Nickel(ii) oxide surface-modified titanium(iv) dioxide as a visible-light-active photocatalyst

Jin, Qiliang; Ikeda, T.; Fujishima, Musashi; Tada, Hiroaki

doi:10.1039/c1cc13096j

Cited by 58 publications

(59 citation statements)

References 23 publications

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“…Similar shifts in the VB edge for other metal oxide-nanocluster modified TiO 2 are explained on the basis of the formation of new VB states coming from the oxide nanocluster. [17][18][19][20][21] This interfacial electron transfer causes efficient charge carrier separation contributing to the increases in the photocatalytic activities and the reduction in the TiO 2 Figure 12. Atomic structure, adsorption energy in eV and Ti 3d and Cu 3d projected electronic density of states (PEDOS) for anatase TiO2 modified with CuO, Cu2O2 and Cu4O4 clusters Figure 11.…”

Section: Resultsmentioning

confidence: 99%

“…We have recently reported that FeO x and NiO cluster-surface modified TiO 2 prepared by the chemisorption-calcination cycle (CCC) technique shows high photocatalytic activities under illumination of visible-and UV-light. [17][18][19][20][21] In both the systems, strong dependence of the photocatalytic activity on the loading amount of the clusters is observed, [17][18][19][20][21] but the reason has not been fully understood.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, visible-light activation of TiO 2 has been achieved by metal halide-and metal ion-grafting [11][12][13][14][15][16] and the surface modification with metal oxide clusters. [17][18][19][20][21][22][23][24] Among them, Cu 2+ ion and CuO have attracted much interest as a promising surface modifier. [25][26][27][28][29][30][31][32] Interestingly, Irie et al have shown that Cu 2+ -grafted TiO 2 (Cu 2+ /TiO 2 ) prepared by the impregnation method has oxidation ability sufficient for completely decomposing 2-propanol under visible-light irradiation.…”

Section: Introductionmentioning

confidence: 99%

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Loading Effect in Copper(II) Oxide Cluster-Surface-Modified Titanium(IV) Oxide on Visible- and UV-Light Activities

et al. 2013

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Cu(acac) 2 is chemisorbed on TiO 2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti−OH groups without elimination of the acac ligand. Post-heating of the Cu(acac) 2 -adsorbed TiO 2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO 2 ). The copper loading amount (Γ/ Cu ions nm −2 ) is controlled in a wide range by the Cu(acac) 2 concentration and the chemisorption−calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO 2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO 2 , which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O 2 . First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO 2 . These results suggest that visible-light excitation of CuO/TiO 2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O 2 to achieve the compatibility of high levels of visible and UV-light activities.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Loading Effect in Copper(II) Oxide Cluster-Surface-Modified Titanium(IV) Oxide on Visible- and UV-Light Activities

et al. 2013

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“…Recently, we have shown that the surface modification of anatase and anatase/rutile TiO 2 , having the highest level of UV-light activity among the commercial ones, with iron oxide [31] and nickel oxide clusters [32] by the chemisorptioncalcination cycle (CCC) technique yields a high level of visiblelight activity and a concomitant increase in the UV-light activity. In contrast, the surface modification by molecular SnO 2 affords no visible-light activity, while the UV-light activity does increase.…”

Section: Introductionmentioning

confidence: 99%

Molecular Metal Oxide Cluster-Surface Modified Titanium(IV) Dioxide Photocatalysts

Nolan¹,

Iwaszuk²,

Tada³

2012

Aust. J. Chem.

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The surface modification of TiO 2 with molecular sized metal oxide clusters has recently been shown to be a promising approach for providing TiO 2 with visible-light activity and/or improved UV activity. This short review summarizes the effects of the surface modification of TiO 2 with the oxides of iron and tin selected from d-and p-blocks, respectively, on the photocatalytic activity. Fe(acac) 3 and [Sn(acac) 2 ]Cl 2 chemisorption on the TiO 2 surface occurs by ligand-exchange and ion-exchange, respectively. Taking advantage of the strong adsorption, we formed extremely small metal oxide clusters on TiO 2 by the chemisorption-calcination cycle (CCC) technique with their loading amount strictly controlled. The iron oxide surface modification of P-25 (anatase/rutile ¼ 4 : 1, w/w, Degussa) gives rise to a high level of visible-light activity and a concomitant increase in the UV-light activity for the degradation of model organic pollutants. On the other hand, only the UV-light activity is increased by the tin oxide surface modification of ST-01 (anatase, Ishihara Sangyo). This striking difference can be rationalized on the basis of the material characterization and DFT calculations, which show that FeO x surface modification of rutile leads to visible-light activity, while SnO 2 -modified anatase enhances only the UV-light activity. We propose the mechanisms behind the FeO x and SnO 2 surface modification, where the surface-to-bulk and bulk-to-surface interfacial electron transfer are taken into account in the former and the latter, respectively.

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“…5C). It has been demonstrated that the surface modification of TiO 2 by a certain amount of Ni(OH) 2 /NiO clusters may enhance the photocatalytic activity of TiO 2 , but the excess loading can result in the reduction of the photocatalytic activity [42,43]. In the present investigation, the loading of a large amount of Ni(OH) 2 in the intervals of the TiO 2 nanorods is responsible for decrease in the photocatalytic activity of the composite film electrode.…”

Section: Resultsmentioning

confidence: 75%

Enhanced energy storage of a UV-irradiated three-dimensional nanostructured TiO2–Ni(OH)2 composite film and its electrochemical discharge in the dark

Zhang¹,

Xu²,

Wang³

et al. 2012

Journal of Electroanalytical Chemistry

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Nickel(ii) oxide surface-modified titanium(iv) dioxide as a visible-light-active photocatalyst

Cited by 58 publications

References 23 publications

Loading Effect in Copper(II) Oxide Cluster-Surface-Modified Titanium(IV) Oxide on Visible- and UV-Light Activities

Loading Effect in Copper(II) Oxide Cluster-Surface-Modified Titanium(IV) Oxide on Visible- and UV-Light Activities

Molecular Metal Oxide Cluster-Surface Modified Titanium(IV) Dioxide Photocatalysts

Enhanced energy storage of a UV-irradiated three-dimensional nanostructured TiO2–Ni(OH)2 composite film and its electrochemical discharge in the dark

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