrimental environmental impacts. Rising global temperatures have triggered a cascade of adverse effects, including melting glaciers and polar ice caps, more frequent and intense heat waves disrupted weather patterns, and the acidification of oceans. These changes adversely affect ecosystems, biodiversity, and human societies, threatening food security, water availability, and livelihoods. One promising solution to mitigate the harmful effects of global warming is the widespread adoption of solar cells, also known as photovoltaic cells. Solar cells harness sunlight to generate electricity without emitting greenhouse gases or other pollutants. By replacing fossil fuel-based energy sources, solar cells can significantly reduce CO2 emissions, a significant contributor to global warming. This transition to clean, renewable energy can help curb the increasing concentration of greenhouse gases in the atmosphere, thereby slowing down the rate of global temperature rise. Solar energy’s positive impact extends beyond emission reduction. As solar panels become more efficient and affordable, they empower individuals, communities, and even entire nations to generate electricity and become less dependent on fossil fuels. This decentralized energy generation can enhance resilience in the face of climate-related challenges. Moreover, implementing solar cells creates green jobs and stimulates technological innovation, further promoting sustainable economic growth. As solar technology advances, its integration with energy storage systems and smart grids can ensure a stable and reliable energy supply, reducing the need for backup fossil fuel power plants that exacerbate environmental degradation. The market-dominant solar cell technology is silicon-based, highly matured technology with a highly systematic production procedure. However, it suffers from several drawbacks, such as: 1) Cost: still relatively high due to high energy consumption due to the need to melt and purify silicon, and the use of silver as an electrode, which hinders their widespread availability, especially in low-income countries. 2) Efficiency: theoretically, it should deliver around 29%; however, the efficiency of most of the commercially available silicon-based solar cells ranges from 18 – 22%. 3) Temperature sensitivity: The efficiency decreases with the increase in the temperature, affecting their output. 4) Resource constraints: silicon as a raw material is unavailable in all countries, creating supply chain challenges. Perovskite solar cells arose in 2011 and matured very rapidly in the last decade as a highly efficient and versatile solar cell technology. With an efficiency of 26%, high absorption coefficients, solution processability, and tunable band gap, it attracted the attention of the solar cells community. It represented a hope for cheap, efficient, and easily processable next-generation solar cells. However, lead toxicity might be the block stone hindering perovskite solar cells’ market reach. Lead is a heavy and bioavailable element that makes perovskite solar cells environmentally unfriendly technology. As a result, scientists try to replace lead with a more environmentally friendly element. Among several possible alternatives, tin was the most suitable element due to its electronic and atomic structure similarity to lead. Tin perovskites were developed to alleviate the challenge of lead toxicity. Theoretically, it shows very high absorption coefficients, an optimum band gap of 1.35 eV for FASnI3, and a very high short circuit current, which nominates it to deliver the highest possible efficiency of a single junction solar cell, which is around 30.1% according to Schockly-Quisser limit. However, tin perovskites’ efficiency still lags below 15% and is irreproducible, especially from lab to lab. This humble performance could be attributed to three reasons: 1) Tin (II) oxidation to tin (IV), which would happen due to oxygen, water, or even by the effect of the solvent, as was discovered recently. 2) fast crystallization dynamics, which occurs due to the lateral exposure of the P-orbitals of the tin atom, which enhances its reactivity and increases the crystallization pace. 3) Energy band misalignment: The energy bands at the interfaces between the perovskite absorber material and the charge selective layers are not aligned, leading to high interfacial charge recombination, which devastates the photovoltaic performance. To solve these issues, we implemented several techniques and approaches that enhanced the efficiency of tin halide perovskites, providing new chemically safe solvents and antisolvents. In addition, we studied the energy band alignment between the charge transport layers and the tin perovskite absorber. Recent research has shown that the principal source of tin oxidation is the solvent known as dimethylsulfoxide, which also happens to be one of the most effective solvents for processing perovskite. The search for a stable solvent might prove to be the factor that makes all the difference in the stability of tin-based perovskites. We started with a database of over 2,000 solvents and narrowed it down to a series of 12 new solvents that are suitable for processing FASnI3 experimentally. This was accomplished by looking into 1) the solubility of the precursor chemicals FAI and SnI2, 2) the thermal stability of the precursor solution, and 3) the potential to form perovskite. Finally, we show that it is possible to manufacture solar cells using a novel solvent system that outperforms those produced using DMSO. The results of our research give some suggestions that may be used in the search for novel solvents or mixes of solvents that can be used to manufacture stable tin-based perovskites. Due to the quick crystallization of tin, it is more difficult to deposit tin-based perovskite films from a solution than manufacturing lead-based perovskite films since lead perovskite is more often utilized. The most efficient way to get high efficiencies is to deposit perovskite from dimethyl sulfoxide (DMSO), which slows down the quick construction of the tin-iodine network that is responsible for perovskite synthesis. This is the most successful approach for achieving high efficiencies. Dimethyl sulfoxide, which is used in the processing, is responsible for the oxidation of tin, which is a disadvantage of this method. This research presents a potentially fruitful alternative in which 4-(tert-butyl) pyridine can substitute dimethyl sulfoxide in the process of regulating crystallization without causing tin oxidation to take place. Perovskite films that have been formed from pyridine have been shown to have a much-reduced defect density. This has resulted in increased charge mobility and better photovoltaic performance, making pyridine a desirable alternative for use in the deposition of tin perovskite films. The precise control of perovskite precursor crystallization inside a thin film is of utmost importance for optimizing the efficiency and manufacturing of solar cells. The deposition process of tin-based perovskite films from a solution presents difficulties due to the quick crystallization of tin compared to the more often employed lead perovskite. The optimal approach for attaining elevated efficiencies entails using dimethyl sulfoxide (DMSO) as a medium for depositing perovskite. This choice of solvent impedes the tin-iodine network’s fast aggregation, which plays a crucial role in the production of perovskite. Nevertheless, this methodology is limited since the utilization of dimethyl sulfoxide leads to the oxidation of tin throughout the processing stage. In this thesis, we present a potentially advantageous alternative approach wherein 4-(tert-butyl) pyridine is proposed as a substitute for dimethyl sulfoxide in regulating crystallization processes while avoiding the undesired consequence of tin oxidation. Films of perovskite formed using pyridine as a solvent have a notably reduced density of defects, resulting in higher mobility of charges and improved performance in solar applications. Consequently, the utilization of pyridine for the deposition of tin perovskite films is considered advantageous. Tin perovskites are suffering from an apparent energy band misalignment. However, the band diagrams published in the current body of research display contradictions, resulting in a dearth of unanimity. Moreover, comprehensive information about the dynamics connected with charge extraction is lacking. This thesis aims to ascertain the energy band locations of tin perovskites by employing the kelvin probe and Photoelectron yield spectroscopy methods. This thesis aims to construct a precise band diagram for the often-utilized device stack. Moreover, a comprehensive analysis is performed to assess the energy deficits inherent in the current energetic structure of tin halide perovskites. In addition, we investigate the influence of BCP on the improvement of electron extraction in C60/BCP systems, with a specific emphasis on the energy factors involved. Furthermore, transient surface photovoltage was utilized to investigate the charge extraction kinetics of frequently studied charge transport layers, such as NiOx and PEDOT as hole transport layers and C60, ICBA, and PCBM as electron transport layers. The Hall effect, KP, and TRPL approaches accurately ascertain the p-doping concentration in FASnI3. The results consistently demonstrated a value of 1.5 * 1017 cm-3. Our research findings highlight the imperative nature of autonomously constructing the charge extraction layers for tin halide perovskites, apart from those used for lead perovskites. The crystallization of perovskite precursors relies mainly on the utilization of two solvents. The first one dissolves the perovskite powder to form the precursor solution, usually called the solvent. The second one precipitates the perovskite precursor, forming the wet film, which is a supersaturated solution of perovskite precursor and in the remains of the solvent and the antisolvent. Later, this wet film crystallizes upon annealing into a full perovskite crystallized film. In our research context, we proposed new solvents to dissolve FASnI3, but when we tried to form a film, most of them did not crystallize. This is attributed to the high coordination strength between the metal halide and the solvent molecules, which is unbreakable by the traditionally used antisolvents such as Toluene and Chlorobenzene. To solve this issue, we introduce a high-throughput antisolvent screening in which we screened around 73 selected antisolvents against 15 solvents that can form a 1M FASnI3 solution. We used for the first time in tin perovskites machine learning algorithm to understand and predict the effect of an antisolvent on the crystallization of a precursor solution in a particular solvent. We relied on film darkness as a primary criterion to judge the efficacy of a solvent-antisolvent pair. We found that the relative polarity between solvent and antisolvent is the primary factor that affects the solvent-antisolvent interaction. Based on our findings, we prepared several high-quality tin perovskite films free from DMSO and achieved an efficiency of 9%, which is the highest DMSO tin perovskite device so far. N2 - Zinn ist eine der vielversprechendsten Alternativen zu Blei, um bleifreie Halogenidperowskite für die Optoelektronik herzustellen. Die Stabilität von Perowskiten auf Zinnbasis wird jedoch durch die Oxidation von Sn(II) zu Sn(IV) beeinträchtigt. Jüngste Arbeiten haben ergeben, dass Dimethylsulfoxid, eines der besten Lösungsmittel für die Verarbeitung von Perowskiten, die Hauptquelle für die Oxidation von Zinn ist. Die Suche nach einem stabilen Lösungsmittel könnte den Ausschlag für die Stabilität von Perowskiten auf Zinnbasis geben. Ausgehend von einer Datenbank mit über 2000 Lösungsmitteln haben wir eine Reihe von 12 neuen Lösungsmitteln identifiziert, die für die Verarbeitung von Formamidinium-Zinniodid-Perowskit (FASnI3) geeignet sind, indem wir 1) die Löslichkeit der Vorläuferchemikalien FAI und SnI2, 2) die thermische Stabilität der Vorläuferlösung und 3) die Möglichkeit zur Bildung von Perowskit experimentell untersucht haben. Schließlich demonstrieren wir ein neues Lösungsmittelsystem zur Herstellung von Solarzellen, das die auf DMSO basierenden Zellen übertrifft. Unsere Arbeit liefert Leitlinien für die weitere Identifizierung neuer Lösungsmittel oder Lösungsmittelmischungen zur Herstellung stabiler Perowskite auf Zinnbasis. Die genaue Steuerung der Kristallisation des Perowskit-Vorläufers in einer Dünnschicht ist entscheidend für die Effizienz und Produktion von Solarzellen. Die Abscheidung von Perowskit-Filmen auf Zinnbasis aus einer Lösung stellt aufgrund der schnellen Kristallisation von Zinn im Vergleich zu dem üblicherweise verwendeten Bleiperowskit eine Herausforderung dar. Die effektivste Methode zur Erzielung hoher Wirkungsgrade ist die Abscheidung von Perowskit aus Dimethylsulfoxid (DMSO), das den schnellen Aufbau des für die Perowskitbildung verantwortlichen Zinn-Jod-Netzwerks behindert. Dieser Ansatz hat jedoch einen Nachteil, da Dimethylsulfoxid während der Verarbeitung eine Zinnoxidation verursacht. In dieser Studie wird eine vielversprechende Alternative vorgestellt, bei der 4-(tert-Butyl)-pyridin Dimethylsulfoxid bei der Steuerung der Kristallisation ersetzen kann, ohne eine Zinnoxidation zu verursachen. Aus Pyridin abgeschiedene Perowskit-Filme weisen eine deutlich geringere Defektdichte auf, was zu einer erhöhten Ladungsbeweglichkeit und einer verbesserten photovoltaischen Leistung führt und es zu einer günstigen Wahl für die Abscheidung von Zinn-Perowskit-Filmen macht. Zinnperowskite haben sich als vielversprechender, umweltverträglicher Ersatz für Bleiperowskite erwiesen, vor allem wegen ihrer besseren optoelektronischen Eigenschaften und ihrer geringeren Bioverfügbarkeit. Dennoch gibt es mehrere Gründe, warum die Leistung von Zinnperowskiten nicht mit der von Bleiperowskiten verglichen werden kann. Einer dieser Gründe ist die Nichtübereinstimmung der Energiebänder zwischen dem Perowskit-Absorberfilm und den ladungstransportierenden Schichten (CTLs). Die in der vorhandenen Literatur dargestellten Banddiagramme sind jedoch uneinheitlich, was zu einem Mangel an Konsens führt. Außerdem ist das Verständnis der mit der Ladungsextraktion verbundenen Dynamik noch unzureichend. In dieser Studie sollen die Energiebandpositionen von Zinnperowskiten mit Hilfe der Kelvinsonde (KP) und der Photoelektronenausbeutespektroskopie (PYS) bestimmt werden. Ziel ist es, ein genaues Banddiagramm für den üblicherweise verwendeten Bauelementestapel zu erstellen. Darüber hinaus führen wir eine Diagnose der energetischen Unzulänglichkeiten durch, die im bestehenden energetischen Rahmen von Zinnhalogenid-Perowskiten vorhanden sind. Unser Ziel ist es, Folgendes zu klären den Einfluss von BCP auf die Verbesserung der Elektronenextraktion in C60/BCP-Systemen, wobei der Schwerpunkt auf den energetischen Aspekten liegt. Darüber hinaus haben wir die transiente Oberflächenphotospannung (tr-SPV) eingesetzt, um Einblicke in die Ladungsextraktionskinetik von allgemein bekannten CTLs zu gewinnen, einschließlich NiOx und PEDOT als Lochtransportschichten (HTLs) und C60, ICBA und PCBM als Elektronentransportschichten (ETLs). In diesem Kapitel verwenden wir den Halleffekt, KP- und TRPL-Techniken, um die genaue p-Dotierungskonzentration in FASnI3 zu bestimmen. Unsere Ergebnisse ergaben durchweg einen Wert von 1.5 * 1017 cm-3. Die Ergebnisse unserer Studie zeigen, dass es notwendig ist, die Ladungsextraktionsschichten von Zinnhalogenidperowskiten unabhängig von den Bleiperowskiten zu entwickeln. Die Kristallisation von Perowskit-Vorstufen beruht hauptsächlich auf der Verwendung von zwei Lösungsmitteln. Das erste löst das Perowskit-Pulver auf und bildet die Vorläuferlösung, die üblicherweise als Lösungsmittel bezeichnet wird. Mit dem zweiten wird der Perowskit-Precursor ausgefällt, wobei sich der Nassfilm bildet, der eine übersättigte Lösung des Perowskit-Precursors und der Reste des Lösungsmittels und des Antisolierungsmittels ist. Später kristallisiert dieser nasse Film beim Ausglühen zu einem vollständig kristallisierten Perowskit-Film. In unserem Forschungskontext haben wir neue Lösungsmittel vorgeschlagen, um FASnI3 aufzulösen, aber als wir versuchten, einen Film zu bilden, kristallisierten die meisten von ihnen nicht. Dies ist auf die hohe Koordinationsstärke zwischen dem Metallhalogenid und den Lösungsmittelmolekülen zurückzuführen, die von den traditionell verwendeten Antisolierungsmitteln wie Toluol und Chlorbenzol nicht aufgebrochen werden kann. Um dieses Problem zu lösen, haben wir ein Hochdurchsatz-Screening von Antisolventien durchgeführt, bei dem wir 73 ausgewählte Antisolventien mit 15 Lösungsmitteln verglichen haben, die eine 1M FASnI3-Lösung bilden können. Wir haben zum ersten Mal bei Zinnperowskiten einen Algorithmus für maschinelles Lernen verwendet, um die Wirkung eines Antisolvens auf die Kristallisation einer Vorläuferlösung in einem bestimmten Lösungsmittel zu verstehen und vorherzusagen. Wir stützten uns auf die Schwärzung des Films als primäres Kriterium zur Beurteilung der Wirksamkeit eines Lösungsmittel-Antisolierungsmittel-Paares. Wir fanden heraus, dass die relative Polarität zwischen Lösungsmittel und Antisolvent der wichtigste Faktor ist, der die Wechselwirkung zwischen Lösungsmittel und Antisolvent beeinflusst. Auf der Grundlage unserer Erkenntnisse haben wir mehrere hochwertige Zinn-Perowskit-Filme ohne DMSO hergestellt und einen Wirkungsgrad von 9 % erzielt, was die bisher höchste DMSO-Zinn-Perowskit-Vorrichtung darstellt. KW - perovskite solar cells KW - lead-free perovskites KW - tin perovskites KW - solar cells KW - perovskite KW - Perowskit-Solarzellen KW - photovoltaische Materialien KW - Solarzellen KW - Lösungsmittel KW - bleifreie Perowskit-Solarzellen Y1 - 2024 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-630375 ER - TY - JOUR A1 - Wang, Peixi A1 - Geiger, Christina A1 - Kreuzer, Lucas A1 - Widmann, Tobias A1 - Reitenbach, Julija A1 - Liang, Suzhe A1 - Cubitt, Robert A1 - Henschel, Cristiane A1 - Laschewsky, André A1 - Papadakis, Christine M. A1 - Müller-Buschbaum, Peter T1 - Poly(sulfobetaine)-based diblock copolymer thin films in water/acetone atmosphere: modulation of water hydration and co-nonsolvency-triggered film contraction JF - Langmuir : the ACS journal of surfaces and colloids N2 - The water swelling and subsequent solvent exchange including co-nonsolvency behavior of thin films of a doubly thermo-responsive diblock copolymer (DBC) are studied viaspectral reflectance, time-of-flight neutron reflectometry, and Fourier transform infrared spectroscopy. The DBC consists of a thermo-responsive zwitterionic (poly(4-((3-methacrylamidopropyl) dimethylammonio) butane-1-sulfonate)) (PSBP) block, featuring an upper critical solution temperature transition in aqueous media but being insoluble in acetone, and a nonionic poly(N-isopropylmethacrylamide) (PNIPMAM) block, featuring a lower critical solution temperature transition in water, while being soluble in acetone. Homogeneous DBC films of 50-100 nm thickness are first swollen in saturated water vapor (H2OorD2O), before they are subjected to a contraction process by exposure to mixed saturated water/acetone vapor (H2OorD2O/acetone-d6 = 9:1 v/v). The affinity of the DBC film toward H2O is stronger than for D2O, as inferred from the higher film thickness in the swollen state and the higher absorbed water content, thus revealing a pronounced isotope sensitivity. During the co-solvent-induced switching by mixed water/acetone vapor, a two-step film contraction is observed, which is attributed to the delayed expulsion of water molecules and uptake of acetone molecules. The swelling kinetics are compared for both mixed vapors (H2O/acetone-d6 and D2O/acetone-d6) and with those of the related homopolymer films. Moreover, the concomitant variations of the local environment around the hydrophilic groups located in the PSBP and PNIPMAM blocks are followed. The first contraction step turns out to be dominated by the behavior of the PSBP block, where as the second one is dominated by the PNIPMAM block. The unusual swelling and contraction behavior of the latter block is attributed to its co-nonsolvency behavior. Furthermore, we observe cooperative hydration effects in the DBC films, that is, both polymer blocks influence each other's solvation behavior. Y1 - 2022 U6 - https://doi.org/10.1021/acs.langmuir.2c00451 SN - 0743-7463 SN - 1520-5827 VL - 38 IS - 22 SP - 6934 EP - 6948 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kuntze, Kim A1 - Viljakka, Jani A1 - Titov, Evgenii A1 - Ahmed, Zafar A1 - Kalenius, Elina A1 - Saalfrank, Peter A1 - Priimagi, Arri T1 - Towards low-energy-light-driven bistable photoswitches BT - ortho-fluoroaminoazobenzenes JF - Photochemical & photobiological sciences / European Society for Photobiology N2 - Thermally stable photoswitches that are driven with low-energy light are rare, yet crucial for extending the applicability of photoresponsive molecules and materials towards, e.g., living systems. Combined ortho-fluorination and -amination couples high visible light absorptivity of o-aminoazobenzenes with the extraordinary bistability of o-fluoroazobenzenes. Herein, we report a library of easily accessible o-aminofluoroazobenzenes and establish structure-property relationships regarding spectral qualities, visible light isomerization efficiency and thermal stability of the cis-isomer with respect to the degree of o-substitution and choice of amino substituent. We rationalize the experimental results with quantum chemical calculations, revealing the nature of low-lying excited states and providing insight into thermal isomerization. The synthesized azobenzenes absorb at up to 600 nm and their thermal cis-lifetimes range from milliseconds to months. The most unique example can be driven from trans to cis with any wavelength from UV up to 595 nm, while still exhibiting a thermal cis-lifetime of 81 days.
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. Y1 - 2022 U6 - https://doi.org/10.1007/s43630-021-00145-4 SN - 1474-905X SN - 1474-9092 VL - 21 IS - 2 SP - 159 EP - 173 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Xie, Dongjiu A1 - Xu, Yaolin A1 - Wang, Yonglei A1 - Pan, Xuefeng A1 - Härk, Eneli A1 - Kochovski, Zdravko A1 - Eljarrat, Alberto A1 - Müller, Johannes A1 - Koch, Christoph T. A1 - Yuan, Jiayin A1 - Lu, Yan T1 - Poly(ionic liquid) nanovesicle-templated carbon nanocapsules functionalized with uniform iron nitride nanoparticles as catalytic sulfur host for Li-S batteries JF - ACS nano N2 - Poly(ionic liquid)s (PIL) are common precursors for heteroatom-doped carbon materials. Despite a relatively higher carbonization yield, the PIL-to-carbon conversion process faces challenges in preserving morphological and structural motifs on the nanoscale. Assisted by a thin polydopamine coating route and ion exchange, imidazoliumbased PIL nanovesicles were successfully applied in morphology-maintaining carbonization to prepare carbon composite nanocapsules. Extending this strategy further to their composites, we demonstrate the synthesis of carbon composite nanocapsules functionalized with iron nitride nanoparticles of an ultrafine, uniform size of 3-5 nm (termed "FexN@C "). Due to its unique nanostructure, the sulfur-loaded FexN@C electrode was tested to efficiently mitigate the notorious shuttle effect of lithium polysulfides (LiPSs) in Li-S batteries. The cavity of the carbon nanocapsules was spotted to better the loading content of sulfur. The well-dispersed iron nitride nanoparticles effectively catalyze the conversion of LiPSs to Li2S, owing to their high electronic conductivity and strong binding power to LiPSs. Benefiting from this well-crafted composite nanostructure, the constructed FexN@C/S cathode demonstrated a fairly high discharge capacity of 1085 mAh g(-1) at 0.5 C initially, and a remaining value of 930 mAh g(-1 )after 200 cycles. In addition, it exhibits an excellent rate capability with a high initial discharge capacity of 889.8 mAh g(-1) at 2 C. This facile PIL-to-nanocarbon synthetic approach is applicable for the exquisite design of complex hybrid carbon nanostructures with potential use in electrochemical energy storage and conversion. KW - poly(ionic liquid)s KW - nanovesicles KW - sulfur host KW - iron nitride KW - Li-S KW - batteries Y1 - 2022 U6 - https://doi.org/10.1021/acsnano.2c01992 SN - 1936-0851 SN - 1936-086X VL - 16 IS - 7 SP - 10554 EP - 10565 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Neffe, Axel T. A1 - Löwenberg, Candy A1 - Julich-Gruner, Konstanze K. A1 - Behl, Marc A1 - Lendlein, Andreas T1 - Thermally-induced shape-memory behavior of degradable gelatin-based networks JF - International journal of molecular sciences N2 - Shape-memory hydrogels (SMH) are multifunctional, actively-moving polymers of interest in biomedicine. In loosely crosslinked polymer networks, gelatin chains may form triple helices, which can act as temporary net points in SMH, depending on the presence of salts. Here, we show programming and initiation of the shape-memory effect of such networks based on a thermomechanical process compatible with the physiological environment. The SMH were synthesized by reaction of glycidylmethacrylated gelatin with oligo(ethylene glycol) (OEG) alpha,omega-dithiols of varying crosslinker length and amount. Triple helicalization of gelatin chains is shown directly by wide-angle X-ray scattering and indirectly via the mechanical behavior at different temperatures. The ability to form triple helices increased with the molar mass of the crosslinker. Hydrogels had storage moduli of 0.27-23 kPa and Young's moduli of 215-360 kPa at 4 degrees C. The hydrogels were hydrolytically degradable, with full degradation to water-soluble products within one week at 37 degrees C and pH = 7.4. A thermally-induced shape-memory effect is demonstrated in bending as well as in compression tests, in which shape recovery with excellent shape-recovery rates R-r close to 100% were observed. In the future, the material presented here could be applied, e.g., as self-anchoring devices mechanically resembling the extracellular matrix. KW - shape-memory hydrogel KW - active polymer KW - biopolymer KW - mechanical KW - properties KW - degradation Y1 - 2021 U6 - https://doi.org/10.3390/ijms22115892 SN - 1422-0067 SN - 1661-6596 VL - 22 IS - 11 PB - Molecular Diversity Preservation International CY - Basel ER - TY - JOUR A1 - Bochove, Bas van A1 - Grijpma, Dirk W. A1 - Lendlein, Andreas A1 - Seppälä, Jukka T1 - Designing advanced functional polymers for medicine JF - European polymer journal : EPJ Y1 - 2021 U6 - https://doi.org/10.1016/j.eurpolymj.2021.110573 SN - 0014-3057 VL - 155 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Hwang, Jinyeon A1 - Zhang, Wuyong A1 - Youk, Sol A1 - Schutjajew, Konstantin A1 - Oschatz, Martin T1 - Understanding structure-property relationships under experimental conditions for the optimization of lithium-ion capacitor anodes based on all-carbon-composite materials JF - Energy technology : generation, conversion, storage, distribution N2 - The nanoscale combination of a conductive carbon and a carbon-based material with abundant heteroatoms for battery electrodes is a method to overcome the limitation that the latter has high affinity to alkali metal ions but low electronic conductivity. The synthetic protocol and the individual ratios and structures are important aspects influencing the properties of such multifunctional compounds. Their interplay is, herein, investigated by infiltration of a porous ZnO-templated carbon (ZTC) with nitrogen-rich carbon obtained by condensation of hexaazatriphenylene-hexacarbonitrile (HAT-CN) at 550-1000 degrees C. The density of lithiophilic sites can be controlled by HAT-CN content and condensation temperature. Lithium storage properties are significantly improved in comparison with those of the individual compounds and their physical mixtures. Depending on the uniformity of the formed composite, loading ratio and condensation temperature have different influence. Most stable operation at high capacity per used monomer is achieved with a slowly dried composite with an HAT-CN:ZTC mass ratio of 4:1, condensed at 550 degrees C, providing more than 400 mAh g(-1) discharge capacity at 0.1 A g(-1) and a capacity retention of 72% after 100 cycles of operation at 0.5 A g(-1) due to the homogeneity of the composite and high content of lithiophilic sites. KW - anodes KW - hybrid materials KW - nitrogen-doped carbon KW - porous carbon KW - lithium-ion capacitors Y1 - 2021 U6 - https://doi.org/10.1002/ente.202001054 SN - 2194-4296 VL - 9 IS - 3 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Pan, Xuefeng A1 - Sarhan, Radwan Mohamed A1 - Kochovski, Zdravko A1 - Chen, Guosong A1 - Taubert, Andreas A1 - Mei, Shilin A1 - Lu, Yan T1 - Template synthesis of dual-functional porous MoS2 nanoparticles with photothermal conversion and catalytic properties JF - Nanoscale N2 - Advanced catalysis triggered by photothermal conversion effects has aroused increasing interest due to its huge potential in environmental purification. In this work, we developed a novel approach to the fast degradation of 4-nitrophenol (4-Nip) using porous MoS2 nanoparticles as catalysts, which integrate the intrinsic catalytic property of MoS2 with its photothermal conversion capability. Using assembled polystyrene-b-poly(2-vinylpyridine) block copolymers as soft templates, various MoS 2 particles were prepared, which exhibited tailored morphologies (e.g., pomegranate-like, hollow, and open porous structures). The photothermal conversion performance of these featured particles was compared under near-infrared (NIR) light irradiation. Intriguingly, when these porous MoS2 particles were further employed as catalysts for the reduction of 4-Nip, the reaction rate constant was increased by a factor of 1.5 under NIR illumination. We attribute this catalytic enhancement to the open porous architecture and light-to-heat conversion performance of the MoS2 particles. This contribution offers new opportunities for efficient photothermal-assisted catalysis. Y1 - 2022 U6 - https://doi.org/10.1039/d2nr01040b SN - 2040-3372 VL - 14 IS - 18 SP - 6888 EP - 6901 PB - RSC Publ. (Royal Society of Chemistry) CY - Cambridge ER - TY - JOUR A1 - Zhao, Yuhang A1 - Sarhan, Radwan Mohamed A1 - Eljarrat, Alberto A1 - Kochovski, Zdravko A1 - Koch, Christoph A1 - Schmidt, Bernd A1 - Koopman, Wouter-Willem Adriaan A1 - Lu, Yan T1 - Surface-functionalized Au-Pd nanorods with enhanced photothermal conversion and catalytic performance JF - ACS applied materials & interfaces N2 - Bimetallic nanostructures comprising plasmonic and catalytic components have recently emerged as a promising approach to generate a new type of photo-enhanced nanoreactors. Most designs however concentrate on plasmon-induced charge separation, leaving photo-generated heat as a side product. This work presents a photoreactor based on Au-Pd nanorods with an optimized photothermal conversion, which aims to effectively utilize the photo-generated heat to increase the rate of Pd-catalyzed reactions. Dumbbell-shaped Au nanorods were fabricated via a seed-mediated growth method using binary surfactants. Pd clusters were selectively grown at the tips of the Au nanorods, using the zeta potential as a new synthetic parameter to indicate the surfactant remaining on the nanorod surface. The photothermal conversion of the Au-Pd nanorods was improved with a thin layer of polydopamine (PDA) or TiO2. As a result, a 60% higher temperature increment of the dispersion compared to that for bare Au rods at the same light intensity and particle density could be achieved. The catalytic performance of the coated particles was then tested using the reduction of 4-nitrophenol as the model reaction. Under light, the PDA-coated Au-Pd nanorods exhibited an improved catalytic activity, increasing the reaction rate by a factor 3. An analysis of the activation energy confirmed the photoheating effect to be the dominant mechanism accelerating the reaction. Thus, the increased photothermal heating is responsible for the reaction acceleration. Interestingly, the same analysis shows a roughly 10% higher reaction rate for particles under illumination compared to under dark heating, possibly implying a crucial role of localized heat gradients at the particle surface. Finally, the coating thickness was identified as an essential parameter determining the photothermal conversion efficiency and the reaction acceleration. KW - Au-Pd nanorods KW - PDA KW - photothermal conversion KW - surface plasmon KW - 4-nitrophenol Y1 - 2022 U6 - https://doi.org/10.1021/acsami.2c00221 SN - 1944-8244 SN - 1944-8252 VL - 14 IS - 15 SP - 17259 EP - 17272 PB - American Chemical Society CY - Washington, DC ER - TY - JOUR A1 - Floyd, Thomas G. A1 - Song, Ji-Inn A1 - Hapeshi, Alexia A1 - Laroque, Sophie A1 - Hartlieb, Matthias A1 - Perrier, Sebastien T1 - Bottlebrush copolymers for gene delivery: influence of architecture, charge density, and backbone length on transfection efficiency JF - Journal of materials chemistry : B, materials for biology and medicine N2 - The influence of polymer architecture of polycations on their ability to transfect mammalian cells is probed. Polymer bottle brushes with grafts made from partially hydrolysed poly(2-ethyl-2-oxazoline) are used while varying the length of the polymer backbone as well as the degree of hydrolysis (cationic charge content). Polyplex formation is investigated via gel electrophoresis, dye-displacement and dynamic light scattering. Bottle brushes show a superior ability to complex pDNA when compared to linear copolymers. Also, nucleic acid release was found to be improved by a graft architecture. Polyplexes based on bottle brush copolymers showed an elongated shape in transmission electron microscopy images. The cytotoxicity against mammalian cells is drastically reduced when a graft architecture is used instead of linear copolymers. Moreover, the best-performing bottle brush copolymer showed a transfection ability comparable with that of linear poly(ethylenimine), the gold standard of polymeric transfection agents, which is used as positive control. In combination with their markedly lowered cytotoxicity, cationic bottle brush copolymers are therefore shown to be a highly promising class of gene delivery vectors. Y1 - 2022 U6 - https://doi.org/10.1039/d2tb00490a SN - 2050-750X SN - 2050-7518 VL - 10 IS - 19 SP - 3696 EP - 3704 PB - Royal Society of Chemistry CY - London [u.a.] ER -