<p>The increased concentration of greenhouse gases in theatmosphere, in particular CO₂, is changing the Earth’s climate. Accordingto the Kyoto protocol, where the international community agreedon binding emission targets, developed countries are committedto reduce their greenhouse gas emissions. The increased use ofbiomass in energy systems is an important strategy to reduce CO₂emissions. The purpose of this thesis has been toanalyse the opportunities for Sweden to further reduce CO₂emissions in the energy system, by rationallyutilising woody biomass energy. The characteristics of currentcommercially operating biofuel-based CHP plants in Sweden aresurveyed and systematically presented. A consistent andtransparent comprehensive reference base for system comparisonsis given. Furthermore, the fuel effectiveness and contributionto CO₂reduction is calculated. The governmentalsubsidies of the CHP plants’investment, expressed as costof specific CO₂reduction, appears to be low.</p><p>The competitiveness of biomass-fuelled energy production inrelation to fossil-based production with carbon capture isanalysed, showing that the biomass-fuelled systems provide acompetitive option, in terms of cost of electricity andefficiencies. The remaining Swedish woody biofuel potential ofat least 100 PJ/yr is principally available in regions with abiomass surplus. Transportation is therefore required to enableits utilisation in a further national and international market.Refining the biofuel feedstock to pellets, or even furtherrefining to motor fuels (DME, methanol or ethanol) or power,could facilitate this transport. Different options for fuelrefining are studied and compared. The entire fuel chain, fromfuel feedstock to end users, is considered and CO₂emissions are quantified. Substituting fuelpellets for coal appears to be the most costeffectivealternative and shows the largest CO₂reduction per energy unit biofuel. Motor fuelsappear more costly and give about half the CO₂reduction. Transportation of the upgraded biofuelpellets is highly feasible from CO₂emissions point of view and does not constitute ahindrance for further utilisation, i.e. the pellets can betransported over long distances efficiently with only limitedemissions of CO₂.</p><p>Bioenergy utilisation has additional features forenvironmental improvement, apart from the CO₂aspect. Waste heat from biofuel-based CHP can becost-effectively used in conjunction with sewage treatment. Theincoming sewage water to the nitrification process can bepreheated with the waste heat, and thereby substantiallyenhance the nitrification and the reduction of ammoniumnitrogen during the winter season.</p><p><b>Keywords:</b>CO₂reduction, energy system, biofuel, CHP, refining,fuel pellets, ethanol, methanol, DME, fuel substitution, sewagewater, nitrification.</p>

Dans ce travail, nous développons deux grands axes de recherche liés aux carbonates fondus. Le premier est l'optimisation des piles à combustible à base de carbonates fondus, avec deux approches : (i) l'amélioration de la durée de vie de la cathode grâce à des couches ultra-minces d'oxydes métalliques élaborés par la technique de dépôt de couches atomiques; (ii) la modification des électrolytes Li-K et Li-Na par addition de Cs ou de Rb. Le second est consacré à la valorisation du CO2 par sa réduction électrochimique dans les électrolytes à carbonates fondus, où nous analysons la réduction du CO2 par chronopotentiométrie et chronoamperométrie. Finalement, afin de tester les modifications subies par certains des composants analysés dans les deux premières parties, nous avons installé et adapté une configuration de cellule complète couplée à la chromatographie en phase gazeuse. Nous avons obtenu quelques résultats significatifs dans l’ensemble des approches abordées ; en ce qui concerne le point (i), nous avons constaté que TiO2 et CeO2 sont appropriés pour protéger la cathode contre la corrosion sans affecter ses propriétés électrochimiques en réduisant presque de moitié la dissolution du Ni. Les résultats obtenus pour le point (ii) sont également fructueux, car nous avons établi une méthode pour comparer deux électrolytes différents en déterminant les coefficients de diffusion des ions superoxyde et du dioxyde de carbone. Nous avons également comparé les performances de la cathode de NiO dans les électrolytes modifiés avec Cs et Rb. De ces études, nous avons constaté que l'addition de Cs améliore significativement le coefficient de diffusion de CO2 en réduisant la résistance de transfert de charge et la résistance totale à l'électrode, étant l'additif le plus prometteur testé ici. En ce qui concerne la réduction du CO2, nous avons constaté que la réaction implique des espèces adsorbées et instables et se produit en deux étapes à un électron ou une étape à deux électrons ; ainsi, il s’agit très probablement d’un mécanisme de réduction simultanée d’espèces adsorbées et dissoutes. Finalement, nous avons effectué les premiers tests sur cellule complète MCFC dans notre laboratoire, obtenant une performance et une puissance acceptables. Cependant, de petites améliorations sont encore nécessaires pour pouvoir tester les composants modifiés de cellule MCFC. / In this work, we develop two major research routes related to molten carbonates. The first one is the molten carbonate fuel cell optimization, with two approaches: (i) cathode lifetime improvement through ultra-thin layers of metal oxides deposited by atomic layer deposition; (ii) Li-K and Li-Na electrolyte modification by Cs or Rb additions. The second one is dedicated to CO2 valorization through its electrochemical reduction in molten carbonate electrolytes, where we analyze CO2 reduction by means of chronopotentiometry and chronoamperometry. Finally, in order to test some of the component modifications described in the two first parts, we installed and adapted a single-cell setup coupled to gas chromatography. We obtained some significant results in all the approaches; concerning point (i), we found that TiO2 and CeO2 are suitable for cathode corrosion protection without affecting the electrochemical properties of the electrode and reducing almost by half the dissolution of Ni. The results obtained from point (ii) are also fruitful, since we established a method for comparing two different electrolytes and obtained the diffusion coefficients of the superoxides and carbon dioxide. We also compared the performance of the state-of-the-art NiO cathode in Cs and Rb modified electrolytes. From these studies, we found that Cs addition improves significantly the CO2 diffusion coefficient and reduces the charge transfer and total resistance at the electrode, being a promising additive. Regarding CO2 reduction, after all the tests performed, we found that the reaction involves adsorbed and instable species and occurs in two one-electron steps or in two-electron unique step; thus, it follows most probably a mechanism of simultaneous reduction of the adsorbed and dissolved species. Finally, we performed the first MCFC single-cell tests in our laboratory obtaining an acceptable cell performance and output power. However, small improvements are still necessary to be able to test MCFC modified components.

[EN] This research work constitutes a first approximation to the study of the viability of carbonic fertirrigation in citrus fruits as a CO2 drain potential. To that effect, carbonic fertirrigation experiments were carried out with citrus fruits of the Nadarcott variety from the year 2010 to the year 2015. The study required the monitoring of parameters related to the leaf surface, the phenological state of the trees, the ground, the leaves and the fruits of the tested trees. The analysis of the results obtained showed there were no significant differences in the size and quality of the fruits irrigated with CO2. Differences were neither observed in the trees' vegetative development nor in the advance or delay of the blooming and formation of fruits. The analysis of the grounds revealed that the content in organic matter of the grounds irrigated with CO2 was higher than in the grounds used as reference in at least two tenths of a percentage. Similarly, it was noted that the content in iron in the leaves of the trees irrigated with CO2 was significantly higher than in the trees used as reference. The statistical analysis carried out confirmed these conclusions, noting a 24% increase over the average value in the case of the organic matter in the ground and of a 16% in the case of the iron content in the leaves. Both factors indicate that carbonic fertirrigation does have relevant agronomic repercussions, especially on the organic fraction of the ground and on the iron soluble fraction. Various authors confirm the mobilisation of the iron produced by the decrease in the pH of the irrigation water - this study confirms this fact and strengthens the usage of carbon dioxide as a potential substitute of strong acids normally used for this purpose. The increase in the content of the ground's organic matter is an especially interesting result, as it was not expected, even though some authors have related the decrease of soil respiration to different cultural practices that improve the ground's texture. The interaction between the CO2 of the irrigation water and the content in organic matter in the ground and, therefore, soil respiration must be studied in further detail in a future, with experiences specially aimed at valuing the repercussions of this practice on both parameters. / [ES] Este trabajo de investigación constituye una primera aproximación al estudio de viabilidad de la fertirrigación carbónica en cítricos como potencial sumidero de CO2. A tal efecto, se llevaron a cabos experimentos de fertirrigación carbónica con cítricos de la variedad Nadarcott desde el año 2010 hasta el año 2015. El estudio requirió la monitorización de parámetros relacionados con la superficie foliar, los estados fenológicos de los árboles, el suelo, las hojas y los frutos de los árboles ensayados. El análisis de los resultados obtenidos mostró que no había diferencias significativas en el tamaño y calidad de los frutos regados con CO2. Tampoco se observaron diferencias en el desarrollo vegetativo de los árboles ni en el avance o retraso de la floración y formación de los frutos. Los análisis de los suelos revelaron que el contenido en materia orgánica de los suelos regados con CO2 era más alto que los suelos tomados como referencia en al menos dos décimas porcentuales. De la misma manera, se observó que el contenido en hierro en las hojas de los árboles regados con CO2 era significativamente más alto que en los árboles tomados como referencia. Los análisis estadísticos realizados confirmaron estas conclusiones, observándose un incremento del 24% sobre el valor promedio en el caso de la materia orgánica del suelo y del 16% en el caso del contenido en hierro de las hojas. Ambos factores indican que la fertirrigación carbónica sí que tiene repercusiones agronómicas relevantes, especialmente sobre la fracción orgánica del suelo y sobre la fracción soluble de hierro. Diversos autores confirman la movilización del hierro producido por la disminución del pH del agua de riego; este estudio confirma este hecho y refuerza la utilización del dióxido de carbono como potencial sustituto de los ácidos fuertes normalmente utilizados para este cometido. El aumento en el contenido de materia orgánica del suelo es un resultado especialmente interesante, pues no era esperado pese a que algunos autores han relacionado la disminución de la respiración edáfica con diferentes prácticas culturales que mejoran la textura del suelo. La interacción entre el CO2 del agua de riego y el contenido en materia orgánica del suelo y, por tanto, la respiración edáfica deben de ser estudiados con más detalle, en un futuro con experiencias especialmente dirigidas a valorar las repercusiones de esta práctica sobre ambos parámetros. / [CAT] Aquest treball d'investigació constitueix una primera aproximació a l'estudi de la viabilitat de la fertirrigació carbònica en cítrics com a potencial embornal de carboni. Amb aquesta finalitat es dugueren a terme experiments de fertirrigació carbònica amb cítrics de la varietat Nadorcott des de l'any 2010 fins l'any 2015. L'estudi va requerir la monitoratge de paràmetres relacionats amb la superfície foliar, els estat fenològics del arbres, el sòl, les fulles i el fruits dels arbres assatjats. L'anàlisi dels resultats obtinguts mostrà que no hi havia diferències significatives en el tamany i qualitat del fruits regats amb CO2. Tampoc es varen observar diferències en el desenvolupament vegetatiu dels arbres ni en l'avanç o retard de la floració i formació dels fruits. Les anàlisis dels sòls revelaren que el contingut de matèria orgànica dels sòls regats amb CO2 era més alt que els sòls considerats com a referència en, almenys, dues dècimes percentuals. De la mateixa manera, s'observà que el contingut de ferro en les fulles dels arbres regats amb CO2 era significativament més alt que en els arbres referència. Les anàlisis estadístiques realitzades confirmaren aquestes conclusions, observant-se un increment del 24% sobre el valor mitjà en el cas de la matèria orgànica del sòl i del 16% en el cas del contingut en ferro de les fulles. Tots dos factors indiquen que la fertirrigació carbònica sí que té repercusions agronòmiques rellevants, especialment, sobre la fracció orgànica del sòl i la fracció soluble de ferro. Diferents autors confirmen la mobilització del ferro produit per la disminució del pH de l'agua de reg; aquest estudi confirma aquest fet i reforça l'ús del diòxid de carboni com a potencial subsutitut dels àcids forts normalment gastats per a aquesta tasca. L'augment en el contingut de matèria orgànica del sòl és un resultat especialment interessant, ja que no era esperat, malgrat que alguns autors han relacionat la disminució de la respiració edàfica amb diferents pràctiques culturals que milloren la textura del sòl. La interacció entre el CO2 de l'aigua de reg i el contingut en matèria orgànica del sòl i, per tant, la respiració edàfica han de ser estudiats amb més detall en un futur amb experiències especialment dirigides a valorar les repercussions d'aquesta pràctica sobre tots dos paràmetres. / Tarazona Díez, JV. (2015). ANÁLISIS DEL POTENCIAL DE LA FERTIRRIGACIÓN CARBÓNICA EN CÍTRICOS [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/59405 / TESIS

Thesis advisor: Matthias Waegele / Heterogeneous electrocatalytic reduction is an environmentally friendly method for the conversion of abundant feedstock molecules into valuable products. Examples include the reduction of carbon dioxide to hydrocarbons and the reduction of nitrate to ammonia. Heterogeneous electrocatalysis occurs at the interface between an electrode and an electrolyte. Interfacial properties, such as surface morphology, interfacial electric field, interfacial water structure, and local pH, can substantially influence the activity and selectivity of electrocatalytic reduction processes. However, a comprehensive, molecular-level understanding of how these interfacial properties control electrocatalysis is still largely lacking to date. To develop such an understanding, it is essential to probe the properties of the electrocatalytic interface under operating conditions. This great experimental challenge is further compounded by the fact that the interface often undergoes dynamic changes during catalysis. In this thesis, we took a multimodal approach to characterize the aqueous electrolyte/copper interface during CO2/CO reduction and hydrogen evolution. Copper is the only pure metal that promotes the reduction of CO2/CO to hydrocarbons at significant reaction rates. The hydrogen evolution reaction is the main competing reaction in aqueous electrolytes. It is therefore essential to understand how these reactions are controlled by the properties of the interface. In the first part of this thesis, we employed in-situ surface-enhanced infrared absorption spectroscopy (SEIRAS) and surface-enhanced Raman spectroscopy (SERS) to investigate dynamic changes of the copper electrode surface. We found that the polycrystalline copper electrode surface undergoes a reconstruction process upon adsorption of CO. The formation of nanoscale metal clusters on the electrode manifests itself by the appearance of a new CO stretch band, which arises from a CO sub-population bound to undercoordinated copper atoms. The formation of these clusters is reversible, that is, they disappear upon desorption of CO. This work demonstratesthat a reaction intermediate such as CO can induce dynamic and reversible changes in the surface morphology of a heterogeneous catalyst. Because the changes are reversible, they would escape ex situ measurements. Our findings highlight the need for probing catalytic surfaces under operating conditions. In the second part of this thesis, we focused on how the electrolyte influences electrocatalysis at the aqueous electrolyte/copper electrode interface. Specifically, we explored the mechanisms by which cations of the supporting electrolyte affect the reduction of CO and the hydrogen evolution reaction on copper. With differential electrochemical mass spectrometry (DEMS), we determined to what extent the reduction of CO to ethylene is affected by the identity of the cations of the supporting electrolyte. Ethylene is produced in the presence of methyl4N+ and ethyl4N+ cations, whereas this product is not synthesized in propyl4N+- and butyl4N+-containing electrolytes. With SEIRAS, we found that an intermolecular interaction between surface-adsorbed CO and interfacial water is disrupted in the presence of the two larger cations. This observation suggests that this interaction promotes the hydrogenation of surface-bound CO to ethylene. This work illustrates that weak intermolecular interactions can substantially influence electrocatalytic processes. In a related study, we examined the effect of alkali metal cations of the supporting electrolyte on the hydrogen evolution reaction. We found that, in alkaline conditions, changing the cation from Na+ to Cs+ has no measurable effect on the HER. Because it is well-established that Cs+ promotes the reduction of CO2/CO to hydrocarbons, the results illustrate the changing the alkali cation enables the selective promotion of this pathway under alkaline conditions. Further, we found that in 0.1 M solutions of NaOH and CsOH of the highest commercially available purity grades, trace impurities of iron deposit on the copper electrode during the hydrogen evolution reaction. Because iron is a better catalyst for the hyrogen evolution reaction than copper, the rate of the hydrogen evolution reaction is enhanced by up to a factor of 5. These findings demonstrate that trace impurities of this ubiquitous metal pose a great challenge for the development of selective catalytic processes for CO2/CO reduction. This thesis provides a critical study of how the interfacial properties change under the electrocatalytic reduction of CO2/CO and hydrogen evolution conditions. The properties of both Cu electrode and the electrolyte contribute to the control of the selectivity of these complex electrocatalytic processes. / Thesis (PhD) — Boston College, 2021. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

No description available.

Piston rings cause significant friction losses within internal combustion engines. Especially the first compression ring, which is pressed onto the liner by high cylinder pressure, contributes significantly to the total friction loss of the piston assembly. The tribological behavior of the oil scraper ring is mainly related to the pretensioning force and can lead to high losses even at low and idle speed. Due to this, there is always a markable risk of wear for the contact surfaces of the piston rings and the cylinder. “Diamond-like carbon” coatings on the surface of the piston rings can prevent wear and are able to reduce friction in the ring-liner-contact. The purpose of this work was to investigate the tribological benefit of this coating-system on the compression and oil scraper ring. Experimental studies were carried out on a fired single-cylinder engine using the Indicated Instantaneous Mean Effective Pressure-method (IIMEP) for the crank angle-resolved detection of the piston assembly’s friction force. To be able to determine the component-related fractions of the friction loss and to quantify the hydrodynamic and asperity related parts locally and time dependent, an EHD/MBS model of the engine was created in AVL EXCITE and a simulative investigation was performed. This simulation was validated by the experimental work and provided detailed information about the individual contact conditions and gap height of each tribological contact of the piston group. The combined approach of measurement and simulation enabled the prediction of tribological aspects and performance in parameter studies on a virtual engine test bed.

Der Komplex aus Kohlenmonoxid-Dehydrogenase und Acetyl-CoA-Synthase (CODH/ACS Komplex) des thermophilen Bakteriums Carboxydothermus hydrogenoformans katalysiert die Fixierung von CO2 in Acetyl-CoA und ist damit ein potenzieller Katalysator für die Erzeugung erneuerbarer Kraftstoffe aus CO2. Die Katalyse erfolgt an zwei verschiedenen Stellen: CO2 wird am Cluster C in der CODH-Untereinheit zu CO reduziert, das dann durch einen Tunnel innerhalb des Proteins zum Cluster A in der ACS-Untereinheit wandert, wo es mit einer Methylgruppe und CoA zu Acetyl-CoA reagiert. Die Art und Weise, wie die beiden katalytischen Aktivitäten zusammenwirken, sind noch unklar. Um hier mehr Licht ins Dunkel zu bringen, verfolgte diese Arbeit drei Ziele: die Bestimmung der Struktur des CODH/ACS-Komplexes von C. hydrogenoformans, die Untersuchung der CO2-Reduktionsaktivität von CODHasen und die Analyse der Rolle des internen Tunnels im CODH/ACS-Komplex. Die Struktur des CODH/ACS-Komplexes von C. hydrogenoformans wurde durch Röntgenkristallographie mit einer Auflösung von 2,04 Å bestimmt. Die CO2-Reduktion am Cluster C wurde kinetisch untersucht. Es zeigte sich, dass die CO2-Reduktion durch einen Ping-Pong-Mechanismus mit zwei Reaktionsstellen erfolgen könnte, der in früheren Studien vorgeschlagen wurde, aber auch durch andere Mechanismen. Um eine Struktur-Funktionsbeziehung für CODHs zu ermitteln, wurde die CO2-Reduktionsaktivität für drei CODHasen von C. hydrogenoformans untersucht, deren Strukturen bekannt sind: CODH-II, CODH-IV, und der CODH/ACS-Komplex. Das Tunnelsystem im CODH/ACS-Komplex ist viel enger als in den anderen CODHs und könnte somit der Grund für die vergleichsweise geringe Aktivität des CODH/ACS-Komplexes sein. Dies wurde auch durch die Manipulation und Analyse des internen Tunnels des CODH/ACS-Komplexes unterstützt. Die Ergebnisse deuten darauf hin, dass der Hauptzweck des Tunnels im CODH/ACS-Komplex die Kompartimentierung von CO und nicht der schnelle Substrattransport ist. / The complex of carbon monoxide dehydrogenase and acetyl-CoA synthase (CODH/ACS complex) of the thermophilic bacterium Carboxydothermus hydrogenoformans catalyses the fixation of CO2 into acetyl-CoA and is thus a potential catalyst for the production of renewable fuels from CO2. Catalysis occurs at two different sites: CO2 is reduced to CO at cluster C in the CODH subunit, which then travels through a tunnel within the protein to cluster A in the ACS subunit, where it reacts with a methyl group and CoA to form acetyl-CoA. The way in which the two catalytic activities interact is still unclear. To shed more light on this, this work pursued three goals: to determine the structure of the CODH/ACS complex of C. hydrogenoformans, to investigate the CO2 reduction activity of CODHases and to analyse the role of the internal tunnel in the CODH/ACS complex. The structure of the CODH/ACS complex of C. hydrogenoformans was determined by X-ray crystallography at 2.04 Å resolution. The CO2 reduction at cluster C was investigated kinetically. It was found that CO2 reduction could occur by a two-site ping-pong mechanism proposed in previous studies, but also by other mechanisms. To establish a structure-function relationship for CODHs, CO2 reduction activity was investigated for three CODHases of C. hydrogenoformans whose structures are known: CODH-II, CODH-IV, and the CODH/ACS complex. The tunnel system in the CODH/ACS complex is much narrower than in the other CODHs and could thus be the reason for the comparatively low activity of the CODH/ACS complex. This was also supported by the manipulation and analysis of the internal tunnel of the CODH/ACS complex. The results suggest that the main purpose of the tunnel in the CODH/ACS complex is to compartmentalise CO and not to rapidly transport substrate.

Photokatalytische Systeme sind in der Lage, lichtinduziert kleine Moleküle zu aktivieren. Für diesen komplexen Katalysevorgang ist ein Zusammenspiel mehrerer Komponenten wichtig, wie dem Photosensibilisator (PS) und dem Katalysator. Im Rahmen der vorliegenden Dissertation wurde auf verschiedenen Wegen versucht, photokatalytische Systeme auf Basis von Rhenium und 3d-Metallen zu optimieren. So konnten neue Komplexe auf Rheniumbasis synthetisiert und charakterisiert werden, welche zugleich als Photosensibilisator sowie Katalysator fungieren. Die Komplexe zeigen dabei nicht nur eine höhere Absorption, sondern auch eine höhere katalytische Produktivität, als deren mononuklearer Verwandte. Mittels DFT-Rechnungen und spektroskopischen Untersuchungen konnte gezeigt werden, dass ein kooperativer Vorgang stattfindet, bei dem eine Rheniumeinheit als PS, und eine als Katalysator agiert. Durch Zugabe eines externen PS konnte die katalytische Produktivität nochmals deutlich erhöht werden. Durch den zusätzlichen PS wird intermediär eine Rhenium-Rhenium-Spezies ausgebildet, welche CO2 kooperativ über beide Rheniumeinheiten aktivieren kann. Neben literaturbekannten PS auf Iridiumbasis wurden zudem neuartige Kupferphotosensibilisatoren genutzt. Verschiedene Derivate des Kupferphotosensibilisators wurden in der CO2-Reduktion und H2-Produktion getestet. Es zeigte sich, dass verschiedene elektronische Eigenschaften der PS Auswirkungen auf die Katalyseproduktivität haben. Zusätzlich wurden Katalysatoren auf Basis von 3d-Metallen konzipiert, welche abhängig von einem zusätzlichen PS sind. Bestrahlungsexperimente mit Iridium- und Kupfer-PS wurden durchgeführt und somit die Produktivität der einzelnen Katalysatoren bestimmt. Es konnte gezeigt werden, dass sowohl die Wahl des Liganden, als auch des Katalysatormetalls Einfluss auf Menge und Selektivität der Produkte hat. / Photocatalytic systems are capable of light-induced activation of small molecules. Among other things, this allows CO2 to be reduced to higher-energetic molecules. The interaction of several components, such as the photosensitizer (PS) and the catalyst, is important for this complex catalysis process. In this dissertation, attempts were made to optimize systems based on rhenium and 3d metals in various ways. One approach was to synthesize and characterize new rhenium-based complexes, which can act as PSs and catalysts at the same time. The complexes showed not only higher absorption but also higher catalytic activity than their mononuclear relative. Using DFT calculations and spectroscopic investigations, it was shown that a cooperative process takes place, in which one rhenium unit acts as a PS and one as a catalyst. By adding an external PS, the activity was significantly increased again. This forms a rhenium-rhenium species which is able to activate CO2 cooperatively via both rhenium units. In addition to iridium-based PS known from the literature, novel copper photosensitizers were also used for this purpose. In order to get a better understanding of the interaction of both components, different derivatives of the copper photosensitizer were tested in the activity towards CO2 reduction and H2 evolution reaction. The electronic influence of the PS on the catalytic activity could be elucidated by means of Stern-Vollmer quenching studies and DFT calculations. In addition, catalysts based on 3d metals were designed. Iron, cobalt and nickel were used as the central atom together with two different macrocyclic ligands. These monomolecular compounds are dependent on a PS. Furthermore, irradiation experiments with iridium and copper PS were carried out and the activity of the individual catalysts was thereby determined. It was shown that the choice of the ligand as well as the catalyst has an influence on the quantity and selectivity of the resulting products.

No description available.

No description available.