TY - JOUR
T1 - Dehydration of 1,5-Pentanediol over ZrO 2 -ZnO Mixed Oxides
AU - Beasley, Charles
AU - Gnanamani, Muthu Kumaran
AU - Martinelli, Michela
AU - Góra-Marek, Kinga
AU - Hamano, Kaichiro
AU - Shafer, Wilson D.
AU - Wanninayake, Namal
AU - Kim, Doo Young
N1 - Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/3/22
Y1 - 2019/3/22
N2 - Zn addition was found to affect both activity and selectivity of ZrO 2 for dehydration of 1,5-pentanediol. ZrO 2 tends to produce more or less equimolar mixture of tetrahydropyran (THP) derivatives and 4-penten-1-ol from 1,5-pentanediol. The conversion of 1,5-pentanediol on ZrO 2 increases with increasing Zn content up to 30–50 mole percent; however, catalyst containing Zn beyond 50 mole percent had an adverse effect on both conversion of diol and the selectivity for unsaturated alcohol (i. e., 4-penten-1-ol). XRD and Raman analysis infer that the presence of tetragonal ZrO 2, the amorphous phase (ZrO 2 , ZrZnO x , ZnO), and hexagonal wurtzite structure of ZnO in the catalysts. The interplanar spacing of ZrO 2 (111) and ZnO (100) planes for catalysts indicate that Zn incorporates into ZrO 2 lattice and vice-versa. Basicity assessed from CO 2 -TPD and acidity from FTIR-pyridine adsorption techniques indicate that both basicity and Lewis acid sites density increases with increasing Zn proportion on ZrO 2 up to 50:50 molar ratios of Zn to Zr. An optimum Zn:Zr mole ratio is required to achieve higher density of oxygen vacant metal sites (i. e., Lewis acidity) and balanced acid-base strength which improves the diol conversion.
AB - Zn addition was found to affect both activity and selectivity of ZrO 2 for dehydration of 1,5-pentanediol. ZrO 2 tends to produce more or less equimolar mixture of tetrahydropyran (THP) derivatives and 4-penten-1-ol from 1,5-pentanediol. The conversion of 1,5-pentanediol on ZrO 2 increases with increasing Zn content up to 30–50 mole percent; however, catalyst containing Zn beyond 50 mole percent had an adverse effect on both conversion of diol and the selectivity for unsaturated alcohol (i. e., 4-penten-1-ol). XRD and Raman analysis infer that the presence of tetragonal ZrO 2, the amorphous phase (ZrO 2 , ZrZnO x , ZnO), and hexagonal wurtzite structure of ZnO in the catalysts. The interplanar spacing of ZrO 2 (111) and ZnO (100) planes for catalysts indicate that Zn incorporates into ZrO 2 lattice and vice-versa. Basicity assessed from CO 2 -TPD and acidity from FTIR-pyridine adsorption techniques indicate that both basicity and Lewis acid sites density increases with increasing Zn proportion on ZrO 2 up to 50:50 molar ratios of Zn to Zr. An optimum Zn:Zr mole ratio is required to achieve higher density of oxygen vacant metal sites (i. e., Lewis acidity) and balanced acid-base strength which improves the diol conversion.
KW - 1,5-pentanediol
KW - 4-penten-1-ol
KW - Dehydration
KW - FTIR
KW - ZrO -ZnO
KW - pyridine adsorption
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U2 - 10.1002/slct.201900400
DO - 10.1002/slct.201900400
M3 - Article
AN - SCOPUS:85063383532
VL - 4
SP - 3123
EP - 3130
JO - ChemistrySelect
JF - ChemistrySelect
IS - 11
ER -