Catalytic hydrogenation of dihydrolevoglucosenone to levoglucosanol with a hydrotalcite/mixed oxide copper catalyst
Abstract
Levoglucosanol (LGOL) is a critical intermediate for the bio-based production of hexane-1,2,5,6-tetrol, 1,2,6-hexanetriol, and 1,6-hexanediol. Here we report on the aqueous-phase hydrogenation of cellulose-derived dihydrolevoglucosenone (Cyrene™) to LGOL using a calcined and reduced heterogeneous copper/hydrotalcite/mixed oxide catalyst, denoted as Cu8/MgAlOx-HP. The turnover frequency for LGOL conversion over this copper-containing catalyst is equal to 0.013 s–1 at 353 K as measured in a flow reactor which is half the one obtained using 0.4 wt% Pd/Al2O3. Moreover, while Cu8/MgAlOx-HP shows a stable activity, the activity of 0.4 wt% Pd/Al2O3 decreases with time-on-stream. Neither Cu- nor Al-leaching is observed (resp. <1 ppb and <1 ppm) but Mg leaching can be seen (5.5 ppm). The latter leaching relates to the acidity of the Cyrene/H2O mixture (pH 3.5–4.5 range), which is due to the occurrence of the geminal diol moiety of Cyrene, an acidic species. In contrast, additional and consecutive oxidation and reduction of the catalyst leads to a gradual decrease in activity over time. Applying still further oxidation/reduction cycles to this catalyst tends to decrease its activity with some overall stabilization being observed from the fourth run onwards. Mg-leaching is shown to change the relative meso-to-macro pore content, but leaves the total pore volumemore »
- Authors:
-
[1];
[2];
[3];
[4];
[2];
[2];
[3];
[2];
[2];
[5]
- Department of chemical and biological engineering, University of Wisconsin-Madison, 53706 Wisconsin, USA, Faculty of Science
- Department of chemical and biological engineering, University of Wisconsin-Madison, 53706 Wisconsin, USA
- Instituto de Química, Unesp - Universidade Estadual Paulista, Araraquara, Brazil
- Department of chemical and biological engineering, University of Wisconsin-Madison, 53706 Wisconsin, USA, DOE Center for Advanced Bioenergy and Bioproducts Innovation
- Faculty of Science, Debye Institute for Nanomaterials Science, Utrecht University, CGUtrecht 3584, The Netherlands
- Publication Date:
- Research Org.:
- Center for Advanced Bioenergy and Bioproducts Innovation, Urbana, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1557907
- Alternate Identifier(s):
- OSTI ID: 1561043
- Grant/Contract Number:
- SC0018420
- Resource Type:
- Published Article
- Journal Name:
- Green Chemistry
- Additional Journal Information:
- Journal Name: Green Chemistry Journal Volume: 21 Journal Issue: 18; Journal ID: ISSN 1463-9262
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
De bruyn, Mario, Sener, Canan, Petrolini, Davi D., McClelland, Daniel J., He, Jiayue, Ball, Madelyn R., Liu, Yifei, Martins, Leandro, Dumesic, James A., Huber, George W., and Weckhuysen, Bert M. Catalytic hydrogenation of dihydrolevoglucosenone to levoglucosanol with a hydrotalcite/mixed oxide copper catalyst. United Kingdom: N. p., 2019.
Web. doi:10.1039/C9GC00564A.
De bruyn, Mario, Sener, Canan, Petrolini, Davi D., McClelland, Daniel J., He, Jiayue, Ball, Madelyn R., Liu, Yifei, Martins, Leandro, Dumesic, James A., Huber, George W., & Weckhuysen, Bert M. Catalytic hydrogenation of dihydrolevoglucosenone to levoglucosanol with a hydrotalcite/mixed oxide copper catalyst. United Kingdom. https://doi.org/10.1039/C9GC00564A
De bruyn, Mario, Sener, Canan, Petrolini, Davi D., McClelland, Daniel J., He, Jiayue, Ball, Madelyn R., Liu, Yifei, Martins, Leandro, Dumesic, James A., Huber, George W., and Weckhuysen, Bert M. Mon .
"Catalytic hydrogenation of dihydrolevoglucosenone to levoglucosanol with a hydrotalcite/mixed oxide copper catalyst". United Kingdom. https://doi.org/10.1039/C9GC00564A.
@article{osti_1557907,
title = {Catalytic hydrogenation of dihydrolevoglucosenone to levoglucosanol with a hydrotalcite/mixed oxide copper catalyst},
author = {De bruyn, Mario and Sener, Canan and Petrolini, Davi D. and McClelland, Daniel J. and He, Jiayue and Ball, Madelyn R. and Liu, Yifei and Martins, Leandro and Dumesic, James A. and Huber, George W. and Weckhuysen, Bert M.},
abstractNote = {Levoglucosanol (LGOL) is a critical intermediate for the bio-based production of hexane-1,2,5,6-tetrol, 1,2,6-hexanetriol, and 1,6-hexanediol. Here we report on the aqueous-phase hydrogenation of cellulose-derived dihydrolevoglucosenone (Cyrene™) to LGOL using a calcined and reduced heterogeneous copper/hydrotalcite/mixed oxide catalyst, denoted as Cu8/MgAlOx-HP. The turnover frequency for LGOL conversion over this copper-containing catalyst is equal to 0.013 s–1 at 353 K as measured in a flow reactor which is half the one obtained using 0.4 wt% Pd/Al2O3. Moreover, while Cu8/MgAlOx-HP shows a stable activity, the activity of 0.4 wt% Pd/Al2O3 decreases with time-on-stream. Neither Cu- nor Al-leaching is observed (resp. <1 ppb and <1 ppm) but Mg leaching can be seen (5.5 ppm). The latter leaching relates to the acidity of the Cyrene/H2O mixture (pH 3.5–4.5 range), which is due to the occurrence of the geminal diol moiety of Cyrene, an acidic species. In contrast, additional and consecutive oxidation and reduction of the catalyst leads to a gradual decrease in activity over time. Applying still further oxidation/reduction cycles to this catalyst tends to decrease its activity with some overall stabilization being observed from the fourth run onwards. Mg-leaching is shown to change the relative meso-to-macro pore content, but leaves the total pore volume unchanged between the fresh and the spent catalyst. In spite of the high copper loading (8 wt%), small Cu-nanoparticles (2–3 nm) are present over the hydrotalcite/mixed oxide surface of the Cu8/MgAlOx-HP material, and these particles do not aggregate during the hydrogenation reaction.},
doi = {10.1039/C9GC00564A},
journal = {Green Chemistry},
number = 18,
volume = 21,
place = {United Kingdom},
year = {Mon Sep 16 00:00:00 EDT 2019},
month = {Mon Sep 16 00:00:00 EDT 2019}
}
Free Publicly Available Full Text
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https://doi.org/10.1039/C9GC00564A
https://doi.org/10.1039/C9GC00564A
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Cited by: 14 works
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Figures / Tables:
Fig. 1: Overview of the synthetic possibilities starting from levoglucosanol (LGOL) as a platform molecule.
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Works referenced in this record:
Cu and Cu-Based Nanoparticles: Synthesis and Applications in Catalysis
journal, March 2016
- Gawande, Manoj B.; Goswami, Anandarup; Felpin, François-Xavier
- Chemical Reviews, Vol. 116, Issue 6
Catalyst stabilization by stoichiometrically limited layer-by-layer overcoating in liquid media
journal, December 2017
- Héroguel, Florent; Le Monnier, Benjamin P.; Brown, Kristopher S.
- Applied Catalysis B: Environmental, Vol. 218
Cobalt toxicity in humans—A review of the potential sources and systemic health effects
journal, July 2017
- Leyssens, Laura; Vinck, Bart; Van Der Straeten, Catherine
- Toxicology, Vol. 387
Highly Dispersed Copper Nanoparticles Supported on Activated Carbon as an Efficient Catalyst for Selective Reduction of Vanillin
journal, July 2018
- Fan, Ruoyu; Chen, Chun; Han, Miaomiao
- Small, Vol. 14, Issue 36
Geminal Diol of Dihydrolevoglucosenone as a Switchable Hydrotrope: A Continuum of Green Nanostructured Solvents
journal, March 2019
- De bruyn, Mario; Budarin, Vitaliy L.; Misefari, Antonio
- ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 8
Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures
journal, January 2017
- He, Jiayue; Liu, Mingjie; Huang, Kefeng
- Green Chemistry, Vol. 19, Issue 15
New methods of heterogeneous catalysis for lignocellulosic biomass conversion to chemicals
journal, July 2013
- Kuznetsov, B. N.; Chesnokov, N. V.; Yatsenkova, O. V.
- Russian Chemical Bulletin, Vol. 62, Issue 7
Transfer hydrogenation of carbonyl compounds and carbon–carbon multiple bonds by zeolite supported Cu nanoparticles
journal, January 2012
- Subramanian, Thirumeni; Pitchumani, Kasi
- Catal. Sci. Technol., Vol. 2, Issue 2
Synthesis of 1,6-Hexanediol from Cellulose Derived Tetrahydrofuran-Dimethanol with Pt-WO x /TiO 2 Catalysts
journal, January 2018
- He, Jiayue; Burt, Samuel P.; Ball, Madelyn
- ACS Catalysis, Vol. 8, Issue 2
Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels
journal, January 2016
- Mariscal, R.; Maireles-Torres, P.; Ojeda, M.
- Energy & Environmental Science, Vol. 9, Issue 4
Formation of copper aluminate spinel and cuprous aluminate delafossite to thermally stabilize simulated copper-laden sludge
journal, September 2010
- Hu, Ching-Yao; Shih, Kaimin; Leckie, James O.
- Journal of Hazardous Materials, Vol. 181, Issue 1-3
A new perspective in bio-refining: levoglucosenone and cleaner lignin from waste biorefinery hydrolysis lignin by selective conversion of residual saccharides
journal, January 2016
- De bruyn, M.; Fan, J.; Budarin, V. L.
- Energy & Environmental Science, Vol. 9, Issue 8
Solvent Applications of 2-Methyltetrahydrofuran in Organometallic and Biphasic Reactions
journal, January 2007
- Aycock, David F.
- Organic Process Research & Development, Vol. 11, Issue 1
Emulsion-mediated synthesis of hierarchical mesoporous-macroporous Al-Mg hydrotalcites
journal, March 2017
- Petrolini, Davi D.; Urquieta-González, Ernesto A.; Pulcinelli, Sandra H.
- Microporous and Mesoporous Materials, Vol. 240
Heterogeneous Catalysis
journal, February 2015
- Schlögl, Robert
- Angewandte Chemie International Edition, Vol. 54, Issue 11
Scaling the rough heights
journal, April 2015
- Medlin, J. Will; Montemore, Matthew M.
- Nature Chemistry, Vol. 7, Issue 5
Hydrogenation of levoglucosenone to renewable chemicals
journal, January 2017
- Krishna, Siddarth H.; McClelland, Daniel J.; Rashke, Quinn A.
- Green Chemistry, Vol. 19, Issue 5
Enhanced stability of cobalt catalysts by atomic layer deposition for aqueous-phase reactions
journal, January 2014
- Lee, Jechan; Jackson, David H. K.; Li, Tao
- Energy & Environmental Science, Vol. 7, Issue 5
Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon–oxygen bonds
journal, January 2018
- Ye, Run-Ping; Lin, Ling; Li, Qiaohong
- Catalysis Science & Technology, Vol. 8, Issue 14
Origin of ligand-driven selectivity in alkyne semihydrogenation over silica-supported copper nanoparticles
journal, August 2018
- Kaeffer, Nicolas; Larmier, Kim; Fedorov, Alexey
- Journal of Catalysis, Vol. 364
Catalytic activity and stability of hydrophobic Mg–Al hydrotalcites in the continuous aqueous-phase isomerization of glucose into fructose
journal, January 2014
- Delidovich, I.; Palkovits, R.
- Catal. Sci. Technol., Vol. 4, Issue 12
The critical role of heterogeneous catalysis in lignocellulosic biomass conversion
journal, January 2009
- Lin, Yu-Chuan; Huber, George W.
- Energy Environ. Sci., Vol. 2, Issue 1
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.