Heterogeneous photosynthesis

1) The HOMO-LUMO principle is derived from molecular orbital theory (e.g., Purcell and Kotz, 1980) it emphasizes the importance of orbital symmetry (proper overlap of reductant and oxidant orbitals). 

Photooxidation and photoreduction of an electron donor and an electron acceptor, respectively, as illustrated schematically with a one-electron molecular orbital scheme. 

D = electron donor HOMO = highest occupied molecular orbital  

A = electron acceptor LUMO = lowest unoccupied molecular orbital. 

For the formation of one 02 molecule four electrons have to be transferred. This requires a quantum storage device . In the photosynthetic system of green plants this is achieved with two photosystems that are linked through an electron transport chain, Fig. 10.2, and by means of the thylakoid-membrane that enables the separation of the photoproducts 02 and the reduced form of nicotinamide adenine dinucleotide phosphate, NADPH. 

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The solid state and the surface chemistry of some of the solid Fe-phases impart to these oxides and sulfides the ability to catalyze redox reactions. Surface complexes and the solid phases themselves acting as semiconductors can participate in photoredox reactions, where light energy is used to drive a thermodynamically unfavorable reaction (heterogeneous photosynthesis) or to catalyze a thermodynamically favorable reaction (heterogeneous photocatalysis). 

Photoinduced ET at liquid-liquid interfaces has been widely recognized as a model system for natural photosynthesis and heterogeneous photocatalysis [114-119]. One of the key aspects of photochemical reactions in these systems is that the efficiency of product separation can be enhanced by differences in solvation energy, diminishing the probability of a back electron-transfer process (see Fig. 11). For instance, Brugger and Gratzel reported that the efficiency of the photoreduction of the amphiphilic methyl viologen by Ru(bpy)3+ is effectively enhanced in the presence of cationic micelles formed by cetyltrimethylammonium chloride [120]. Flash photolysis studies indicated that while the kinetics of the photoinduced reaction,... 

The second article also deals with PET in arranged media, however, this time by discussing comprehensively the various types of heterogeneous devices which may control supramolecular interactions and consequently chemical reactions. Before turning to such applications, photosynthetic model systems, mainly of the triad type, are dealt with in the third contribution. Here, the natural photosynthetic electron transfer process is briefly discussed as far as it is needed as a basis for the main part, namely the description of artificial multicomponent molecules for mimicking photosynthesis. In addition to the goal to learn more about natural photosynthetic energy conversion, these model systems may also have applications, which, for example, lie in the construction of electronic devices at the molecular level. 

Artificial Photosynthesis Water Cleavage into Hydrogen and Oxygen by Visible Light Review deals mostly with micro-heterogeneous (particulate) systems for water splitting. 30... 

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