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Zeolites: Promised Materials for the Sustainable Production of Hydrogen.

Dr. Antonio Chica Instituto de Tecnologa Qumica (UPV-CSIC), Universidad Politcnica de Valencia, Avenida de los Naranjos s/n, 46022-Valencia, Spain achica@itq.upv.es Abstract. The diminishing of oil sources and the environmental problems due to their combustion, make necessary to develop renewable and cleaned energy alternatives independent of them. Hydrogen is believed to be critical for the energy and environmental sustainability. It is a clean energy carrier which can be used for transportation and stationary power generation. Hydrogen can be produced from a wide variety of resources such as coal, oil, natural gas, biomass, and water. This versatility contributes to the promise of hydrogen, allowing it to be produced where and when we need it. Currently, about 95% of the hydrogen that we use comes from the steam reforming of natural gas, while only a 5% comes from water electrolysis, which uses electricity generated by burning fossil fuels. But to realize the full benefits of a hydrogen economy, increased energy security, diverse energy supply and reduced air pollution, hydrogen must be produced cleanly and efficiently from available renewable resources. In the production of hydrogen the development of new catalysts is one of the most important and effective ways to address the problems related to the sustainable production of hydrogen. Catalysis makes possible to produce hydrogen more efficiently, saving energy in the production process. In addition, catalysts reduce waste by enhancing selectivity, thus can help to decrease the environment impact (i.e. decreasing the CO2 emissions). Zeolites have been shown to be useful catalysts in a large variety of reactions, from acid to base and redox catalysis. The particular properties of these materials (high surface area, uniform porosity, inter-connected pore/channel system, accessible pore volume, high adsorption capacity, ion-exchange ability, and shape/size selectivity) provide crucial features as effective catalysts and catalysts supports. Currently, new applications are being developed from the considerable existing knowledge about these important and remarkable materials. Among them, those applications related to
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development of processes with less impact on the environment (gree procceses) and with the production of alternative and cleaner energies are considered of paramount importance. This review explores the possibility to use zeolites as catalysts or supports of catalysts to produce hydrogen from renewable resources. Specifically, it has been considers two approachs: reforming of biomass derived compound (reforming of bioetanol) and water splitting using solar energy. Keywords: Zeolites, Hydrogen Produciton, Bioethanol, Steam Reforming, , Water Splitting.

1.- Zeolites: composition, structure, properties and applications. Zeolites were first described in 1756 by the Swedish mineralogist A. Frederik Cronstedt.1 However, the systematic research efforts on synthetic zeolites were initiated by Richard M. Barrer in the late 1930s.2,3 Barret offered the first classification of zeolites based on molecular size.4 Inspired by the work of Barrer researchers at Union Carbide developed synthesis procedures for preparation of the first synthetic zeolites (i.e., zeolites A, X and Y) that would find industrial applications.5-7 Initially zeolites were applied as materials for drying and separation substances. Later, with the development of the concept of acid zeolite catalyst, in 1959, were used as catalysts in the isomerization of hydrocarbons.8 Previously Houndry et al.9 used them in catalytic cracking of hydrocarbons. Since the development of the first concepts to date many business processes based on zeolites as catalysts have been implemented. The specialization and knowledge of zeolites have grown so much that it has been founded the International Zeolite Association (IZA)10 and currently there are numerous specialized scientific publications that collect not only the current knowledge about these materials but also their outstanding commercial application. 1.1.- Composition and structure. Zeolites are microporous crystalline aluminosilicates whose chemical composition is defined by the general formula:11 M2/nO; Al2O3, x SiO2, and H2O where M is a metal cation of valence n, x> 2 and y> 1. Zeolite framework is formed from corner sharing [SiO4]4- and [AlO4]5tetrahedra which define the cavities and channels, in which the cations can be found coordinating to framework oxygens and/or water molecules. Figure 1 shows the different representations, typical of those used in literature, of the framework of one zeolite.

Figure 1. Representation of the projection of the framework structure of zeolites; (a) Tsite connectivity only, (b) ball and stick, (c) space filling and (d) (Si, Al) O4 tetrahedra.

The ways to combine each tetrahedron are extremely wide. The structure of the zeolite is defined by its corner sharing tetrahedra of [SiO4]4- and [AlO4]5-, these are called Secondary Building Units (SBUs)12 (see Figure 2).

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Figure 2. Basic Secondary Units (BSUs) to define the structure of zeolites. The utility of these constructions is that the angles and distances of zeolites are contained in these SBUs, so it can be obtained a certain structural characterization of one zeolite by examining the SBUs that contain. There are 16 different SBUs, and the structure of each zeolite can be described using one or more of these SBUs. In zeolites, the organization of TO4 tetrahedra can result in the formation of rings with different numbers of T atoms (Si, Al). The most common rings are 4-T, 6-T, 8-T, 10-T and 12-T; however zeolitic structures containing 14, 18 and 30 member rings have been also synthesized.13-18 The size of the micropores of the zeolite varies depending on the number of members in the rings, between 4 and 12 . On rings, T-O-T angles vary mostly in the range 130-180. The flexibility of this angle is one of the most important factors determining the huge variety of existing zeolites. 1.2.- Properties. Zeolites may act as molecular sieves, thus one of their main physical properties is the porosity. The microporous properties of zeolites make that they present an extremely large
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internal surface area in relation to their external surface. Micropores are open to the outside allowing the transfer of matter between the intracrystalline space and the surrounding environment. Tridimensional networks of well-defined micropores can act as reaction channels whose activity and selectivity will be enhanced by introducing active sites. The presence of strong electric fields and controllable adsorption properties within the pores will produce a unique type of catalyst, which by itself can be considered as a catalytic microreactor. The size of the pores and channels of zeolites ranges between 4 and 12 19 and the channel system may be mono, bi or three-directional. Table 1 shows the classification of zeolites based on the number of tetrahedrals that form the pores and give access to the intracystalline space.20-23

Table 1. Zeolite classification according to the pore size Zeolite Classification Small Pore Medium Pore Large Pore Extralarge Pore Number of the oxygen atoms in the opening ring 8 10 12 18 Pore Diameter () 3<<5 5<<6 6<<9 9< Example of Zeolites Erionite, A, ITQ-3 ZSM-5, ZSM-11, ITQ-1 X, Y, Beta, , Mordenite, ITQ-7, ITQ-21 MCM-9, VIP-5, ITQ-33

Summarizing, the main properties of zeolites are: High surface area. Molecular dimensions of the pores. High adsorption capacity. Partitioning of reactant/products. Possibility of modulating the electronic properties of the active sites. Possibility for preactivating the molecules when in the pores by strong electric fields and molecular confinement.

1.3.- Aplications. Zeolites have a variety of industrial applications, especially as ion exchangers, adsorbents and chemicals catalysts. Zeolites as adsorbents are used in processes of separation and purification of gases and liquids due to their ability to selectively adsorb molecules of different size or polarity. They are used in the separation of oxygen from air to remove the water and CO2 from gas streams, separation of the linear branched hydrocarbons, and in the elimination of volatile organic compounds from automobile and industrial exhausted gasses.24-34 The most important application of zeolites as ion exchangers is the extraction of cations Ca2+ and Mg2+ of domestic and industrial waste water34. Sodium zeolite A is used in the formulation of detergents, replacing to polyphosphates, highly polluting compounds. They are also used in extraction of NH4+ from waste water33 and they have been also used extensively in nuclear waste cleanup (i.e. after the Three Mile Island and Chernobyl nuclear accidents). Regarding to the use of zeolites as catalysts or catalyst supports is very common their use in industrial processes of refining, petrochemical and fine chemical. The replacement of conventional catalysts in many processes by zeolite is due to improvements that these materials introduce in the catalytic activity and selectivity. For the commercial application of zeolites as catalysts together to a good texturerelated properties (area, porosity), and a high number of active sites, zeolites must to have good thermal stability, since a large part of catalytic processes are conducted at elevated temperatures. Moreover, it is very frequent that the catalysts used in reactions involving hydrocarbons, are deactivated by coke deposits formed during the reaction. Thus, they need to be regenerated. The regeneration is conducted by burning the coke at temperatures above 500C.35-37 The thermal stability of a zeolite depends on the aluminum content. Al-O bonds are weaker than the Si-O one (Al-O distance is larger than Si-O), therefore the stability depends on aluminum content.38 Thus, in order to carry out a sufficient number of reactionregeneration cycles is required zeolites with high thermal stability, i.e. zeolites with Si/Al 5.39 These compositions in some cases can be achieved by direct synthesis (i.e. Beta and ZSM-5 zeolites), and in other cases in which it is not possible by direct synthesis it can be achieved by chemical or hydrothermal treatments of synthesized zeolite (i.e. zeolite Y).40 The substitution of Si by Al together with corresponding compensation cations, has another additional effect on the properties of the zeolites, hydrophilicity/hydrophobicity.41
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The hydrophilic-hydrophobic character has focused applications of great practical interest. Thus, the hydrophobic zeolites are able to carry out reactions that require absence of water, without the necessity to remove it from the medium, because the reaction takes place almost entirely inside of the zeolite, which being hydrophobic will be water free.42 For example, silicalite (ZSM-5 structure with Si / Al> 1000)43 has very low amount of aluminum, in such a way that its crystals (d =1.7 g/cc) can float in the water.44 By contrast, zeolite X, with high Al content, has a pronounced hydrophilic character, which permits separating a mixture of oxygen and nitrogen45 due to the higher quadrupole moment of the nitrogen. The negative charge associated with the tetracoordinated aluminum is compensated by cations that can be easily exchanged for others cations by ion exchange processes.46 The exchange of cations is favored by the fact that the cations are not covalently bonded to the structure; they are placed inside the zeolite cavities compensating the defect of charge. The size and charge of the exchanged cations are important variables in the zeolite reactivity. Large size cations and less positive charge will leave to lower space in the cavities difficulting the entrance of reactants. This effect can be used in certain reactions where the selective control is based on geometric effects.47 Among the exchangeable cations that can be introduced into the zeolite, the proton occupies a special place. The protons are bonded to an oxygen bridge between one silicon and one aluminum.48 Due to the presence of channels and cavities of different sizes within the same structure, as well as the existence of non-equivalent positions, is the paramount importance can predict minimum energy positions, and therefore the location of the exchangeable cations,49 and especially the localization of the protons that will determine the activity in acid catalyzed reactions. New scientific applications were considered in the 1980s and 1990s for exploring zeolites as advanced solid state materials. Ozin et al.50 considered that zeolites could represent a new frontier of solid state chemistry with interesting properties (nanometer dimension window, channel and cavity architecture) for innovative research and development. Among others they consider applications as follow: molecular electronics, quantum dots/chains, zeolite electrodes, batteries, non-linear optical materials and chemical sensors. Others applications recently reported are related to the use of zeolites as low k dielectric materials for microprocessors.51 Future trends in zeolites include: (i) discovery of new zeolitic materials, (ii) continue use in petroleum refining (high octane and reformulated gasoline, processing of heavy crudes, production of diesel, etc), (iii) use in the preparation of organic

chemical intermediates or end-products and (iv) use in sustainable processes to produce biocompounds and green fuels. Considering the future trends it is quite evident that zeolites are of great interest for the industry, especially due to the potential they present in fields that are of paramount importance for the future of our industrialized society, such as raw material transformation, environmental pollution control and energy production and storage. This review focus on the application of the zeolites for energy production. Specifically, it is collected the use of zeolites in the production of hydrogen from renewable energy sources: biomass (ethanol reforming) and solar (water splitting). 2.- Zeolites for hydrogen production. The future energy economy will have an important role for hydrogen (H2) as a clean and CO2-neutral energy source.52 Thus, it has been projected as one of the few long-term sustainable clean energy carriers. Currently the synthesis of molecular hydrogen occurs mostly by non sustainable methods such as steam reforming (SR) of natural gas or gasification of coal, which is associated with the emission of large quantities of greenhouse gases (GHG), especially carbon dioxide (CO2).53-56 Thus, to realize the full benefits of a hydrogen economy, increased energy security, diverse energy supply and reduced air pollution, hydrogen must be produced cleanly and efficiently from available renewable resources. Hydrogen can be produced from renewable resources (e.g. biomass and water) using renewable energy sources (e.g. sunlight, wind, wave or hydro-power).57-62 Two important approaches are considered in this review to produce hydrogen from renewable sources and reduce de CO2 emissions. One approach is to apply reforming methods to biomass-derived compounds, for example bioethanol. Because biomass consumes atmospheric carbon dioxide (CO2) during growth, it can have a small net CO2 impact compared with fossil fuels. Second approach considers the production of hydrogen by water splitting using solar energy. Hydrogen production by water splitting corresponds to those methods include outside the C-cycle. This process is a very attractive due to the potential to use the solar energy, very abundant. The use of catalysts to improve the production of hydrogen by reforming of bioethanol and water splitting has been reported. Among them, zeolites seem to be a promised future as catalysts and catalysts supports. Here will be reviewed first the use of different zeolites in the production of hydrogen by ethanol (or bioethanol) steam
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reforming. It will be show the influence that the zeolites have as support to prepare ethanol reforming catalysts with high activity, selectivity and stability. Sencond will be shown the last advances in the use of the zeolites to produce hydrogen by water splitting process and the promised future that these materials have to take advantage of solar energy. 2.1.- Zeolites as constituents of catalysts for the sustainable production of hydrogen via ethanol/bioethanol reforming. Among the liquid biomass-derived molecules that can be used as hydrogen source, primary alcohols are interesting compounds because they can be converted to hydrogen by steam reforming using moderate reaction conditions. The most part of the reforming studies related to alcohols from biomass are focused on ethanol. Ethanol is considering an interesting alternative for the sustainable hydrogen production because of: (i) its low toxicity; (ii) its low production costs; (iii) the fact that it is a relative clean fuel in terms of composition; (iv) its relatively high hydrogen content and (v) its availability and easiness of handling. Catalytic hydrogen production from ethanol can be performed by (i) steam reforming (SR), represented by the reaction (1), (ii) partial oxidation (PO), represented by the reaction (2) and (iii) autothermal reforming (ATR), represented by the reaction (3).

C2H5OH + 3H2O C2H5OH + 1.5O2 C2H5OH + xO2 + (3-2x)H2O

2CO2 + 6H2 2CO2 + 3H2 2 CO2 + (6-2x)H2

H0 = +173.3 kJ/mol H0 = -552.0 kJ/mol H0=173.3x*552kJ/mol

(1) (2) (3)

The SR of ethanol, reaction (1), is an endothermic reaction which takes place at temperatures between 673 and 1073 K and with a kinetic slower than the PO reaction. SR operates at lower temperature and produces a higher number of molecules of H2 per molecule of converted ethanol (H2/C2H5OH=6) thus, the overall efficiency of this reaction is higher than that obtained by PO processes. The PO of ethanol, reaction (2), occurs between 973 and 1273 K. It is an exothermic reaction. It has several advantages: allows working with adiabatic reactors without the necessity to supply external heat and the kinetics is rapid. Obtaining
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hydrogen from bioethanol by reaction PO is an option that has been very few investigated, because it would involve the separation of water included in raw bioethanol, what would mean a high energy cost. The third option combines the advantages of both approaches, SR and PO. This option includes the simultaneous reaction of ethanol with water vapor and oxygen in an oxidative reforming process (Autothermal Reforming, ATR), reaction (3). The input of external heat is not necessary since it is generated by introducing small amounts of oxygen. The moles of H2 obtained per mole of ethanol is higher than in the case of the PO reaction but lower than in the case of SR. The choice of the reforming route is based on the type of fuel cell, the demands and volume of the system and management strategy. Nevertheless, the SR of ethanol has been the most studied route. The amount of published studies on the SR of ethanol is lower than that on hydrocarbons or methanol. Several reviews about the development of catalysts applied to ethanol SR have been published lately.63-66 Catalytic materials such as metallic oxides (ZnO, MgO, V2O5, Al2O3, TiO2, La2O3, CeO2, SmO3),67-69 supported metals (Co/Al2O3, Co/La2O3, Co/SiO2, Co/MgO, Co/ZrO2, CoZnO, Co/TiO2, Co/V2O5, Co/CeO2, Co/Sm2O3, Co/CeO2ZrO2, Co/C, Ni/La2O3, Ni/(La2O3 Al2O3), Ni/Al2O3, Ni/MgO, NiCu/SiO2, NiCu/Al2O3, NiCuK/Al2O3)70-81 and precious metals supported on oxides (Rh/TiO2, Rh/SiO2, Rh/CeO2,Rh/ZrO2, Rh/Al2O3, Rh/MgO, Rh/Al2O3, Rh/CeO2ZrO2, RhAu/CeO2, RhPt/CeO2, Pd/CeO2, Pt/CeO2, Au/CeO2, Pd/Al2O3, PtPd/CeO2)82-95 are reported in these reviews. Thermodynamic analyses have shown that a high conversion of ethanol to hydrogen is possible above 250C and also that the high water/ethanol molar ratio of raw bioethanol is beneficial to increase hydrogen yield and to decrease the formation of byproducts such as methane, carbon monoxide and carbon deposition. Table 2 shows a summary of the possible reaction pathways follows by the ethanol during its catalytic SR. The extension in which each reaction takes place over the catalyst will depend on the nature of metal, type of precursor, preparation method, type of support, presence of additives, and operating conditions.

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Table 2 Reaction network for the steam reforming of bioethanol. Reaction Equation

Reforming with excess of water

CH3CH2OH + 3H2O

2CO2 +6H2

Reforming with deficit of water Dehydrogenation Acetaldehyde decomposition Acetaldehyde reforming Dehydration Coke formation Decomposition

CH3CH2OH + H2O CH3CH2OH + 2H2 CH3CH2OH C2H4O C2H4O + H2O

2CO +4H2 2CH4 +H2O C2H4O +H2 CH4 + CO 3H2 + 2CO

CH3CH2OH C2H4 +H2O polymeric deposits (coke) C2H4 CH3CH2OH 2CH3CH2OH CH3CH2OH CO + 3H2 CO2 + 4H2 CH4 2CO CO + H2O CO + CH4 + H2 C3H6O + CO +3H2 0.5CO2 + 1.5 CH4 CH4 + H2O CH4 + 2H2O 2H2 + C CO2 + C CO2 + H2

Methanation Decomposition of methane Boudouard reaction Water gas shift reaction

Among them, it is found that support plays an important role in the preparation of highly active and selective ethanol steam reforming catalysts since it helps in the dispersion of metal catalyst and enhances its activity via metal-support interactions. Specifically it has been found that high surface areas of the support improve the catalytic activity69,96 and the particular topology or crystalline structure of one support can affect the metal dispersion of the metallic particles improving their stability against sinterization97,98. Taking this into account the singular structure of zeolites would make these materials attractive to be used as supports for dispersing active metal phases.98-101 Cantao et al.99 reported the first work in the steam reforming of ethanol using zeolites as support. Specifically they studied the Y-Zeolite exchanged with Na. According to the results reported by these authors the NaY zeolite had the prime function of increasing the surface area, aiming higher reforming reaction efficiency. Potassium and rhodium were added to NaY zeolite in order to improve reforming
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performance. They found that the addition of Rh and K allowed to prepare an ethanol steam reforming catalyst with high activity and H2 selectivity. Best conversion values were achieved for higher H2O/Ethanol ratio and higher reagent flow. They also verified that reagent flow has greater influence on hydrogen yield than K addition. They concluded that NaY zeolite-supported Rh can be considered promising catalysts for ethanol steam reforming, when compared with other existing studies. Chica et al.98,101 also studied zeolitic materials as support of catalyst for the SR of bioethanol. They used two delaminated zeolites (ITQ-2 and ITQ-18) with high external surface area (835 and 611 m2/g, respectively) to support Ni and Co. ITQ-2 delaminated zeolite consists of thin sheets of 2.5 nm in height presenting a hexagonal array of cups (0.7 nm x0.7 nm) that penetrate into the sheet from both sides connected by a double 6-member ring (MR) window (Figure 3).98 ITQ-18 is another delaminated zeolite which has been obtained by expanding and exfoliating a laminar precursor of NU-6 zeolite,103 Figure 4. The singular structure of these delaminated zeolites, and particularly the very high and well-defined external surface area, makes these materials very attractive to be used as supports for dispersing active metal phases.

Figure 3. Structure of delaminated zeolite ITQ-299.

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Figure 4. Synthesis of delaminated zeolite ITQ-18. (Adapted from referencia 101). Ni and Co were supported on pure silica ITQ-2 and Co on ITQ-18 with low aluminum content (Si/Al=100). For comparison reasons a catalysts based on amorphous silica containing the same amount of Co and Ni (20 wt.%) were also prepared. High catalytic activity, selectivity and stability (again coke deposition) were reported for the delaminated zeolite-based catalysts. The excellent catalytic performance exhibited was attributed to the combination of three effects. First to the absence or very low concentrations of acid sites in the delaminated ITQ-2 and ITQ-18 zeolites, respectively. The absence of acid sites would help to decrease the dehydration reaction that leads to the formation of ethylene and subsequent formation of coke, an important responsible of the catalyst deactivation. Second to their high external surface, which can provide a large surface for coke deposition and help to slow down the deactivation effects, and third to the especial structure of these delaminated zeolites formed by array of cups distributed along of sheets (see Figures 3 and 4), which can provide an excellent position for the stabilization of the Ni and Co metal particles improving their dispersion and preventing their agglomeration during the reduction and reaction stages. An important conclusion was that while an amorphous support such as SiO2 leads to Co and Ni-based catalysts with low stability, the use of delaminated zeolites, with a crystalline structure, allowed to prepare a much more stable bioethanol steam reforming catalyst.
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In the before reported studies zeolites acting as simple supports for metals for ethanol steam reforming.98-101 However, since zeolites exhibit functional properties such as ion exchange, the charge state of the metal could be affect to the SR of ethanol. In this line Miyake et al.100 compared the ethanol reforming properties of zeolite Y supporting transition metals and encapsulating transition metal cations. They studied the catalytic activity of conventional zeolite Y with a Si/Al ratio of 2.75, loaded with Ni and Co and their cations. The results obtained suggest that transition metals selectively enhanced the dehydrogenation of ethanol. In addition, the incorporated transition metal cations by ion exchange led to the production of mainly C2H4 during ethanol steam reforming, indicating that the presence of the cations accelerates the dehydration of ethanol. Thus, the presence of transition metal cations in zeolite Y seems to have a significant influence on the ethanol reforming reaction. These authors suggest that conventional zeolites supporting transition metals are more attractive for industrial applications than zeolites with a high Si/Al ratio supporting noble metals, due to advantages of cost and availability, although the H2 yields produced by Y zeolite containing Co and Ni cations were inferior to that for zeolite Y supporting Rh99. In addition, they think that H2 production from ethanol using zeolites with low or medium Si/Al ratios supporting transition metals such as Co and Ni could be improved by the removal of the metal cations within the zeolites. One important factor affecting the stability of steam reforming catalysts is the formation of carbonaceous deposits. These deposits can block the active sites and finally encapsulate the metallic particles deactivating the catalyst completely. Therefore, the stability of the catalysts is directly related to their tendency to form carbon. The coke formation on the catalysts during reforming of ethanol is due to the imbalance between their formation and consumption reactions (Table 2). This balance formation/consumption is determined by the reaction conditions and especially by the selected catalyst composition: active phase and support. In order to reduce the coke formation over zeolite based catalysts and increase the ethanol SR activity at low temperature, Kang et al.104 prepared MgO/Zeolite Y catalysts loaded with bimetallic Ni-Ga. The impregnation of Ga between the Ni and Mg components led to significantly higher reforming activity compared to the conventional Ni/Mg/Zeolite Y catalyst. The main products from steam reforming over the Ni/Ga/Mg/Zeolite Y catalyst were only H2 and CH4 at above 550C, and the catalytic performances depended on the amount of Ga. H2 production and ethanol conversion
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were maximized over Ni(10)/Ga(30)/Mg(30)/Zeolite Y at 700C, Ethanol:H2O=1:3 and a gas hourly space velocity (GHSV) of 6740 h-1. maintained for up to 59 h. These authors also studied the deactivation of these catalysts. They found that deactivation was largely retarded in the zeolite-based catalyst containing Ga compared to that of the catalyst without Ga. The authors reported that after 60 h the XRD peaks of the carbon and Ni metal were too enlarged while the other peaks assigned to metal or metal oxides species were very small, Figure 5. The improved stability at the slower deactivation rate achieved with the Ni/Ga sample could not be unequivocally attributed to carbon formation. The simultaneous addition of Ni/Ga could also have depressed the sintering between the Ni and the support, contributing to retard the catalytic deactivation. This high performance was

Figure 5. Comparison of XRD patterns of the catalysts, Ni(10)/Ga(x)/Mg(30)/Zeolite Y (x =0,10,20,30), according to the reaction temperature, before and after reaction104.

It is clear that basicity decreases significantly the formation of coke since contributes to the inhibition of side reactions that would led to the formation of coke
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precursors (Table 2). In this sense Miyake et al.105 studied the ethanol steam reforming over Ni supported on zeolite Y with basicity controlled by the exchange of alkali cations. As a result, it was found that the exchange of Na+ for K+ and Cs+ affected not only characteristics of the zeolites such as adsorption and basicity, but also those of Ni, such as reducibility and catalytic activity. Ion exchange mainly brought an increase of basic sites, which were slightly strengthened. It was found that Ni species on the Cs-Y zeolite were reduced at a lower temperature than Na-Y zeolite. H2 production at 300C was improved in the order of Ni/Na-Y < Ni/K-Y < Ni/Cs-Y, according to the size of the cation in the zeolite and the amount of basic sites. Improvement of the catalytic performance was considered to be due to the increase of basic sites, which weaken the OH bond of ethanol adsorbed on the zeolite. In terms of elementary reactions, the dehydrogenation reaction of ethanol was accelerated by the basicity of the zeolite, whereas the dehydration reaction that produces ethylene was inhibited. The basicity of the zeolite was found to be effective for the inhibition of coke deposition, because Ni/Cs-Y with higher H2 production than Ni/Na-Y also exhibited higher resistance to carbon deposition. In summary, an increase of the zeolite basicity by cation exchange can selectively promote the dehydrogenation of ethanol by Ni on the zeolite, and improve H2 production and resistance to carbon deposition. Ni and Co has been the active site more studied in the SR of ethanol using zeolites as support. Nevertheless, other metals as Sn has been also found actives. Kang et al.106 studied the production of hydrogen using Y zeolite promoted with Sn and K. They studied the effects of the Sn and K presence on the H2 production and on the catalytic deactivation. They reported that the Sn component played an important role in the oxidation of the feed gases during ethanol reforming, while the addition of the K depressed the formation of CH4 or others hydrocarbon intermediates. Based on the results of H2-TPR and NH3-TPD, they suggest that the reduction of Sn oxides (Sn4+ to Sn0) on SnO2-K2O/Y catalyst at low temperatures easily occurs compared to conventional Ni/-Al2O3 catalysts. In addition, the acidity of the Ni/-Al2O3 catalyst induced by the existing Al is higher than that presented in the SnO2-K2O/Y catalyst. Thus, the condensation of ethanol on the last catalyst is more difficult and consequently the formation of the coke is lower, and eventually the higher activity over SnO2K2O/ZY catalyst is maintained. Considering all the before mentioned it seem that the use of zeolites as metal support to prepare active and stable reforming catalyst to produce hydrogen could be an
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attractive option since they have a high external surface area, and can be prepared with neutral behaviors if they are synthesized all silica, with high Si/Al ratios or exchanged with alkaline metals. However, pore opening of zeolites can limit their application to the reforming of large molecules. Thus, mesoporous molecular sieves with size-tunable mesopores have attracted a great deal of attention because of their controllable structure and composition.107,108 However, unlike zeolites, the wall of the mesoporous is amorphous, not crystalline. Therefore, mesoporous aluminosilicates cannot exhibit the excellent catalytic properties unlike acidic zeolites. Moreover, their hydrothermal stability is especially low. To overcome this problem, one strategy has been the generation of mesoporosity on zeolites.109-111 The presence of mesopores in the crystalline of the zeolite would be equivalent to increasing the external surface of the zeolites making a larger number of pore openings accessible to the large reactants.112-118 On the other hand, the presence of mesoporous could improve the diffusion affecting to the ion exchange processes and catalytic reaction.119-126 Although ethanol is a small molecule from biomass processing, most part of the molecules from biomas susceptible to be reformed are large (i.e. glycerin, sugars, cellulose, lignin, hemicellulose, etc), making of the mesopore-modified zeolites an attractive material to prepared hydrothermally stable steam reforming catalysts. In this line Chica et al.127 studied the effect of mesopores-modified Mordenite zeolite promoted with Ni in the steam reforming of bioetanol. They reported the alkaline treatment of a commercial Mordenite to generate mesoporosity (Figure 6). The idea was to generate mesoporosity in the commercial Mordenite zeolite in order to improve the exchange of alkaline cation (to remove the acidity) and create good positions for the incorporation and stabilization of Ni metallic particles (active sites for steam reforming of bioethanol). They found that reforming activity of catalyst based on mesopores-modified Mordenite was significantly higher than that shown by the commercial one (without mesopores). The lower size of the Ni metallic particles supported on mesopores-modified Mordenite was the main responsible of this high activity. H2 selectivity and catalytic stability were also found higher for the mesopore-modified material. They reported that the formation of coke precursors (favored by acid sites) and the subsequent deposition of carbon was lower in the mesopore-modified Mordenite. This effect is explained by the generated mesoporosity, which would be improving first the Na exchange and thus, the neutralization of the acid sites, and second the diffusion of the reactants and products, avoiding the blockage of micropores. Indeed, for the same Na exchange conditions the
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amount of Na exchanged was found higher in the mesopores-modified Mordenite (4.2 wt.% against 2.9 wt.% for original Mordenite), suggesting that the presence of mesopores would improve the exchange of protons (responsible of acid sites) by sodium cations. On the other hand, they observed a higher enlargement of the Ni metallic particles supported on not treated Mordenite (without mesopores), suggesting that generated mesoporosity could be contributing the generation of good position for the incorporation and stabilization of Ni metallic particles, avoiding or decreasing the Ni sinterization and thus, improving the catalytic activity and stability.

Figure 6. TEM microphotographs of original and alkaline treated Mordenite to generate mesoporosity. Adapted from reference 127.

All the works mentioned above have been centered in the reforming of ethanol or bioethanol in gas phase. Nevertheless, in literature is also reported the use of zeolites in the reforming of ethanol in liquid phase. Aqueous phase reforming (APR) has been recently reported by Dumesic et al..128-130 This process operates at low temperatures (<300 C), at which the WGS reaction is also thermodynamically favored, making it capable of producing hydrogen with high yields. The low reaction temperature minimizes the decomposition reactions and, hence, avoids carbonization and catalyst deactivation. Weikau et al.131 studied the feasibility of platinum-loaded NaY zeolite catalysts for APR of methanol and ethanol. The feasibility of APR of ethanol was demonstrated on the Pt/NaY catalysts. The results were compared with the data on Pt/Al2O3 catalysts. At 538 K, the 0.5 wt % Pt/NaY achieved higher H2 selectivity and lower alkane selectivity than the 3 wt % Pt/-Al2O3 catalyst with similarly high ethanol conversion of 97% on both catalysts. The zeolite-based catalysts, with the advantages of high activity, reduced use of precious metal, and low cost of zeolite materials,
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deserve further investigations. They report that research is ongoing into the effect of substrate properties on the catalytic performance of platinum catalysts in APR reactions. 2.2.- Zeolites as constituent of photocatalysts for the sustainable production of hydrogen via water splitting. 2.2.1.- Solar energy and water splitting reaction. The incidence of solar energy on the surface of the earth (180.000 TW) by far exceeds all human energy needs.132 Thus, it is easy to understand that the solar energy could be considered one of the most important renewable energy sources potentialy available in the earth. Undoubtedly, solar energy is the largest renewable carbon-free resource amongst all other renewable energy options. However, to make usable this energy by the currently human technology, solar energy must be captured, converted, and stored in order to assure a continue supply of energy and overcome the diurnal cycle and the intermittency of the terrestrial solar resource. Among the different energy carries capturing the solar energy, hydrogen from photocatalytic water splitting is considered as one of the most promised carriers since allows storing solar energy in the form of chemical energy and makes available solar energy for 24 hours a day, 7 days a week. In the photocatalytic water splitting, hydrogen is produced from water using sun light and specialized semiconductors. The semiconductor uses light energy to directly dissociate water molecules into hydrogen and oxygen. The water splitting takes place when the semiconductor is irradiated with light in the presence of an electron donor and acceptor, oxidizing OH- ions to produce O2 and reducing H+ ions to H2. Specifically, the electrons in the valence band of the photocatalyst are excited to the conduction band, while the holes are left in the valence band. This, therefore, creates the negativeelectron (e-) and positive-hole (h+) pairs. This stage is referred to the semiconductors photo-excited state, and the energy difference between the valence band and the conduction band is known as the band gap. This must correspond to the wavelength of the light for it to be effectively absorbed by the photocatalyst. After photoexcitation, the excited electrons and holes separate and migrate to the surface of photocatalyst. In the photocatalytic water-splitting reaction, they are used as reducing agent and oxidizing agent to produce H2 and O2, respectively. A esquematic representation of the principle
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of the photocatalytic system for water is shown in Figure 7.133 As it can be seen, first, the O-H bonds of two water molecules need to be broken with the simultaneous formation of one O=O double bond as follows.134
H2O O2 +4e- + 4H+, Eanodic=1.23 V 0.059 (pH) V (NHE)

Since this reaction requires a high oxidizing potential, 1.23 V vs. NHE (normal hydrogen electrode) (pH=0), the top level of valence band has to be more positive than this potential, so that the photogenerated holes have enough energy to oxidize water. This reaction releases four protons (H+) and four electrons (e-), which need to be combined to form two H2 molecules, as follows:133
4H+ + 4e- 2H2, Ecathodic = 0 V 0.059 (pH) V (NHE)

Therefore, the conduction band of the semiconductor has to be more negative than water reduction potential [0 V vs. NHE (pH=0)]. Thus, water molecules are oxidized by the holes to form O2 and reduced by the electrons to form H2 for overall water splitting. Therefore, the theoretical minimum band gap for water splitting is 1.23 eV that corresponds to light wavelength of about 1000 nm.

Figure 7. Schematic diagram of band edge requirements for water splitting reaction. Adapted from 134.

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2.2.2.- Photocataysts and zeolites for water splitting.

Currently, the photocatalytic water splitting over semiconductor materials is an area of great interest due to the potential of hydrogen as a clean-energy fuel source. Since the initial works of Fujishima and Honda,135 who discovered that water can be photoelectrochemically decomposed into hydrogen and oxygen using a semiconductor (TiO2) electrode under UV irradiation, a extensive variety of materials (TiO2, CdS, ZnO, ZrO2, titanates, niobates, and tantalates)136-148 have been reported to be effective for the photocatalytic decomposition of water. Initial efforts in this area involved large bandgap (Eg > 3.0 eV) semiconductors that used only UV light. Currently, the most important efforts are being focused on using visible light as the energy source149-167 as the ultimate goal to produce hydrogen fuel using solar energy. While the overall redox potential of the reaction:
H2O + h H2 + O2

is only -1.23 eV (1000 nm) at pH 7, the crucial reaction for hydrogen production is believed to be the initial one-electron transfer to H+ ion
H+ + e-aq Haq

where EH = -2.5V at pH 7, which falls energetically within the visible region of light. Taking int account the basic mechanism and reactions of photocatalytitc water splitting process the photocalysts should meet several characteristics with respect to semiconducting and electrochemical properties:169-173 (1) narrow band gap (1.23 eV< Eg < 3.0 eV) and band edge potentials suitable for overall water splitting to be activated under visible light, (2) successive separation of photo-excited electrons from reactive holes, (3) minimum energy losses associated with charge transport and recombination of photo-excited charges , (4) corrosion and photocorrosion resistivity in aqueous mediums, (5) facilitated electron transfer properties from photocatalyst surface to water, and (6) low production cost. To meet part of the above mentioned expectations extensive studies have been performed based on the use of support where effective photocatalysts have been impregnated.174-181 The major incentives for implementing the supported photocatalyst idea are: (1) inhibition of the back electron transfer as limiting parameter in redox
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systems, (2) taking advantage of nano-sized semiconductors while using them in easily separable micro-sized level of the support, (3) utilizing the support to add more solid chemical promoters, and (4) structural and chemical characteristics of the support by itself. Among the different supports used to prepare efficient water splitting photocatalysts zeolites are presented as promised materials. Zeolites exhibit high surface area, unique nanoscaled porous structure and ion exchange properties which can be used in the design of highly efficient photocatalysts.182 Unique photocatalytic properties, which cannot be realized in normal catalytic systems, have been observed recently in such modified spaces.183-188 It is important to note that zeolites can are also provide specific photo physical properties such as the control of charge transfer and electron transfer processes189-192 very important in photocatalytic reactions. There are several advantages that zeolites afford as support or host of semiconductor particles. For example, the pore sizes of the host support material control the resulting particle size of the supported semiconductor. Particle size is a crucial factor in the dynamics of electron/hole recombination processes, especially in semiconductor nanomaterials, and that the movement of electrons and holes is primarily governed by thewell-known quantum confinement.193 Generally, a decrease in particle size could be expected to lead to a higher efficiency in photocatalysis.194-199 This was because the bulk charge recombination of photogenerated electrons and holes, dominant in the wellcrystallized large semiconductor particles, was reduced by decreasing particle size. Reductionin particle size could also lead to a larger surface area and increased the available surface active sites.200-202 Decreasing particle size has a known beneficial effect on catalyst efficiency.203206

Furthermore, encapsulation into a porous structure should provide some protection

against surface-mediated reactions that corrode the catalyst, as exposed surface area will be limited. In addition, a major factor that limits the efficiency of the most part of the photocatalysts, is electron-hole recombination. The incorporation of photocatalysts into the micropore structure of zeolite in order to prepare nanoparticles, is an attempt to improve their photocatalytic activity and photostability. Small nanoparticles show a higher photocatalytic activity compared to the bulk materials due to changes in the surface area, band gap, morphology and generation of surface defects.207,208 In addition, the incorporation of photocatalyst into solid matrices as zeolites is reported to suppress photocorrosion and improve the
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activity for water reduction. The incorpoared photocatalysts nanoparticles, whose sizes are determined by the nanometric size of zeolite cages, show some novel physical properties such as blue shift of optical absorption spectra, increased photooxidation potentials, and third-order nonlinear optical properties. In this line Satish et al.209 reported the preparation of cadmium sulphide (CdS) nanoparticles by precipitation process using different zeolite matrices as templates (H-Y, HZSM5 and H-). In this study the micropores of zeolites were used as mold to prepare nanoparticles of CdS with different size. After removed the zeolite phase the CdS nanoparticles were used as catalysts for the photocatalytic decomposition of water. The hydrogen evolution rate was found higher than that presented by the bulk samples which correlated quite well with the particle size and surface area. Of particular interest is the use of zeolites as support, because of the welldefined microporous extructure and ion-exchange properties, as before was mentioned. One of the frist work reported in literature about the use of zeolites as support to produce hydrogen by water splitting process was carried out by Pettit et al..207 They estudied the photocatalytic hydrogen evolution on zeolite-supported CdS particles modified by surface modification with an appropriate hydrogen evolution catalyst (Pt or ZnS). Particles formed within the zeolite cavities aggregate upon exposure to water, and small clusters were isolated within individual cavities only in nonaqueous solvents at low CdS loading levels (<3%). Sustained hydrogen evolution required the presence of an added sacrificial donor (S2-/SO32-). Platinum deposited on the photoactive CdS surface is exclusively found inside the cavity, where it was inaccessible to large anionic reagents. Hoffman et al.210 also studied the water splitting activity of CdS particles supported on several micro and mesoporous silicas (zeolites: Y and L, mesoporous: SBA-15). Specifilly they studied the hydrogen production from water/ethanol solutions using visible light. All catalysts were active in the photocalytic water splitting with the following order of photoreactivity: zeolite-Y > SBA-15 > zeolite-L. They found that optimization of reaction conditions (i.e.: pH, ionic strength, and water-to-alcohol ratios) was critical to achieving a high level of hydrogen production. Preventing loss of CdS during the course of the photoreaction is also paramount to creating a stable, long term use catalyst. Specifically, they found that there was an efficient dispersion of CdS nanoclustes into the cages and micropores of zeolite Y, the quantum confinement of hydrated CdS increased the reduction potential for the bound proton to hydrogen atom
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electron transfer, and finally the confined CdS supercluster in a more efficient chromophore in the visible portion of the spectrum. The water splitting activity with visible light using CdS nanocomposites [quantum-sized (Q-sized) CdS, CdS nanoparticles embedded in zeolite cavities (CdS/zeolite), and CdS quantum dots (Q-CdS) deposited on KNbO3 (CdS/KNbO3 and Ni/NiO/KNbO3/CdS)], was also investiges by Hoffmann et al..211 They reported that the rate of H2 production in alcohol/water mixtures and other electron donors at 400 nm was clearly higher in the the hybrid catalysts, including zeolite-based photocatalys. The relative order of reactivity as a function of catalyst is Ni(0)/NiO/KNbO3/CdS > Ni(0)/KNbO3/CdS > KNbO3/CdS > CdS/NaY-zeolite >CdS/TiY-zeolite > CdS, while the reactivity order with respect to the array of electron donors is 2-propanol > ethanol > methanol > sulfite > sulfide. Titanum exchanged zeolites have been also studied in the water splitting reaction. Khan et al.212 were one of the first reporting the use of titano-zeolites to produce hydrogen by water splitting. In their study the Ti was exchanged and incorporated into the framework of zeolite A. Specifically, they estudied the effect of several variables on the photo-assisted production of hydrogen over this titaniumexchanged zeolite. They tried to increase the hydrogen yield keeping the catalytst losses during exchange with TiCl3 to a miniumun. During the reaction oxygen tended to react with titanium ions exchanged on zeolite forming titanium oxides with ultimely left the zeolite surface thereby creating vacant sites. These vacant sites were occupied by hydrogen. After the absorbed hydrogen was suscesfully displaced from the zeolite structure by the addicion of base. Zeolites containg titanium in their framework have been also used as support of CdS nanoparticles. In this line Guan et al.213,214 studied the water splitting activity of CdS encapsulated on ETS-4 and ETS-10 titanosilicalite zeolite. They found a stable photocatalytic activity uner visible light irradiation (>420 nm) in aqueous solution containing Na2S and Na2SO3 as electron donors. Specifically, the catalytic activity for the zeolite-based photocatalyts was found higher than for CdS bulk (17.5 and 13,3 mol H2/h/g catalyst for CdS/ETS-4 and CdS/ETS-10 respectively, and 8.3 mol H2/h/g catalyst for CdS bulk). These results seem to indicate that the encapsulation of CdS in these titanosilicalite zeolites is efective for separating charge-carries photogenerated in CdS and for improving the activity as well as the stability.

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Devotta et al.215 reported the use of zeolite Y to prepare highly efficient water splitting catalysts under visible light. The reported the incorporation in the zeolite Y of titanium dioxide (TiO2), heteropolyacid (HPA) and transition metals like cobalt (Co). They got a photocatalyst where the TiO2 was effectively dispersed and stabilized on the zeolite surface. The high efficiency of the composite photocatalyst was explained by the sinergetic work of TiO2 with Co and heteropolyacid , which made the material active in visible light for photoreduction of water to hydrogen. They also reported that the aluminosilicate framework of zeolite also contributed towards delayed charge separation. In the before studies zeolites have been used for the separated incorporation of nanoparticles of CdS and titanium (as titanium oxide particles (TiO2) or Ti3+ taking part of the zeolite framework). In this way improved water splitting catalysts were obtained. Recenty works carried out by Dutta et al.216 report the incorporation of both semiconductors in zeolite Y. They observed improvements in H2 evolution rates of 300 for CdS/TiO2-zeolite Y over TiO2-zeolite Y and 18 for CdS/TiO2-zeolite Y over CdS-zeolite Y. These improvements exceed colloidal binary systems reported in the literature. On the other hand, improvements in the H2 evolution rate of the ternary system Pt/CdS/TiO2-zeolite Y was not as marked, as compared to the best colloidal ternary systems reported in the literature. They proposed an interesting model to explain the colocalization of the TiO2 and CdS nanoparticles supported on zeolite Y. This model explains quite well the high activity of binary system (CdS/TiO2-zeolite Y) and also why the incorporation of Pt did not improve the catalytic activity of the ternary system (Pt/CdS/YiO2-zeolite Y). The main reason was that Pt needed to be associated only with TiO2 for best H2 evolution, and the zeolite promoted self-assembly did not provide a route for positioning the Pt only on the TiO2 particles. New strategies for the incorporation of Pt will be required in order to promote the association of Pt only with TiO2. 3.- Conclusions. The intense exploitation of fossil fuels to satisfy the globally growing energy demand has caused an increase of CO2 in the atmosphere and therefore, a significant global warming (green house effect). Furthermore, the reserves of fossil fuels on earth are finite and no matter how long they will last, a cleaned and renewable energy alternative independent of fossil fuels has to be developed for the future. Hydrogen
26

could be a good option because exhibits the greatest heating value (39.4 kWh/kg) of all chemical fuels. Its combustion to heat or power is simple and clean. When combusted with oxygen hydrogen forms water and no pollutants are generated or emitted. About 95% of the hydrogen we use today comes from reforming natural gas. But to realize the full benefits of a hydrogen economy, increased energy security, diverse energy supply and reduced air pollution hydrogen must be produced cleanly, efficiently, and affordably from available renewable resources. Thus, renewables are a desired energy source for hydrogen production. However, there are many challenges to produce hydrogen from renewables and probably the major one is developing new catalytic process to produce sustainable hydrogen and reducing the cost to be competitive with the current fuels (gasoline and diesel). Zeolites are presented as excellent catalysts and support of catalysts due their very special physico-chemial properties: High surface area. Molecular dimensions of the pores. High adsorption capacity. Partitioning of reactant/products. Possibility of modulating the electronic properties of the active sites. Possibility for preactivating the molecules when in the pores by strong electric fields and molecular confinement. Currently, new scientific applications are been developed for these materials. Among them the production of green fuels from renewable sources is focousing a large part of the research efforts. Two different routes to produce sustainable hydrogen using zeolites have been described and revised in this review. One of them is based in the biomass conversion via indirect thermochemical conversion to intermediate products. The indirect thermochemical option is related to the conversion of biomass to biofuels (bioethanol, biodiesel, biogas), followed by catalytic steam reforming of them to hydrogen. An advantage of this approach is that the biofuels, as an intermediate product, has a higher energy density than the biomass feedstock and can more easily be transported. Specifically, in this review has been considered the steam reforming of bioethanol. Renewable bioethanol is an interesting hydrogen source through steam reforming, but its CC bond promotes parallel reactions, mainly coke and by-products formation. In this way, good ethanol reforming catalysts are still needed. The use of
27

zeolites has been shown that can improve the catalytic activity, selectivity and stability of the bioethanol steam reforming catalytsts. It has been reported that zeolites play an important role in the preparation of highly active and selective ethanol steam reforming catalysts since they help in the dispersion of metal active sites and enhance their activity via metal-support interactions. Specifically it has been found that high surface areas of the support improve the catalytic activity and the particular topology or crystalline structure of one support can affect the metal dispersion of the metallic particles improving their stability against sinterization. Another interesting option analyzed in this reviewer, with enormous potential but requiring more development time, has been the photocatalytic decompsiton of water using solar energy, also called watter splitting. In the photolysis of water solar photons area used to produce hydrogen directly via electrochemical systems. This method involves the disassociation of water into hydrogen and oxygen directly at the surface of a semiconductor through the irradiation the semiconductor by solar photons. The photovoltaic semiconductor material acts as a catalyst to produce hydrogen directly at the semiconductor and water interface. It has been shown that among the different supports used to prepare efficient water splitting photocatalysts zeolites are presented as promised materials. Zeolites exhibit high surface area, unique nanoscaled porous structure and ion exchange properties which can be used in the design of highly efficient photocatalyst. In addition, zeolites can are also provide specific photo physical properties such as the control of charge transfer and electron transfer processes very important in photocatalytic reactions. It has been seen that there are several advantages that zeolites afford as support or host of semiconductor particles. For example, the pore sizes of the host support material control the resulting particle size of the supported semiconductor. Semiconductors such as TiO2 and CdS have been incorporated in zeolites in order to improve their photocatalytic activity and photostability. Small nanoparticles of these semiconductors incorporated in zeolites have been reported that show a higher photocatalytic activity compared to the bulk materials due to changes in the surface area, band gap, morphology and generation of surface defects. In addition, the incorporation of photocatalyst into zeolites helps to suppress photocorrosion and improves the activity for water reduction. Although the studies here presented using zeolites can be considered promised, the major problem to solve would be to find a
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semiconductor material that had the right photoelectrochemical properties, while being economical and robust enough to withstand the severe chemical and physical environment. 4.- References. [1] Cronstedt A F, Akad Handl. Stockholm, 1756, 18, 120 [2] Barrer R.M, D.A. Ibbison, Trans. Faraday Soc., 1944, 40, 195. [3] Barrer R.M., British Patent 574911, 1944. [4] Barrer R.M., J. Soc. Chem. Ind., 1945, 64, 130. [5] Breck D.W., J. Chem. Education, 1964, 48, 678. [6] Milton R.M., in: Molecular Sieves, Soc. Chem. Industry, London, 1968, p. 199. [7] Rabo J.A, Catal. Rev. Sci. Eng., 1981, 23, 293. [8] Flanigen E. M., (Ed: H. van Bekkum, E.M. Flanigen, J.C. Jander), Elservier, Amsterdan, 1991, 1, 1930. [9] Houdry E., Burt W.F., Pew A.E., Peters W.A., Oil and Gas Journal, Engineering and Operating Section, 1938, 37, 40-45. [10] http://www.iza-online.org/ [11] Newsman J.M, Science, 1986, 231, 1093. [12] Meier W.M., Olson D.H., Atlas of Zeolite Structure Types (Structure Commission of the International Zeolite Asociation), 1978. [13] Freyhardt C. C., Tsapatsis M., Lobo R. F., Balkus K. J., Jr., Davis M. E., Nature, 1996, 381, 295; Lobo R. F., Tsapatsis M., Freyhardt C. C., Khodabandeh S., Wagner P., Chen C. Y., Balkus K. J., Zones S. I., Davis M. E., J. Am. Chem. Soc., 1997, 119, 8474; Wessels T., Baerlocher C., McCusker L. B., Creyghton E. J., J. Am. Chem. Soc., 1999, 121, 6242. [14] Wagner P., Yoshikawa M., Lovallo M., Tsuji K., Taspatsis M., Davis M. E., Chem. Commun,. 1997, 2179. [15] Burton A., Elomari S., Chen C. Y., Medrud R. C., Chan I. Y., Bull L. M., Kibby C., Harris T. V., Zones S. I., Vittoratos E. S., Chem. Eur. J., 2003, 9, 5737. [16] Strohmaier K. G., Vaughan D. E. W., J. Am. Chem. Soc., 2003, 125, 16035. [17] Corma A., Diaz-Cabaas M. J., Jorda J. L., Martinez C., M. Moliner, Nature, 2006, 443, 842. [18] Sun J. L., Bonneau C., Cantin A., Corma A., Diaz-Cabanas M. J., Moliner M., Zhang D. L., Li M. R., Zou X. D., Nature, 2009, 458, 1154.
29

[19] Davies M.E., Saldarriaga C., Montes C., Garces J., Crowder C., Nature, 1988, 331, 698. [20] Csicsery S. M., Zeolite Chemistry and Catalysis. ACS, Monograph, 1976, 171, 680. [21] Csicsery S. M., Zeolites, 1984, 4, 202. [22] Derouane E. G., Stud. Surf. Sci. Catal, 1980, 5, 5. [23] Derouane G.E., Zeolite Science and the Technology. NATO ASI series E80, Martinus Nijhoff Pub, The Hague, 1984, 374. [24] Corma A., Chem. Rev., 1995, 95, 559. [25] Corma A., Martinez A., Adv. Mater., 1995, 7, 137. [26] Weitkamp J., Ernst S., Catal. Today, 1994, 19, 107. [27] Kaeding W. W., Young L. B., Weinstein B., Butter S. A., J. Catal., 1981, 67, 159. [28] Milton R. M., Molecular Sieves. Soc. Chem. Ind., London, 1968, 199. [29] Anderson R. A., ACS Symposium, Ser., 1977, 40, 637. [30] Minato H., Tamura T., Natural Zeolites: Ocurrence, Properties and Use. Pergamon, London, 1978. [31] Flanigen E. M., Proc. Conf. Properties and Applications of Zeolites Conf. Naples, 1980, 760. [32] Broughton D. B., Chem. Eng. Progr., 1977, 73, 49. [33] Odawara H., Noguchi Y., Ohno M., US Patent 4,014,711, 1977. [34] Neuziland R. W., Preighitz J. W., US Patent 4,024,331, 1977. [35] Novkov J., Dolejek Z., Zeolites, 1990, 10 (3), 189. [36] Antunes A.P., Ribeiro M.F., Silva J.M., Ribeiro F.R., Magnoux P., Guisnet M., Appl. Catal. B: Environmental, 2001, 33 (2), 149. [37] Bolton A.P., Experimental Methods in Catalytic Research, Vol. II, Academic Press, NY, 1976. [38] Flanigen E. M., Zeolites; Science and Technology, NATO ASI, (Ed. F. R. Ribeiro y col.), p. 4 artinus Nijhoff Publishers, The Hage, 1984. [39] Haynes H.W., Catal. Rev. Sci-Eng., 1978, 17(2), 273. [40] Flanigen E.M., Proc. 5th International Zeolite Conference, p. 760, (Ed. L.V.C. Rees), Heyden, London, 1980; Beyer H., Belenykaja I., Catalyisis by Zeolites, p. 203, (Eds. Imelik y col.), Elsevier Sc. Publisher Co., Amsterdam, 1987; Scherzer J., Bass J.L., J. Catal., 1973, 28, 101. [41] Anderson R.A., ACS Symposium Series, 1977, 40, 637. [42] Chen N.Y., J. Phys. Chem., 1976, 80, 60.

30

[43] Flanigen E.M., Bennet J.M., Grose R.W., Cohen J.P., Patton R.L., Kirchner R.M., Nature, 1978, 271, 512. [44] Flanigen E.M., Patton R.L., US Patent 4,073,865, 1978. [45] Breck D.W., Proceeding of the Conference on the Properties and Applications of Zeolties, Soc. Chem. In., London, 18-20 abril, 1979. [46] Barret R.M., Zeolites and Clay Minerals as Sorbents and Molecular Sieves, Academic Press, London, 1978. [47] Breck D.W., Zeolite Molecular Sieves, Ed. Wiley, New York, 1974; Scherzer J., Bass J.L., Hunter F.G., J. Phys. Chem., 1975, 79, 1194. [48] Venuto P.B., Hamilton L.A., Landis P.S., J. Catal., 1996, 5, 484; Ward J. W., J. Phys. Chem., 1968, 69, 4211. [49] Scherzer J., Bass J. L., Hunter F. G., J. Phys. Chem., 1975, 79, 1194. [50] Ozin G.A. , Kuperman A., Stein A., Angew. Chem. Int. Ed. Engl., 1989, 28, 359. [51] Wang Z., Mitra A. , Wang H., Huang L., Yan Y., Adv. Mater., 2001, 13fi, 746. [52] European Communities Office for Official Publications (2002). Hydrogen and electricity. New carriers and novel technologies for a future clean and sustainable energy economy. EU Brochure for the Sixth Framework Programme. KI-46-02-533EN-D. [53] Pea M. A, Gomez J. P., G. Fierro J. L., Appl. Catal. A, 1996, 144, 7. [54] Armor J. A., Appl. Catal, A, 1998, 176, 159. [55] Trimm D. L., Onsan Z. I., Catal. Rev. Sci. Eng., 2001, 43, 31. [56] Navarro R. M., Pea M. A., Fierro J. L. G., Chem. Rev., 2007, 107, 3952. [57] Milne T. A., Elam C. C., Evans R. J., Hydrogen from Biomass, Report for the International Energy Agency, No. IEA/H2/TR-02/001, 2002. [58] Hallenbeck P. C., Benemann J. R., Int. J. Hydrogen Energy, 2002, 27, 1185. [59] Gardner D., Renewable Energy Focus, 2009, 9 (7), 34. [60] Deluga G. A., Salge J. R., Schmidt L. D., Verykios X. E., Science, 2004, 303, 993. [61] Salge J. R., Dreyer B. J., Dauenhauer P. J., Schmidt L. D., Science, 2006, 314, 801. [62] Navarro R. M., Sanchez-Sanchez M. C., Alvarez-Galvan M. C., del Valle F.,. Fierro J. L. G, Energy Environ. Sci., 2009, 2, 35. [63] Vaidya P.D., Rodrigues A.E., Chem. Eng. J., 2006, 117, 39. [64] Kolios G., Glckler B., Gritsch A., Morillo A., Eigenberger G., Fuel Cells, 2005, 5, 52. [65] Haryanto A., Fernando S., Murali N., Adhikari S., Energy Fuels, 2005, 19, 2098.
31

[66] Meng M., Leung D.Y.C., Leung M.K.H., Int. J. Hydrogen Energy, 2007, 32, 3238. [67] Deluga G.A., Salge J.R., Schmidt L.D., Verykios X.E., Science, 2004, 303(5660), 993. [68] Fatsikostas N.A., Verykios X.E., J. Catal., 2004, 225, 439. [69] Llorca J., de la Piscina P.R., Sales J., Homs N., Chem. Commun., 2001, 641. [70] Diagne C., Idriss H., Kiennemann A., Catal. Commun., 2002, 3, 565. [71] Llorca J., de la Piscina P.R., Dalmon J.A., Sales J., Homs N., Appl. Catal. B, 2003, 43, 355. [72] Vanhaecke E., Roger A.C., Vargas J.C., Kiennemann A., 1st European Hydrogen Energy Conference, September, Grenoble, France, (2003), p. 2. [73] Batista M.S., Santos R.K.S., Assaf E.M., Assaf J.M., Ticianelli E.A., J. Power Sources, 2004, 134, 27. [74] Kaddouri A., Mazzocchia C., Catal. Commun., 2004, 5, 339. [75] Llorca J., Dalmon J.A., de la Piscina P.R., Homs N., Appl. Catal. A, 2003, 243, 261. [76] Haga F., Nakajima T., Miya H., Mishima S., Catal. Lett., 1997, 48, 223. [77] Idriss H., Platinum Met. Rev., 2004, 48, 105. [78] Bussi J., Bespalko N., Veiga V., Amaya A., Faccio R., Abello M.C., Catal. Commun., 2008, 10, 33. [79] Sun G.B., Hidajat K., Wu X.S., Kawi S., Appl. Catal. B, 2008, 81, 303. [80] Pereira E.B., Homs N., Marti S., Fierro J.L.G., de la Piscina P.R., J. Catal., 2008, 257, 206. [81] Fajardo H.V., Probst L.F.D., Carreno N.L.V., Garcia I.T.S., Valentini A., Catal. Lett., 2007, 119, 228. [82] Cavallaro S., Energy Fuels, 2000, 14, 1195. [83] Tth M., Dmk M., Raskx J., Hancz A., Erdohelyi A., Presented in the Technical Program, May 1619, Pisa, Italy, 2004. [84] Fierro V., Klouz V., Akdim O., Mirodatos C., Catal. Today, 2002, 75, 141. [85] Velu S., Satoh N., Gopinath C.S., Suzuki K., Catal. Lett., 2002, 82, 145. [86] Goula M.A., Kontou S.K., Tsiakaras P.E., Appl. Catal. B, 2004, 49, 135. [87] Sheng P., Idriss H., Vac J.. Sci. Technol. A, 2004, 22, 1652. [88] Srinivas D., Satyanarayana C.V.V., Potdar H.S., Ratnasamy P., Appl. Catal. A, 2003, 246, 323. [89] Machado N.R.C.F., Rizzo R.C.P., Peguen P.P.S., Acta Sci. 26, 2002, 1637.
32

[90] Galvita V.V., Belyaev V.D., Semikolenov V.A., Tsiakaras P., Frumin A., Sobyanin V.A., React. Kinet. Catal. Lett., 2002, 76, 343. [91] Platon A., Roh H.S., King D.L., Wang Y., Top. Catal., 2007, 46, 374. [92] Birot A., Epron F., Descorme C., Duprez D., Appl. Catal. B, 2008, 79, 17. [93] Cai W.J., Wang F.G., Zhan E.S., Van Veen A.C., Mirodatos C., Shen W.J., J. Catal., 2008, 257, 96. [94] Domok M., Baan K., Kecskes T., Erdohelyi A., Catal. Lett., 2008, 126, 49. [95] Bagasiannis A.C., Panagiotopoulou P., Verykios X.E., Top. Catal., 2008, 51, 1. [96] Llorca J, Homs N, Sales J, Ramirez de la Piscina P., J. Catal., 2002, 209, 306. [97] Da Costa-Serra JF, Guil-Lpez R, Chica A., Int. J Hydrogen Energy, 2010, 13, 6709. [98] Chica A, Sayas S., Catal Today, 2009, 146, 37. [99] Campos-Skrobotm F.C., Rizzo-Domingues R.C.P., Fernandes-Machado N.R.C., Cantao M.P., J. Power Sources, 2008, 183, 713. [100] Inokawa H., Nishimoto S., Kameshima Y., Miyake M., Int. J. Hydrogen Energy, 2010, 35, 11719. [101] Da Costa-Serra J.F., Chica A., Int. J. Hydrogen Energy, 2011, 36, 3862. [102] Corma A., Fornes V., Pergher S.B., Patent EP 9605004 (1996) and WO 9717290 (1997). [103] Corma A, Fornes V, Daz U., Chem Commun, 2001, 2642. [104] Kwak B.S., Lee J.S., Lee J.S., Choi B-H., Ji M.J., Kang M., Applied Energy, 2011, 88, 4366. [105] Inokawa H., Nishimoto S., Kameshima Y., Miyake M., Int. J. Hydrogen Energy, 2011, 36, 15195. [106] Lee J.S., Kim J., Kang M., Bull. Korean Chem. Soc., 2011, Vol. 32, N 6, 1912. [107] Kresge C.T., Leonowicz M.E., Roth W.J., Vartuli J.C., Beck J.S., Nature, 1992, 359, 710. [108] Inagaki S., Fuhushima Y., Kuroda K., J. Chem. Soc. Chem. Commun., 1993, 680. [109] Tao Y., Kanoh H., Abrams L., Kaneko K., Chem. Rev., 2006, 106, 896. [110] Perez-Ramirez J., Christensen C.H., Egeblad K., Christensen C.H., Groen J.C., Chem. Soc. Rev., 2008, 37, 2530. [111] Ogura M., Catal. Surv. Asia, 2008, 12, 16. [112] Corma A., Stud. Surf. Sci. Catal., 1989, 49, 49. [113] Groen J.C., Moulijn J.A., Prez-Ramirez J., J. Mater. Chem., 2006, 16, 2121.
33

[114] Verboekend D., Perez-Ramirez J., Catal. Science & Tecnology, 2011, 1, 879. [115] Groen J.C., Peffer L.A.A., Moulijn J.A., Prez-Ramrez J., Colloid. Surface. A: Physicochem. Eng. Aspect., 2004, 24, 5358. [116] Groen J.C., Caicedo-Realpe R., Abell S., Prez-Ramirez J., Mater. Lett., 2009, 63, 1037. [117] Tao Y., Kanoh H., Kaneko K., Adsorption, 2006, 12, 309. [118] Otten M.M., Clayton M.J., Lamb H.H., J. Catal., 1994, 149, 211. [119] Carvill B.T., Lerner B.A., Adelman B.J., Tomazack D.C., Sachtler V.M.W., J. Catal., 1993, 144, 1. [120] Holm M.S., Taarning E., Egeblad K., Christensen C.H., Catal. Today, 2011, 168, 3 [121] Park D.H., Kim S.S., Wang H., Pinnavaia T.J., Papapetrou M.C., Lappas A.A., Triantafyllidis K.S., Angew. Chem. Int. Ed., 2009, 48, 7645. [122] Park H.J., Park K.H., Jeon J.K., Kim J., Ryoo R., Jeong K.E., Park S.H., Park Y.K., Fuel, 2012, 97, 379. [123] Foster A.J., Jae J., Cheng Y.T., Huber G.W., Lobo R.F., Applied Catalysis A: General, 2012, 423-424, 154. [124] Neumann G.T., Hicks J.C., ACS Catal, 2012, 2, 642. [125] Jeon M.J, Kim S.S., Jeon K.J., Park S.H., Kim J.M, Sohn J.M., Lee S.H., Park Y.K., Nanoscale Research Letters, 2012, 7, 18. [126] Paixao V., Carvalho A.P., Rocha J., Fernandes A., Martins A., Micro and Mesoporous Materials, 2010, 131, 350. [127] Da Costa-Serra J.F., Navarro M.T., Rey F., Chica A., Int. J. Hydrogen Energy, 2012, 37, 7101. [128] Cortright R.D., Davda R.R., Dumesic J.A., Nature, 2002, 418, 964. [129] Davda R.R., Shabaker J.W., Huber G.W., Cortright R D., Dumesic J.A., Appl. Catal. B, 2005, 56, 171. [130] Huber G.W., Dumesic J.A., Catal. Today, 2006, 111, 119. [131] Tang Z., Monroe J., Dong J., Nenoff T., Weinkauf D., Ind. Eng. Chem. Res., 2009, 48, 2728. [132] Lewis N.S., Nocera D.G., Proceedings of the National Academy of Sciences of the United States of America, 2006, 103(43), 15729. [133] Chen X., Shen S., Guo L., Mao S.S., Chem. Rev., 2010, 110, 65036570. [134] Kudo A., Miseki Y., Chem. Rev., 2009, 38, 253.
34

[135] Fujishima A., Honda K., Nature, 1972, 238, 37. [136] Kudo A., Kato H., Tsuji I., Chem. Lett., 2004, 33(12), 1534. [137] Domen K., Naito S., Onishi T., Tamaru K., Chem. Phys. Lett., 1982, 92, 433. [138] Inoue Y., Kubokawa T., Sato K., Chem. Commun., 1990, 1298. [139] Takata T., Furumi Y., Shinohara K., Tanaka A., Hara M., Kondo J.N., Domen K., Chem. Mater, 1997, 9, 1063. [140] Kudo A., Sayama K., Tanaka A., Asakura K., Domen K., Maruya K., Onishi T., J. Catal., 1989, 120, 337. [141] Sayama K., Tanaka A., Domen K., Maruya K., Onishi T., J. Phys. Chem., 1991, 95, 1345. [142] Kudo A., Kato H., Chem. Lett., 1997, 867. [143] Ishihara T., Nishiguchi H., Fukamachi K., Takita Y., J. Phys. Chem. B, 1999, 1, 103. [144] Kudo A., Kato H., Nakagawa S., J. Phys. Chem. B, 2000, 104, 571. [145] Kato H., Kudo A., J. Phys. Chem. B, 2001, 105, 4285. [146] Kudo A., Asakura K., Kato H., J. Am. Chem. Soc., 2003, 125, 3082. [147] Zou Z., Ye J., Sayama K., Arakawa H., Nature, 2001, 414, 625. [148] Machida M., Yabunaka J., Kijima T., Chem. Mater., 2000, 12, 812. [149] Kato H., Kudo A., J. Phys. Chem. B, 2002, 106, 5029. [150] Ishii T., Kato H., Kudo A., J. Photochem. Photobiol. A, 2004, 163, 181. [151] Tsuji I., Kato H., Kobayashi H., Kudo A., J. Am. Chem. Soc., 2004, 126, 13406. [152] Tsuji I., Kato H., Kudo A., Chem. Mater., 2006, 18, 1969. [153] Yamasita D., Takata T., Hara M., Kondo J. N., Domen K., Solid State Ionics, 2004, 172, 591. [154] Niishiro, R., Kato H., Kudo A., Phys. Chem. Chem. Phys., 2005, 7, 2241. [155] Tsuji I., Kudo A., J. Photochem. Photobiol. A, 2003, 156, 249. [156] Diwald O., Thompson T. L., Goralski E. G., Walck S. D., Yates J. T. J., Phys. Chem. B, 2004, 108, 52. [157] Konta R., Ishii T., Kato H., Kudo A., J. Phys. Chem. B, 2004, 108, 8992. [158] Tsuji I., Kato H., Kudo A., Angew. Chem., Int. Ed., 2005, 44, 3565. [159] Thompson T. L., Yates J. T., Chem. Rev., 2006, 106, 4428. [160] Gole J. L., Stout J. D., Burda C., Lou Y. B., Chen X. B., J. Phys. Chem. B, 2004, 108, 1230. [161] Di Valentin C., Pacchioni G., Selloni A., Phys. Rev. B, 2004, 70, 18202.
35

[162] Hitoki G., Ishikawa A., Takata T., Kondo J. N., Hara M., Domen K., Chem. Lett., 2002, 736. [163] Kasahara A., Nukumizu K., Hitoki G., Takata T., Kondo J. N., Hara, M., Kobayashi H., Domen K. J., Phys. Chem. A, 2002, 106, 6750. [164] Kato H., Asakura K., Kudo A., J. Am. Chem. Soc., 2003, 125, 3082. [165] Shangguan W., Yoshida A. J., Phys. Chem. B, 2002, 106, 12227. [166] Koca A, Sahin M., Int. J. Hydrog. Energy, 2002, 27, 363. [167] Milczarek G., Kasuya A., Mamykin S., Arai T., Shinoda K., Tohji K., Int. J. Hydrog. Energy, 2003, 28, 919. [168] Mrowetz M., Balcerski W., Colussi A. J., Hoffmann M. R., J. Phys. Chem. B, 2004, 108, 17269. [169] Plunkett, J.R. and United States. Energy Information Administration., International energy outlook and projections, Nova Science Publishers, Hauppauge, N.Y., 2011. [170] Kudo A., Miseki Y., Chem. Soc. Rev., 2009, 38(1), 253. [171] Ni M., Leung M.K.H., Leung D.Y.C., Sumathy K., Renewable and Sustainable Energy Reviews, 2007, 11(3), 401. [172] Matsuoka M., Kitano M., Takeuchi M., Tsujimaru K., Anpo M.,. Thomas J.M., Catalysis Today, 2007, 122(1-2), 51. [173] Bak T., Nowotny J., Rekas M., Sorrell C.C., In. J. Hydrogen Energy, 2002, 27(10), 991. [174] Shaban Y.A., Khan S.U.M., Int. J. Hydrogen Energy, 2008, 33(4), 1118. [175] Lin H.Y., Lee T.H., Sie C.Y,. Int. J. Hydrogen Energy, 2008, 33(15), 4055. [176] Lin H.Y., Chen Y.F., Chen Y.W., Int. J. Hydrogen Energy, 2007, 32(1), 86. [177] Lunawat P.S., Senapati S., Kumar R., Gupta N.M., Int. J. Hydrogen Energy, 2007, 32(14), 2784. [178] Sathish M., Viswanathan B., Viswanath R.P., Int. J. Hydrogen Energy, 2006. 31(7), 891. [179] Koriche N., Bouguelia A., Aider A., Trari M., Int. J. Hydrogen Energy, 2005. 30(7), 693. [180] Ye J., Zou Z., Matsushita A., Int. J. Hydrogen Energy, 2003. 28(6), 651. [181] Bessekhouad Y., Trari M., Int. J. Hydrogen Energy, 2002. 27(4), 357. [182] Dutta P.K., Turbeville W., J Phys Chem, 1992, 96, 9410.

36

[183] Yamashita H., Fujii Y., Ichihashi Y., Zhang S.G., Ikeue K., Ryung D., Catal. Today, 1998, 45, 221. [184] Anpo M., Yamashita H., Ichihashi Y., Fujii Y., Honda M., J. Phys. Chem. B, 1997, 101, 2632. [185] Zhang S.C., Fujii Y., Yamashita H., Koyano K., Tatsumi T., Anpo M., Chem. Lett., 1997, 7, 659. [186] Anpo M., Matsuoka M., Shioya Y., Yamashita H., Giamello E., Morterra C., J. Phys. Chem., 994, 98(22), 5744. [187] Anpo M., Yamashita H., In: Anpo M, editor. Surface photochemistry. London: Wiley; 1996, p. 117. [188] Yamashita H., Ichihashi Y., Anpo M., Louis C., Che M., J. Phys. Chem., 1996, 100, 16041. [189] Chen H., Matsumoto A., Nishimiya N., Tsutsumi K., Colloids Surf., 1999, 157, 295. [190] Liu X., Lu K.K., Thomas J.K., Chem. Phys. Lett., 1992, 195, 163. [191] Liu X., Lu K.K., Thomas J.K., J. Chem. Soc. Faraday Trans., 1993, 89, 1861. [192] Kim Y., Yoon M., J. Mol. Catal. A Chem., 2000, 168, 257. [193] Chen X., Mao S.S., Chem. Rev., 2007, 107, 2891. [194] Ikeda S., Tanaka A., Shinohara K., Hara M., Kondo J.N., Maruya K., Domen K., Microporous Mater., 1997, 9, 253. [195] Hidalgo M.C., Aguilar M., Maicu M., Navo J.A., Coln G., Catal. Today, 2007, 129, 50. [196] Testino, A.; Bellobono, I. R.; Buscaglia, V.; Canevali, C.; DArienzo,M.; Polizzi, S.; Scotti R., Morazzoni F., J. Am. Chem. Soc., 2007,129, 3564. [197] Datta, A.; Priyama, A.; Bhattacharyya, S. N.; Mukherjea, K. K.;Saha, A. J. Colloid Interface Sci. 2008, 322, 128. [198] Chae S.Y., Park M.K., Lee S.K., Kim T.Y., Kim S.K., Lee W.I., Chem. Mater. 2003, 15, 3326. [199] Liu G., Sun C., Yang H.G., Smith S.C., Wang L., Lu G.Q., Cheng H.M., Chem. Commun., 2010, 46, 755. [200] Lee Y., Watanabe T., Takata T., Hara M., Yoshimura M., Domen K., Bull. Chem. Soc. Jpn., 2007, 80, 423. [201] Zhang Z., Wang C.C., Zakaria R., Ying J.Y., J. Phys. Chem. B, 1998, 102, 10871.

37

[202] Sun W., Zhang S., Liu Z., Wang C., Mao Z., Int. J. HydrogenEnergy, 2008, 33, 1112. [203] Bahnemann D. W., Kormann C., Hoffmann M. R., J. Phys. Chem., 1987, 91, 3789. [204] Hoffman A. J., Carraway E. R., Hoffmann M. R., Environ. Sci. Technol., 1994, 28, 776. [205] Hoffman A. J., Mills G., Yee H., Hoffmann M. R., J. Phys. Chem., 1992, 96, 5546. [206] Hoffman A. J., Yee H., Mills G., Hoffmann M. R., J. Phys. Chem., 1992, 96, 5540. [207] Fox M.A., Pettit T.L., Langmuir, 1989, 5, 1056 [208] Warrier M., Lo M.K.F, Monbouquette H., Garcia-Garibay M.A., Photochem Photobiol Sci, 2004, 3, 859. [209] Sathish M, Vishwanathan B, Vishwanath RP. Int J Hydrogen Energy 2006, 31, 891. [210] Ryu S.Y., Balcerski W., Lee T. K., Hoffmann M.R., J. Phys. Chem. C, 2007, 111, 18195. [211] Ryu S.Y., Choi J., Balcerski W., Lee T.K., Hoffmann M.R., Ind. Eng. Chem. Res. 2007, 46, 7476. [212] Yue P., Khan F., Int. J. Hydrogen Energy, 1991, 16(9), 609. [213] Guan G, Kida T, Kusakabe K, Kimura K, Fang X, Ma T, Chem Phys Lett 2004;385:31922. [214] Guan G., Kida T., Kusakabe K., Kimura K., Abe E., Yoshida A., Chem. Phys. Lett., 2004, 385, 319. [215] Dubey N., Rayalu S.S., Labhsetwar N.K., Devotta S., Int. J. Hydrogen Energy, 2008, 33, 5958. [216] White J.C., Dutta P.K., J. Phys. Chem. C, 2011, 115, 2938.

38

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