Heterogeneous Selective Oxidation Catalysts Based on Coordination Polymer MIL-101 and Transition Metal-Substituted Polyoxometalates
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Journal of Catalysis
ISSN: 0021-9517
, E-ISSN: 1090-2694
|
| Output data |
Year: 2008,
Volume: 257,
Number: 2,
Pages: 315-323
Pages count
: 9
DOI:
10.1016/j.jcat.2008.05.014
|
| Tags |
Alkene, Co(II), Composite materials, Hydrogen peroxide, Metal-organic framework, MIL-101, Molecular oxygen, Selective oxidation, Supported polyoxometalate, Ti(IV) |
| Authors |
Maksimchuk N.V.
1
,
Timofeeva M.N.
1
,
Melgunov M.S.
1
,
Shmakov A.N.
1
,
Chesalov Yu.A.
1
,
Dybtsev D.N.
2
,
Fedin V.P.
2
,
Kholdeeva O.A.
1
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
|
| 2 |
Nikolaev Institute of Inorganic Chemistry, Prospekt Akademika Lavrentieva 3, Novosibirsk 630090, Russia
|
|
Funding (1)
|
1
|
Russian Foundation for Basic Research
|
05-03-34760
|
Titanium- and cobalt-monosubstituted Keggin heteropolyanions, [PW11CoO39]5− and [PW11TiO40]5−, were electrostatically bound to the chromium terephthalate polymer matrix MIL-101. The MIL-supported polyoxometalate (POM) catalysts were characterized by elemental analysis, XRD, N2 adsorption, and FT-IR-spectroscopy. The catalytic performance of both MIL-101 and the novel composite materials M-POM/MIL-101 was assessed in the oxidation of three representative alkenes—α-pinene, caryophyllene, and cyclohexene—using molecular oxygen and aqueous hydrogen peroxide as oxidants. Ti-POM/MIL-101 demonstrated fairly good catalytic activity and selectivity in α-pinene allylic oxidation and caryophyllene epoxidation with hydrogen peroxide, whereas Co-POM/MIL-101 catalyzed α-pinene allylic oxidation by molecular oxygen. Both composite materials are stable to POM leaching, behave as true heterogeneous catalysts, and can be used repeatedly without sustaining a loss of activity and selectivity in oxidations with O2 and H2O2, provided that rather mild reaction conditions (T < 50 °C, [H2O2] < 0.2 M) are used with the latter oxidant.