TY - JOUR
T1 - Selective hydrogenation of lactic acid to 1,2-propanediol over highly active ruthenium-molybdenum oxide catalysts
AU - Takeda, Yasuyuki
AU - Shoji, Tomohiro
AU - Watanabe, Hideo
AU - Tamura, Masazumi
AU - Nakagawa, Yoshinao
AU - Okumura, Kazu
AU - Tomishige, Keiichi
N1 - Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/4/13
Y1 - 2015/4/13
N2 - Modification of Ru/C with a small amount of MoOx (Ru-MoOx/C) enhanced the catalytic activity in the hydrogenation of L-lactic acid to form 1,2-propanediol and maintained high selectivity. The turnover frequency based on the amount of Ru over the optimized Ru-MoOx/C catalyst (Mo/Ru molar ratio=1:16) was 114 h-1 at 393 K, which was about 4 times higher than that over Ru/C. The same effect of MoOx was obtained over Ru-MoOx/SiO2, although Ru-MoOx/SiO2 showed slightly lower activity than that of Ru-MoOx/C. Ru-MoOx/C achieved a high yield of 95 % in 18 h at 393 K and was applicable to various carboxylic acids to provide the corresponding alcohols in high yields. Modification with MoOx also brought about suppression of racemization and (S)-1,2-propanediol was obtained in high enantiomeric excess at 353 K. Based on kinetic analysis and characterization data, such as XRD, TEM, CO adsorption by a volumetric method, FTIR spectroscopy, and X-ray absorption spectroscopy, for Ru-MoOx/C and Ru-MoOx/SiO2, the catalyst structure and reaction mechanism are proposed.
AB - Modification of Ru/C with a small amount of MoOx (Ru-MoOx/C) enhanced the catalytic activity in the hydrogenation of L-lactic acid to form 1,2-propanediol and maintained high selectivity. The turnover frequency based on the amount of Ru over the optimized Ru-MoOx/C catalyst (Mo/Ru molar ratio=1:16) was 114 h-1 at 393 K, which was about 4 times higher than that over Ru/C. The same effect of MoOx was obtained over Ru-MoOx/SiO2, although Ru-MoOx/SiO2 showed slightly lower activity than that of Ru-MoOx/C. Ru-MoOx/C achieved a high yield of 95 % in 18 h at 393 K and was applicable to various carboxylic acids to provide the corresponding alcohols in high yields. Modification with MoOx also brought about suppression of racemization and (S)-1,2-propanediol was obtained in high enantiomeric excess at 353 K. Based on kinetic analysis and characterization data, such as XRD, TEM, CO adsorption by a volumetric method, FTIR spectroscopy, and X-ray absorption spectroscopy, for Ru-MoOx/C and Ru-MoOx/SiO2, the catalyst structure and reaction mechanism are proposed.
KW - carboxylic acids
KW - enantioselectivity
KW - hydrogenation
KW - molybdenum
KW - ruthenium
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U2 - 10.1002/cssc.201403011
DO - 10.1002/cssc.201403011
M3 - Article
C2 - 25510671
AN - SCOPUS:84926614579
SN - 1864-5631
VL - 8
SP - 1170
EP - 1178
JO - ChemSusChem
JF - ChemSusChem
IS - 7
ER -