2 research outputs found
Selective CO<sub>2</sub> Hydrogenation to Formic Acid with Multifunctional Ionic Liquids
The
development of simple, cost-effective, and sustainable methods
to transform CO<sub>2</sub> into feedstock chemicals is essential
to reduce the dependence of the chemical industry on fossil fuels.
Here, we report the selective and efficient catalytic hydrogenation
of CO<sub>2</sub> to formic acid (FA) using a synergistic combination
of an ionic liquid (IL) with basic anions and relatively simple catalysts
derived from the precursor [Ru<sub>3</sub>(CO)<sub>12</sub>]. Very
high TON (17000) and TOF values have been observed, and FA solutions
with concentrations of up to 1.2 M have been produced. In this system,
the imidazolium-based IL associated with the acetate anion acts as
a precursor for the formation of the catalytically active Ru–H
species, as a catalyst stabilizer, and as an acid buffer, shifting
the equilibrium toward free formic acid. Moreover, the IL acts as
an entropic driver (via augmentation of the number of microstates),
lowering the entropic contribution imposed by the IL surrounding the
catalytically active sites. The favorable thermodynamic conditions
enable the reaction to proceed efficiently at low pressures, and furthermore
the immobilization of the IL onto a solid support facilitates the
separation of FA at the end of the reaction
Selective Carbon Dioxide Hydrogenation Driven by Ferromagnetic RuFe Nanoparticles in Ionic Liquids
CO<sub>2</sub> is selectively hydrogenated to HCO<sub>2</sub>H
or hydrocarbons (HCs) by RuFe nanoparticles (NPs) in ionic liquids
(ILs) under mild reaction conditions. The generation of HCO<sub>2</sub>H occurs in ILs containing basic anions, whereas heavy HCs (up to
C<sub>21</sub> at 150 °C) are formed in the presence of ILs containing
nonbasic anions. Remarkably, high values of TONs (400) and a TOF value
of 23.52 h<sup>–1</sup> for formic acid with a molar ratio
of 2.03 per BMI·OAc IL were obtained. Moreover, these NPs exhibited
outstanding abilities in the formation of long-chain HCs with efficient
catalytic activity (12% conversion) in a BMI·NTf<sub>2</sub> hydrophobic
IL. The IL forms a cage around the NPs that controls the diffusion/residence
time of the substrates, intermediates, and products. The distinct
CO<sub>2</sub> hydrogenation pathways (HCO<sub>2</sub>H or FT via
RWGS) catalyzed by the RuFe alloy are directly related to the basicity
and hydrophobicity of the IL ion pair (mainly imposed by the anion)
and the composition of the metal alloy. The presence of Fe in the
RuFe alloy provides enhanced catalytic performance via a metal dilution
effect for the formation of HCO<sub>2</sub>H and via a synergistic
effect for the generation of heavy HCs