Conversion of Cellulose to Hexitols Catalyzed by Ionic Liquid‐Stabilized Ruthenium Nanoparticles and a Reversible Binding Agent

Eric V. Anslyn, Ludger P. Stubbs, John A. Maguire, Yinghuai Zhu, Shoucang Shen, Zhen Ning Kong, Lin Huang, Huang Lin
2009-12-18

1-n-butyl-3-methylimidazolium chloride ([BMIM]Cl)cellulose conversion to hexitolsionic liquid-stabilized ruthenium nanoparticlesreversible boronic acid binding agentsodium formate/formic acid hydrogen donors
A reversible cellulose binding agent, 1-(4′-(4′′-(2′′′-boronobenzyl)piperazinyl)-2′-butenyl)-3-n-butylimidazolium chloride 1, is synthesized by reacting 2-((4′-allylpiperazinyl)methyl) phenylboronic acid with 3-allyl-1-n-butylimidazolium chloride. 1 is miscible with ionic liquids, and when combined with Ru nanoparticles as a catalyst, cellulose can be converted to polyols under mild conditions. The catalyst can be recycled with sustained activity.
1
A conjugate reversible cellulose binding agent (compound 1) combining a boronic acid and an ionic liquid moiety was synthesized and is fully miscible with common ionic liquids.
2
Compound 1 binds reversibly to cellulose diols, solubilizes/activates cellulose, and alone hydrolyzes cellulose to α-glucose with 95% conversion after 5 h at 80 °C.
3
Ionic liquid-stabilized Ru0 nanoparticles (~4.0 nm) combined with compound 1 convert cellulose to hexitols in high yields (up to 100% conversion and 94% sorbitol yield using sodium formate).
4
The catalytic system is recyclable with sustained activity over at least five runs and shows Ru leaching below 3 ppm by ICP analysis.
5
Using formic acid/Na+ formate as hydrogen donors and ionic liquids likely facilitates hydrogen release and efficient glucose hydrogenation to hexitols by the Ru nanoparticles.

Cellulose being converted to hexitols using ionic liquid-stabilized ruthenium nanoparticles and a reversible boronic-acid-based binding agent

Catalytic conversion process efficiency and mechanism by which the reversible binding agent (compound 1) combined with ionic-liquid-stabilized Ru nanoparticles solubilizes cellulose, promotes hydrolysis to glucose and hydrogenation to hexitols, catalyst recyclability, and yields under mild conditions

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2009-12-18
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Authors
Eric V. Anslyn
Ludger P. Stubbs
John A. Maguire
Yinghuai Zhu
Shoucang Shen
Zhen Ning Kong
Lin Huang
Huang Lin
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