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Ammonia is a chemical of fundamental importance for nature`s vital nitrogen cycle. It is crucial for the growth of living organisms as well as food and energy source. Traditionally, industrial ammonia production is predominated by Haber- Bosch process (HBP) which is based on direct conversion of N2 and H2 gas under high temperature and high pressure (~500oC, 150-300 bar). However, it is not the favorite route because of its thermodynamic and kinetic limitations, and the need for the energy intense production of hydrogen gas by reforming processes. All these disfavors of HBP open a target to search for an alternative technique to perform efficient ammonia synthesis via electrochemical catalytic processes, in particular via water electrolysis, using water as the hydrogen source to save the process from gas reforming. In this study, the investigation of the interface effects between imidazolium-based ionic liquids and the surface of porous carbon materials with a special interest in the nitrogen absorption capability. As the further step, the possibility to establish this interface as the catalytically active area for the electrochemical N2 reduction to NH3 has been evaluated. This particular combination has been chosen because the porous carbon materials and ionic liquids (IL) have a significant importance in many scientific fields including catalysis and electrocatalysis due to their special structural and physicochemical properties. Primarily, the effects of the confinement of ionic liquid (EmimOAc, 1-Ethyl-3-methylimidazolium acetate) into carbon pores have been investigated. The salt-templated porous carbons, which have different porosity (microporous and mesoporous) and nitrogen species, were used as model structures for the comparison of the IL confinement at different loadings. The nitrogen uptake of EmimOAc can be increased by about 10 times by the confinement in the pores of carbon materials compared to the bulk form. In addition, the most improved nitrogen absorption was observed by IL confinement in micropores and in nitrogen-doped carbon materials as a consequence of the maximized structural changes of IL. Furthermore, the possible use of such interfaces between EmimOAc and porous carbon for the catalytic activation of dinitrogen during the kinetically challenging NRR due to the limited gas absorption in the electrolyte, was examined. An electrocatalytic NRR system based on the conversion of water and nitrogen gas to ammonia at ambient operation conditions (1 bar, 25 °C) was performed in a setup under an applied electric potential with a single chamber electrochemical cell, which consists of the combination of EmimOAc electrolyte with the porous carbon-working electrode and without a traditional electrocatalyst. Under a potential of -3 V vs. SCE for 45 minutes, a NH3 production rate of 498.37 μg h-1 cm-2 and FE of 12.14% were achieved. The experimental observations show that an electric double-layer, which serves the catalytically active area, occurs between a microporous carbon material and ions of the EmimOAc electrolyte in the presence of sufficiently high provided electric potential. Comparing with the typical NRR systems which have been reported in the literature, the presented electrochemical ammonia synthesis approach provides a significantly higher ammonia production rate with a chance to avoid the possible kinetic limitations of NRR. In terms of operating conditions, ammonia production rate and the faradic efficiency without the need for any synthetic electrocatalyst can be resulted of electrocatalytic activation of nitrogen in the double-layer formed between carbon and IL ions., Ammoniak ist eine Chemikalie von grundlegender Bedeutung für den lebenswichtigen Stickstoffkreislauf der Natur. Es ist entscheidend für das Wachstum lebender Organismen sowie von Nahrungsmitteln und Energiequellen. Traditionell wird die industrielle Ammoniakproduktion nach dem Haber-Bosch-Verfahren (HBP) dominiert, das auf der direkten Umwandlung von N2- und H2-Gas unter hoher Temperatur und hohem Druck (~ 500 ° C, 150-300 bar) basiert. Aufgrund seiner thermodynamischen und kinetischen Einschränkungen und der Notwendigkeit einer energieintensiven Erzeugung von Wasserstoffgas durch Reformierungsprozesse ist dies jedoch nicht der bevorzugte Weg. All diese Nachteile von HBP eröffnen ein Ziel für die Suche nach einer alternativen Technik zur Durchführung einer effizienten Ammoniaksynthese über elektrochemische katalytische Prozesse, insbesondere durch Wasserelektrolyse, wobei Wasser als Wasserstoffquelle verwendet wird, um den Prozess vor einer Gasreformierung zu bewahren. In dieser Studie wurde die Untersuchung der Grenzflächeneffekte zwischen ionischen Flüssigkeiten auf Imidazoliumbasis und der Oberfläche poröser Kohlenstoffmaterialien mit besonderem Interesse an der Stickstoffabsorptionsfähigkeit untersucht. Als weiterer Schritt wurde die Möglichkeit geprüft, diese Grenzfläche als katalytisch aktiven Bereich für die elektrochemische N2-Reduktion zu NH3 zu etablieren. Diese besondere Kombination wurde gewählt, weil die porösen Kohlenstoffmaterialien und ionischen Flüssigkeiten (IL) aufgrund ihrer besonderen strukturellen und physikochemischen Eigenschaften in vielen wissenschaftlichen Bereichen, einschließlich Katalyse und Elektrokatalyse, eine bedeutende Bedeutung haben. In erster Linie wurden die Auswirkungen des Einschlusses von ionischer Flüssigkeit (EmimOAc, 1-Ethyl-3-methylimidazoliumacetat) in Kohlenstoffporen untersucht. Die porösen Kohlenstoffe mit Salzschablonen, die unterschiedliche Porosität (mikroporös und mesoporös) und Stickstoffspezies aufweisen, wurden als Modellstrukturen für den Vergleich des IL-Einschlusses bei unterschiedlichen Beladungen verwendet. Die Stickstoffaufnahme von EmimOAc kann durch den Einschluss in den Poren von Kohlenstoffmaterialien im Vergleich zur Massenform um das Zehnfache erhöht werden. Zusätzlich wurde die am besten verbesserte Stickstoffabsorption durch IL-Einschluss in Mikroporen und in stickstoffdotierten Kohlenstoffmaterialien als Folge der maximierten strukturellen Änderungen von IL beobachtet. Darüber hinaus wurde die mögliche Verwendung solcher Grenzflächen zwischen EmimOAc und porösem Kohlenstoff für die katalytische Aktivierung von Distickstoff während des kinetisch herausfordernden NRR aufgrund der begrenzten Gasabsorption im Elektrolyten untersucht. Ein elektrokatalytisches NRR-System, das auf der Umwandlung von Wasser und Stickstoffgas in Ammoniak bei Umgebungsbetriebsbedingungen (1 bar, 25 ° C) basiert, wurde in einem Aufbau unter einem angelegten elektrischen Potential mit einer elektrochemischen Einkammerzelle durchgeführt, die aus der Kombination von besteht EmimOAc-Elektrolyt mit poröser Kohlenstoff-Arbeitselektrode und ohne herkömmlichen Elektrokatalysator. Bei einem Potential von -3 V gegen SCE für 45 Minuten wurde eine NH3-Produktionsrate von 498,37 ug h & supmin; ¹ cm & supmin; ² und eine FE von 12,14% erreicht. Die experimentellen Beobachtungen zeigen, dass eine elektrische Doppelschicht, die dem katalytisch aktiven Bereich dient, zwischen einem mikroporösen Kohlenstoffmaterial und Ionen des EmimOAc-Elektrolyten in Gegenwart eines ausreichend hohen bereitgestellten elektrischen Potentials auftritt. Im Vergleich zu den typischen NRR-Systemen, über die in der Literatur berichtet wurde, bietet der vorgestellte Ansatz der elektrochemischen Ammoniaksynthese eine signifikant höhere Ammoniakproduktionsrate mit der Möglichkeit, die möglichen kinetischen Einschränkungen der NRR zu vermeiden. In Bezug auf die Betriebsbedingungen können die Ammoniakproduktionsrate und die Faradic-Effizienz ohne die Notwendigkeit eines synthetischen Elektrokatalysators aus der elektrokatalytischen Aktivierung von Stickstoff in der zwischen Kohlenstoff- und IL-Ionen gebildeten Doppelschicht resultieren.

Son yıllarda dünyanın içinde bulunduğu enerji krizine alternatif olarak sunulan güneş enerjisi limitsiz olması, ücretsiz elde edilebilirliği ve çevre duyarlılığı ile alternatif enerji kaynağı araştırmaların en popüler konusu haline gelmiştir. Kullanıcılar için maliyetli olmayacak ve güneş enerjisini en verimli şekilde hayatımıza dahil edebilcek sistemleri arttırmak ve geliştirmek amacıyla birçok teknolojik ve bilimsel araştırma yapılmaktadır. Güneş enerjisinin kimyasal enerji olarak depolanmasıyla dolaylı yoldan elektrik üretimi sağlayan güneş yakıtlarını ve bu yakıtların fotokatalitik su ayrıştırması (FSA) basamağındaki sistemlerinin geliştirilmesini temel alan bu çalışmada; suyun fotokatalizi sırasında ihtiyaç duyduğu enerjiyi verimli şekilde güneşten almasına yardımcı ışığa duyarlı fotokatalitik bir malzeme ve hem bu malzemenin hem de önerilen tüm fotokatalitik malzemelerin küçük hacimlerde analiz edilebileceği bir deneysel düzenek önerilmiştir. Bu düzenek için ince uçlu gaz mikro-sensörleri kullanılmış ve 3D çizim/baskı teknikleri kullanılarak ufak bir fotoreaktör tasarlanıp bu reaktörün FSA yöntemindeki amacına uygunluğu test edilmiştir. Ayrıca, 2007'de Mehtap Emirdağ Eanes ve ekibi tarafından bulunan kurşun (II) trioksovanadat (V) klorür [PbVO3Cl] kristalinin elektronik bant yapısı ve bant enerjisinin tespiti için hem teorik (DFT yaklaşımları; LDA, GGA, HSE06) hem de deneysel karakterizasyon metotları (XRD, Diffuse Reflectance Method- Tauc Plot, Raman Spectroscopy, Four Probe) uygulanmış ve güneş yakıtı cihazlarında yarı iletken madde olarak kullanılabilirliği incelenmiştir. İlaveten, ileride PbVO3Cl'nin fotoanot, silikonun (Si) fotokatot olarak kullanıldığı çift katmanlı bir güneş yakıtı cihazının verimliliği ve PbVO3Cl'nin tahmini fiyatı teorik olarak hesaplanmış ve tartışılmıştır. Sonuçta, dizayn edilen mini fotoreaktör sisteminin FSA'nın amacına uygun ve geliştirilmeye açık bir deneysel düzenek olduğu, PbVO3Cl'nin ise `dolaylı geçiş` bant yapısına ve ~2.2 eV'lik bant enerjisine sahip olduğu ve FSA'da etkili bir sonuç vermese de optik özelliklerinin ve bant enerjisinin uygunluğu sebebiyle bu alanda yapılan diğer çalışmalar için daha detaylı incelenip geliştirilmeye değer bir yarı iletken olduğu söylenebilmektedir. Methods of generating electricity with unlimited, clean and cheap energy from solar energy are tried to be investigated and developed in practical and theoretical academic fields. Especially, photocatalytic water splitting (PWS) systems have been identified as the main method in this study as well as in many studies due to the advantages provided by production of solar fuels from water. In this research, a study was carried out on the alternatives of the both used experimental set-up and used photocatalytic material for PWS systems. A study has been carried out on both the used experimental setup and the used photocatalytic material alternatives in PWS systems. As an alternative experimental setup that allows small volume analysis for PWS by Unisense gas microsensors, a mini photoreactor was designed using 3-D drawing and printing techniques and its usability was tested for PWS applications. Moreover, some characterization results for the electronic band structure and the band gap of the lead (II) trioxovanadate (V) chloride [PbVO3Cl] crystal, which was discovered by Eanes and co-workers in 2007 at IZTECH, was introduced in this study by not only theoretical (DFT approximations; LDA, GGA and HSE06) but also experimental (XRD, Diffuse Reflectance Method- Tauc Plot, Raman Spectroscopy, Four Probe) methods. Also, its estimated theoretical price and its potential for future application in tandem solar fuel device as a photoanode in combination with Si photocathode was calculated and discussed. The results showed that the designed mini photoreactor system is an open to development apparatus that is suitable for PWS, besides, PbVO3Cl has an `indirect transition` band structure and a band energy of ~ 2.2 eV. Although it did not give an effective result in PWS applications done by the designed mini photoreactor, it can be said that it is a semiconductor which is worth studying and developing in detail for other researches in this field due to the compatibility of its band energy amount and optical properties for PWS. 122