Hydrogen Production by Selective Dehydrogenation of
HCOOH Catalyzed by Ru-Biaryl Sulfonated Phosphines in Aqueous Solution
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Abstract
The selective dehydrogenation of
aqueous solutions of HCOOH/HCOONa
to H<sub>2</sub> and CO<sub>2</sub> gas mixtures has been investigated
using RuCl<sub>3</sub>·3H<sub>2</sub>O as a homogeneous catalyst precursor
in the presence of different monoaryl-biaryl or alkyl-biaryl phosphines
and aryl diphosphines bearing sulfonated groups. All catalytic systems
were used in water without any additives and proved to be active at
90 °C, giving high conversions and good TOF values. As an alternative
Ru(II) metal precursor, the known dimer [Ru(η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)Cl<sub>2</sub>]<sub>2</sub> was also tested
as in situ catalyst with selected phosphines as well as an isolated
Ru(II)-catalyst with one of them. By using high-pressure NMR (HPNMR)
techniques, indications on the nature of the active species involved
in the catalytic cycles were obtained
