ABSTRACT
All cyanobacteria, algae, and plants use a similar water-oxidizing catalyst for water oxidation. This catalyst is housed in Photosystem II, a membrane-protein complex that functions as a light-driven water oxidase in oxygenic photosynthesis. Water oxidation is also an important reaction in artificial photosynthesis because it has the potential to provide cheap electrons from water for hydrogen production or for the reduction of carbon dioxide on an industrial scale. The water-oxidizing complex of Photosystem II is a Mn-Ca cluster that oxidizes water with a low overpotential and high turnover frequency number of up to 25-90 molecules of O2 released per second. In this Review, we discuss the atomic structure of the Mn-Ca cluster of the Photosystem II water-oxidizing complex from the viewpoint that the underlying mechanism can be informative when designing artificial water-oxidizing catalysts. This is followed by consideration of functional Mn-based model complexes for water oxidation and the issue of Mn complexes decomposing to Mn oxide. We then provide a detailed assessment of the chemistry of Mn oxides by considering how their bulk and nanoscale properties contribute to their effectiveness as water-oxidizing catalysts.
Subject(s)
Coordination Complexes/chemistry , Manganese Compounds/chemistry , Photosystem II Protein Complex/chemistry , Water/chemistry , Biomimetics , Catalysis , Oxidation-Reduction , Oxides/chemistryABSTRACT
The resolution of Photosystem II (PS II) crystals has been improved using isolated PS II from the thermophilic cyanobacterium Thermosynechococcus vulcanus. The new 1.9 Å resolution data have provided detailed information on the structure of the water-oxidizing complex (Umena et al. Nature 473: 55-61, 2011). The atomic level structure of the manganese-calcium cluster is important for understanding the mechanism of water oxidation and to design an efficient catalyst for water oxidation in artificial photosynthetic systems. Here, we have briefly reviewed our knowledge of the structure and function of the cluster.
Subject(s)
Calcium/chemistry , Cyanobacteria/metabolism , Manganese/chemistry , Photosynthetic Reaction Center Complex Proteins/chemistry , Photosystem II Protein Complex/chemistry , Water/chemistry , Crystallography, X-Ray , Hydrogen Bonding , Models, Chemical , Oxidation-Reduction , Oxides , Oxygen/chemistryABSTRACT
According to UV-visible spectroscopy, X-ray diffraction spectrometry, dynamic light scattering, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy, nano-sized manganese oxides are proposed as active catalysts for water oxidation in the reaction of some manganese complexes and cerium(IV) ammonium nitrate.
Subject(s)
Cerium/chemistry , Manganese Compounds/chemistry , Nanostructures/chemistry , Oxides/chemistry , Water/chemistry , Catalysis , Coordination Complexes/chemistry , Oxidation-ReductionABSTRACT
Hydrogen production by water splitting may be an appealing solution for future energy needs. To evolve hydrogen efficiently in a sustainable manner, it is necessary first to synthesize what we may call a 'super catalyst' for water oxidation, which is the more challenging half reaction of water splitting. An efficient system for water oxidation exists in the water oxidizing complex in cyanobacteria, algae and plants; further, recently published data on the Manganese-calcium cluster have provided details on the mechanism and structure of the water oxidizing complex. Here, we have briefly reviewed the characteristics of the natural system from the standpoint of what we could learn from it to produce an efficient artificial system. In short, to design an efficient water oxidizing complex for artificial photosynthesis, we must learn and use wisely the knowledge about water oxidation and the water oxidizing complex in the natural system. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial.
