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Ru-containing Magnetically Recoverable Catalysts: A Sustainable Pathway from Cellulose to Ethylene and Propylene Glycols Oleg V. Manaenkov, Joshua J. Mann, Olga V. Kislitza, Yaroslav B. Losovyj, Barry D. Stein, David Gene Morgan, Maren Pink, Olga L. Lependina, Zinaida B. Shifrina, Valentina Gennadievna Matveeva, Esther M. Sulman, and Lyudmila M. Bronstein ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b05096 • Publication Date (Web): 03 Aug 2016 Downloaded from http://pubs.acs.org on August 5, 2016
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ACS Applied Materials & Interfaces
Ru-containing Magnetically Recoverable Catalysts: A Sustainable Pathway from Cellulose to Ethylene and Propylene Glycols Oleg V. Manaenkov1*, Joshua J. Mann2, Olga V. Kislitza1, Yaroslav Losovyj2, Barry D. Stein,3 David Gene Morgan,2 Maren Pink2, Olga L. Lependina4, Zinaida B. Shifrina4, Valentina G. Matveeva1, Esther M. Sulman1, Lyudmila M. Bronstein2,4,5* 1
Tver State Technical University, Department of Biotechnology and Chemistry, 22 A. Nikitina
St, 170026, Tver, Russia 2
Indiana University, Department of Chemistry, Bloomington, IN 47405, USA
3
Indiana University, Department of Biology, Bloomington, IN 47405, USA
4
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 Vavilov St., Moscow, 119991 Russia 5
King Abdulaziz University, Faculty of Science, Department of Physics, Jeddah, Saudi Arabia
Keywords:
Magnetically
recoverable
catalysts,
ruthenium,
cellulose,
hydrogenolysis,
nanoparticles
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ABSTRACT. Biomass processing to value-added chemicals and biofuels received considerable attention due to the renewable nature of the precursors. Here, we report the development of Rucontaining magnetically recoverable catalysts for cellulose hydrogenolysis to low alcohols, ethylene glycol (EG) and propylene glycol (PG). The catalysts are synthesized by incorporation of magnetite nanoparticles (NPs) in mesoporous silica pores followed by formation of 2 nm Ru NPs. The latter are obtained by thermal decomposition of ruthenium acetylacetonate in the pores. The catalysts showed excellent activities and selectivities at 100% cellulose conversion, exceeding those for the commercial Ru/C. High selectivities as well as activities are attributed to the influence of Fe3O4 on the Ru0/Ru4+ NPs. A facile synthetic protocol, easy magnetic separation and stability of the catalyst performance after magnetic recovery make these catalysts promising for industrial applications.
1. Introduction
Biomass-derived polyols are emerging as promising building blocks for value-added chemicals.1 In particular, ethylene glycol (EG) and propylene glycol (PG), are important precursors for pharmaceuticals, liquid fuels, emulsifiers, and surfactants.2-3 They are also used for syntheses of polyesters, for example, poly(ethylene terephthalate) and poly(ethylene naphthalate).4 In addition, PG is used for the synthesis of lactic acid which, in turn, is employed in preparation of biodegradable polymers.5-6 The natural resource for the industrial production of these glycols, however, is a fossil fuel, oil. An alternative, “green”, pathway to EG and PG is cellulose catalytic hydrogenolysis in water. Cellulose is a major component of biomass and a renewable and widely available resource. Recent estimates indicate that cellulose stocks are sufficient to fully cover needs of the chemical industry.7-8
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Scheme 1 depicts pathways for the transformation of cellulose to EG and PG.9-11 This reaction can be carried out as a one-pot process in subcritical water with various heterogeneous catalysts.8 Ru-containing catalysts are considered to be the most active.10, 12-14 When catalysts are magnetically retrievable, an additional advantage from the environmental point of view is realized.15-20 Such catalysts are easily recovered, thus resulting in the conservation of energy and the rare metal catalyst and in cheaper target products.21-27 In the majority of cases, magnetically recoverable catalysts are formed by functionalization of magnetic NPs with ligands followed by the formation of catalytic complexes or nanoparticles in the magnetic NP shell.15 To date, Ru-containing magnetically recoverable catalysts have been used in olefin metathesis, azide-alkyne cycloaddition, hydrogenation, oxidation, and nitrile hydration.28 Cellulose Sorbitol
hydrolysis Glucose OH OH
O
HO
OH OH
hydrogenation
OH
HO OH OH
OH OH
Mannitol
isomerization hydrogenation
Fructose OH O OH
HO
OH OH OH
HO OH OH
OH OH
hydrogenolysis
hydrogenolysis
HO
OH Ethylene glycol HO
OH
CH3 1,2-propylene glycol
Polyols C5-C3: 1,4-sorbitan, xylitol, erythritol, glycerol, etc.
hydrogenolysis
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Scheme 1. Direct transformation of cellulose to EG and PG. Recently, magnetically recoverable catalysts have been reported in transformations of cellulose to glucose29-30 and sorbitol.31 To the best of our knowledge, however, there are no reports so far on the use of magnetically recoverable catalysts for the EG and PG syntheses. Here, we describe successful one-pot syntheses of EG and PG from cellulose in a sustainable environment of subcritical water using Ru-containing magnetically recoverable catalysts based on magnetic silica. The robust synthesis of magnetic silica, facile incorporation of small Rucontaining nanoparticles in the silica pores, and stable catalytic performance makes these catalysts promising for commercial applications.
2. Experimental 2.1.
Materials
Iron (III) nitrate, mesoporous silica gel (6 nm porosity, 200-425 mesh particle size) and ruthenium (III) acetylacetonate (Ru(acac)3, 97%) were purchased from Sigma-Aldrich and used without purification. Ethylene glycol (99.0%) and tetrahydrofuran (THF) were purchased from Macron Fine Chemicals and used as received. Ethanol (95%) was purchased from EMD and used without purification. Cellulose (degree of crystallinity of 75-80%) was purchased from ChimMedService (Russia). A fraction with the particle size
