Development of High Performance Heterogeneous Catalysts for Valorization of Biogenic Chemicals

Development of High Performance Heterogeneous Catalysts for Valorization of Biogenic Chemicals

Tomoo Mizugaki,¹ Kohei Uesugi,¹ Kodai Nitta,1 Zen Maeno,¹ Takato Mitsudome,¹ Koichiro Jitsukawa,¹ and Kiyotomi Kaneda*^1,2

1. Graduate School of Engineering Science, Department of Materials Engineering Science, Osaka University

2. Research Center for Solar Energy Chemistry, Osaka University

kaneda@cheng.es.osaka-u.ac.jp

Biomass has attracted significant attention as a carbon-neutral resource with the potential to reduce the vast quantity of CO₂ emissions. Recently, the biomass-derived compounds such as glycerol, furfural, and levulinic acid are identified as the best suited alternatives for petroleum-derived chemicals. From the stand point of green sustainable chemistry, development of highly selective and efficient catalytic transformation of the above compounds has been desired.

We have developed novel nanostructured heterogeneous catalysts capable of cooperative activation by several active species using inorganic crystallites as unique macro ligands. We report here the precise design of heterogeneous metal catalysts for highly selective transformation of glycerol,^1-5 furfural,⁶ and levulinic acid ^7,8 into value added chemicals. For example, highly selective hydrogenolysis of glycerol to 1,3-propanediol could be catalyzed by Pt-WO_x supported on aluminum oxide. The combination catalyst system using the lanthanum-exchanged montmorillonite and the aluminum oxide-embedded Cu nanoparticles enabled one-pot transformation of glycerol to 1,3-diacetoxyacetone via the acetylation, oxidation, isomerization, and hydrogenation. Furthermore, the Pt nanoparticles supported on hydrotalcite and Pt-MoO_x on hydroxyapatite selectively converted furfural and levulinic acid into 1,2-pentanediol and 1,4-pentandiol, respectively. The unique activities of the above nanostructured heterogeneous catalysts will be also discussed.

References

[1] T. Mizugaki, R. Arundhathi, T. Mitsudome, K. Jitsukawa, K. Kaneda, ACS Sustainable Chem. Eng. 2014, 2, 574.

[2] R. Arundhathi, T. Mizugaki, T. Mitsudome, K. Jitsukawa, K. Kaneda, ChemSusChem 2013, 6, 1345.

[3] T. Mizugaki, R. Arundhathi, T. Mitsudome, K. Jitsukawa, K. Kaneda, Chem. Lett. 2013, 42, 729.

[4] T. Mizugaki, T. Yamakawa, R. Arundhathi, T. Mitsudome, K. Jitsukawa, K. Kaneda, Chem. Lett. 2012, 41, 1720.

[5] T. Mitsudome, T. Matsuno, S. Sueoka, T. Mizugaki, K. Jitsukawa, K. Kaneda, Heterocycles 2012, 84, 371.

[6] T. Mizugaki, T. Yamakawa, Y. Nagatsu, Z. Maeno, T. Mitsudome, K. Jitsukawa, K. Kaneda, ACS Sustainable Chem. Eng. 2014, 2, 2243.

[7] T. Mizugaki, Y. Nagatsu, K. Togo, Z. Maeno, T. Mitsudome, K. Jitsukawa, K. Kaneda, Green Chem. 2015, 17, 5136–5139.

[8] T. Mizugaki, K. Togo, Z. Maeno, T. Mitsudome, K. Jitsukawa, K. Kaneda, ACS Sustainable Chem. Eng. 2016, 4, 682–685.