Applied Catalysis A: General 397 (2011) 121126

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Gold nanoparticles supported on cerium(IV) oxide powder for mineralization of organic acids in aqueous suspensions under irradiation of visible light of = 530 nm
Hiroshi Kominami , Atsuhiro Tanaka, Keiji Hashimoto
Department of Applied Chemistry, Faculty of Science and Engineering, Kinki University, Kowakae, Higashiosaka, Osaka 577-8502, Japan

a r t i c l e

i n f o

a b s t r a c t
Gold (Au) nanoparticles supported on cerium(IV) oxide (CeO2 ) were prepared by the photodeposition method. These samples showed strong absorption at around 550 nm due to localized surface plasmon resonance (LSPR) of Au. These Au/CeO2 samples were used for mineralization of organic acids (formic acid, oxalic acid and acetic acid) in the aqueous suspensions under irradiation of visible light (>ca. 520 nm) and three acids were stoichiometrically decomposed to carbon dioxide. Apparent activation energy for mineralization of formic acid was very small (2.4 kJ mol1 ) compared with those by thermocatalytic reactions, and the action spectrum was in good agreement with the photoabsorption spectrum, indicating that the rate-determining step in mineralization of organic acids in the irradiated Au/CeO2 system was different from the thermal activation process and that this mineralization involved a photoinduced step by LSPR of Au supported on CeO2 . When a green light-emitting diode (center wavelength = 530 nm) was used as the light source of visible light, mineralization of formic acid also occurred. Apparent quantum efciency of formic acid mineralization increased with decrease in the intensity of the green light and reached 4.7% at 0.4 mW cm2 . 2011 Elsevier B.V. All rights reserved.

Article history: Received 31 December 2010 Received in revised form 17 February 2011 Accepted 19 February 2011 Available online 24 February 2011 Keywords: Photocatalyst Gold nanoparticles Cerium(IV) oxide Mineralization of organic acids Visible light Localized surface plasmon resonance

1. Introduction Many efforts have been devoted to synthesis of photocatalysts that respond to visible light. To the best of our knowledge, these photocatalysts can be roughly classied into four types. The rst type is TiO2 doped with various elements such as nitrogen [1,2], sulfur [3] and transition metals [4]. In the two former cases, the energy levels of nitrogen and sulfur were inserted in the forbidden band of TiO2 , resulting in response to visible light. The second type is a photocatalyst having a narrow band-gap loaded with a co-catalyst. Recently, Abe et al. [5] and Sayama and co-workers [6] reported that platinum- and palladium-loaded tungsten(VI) oxide (WO3 ) exhibited a high level of photocatalytic activity for decomposition of organic compounds under irradiation of visible light. The third and fourth types are semiconductors modied with copper ions (Cu2+ ) utilizing interface charge transfer (IFCT) [7] and TiO2 samples modied with an inorganic sensitizer such as platinum(IV) and rhodium(III) chlorides [814]. The third and fourth types of photocatalysts have various good properties such as high activity, excellent light absorption and high stability because of the varieties of semiconductors, metal ions and sensitizers. Most

Corresponding author. Tel.: +81 6 6721 2332; fax: +81 6 6727 2024. E-mail address: hiro@apch.kindai.ac (H. Kominami). 0926-860X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2011.02.029

of the visible light-responding photocatalysts such as doped and modied TiO2 [3] and tungsten oxide with co-catalysts [13] work under irradiation of light of which the wavelength is shorter than about 480 nm. Therefore, development of photocatalysts working under irradiation of light of which the wavelength is larger than about 480 nm is important in order to utilize solar energy efciently. In our previous communication [15], we briey reported a new application of CeO2 as a photocatalytic material, i.e., an excellent supporting material of gold (Au) nanoparticles inducing strong localized surface plasmon resonance (LSPR) of Au at around 550 nm [1618]. Kowalska et al. [17,18] observed photoinduced oxidation of 2-propanol over Au/TiO2 under visible light irradiation and proposed the following reaction mechanism: (1) Incident photons are absorbed by Au particles through their LSPR excitation, (2) electrons may be injected from Au particles into the conduction band of TiO2 , and (3) the resultant electron-decient Au could oxidize 2-propanol to be recovered to the original metallic state. In this paper, we investigated photocatalysis of Au/CeO2 in detail to further expand of the possibility of Au/CeO2 and we found that various organic acids were stoichiometrically decomposed to carbon dioxide under irradiation of visible light. Since organic acids are observed as one of intermediates in various processes for degradation of organic compounds in aqueous solutions, the mineralization of organic acids is important for total mineralization of organic compounds.

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2. Experimental 2.1. Preparation of Au/CeO2 Loading of Au on CeO2 was performed by the photodeposition method. Commercial CeO2 powder (Nanotech, 47 m2 g1 ) having a cubic structure was supplied by Kanto Chemical. The CeO2 powder (198 mg) was suspended in water (10 cm3 ) in a test tube and the test tube was sealed with a rubber septum under argon (Ar). Aqueous solutions of citric acid (30 mol) and tetrachloroauric acid (as 2 mg Au) were injected into the sealed test tube and then photoirradiated at > 300 nm by a 400-W high-pressure mercury arc (Eiko-sha, Osaka) under Ar with magnetic stirring in a water bath continuously kept at 298 K. The Au source was reduced by photogenerated electrons, and Au metal was deposited on CeO2 particles, resulting in the formation of Au/CeO2 . Analysis of the liquid phase after the photodeposition revealed that the Au source was almost completely (>99.9%) deposited as Au metal on the CeO2 particles. The resultant powder was washed repeatedly with distilled water and then dried at 310 K overnight under air.

2 300

(b)
1

200

100

(a)
0 400 500 600 0 700

Wavelength / nm
Fig. 1. Absorption spectra of (a) CeO2 and (b) 1 wt% Au/CeO2 , and visible light irradiated to reaction systems (formic acid in aqueous suspensions of various powders) from a Xe lamp with an O-54 cut-lter (solid line) and green LED (broken line).

2.2. Characterization Diffuse reectance spectra were obtained with a UVvisible spectrometer (UV-2400, Shimadzu, Kyoto) equipped with a diffuse reectance measurement unit (ISR-2000, Shimadzu) and recorded after KubelkaMunk analysis. Powder X-ray diffraction (XRD) (Multi Flex, Rigaku, Tokyo) was measured using CuK radiation and a carbon monochromator and revealed that the sample consisted of cubic phase of CeO2 (ICDD No. 43-1002). In the XRD pattern of the Au/CeO2 sample with 1 wt% Au, peaks attributed to Au were not observed, indicating that Au was nely dispersed on the surface of CeO2 . The crystallite size of CeO2 was calculated to be 22 nm from the half-height width of the 1 1 1 diffraction peak of the cubic phase of CeO2 using the Scherrer equation; the value of the shape factor, K, was arbitrarily taken to be 0.9. The morphology of Au/CeO2 was observed under a JEOL JEM-3010 transmission electron microscope (TEM) operated at 300 kV in the Joint Research Center of Kinki University and, in the TEM photograph of 1 wt% Au/CeO2 , ne Au particles of 510 nm in size were clearly observed (Fig. S1).

3. Results and discussion 3.1. Preparation of Au/CeO2 and mineralization of formic acid in an aqueous suspension of Au/CeO2 under visible light irradiation Fig. 1 shows absorption spectra of CeO2 and 1 wt% Au/CeO2 . Bare sample, CeO2 , exhibited strong photoabsorption at < 410 nm due to the band-gap excitation. In the spectrum of Au/CeO2 , additional photoabsorption was observed at around 550 nm. Kowalska et al. [17,18] reported that photoabsorption due to LSPR of Au particles supported on TiO2 was observed at around 550 nm. Therefore, photoabsorption observed in Au/CeO2 was attributed to LSPR of the supported Au particles. Fig. 2 shows the time course of evolution of CO2 from aqueous solutions of formic acid in the presence of 1 wt% Au/CeO2 under irradiation of visible light from a Xe lamp with an O-54 cut-lter at 298 K. Visible light irradiated to the reaction system is shown
100

2.3. Mineralization of organic acid in an aqueous suspension of Au/CeO2 under irradiation of visible light The dried Au/CeO2 powder (50 mg) was suspended in distilled water (5 cm3 ), bubbled with oxygen (O2 ), and sealed with a rubber septum. Organic acid (formic acid, oxalic acid or acetic acid, 100 mol-C) was injected into the suspension and then irradiated with visible light of a 500 W xenon (Xe) lamp (Ushio, Tokyo) ltered with an O-54 cut-lter (AGC Techno Glass) with magnetic stirring in a water bath continuously kept at 298 K. The amount of carbon dioxide (CO2 ) in the gas phases of reaction mixtures was measured using a gas chromatograph (GC-8A, Shimadzu) equipped with Porapak QS columns. In some experiments, a green light-emitting diode (HDMS8G, Hayashi Watch Works, Tokyo, maximum energy at 530 nm, designated green LED hereafter) was also used to evaluate activity of formic acid mineralization under irradiation of visible light coming from a light source other than the Xe lamp. In some condition, the brightness and light intensity on the surface of the test tube were 8000 lx and 1.7 mW cm2 , respectively. To obtain an action spectrum, the full arc from the Xe lamp was monochromated using SM-100 (Bunkoukeiki, Tokyo). Spectra and light intensity of the green LED and Xe lamp (ltered and monochromated) were determined using a spectroradiometer USR-45D (Ushio, Tokyo).

80

CO2 evolved / mol

60

40

20

0 0 5 10 15 20 25 30

Time / h
Fig. 2. Time courses of evolution of CO2 from aqueous solutions of formic acid in the presence of 1 wt% Au/CeO2 under irradiation of visible light (circles), in the absence of 1 wt% Au/CeO2 under irradiation of visible light (squares), in the presence of bare CeO2 under irradiation of visible light (triangles), in the presence of 1 wt% Au/CeO2 in the dark (diamonds), and in the presence of 1 wt% Au/CeO2 under irradiation of visible light in the absence of oxygen (crosses).

Light intensity / W cm nm-1

KM function

-2

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123

Evacuation and injection of formic acid

(d) KM function
60

(e)

(c)

CO2 evolved / mol

40

(b)
0 400

(a)
500 600 700

20

Wavelength / nm
Fig. 4. Absorption spectra of (a) CeO2 , (b) 0.1 wt% Au/CeO2 , (c) 0.5 wt% Au/CeO2 , (d) 1 wt% Au/CeO2 , and (e) 2 wt% Au/CeO2 .

0 0 5 10 15 20 25

Time / h
Fig. 3. Time course of evolution of CO2 from formic acid (60 mol) in an aqueous suspension of 1 wt% Au/CeO2 under irradiation of visible light. After 12-h irradiation and evacuation, additional formic acid (60 mol) was injected and the suspension was irradiated again.

in Fig. 1. Just after irradiation of visible light, CO2 was evolved in the presence of 1 wt% Au/CeO2 , and formation of CO2 continued linearly with irradiation time in the early stage within 6 h. After irradiation for 28 h, CO2 evolution was almost saturated at around 100 mol, which corresponded to the initial amount of formic acid (100 mol), indicating that formic acid was almost completely decomposed to CO2 (Eq. (1)) under visible light irradiation in the presence of 1 wt%Au/CeO2 . HCOOH + 1/2O2 = CO2 + H2 O (1)

no thermocatalytic or photocatalytic activity toward formic acid under visible light irradiation at 298 K. From results for support and unsupported Au particles, it can be concluded that metal oxide supporting Au particles played important roles such as stabilization of Au particles and adsorption of formic acid in photoinduced mineralization of formic acid under visible light. Fig. 4 shows the effect of Au loading on the absorption due to LSPR of Au loaded on CeO2 . The intensity increased with increase in Au loading and was almost saturated at 1 wt% loading. These Au/CeO2 samples were used for mineralization of formic acid under irradiation of visible light from a Xe lamp with an O-54 cut-lter and effect of the amount of Au loading on the rate of evolution of CO2 was examined. The amount of CO2 increased linearly with time of photoirradiation in all Au/CeO2 samples (Fig. S2) and the effect of amount of Au loading on the rate of CO2 evolution is shown in Fig. 5. The reaction rate increased with increase in Au loading and was almost saturated at 1 wt% loading. This tendency was the same
6

To evaluate the stability of 1 wt% Au/CeO2 in mineralization of formic acid, 1 wt%Au/CeO2 was used repeatedly, indicating that it continuously decomposed formic acid under visible light irradiation without losing its activity (Fig. 3). Fig. 2 also shows results of four blank reactions: (1) in the absence of 1 wt% Au/CeO2 , (2) in the absence of Au (photocatalytic reaction induced by bare CeO2 ), (3) in the absence of visible light (dark reaction), and (4) in the absence of O2 . In the four blank tests operated at 293 K, no decomposition of formic acid was observed. The results of the rst test indicate that photochemical reaction of formic acid under irradiation of visible light did not occur. The results of the second test indicate that bare CeO2 shows neither photocatalytic activity under irradiation of visible light from an O-54-ltered Xe lamp nor thermocatalytic activity toward formic acid. From the results of the third test, it was concluded that Au/CeO2 did not exhibit thermocatalysis for decomposition of formic acid at 298 K. The results of the fourth test suggest that O2 played an important role probably as an electron scavenger in the photoinduced mineralization of formic acid in the presence of Au/CeO2 under irradiation of visible light. In addition, formic acid was not decomposed at 298 K in an aqueous suspension of ne Au particles prepared by reduction of tetrachloroauric acid using sodium borohydride (NaBH4 ), although the results are not shown in Fig. 2, indicating that unsupported Au particles showed

Reaction rate / mol h-1

0 0 0.5 1 1.5 2

Amount of Au / wt%
Fig. 5. Effect of the amount of Au loading on the rate of evolution of CO2 from aqueous solutions of formic acid in the presence of Au/CeO2 under irradiation of visible light.

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100

20

CO2 evolved / mol

80

15

CO2 evolved / mol

10

60

40 0 0 20 2 4 6 8 10 12 14 16

Time / h
Fig. 7. Time courses of evolution of CO2 from aqueous solutions of formic acid in the presence of 1 wt% Au/CeO2 under various conditions.

0 0 10 20 30 40

Time / h
Fig. 6. Time courses of evolution of CO2 from formic acid (100 mol: circles), oxalic acid (50 mol: squares) and acetic acid (50 mol: triangles) in an aqueous suspension of 1 wt% Au/CeO2 under irradiation of visible light.

alytic reactions [1921]. Therefore, these results indicate that the rate-determining step of mineralization in the present irradiated Au/CeO2 system is different from the oxygen activation process catalyzed by supported metals such as platinum shown above. 3.3. Effects of wavelength and intensity of visible light

as that of photoabsorption due to LSPR of Au and linear correlation was observed between the reaction rate and photoabsorption at 550 nm (Fig. S3), suggesting that the reaction rate was determined by photoabsorption due to LSPR of Au. To elucidate the applicability of Au/CeO2 , mineralization of oxalic acid and acetic acid in aqueous solutions was examined under irradiation of visible light from a Xe lamp with an O-54 cutlter at 298 K. Fig. 6 shows the time courses of evolution of CO2 from aqueous solutions of formic acid (100 mol), oxalic acid (50 mol) and acetic acid (50 mol) in the presence of 1 wt% Au/CeO2 . In all cases, CO2 was evolved just after irradiation of visible light. The amount of CO2 increased linearly with irradiation time just before saturation at 100 mol, which corresponded to the initial amount of carbon (100 mol). These results show that oxalic acid and acetic acid were almost completely decomposed to CO2 as well as formic acid under visible light irradiation in the presence of 1 wt%Au/CeO2 . 3.2. Effect of reaction temperature Mineralization of formic acid in aqueous suspensions of Au/CeO2 was carried out at various temperatures under irradiation of visible light from a Xe lamp with an O-54 cut-lter to evaluate the effect of reaction temperature and to determine the apparent activation energy of this reaction system. Fig. 7 shows the time course of evolution of CO2 from aqueous solutions of formic acid in the presence of 1 wt%Au/CeO2 under irradiation of visible light in the temperature range between 288 and 303 K. At all temperatures, CO2 was evolved in the presence of 1 wt% Au/CeO2 , and formation of CO2 continued linearly with irradiation time, indicating that zero-order kinetics was preserved in the temperature range examined in this study. In the case of zero-order kinetics, the reaction rate (slope of the linear plot in Fig. 7) is equal to the reaction rate constant. Therefore, the reaction rate constant (k) at each temperature was determined from Fig. 7, and the Arrhenius plot (logarithm of k vs reciprocal of T) is shown in Fig. 8. A linear correlation was observed in the Arrhenius plot, and apparent activation energy in this reaction system was determined to be 2.4 kJ mol1 from the slope of the plot. This value is much smaller than the values of 24.6, 26.4 and 36 4 kJ mol1 for thermocatalytic wet air oxidation of formic acid over Pt/Al2 O3 , Pt/C and Pt/Cex Zr1x O2 , respectively and the activation of oxygen was the rate-limiting step in these thermocat-

Mineralization of formic acid in an aqueous suspension of 1 wt% Au/CeO2 was carried out at 298 K under irradiation of monochromated visible light from a Xe lamp with light width of 5 nm to obtain an action spectrum in this reaction system. Assuming that one photon is required for formation of one CO2 molecule by mineralization of formic acid, apparent quantum efciency (AQE) at each centered wavelength of light was calculated from the ratio of the amount of CO2 and the amount of photons irradiated, using the following equation: AQE = amount of CO2 100. amount of incident photons

Fig. 9 shows the results. The apparent quantum efciency was in good agreement with the photoabsorption (1 [reectance]) of 1 wt% Au/CeO2 . This result indicates that mineralization of formic acid was induced by photoabsorption due to LRPS of Au supported on CeO2 . Since an LED consumes less energy than that of a uorescent lamp, LED has been preferably used as light sources of photochem-12.2

-12.22

ln k
-12.24 -12.26 0.0033 0.00335 0.0034 0.00345 0.0035

1/T / K -1
Fig. 8. Arrhenius plot (logarithm of k vs reciprocal of T).

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125

85 10

80

1-Reflection / %

6 75 4 70 2

AQE / %

AQE / %

1 65 400 500 600 0 700 0 0 1 2

-2

Wavelength / nm
Fig. 9. Absorption spectrum of 1 wt% Au/CeO2 measured with barium sulfate as a reference (left axis) and action spectrum (circle) in formic acid oxidation (right axis).

Light intensity / mW cm

ical processes in industry and advertisement in commerce because of its low energy consumption. Recently, LEDs have also been used for lighting in ofces in buildings and in living rooms, kitchens and bathrooms in houses because LEDs, especially white LEDs, are now supplied at low cost. As shown in Fig. 1, the photoabsorption property of Au/CeO2 matches the light emission property of a green LED. If Au/CeO2 works effectively under irradiation of light from a green LED, mineralization of organic acid can be attained with low energy consumption. Therefore, mineralization of formic acid in aqueous suspensions of 1 wt% Au/CeO2 was examined under irradiation of light from a green LED with various light intensities (0.41.7 mW cm2 ) at 298 K (Fig. S4). Just after irradiation of green light from the LED, CO2 was evolved in the presence of 1 wt% Au/CeO2 , and formation of CO2 continued linearly with irradiation time in the early stage within 4 h. The light intensity of visible light from the green LED was much smaller than that from the Xe lamp with a lter (ca. one twenty-fth). However, the reaction rate under irradiation of light from the green LED was half of that in the case of the ltered Xe lamp. These results indicate that Au/CeO2 worked effectively even under irradiation of weak green light from the green LED. Apparent quantum efciency under irradiation of green light of an LED was determined to be 2.4% at 1.7 mW cm2 . The effect of intensity of light coming from the green LED on apparent quantum efciency in evolution of CO2 from aqueous solutions of formic acid in the presence of 1 wt%Au/CeO2 is shown in Fig. 10. As expected, apparent quantum efciency increased with decrease in light intensity of the LED and the value nally reached 4.7% at 0.4 mW cm2 , suggesting that Au/CeO2 can be used under irradiation of weak visible light from a solar and articial light source. 3.4. Expected working mechanism Expected working mechanism for mineralization of organic acids in aqueous suspension of Au/CeO2 under irradiation of visible light is shown in Fig. 11. In the previous communication [15], effect of metal oxides supporting Au nanoparticles on mineralization of formic acid was examined and the rate of CO2 formation increased in the order Au/ZrO2 < Au/TiO2 Au/CeO2 . Rapid electron transfer from Au to TiO2 lm under visible light irradiation was observed using femtosecond transient absorption spectroscopy with visible pump and IR probe [22]. Kowalska et al. [17,18] observed photoinduced oxidation of 2-propanol over Au/TiO2 under visible light irradiation and proposed the following reaction mechanism: (1) Incident photons are absorbed by Au particles through their

Fig. 10. Effect of intensity of light coming from a green LED on apparent quantum efciency in evolution of CO2 from aqueous solutions of formic acid in the presence of 1 wt% Au/CeO2 . Original data are shown in Fig. S4.

Fig. 11. Expected working mechanism for mineralization of organic acids in aqueous suspension of Au/CeO2 under irradiation of visible light.

LSPR excitation, (2) electrons may be injected from Au particles into the conduction band of TiO2 , and (3) the resultant electrondecient Au could oxidize 2-propanol to be recovered to the original metallic state. The rst process seems to be one of the important factors controlling the rate of mineralization of formic acid because the series of Au/CeO2 samples exhibited stronger LSPR of Au than did other Au-supporting samples [15]. The potential of the conduction band of metal oxides used in the present study positively shifts in the following order: ZrO2 > TiO2 > CeO2 . Injection of photoexcited electrons into the conduction band of metal oxides becomes easier with lowering of the conduction band of metal oxides. The order in the conduction band potential was in agreement with the order in the reaction rate. We do not have clear evidence for the third processes proposed by Kowalska et al. [17,18]. Injection of electrons into the conduction band may also be a key factor determining the reaction rate although other electron transfers such as direct electron transfer to oxygen may occur. 4. Conclusions Using the photodeposition method, Au nanoparticles were supported on CeO2 . These Au/CeO2 samples showed absorption at around 550 nm due to LSPR of Au. The CeO2 samples investigated

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in this study were excellent supporting materials of Au nanoparticles, inducing strong LSPR of Au, and the new materials, i.e., the Au/CeO2 samples, almost quantitatively decomposed organic acids (formic acid, oxalic acid and acetic acid) to CO2 in the aqueous suspensions under irradiation of visible light (>ca. 520 nm). The small apparent activation energy (2.4 kJ mol1 ) and action spectrum in the mineralization of formic acid indicate that ratedetermining step in mineralization of formic acid in the irradiated Au/CeO2 system was different from the thermal activation process and that this mineralization involved a photoinduced step by LSPR of Au supported on CeO2 . The Au/CeO2 samples mineralized formic acid even under irradiation of green light (center wavelength = 530 nm) from a green light-emitting diode. Apparent quantum efciency of formic acid mineralization increased with decrease in intensity of the green light and reached 4.7% at 0.4 mW cm2 . Acknowledgements This work was partly supported by a fund (Project no. P07020) from the Environmental Technology Development Department of New Energy and Industrial Technology Development Organization (NEDO). One of authors (H.K.) is also grateful for nancial support from the Faculty of Science and Engineering, Kinki University. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.apcata.2011.02.029.

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