Nano cerium oxides are efficient photocatalysts for pollutants degradation with highly dispersed Ce(III) ions as the sug-gested active species to promote the reaction, while Ce(IV) species do not behave as a catalyst. In this paper, to understand the mechanism of Ce-based photocatalysts, we studied the comparison of simple cerium ions, Ce(III) and Ce(IV) in aqueous solution for organic pollutants degradation under UV irradiation. Orange II (AOII), methyl orange, andp-nitrophenol were selected as the target pollutants. The formation and contribution of reactive oxygen species, the kinetics of Ce(IV) photoreduction and Ce(III) photooxida-tion, and the influence of solution pH were investigated in detail. It was found that at low pH Ce(IV) ions showed a higher activity for hydroxyl radicals production and AOII degradation than Ce(III) ions, which could be attributed to its fast reduction rate to Ce(III). However, its activity dramatically decreased when solution pH increased, and was also strongly influenced by the type of pollutants; while Ce(III) exhibited high degradation efficiency of all the tested pollutants over a wide pH range.
参考文献
[1] | Hernandez-Alonso M D;Hungria A B;Martinez-Arias A;Fernandez-Garcia M, Coronado J M, Conesa J C, Soria J .EPR study of the photoassisted formation of radicals on CeO2 nanoparticles employed for toluene photooxidation[J].Appl Catal,B:Environ,2004,50:167. |
[2] | Robinson J R;Carroll P J;Walsh P J;Schelter E J .The impact of ligand reorganization on cerium(III)oxidation chemistry[J].ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2012,51:10159. |
[3] | Castano C E;O'Keefe M J;Fahrenholtz W G .Photo-as-sisted reduction in nanostructured cerium-based coatings[J].Scripta Materialia,2013,69:489. |
[4] | Ji P F;Zhang J L;Chen F;Anpo M .Ordered mesoporous CeO2synthesized by nanocasting from cubic Ia3d mesoporous MCM-48 silica:formation,characterization and photocatalytic activity[J].J Phys Chem C,2008,112:17809. |
[5] | Wang Y G;Li B;Zhang C L;Cui L F, Kang S F, Li X, Zhou L H .Ordered mesoporous CeO2-TiO2 composites:Highly efficient photocatalysts for the reduction of CO2 with H2O under simulated solar irradiation[J].Appl Catal,B:Environ,2013,130-131:227. |
[6] | Wang Y G;Wang F;Chen Y T;Zhang D F, Li B, Kang S F, Li X, Cui L F .Enhanced photocatalytic performance of ordered mesoporous Fe-doped CeO2 catalysts for the re-duction of CO2 with H2O under simulated solar irradiation[J].Appl Catal,B:Environ,2014,147:602. |
[7] | Valente J S;Tzompantzi F;Prince J .Highly efficient photocatalytic elimination of phenol and chlorinated phe-nols by CeO2/MgAl layered double hydroxides[J].Appl Catal,B:Environ,2011,102:276. |
[8] | Ji P F;Zhang J L;Chen F;Anpo M .Study of adsorption and degradation of acid orange 7 on the surface of CeO2 under visible light irradiation[J].Appl Catal,B:Environ,2009,85:148. |
[9] | Pavel J;Pavel K;Martin K;Vaclav S Tomas M G Marek D Martin S Jakab E Vora P Lubos V .Cerium dioxide as a new reactive sorben for fast degradation of parathion methyl and some other organophosphates[J].Journal of Rare Earths,2014,32:360. |
[10] | Reddy J K;Kumari V D;Subrahmanyam M .Ce dispersed Al-MCM-41:A photocombinate for phenol degradation activity[J].Catalysis Letters,2008,123:301. |
[11] | Yuliati L;Hamajima T;Hattori T;Yoshida H .Ce(III)spe-cies supported zeolites as novel photocatalysts for hydro-gen production from water[J].Chemistry Communications,2005,38:4824. |
[12] | Ji P F;Wang L Z;Chen F;Zhang J L .Ce3+-centric organic pollutant elimination by CeO2 in the presence of H2O2[J].Chem Cat Chem,2010,2:1552. |
[13] | Ruan X C;Zhong H;Cao W B;Zeng Q F Li X X Xu A H .Photocatalytic degradation of organic pollutants by simple cerium(III)salt[J].CATALYSIS COMMUNICATIONS,2013,40:76. |
[14] | Zhong H;Cao W B;Xiong Z D;Xia D S Zeng Q F Xu A H .The property and mechanism of photo catalytic degra-dation of alizarin green by ceriums[J].Chin J Environ Eng (in Chin ),2014,8(2):448. |
[15] | Simon A;Ballai C;Lente G;Fabian I .Structure-reactivity relationships and substituent effect additivity in the aque-ous oxidation of chlorophenols by cerium(IV)[J].New Journal of Chemistry,2011,35:235. |
[16] | Xu A H;Li X X;Ye S;Yin G C, Zeng Q F .Catalyzed oxi-dative degradation of methylene blue byin situ generated cobalt(II)-bicarbonate complexes with hydrogen peroxide[J].Appl Catal,B:Environ,2011,102:37. |
[17] | Li X X;Shi W;Cheng Q;Huang L H, Wei M Y, Cheng L, Zeng Q F, Xu A H .Catalytic activation of dioxygen to hydroxyl radical and efficient oxidation of o-aminophenol by cobalt(II)ions in bicarbonate aqueous solution[J].Appl Catal,A:Gen,2014,475:297. |
[18] | Bouchaud B;Balmain J;Bonnet G;Pedraza F .pH-distri-bution of cerium species in aqueous systems[J].Journal of Rare Earths,2012,30:559. |
[19] | Pouretedal H R;Kadkhodaie A .Synthetic CeO2 nanoparti-cle catalysis of methylene blue photodegradation:kinetics and mechanism[J].Chinese Journal of Catalysis,2010,31:1328. |
[20] | Naganuma T;Traversa E .Stability of the Ce3+ valence state in cerium oxide nanoparticle layers[J].Nanoscale,2012,4:4950. |
[21] | Park P W;Ledford J S .Effect of crystallinity on the photoreduction of cerium oxide:a study of CeO2 and Ce/Al2O3 catalysts[J].LANGMUIR,1996,12:1794. |
[22] | Robinson J R;Gordon Z;Booth C H;Carroll P J Walsh P J Schelter E J .Tuning reactivity and electronic properties through ligand reorganization within a cerium heterobi-metallic framework[J].Journal of the American Chemical Society,2013,135:19016. |
[23] | Bogart, J.A.;Lewis, A.J.;Medling, S.A.;Piro, N.A.;Carroll, P.J.;Booth, C.H.;Schelter, E.J. .Homoleptic cerium(III) and cerium(IV) nitroxide complexes: Significant stabilization of the 4+ oxidation state[J].Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics,2013(19):11600-11607. |
[24] | Radaki S;Giannotti C .Photochemical reduction and oxi-dation of cerium(IV)porphyrin sandwich complexes[J].ACTA PHYSICA POLONICA A,1996,90:385. |
[25] | Beck S M;Brus L E .Transient Raman scattering study of the initial semiquinone radical kinetics following photoly-sis of aqueous benzoquinone and hydroquinone[J].Journal of the American Chemical Society,1982,104:4789. |
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