(560ad) Bifunctional Co-Mn Oxide Catalysts for Catalytic Transfer Hydrogenation of Levulinic Acid to ?-Valerolactone

The rapidly diminishing fossil fuel reserves and significant exhaust emission to environment have promoted the transition from fossil energy to renewable alternatives. Biomass, known as the most abundant and renewable carbon resource, can be used to product value-added chemicals and transportation fuels ^[1]. Therefore, conversion of biomass is of great significance to solve current energetic and environmental issues. Levulinic acid (LA) was considered as one of the most promising platform molecules and can be formed as a as by-product from 5-hydroxymethylfurfural (HMF) ^[2-4]. Hydrogenation of LA can produce γ-valerolactone (GVL), which is a versatile building blocks agent for green solvent, food additive and energy storage intermediates ^[5]. Up to date, LA conversion to GVL is primarily achieved under elevated temperature and H₂ pressure. Poor activity of catalysts and significant generation of various by-products are major issues. Catalytic transfer hydrogenation (CTH) display several economic and environmental advantages over traditional hydrogenation. In this work, we studied inexpensive CuMn oxide catalysts for CTH of LA to GVL under mild condition.

Formic acid (FA) is a co-product in production of LA, using FA as H-donor can make the conversion process of LA more economical ^[6]. In our work, we first propose a cheap bifunctional CoMn oxide catalyst to convert the mixture of LA and FA. It is found that conversion of LA and selectivity of GVL could reach to 45% and 50% separately without external H₂. To study the effect of catalyst’s structure on reaction, we tune valence state of Co or Mn active site, interaction of metal support and component of the bifunctional catalyst. The catalysts are characterized by XRD, XPS, BET, TEM and SEM technique. In addition, we will also study the reaction pathway.

Reference

[1] Osatiashtiani, A.; Lee, A. F.; Wilson, K. Journal of Chemical Technology and Biotechnology 2017, 92 (6), 1125-1135.

[2] Besson, M.; Gallezot, P.; Pinel, C. Chemical Reviews 2014, 114 (3), 1827-1870.

[3] Luterbacher, J. S.; Rand, J. M.; Alonso, D. M.; Han, J.; Youngquist, J. T.; Maravelias, C. T.; Pfleger, B. F.; Dumesic, J. A. Science 2014, 343 (6168), 277-280.

[4] Mika, L. T.; Csefalvay, E.; Nemeth, A. Chemical Reviews 2018, 118 (2), 505-613.

[5] Yan, L.; Yao, Q.; Fu, Y. Green Chemistry 2017, 19 (23), 5527-5547.

[6] Upare, P. P.; Jeong, M. G.; Hwang, Y. K.; Kim, D. H.; Kim, Y. D.; Hwang, D. W.; Lee, U. H.; Chang, J. S. Applied Catalysis a-General 2015, 491, 127-135.