Pincer complexes moieties have attracted much attention in the past years. They have been proved that they are highly active catalysts in many different known transition metal-catalyzed organic reaction and some unpredictable organic transformation. In this thesis, we will use PN3P Cobalt pincer complex in two different applications. The first application is the unpresented Cobalt-catalyzed hydrogenation of nitriles to secondary imines. The selective hydrogenation of nitriles into secondary imines is a very challenging task and the catalysts play a very important role in the reaction and the selectivity. Herein in the thesis, we report the first selective hydrogenation of nitriles to secondary imines catalyzed by a well-defined and accessible PN3P cobalt pincer complex. Our results show different selectivity compared with the known PNP cobalt catalytic system during the nitriles hydrogenation. A set of aliphatic and aromatic nitriles are hydrogenated to the secondary imine under relatively mild conditions. The second application is the alkylation of nitriles with alcohols using PN3P cobalt pincer complex. The alcohol is being used here as alkylating agent in state of using toxic alkyl halides or excess amount of base to avoid any salt waste. The cobalt pincer complex work as catalyst for transformation that undergoes alkylation via hydrogen transfer pathways. The beauty of this reaction that it is delver water as the only byproduct. A different nitriles and alcohol are tolerated in this reaction.

Stickoxide NOx werden von Menschenhand in verschiedenen Verbrennungsprozessen emittiert. Die selektive katalytische Reduktion mit Ammoniak (NH3-SCR) hat sich weltweit als wichtigste Methode zur Minderung von NOx-Emissionen etabliert. Derzeit erhältliche Katalysatoren für die NH3-SCR werden bei Temperaturen unterhalb von 473 K stark in Gegenwart von Wasser desaktiviert, welches unvermeidbar in Abgasen aus der Verbrennung von organischen Stoffen enthalten ist. In dieser Arbeit werden drei verschiedene Arten der Modifikation von SCR-Katalysatoren diskutiert, die eine gesteigerte H2O-Resistenz bewirken. Eine Methode ist die Verwendung von mischoxidischen Trägermaterialien, eine Andere ist eine mischoxidische aktive Komponente und schließlich eine postpräparative Oberflächenmodifikation mit Organosilylgruppen. Die Katalysatoren wurden sowohl auf ihre katalytische Aktivität als auch auf ihre adsorptiven, redox und andren Oberflächeneigenschaften untersucht. Die Wechselwirkungen zwischen H2O und der Katalysatoroberfläche wurden mittels temperaturprogrammierter Desorption (TPD), isothermaler Adsorption bei erhöhtem Druck und einer gravimetrischen Methode untersucht. Besonders die H2O-TPD hat sich als eine leistungsstarke Methode für diesen Zweck herausgestellt. Jede der drei Modifikationen bewirkte eine Verminderung der Wechselwirkungen zwischen H2O und der Katalysatoroberfläche. Neben einer allgemeinen Erhöhung der Aktivität eines SCR-Katalysators, wird die gezielte Verminderung dieser Wechselwirkungen als Schlüsselrolle in der Entwicklung von Katalysatoren mit verbesserter H2O-Resistenz angesehen. Jedoch gibt es zur Zeit kaum Publikationen, die diesen Zusammenhang behandeln. Daneben wurde auch die Bildung von N2O als ungewünschtes Nebenprodukt bei der SCR-Reaktion untersucht. Dessen Treibhauspotential entspricht ungefähr dem 300-fachen von CO2. Die Verwendung von einem mischoxidischem Trägermaterial kann die Freisetzung von N2O während der SCR verringern, was größtenteils auf die Unterdrückung der Bildung nach einem ER-Mechanismus zurückgeführt wurde. Auch die N2O-Bildung wird in vielen Publikationen über die Entwicklung von SCR-Katalysatoren nicht betrachtet.:0.1 Abbreviations 0.2 Symbols 1 Introduction and Objectives 2 Literature Overview 2.1 NH3-SCR 2.1.1 NH3-SCR Catalysts 2.1.2 Mechanisms of NH3-SCR Reaction 2.1.3 N2O-Formation under SCR-Conditions 2.2 Deactivation of NH3-SCR Catalysts 2.2.1 Deactivation by H2O 2.2.2 Deactivation by SO2 2.3 Low-Temperature NH3-SCR 2.3.1 Requirements and Challenges of LT-SCR 2.3.2 LT-SCR Catalysts 2.4 Silylation of Metal Oxide Surfaces 3 Experimental Section 3.1 Catalyst Preparation 3.1.1 Support Modification with Different Metal Oxides 3.1.2 Deposition of Active Component 3.1.3 Catalyst Modification with Organosilyl Groups 3.2 Catalyst Characterization 3.2.1 Texture Analysis 3.2.2 Phase Analysis 3.2.3 Elementary Analysis 3.2.4 Adsorption Properties 3.2.5 Surface Spectroscopy 3.2.6 Redox Properties 3.3 Catalytic Experiments 4 Results and Discussion 4.1 Impact of Mixed-Oxide Support on Catalyst Activity 4.1.1 Impact in Dry Gas-Flow: Reduced N2O-Emission 4.1.1.1 Catalytic Activity 4.1.1.2 Catalyst Characterization 4.1.1.3 Discussion 4.1.2 Impact in Wet Gas-Flow: Higher H2O-Resistance 4.1.2.1 Catalytic Activity 4.1.2.2 Catalyst Characterization 4.1.2.3 Discussion 4.1.3 Summary of SiO2-Impact 4.2 Mn-Ce Mixed-Oxide as Active Component 4.2.1 Catalytic Activity 4.2.2 Catalyst Characterization 4.2.3 Discussion and Summary 4.3 Catalyst Modification with Organosilyl Groups 4.3.1 Stability of Organosilyl Groups 4.3.2 Impact of Organosilyl Modification on H2O-Adsorption 4.3.3 Impact of Organosilyl Modification on Catalytic Activity in Pre- and Absence of H2O 4.3.3.1 Catalytic Activity 4.3.3.2 Catalyst Characterization 4.3.3.3 Discussion 4.3.4 Summary of Organosilyl Modification 4.4 Discussion on the Investigation of H2O-Adsorption 5 Conclusions and Outlook 5.1 Conclusions 5.2 Outlook 6 References 7 Appendix 7.1 Evaluation of H2O-Sorption Data through BET-Theory 7.2 Evaluation of Kinetic SCR Investigation 7.3 Calculation of the Average Oxidation State of Mnz+ from H2-TPR 7.4 Calculation of the Surface-Density of Mn 7.5 Supplementary Data 7.6 Scientific Contributions 7.7 Curriculum Vitae 8 Summary (german) 8.1 Einleitung 8.2 Experimentelles 8.3 Ergebnisse und Diskussion 8.3.1 Einfluss eines mischoxidischen Trägermaterials auf die katalytische Aktivität 8.3.2 Mn-Ce-Mischoxide als aktive Komponente 8.3.3 Modifikation von Katalysatoren mit Organosilyl-Gruppen 8.4 Schlussfolgerungen / Nitrogen oxides NOx were anthropogenically emitted by various combustion processes. The selective catalytic reduction with ammonia (NH3-SCR) has been established worldwide as the most important technique for the abatement of NOx . Currently available catalysts for NH3-SCR become strongly deactivated at temperatures below 473 K in presence of H2O which is unavoidable present in the exhaust gas arising from the combustion of organic matter. In this work three different kinds of a modification of an SCR-catalyst were discussed that cause a higher H2O-resistance. One is the application of a mixed-oxide support material, the other is a mixed-oxide active component and finally a post-preparative surface modification with organosilyl-groups. The catalysts were assessed for their catalytic activity as well as their adsorptive, redox and other surface properties. The interactions between H2O and the catalyst surface were investigated by means of temperature programmed desorption (TPD), isothermal adsorption at elevated pressure and a gravimetric method. Especially the H2O-TPD turned out to be a powerful method for this purpose. Each of the three modifications caused a reduction in the H2O-catalyst interactions. Beside a general increase of the activity of an SCR-catalyst, the purposeful reduction of these interactions is considered to play a key role in the development of catalysts with an enhanced H2O-resistance. However, there is a lack of publications that deal with this correlation. Also the formation of the unwanted by-product N2O was investigated. Its global warming potential is about 300-times that of CO2. The application of a mixed-oxide support can reduce the release of N2O during SCR which was attributed mainly to the suppression of the ER-type formation pathway. Also the N2O-formation is not considered in many publications dealing with the development of SCR-catalysts.:0.1 Abbreviations 0.2 Symbols 1 Introduction and Objectives 2 Literature Overview 2.1 NH3-SCR 2.1.1 NH3-SCR Catalysts 2.1.2 Mechanisms of NH3-SCR Reaction 2.1.3 N2O-Formation under SCR-Conditions 2.2 Deactivation of NH3-SCR Catalysts 2.2.1 Deactivation by H2O 2.2.2 Deactivation by SO2 2.3 Low-Temperature NH3-SCR 2.3.1 Requirements and Challenges of LT-SCR 2.3.2 LT-SCR Catalysts 2.4 Silylation of Metal Oxide Surfaces 3 Experimental Section 3.1 Catalyst Preparation 3.1.1 Support Modification with Different Metal Oxides 3.1.2 Deposition of Active Component 3.1.3 Catalyst Modification with Organosilyl Groups 3.2 Catalyst Characterization 3.2.1 Texture Analysis 3.2.2 Phase Analysis 3.2.3 Elementary Analysis 3.2.4 Adsorption Properties 3.2.5 Surface Spectroscopy 3.2.6 Redox Properties 3.3 Catalytic Experiments 4 Results and Discussion 4.1 Impact of Mixed-Oxide Support on Catalyst Activity 4.1.1 Impact in Dry Gas-Flow: Reduced N2O-Emission 4.1.1.1 Catalytic Activity 4.1.1.2 Catalyst Characterization 4.1.1.3 Discussion 4.1.2 Impact in Wet Gas-Flow: Higher H2O-Resistance 4.1.2.1 Catalytic Activity 4.1.2.2 Catalyst Characterization 4.1.2.3 Discussion 4.1.3 Summary of SiO2-Impact 4.2 Mn-Ce Mixed-Oxide as Active Component 4.2.1 Catalytic Activity 4.2.2 Catalyst Characterization 4.2.3 Discussion and Summary 4.3 Catalyst Modification with Organosilyl Groups 4.3.1 Stability of Organosilyl Groups 4.3.2 Impact of Organosilyl Modification on H2O-Adsorption 4.3.3 Impact of Organosilyl Modification on Catalytic Activity in Pre- and Absence of H2O 4.3.3.1 Catalytic Activity 4.3.3.2 Catalyst Characterization 4.3.3.3 Discussion 4.3.4 Summary of Organosilyl Modification 4.4 Discussion on the Investigation of H2O-Adsorption 5 Conclusions and Outlook 5.1 Conclusions 5.2 Outlook 6 References 7 Appendix 7.1 Evaluation of H2O-Sorption Data through BET-Theory 7.2 Evaluation of Kinetic SCR Investigation 7.3 Calculation of the Average Oxidation State of Mnz+ from H2-TPR 7.4 Calculation of the Surface-Density of Mn 7.5 Supplementary Data 7.6 Scientific Contributions 7.7 Curriculum Vitae 8 Summary (german) 8.1 Einleitung 8.2 Experimentelles 8.3 Ergebnisse und Diskussion 8.3.1 Einfluss eines mischoxidischen Trägermaterials auf die katalytische Aktivität 8.3.2 Mn-Ce-Mischoxide als aktive Komponente 8.3.3 Modifikation von Katalysatoren mit Organosilyl-Gruppen 8.4 Schlussfolgerungen

The rapid global climate change associated with increasing planetary CO$_2$ levels is possibly one of the greatest challenges existing currently. In order to address this grave problem, a variety of solutions and approaches have been proposed. It is likely that a combination of these approaches would be required to solve the multi-dimensional problem of climate change. One potential approach to mitigate carbon emissions is the concept of a ‘Circular Carbon Economy’. This approach encompasses the concept of capturing carbon emissions and reusing the captured CO$_2$ to make fuels and chemicals using renewable energy. Use of fuels and chemicals manufactured via this approach would thus avoid ‘new’ CO$_2$ emissions and prevent the accumulation of additional CO$_2$ in the atmosphere as these products will be CO$_2$-neutral. The use of CO$_2$-neutral fuels would especially be beneficial as not only would it cause a significant impact on CO$_2$ emissions in terms of volume but also it would provide a way to store energy from intermittent sources like solar, wind etc. Furthermore, these fuels can be used without requiring a significant overhaul of the energy infrastructure. One of the most promising routes for the synthesis of fuels and chemicals from CO$_2$ is via the thermal hydrogenation of CO$_2$ using multifunctional heterogeneous catalysis. Multifunctional catalysis refers to the combination of catalysts having different functionalities into a single reactor (one-pot). This catalytic route is a powerful tool for tuning the product distribution during a reaction and for enhancing the yield of target products. Thus, this PhD Thesis describes the design of several multifunctional catalyst combinations which have been applied for producing various hydrocarbon products of interest from CO$_2$ ranging from light olefins, aromatics and fuel range paraffins. The catalyst combinations consisted of a metal/metal oxide and a zeolite and depending on the configuration used, enhanced the selectivity to target products. Various advanced characterization techniques have also been utilized in order to reveal the status of active species and the underlying reaction mechanism(s).

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第23292号 / エネ博第417号 / 新制||エネ||79(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 河本 晴雄, 教授 石原 慶一, 教授 上髙原 浩 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・論文博士 / 博士(工学) / 乙第12929号 / 論工博第4122号 / 新制||工||1626(附属図書館) / 32139 / (主査)教授 田中 庸裕, 教授 田中 勝久, 教授 佐藤 啓文 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21780号 / 工博第4597号 / 新制||工||1716(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 中村 正治, 教授 大江 浩一, 教授 村田 靖次郎 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements of the degree of Master of Science. November 1995. / The preparation of supported cobalt and gold catalysts by the technique of electroless plating, and the establishment of the influence of synthesis variables on the physical properties of the supported catalyst, forms the basis of this dissertation. In both the cases of cobalt and gold supported on extruded cylindrical alumina pellets, the penetration profile of the metal into the support showed dependence on the pH of the activation solution, while the metal loading onto the same support showed no dependence on pH of the activation solution at all. The variables involved in the plating process of the activated pellets, namely: i) the concentration of the activation solution, ii) pH and temperature of the plating bath, iii) plating time, and Iv) variation of the concentrations of components of the plating bath all influenced the mass of metal loaded onto the support, but not the penetration characteristics. It is therefore possible to prepare a supported catalyst with very specific , properties using the above information. Under similar conditions, with extruded alumina pellets as support and with the specific plating formulations used, gold showed higher metal loadings at lower gold concentrations than cobalt.

Several self-supported and metal oxide supported cobalt Fisher-Tropsch (FT) catalysts were prepared applying incipient wetness impregnation method. The catalysts were characterized by TPR, adsorption-desorption, XRD, TEM and SEM. The gas products were characterized by GC. The effect of support was investigated. The selfsupported 3D ordered macro-porous (3DOM) Fe-Co and self-supported 2D ordered mesoporous catalyst showed low or no activity under typical F-T reaction conditions. The 3DOM Al2O3 supported cobalt catalyst showed much higher CO conversion and C4+ selectivity than conventional Co/Gamma-Al2O3 catalyst. However, the 3DOM Co/Al2O3 prepared by incorporated method showed no activity. The supported Co/SBA-15 performed better CO conversion than the conventional Co/SiO2. The effects of temperature and time on 3DOM Co/Al2O3 and Co/SBA-15 system were coherent with traditional catalysts. The well-defined structure of 3DOM Al2O3 and SBA-15 may favor to the selectivity of C4+ hydrocarbons product.