Introducing a dark reaction to photochemistry: photocatalytic hydrogen from [FeFe] hydrogenase active site model complexes

被引:106
作者
Lomoth, Reiner [1 ]
Ott, Sascha [1 ]
机构
[1] Uppsala Univ, Dept Photochem & Mol Sci, Angstrom Labs, S-75120 Uppsala, Sweden
基金
瑞典研究理事会;
关键词
IRON-ONLY HYDROGENASE; ELECTRON-TRANSFER; VISIBLE-LIGHT; RUTHENIUM PHOTOSENSITIZER; PHOTOPHYSICAL PROPERTIES; ACETONITRILE SOLUTIONS; BIOMIMETIC MODEL; PROTON REDUCTION; EVOLUTION; WATER;
D O I
10.1039/b911129h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The light-driven splitting of water into its constituting elements gives access to a valuable fuel from an abundant substrate, using sunlight as the only energy source. Synthetic diiron complexes as functional models of the [FeFe] hydrogenase H(2)ase enzyme active site have moved into the centre of focus as potentially viable catalysts for the reductive side of this process, i.e. the reduction of protons to molecular hydrogen. The active site of the enzyme, as well as its mimics in an artificial system, are required to accumulate two electrons from single electron transfer events and to combine them with two protons to form hydrogen. Whereas in biology this reaction is not coupled to photosynthesis and thus proceeds in the dark, additional aspects need to be considered when designing a functional artificial system for the light-driven reduction of protons. Suitable photosensitizers have to be chosen that not only provide sufficient driving force for the reduction of the synthetic diiron catalyst, but also allow for selective excitation to minimize photodegradation. Electron transfer efficiencies have to be optimized for all steps and the sequential nature of the catalyst reduction requires a sufficient stability of potentially labile intermediates of the catalytic cycle. In this perspective, systems for the light-driven conversion of protons to molecular hydrogen are discussed where the catalyst is based on model complexes of the [FeFe] H(2)ase active site. Covalently linked dyads, supramolecular assemblies and multi-component systems will be examined with an emphasis on mechanistic electron transfer schemes, the properties of the individual components, their scope and their potential limitations.
引用
收藏
页码:9952 / 9959
页数:8
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