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Title: 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/MgAlO x-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/Al 2O 3. Moreover, while Cu8/MgAlO x-HP shows a stable activity, the activity of 0.4 wt% Pd/Al 2O 3 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/H 2O 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-macromore » 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/MgAlO x-HP material, and these particles do not aggregate during the hydrogenation reaction.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [4]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States); Utrecht Univ., Utrecht (The Netherlands)
  2. Univ. of Wisconsin-Madison, Madison, WI (United States)
  3. Unesp - Univ. Estadual Paulista, Araraquara (Brazil)
  4. Utrecht Univ., Urecht (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) (SC-23)
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 Volume: 21; Journal Issue: 18; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
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 States: 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 States. 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., and Weckhuysen, Bert M. Tue . "Catalytic hydrogenation of dihydrolevoglucosenone to levoglucosanol with a hydrotalcite/mixed oxide copper catalyst". United States. doi: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 States},
year = {2019},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9GC00564A

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Works referenced in this record:

Cu and Cu-Based Nanoparticles: Synthesis and Applications in Catalysis
journal, March 2016


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
  • DOI: 10.1016/j.apcatb.2017.07.006

Cobalt toxicity in humans—A review of the potential sources and systemic health effects
journal, July 2017


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
  • DOI: 10.1021/acssuschemeng.9b00470

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
  • DOI: 10.1039/C7GC01688C

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
  • DOI: 10.1007/s11172-013-0213-z

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
  • DOI: 10.1039/C1CY00383F

Synthesis of 1,6-Hexanediol from Cellulose Derived Tetrahydrofuran-Dimethanol with Pt-WO x /TiO 2 Catalysts
journal, January 2018


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
  • DOI: 10.1039/C5EE02666K

Formation of copper aluminate spinel and cuprous aluminate delafossite to thermally stabilize simulated copper-laden sludge
journal, September 2010


Solvent Applications of 2-Methyltetrahydrofuran in Organometallic and Biphasic Reactions
journal, January 2007

  • Aycock, David F.
  • Organic Process Research & Development, Vol. 11, Issue 1
  • DOI: 10.1021/op060155c

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
  • DOI: 10.1016/j.micromeso.2016.11.011

Heterogeneous Catalysis
journal, February 2015


Scaling the rough heights
journal, April 2015

  • Medlin, J. Will; Montemore, Matthew M.
  • Nature Chemistry, Vol. 7, Issue 5
  • DOI: 10.1038/nchem.2245

Hydrogenation of levoglucosenone to renewable chemicals
journal, January 2017

  • Krishna, Siddarth H.; McClelland, Daniel J.; Rashke, Quinn A.
  • Green Chemistry, Vol. 19, Issue 5
  • DOI: 10.1039/C6GC03028A

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
  • DOI: 10.1039/c4ee00379a

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
  • DOI: 10.1039/C8CY00608C

Origin of ligand-driven selectivity in alkyne semihydrogenation over silica-supported copper nanoparticles
journal, August 2018


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
  • DOI: 10.1039/B814955K