TY - JOUR
T1 - Hydrogenolysis of tetrahydrofuran-2-carboxylic acid over tungsten-modified rhodium catalyst
AU - Asano, Takehiro
AU - Nakagawa, Yoshinao
AU - Tamura, Masazumi
AU - Tomishige, Keiichi
N1 - Funding Information:
This work is supported by JSPS KAKENHI grant numbers of 18H05247 , 20H02519 and 20H02520 . We thank Mr. Lujie Liu and Ms. Ayaka Kuwata for their help with experiments.
Publisher Copyright:
© 2020 Elsevier B.V.
PY - 2020/7/25
Y1 - 2020/7/25
N2 - Catalysts for reduction of tetrahydrofuran-2-carboxylic acid (THFCA), which can be synthesized from furfural via oxidation and hydrogenation, were explored among the combinations of noble metal and reducible metal oxide supported on SiO2. Rh-WOx/SiO2 catalysts showed activity in C-O hydrogenolysis at 2-position of THFCA (to δ-valerolactone and 5-hydroxyvaleric acid) and higher yield ratio of these C-O hydrogenolysis products to carboxylic acid hydrogenation products than other bimetallic catalysts. The activity of Rh-WOx/SiO2 catalysts was highest at W/Rh = 0.25 mol/mol. XRD, TPR, CO adsorption and XAFS characterizations showed that the Rh-WOx/SiO2 (W/Rh = 0.25) catalyst contained Rh metal particles with surface modification with isolated W2+ oxide species. The mechanism that hydride-like species formed on Rh atom attacks the C atom at the α-position (2-position) of adsorbed carboxylate on W atom is proposed based on the similar kinetics and similar catalyst structure to Rh-MOx/SiO2 (M = Re, Mo) which is known to be active in THFA hydrogenolysis to 1,5-pentanediol.
AB - Catalysts for reduction of tetrahydrofuran-2-carboxylic acid (THFCA), which can be synthesized from furfural via oxidation and hydrogenation, were explored among the combinations of noble metal and reducible metal oxide supported on SiO2. Rh-WOx/SiO2 catalysts showed activity in C-O hydrogenolysis at 2-position of THFCA (to δ-valerolactone and 5-hydroxyvaleric acid) and higher yield ratio of these C-O hydrogenolysis products to carboxylic acid hydrogenation products than other bimetallic catalysts. The activity of Rh-WOx/SiO2 catalysts was highest at W/Rh = 0.25 mol/mol. XRD, TPR, CO adsorption and XAFS characterizations showed that the Rh-WOx/SiO2 (W/Rh = 0.25) catalyst contained Rh metal particles with surface modification with isolated W2+ oxide species. The mechanism that hydride-like species formed on Rh atom attacks the C atom at the α-position (2-position) of adsorbed carboxylate on W atom is proposed based on the similar kinetics and similar catalyst structure to Rh-MOx/SiO2 (M = Re, Mo) which is known to be active in THFA hydrogenolysis to 1,5-pentanediol.
KW - Carboxylic acid
KW - Hydrogenolysis
KW - Rhodium
KW - Ring opening
KW - Tungsten
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U2 - 10.1016/j.apcata.2020.117723
DO - 10.1016/j.apcata.2020.117723
M3 - Article
AN - SCOPUS:85087158121
SN - 0926-860X
VL - 602
JO - Applied Catalysis A: General
JF - Applied Catalysis A: General
M1 - 117723
ER -