TY - THES A1 - Lian, Tingting T1 - Efficient activation of peroxymonosulfate by carbon-based catalysts for water purification N2 - The increasing global population has led to a growing demand for cost-effective and eco-friendly methods of water purification. This demand has reached a peak due to the increasing presence of impurities and pollutants in water and a growing awareness of waterborne diseases. Advanced oxidation processes (AOPs) are effective methods to address these challenges, due to the generation of highly reactive radicals, such as sulfate radical (SO4•-), hydroxyl radical (•OH), and/or superoxide radical (•O2-) in oxidation reactions. Relative to conventional hydrogen peroxide (H2O2)-based AOPs for wastewater treatment, the persulfate-related AOPs are receiving increasing attention over the past decades, due to their stronger oxidizing capability and a wider pH working window. Further deployment of the seemingly plausible technology as an alternative for the well-established one in industry, however, necessitates a careful evaluation of compounding factors, such as water matrix effects, toxicological consequences, costs, and engineering challenges, etc. To this end, rational design of efficient and environmentally friendly catalysts constitutes an indispensable pathway to advance persulfate activation efficacy and to elucidate the mechanisms in AOPs, the combined endeavors are expected to provide insightful understanding and guidelines for future studies in wastewater treatment. A dozens of transition metal-based catalysts have been developed for persulfate-related AOPs, while the undesirable metal leaching and poor stability in acidic conditions have been identified as major obstacles. Comparatively, the carbonaceous materials are emerging as alternative candidates, which are characterized by metal-free nature, wide availability, and exceptional resistance to acid and alkali, as well as tunable physicochemical and electronic properties, the combined merits make them an attractive option to overcome the aforementioned limitations in metal-based catalytic systems. This dissertation aims at developing novel carbonaceous materials to boost the activity in peroxymonosulfate (PMS) activation processes. Functionalized carbon materials with metal particles or heteroatoms were constructed and further evaluated in terms of their ability to activate PMS for AOPs. The main contents of this thesis are summarized as follows: (1) Iron oxide-loaded biochar: improving stability and alleviating metal leakage Metal leaching constitutes one of the main drawbacks in using transition metals as PMS activators, which is accompanied by the generation of metal-containing sludge, potentially leading to secondary pollution. Meanwhile, the metal nanoparticles are prone to aggregate, causing rapid decay of catalytic performance. The use of carbons as supports for transition metals could mitigate these deficiencies, because the interaction between metals and carbons could in turn disperse and stabilize metal nanoparticles, thus suppressing the metal leaching. In this work, the environmentally benign lignin with its abundant phenolic groups, which is well known to serve as carbon source with high yields and flexibility, was utilized to load Fe ions. The facile low-temperature pre-treatment pyrolytic strategy was employed to construct a green catalyst with iron oxides embedded in Kraft-lignin-derived biochar (termed as γ-Fe2O3@KC). The γ-Fe2O3@KC was capable of activating PMS to generate stable non-radical species (1O2 and Fe (V)=O) and to enhance electron transfer efficiency. A surface-bound reactive complex (catalyst-PMS*) was identified by electrochemical characterizations and discussed with primary surface-bound radical pairs to explain the contradictions between quenching and EPR detection results. The system also showed encouraging reusability for at least 5 times and high stability at pH 3-9. The low concentration of iron in γ-Fe2O3@KC/PMS system implied that the carbon scaffold of biochar substantially alleviated metal leakage. (2) MOF-derived nanocarbon: new carbon crystals Traditional carbon materials are of rather moderate performance in activation PMS, due to the poor electron transfer capacity within the amorphous structure and limited active sites for PMS adsorption. Herein, we established crystalline nanocarbon materials via a simple NaCl-templated strategy using the monoclinic zeolitic imidazolate framework-8 (ZIF-8) sealed with NaCl crystals as the precursors. Specifically, NaCl captured dual advantages in serving as structure-directing agent during hydrolysis and protective salt reactor to facilitate phase transformation during carbonization. The structure-directing agent NaCl provided a protective and confined space for the evolution of MOF upon carbonization, which led to high doping amounts of nitrogen (N) and oxygen elements (O) in carbon framework (N: 14.16 wt%, O: 9.6 wt%) after calcination at a high temperature of 950 oC. We found that N-O co-doping can activate the chemically inert carbon network and the nearby sp2-hybridized carbon atoms served as active sites for adsorption and activation. Besides, the highly crystallized structure with well-established carbon channels around activated carbon atoms could significantly accelerate electron transfer process after initial adsorption of PMS. As such, this crystalline nanocarbon exhibited excellent catalytic kinetics for various pollutants. (3) MOF-derived 2D carbon layers: enhanced mass/electron transfer The two-dimensional (2D) configuration of carbon-based nanosheets with inherent nanochannels and abundant active sites residing on the layer edges or in between the layers, allowed the accessible interaction and close contact between the substrates and reactants, as well as the dramatically improved electron- and mass-transfer kinetics. In this regard, we developed dual-templating strategy to afford 2D assembly of the crystalline carbons, which found efficiency in reinforcing the interactions between the catalyst surface and foreign pollutants. Specifically, we found that the ice crystals and NaCl promoted the evolution of MOF in a 2D fashion during the freezing casting stage, while the later further allowed the formation of a graphitic surface at high calcination temperature, by virtue of the templating effect of molten salt. Due to the highly retained co-doping amounts, N and O heteroatoms created abundant active sites for PMS activation, the 2D configuration of carbon-based nanosheets enable efficient interaction of PMS and pollutants on the surface, which further boosted the kinetics of degradation. KW - Carbon KW - Water treatment KW - PMS activation Y1 - 2023 ER - TY - THES A1 - Ribacki, Enrico T1 - Intra-granitic pegmatites of the Las Chacras-Potrerillos batholith, Argentina Y1 - 2023 ER - TY - JOUR A1 - Balderjahn, Ingo A1 - Hoffmann, Stefan T1 - The Effectiveness of consume-less appeals in social marketing JF - Journal of macromarketing N2 - Consume-less appeals in social marketing can help reduce the lavish consumption in wealthy countries, which poses a major threat to the climate. This study experimentally examines the effectiveness of three different types of consume-less appeals (informative, social normative, and emotional appeals) on participants’ actual spending levels during a real shopping trip compared to a control group (no appeal). In addition, the study tests whether these appeals evoke negative rebounds (in terms of post-purchase climate donation) or positive rebounds (in terms of accepting post-purchase material giveaways). A field experiment in a grocery store in Germany with 170 participants shows that social normative and the emotional appeals reduce actual shopping spending. Informative and social normative appeals increase donations, and emotional appeals reduce the items of taken giveaways. The findings further support certain indirect impacts of the consume-less appeals on rebounds in terms of spending levels. KW - consume-less appeals KW - emotional appeals KW - rebound effects KW - social marketing social norms Y1 - 2023 U6 - https://doi.org/10.1177/02761467231205448 SN - 0276-1467 SN - 1552-6534 PB - Sage CY - Thousand Oaks, Calif. ER - TY - CHAP A1 - Tipold, Marc T1 - In the shadow of Valerian BT - Galerius’ Persian campaigns and the communication startegies of tetrarchic eastern policy T2 - The Tetrarchy as Ideology : Reconfigurations and Representations of an Imperial Power Y1 - 2023 SN - 978-3-515-13400-2 SN - 978-3-515-13403-3 SP - 267 EP - 287 PB - Franz Steiner Verlag CY - Stuttgart ER - TY - THES A1 - Iqbal, Zafar T1 - Interface design and characterization for stable inorganic perovskite solar cells T1 - Grenzflächendesign und- charakterisierung für stabile anorganische Perowskit-Solarzellen BT - inorganic perovskite solar cells N2 - We live in an era driven by fossil fuels. The prevailing climate change suggests that we have to significantly reduce greenhouse gas emissions. The only way forward is to use renewable energy sources. Among those, solar energy is a clean, affordable, and sustainable source of energy. It has the potential to satisfy the world’s energy demand in the future. However, there is a need to develop new materials that can make solar energy usable. Photovoltaics (PV) are devices that convert photon energy into electrical energy. The most commonly used solar cells are based on crystalline silicon. However, the fabrication process for silicon solar cells is technologically difficult and costly. Solar cells based on lead halide perovskites (PSCs) have emerged as a new candidate for PV applications since 2009. To date, PSCs have achieved 26% power-conversion-efficiency (PCE) for its single junction, and 33.7% PCE for tandem junction devices. However, there is still room for improvement in overall performance. The main challenge for the commercialization of this technology is the stability of the solar cells under operational conditions. Inorganic perovskite CsPbI3 has attracted researchers’ interest due to its stability at elevated temperatures, however, inorganic perovskites also have associated challenges, e.g. phase stability, larger voltage loss compared to their organic-inorganic hybrid counterparts, and interface energy misalignment. The most efficient inorganic perovskite solar cell is stable for up to a few hundred hours while the most stable device in the field of inorganic PSCs reported so far is at 17% PCE. This suggests the need for improvement of the interfaces for enhanced open circuit voltage (VOC), and optimization of the energy alignment at the interfaces. This dissertation presents the study on interfaces between the perovskite layer and hole transport layer (HTL) for stable CsPbI3 solar cells. The first part of the thesis presents an investigation of the CsPbI3 film annealing environment and its subsequent effects on the perovskite/HTL interface dynamics. Thin films annealed in dry air were compared with thin films annealed in ambient air. Synchrotron-based hard X-ray spectroscopy (HAXPES) measurements reveal that annealing in ambient air does not have an adverse effect; instead, those samples undergo surface band bending. This surface band modification induces changes in interface charge dynamics and, consequently, an improvement in charge extraction at the interfaces. Further, transient surface photovoltage (tr-SPV) simulations show that air-annealed samples exhibit fewer trap states compared to samples annealed in dry air. Finally, by annealing the CsPbI3 films in ambient air, a PCE of 19.8% and Voc of 1.23 V were achieved for an n-i-p structured device. Interface engineering has emerged as a strategy to extract the charge and optimize the energy alignment in perovskite solar cells (PSCs). An interface with fewer trap states and energy band levels closer to the selective contact helps to attain improved efficiencies in PSCs. The second part of the thesis presents a design for the CsPbI3/HTM interface. In this work, an interface between CsPbI3 perovskite and its hole selective contact N2,N2,N2′,N2′,N7,N7,N7′,N7′-octakis(4-methoxyphenyl)-9,9′-spirobi[9H-fluorene]-2,2′,7,7′-tetramine(Spiro-OMeTAD), realized by trioctylphosphine oxide (TOPO), a dipole molecule is introduced. On top of a perovskite film well-passivated by n-octyl ammonium Iodide (OAI), it created an upward surface band-bending at the interface byTOPO that optimizes energy level alignment and enhances the extraction of holes from the perovskite layer to the hole transport material. Consequently, a Voc of 1.2 V and high-power conversion efficiency (PCE) of over 19% were achieved for inorganic CsPbI3 perovskite solar cells. In addition, the work also sheds light on the interfacial charge-selectivity and the long-term stability of CsPbI3 perovskite solar cells. The third part of the thesis extends the previous studies to polymeric poly(3-hexylthiophene-2,5-diyl) (P3HT) as HTL. The CsPbI3/P3HT interface is critical due to high non-radiative recombination. This work presents a CsPbI3/P3HT interface modified with a long-chain alkyl halide molecule, n-hexyl trimethyl ammonium bromide (HTAB). This molecule largely passivates the CsPbI3 perovskite surface and improves the charge extraction across the interface. Consequently, a Voc of over 1.00 V and 14.2% PCE were achieved for CsPbI3 with P3HT as HTM. Overall the results presented in this dissertation introduce and discuss methods to design and study the interfaces in CsPbI3-based solar cells. This study can pave the way for novel interface designs between CsPbI3 and HTM for charge extraction, efficiency and stability. N2 - Wir leben in einem Zeitalter, das von fossilen Brennstoffen geprägt ist. Der fortschreitende Klimawandel erfordert eine merkliche Reduktion der Treibhausgasemissionen. Der einzige Weg hin zu einer nachhaltigen Energiewirtschaft ist die Implementierung erneuerbarer Energiequellen. Solarenergie hat das Potential, den Energiebedarf der Welt langfristig auf saubere und kostengünstige Weise zu decken. Es müssen jedoch neue Materialien zur Marktreife entwickelt werden, die die Solarenergie nutzbar machen können. In der Photovoltaik (PV) wird Lichtenergie in elektrische Energie umwandelt, wobei die gängisten Solarzellen aus kristallinem Silizium bestehen. Die Herstellung von Silizium-Solarzellen ist jedoch technisch aufwending und kostspielig. Deshalb haben sich Solarzellen auf Basis von Bleihalogenid-Perowskiten (engl. perovskite solar cells, PSCs) seit 2009 als mögliche Alternative zur Siliziumtechnologie entwickelt. Bisweilen konnten Wirkungsgrade (engl. power conversion efficiency, PCE) von 26% in einem einzelnen Halbleiterübergang und von 33.7% in einem Tandemübergang erzielt werden. Diese Werte sind jedoch steigerbar und werden regelmäßig übertroffen. Die größte Herausfoderung für die Entwicklung dieser Technologie ist die Stabilität der Solarzellen unter Betriebsbedingungen. Der anorganische Perowskit CsPbI3 ist aufgrund seiner Stabilität bei hohen Temperaturen deshalb besonders interessant für die Forschung, obwohl das Material seine eigenen Herausforderungen birgt, wie zum Beispiel seine Phaseninstabilität, größere Leerlaufspannungsverluste im Vergleich zu seinen organisch-anorganisch-hybriden Analoga und Fehlaurichtung der Energiebänder an der Grenzfläche. Die Stabilität der effizientesten Solarzelle auf CsPbI3-Basis liegt bei einigen hundert Stunden, während die stabilste Solarzelle einen Wirkungsgrad von nunmehr 17% erzielt. Dies deutet auf die Notwendigkeit hin, die Grenzflächen zu den angrenzenden ladungsselektiven Kontakten zu verbessern – mit dem Ziel, die Leerlaufspannung (engl. open-circuit voltage, VOC) zu erhöhen und die Ausrichtung der Energiebänder an den Grenzflächen zu optimieren. Diese Dissertation befasst sich mit der Untersuchung der Grenzflächen zwischen der Perowskitschicht und der Lochtransportschicht (engl. hole transport layer, HTL) für stabile CsPbI3-Solarzellen. Im ersten Teil der Arbeit werden die Temperbedingungen für CsPbI3-Dünnfilme und ihre Auswirkungen auf die Ladungsträgerdynamik an der Perowskit/HTL-Grenzfläche untersucht. Dünnfilme, die in trockener Atmosphäre getempert wurden, wurden mit Dünnfilmen verglichen, die in Standardatmosphäre getempert wurden. Synchrotrongestützte Messungen der Photoelektronenspektroskopie mit harter Röntgenstrahlung (engl. hard X-ray photoelectron spectrpscopy, HAXPES) zeigen, dass das Tempern in Umgebungsluft keine nachteiligen Auswirkungen hat; stattdessen erfahren jene Proben eine Verbiegung der Energiebänder an der Oberfläche. Diese Modifikation der Oberflächenbänder führt zu Veränderungen in der Grenzflächenladungsdynamik und in der Folge zu einer Verbesserung der Ladungsträgerextraktion über die Grenzfläche. Darüber hinaus zeigen Simulationen der transienten Oberflächenphotospannung (engl. transient surface photovoltage, trSPV), dass luftgetemperte Proben im Vergleich zu trockengetemperten Proben weniger Fallenzustände aufweisen. Letztlich wurde durch das Tempern der CsPbI3-Filme in Umgebungsluft eine PCE von 19,8% und ein VOC von 1,23 V für eine Solarzelle in n-i-p-Architektur erreicht. Die Manipulation der Grenzflächen ist eine Strategie, um die Extraktion von Ladungsträgern und die Ausrichtung der Energiebänder in PSCs zu kontrollieren. Eine Grenzfläche mit geringerer Dichte an Fallenzuständen sowie der Fähigkeit, das Energiebandniveau näher an das des selektiven Kontakts zu verschieben, trägt zur Verbesserung des Wirkungsgrads von PSCs bei. Im zweiten Teil der Arbeit wird ein Design für die CsPbI3/HTM-Grenzfläche vorgeschlagen. Dabei wird das Dipolmolekül Trioctylphosphinoxid (TOPO) an der Grenzfläche zwischen CsPbI3-Perowskit und dem lochselektiven Kontakt N2, N2, N2′, N2′, N7, N7, N7′, N7′-octakis(4-Methoxyphenyl) -9,9′-Spirobi[9H-Fluoren] -2,2′,7,7′-Tetramin (spiro-OMeTAD) eingeführt. Auf einem mit n-Octylammoniumiodid (OAI) passivierten Perowskitfilm erzeugt TOPO eine nach oben gerichtete Oberflächenbandverkrümmung, die die Ausrichtung der Energieniveaus optimiert und die Extraktion von Löchern aus CsPbI3 in den HTL verbessert. Infolgedessen wurden in den hergestellten Solarzellen ein VOC von 1,2 V und eine PCE von über 19% erzielt. Darüber hinaus nimmt die Arbeit auch die Ladungsträgerselektivität an der Grenzfläche und die Langzeitstabilität von CsPbI3-Perowskit-Solarzellen in den Fokus. Der dritte Teil der Arbeit erweitert die bisherigen Untersuchungen auf das Polymer Poly-(3-hexylthiophen-2,5-diyl) (P3HT) als HTL. Die CsPbI3/P3HT-Grenzfläche ist aufgrund der hohen nicht-radiativen Rekombination kritisch. In dieser Arbeit wird eine CsPbI3/P3HT-Grenzfläche vorgestellt, die mit einem langkettigen Alkylhalogenidmolekül, n-Hexyltrimethylammoniumbromid (HTAB), modifiziert wurde. Dieses Molekül passiviert die CsPbI3-Perowskit-Oberfläche weitgehend und verbessert die Ladungsträgerextraktion an der Grenzfläche. Für CsPbI3 mit P3HT als HTM konnte ein VOC von über 1,00 V und 14,2% PCE erreicht werden. Insgesamt werden in dieser Dissertation Methoden zur Entwicklung und Untersuchung von Grenzflächen für Solarzellen auf CsPbI3-Basis vorgestellt und diskutiert. Diese Studie kann Wege für neuartiges Grenzflächendesign zwischen CsPbI3 und HTM im Hinblick auf Ladungsträgerextraktion, Effizienz und Stabilität eröffnen. KW - CsPbI3 KW - interfaces KW - perovskite solar cells KW - CsPbI3 KW - Grenzflächen KW - Perowskit-Solarzellen Y1 - 2023 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-618315 ER - TY - BOOK A1 - Kosman, Admiʾel T1 - So Many Things are Yours BT - New Hebrew Poetry by Admiel Kosman N2 - The poet and Talmud scholar examines Jewish texts, sexuality, and human vulnerability in poems that brim with wonder, sadness, sensuality, and humor. Kosman’s second volume in English explores Jewish texts ―Bible, Talmud, midrash ― alongside bodies, physical desires, military experiences, even a refrigerator. Demons and fantasy enter these poems; so do politics, so does God. These are not religious poems in a conventionally liturgical, “inspirational” sense; yet they point to the big questions that religion asks: about love, hate, desire, violence, transgression, disappointment. Y1 - 2023 SN - 978-1938890918 PB - Zephyr Press CY - Brookline ER - TY - JOUR A1 - Keser, Claudia A1 - Kliemt, Hartmut A1 - Späth, Maximilian T1 - Charitable giving BT - the role of framing and information JF - PLoS ONE N2 - We investigate how different levels of information influence the allocation decisions of donors who are entitled to freely distribute a fixed monetary endowment between themselves and a charitable organization in both giving and taking frames. Participants donate significantly higher amounts, when the decision is described as taking rather than giving. This framing effect becomes smaller if more information about the charity is provided. KW - experimental economics KW - dictator game KW - experimental design KW - labor economics KW - welfare economics KW - language KW - prosocial behavior KW - university laboratories Y1 - 2023 U6 - https://doi.org/10.1371/journal.pone.0288400 SN - 1932-6203 VL - 18 IS - 7 PB - Public Library of Science (PLoS) CY - San Francisco, California ER - TY - JOUR A1 - Wenz, Leonie A1 - Carr, Robert Devon A1 - Kögel, Noah A1 - Kotz, Maximilian A1 - Kalkuhl, Matthias T1 - DOSE - global data set of reported sub-national economic output JF - Scientific data N2 - Many phenomena of high relevance for economic development such as human capital, geography and climate vary considerably within countries as well as between them. Yet, global data sets of economic output are typically available at the national level only, thereby limiting the accuracy and precision of insights gained through empirical analyses. Recent work has used interpolation and downscaling to yield estimates of sub-national economic output at a global scale, but respective data sets based on official, reported values only are lacking. We here present DOSE — the MCC-PIK Database Of Sub-national Economic Output. DOSE contains harmonised data on reported economic output from 1,661 sub-national regions across 83 countries from 1960 to 2020. To avoid interpolation, values are assembled from numerous statistical agencies, yearbooks and the literature and harmonised for both aggregate and sectoral output. Moreover, we provide temporally- and spatially-consistent data for regional boundaries, enabling matching with geo-spatial data such as climate observations. DOSE provides the opportunity for detailed analyses of economic development at the subnational level, consistent with reported values. KW - economics KW - environmental health KW - geography Y1 - 2023 U6 - https://doi.org/10.1038/s41597-023-02323-8 SN - 2052-4463 VL - 10 IS - 1 SP - 1 EP - 17 PB - Nature Publishing Group CY - London ER - TY - JOUR A1 - Merfort, Leon A1 - Bauer, Nico A1 - Humpenöder, Florian A1 - Klein, David A1 - Strefler, Jessica A1 - Popp, Alexander A1 - Luderer, Gunnar A1 - Kriegler, Elmar T1 - Bioenergy-induced land-use-change emissions with sectorally fragmented policies JF - Nature climate change N2 - Controlling bioenergy-induced land-use-change emissions is key to exploiting bioenergy for climate change mitigation. However, the effect of different land-use and energy sector policies on specific bioenergy emissions has not been studied so far. Using the global integrated assessment model REMIND-MAgPIE, we derive a biofuel emission factor (EF) for different policy frameworks. We find that a uniform price on emissions from both sectors keeps biofuel emissions at 12 kg CO2 GJ−1. However, without land-use regulation, the EF increases substantially (64 kg CO2 GJ−1 over 80 years, 92 kg CO2 GJ−1 over 30 years). We also find that comprehensive coverage (>90%) of carbon-rich land areas worldwide is key to containing land-use emissions. Pricing emissions indirectly on the level of bioenergy consumption reduces total emissions by cutting bioenergy demand but fails to reduce the average EF. In the absence of comprehensive and timely land-use regulation, bioenergy thus may contribute less to climate change mitigation than assumed previously. KW - agriculture KW - climate-change mitigation KW - energy policy KW - energy supply and demand KW - environmental economics Y1 - 2023 U6 - https://doi.org/10.1038/s41558-023-01697-2 SN - 1758-678X SN - 1758-6798 VL - 13 IS - 7 SP - 685 EP - 692 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Merfort, Leon A1 - Bauer, Nico A1 - Humpenöder, Florian A1 - Klein, David A1 - Strefler, Jessica A1 - Popp, Alexander A1 - Luderer, Gunnar A1 - Kriegler, Elmar T1 - State of global land regulation inadequate to control biofuel land-use-change emissions JF - Nature climate change N2 - Under current land-use regulation, carbon dioxide emissions from biofuel production exceed those from fossil diesel combustion. Therefore, international agreements need to ensure the effective and globally comprehensive protection of natural land before modern bioenergy can effectively contribute to achieving carbon neutrality. KW - agriculture KW - climate-change mitigation KW - energy policy KW - energy supply and demand KW - environmental economics Y1 - 2023 U6 - https://doi.org/10.1038/s41558-023-01711-7 SN - 1758-678X SN - 1758-6798 VL - 13 IS - 7 SP - 610 EP - 612 PB - Nature Publ. Group CY - London ER -