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In this contribution we report on investigations of the electronic structure and composition of regioregular poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) based films by using Near Edge X-Ray Absorption Fine Structure (NEXAFS). The measurements were done at the U49/2-PGM2 beam line of BESSY II, Berlin using TEY (total electron yield) and TFY (total fluorescence yield) detection. The samples were produced by spin casting a mixture of P3HT (dissolved in chloroform) and PCBM (dissolved in chlorobenzene) on ITO (indium tin oxide) coated glass slides. Measurements of pure P3HT and PCBM show all typical excitations, whereas the blended system is a weighted superposition of the related peaks. Analyzing these weighted superposition, we observe in the surface sensitive TEY data an accumulation of P3HT, whereas in the bulk sensitive TFY signal an as expected mixture is found. We also show angular dependent NEXAFS measurements of the P3HT/PCBM blend in order to measure the orientation and distribution of the P3HT polymer. Additionally, we will show a new approach for organic solar cell application by introducing ferroelectric nanoparticles into the mixture.
Background. Features of schools and classes are closely related to students´ health and wellbeing. However, class composition (e.g. in terms of school performance) has rarely been examined in relation to students´ health and wellbeing. This study focuses on the so called Big-Fish-Little-Pond-Effect (BFLPE), by investigating whether the level of high-performing students in classroom is negatively associated with psychosomatic complaints of students who perceive themselves as poor performers.
Methods. Data were derived from the German sample of the WHO-Collaborative “Health Behaviour in School-aged Children (HBSC)” study 2013/2014. The sample included 5226 11-, 13- and 15-year-old students. Individual perceived school performance (PSP) was included (very good/good vs. average/below average PSP) at the individual student-level. At the class-level, school performance in class was generated by aggregating the share (in percentage) of students who report a very good/good PSP to the class-level, indicating the percentage of students with good/very good PSP in classroom. Using multilevel regression models, the association between class-level school performance (in percentage of students with very good/good PSP) and individual psychosomatic complaints were analyzed, stratified by students´ individual PSP.
Results. Students who report average/below average PSP showed higher likelihoods of psychosomatic complaints (Odds Ratio: 1.75; 95% Confidence Interval: 1.52–2.03) compared to counterparts with very good/good PSP. The aggregated class-level PSP was not significantly associated with psychosomatic complaints. However, in line with the BFLPE, results further revealed that students with average/below average PSP, who attend classes with a higher percentage of students who report very good/good PSP, had higher likelihoods of psychosomatic complaints (Odds Ratio: 1.91; 95% Confidence Interval: 1.01–4.01) compared to classmates with very good/good PSP.
Conclusions. This study revealed that class composition in terms of PSP was differentially associated with students´ psychosomatic complaints, depending on their individual PSP. Findings highlight the vulnerability of students with poor PSP placed in classes with a higher percentage of students with good PSP. Results of this study therefore indicate a need for initiatives for low performing students from teachers and school staff in class.
The Sabatier reaction is a key process in the "power-to-gas" application which is considered to con-tribute to future chemical energy storage systems. In this
contribution we focus on the catalytic active sites of a NiO catalyst supported on SiO2(NiO/SiO2) which is commonly used in the Sabatier reaction. A novel technique for the characterization of the active sites is presented and dis-cussed using thermal desorption spectroscopy at ambient pressure. This analytical tool is operated under reaction conditions and allows element specific measurements during the catalytic process of CO2 reforming towards methane. Beside the desorption experiments, XPS and XAS measurements of pristine and catalytically used samples are performed to determine the influence of the Sabatier reaction conditions on the surface structure of the catalyst.
Spectroscopic characterization of Cobalt–Phthalocyanine electrocatalysts for fuel cell applications
(2012)
For polymer–electrolyte–membrane fuel cells (PEM-FC), platinumcatalysts on carbon based substrates are state
of the art, due to high electrochemical activity and chemical stability in acid electrolytes. High costs of platinum force investigations of alternative catalysts. With respect to the oxygen reduction reaction, possible candidates are transition metal (TM) complexes like TM-porphyrines or TM-phthalocyanines. Pyrolysis on carbon based substrates improves the catalytic activity. Highest activities were found for Fe or Co as transition metal centers. We present results of the pyrolysis of Co-phthalocyanine (CoPc) on carbon black. Besides an investigation of morphology by scanning electron microscopy (SEM) and chemical composition by energy dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) during pyrolysis, we present a near edge X-ray absorption fine structure (NEXAFS) study of the chemical composition for the related annealing steps. This investigation is accompanied by an electrochemical characterization of the catalytic activity and selectivity. The XPS and NEXAFS data indicate a decomposition of the CoN4(chelate-) complex during pyrolysis. The N1s data for 800 °C show graphite-like, formally pyrrolic and pyridinic like features, without any significant contri-bution of Co. The Co2p data for both, XPS and NEXAFS are dominated by CoO/Co2O3. It can be concluded that during the pyrolysis cobalt particles are formed by the disintegration of CoN4-centers, after pyrolysis these par-ticles become oxidized upon contact with air.
Organic semiconductors efficiently harvest light in the region of the solar spectrum due to a high absorption/extinction coefficient.In our work we study the electronic structure and the charge carrier dynamics of polymeric organic semiconductor regioregular poly(3-hexylthiophen-2,5-diyl) (P3HT), an ideal p-type semiconductor and a widely used conjugated polymer, and blends with the fullerene derivative phenyl-C61-butyric acid methyl ester (PCBM), an electron acceptor material. The study was done with the help of time resolved microwave conductivity (TRMC) for contactless investigation of bulk carrier dynamics, optical spectroscopy, ultraviolet photoelectron spectroscopy(UPS) and high resolution X-ray absorption spectroscopy(XAS) which investigates excited states of rr-P3HT. From the data obtained we could infer the positions of the valence and conduction band, the existence of two excitons as well as the co-existence of one dimensional and two dimensional polarons. Based on our spectroscopic data we propose a model in which the scattering of virtual polarons and excitons are shown to create mobile polaronic charge carriers.
Increasing green house emissions amplify global warming concerns worldwide. Fuel cells, based on polymer electrolyte membranes (PEM) are part of the solution to this issue. We aim at developing and testing new catalysts for fuel cells. Platinum catalysts perform best in PEM fuel cells to date but they are very expensive. For fuel cells to be perfectly applicable and economically affordable, an alternative catalyst with similar or even greater efficiency should be developed.
Metal phthalocyanines are known to be good oxygen reduction catalysts and are associated with high electron transfer properties. We investigated Cobalt Phthalocyanine in its pure state mixed with Carbon Black (CoPc:Carbon Black=1:9) untreated and also after a treatment in N2 at several temperatures, up to 1000°C for 30 minutes.
Results of XPS and EDX analyses reveal that the treatment at higher temperatures causes a rearrangement in the chemical states of Co, N and C atoms. Furthermore, results of cycling voltammetry (CV) analysis reveal that CoPc treated in N2 at 800°C exhibited a higher current density, in conclusion, a higher catalytic activity than the untreated CoPc.
Investigations of the electronic structure and composition of regioregular poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) based films using Near Edge X-Ray Absorption Fine Structure (NEXAFS) are presented. The measurements were performed at the U49/2-PGM2 beam line of BESSY II, Berlin recording TEY (total electron yield) and TFY (total fluorescence yield) data. Samples prepared by spin coating a mixture of P3HT dissolved in chloroform and PCBM dissolved in chlorobenzene onto ITO (indium tin oxide) coated glass slides were analyzed. Upon measuring the pure P3HT and PCBM, all reported excitations were observed, whereas the blended system is a weighted superposition of the related peaks. Analyzing the data we calculate the composition of the mixture. We also show angular dependent NEXAFS measurements of the P3HT/PCBM blend in order to measure the orientation and distribution of the P3HT polymer. Additionally, we show a new approach for organic solar cell application. BaTiO3 nanoparticles were incorporated as nanodispersion into the donor-acceptor blend or the ferroelectric copolymer poly(vinylidene fluoride trifluoroethylene) (P(VDF-TrFE)) was spincoated as an ultrathin film below the blend.
Charge dissociation and recombination are important factors for the efficiency of organic solar cells, even in blended systems of different polymers. As a new approach, the influence of additional blended ferroelectric nanoparticles on the solar cell performance is investigated. The ferroelectric dipole of the nanoparticle causes a local field, which could lead to a longer recombination time of the polaron pairs. As solar cell system we use bulk heterojunction cells or bilayer structures based on regioregular poly(3-hexylthiophene) (P3HT) as the donor and phenyl-C61-butyric acid methyl ester (PCBM) as the acceptor molecule. As ferroelectric additive we use the ferroelectric copolymer poly(vinylidene fluoride trifluoroethylene) (P(VDF-TrFE)) or BaTiO3. The copolymer is spincoated as ultrathin film of 20nm, whereas the BaTiO3 is incorporated as nanodispersion into the donor-acceptor blend. We present the solar cell parameters for the different geometries and ferroelectric materials as a function of ferroelectric content and of the alignment of the ferroelectric dipoles after application of an external electric field.
The influence of an annealing step on the parameters of bulk heterojunction organic solar cells is investigated. In order to fabricate the solar cells we use glass coated with ITO (Indiumtinoxide) as a substrate on which the active layer consisting of P3HT and PCBM is spincoated. Al-electrodes are evaporated on top of the active layer. We use PEDOT:PSS as buffer layer. Each sample is annealed at different temperatures for a short time. Between every temperature step the I-V characteristic of the cell is measured. The following parameters are derived afterwards: FF, Isc (density), Voc. Also the efficiency is estimated. The results show a maximum cell efficiency for drying at 100°C for 20sec. A further important step for preparation is the drying procedure of the PEDOT:PSS layer. Here an improvement of about 50% in cell efficiency is measured after drying at 50°C for 5 days under inert gas atmosphere.
This study investigates whether class-level school performance affects students’ life satisfaction and if there are differential effects for high- and low-performing students. Data were derived from the National Educational Panel Study, including n = 5196 students (49.6% girls), nested in 478 classes and 250 secondary schools. School performance in class was measured by aggregating individual grade point average in Mathematics and German. The study could not reveal the “big-fish-little-pond”-effect regarding students’ life satisfaction but found differential effects for high- vs. low performing students. There was no significant association for low-performing students attending classes with higher class-level performance However, low-performing students revealed the lowest life satisfaction. High-performing students placed in classes with higher average performance reported lower life satisfaction compared to high-performing students in classes with lower average performance. This study provides evidence for the impact of the learning environment in class on school-aged children’s life satisfaction, by highlighting the differential sensitivity of high-performing students when placed in classes with higher or lower average performance.