In this article we have consolidated our recent studies on anchoring of uranyl groups and encapsulation of highly dispersed nano-particles of α-U3O8 in mesoporous MCM samples. The size of uranium oxide crystallites and the binding of uranyl groups at framework sites of host matrix depended on the preparation method, viz. wet impregnation, exchange of template cations, and the hydrothermal route. These uranium species contributed individually to the catalytic oxidation of organic molecules, such as methanol, toluene and benzyl alcohol; the uranyl groups playing a more important role at lower reaction temperatures. Also, the size and the lattice oxygen of uranium oxide crystallites played a vital role, not only in the lowering of reaction onset temperature but also in deciding the nature and the reactivity of the transient surface species formed during the oxidation of above mentioned organics. For instance, the results of in situ IR spectroscopy experiments have shown that while larger-size U3O8 crystallites help in the growth of certain oxymethylene (–OCH2) and polymerized oxymethylene (–OCH2) n species, adsorption of methanol on smaller size particles helped in the additional formation of formate-type complexes. Thus, a relationship was found between the size of uranium oxide crystallites, the nature of the transient species formed and the catalytic conversion of methanol to form CO2, CO and methane. In addition, the uranyl ions anchored within the pore system of host matrix are found to serve as efficient heterogeneous photocatalysts for the sunlight-assisted deep oxidation of organic molecules in the vapor phase and at room temperature. The reaction mechanisms, accounting for the catalytic properties of occluded UO x species without and in the presence of radiation, are discussed in the light of the above mentioned results.
Similar content being viewed by others
References
P Weiss (2000) Sci. News 157 204
J.J Katz G.T Seaboarg L.R Morss (Eds) (1986) The Chemistry of Actinide Elements Chapman-Hall London
Gmelin Handbook, Uranium Supplement, vol. C5 (1979)
G.C Allen J.A Crofts A.J Griffiths (1976) J. Nuclear Mater. 62 273 Occurrence Handle10.1016/0022-3115(76)90024-6 Occurrence Handle1:CAS:528:DyaE2sXitlyrsA%3D%3D
M.R Castell C Muggelberg G.A.D Briggs D.T Goddard (1976) J. Vac Sci. Technol. B 14 966 Occurrence Handle10.1116/1.589185
C.A Colmenares (1984) Prog. Solid St. Chem. 15 257 Occurrence Handle10.1016/0079-6786(84)90003-7 Occurrence Handle1:CAS:528:DyaL2MXkslKkur4%3D
H Collette V Deremince-Mathieu Z Gabelica J.N Nagy E.G Derouane J.J Verbist (1987) J. Chem. Soc., Faraday Trans. 283 1263
H.W.G Heynen H.S Van Der Baan (1974) J. Catal. 34 167 Occurrence Handle10.1016/0021-9517(74)90025-6 Occurrence Handle1:CAS:528:DyaE2cXkvFSrsb8%3D
R.K Grasselli J.D Burrington D.D Suresh M.S Friedrich M.A.S Hazle (1981) J. Catal. 68 109 Occurrence Handle10.1016/0021-9517(81)90044-0 Occurrence Handle1:CAS:528:DyaL3MXkvFKmur4%3D
(a) F. Nozaki, and K. Ohki, Bull. Chem. Soc. Jpn. 45 (1972) 3473; (b) F. Nozaki, F. Matsukawa and Y. Mano, Bull. Chem. Soc. Jpn. 48 (1975) 2764
(a) H. Madhavaram and H. Idriss, J. Catal. 184 (1999) 553; (b) H. Madhavaram and H. Idriss, J. Catal. 206 (2002) 155; (c) H. Madhavaram, P. Buchanan and H. Idriss, J. Vac. Sci. Technol. A 15 (1997) 1685
(a) G.J. Hutchings, C.S. Heneghan, I.D. Hudson and S.H. Taylor, Nature 384 (1996) 341; (b) C.S. Heneghan, G.J. Hutching, S.R. O’Leary, S.H. Taylor, V.J. Boyd and I.D. Hudson, Catal. Today 54 (1999) 3; (c) S.H. Taylor and S.R. O’Leary, Appl. Catal. B: Enviornmental 25 (2000) 137
M Sarakha M Bolte H.D Burrows (1999) J. Photochem. and Photobio. A: Chemistry 107 101 Occurrence Handle10.1016/S1010-6030(97)00064-6
W.D Wang A Bakac J.H Espenson (1995) Inorg. Chem. 34 6034 Occurrence Handle10.1021/ic00128a014 Occurrence Handle1:CAS:528:DyaK2MXptVeisLg%3D
M.Z Hoffman F Bolletta L Moggi G.L Hug (1989) J. Phys. Chem. 18 219 Occurrence Handle1:CAS:528:DyaL1MXksVGnsbg%3D
S.S Sandhu K.B Kohli A.S Brar (1984) Inorg. Chem. 23 3609 Occurrence Handle10.1021/ic00190a036 Occurrence Handle1:CAS:528:DyaL2cXlvVSqtbw%3D
T.M McCleskey C.J Burns W Tumas (1999) Inorg. Chem. 38 5924 Occurrence Handle10.1021/ic9909126 Occurrence Handle1:CAS:528:DyaK1MXnsFOktbs%3D
H.D Burrows S.J Formosinho M.G Miguel F.P Coelho (1976) Mern. Acad. Ciencias Lisbao (Classe de Ciencias) 19 185
Balzani V. F Bolletta M.T Gandolfi M Maestri (1978) Top. Curr. Chem. 75 1
S.L Suib A Kostapapas D Psaras (1984) J. Am. Chem. Soc. 106 1614 Occurrence Handle10.1021/ja00318a011 Occurrence Handle1:CAS:528:DyaL2cXht1Shu74%3D
S.L Suib K.A Corrado (1985) Inorg. Chem. 24 863 Occurrence Handle10.1021/ic00200a013 Occurrence Handle1:CAS:528:DyaL2MXht1aqt7c%3D
S Dai D.H Metcalf G.D Del Cul L.M Toth (1996) Inorg. Chem. 35 7786 Occurrence Handle10.1021/ic9604066
K Vidya S.E Dapurkar P Selvam S.K Badamali N.M Gupta (2001) Microporous Mesoporous Mater. 50 173 Occurrence Handle10.1016/S1387-1811(01)00445-0 Occurrence Handle1:CAS:528:DC%2BD3MXpt1arur8%3D
K Vidya S.E Dapurkar P Selvam S.K Badamali D Kumar N.M Gupta (2002) J. Mol. Catal. A: Chem. 181 91 Occurrence Handle10.1016/S1381-1169(01)00350-8 Occurrence Handle1:CAS:528:DC%2BD38XhvFOmsrk%3D
D Kuamr S Bera A.K Tripathi G.K Dey N.M Gupta (2003) Microporous Mesoporous Mater. 66 157 Occurrence Handle10.1016/j.micromeso.2003.08.027
S.K Badamali D.P Dutta A.K Tripathi V.K Jain N.M Gupta (2003) Catal. Lett. 85 13 Occurrence Handle10.1023/A:1022104421047 Occurrence Handle1:CAS:528:DC%2BD3sXmsFCqsA%3D%3D
D Kumar V.S Kamble N.M Gupta (2003) Catal. Lett. 88 175 Occurrence Handle10.1023/A:1024065807057 Occurrence Handle1:CAS:528:DC%2BD3sXkt1Kmt70%3D
D Kumar K.T Pillai V Sudershanan G.K Dey N.M Gupta (2003) Chem. Mater. 15 3859 Occurrence Handle10.1021/cm030269s Occurrence Handle1:CAS:528:DC%2BD3sXms1aqt78%3D
D Kumar G.K Dey N.M Gupta (2003) Phys. Chem. Chem.l Phys. 5 5477 Occurrence Handle1:CAS:528:DC%2BD3sXpsVKqt74%3D
D Kumar K Vidya P Selvam G.K Dey N.M Gupta ( 2004) NoChapterTitle A Sharma J Bellare A Sharma (Eds) Advances in Nanoscience and Nanotechnology. NISCAIR Delhi 265–276
D. Kumar S. Varma N.M. Gupta (2004) Catal. Today 93–95 541 Occurrence Handle10.1016/j.cattod.2004.06.002
D. Kumar S. Varma G.K. Dey N.M. Gupta (2004) Microporous Mesoporous Mater 73 181 Occurrence Handle10.1016/j.micromeso.2004.05.010 Occurrence Handle1:CAS:528:DC%2BD2cXmvVOrsrY%3D
K. Vidya V.S. Kamble P. Selvam N.M. Gupta (2004) Appl. Catal. B Environment 54 145 Occurrence Handle10.1016/j.apcatb.2004.07.001 Occurrence Handle1:CAS:528:DC%2BD2cXovVKrurc%3D
K.S.W Sing D.H Everett R.A.W Haul L Moscou R.A Pierotti J Rouquerol T Siemieniewska (1985) J. Pure Appl. Chem. 57 603 Occurrence Handle1:CAS:528:DyaL2MXhvFWrtb4%3D
S.P McGlynn J.K Smith (1961) J. Mol. Spectroscopy 6 164 Occurrence Handle10.1016/0022-2852(61)90237-5 Occurrence Handle1:CAS:528:DyaF3MXhtV2rsb0%3D
B Jeżowska-Trzebiatowska A Bartecki (1962) Spectrochim. Acta 18 799
J.S Beck J.C Vartuli W.J Roth M.E Leonowicz C.T. Kresge K.D. Schmitt C.T.W Chu D.H Olson E.W Sheppard S.B McCullen J.B Higgins J.L Schlenker (1992) J. Am. Chem. Soc. 114 10834 Occurrence Handle10.1021/ja00053a020 Occurrence Handle1:CAS:528:DyaK38Xms1entr8%3D
M Morey A Davidson H Eckert G Stucky (1996) Chem. Mater. 8 486 Occurrence Handle10.1021/cm950397j Occurrence Handle1:CAS:528:DyaK28XlvVCjsA%3D%3D
M Froba R Kohn G Bouffaud et al. (1999) Chem. Mater. 11 2858 Occurrence Handle10.1021/cm991048i
K.M. Reddy, I. Moudrakovski and A. Sayari, J. Chem. Soc. Chem. Commun. (1994) 1059
Z Luan H He W Zhou C.-F Cheng J Klinowski (1995) J. Chem. Soc. Faraday Trans. 91 2955 Occurrence Handle10.1039/ft9959102955 Occurrence Handle1:CAS:528:DyaK2MXnvVOls78%3D
W Zhang M Froba J Wang P.T Tanev J Wong T.J Pinnavaia (1996) J. Am. Chem. Soc. 118 9164 Occurrence Handle10.1021/ja960594z Occurrence Handle1:CAS:528:DyaK28XmtF2itr0%3D
R Drot E Simoni M Alnot J.J Ehrhardt (1998) J. Colloid Interface Sci. 205 410 Occurrence Handle10.1006/jcis.1998.5652 Occurrence Handle1:CAS:528:DyaK1cXmtVSkurY%3D Occurrence Handle9735204
C Lomenech E Simoni R Drot J.J Ehrhardt J Mielczarski (2003) J. Colloid Interface Sci. 261 221 Occurrence Handle10.1016/S0021-9797(03)00101-2 Occurrence Handle1:CAS:528:DC%2BD3sXjtl2rt7s%3D
N Ollier M.J Guittet M.G Soyer G Panczer B Champagnon P Jollivet (2003) Optical Mater. 24 63 Occurrence Handle10.1016/S0925-3467(03)00106-X Occurrence Handle1:CAS:528:DC%2BD3sXnvVekt7k%3D
Z Luan J Xu H He J Klinowski L Kevan (1996) J. Phys. Chem. B 100 19595 Occurrence Handle10.1021/jp962353j Occurrence Handle1:CAS:528:DyaK28XntVaju7w%3D
I.A Fischer A.T Bell (1999) J. Catal. 184 357 Occurrence Handle10.1006/jcat.1999.2420
C Flego A Carati C Perego (2001) Microporous Mesoporous Mater. 44–45 733 Occurrence Handle10.1016/S1387-1811(01)00255-4
G Busca A.S Elmi P Forzatti (1987) J. Phys. Chem. 91 5263 Occurrence Handle10.1021/j100304a026 Occurrence Handle1:CAS:528:DyaL2sXlvFOgsr0%3D
(a) G.J. Millar, C.H. Rochester and K.C. Waugh, J. Chem. Soc. Faraday, Trans. 87 (1991) 2785; (b) G.J. Millar, C.H. Rochester and K.C. Waugh, J. Chem. Soc. Faraday Trans. 87 (1991) 2795
K. Vidya, V.S. Kamble, P. Selvam and N.M. Gupta, Catal. Lett. under publication 98 (2004) 113
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Kumar, D., Gupta, N. An overview of studies on the highly dispersed uranium oxide species occluded within mesoporous MCM-41 and MCM-48 host materials. Catal Surv Asia 9, 35–49 (2005). https://doi.org/10.1007/s10563-005-3336-x
Issue Date:
DOI: https://doi.org/10.1007/s10563-005-3336-x