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Catalytic Semi‐Water–Gas Shift Reaction: A Simple Green Path to Formic Acid Fuel
Author(s) -
Qadir Muhammad I.,
Castegnaro Marcus V.,
Selau Felipe F.,
Samperi Mario,
Fernandes Jesum Alves,
Morais Jonder,
Dupont Jairton
Publication year - 2020
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201903417
Subject(s) - chemistry , catalysis , formic acid , ionic liquid , water gas shift reaction , amide , nanoparticle , imidazolate , inorganic chemistry , organic chemistry , materials science , nanotechnology
Abstract Formic acid (FA) is a promising CO and hydrogen energy carrier, and currently its generation is mainly centered on the hydrogenation of CO 2 . However, it can also be obtained by the hydrothermal conversion of CO with H 2 O at very high pressures (>100 bar) and temperatures (>200 °C), which requires days to complete. Herein, it is demonstrated that by using a nano‐Ru/Fe alloy embedded in an ionic liquid (IL)‐hybrid silica in the presence of the appropriate IL in water, CO can be catalytically converted into free FA (0.73 m ) under very mild reactions conditions (10 bar at 80 °C) with a turnover number of up to 1269. The catalyst was prepared by simple reduction/decomposition of Ru and Fe complexes in the IL, and it was then embedded into an IL‐hybrid silica {1‐ n ‐butyl‐3‐(3‐trimethoxysilylpropyl)‐imidazolium cations associated with hydrophilic (acetate, SILP‐OAc) and hydrophobic [bis((trifluoromethyl)sulfonyl)amide, SILP‐NTf 2 ] anions}. The location of the alloy nanoparticles on the support is strongly related to the nature of the anion, that is, in the case of hydrophilic SILP‐OAc, RuFe nanoparticles are more exposed to the support surface than in the case of the hydrophobic SILP‐NTf 2 , as determined by Rutherford backscattering spectrometry. This catalytic membrane in the presence of H 2 O/CO and an appropriate IL, namely, 1,2‐dimethyl‐3‐ n ‐butylimidazolium 2‐methyl imidazolate (BMMIm⋅MeIm), is stable and recyclable for at least five runs, yielding a total of 4.34 m of free FA.