Raman Spectroscopy of Oxygen Evolution Catalysts and PSII Manganese Model Compounds

Photosynthesis is the basis of life on earth, and oxygen evolution catalysts are key components of this complicated, yet not fully understood process. Photosystem II, a large membrane bound pigment-protein complex, is the key system that facilitates oxygenic photosynthesis via the oxygen evolving complex (a natural oxygen evolving catalyst). It is a key component in oxygen producing catalysts, which can be used in fields such as energy production and biomimetic catalysts. The oxygen evolution cycle, or Kok cycle going within it is still not studied completely. In this project, we were studying the vibrational (and structural) state of a Manganese model compound for PSII and functioning Ruthenium water oxidizing catalyst. The method for this experiment was Raman spectroscopy at two wavelengths in the visible region: 532nm and 442nm. The results obtained from our Manganese model compound are various Raman spectra which will be analyzed using DFT (Density Function theory) and can now be used to predict vibrations relevant to PSII while insights gained from functioning Ruthenium water oxidizing catalysts give clues to the chemistry of PSII

An Investigation in the Mechanism of [Ru(tpy)(bpy)(H2O)]2+ and [Ru(bpy)2(bpyNO)]2+with the Emphasize on the N-oxide: A Redox Active Ligand

Climate change and the energy crisis are substantial challenges facing the human species, and they are projected to threaten life on our planet. For millions of years, the sun has been the main source of energy for life on Earth; this inspires ongoing research efforts focusing on a “sunlight to fuel” energy solution. Photosynthesis is nature’s tool to derive energy from the sun. Hence, scientists focus on the biochemistry of this phenomenon to employ photosynthesis in a man-made device. Such a device is able to convert solar energy to chemical energy through a light-driven cycle of the chemical reactions which produce hydrogen gas, later used as fuel. This process, often called “artificial photosynthesis,” needs efficient catalysts which can be incorporated into a molecular assembly and other microscopic structures or immobilized on an electrode surface. Additionally, evolution, in the course of billions of years, chose manganese as an abundant and effective metal to facilitate the process of photosynthesis. These manganese atoms formed a cluster and an optimized ligand field to maximize efficiency. The photochemistry and photo-physics process behind photosynthesis is yet to be fully understood and implemented in a man-made apparatus with comparable efficiency and durability. Photosynthesis requires a source of electrons. Water is an abundant molecule on earth that can provide the electrons needed for the photosynthesis. Although water is ubiquitous, it is one of the most stable molecules; hence, splitting it demands a well-designed system with strong oxidizing capability. Because a single atom of oxygen is highly reactive, there should be at least four oxidation states in the system to remove four electrons and release molecular oxygen: O2. The O-O bond formation is one of the most important steps in photosynthesis to fully understand. Lacking a thorough knowledge of this step prevents design and fabrication of robust and active water oxidizing catalysts. To fully understand O-O formation, one should perform a comprehensive study of each of the intermediates of the system. In other words, we need an understanding of the structure and electronic configuration of the system (natural or artificial) from the moment that a water molecule attaches to the catalyst (usually a metal core, central in the complex), until the moment that oxygen released as an O2molecule. There are multiple possible mechanisms to explain O-O formation. Two mechanisms that were extensively studied in this thesis are water nucleophilic attack and radical coupling. The prevailing view about oxygen formation in the catalysts that we study here explains the O-O bond formation by nucleophilic attack of a water molecule to a highly oxidized ruthenium (RuV=O) species. In this hypothesis, all polypyridine ligands that are coordinated to ruthenium remain neutral during the water oxidation process, while the formation of RuV=O (the key intermediate) would require a relatively high free energy (about 1.8 to 2 eV); use of computational (numerical) calculations determine this to be thermodynamically inaccessible. Furthermore, the failure of spectroscopic techniques to confirm the presence of RuV=O calls the validity of this model into question.