CATALYTIC WATER SPLITTING FOR H2 PRODUCTION BY A RU COMPLEX IDENTIFIED WITH FIRST-PRINCIPLES STUDY

摘要

The storage of renewable energy through the production of fuels is long sought-after strategy to cope with the intrinsic variability of clean energy sources like wind and solar.The sunlight-driven splitting of water in H2 and O2 is possibly the simplest way in which solar energy could be stored, by rearranging the chemical bonds of water and forming molecular hydrogen, which could be later used in fuel cells. Several artificial molecular catalysts for water oxidation have been reported in the literature, starting in 1982 with the well known "blue dimer" of Meyer. While most of these catalysts are multicenter complexes, single center Ir and Rucomplexes have also been reported. Kohl et al, recently discovered a Ru(II)-pincer complex (P-da-PNN)RuH(CO) (0, P-da = dearomatized at the phosphorus side arm, PNN = (2-(di-rert-butylphosphinomethyl)-6-diethylaminomethyl)pyridine) able to promote the consecutive thermal-driven release of hydrogen and light-driven release of oxygen from water,8 thus demonstrating that a single metal center is able to promote the overall splitting of water. This represents a new paradigm in the search for artificial means to promote water splitting. The reaction mechanism promoted by Ru-complex 0 has been investigated both experimentally and theoretically.