Hydrogen Production by Selective Dehydrogenation of HCOOH Catalyzed by Ru-Biaryl Sulfonated Phosphines in Aqueous Solution

Abstract

The selective dehydrogenation of aqueous solutions of HCOOH/HCOONa to H 2 and CO 2 gas mixtures has been investigated using RuCl 3 •3H 2 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 6 -C 6 H 6 )Cl 2 ] 2 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.

Homogenous catalytic hydrogenation of bicarbonate with water soluble aryl phosphine ligands

“…58 ppm could be observed in the 31 P{ 1 H} NMR spectrum as soon as the solution was heated, which was maintained throughout the recycling experiments, possibly explaining the prolonged activity of the system under these conditions. By analogy with previous HPNMR studies involving L2, we attribute this signal to trans-[RuH(MBMS) 2 (H 2 O) 3 ] + , [19]. In this case a broad hydride signal at À8.44 ppm was also detected in the water suppressed 1 H NMR spectrum, although degradation occurred over time.…”

“…Therefore, in this study a series of hydrophilic phosphine ligands bearing biaryl groups and aryl bis(phosphines) containing anionic sulfonate substituents were prepared and tested in the bicarbonate hydrogenation reaction in water without any basic additives. These ligands have recently been reported to be active in the FA dehydrogenation reaction, an important feature for the realization of a carbon neutral hydrogen storage and delivery system [19]. All the ligands were used in combination with the ruthenium precursor RuCl 3-Á3H 2 O, and the catalysis followed by applying high pressure NMR techniques.…”

Anchoring Pt Single Atoms on Te Nanowires for Plasmon‐Enhanced Dehydrogenation of Formic Acid at Room Temperature

“…[1][2][3][4][5][6][7][8][9][10][11] Noble metal based catalysts such as Ir complexes, Ru-biaryl sulfonated phosphines, bimetallic Pd/M (M = late transition fcc metal), PdAg nanoparticles, Figure 4. [1][2][3][4][5][6][7][8][9][10][11] Noble metal based catalysts such as Ir complexes, Ru-biaryl sulfonated phosphines, bimetallic Pd/M (M = late transition fcc metal), PdAg nanoparticles, Figure 4.…”

“…[2][3][4][5][6] Such catalysts suffered from the elevated temperature (60-150 °C) to enhance their performance, which became troublesome barriers to their usages in a wider range. [2][3][4][5][6] Such catalysts suffered from the elevated temperature (60-150 °C) to enhance their performance, which became troublesome barriers to their usages in a wider range.…”

“…Modulating the metal-support interaction is a feasible approach to construct efficient supported catalysts. [1][2][3][4][5][6][7][8][9][10][11] Noble metal based catalysts such as Ir complexes, Ru-biaryl sulfonated phosphines, bimetallic Pd/M (M = late transition fcc metal), PdAg nanoparticles, Figure 4. [7] Besides, NiPd ultrafine particles supported on NH 2 -functionalized and N-doped graphene oxide were capable of catalyzing HCOOH selective dehydrogenation at 25 °C.…”