TY - JOUR

T1 - Isostructural metal-carboxylates MIL-100(M) and MIL-53(M) (M

T2 - V, Al, Fe and Cr) as catalysts for condensation of glycerol with acetone

AU - Timofeeva, Maria N.

AU - Panchenko, Valentina N.

AU - Khan, Nazmul Abedin

AU - Hasan, Zubair

AU - Prosvirin, Igor P.

AU - Tsybulya, Sergey V.

AU - Jhung, Sung Hwa

N1 - Publisher Copyright: © 2016 Elsevier B.V.

PY - 2017/1/5

Y1 - 2017/1/5

N2 - The synthesis of solketal from acetone and glycerol (I) was investigated in the presence of the isostructural MOFs of the families MIL-100(M) and MIL-53(M) (M = V, Al, Fe and Cr) and mixed MIL-53(Al,V) (Al/V – 100/0, 75/25, 50/50, 25/75 and 0/100 atom/atom). The main products were a five-membered solketal (2,2-dimethyl-1,3-dioxane-4-methanol, (II)) and a six-membered acetal (2,2-dimethyl-dioxane-5-ol, (III)). It was demonstrated that the reaction rate and isomer selectivity depend on different parameters such as the type of metal ion, the length of the M-O bond, the rate constant for the exchange of the water molecules from the first coordination sphere of a metal ion and the value of the zero point of the surface charge (pHPZC). Investigation of mixed MIL-53(Al,V) shows that the reaction rate and selectivity towards (II) increase with increasing V3+ content in MIL-53(Al,V). V-containing MOFs possess a high activity and selectivity at 25 °C. The efficiencies of MIL-100(V) and MIL-47(V) were higher than those of H2SO4, SnCl2 and p-toluenesulfonic acid at 25 °C. The MIL-100(V) catalyst showed good reusability for 4 catalyst recycles.

AB - The synthesis of solketal from acetone and glycerol (I) was investigated in the presence of the isostructural MOFs of the families MIL-100(M) and MIL-53(M) (M = V, Al, Fe and Cr) and mixed MIL-53(Al,V) (Al/V – 100/0, 75/25, 50/50, 25/75 and 0/100 atom/atom). The main products were a five-membered solketal (2,2-dimethyl-1,3-dioxane-4-methanol, (II)) and a six-membered acetal (2,2-dimethyl-dioxane-5-ol, (III)). It was demonstrated that the reaction rate and isomer selectivity depend on different parameters such as the type of metal ion, the length of the M-O bond, the rate constant for the exchange of the water molecules from the first coordination sphere of a metal ion and the value of the zero point of the surface charge (pHPZC). Investigation of mixed MIL-53(Al,V) shows that the reaction rate and selectivity towards (II) increase with increasing V3+ content in MIL-53(Al,V). V-containing MOFs possess a high activity and selectivity at 25 °C. The efficiencies of MIL-100(V) and MIL-47(V) were higher than those of H2SO4, SnCl2 and p-toluenesulfonic acid at 25 °C. The MIL-100(V) catalyst showed good reusability for 4 catalyst recycles.

KW - Acetone

KW - Glycerol

KW - Metal-organic frameworks

KW - MIL-100

KW - MIL-53

KW - Solketal

KW - OXIDATION

KW - SOLKETAL

KW - ADSORPTION

KW - ACID SITES

KW - MIXED-METAL

KW - CHROMIUM(III)

KW - FUEL

KW - ACETALIZATION

KW - ORGANIC FRAMEWORKS

KW - WATER

UR - http://www.scopus.com/inward/record.url?scp=84995577366&partnerID=8YFLogxK

U2 - 10.1016/j.apcata.2016.11.006

DO - 10.1016/j.apcata.2016.11.006

M3 - Article

AN - SCOPUS:84995577366

VL - 529

SP - 167

EP - 174

JO - Applied Catalysis A: General

JF - Applied Catalysis A: General

SN - 0926-860X

ER -