Journal of CO2 Utilization 1 (2013) 817

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Journal of CO2 Utilization

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

Review

Photocatalytic reduction of CO2 with H2O on highly dispersed Ti-oxide catalysts as a model of articial photosynthesis
Masakazu Anpo *
Research Organization for the 21st Century, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai, Osaka 599-8531, Japan

A R T I C L E I N F O

A B S T R A C T

Article history: Received 30 January 2013 Received in revised form 23 March 2013 Accepted 23 March 2013 Available online 29 May 2013 Keywords: Photocatalysis Reduction of CO2 with H2O Photosynthesis Sunlight

The results of investigations on the photocatalytic reduction of CO2 with H2O to produce CH4, CH3OH and O2, articial photosynthesis, obtained on the highly active tetrahadrally-coordinated Ti-oxide species with TiO4 units constructed within micro- and meso-porous framework structures are summarized. The yields of these products were found to change remarkably depending on the reaction conditions such as the ratio of H2O/CO2 ratio. Advanced metal ion-implantation method to modify the catalysts to enable the absorption and operation under visible light was shown to open the way to more innovative possibilities in articial photosynthesis as well as in the use of clean, unlimited and sustainable solar light to produce useful organic compounds such as CH3OH from CO2 and H2O. The hybridization of natural photosynthesis in green plants and articial photosynthesis realized by the utilization of thin lm photocatalysts is proposed to be promising to produce H2, sugars and O2 from wastewater with excretions from the roots of the vegetables in plant factory under sunlight irradiation. 2013 Elsevier Ltd. All rights reserved.

Contents 1. 2. 3. 4. 5. 6. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Photocatalytic reduction of CO2 with H2O on highly dispersed Ti-oxides anchored on porous silica glass . . . . . . . . . . . . . . . . . . . . Photocatalytic reduction of CO2 with H2O on a Ti-oxide single site photocatalyst constructed within micro- and meso-porous framework structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Design and development of Ti-oxide single site catalysts able to absorb and operate under visible light irradiation . . . . . . . . . . . . Hybridization of natural photosynthesis and articial photosynthesis using thin lm photocatalysts for the efcient use of solar energy in the evolution of clean H2 and O2 as well as in food production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ 8 . . . . . . . 10 ....... ....... . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 13 14 15 16 16

1. Introduction In recent years, there has been great concern over the many serious environmental problems and lack of natural energy resources that we face on a global scale. The increase in world population and industrial growth have all led to accelerated energy consumption and the unabated release of toxic agents and industrial wastes into the air and waterways, leading to pollution-related diseases, global warming and abnormal climatic changes. We, thus, hope to contribute to the development

* Tel.: +81 722549139; fax: +81 722549941. E-mail address: anpo@chem.osakafu-u.ac.jp 2212-9820/$ see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jcou.2013.03.005

ecologically clean, safe and sustainable chemical technologies, materials and processes [16]. Highly efcient titanium oxide-based photocatalytic materials have been applied to the development of various sustainable, nonhazardous and economic chemical processes under different reaction systems and conditions, as shown in Fig. 1. However, unlike natural photosynthesis in green plants, they make use of only 34% of the solar light that reaches Earth, necessitating the use of a UV light source. Signicantly, investigations are, thus, underway to modify or sensitize TiO2 to operate under irradiation of much larger visible light regions of sunlight [16]. In 1997, we successfully applied a physical method of metal-ion implantation to modify the electronic properties of various TiO2 photocatalysts, enabling them to absorb visible light and operate

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Fig. 1. Applications of titanium oxide-based photocatalysts in the reaction systems with H2O and O2 (a), and reaction systems with only H2O (O2 free) (b). Inserted gure shows the production of electrons in the conduction band and holes in the valence band under UV light irradiation of TiO2 semiconducting materials.

under visible light irradiation without any loss of their original photocatalytic reactivity under UV light irradiation. This modication method was completely different from the chemical doping method which leads to a dramatic decrease in their original

photocatalytic reactivity under UV light irradiation [720]. In 2000, we reported on a RF magnetron sputtering deposition method as a much simpler, less costly method as compared with metal ionimplantation [2124]. Unique and highly efcient Ti-oxide thin

Fig. 2. Separate evolution of H2 and O2 from H2O under sunlight irradiation using HF-treated Vis-TiO2 thin lm photocatalysts in an H-type reaction cell under sunlight irradiation (TiO2 side, 1N NaOH aq; Pt side, 0.5N H2SO4) [7477] (yield of H2: 18 mmol h1, 322 mmol h1 m2, 14.3 mmol h1 g1: h (quantum efciency) = 0.3% (against to total solar beams)).

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lm photocatalytic materials which enable the absorption of visible light of longer than 550 nm were developed to operate as an effective environmentally-friendly photocatalyst, leading to the efcient use of solar energy for the separate production of clean H2 and O2 from water, as shown in Fig. 2 [46,2532]. However, the design and development of photocatalytic systems that work effectively under sunlight irradiation to reduce CO2 with H2O to produce useful organic compounds and O2, i.e., an articial system which resembles the photosynthesis in green plants is still one of the most important challenges facing chemical scientists. In this review article, our work will focus on the possibility of developing an articial photosynthesis system using highly dispersed and reactive Ti-oxide single site photocatalysts constructed within various zeolitic framework structures such as TiMCM-48 and Ti/Y-zeolite, etc. 2. Photocatalytic reduction of CO2 with H2O on highly dispersed Ti-oxides anchored on porous silica glass In Fig. 3, the electronic properties, i.e., the energy levels of the conduction and valence band positions, and the photocatalytic activity of various types of titanium oxide photocatalysts are illustrated depending on their local structures from an

extended-semiconducting structure to extremely small nanoparticles and molecular-sized Ti-oxide single site catalysts. There are two research approaches, as shown by the arrows in Fig. 3, and one is to follow the right direction from normal TiO2 semiconducting photocatalysts (UV-type) to develop much smaller TiO2 photocatalysts such as titanium oxide nano-clusters and then nally on to Ti-oxide highly dispersed TiO4 unit single site catalysts. In this case, the energy gap between the conduction band and valence band becomes larger as the size of the TiO2 becomes smaller, and with the TiO4 unit single site, the energy gap becomes larger, enabling the absorption of very short UV light in the 230280 nm regions [46,3342]. Another research approach is to develop visible light-responsive TiO2 photocatalysts by designing catalysts with much smaller band gaps as compared with the normal UV-type photocatalysts. In this case, the left side direction from the normal TiO2 should be taken. We have reported that one of the reasons the TiO4 unit single site catalysts exhibit a very high and unique photocatalytic reactivity as compared with normal TiO2 semiconducting photocatalysts is that, within the TiO4 unit single site catalysts, the photo-formed electrons and holes are present on the same site, such as a pair of Ti3+ and O, and work together to lead to a very high reactivity. This is in stark contrast to TiO2 semiconducting photocatalysts in which the photoformed electrons and holes are present separately in the conduction

Fig. 3. Relationship between structure and electronic state of Ti-oxides. It shows that the energy gap between the valence band and conduction band changes with the changing the sizes of titanium oxide catalysts. It also shows that with changing the particle sizes of the catalysts, we can nd a high dispersion effect, a size quantization effect, and a visible light response. Inserted gures, a. UV absorption spectra of various titanium oxide catalysts, b. Transmittance of the visible light-responsive TiO2 thin lms prepared on the substrates at various different temperatures, c. The absorption (left) and photoluminescence spectrum of Ti-oxide (right) and its quenching by an increase in the pressure of added O2, and d. The XANES and ET-EXAFS spectrum of highly dispersed tetrahedrally coordinated Ti-oxide single site catalysts prepared with the zeolite framework structures [6].

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band and valence band, leading to the reduction and oxidation reaction, respectively [3342]. We have found that the highly dispersed Ti-oxide species can be prepared and anchored on porous silica glass by using a facile reaction of TiCl4 with the surface OH groups at 473 K, followed by treatment with H2O vapor to hydrolyze the anchored compounds [4349]. The thus-prepared anchored Ti-oxide exhibited a typical photoluminescence spectrum at around the 500 nm region when it was excited by UV light of around 250280 nm. Such excitation brought about an electron transfer from oxygen (O2) to titanium ion (Ti4+), resulting in the transient formation of a pair of the hole center (O) and electron center (Ti3+). XANES and FT-EXAFS measurements of the anchored Ti-oxide catalysts clearly showed the presence of tetrahedrally-coordinated Ti-oxide species on the surface. Thus, the photoluminescence is attributed to the radiative decay process from the charge-transfer excited state to the ground state of the highly dispersed Ti-oxide species in tetrahedral coordination [4951]. This emission was found to be quenched by the addition of H2O and/or CO2, suggesting that the charge-transfer excited state reacts with the added H2O and CO2. In fact, UV irradiation of the highly dispersed Ti-oxides anchored on porous silica glass in the presence of H2O and/or CO2 led to the formation of CH4, CH3OH, and CO as well as O2. The yields of these products were in a good linear relationship with the irradiation time for a prolonged period of up to 68 h. It was also found that the efciency of the photocatalytic reaction depended on the ratio of H2O to CO2 [5261]. On the other hand, UV irradiation of the powdered semiconducting TiO2 catalysts in the presence of a mixture of H2O and CO2 led to the formation of CH4 into the gas phase with trace amounts of C2H4 and C2H6. Without H2O and/or UV light, the formation of CH4 was not detected, suggesting that the photocatalytic reduction of CO2 with H2O takes place in the solid-gas phase system with the powered bulk TiO2 semiconductor catalysts [43,45]. In fact, in such solid-gas phase reaction systems, the ESR signals due to CH3 and H radicals were detected under UV light irradiation

of the powdered TiO2 catalysts in the presence of H2O and CO2 at 77 K, suggesting that these radical species are the intermediate species for the formation of CH4. We also detected peaks at 2920 and 3630 cm1 in addition to the phonon peak, which could be assigned to the C-H stretching vibration of the CHx species and the OH stretching of the surface OH groups, respectively, in the HREELS spectra of a clean TiO2 single crystal after UV light irradiation in the presence of H2O and CO2 [4347]. Thus, UV light irradiation of various active titanium oxide catalysts in the presence of a mixture of H2O and CO2 at around 275323 K led to the photocatalytic reduction of CO2 with H2O to produce CH4, CH3OH, CO as well as O2. The yields of the reactions were found to strongly depend on the kind of Ti-oxide catalysts, the ratio of CO2 to H2O, and the reaction temperature. 3. Photocatalytic reduction of CO2 with H2O on a Ti-oxide single site photocatalyst constructed within micro- and meso-porous framework structures Catalytic systems incorporated or constructed within the zeolite cavities or framework structures have been shown to be effective and selective for various catalytic reactions due to their specic properties in molecular diffusion, high surface area, and shape selectivity, etc. We have investigated the construction of molecular-sized Ti-oxide single site catalysts within the framework structures of various porous materials such as micro-porous zeolites and meso-porous molecular sieves to apply them as photocatalysts for the reduction of CO2 with H2O based on the favorable results obtained on highly dispersed Ti-oxides anchored on silica glass [5461]. Fig. 4 shows the diffuse reectance UVvis absorption spectrum and its photoluminescence spectrum. These absorption and emission processes are attributed to the charge-transfer from an oxygen (O2) to a titanium ion (Ti4+) and its reverse process, respectively, as shown in Fig. 4. Here, the Ti K-edge XANES and

Fig. 4. (A) TiK-edge XANES (a, b, c, d) and FT-EXAFS (A, B, C, D) spectra of tetrahedrally coordinated Ti-oxide species constructed within various porous framework structures. (B) Diffuse reectance UVvis absorption spectrum of tetrahedrally coordinated Ti-oxide species. (C) Photoluminescence spectrum as a reverse radiative decay from the charge transfer excited state of the tetrahedrally coordinated Ti-oxide species [35,39,57].

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Table 1 Photocatalytic reduction of CO2 with H2O on tetrahedrally coordinated Ti-oxide single-site catalysts constructed within various mico- and meso-porous materials and their characteristic physicochemical properties. TS-1 Coordination ) Pore size (A ) TiO bond length (A Photoluminescence wavelength (nm) Lifetime of photoluminescence (ms) Selectivity for the CH3OH formation (%) Tetra 5.6 5.3 1.83 480 0.20 25 Ti-Beta(OH) Tetra 7.6 6.4 1.84 480 0.42 21 Ti-Beta(F) Tetra 7.6 6.4 1.83 480 0.28 41 Ti-MCM-41 Tetra >20 1.86 480 0.52 35 Ti-PS(c) Tetra 18 1.83 480 0.52 58 Ti-PS(h) Tetra 19 1.82 480 0.68 31

FT-EXAFS spectra of the Ti-oxides constructed within Beta, i.e., an OH zeolite treated with H2O, (Ti-Beta(OH)), Beta (F) zeolite treated with uorine (Ti-Beta(F)), HMS (Ti-HMS), and MCM-41 (Ti-MCM-41) are also shown. Analyses of these spectra are summarized in Table 1 including the results obtained with Tioxides constructed within porous silica thin lm materials. It is clear that all Ti-oxide species are constructed within these porous materials having a tetrahedral coordination and 4 TO bonds with their bond lengths in the range of 1.821.85 A [5660]. We also found that the addition of CO2 and H2O onto these Tioxide catalysts led to the efcient quenching of the photoluminescence, suggesting not only that the tetrahedrally-coordinated Ti-oxide species are constructed within the porous materials at positions accessible to the added CO2 or H2O but also that CO2 or H2O interacts and reacts with the Ti-oxide species in both its ground and excited states. In fact, UV light irradiation of Ti-oxide catalysts constructed within various porous materials in the presence of a mixture of CO2 and H2O led to the formation of CH3OH, CH4, CO and O2, similarly to Ti-oxide anchored on silica glass with differing efciencies, suggesting that the photocatalytic reduction may also proceed on tetrahedrally-coordinated Tioxides containing various porous materials [5267]. In Fig. 5,

the reaction time proles of the photocatalytic reduction of CO2 and H2O to produce CH4 and CH3OH on the Ti-oxides containing porous silica are shown. The yields of CH4 and CH3OH in the photocatalytic reduction of CO2 and H2O on the Ti-oxides containing various porous materials are shown in Fig. 6. We investigated the relationship between the selectivity for the formation of CH3OH in the photocatalytic reduction of CO2 with H2O and the number of surface OH groups for the porous materials in relation to its affect on the reactivity of the Ti-oxide. We found that the apparent photocatalytic reactivity for the formation of CH3OH on the transparent Ti-PS (h, 50) thin lm catalyst with a hexagonal meso-pore structure is the highest, though the selectivity for the formation of CH3OH was the highest on Ti-PS (c, 50) with a cubic meso-pore structure and the lowest value in the number of surface OH groups. [6264] With such a transparent thin lm catalyst, the numbers of photons absorbed by the Ti-oxide catalysts were obtained by subtracting the numbers of outlet photons from the numbers of incident photons. As a result, it was possible to determine a real quantum yield of the photocatalytic reduction of CO2 with H2O on tetrahedrally-coordinated Ti-oxides constructed within porous silica materials to be 0.3% at room temperature (at 25 8C) by dividing the total number of

Fig. 5. Reaction time proles of the photocatalytic reduction of CO2 with H2O to produce CH4 and CH3OH on a Ti-oxide single-site containing a meso-porous silica thin lm photocatalyst at 298 K (CO2: 36 mmol, H2O: 180 mmol). Inserted gure shows how to measure the real quantum yields of the reaction [62,64].

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4. Design and development of Ti-oxide single site catalysts able to absorb and operate under visible light irradiation The highly active tetrahedrally-coordinated Ti-oxide species absorb only very short UV light in the wavelength region of 220 280 nm and are unable to absorb and operate under longer UV, visible or natural sunlight [3342]. As has been mentioned, the modication of various commercially available powdered TiO2 photocatalysts was found to absorb and operate under visible light irradiation without any loss in their photocatalytic activity under UV light irradiation by applying an advanced metal ion implantation method as a physical doping method [220]. Fig. 7 shows the implantation of a metal cation into TiO2 samples by applying high voltage acceleration in vacuum. We found that after calcination of the cation-implanted TiO2 sample at around 450 8C in air for several hrs, the absorption band of TiO2 shifts smoothly to the visible light region and absorbs sunlight of more than 25% as compared with its original short UV light absorption of only about 34% sunlight [36,1016]. This unique metal ion-implantation method was applied to modify the active Ti-oxides constructed within porous materials. The absorption spectra of the Ti-oxide constructed within HMS (TiHMS catalyst) and MCM-41 (Ti-MCM-41 catalyst) at around 220 280 nm could be attributed to the charge-transfer absorption process involving an electron transfer from the oxygen ion (O2) to titanium cation (Ti4+) of the highly dispersed tetrahedrallycoordinated TiO4 unit [3339,5761,67,68]. As shown in Fig. 8, these absorption spectra shift smoothly toward visible light regions, the extent strongly depending on the amount of implanted metal cations (in this case, V+) [68]. These results clearly indicated that the interaction of the implanted V ions with the TiO4 units led to a modication of the electronic properties of the Ti-oxide species within the porous structure frameworks. The V K-edge FT-EXAFS spectra of the Ti-HMS catalyst implanted with V cations indicated that the next-neighbors of the V environment are not the same as vanadium oxide based catalysts and suggests the formation of tetrahedral Ti-oxide having a VOTi bond instead of VOV linkages. The possibility of the formation of VOTi bonds by the implantation of V cations into

Fig. 6. The yields of CH4 and CH3OH in the photocatalytic reduction of CO2 with H2O on Ti-PS(h 25), Ti-PS(c, 50), Ti-MCM-41, powdered form of Ti-PS(h, 50) and Ti-PS(h, 50) potocatalysts at 295 K. Intensity of the irradiated light: 265 mW cm2 [6264].

photo-formed products (such as CH4 and CH3OH, etc.) by the number of photons absorbed by the catalysts. In Table 1, the experimental results obtained with the catalysts and the photocatalytic reactions are summarized. From these results, it is clear not only that the photocatalytic reduction of CO2 with H2O to form CH4 and CH3OH as well as O2 does, in fact, proceed under UV light irradiation of the tetrahedrally-coordinated Ti-Oxide species constructed within various porous materials but also that their reaction efciency depends on the local structure of the catalysts such as pore size and lifetime of the charge-transfer excited state as well as the number of surface OH groups.

Fig. 7. (A) Schematic diagram of ion-implantation method to modify the electronic state of the solid materials. (B) Outlook of the 200 keV ion-implanter. (C) The absorption spectra of TiO2 implanted with V ion smoothly shifts to longer wavelength regions with increasing the amount of the implanted V cations and enables the absorption of sunlight much more (ca. 25%) as compared with original un-implanted TiO2 catalysts (4%) [36,1417].

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Fig. 8. (A) Diffuse reectance UVvis absorption spectra of an original Ti-HMS and the V ion-implanted Ti-HMS, and (B) diffuse reectance UVvis absorption spectra of an original Ti-MCM-41 and the V ion-implanted Ti-MCM-41 catalysts. Implanted-V ions (from left to right): 0, 0.66, 1.3, 2.0 (mmol/g cat) [38,39,68].

Ti-HMS and Ti-MCM-41 was considered since Si is a major element in the catalyst and expected to have an easier interaction with the V cation than a minor element of Ti. In order to clarify why the absorption spectrum of these catalysts can be modied by V ion implantation, cluster quantum chemical ab initio and DFT calculations were carried out for the Ti-HMS and Ti-MCM-41 frameworks structures with a VOTi bond suggested by the results obtained by V K-edge FT-EXAFS [6973]. The results were compared with the results obtained with the Ti-HMS and Ti-MCM41 frameworks structures with a VOSi bond in place of the TiO V bond. Fig. 9 clearly shows not only that the cluster of Ti-HMS and Ti-MCM-41 with a VOTi bond is energetically stable by easier formation of these structures after V ion implantation but also that the energy band gap between the HOMO and LUMO of the TiMCM-41 with a VOTi bond is greatly reduced, suggesting the absorption of visible light and showing good agreement with the experimental results shown in Fig. 8. [6873] Although the detailed nature of the modication is still under investigation, as shown in Fig. 10, the development of an articial photosynthesis reaction system using highly active Ti-oxide single site catalysts constructed within meso- and/or micro-porous and

transparent thin lm materials which can operate under sunlight, just as the photosynthesis in green plants, is quite promising. 5. Hybridization of natural photosynthesis and articial photosynthesis using thin lm photocatalysts for the efcient use of solar energy in the evolution of clean H2 and O2 as well as in food production Fig. 2 shows the yields of the evolved H2 and O2 under outdoor sunlight irradiation from 9:00 AM to 4:00 PM for one day. As can be seen, applying the newly developed and highly active visible lightresponsive TiO2 thin lm photocatalysts initiated the photocatalytic decomposition of H2O into H2 and O2 by separate evolution under sunlight irradiation, their yields increasing linearly with the sunlight irradiation time [2532,7476]. As shown in Fig. 11, adding some organic compounds such as alcohol into the aqueous system remarkably enhanced the yield of photocatalytic H2 evolution, while CO2 was produced in place of O2 evolution. Such an enhancement of photocatalytic H2 production from H2O involving organic compounds can be attributed to the fact that the photo-formed holes in the TiO2 reacts much faster with such

Fig. 9. (A) Models of the local structure for the V ion-implanted Ti-zeolite with SiOV and TiOV bond for the ab initio calculations and the DFT method. (B) The changes in the energy gap between the LUMO and HOMO of the Ti-oxide species with local structures with SiOV bond or TiOV bond [72,73].

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Fig. 10. Description of the reaction schemes in the photosynthesis reaction in green plant (above) and the visible light-responsive Ti-oxide single sites photocatalysts (articial photosynthesis) constructed within porous framework structure (below).

organic compounds to produce CO2 than with H2O to produce O2. In other words, the added organic compounds in H2O work as a sacricial agent to form CO2 while the remaining photo-formed electrons in TiO2 led to enhanced H2 production from aqueous solutions involving organic compounds. It was also found that the extent of the enhanced yields of H2 evolution from aqueous solutions involving various kinds of organic compounds strongly depended on the kind of compounds. And, any kind of organic compounds can work as a sacricial agent [76]. These results clearly suggest that such photocatalytic reaction systems can be applied to wastewater involving various biomass to produce clean H2 and CO2, providing pure water if reaction systems which require and consume CO2 selectively were developed. In a multidisciplinary effort, we have constructed a completely closed, fully articially lighted plant factory which uses no natural sunlight. These plant factories are cultivation facilities that, through advanced and precise control of the environment by monitoring the cultivation conditions and growth of plants, enable year-round production of vegetables and other produce [77,78]. Their development and widespread implementation is expected to allow a new agricultural system that can supply safe, tasty and nutritious produce regardless of any natural or manmade phenomena such as global warming, climatic change, pollution or the damage or destruction of agricultural elds. As shown in Fig. 12, complete articial LED lamp lighting is being used in a closed clean room where the concentration of CO2

is much higher by 34 times that in atmosphere. Conditions of a high concentration of CO2 and controlled lighting enhances photosynthesis and the growth of vegetables having good taste and coloring, resistance, nutritious elements, and shorter growth periods as compared with produce grown outdoors in elds under sunlight. As shown in Fig. 12 (left side), the high concentration of CO2 remarkably enhanced photosynthesis in lettuce, leading to efcient growth as compared with lettuce grown outdoors. Two to three days less was required until harvest as compared with outdoor eld-grown produce, allowing vegetables to be delivered to market within a short period of around two weeks as compared to around four weeks for outdoor eld-grown produce [77,78]. A photocatalytic reaction system, as shown in Fig. 11, may be applied to supply CO2 while pure H2 is also produced at the same time. The hybridization of the natural photosynthesis of green plants (i) and an articial photosynthesis method using thin lm photocatalysts (ii) would enable the production of (ii), sugars and O2 (i), using wastewater that includes excretions from the roots of the vegetables as biomass with natural sunlight. 6. Summary In the present article, the results of investigations on the photocatalytic reduction of CO2 with H2O, articial photosynthesis, highly active tetrahadrally-coordinated Ti-oxide species with TiO4 units within micro- and meso-porous framework structures, and

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Fig. 11. An enhancement in the photocatalytic H2 evolution on the visible light-responsive TiO2 (Vis-TiO2) thin lm under visible light irradiation from aqueous solution of methanol as compared with that from pure H2O. Fig. 110 Reaction time prole of the evolution of H2 from aqueous solution of methanol under visible light irradiation [76] (evolution of H2 from an aqueous solution of CH3OH proceeds efciently using the Vis-TiO2 thin lm photocatalysts under visible light irradiation).

Fig. 12. Outlook of the inside of a complete articial lights (LEDs) plant factory, lettuces production room (there are 15 shelves, and 250 lettuces per day are produced). Inserted gures, Fig. 120 shows a hybrid eco-energy system of the plant factory using solar panels, and Fig. 1200 shows an outlook of the outside of a clean room laboratory (cultivation environment simulator room) in the plant factory [76,78].

how to modify these catalysts to enable the absorption of and operation under visible light were covered. Advanced metal ionimplantation was shown to open the way to more innovative possibilities in articial photosynthesis as well as in the use of clean, unlimited and sustainable solar light to produce useful organic compounds such as CH3OH from CO2 and H2O. The hybridization of natural and articial photosynthesis using thin lm photocatalysts as a reaction system is also promising to produce H2, sugars and O2, and in using sunlight and wastewater with excretions from the roots of the vegetables as biomass. Acknowledgements The author (M. A.) would like to thank his graduate students, colleagues and collaborators for their hard work and efforts in realizing the photocatalytic reduction of CO2 with H2O. They are acknowledged as follows: Assoc. Prof. K. Ikeue (Tokyo Uni. Sci.

Technol., Yamaguchi), Prof. H. Yamashita (Osaka Uni.), Prof. M. Ogawa (Waseda Uni.), Dr. M. Harada (Tokyo Electro. Ltd.), Assoc. Prof. Y. Hu (South China Uni. of Technol.), Assoc. Prof. M. Kitano (Tokyo Institute Technol.), Assoc. Prof. Y. Ichihashi (Kobe Uni.), Assoc. Prof. S. Higashimoto (Osaka Uni. Technol.), Dr. S. G. Zhang (KRI), Assoc. Prof. N. U. Zhanpeisov (Tohoku Uni.), Assoc. Prof. M. Takeuchi (Osaka Prefecture. Uni.), Prof. M. Matsuoka (Osaka Prefecture Uni.), Prof. J. L. Zhang (East China Uni. Sci Technol.), Prof. J. C. S. Wu (National Taiwan Uni.), Prof. S. E. Park (Inha Uni.), Prof. M. Che (P. M. Curie Uni.).

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Masakazu Anpo is presently a Vice President and Executive Director of Osaka Prefecture University. He is a pioneer in the study of photochemical reactions on solid surfaces including catalysts and has published the rst Japanese book in this eld, Photocatalysis, with Profs. Y. Kubokawa, K. Honda, Y. Saito in 1988. An English book, Photochemistry on Solid Surfaces, was published with Prof. T. Matsuura in 1989 from Elsevier. He has published more than 100 books. Dr. Anpo has received awards from the Japan Photochemical Society (1994), Chemical Society of Japan and Ministry of Education of Japan (2009) as well as other awards and honors. He has published over 475 original papers, serves on the editorial boards of numerous international journals and is Editor-inChief of the international journal, Research on Chemical Intermediates (Springer, USA). Dr. Anpo served as an active member of the International Association of Catalysis Societies (IACS), Catalysis Society of Japan and as a founding member of the Asia-Pacic Association of Catalysis Societies (APACS) established in 2004. Dr. Anpo has currently elected as one of only a few Members of the Academia Europaea from Asia. Since April 1st, 2009, Dr. Anpo plays an important role in organizing university as Vice-President & Executive Director of Osaka Prefecture University. Dr. Anpos current research topics deal with the design and development of highly efcient visible-light-responsive TiO2 photocatalysts and their application to the decomposition of water into H2 and O2 with a separate evolution as well as the design of highly active single-site transition metal oxide catalysts within the framework of zeolites and meso-porous materials as photocatalysts for environmental remediation and preservation processes and the production of clean energies. His dream is the establishment of solar chemistry as a new environmentally-friendly science and technology.