TY - JOUR
T1 - Competitive adsorption of substrate and solvent in Sn‐beta zeolite during sugar isomerization
AU - van der Graaff, W.N.P.
AU - Tempelman, C.H.L.
AU - Li, G.
AU - Mezari, B.
AU - Kosinov, N.
AU - Pidko, E.A.
AU - Hensen, E.J.M.
PY - 2016
Y1 - 2016
N2 - The isomerization of 1,3-dihydroxyactone and d-glucose over Sn-Beta zeolite was investigated by in situ 13C NMR spectroscopy. The conversion rate at room temperature is higher when the zeolite is dehydrated before exposure to the aqueous sugar solution. Mass transfer limitations in the zeolite micropores were excluded by comparing Sn-Beta samples with different crystal sizes. Periodic density functional theory (DFT) calculations show that sugar and water molecules compete for adsorption on the active framework Sn centers. Careful solvent selection may thus increase the rate of sugar isomerization. Consistent with this prediction, batch catalytic experiments show that the use of a co-solvent, such as tetrahydrofuran, that strongly interacts with the Sn centers suppresses glucose isomerization. On the other hand, the use of ethanol as cosolvent results in significantly higher isomerization activity in comparison with pure water because of decreased competition with glucose adsorption on zeolitic Sn sites.
AB - The isomerization of 1,3-dihydroxyactone and d-glucose over Sn-Beta zeolite was investigated by in situ 13C NMR spectroscopy. The conversion rate at room temperature is higher when the zeolite is dehydrated before exposure to the aqueous sugar solution. Mass transfer limitations in the zeolite micropores were excluded by comparing Sn-Beta samples with different crystal sizes. Periodic density functional theory (DFT) calculations show that sugar and water molecules compete for adsorption on the active framework Sn centers. Careful solvent selection may thus increase the rate of sugar isomerization. Consistent with this prediction, batch catalytic experiments show that the use of a co-solvent, such as tetrahydrofuran, that strongly interacts with the Sn centers suppresses glucose isomerization. On the other hand, the use of ethanol as cosolvent results in significantly higher isomerization activity in comparison with pure water because of decreased competition with glucose adsorption on zeolitic Sn sites.
U2 - 10.1002/cssc.201600800
DO - 10.1002/cssc.201600800
M3 - Article
C2 - 27791334
SN - 1864-5631
VL - 9
SP - 3145
EP - 3149
JO - ChemSusChem
JF - ChemSusChem
IS - 22
ER -