INTERNATIONAL JOURNAL OF ENERGY RESEARCH Int. J. Energy Res. 2007; 31:619636 Published online in Wiley InterScience (www.interscience.wiley.

com) DOI: 10.1002/er.1283

Selected nanotechnologies for renewable energy applicationsz

Samuel S. Mao*,y and Xiaobo Chen
Lawrence Berkeley National Laboratory, University of California at Berkeley, CA 94720, U.S.A.

SUMMARY As the world faces serious energy challenges, the development and implementation of renewable energy technologies become increasingly important. In this article, we oer a glimpse of the role nanotechnology, in particular, innovations of nanostructures and nanomaterials, is playing in the development of selected renewable energy technologies. These technologies, based on the authors research interests, include (1) converting the energy of sunlight directly into electricity using solar cells; (2) converting solar energy into hydrogen fuel by splitting water into its constituents; (3) storing hydrogen in solid-state forms; and (4) utilizing hydrogen to generate electricity through the use of fuel cells. It is clear that nanotechnologyenabled renewable energy technologies are starting to scale up dramatically. As they become mature and cost eective in the decades to come, renewable energy could eventually replace the traditional, environmentally unfriendly, fossil fuels. Published in 2007 by John Wiley & Sons, Ltd.
KEY WORDS:

renewable energy; nanotechnology

1. INTRODUCTION Today, about 80% of worldwide energy use is rooted in chemical energy stored in fossil fuel reserves. World Energy consumption is to increase by 71% from 2003 to 2030, according to the U.S. Department of Energys International Energy Outlook 2006, and fossil fuels (oil, natural gas, and coal) continue to supply much of the energy used worldwide. Since fossil fuels are being consumed much more rapidly than they are created, we have to face the issue of energy sustainability, due to expected depletion of the fossil fuel reserves. In addition, greenhouse gas emissions from oil, natural gas, and coal consumption contribute signicantly to global warming, as the International Energy Outlook 2006 projected that world carbon dioxide emissions are to increase steadily from 25.0 billion metric tons in 2003 to 43.7 billion metric tons in 2030.
*Correspondence to: Samuel S. Mao, Lawrence Berkeley National Laboratory, University of California at Berkeley, CA 94720, U.S.A. y E-mail: ssmao@lbl.gov z This article is a U.S. Government work and is in the public domain in the U.S.A. Contract/grant sponsor: Lawrence Berkeley National Laboratory Contract/grant sponsor: U.S. Department of Energy Received 6 September 2006 Accepted 23 September 2006

Published in 2007 by John Wiley & Sons, Ltd.

620

S. S. MAO AND X. CHEN

Figure 1. Selected renewable energy technologies to be discussed in this article.

There is a pressing need for alternative energy sources that are both renewable and environmentally benign. Among a limited number of options, solar energy represents an important renewable energy resource that can be directly converted into electricity using photovoltaic (PV) devices. Solar radiation is also a renewable energy resource for splitting water to produce hydrogen, which is regarded as the cleanest transportation fuel. The oxidation of hydrogen through the use of fuel cells generates electricity, where water constitutes the only emission. Fuel cells represent an eective and practical approach to convert hydrogen produced from solar and other sources into electricity. While solar energy is virtually inexhaustible, it is limited in the amount of the energy that can be converted and stored for practical utilization at a given time. In order for solar energy to be the major contributor to the generation of electricity and clean transportation fuel (hydrogen), the eciencies of PV and solar water-splitting devices need to be improved. Likewise, highperformance fuel cells as well as high-capacity hydrogen-storage materials have to be realized, in order for hydrogen to become the primary fuel for transportation systems. Technological breakthroughs and revolutionary developments are needed in order to achieve eective conversion, storage, and utilization of renewable energy resources. Nanotechnology, particularly the development of nanoscale materials and structures, including the methods to create them, oers a new paradigm for realizing the goals of renewable energy research. In this article, we provide a brief overview of some topics the authors are studying in the crossdisciplinary eld of renewable energy and nanotechnology. We attempt to examine the role nanotechnology will play in a chain of selected renewable energy technologies as schematically illustrated in Figure 1. The topics were chosen based on the authors current research interests, which include harvesting solar energy with nanostructures to generate electricity and to split water for hydrogen production, realizing nanoporous media for high capacity hydrogen storage, and improving fuel cell performance by screening nanostructured catalysts as well as their support.

2. ELECTRICITY GENERATION WITH SOLAR ENERGY Harvesting energy from sunlight using PV technology has been considered an essential pathway to energy sustainability. Typically, a photovoltage is generated when light-induced excess charge carriers (e.g. electrons and holes) in a semiconductor are separated in space, so the process is
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

SELECTED NANOTECHNOLOGIES FOR RENEWABLE ENERGY APPLICATIONS

621

determined by the fundamental properties of light absorption and carrier transport of the semiconductor material. A PV device, or solar cell, converts absorbed photons directly into electrical charges that are used to energize an external circuit. Large-scale manufacturing of these devices would enable a signicant fraction of future energy needs to be supplied by solar energy. Current production of PV devices is dominated by a pn junction type, single-crystalline and polycrystalline silicon modules, termed as the rst-generation technology, which occupies over 90% of the market with a cost of approximately $4/W. While the second-generation technologies based on CdS/CdTe, Cu(In,Ga)Se2 ; and other types of multiple semiconductor layers are still under development, nanostructured third-generation PV technologies have gained much attention due to their potential of achieving competitive cost/eciency ratios (Shaheen et al., 2005). One class of nanostructured PV devices that may have signicant benets as a low-cost alternative to conventional pn junction type modules is the dye-sensitized solar cell (DSSC), also known as the Gratzel cell. Central to a DSSC is a nanostructured network of a wide band gap semiconductor, usually titanium dioxide TiO2 ; which is covered with a monolayer of organic dye molecules. Deposited onto a transparent conductive oxide layer and in contact with a redox electrolyte or an organic hole conductor, the TiO2 nanomaterial oers a large surface area for the adsorption of light-harvesting molecules. While pure TiO2 absorbs light only in the UV region, when modied with dye molecules, it can absorb light in the visible wavelengths. Figure 2 is a schematic illustration of a basic DSSC structure. The operation of the cell is based on rapid electron injection from photo-excited dye molecules into the semiconductor, while the electrolyte reduces the oxidized dye with the hole being lled by a suitable electron donor (electrolyte). Dye-sensitized solar cell technology has been extensively studied and its structure has been continuingly optimized over the years (Gratzel, 2003, 2004, 2005; Tributsch, 2004; Kalyanasundaram and Gratzel, 1998). The organic hole conductor currently used is 2; 20 ;7; 70 -tetrakis-(N;N-di-p-methoxyphenyl-amine)-9,90 -spirobiuorene (spiro-MeOTAD). The

Figure 2. Schematic illustration of a dye-sensitized mesoporous TiO2 solar cell.

Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

622

S. S. MAO AND X. CHEN

ruthenium complex cis-RuL2 NCS2 (L-2,20 -bipyridine-4,40 -dicarboxylic acid), known as N3 dye (or N-719 for the ditetrabutylammonium salt of N3 ; has been the sensitizer in mesoporous TiO2 solar cells, which have absorption maxima at 518 and 380 nm. Whereas DSSCs have achieved a solar-to-electric conversion eciency of about 10%, one challenge is to eliminate the liquid phase by discovering alternative solid-state electron donors, or making heterojunction polymer devices that contain blends of conjugated polymers (e.g. MEHPPV) with nanostructured inorganic semiconductors. Much eort has been devoted to the development of organic dyes that can extend light absorption into the near infrared and have good photo and thermal stability for DSSCs (Kalyanasundaram and Gratzel, 1998). In addition, synthesis and modication of various types of TiO2 nanomaterials have attracted signicant attention recently due to the improvement of material-processing techniques, which is a focus of our current research (Chen and Mao, 2006; Chen et al., 2005a). For instance, ordered mesoporous TiO2 nanocrystalline lm was found to improve the solar conversion eciency by about 50% compared to that of traditional lms of the same thickness made from randomly oriented anatase nanocrystals (Zukalova et al., 2005). Other than nanocrystals, TiO2 nanotube-based DSSCs were found to display higher eciency, possibly due to the increase of electron density in nanotube electrodes (Macak et al., 2005; Adachi et al., 2003; Mor et al., 2006; Ohsaki et al., 2005). Additionally, large-surface inverse TiO2 opal lm-based solid-state dye sensitized organicinorganic hybrid solar cells showed improved light conversion eciency (Somani et al., 2005), and a hybrid TiO2 electrode composed of a mixture of anatase and rutile phases showed a higher solar-toelectric energy conversion eciency than that made of pure anatase phase electrodes (Han et al., 2005a,b). Various elements have been used as dopants to modify the physical properties of TiO2 nanostructures and extend optical absorption into the visible region. For instance, it was found that TiO2 nanocrystals can take up to 8% of nitrogen (N) atoms into the lattice, compared to 2% in thin lms and microscale TiO2 powders (Chen et al., 2005b; Gole et al., 2004; Burda et al., 2003). Such doped nanomaterials absorb well into the visible spectrum of light (up to 600 nm) as compared to the pure TiO2 material that only absorbs in the UV region. N-doped TiO2 nanocrystalline porous thin lms showed visible-light absorption in the wavelength range from 400 to 535 nm, and the photo-current due to visible light at moderate bias was increased about 200 times compared to the case when pure TiO2 electrodes were used (Lindgren et al., 2003). In addition to nitrogen, a handful of other elements were successfully doped into TiO2 nanostructured materials. Figure 3 shows an absorption spectrum and XPS measurement of a layer of B-doped TiO2 nanoparticles fabricated by a pulsed laser-assisted deposition process developed in our laboratory. Dierent from DSSCS, semiconductor quantum dots (QDs) based solar cells represent another category of nanostructured PV devices. Solar cells utilizing miniband in QD array photoelectrodes and with enhanced impact ionization processes were predicted to have the potential of reaching a thermodynamic conversion eciency of solar photon conversion up to approximately 66% (Nozik, 2002). Ordered 3-D QDs array placed in the intrinsic region of a pin structure was also predicted to yield strong electronic coupling and allow long-range electron transport (Nozik, 2001). Signicant progress is being made in forming 3-D arrays of QDs (Murray et al., 2000; Shevchenko et al., 2006a,b; Burda et al., 2005). Hybrid solar cells consisting of QDs and organic semiconductor polymers have also been reported, for example, with CdSe QDs embedded in a hole-conducting polymer (MEHPPV) (Greenham et al., 1996).
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

SELECTED NANOTECHNOLOGIES FOR RENEWABLE ENERGY APPLICATIONS

623

0.5
B-doped TiO2

0.4 Absorption 0.3 0.2 0.1

XPS Count (a.u.)

205

200

195

190

185

B-doped TiO2

Binding Energy (eV)

glass substrate

0.0 4 3 2 1 Photon Energy (eV) 0

Figure 3. Absorption spectrum and XPS measurement of B-doped TiO2 nanoparticles.

Although the conversion eciency of hybrid QD solar cells were relatively low, improvements have been made over time (Huynh et al., 1999; Arango et al., 1999).

3. HYDROGEN PRODUCTION WITH SOLAR ENERGY Besides direct generation of electricity using PV devices, another path of utilizing solar energy, especially for energy supply to the transportation systems, is the production of hydrogen by splitting water. Solar-driven water splitting through the use of photoelectrochemical (PEC) cells has many attractive features over other hydrogen production approaches; both the energy source and the reactive medium (water) are renewable and readily available, and the resultant fuel product (hydrogen) as well as the emissions (water) from the utilization of the fuel is environmentally benign. TiO2 nanomaterials represent the most important semiconductor catalysts for splitting water and producing hydrogen. As schematically shown in Figure 4, when TiO2 absorbs light with energy larger than its band gap, electrons and holes are generated in the conduction and valence bands, respectively. The photogenerated electrons and holes induce redox reactions}water molecules are reduced by the electrons to form H2 and oxidized by the holes to form O2 ; leading to overall water splitting (Fujishima and Honda, 1972; Fujishima et al., 2000; Tryk et al., 2000; Yamakata et al., 2003a,b; Hameed and Gondal, 2004). The width of the band gap and the potentials of the conduction and valence bands are critical to the eciency of solar water splitting. The bottom level of the conduction band has to be more negative than the reduction potential of H =H2 (0 V vs normal hydrogen electrode), while the top level of the valence band has to be more positive than the oxidation potential of O2 =H2 O (1.23 V). The photocatalytic characteristics of TiO2 are strongly aected by the surface properties, such as surface states, surface chemical groups, surface area, and active reaction sites, as well as charge separation, mobility, and lifetime of photogenerated carriers (Schwarz et al., 1986). Pure TiO2 may not easily split water into H2 and O2 in a simple aqueous suspension system (Abe et al., 2003; Moon et al., 2000; Sato and White, 1980). The main problem is the fast, undesired electronhole recombination reaction (Matsumato et al., 2004). Laser-induced
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

624

S. S. MAO AND X. CHEN

Figure 4. Schematic illustration of the potentials for solar water splitting with pure and modied TiO2 : The empty and lled boxes represent the conduction and valence band, respectively. The modied TiO2 suitable for solar water splitting should have a narrower band gap with up-shifted valence band edge.

photocatalytic oxidation and water splitting over TiO2 catalysts were studied (Hameed and Gondal, 2004; Gondal et al., 2004; Hameed et al., 2005), and co-catalysts such as Pt and NiO were often loaded, in order to introduce active sites for H2 evolution. Well-dispersed metal nanoparticles can act as mini-photocathode trapping electrons, while addition of carbonate salts to Pt-loaded TiO2 suspensions was shown to yield ecient water splitting (Sayama and Arakawa, 1997). A bare n-TiO2 nanocrystalline lm electrode was unstable during watersplitting reactions under illumination, but its stability could be signicantly improved when covered with Mn2 O3 (Khan and Akikusa, 1998). The overvoltage for the evolution of oxygen was measured to be on the order of 0.6 eV for n-TiO2 electrodes loaded with RuO2 (Salvador, 1998). The morphology of TiO2 nanomaterials aects their photocatalytic activities. Highly ordered TiO2 nanotube arrays were reported to be able to eciently decompose water under UV irradiation (Mar et al., 2005). Figure 5 shows a SEM image of TiO2 nanotubes synthesized by an electrochemical process using HCl and a non-Pt counter-electrode. The nanotube wall thickness was considered to be a key parameter inuencing the magnitude of the photoanodic response and the overall eciency of the water-splitting reaction. For TiO2 nanotubes with 22 nm porediameter, 34 nm wall thickness, upon 320400 nm illumination at an intensity of 100 mW cm2 ; hydrogen gas was generated at the power-time normalized rate of 960 mmol h1 W 24 mL h1 W at an overall conversion eciency of approximately 6.8% (Mor et al., 2005). In order to improve the eciency of solar water splitting by semiconductor nanostructures, it is also necessary to shift the wavelength of light absorption away from ultraviolet ($2% of sunlight) to the visible range of the solar spectrum (Kudo, 2003). A variety of dopants have been employed to modify the optical properties of TiO2 nanomaterial for solar hydrogen production. Water splitting was induced with visible light in colloidal solutions of Cr-doped TiO2 nanoparticles deposited with ultrane Pt or RuO2 (Borgarello et al., 1982). Br and Cl co-doped nanocrystalline TiO2 with the absorption edge shift to a lower energy region displayed higher eciency for water splitting than pure TiO2 (Luo et al., 2004). Visible-light response was
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

SELECTED NANOTECHNOLOGIES FOR RENEWABLE ENERGY APPLICATIONS

625

Figure 5. A SEM image of TiO2 nanotubes synthesized by an electrochemical approach.

measured by controlled combustion of Ti metal in a natural gas ame for a C-doped TiO2 nanocrystalline lm. It had a high water-splitting performance with a total conversion eciency of 11% and a maximum photoconversion eciency of 8.35% when illuminated at 40 mW per square centimeter (Khan et al., 2002). Additionally, organic dyes (Abe et al., 2005) have been employed to shift the optical response of TiO2 into the visible regime for solar water splitting. TiO2 loaded simultaneously with ultrane Pt and RuO2 displayed high activity as H2 O decomposition catalysts under band-gap excitation of the TiO2 ; and when Rubipy2 3 or rhodamine B was used as a sensitizer, H2 O was decomposed under visible light (Duonghong et al., 1981). Composite nanostructured semiconductors have also been developed for visible-light water splitting. A self-driven system for a water-splitting reaction under illumination was achieved with the combination of single crystal p-SiC and nanocrystalline n-TiO2 photoelectrodes (Akikusa and Khan, 2002). The open-circuit potential under illumination was found to be 1.24 V between n-TiO2 and p-SiC photoelectrodes and with a maximum photocurrent density of 0:05 mA cm2 under a closed-circuit potential of 0.23 V, corresponding to 0.06% eciency. A nanocomposite polycrystalline Si/doped TiO2 solar water-splitting structure was proposed for high eciency and low cost by combining the advantages of Si and doped TiO2 : An n-Si electrode with surface alkylation and metal nanoparticle coating oers an ecient and stable PV characteristic, and TiO2 doped with other elements, such as nitrogen and sulphur, could induce water photooxidation (oxygen photoevolution) by visible-light illumination. A high solar-tochemical conversion eciency of more than 10% was predicted for such a system (Takabayashi et al., 2004).

4. SOLID-STATE HYDROGEN STORAGE Among the various alternative energy strategies is the building of an energy infrastructure that uses hydrogen as the primary energy carrier. The energy produced by the Sun can be converted,
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

626

S. S. MAO AND X. CHEN

stored, and distributed in the form of hydrogen. A major challenge to realizing a hydrogen economy is the development of high capacity and safe hydrogen-storage materials. In general, hydrogen may be stored in the form of pressurized gas, liqueed hydrogen, or can be chemically or physically bonded to a suitable solid-state material. Of the three hydrogen-storage approaches, solid-state storage has the highest volumetric density of hydrogen. While gaseous and liquid-state storage requires extremely high pressure or low temperature, solid-state hydrogen-storage materials could store hydrogen at near-ambient temperatures and pressures. Particularly for transportation applications, storing pressurized or liqueed hydrogen requires a large footprint container that is not only a safety concern but also easily takes up a signicant fraction of space in the vehicle. Therefore, solid-state storage is potentially the most convenient and the safest method for storing and distributing hydrogen for transportation systems. The use of nanostructured solid-state materials serves multiple functions; they improve the kinetics by increasing the diusivity, reducing the reaction distance, and increasing the reaction surface area. The fundamental mechanisms (Figure 6) for solid-state hydrogen storage in nanomaterials include chemisorption and physisorption (Fichtner, 2005; Antonelli and Seayad, 2004). Chemisorption starts with dissociation of hydrogen molecules and chemical bonding of the hydrogen atoms by integration in the lattice of a solid material, e.g. metal hydrides. This process inherently involves large enthalpy changes and normally requires high operation temperatures and a catalyst for fast hydrogen uptake and release. In contrast, physisorption mainly involves the adsorption of hydrogen molecules on the surface of nanomaterials through weak intermolecular forces}the van der Waals interaction. As a consequence, the force is less material specic compared to the case of chemisorption. Since the van der Waals force between the hydrogen molecule and the surface is in the lower kJ mol1 range, it is necessary to apply low temperatures (e.g. 77 K of liquid nitrogen temperature) to achieve a sucient amount of adsorbed hydrogen. Nevertheless, release of physisorbed hydrogen can be fast because of the weak molecular forces. The ideal material for hydrogen storage would achieve a compromise between having the hydrogen too weakly bonded to the storage material, resulting in a low storage capacity at room

Figure 6. Schematic illustration of basic mechanisms of solid-state hydrogen storage. By physisorption, hydrogen is attached to the surface of a material either as hydrogen molecules or as hydrogen atoms. By chemisorption, a hydrogen molecule is dissociated into hydrogen atoms, and then the hydrogen atoms are incorporated/distributed into the solid lattice. The potential energy for hydrogen sorption is also illustrated.
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

SELECTED NANOTECHNOLOGIES FOR RENEWABLE ENERGY APPLICATIONS

627

temperature and too strong a bonding, thus requiring high temperatures to release the hydrogen. Solid-state nanomaterials currently being investigated for hydrogen storage include carbon nanomaterials, metalorganic frameworks, nanocrystalline metal and complex hydrides, among others. Physisorption of hydrogen molecules in nanostructured materials has been explored extensively; examples include various forms of carbon (Darkrim et al., 2002; Guay et al., 2004), clathrates (Sluiter et al., 2004; Mao et al., 2002), and metalorganic frameworks (Rosi et al., 2003; Rowsell et al., 2005). Signicant storage capacity was initially reported for hydrogen storage using carbon nanotubes (Dillon et al., 1997). Later investigations suggested that the desorption of hydrogen appear to originate from Ti alloy particles introduced during the ultrasonic treatment rather than from the CNTs (Hirscher et al., 2001). Theoretical studies on hydrogen adsorption in carbon nanostructures indicated that at 50 K, the adsorption potential for hydrogen molecules inside zigzag nanotubes ($ 1 nm diameter) can be 25% higher than that of the at surface of graphite due to the curvature of the surface (Stan and Cole, 1998). The adsorbed hydrogen was found to increase from 1.4 wt% at 300 K to 9.6 wt% at 77 K under 10 MPa (Williams and Eklund, 2000), and the amount of adsorbed hydrogen depends on the surface area of the sample (Rzepka et al., 1998; Strobel et al., 1999; Nijkamp et al., 2001; Ye et al., 1999). The measured adsorption isotherms approximately follow the Langmuir adsorption model (Strobel et al., 1999). Geometrical considerations lead to a maximum amount of 3.3 wt% of condensed hydrogen in a surface monolayer for single-wall carbon nanotubes with a specic surface area of 1315 m2 g1 (Zuttel et al., 2002). High-pressure (12 MPa) hydrogen adsorption experiments on single-wall carbon nanotubes indicated that equilibrium is reached after approximately 300 min with a maximum adsorption of 4.2 wt% H=C 0:5 at room temperature (Liu et al., 1999). A high hydrogen uptake was reported for K- and Li-doped multi-wall carbon nanotubes (Chen et al., 1999); however, the mass change was considered largely due to impurities such as oxygen and water and the oxidation of the alkali metals rather than a hydrogen uptake. Metalorganic frameworks represent another important example of solid-state hydrogenstorage materials due to the possibility of designing a functionalized porous structure for physisorption, as well as their low density 51:00 g cm3 and high specic surface area > 500 m2 g1 : For example (Rosi et al., 2003; Rowsell et al., 2005), the metalorganic framework of composition Zn4 OBDC3 (BDC=1,4-benzenedicarboxylate) with a cubic 3-D extended porous structure was demonstrated to be able to adsorb hydrogen over 7 wt% at cryogenic temperature. For hydrogen chemisorption, the most studied materials are metal hydrides and related complex hydrides (Mutschele and Kirchheim, 1987a,b; Kirchheim et al., 1988). Small hydrogen atoms can readily enter the interstitials of many metals and alloys to form hydrides. Since a high weight fraction of hydrogen in the solid-state hydrogen-storage materials are required for practical transportation system applications, research to enhance the hydrogen capacity in metal hydrides has been focused on those based on light weight elements such as magnesium. Metal hydrides with theoretically large hydrogen-storage capacity are known, for example, MgH2 ; which has a theoretical capacity of $ 7:6 wt%: However, the desorption characteristics of these materials in the bulk are inconvenient for practical applications. Whereas polycrystalline Mg was found not exhibiting signicant hydrogen-storage reactions at 573 K, nanostructured Mg could absorb hydrogen readily, even without any activation (Zaluska et al., 1999, 2001; Liang et al., 1999, 2000; Huot et al., 2001).
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

628

S. S. MAO AND X. CHEN

The main dierence between the complex and metal (interstitial) hydrides is the transition to an ionic or covalent compound upon hydrogen absorption. Unlike metal hydrides, complex hydrides release hydrogen through a series of decomposition and recombination reactions. Group 13 light metals, such as Li, Mg, B, and Al, form a large variety of complex hydrides. Tetrahydroborates M(BH4 and tetrahydroaluminates M(AlH4 are two families of promising complex hydrides for hydrogen storage. The hydrogen in these materials is often located in the corners of a tetrahedron with B or Al in the centre. Pure tetrahydroaluminates can contain more than 10 wt% hydrogen. However, once the hydrogen is released, they do not absorb hydrogen again below 100 atm H2 : Re-hydrogenation of NaAlH4 below 100 atm H2 has been achieved by adding Ti and Fe organometallic compounds (Bogdanovic and Schwickardi, 1997; Bogdanovic et al., 2000). Graphite was found to have some advantages for surface modication of Mg-related materials. Surface modication by mechanical milling with graphite eectively improved the electrochemical properties of the samples (Zaluska et al., 1999, 2001; Liang et al., 1999, 2000; Huot et al., 2001; Iwakura et al., 1996, 1999a,b; Nohara et al., 1997). For example, the hydrogen-storage kinetics of amorphous MgNi at room temperature is increased after the surface modication. Formation of nanocomposites led not only to the increase in hydrogenstorage kinetics, but also to the appearance of additional hydrogen trapping sites (in addition to within Mg itself) due to the defective structures in carbon materials (Imamura et al., 1996, 1997, 1999, 2000). Oxide nanostructures such as TiO2 nanotubes were recently found to be able to store up to approximate 2 wt% H2 at room temperature and 6 MPa (Lim et al., 2005). About 75% of this stored hydrogen could be released when the hydrogen pressure was lowered to ambient conditions due to physisorption. Hydrogen may intercalate between layers in the walls of TiO2 nanotubes, forming hostguest compounds TiO2 xH2 ; with x41:5 (Bavykin et al., 2005). Almost 1.5 hydrogen molecules per one Ti atom could be adsorbed at a 2 bar pressure of hydrogen. During the hydrogen desorption process, a large hysteresis was observed, and the adsorption of hydrogen was a reversible process. Heating the sample in a vacuum to 2008C led to a complete desorption of hydrogen, returning the weight of the sample to its initial value. We developed a class of nanostructured all-inorganic materials, the nanoporous metal inorganic (oxide) networks, for solid-state hydrogen storage. The nanoporous metalinorganic materials have a linked 3-D network of M : SiO2 and similar nanostructures that include a monolayer or nanoparticles of metal/alloy (denoted M; implemented into a nanoporous oxide network. Taking Mg : SiO2 as an example, the synthesis process started with pH-dependent hydrolysis and condensation of an alkoxysilane in an alcohol solution, followed by CO2 substitution and supercritical drying to form a porous SiO2 nanoparticle network. Under a high-vacuum environment, the resulting SiO2 nanoparticle network was subject to vapour inltration through the use of a pulsed laser to vapourize a solid-state Mg target. An example of pressure-dependent hydrogen concentration measurements of Mg : SiO2 nanoporous networks is shown in Figure 7.

5. UTILIZATION OF HYDROGEN WITH FUEL CELLS One eective way to use the chemical energy stored in hydrogen is to directly convert it into electricity through the use of a fuel cell. Fuel cells harness the chemical energy of hydrogen to
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

SELECTED NANOTECHNOLOGIES FOR RENEWABLE ENERGY APPLICATIONS

629

0.4 concentration (mmol) sorption 0.3 0.2 0.1 0.0 0 2 4 pressure (bar) 6 8 10 desorption

Figure 7. Pressure-dependent hydrogen concentration of a nanoporous Mg : SiO2 network material at room temperature. The data were obtained based on gravimetric measurement.

generate electricity without combustion and pollution. A major advantage of using fuel cells is their energy conversion eciency, which is superior to that of combustion engines. An important class of fuel cells that could potentially replace combustion engines in future hydrogen-driven vehicles is the proton exchange membrane (or polymer electrolyte membrane) fuel cell. The electrochemical reactions in a proton exchange membrane fuel cell consist of hydrogen oxidation reaction at the anode catalyst layer and oxygen reduction reaction at the cathode catalyst layer. Figure 8 is a schematic illustration of the basic structure of a proton exchange membrane fuel cell. Upon entering the fuel cell at its anode, hydrogen molecules dissociate into hydrogen ions (protons) and electrons. The protons pass through an electrolyte membrane to the cathode catalyst layer and react with oxygen ions on the cathode. The electrons produced at the anode side travel to the cathode through an external circuit connecting the electrodes. Attached to either side of the electrolyte membrane are porous gas diusion electrodes consisting of the catalytic active layer with electrocatalysts. To achieve the highest possible electroactive catalyst surface, the catalysts are usually in the form of nanoparticles of diameter a few nanometers supported on carbon particles (with size $ 50 nm). Materials that in the bulk form have little or no catalytic activity can exhibit exceptional catalytic behaviour at the nanoscale. The carbon support ensures electron conductivity throughout the entire electroactive layer, whereas the porous structure enables gas transport to the electrocatalysts and oers a path for water removal from the electrode. The cathode is primarily responsible for energy losses in a proton exchange membrane fuel cell, due to the slow kinetics of the oxygen reduction reaction. Improvements in the voltage output requires the development of more eective, as well as durable catalysts, that not only can enhance the rate of the reaction but also be capable of withstanding the acidic environment of proton exchange membrane fuel cells. Of elemental metals, platinum (Pt) represents the state-ofthe-art electrocatalyst for proton exchange membrane fuel cells. However, the development of proton exchange membrane fuel cells would ultimately be bound to platinum availability unless low-Pt containing alloys or non-Pt electrocatalysts are developed. For instance, fuel cell catalysts based on nanoparticles of rutheniumplatinum (RuPt) appear to out-perform some
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

630

S. S. MAO AND X. CHEN

Figure 8. Schematic illustration of the basic structure of a proton exchange membrane fuel cell.

traditional catalysts; they are more resistant to carbon monoxide poisoning and show longer operating lifetime (Chrzanowski and Wieckowski, 1998; Gasteiger et al., 1994a,b; Petukhov et al., 1998; Friedrich et al., 1996). While research on fuel cell catalysts have been performed for decades, the results as reported in the literature have not been very consistent. One has to take into consideration for comparison that the catalytic activity of nanoparticles can depend on the size, shape, and surface composition of the particles (Bead and Ross, 1990). For platinum, large deviations in the oxygen reduction activity were found for the three low-index single-crystal planes Pt(111), Pt(110), and Pt(100) (Markovic et al., 1997). The particle size eect for oxygen reduction on platinum catalysts was studied, as well as the dierence in the ratio of atoms localized on dierent sites of the particle (e.g. edge or corner vs plane) (Kinoshita, 1990). An experimental Electrocatalysts-by-design approach for developing fuel cell catalysts was proposed by Markovic and Ross (2000), which includes three successive steps starting with the study of the electrocatalytic activity of model systems (single crystals of pure catalysts) to gain insight into the relationship between the atomic scale structure and the properties of reactants and intermediates. In the second step, catalyst nanoparticles are synthesized and characterized to acquire the information of particle size distribution, composition, and microstructure. In the last step, the electrocatalytic activity of supported nanoparticles is studied, which would reveal the dependence of catalytic activity on the structure, oxidation state, and composition of nanoparticles. It is known that alloying of Pt with non-noble transition metals may potentially improve catalyst performance (Mukerjee et al., 1995), and tuning the elemental ratio of alloys would yield a great variety of catalysts with dierent composition (Chen et al., 2001). Therefore, a high throughput combinatorial material synthesis method combined with the experimental electrocatalysts-by-design approach would be an eective way of experiments to screen candidate catalysts for fuel cells. The technology of combinatorial material discovery creates a combinatorial material library by depositing elemental precursors in a spatially addressable
Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

SELECTED NANOTECHNOLOGIES FOR RENEWABLE ENERGY APPLICATIONS

631

fashion (Xiang et al. 1995). In principle, an unlimited number of distinct composition possibilities can be realized and optimal spatial mapping strategy can be applied to maximize composition variations on a single material chip. At present, combinatorial material discovery technology is attracting much attention due to its high throughput as well as cost-eective nature in fabricating and screening unknown materials. This approach is particularly valuable for multi-component materials development where experimental results are not readily predictable by microscopic theoretical models. We are developing a pulsed laser-based combinatorial deposition technique to fabricate libraries of alloy catalyst nanoparticles. One benet of using ultrafast lasers is the possibility of synthesizing materials with certain phases otherwise not readily achievable by conventional equilibrium approaches. Figure 9 is a photo of a 16 16 material library fabricated by laser-assisted deposition method in our laboratory. The interest in the research of proton exchange membrane fuel cells is not only the discovery of a low-Pt or non-Pt nanoparticle catalysts, but also the development an improved catalyst support/electrode. Due to their unique structural, mechanical, and electrical properties, carbon nanotubes have been proposed to serve as an alternative support to traditional carbon powders (Li et al., 2003; Liu et al., 2002). Not only is the surface area of carbon nanotubes extremely large, it is also easier for gas and liquid to permeate through the ensemble of carbon nanotubes than through activated carbon powders. As demonstrated recently, carbon nanotube arrays were directly grown on carbon papers with Pt subsequently electrodeposited on the tubes (Wang et al., 2004). With catalysts on conducting carbon nanotubes, the traditional problem of isolation of carbon particles from the electrode is eliminated. Comparison of carbon nanotubebased and traditional carbon powder-based electrodes revealed that carbon nanotube-based catalysts support improved Pt utilization substantially (Kongkanand et al., 2006; Wang et al., 2005). At a similar wt% of Pt, the eective surface area of the catalysts supported on carbon nanotubes is about half of that of the catalysts on conventional carbon black. Still the similar reduction activities were observed on both types of catalysts, indicating more eective utilization of Pt catalyst for a given accessible surface area. The activation enthalpy for carbon nanotube-supported catalysts was found to be similar to that of the conventional catalysts and thus the increased activity with carbon nanotube support could be attributed to their superior electron conductivity. Accelerated tests also showed that carbon nanotube-supported catalysts are more durable than traditional carbon powder-supported catalysts (Kongkanand et al., 2006).

Figure 9. A 16 16 material library fabricated by laser-assisted deposition method.

Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

632

S. S. MAO AND X. CHEN

In addition to oering advantages as catalyst supports, carbon nanotubes would enable the fabrication of freestanding fuel cell electrodes, through which there is no need of a binder to provide mechanical integrity and the electrodes can be fabricated independently of other fuel cell elements. Freestanding electrodes have the potential to be considerably more powerful than those currently used, in the meantime greatly simplify the fabrication of membrane electrode assemblies, the heart of a proton exchange membrane fuel cell. Carbon nanotube electrodes could also signicantly extend the lifetime of the fuel cell, as one of the main causes of electrode failure is corrosion of the catalyst supporting material. Carbon nanotubes have almost no exposed graphite-like edges, the location where corrosion typically begins.

6. CONCLUDING REMARKS Nanotechnology, particularly the creation of innovative nanomaterials and nanostructures, could help overcome the dilemma of increasing energy demands with depleting energy resources through more ecient generation, storage, and utilization. Enabled by nanotechnology innovations, exciting new opportunities have opened up in renewable energy technologies that would deliver performance characteristics, such as more ecient conversion of solar energy to generate electricity and hydrogen, higher-capacity solid-state storage of hydrogen, and more eective utilization of hydrogen in fuel cells. The selected nanotechnologies discussed here are likely to be introduced to the renewable energy marketplace over the next decades. It is expected that nanotechnology could make solar cells radically more ecient than what they are today, nanotechnology-enabled hydrogen production, storage, and fuel cell technologies would make the dream of a hydrogen economy a reality.

ACKNOWLEDGEMENTS

The authors thank A. Hunt, M. Schriver, and X. Zhang for nanomaterials fabrication, M. Roper for hydrogen storage capacity testing, and R. Greif for discussions and careful reading of the manuscript.

REFERENCES Abe R, Sayama K, Arakawa H. 2003. Signicant eect of iodide addition on water splitting into H2 and O2 over Pt-loaded TiO2 photocatalyst: suppression of backward reaction. Chemical Physics Letters 371:360. Abe R, Sayama K, Sugihara H. 2005. Eect of water/acetonitrile ratio on dye-sensitized photocatalytic H2 evolution under visible light irradiation. Journal of Solar Energy Engineering 127:413. Adachi M, Murata Y, Okada I, Yoshikawa S. 2003. Formation of titania nanotubes and applications for dye-sensitized solar cells. Journal of the Electrochemical Society 150:G488. Akikusa J, Khan SUM. 2002. Photoelectrolysis of water to hydrogen in p-SiC/Pt and p-SiC/n-TiO2 cells. International Journal of Hydrogen Energy 27:863. Antonelli DM, Seayad AM. 2004. Recent advances in hydrogen storage in metal-containing inorganic nanostructures and related materials. Advances in Materials 16:765. Arango AC, Carter SA, Brock PJ. 1999. Charge transfer in photovoltaics consisting of interpenetrating networks of conjugated polymer and TiO2 nanoparticles. Applied Physics Letters 74:1698. Bavykin DV, Lapkin AA, Plucinski PK, Friedrich JM, Walsh FC. 2005. Reversible storage of molecular hydrogen by sorption into multilayered TiO2 nanotubes. Journal of Physical Chemistry 109:19422. Bead BC, Ross JPN. 1990. The structure and activity of Pt-Co alloys as oxygen reduction electrocatalysts. Journal of the Electrochemical Society 137:3368. Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

SELECTED NANOTECHNOLOGIES FOR RENEWABLE ENERGY APPLICATIONS

633

Bogdanovic B, Schwickardi M. 1997. Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materials. Journal of Alloys and Compounds 253:1. Bogdanovic B, Brand RA, Marjanovic A, Schwickardi M, Toelle J. 2000. Metal-doped sodium aluminium hydrides as potential new hydrogen storage materials. Journal of Alloys and Compounds 302:36. Borgarello E, Kiwi J, Gratzel M, Pelizzetti E, Visca M. 1982. Visible light induced water cleavage in colloidal solutions of chromium-doped titanium dioxide particles. Journal of American Chemical Society 104:2996. Burda C, Lou Y, Chen X, Samia ACS, Stout J, Gole JL. 2003. Enhanced nitrogen doping in TiO2 nanoparticles. Nano Letters 3:1049. Burda C, Chen X, Narayanan R, El-Sayed MA. 2005. Chemistry and properties of nanocrystals of dierent shapes. Chemical Reviews 105:1025. Chen X, Mao SS. 2006. Synthesis of titanium dioxide nanomaterials. Journal of Nanoscience and Nanotechnology 6:906. Chen P, Wu X, Lin J, Tan KL. 1999. High H2 uptake by alkali-doped carbon nanotubes under ambient pressure and moderate temperatures. Science 285:91. Chen G, Delafuente DA, Sarangapani S, Mallouk TE. 2001. Combinatorial discovery of bifunctional oxygen reduction water oxidation electrocatalysts for regenerative fuel cells. Catalysis Today 67:341. Chen X, Lou Y, Samia ACS, Burda C, Gole JL. 2005b. Formation of oxynitride as the photocatalytic enhancing site in nitrogen-doped titania nanocatalysts: comparison to a commercial nanopowder. Advanced Functional Materials 15:41. Chen X, Lou Y, Daytal S, Qiu X, Krolicki R, Burda C, Zhao C, Becker J. 2005a. Doped semiconductor nanomaterials. Journal of Nanoscience and Nanotechnology 5:1408. Chrzanowski W, Wieckowski A. 1998. Surface structure eects in platinum/ruthenium methanol oxidation electrocatalysis. Langmuir 14:1967. Darkrim FL, Malbrunot P, Tartaglia GP. 2002. Review of hydrogen storage by adsorption in carbon nanotubes. International Journal of Hydrogen Energy 27:193. Dillon AC, Jones KM, Bekkedahl TA, Kiang CH, Bethune DS, Heben MJ. 1997. Storage of hydrogen in single-walled carbon nanotubes. Nature 386:377. Duonghong D, Borgarello E, Gratzel M. 1981. Dynamics of light-induced water cleavage in colloidal systems. Journal of the American Chemical Society 103:4685. Fichtner M. 2005. Nanotechnological aspects in materials for hydrogen storage. Advances in Engineering Materials 7:443. Friedrich KA, Geyzers KG, Linke U, Stimming U. 1996. CO adsorption and oxidation on a Pt(111) electrode modied by ruthenium deposition: an IR spectroscopic study. Journal of Electroanalytical Chemistry 402:123. Fujishima A, Honda K. 1972. Electrochemical photolysis of water at a semiconductor electrode. Nature 37:238. Fujishima A, Rao TN, Tryk DA. 2000. Titanium dioxide photocatalysis. Journal of Photochemistry and Photobiology 1:1. Gasteiger HA, Markovic N, Ross PNJ, Cairns EJ. 1994a. Carbon monoxide electrooxidation on well-characterized platinum-ruthenium alloys. Journal of Physical Chemistry 98:617. Gasteiger HA, Markovic N, Ross PNJ, Cairns EJ. 1994b. Electro-oxidation of small organic molecules on wellcharacterized Pt-Ru alloys. Electrochimica Acta 39:1825. Gole JL, Stout JD, Burda C, Lou Y, Chen X. 2004. Highly ecient formation of visible light tunable TiO2xNx photocatalysts and their transformation at the nanoscale. Journal of Physical Chemistry 108:1230. Gondal MA, Hameed A, Yamani ZH, Suwaiyan A. 2004. Laser induced photo-catalytic oxidation/splitting of water over a-Fe2O3, WO3, TiO2 and NiO catalysts: activity comparison. Chemical Physics Letters 385:111. Gratzel M. 2003. Dye-sensitized solar cells. Journal of Photochemistry and Photobiology 4:145. Gratzel M. 2004. Conversion of sunlight to electric power by nanocrystalline dye-sensitized solar cells. Journal of Photochemistry and Photobiology 164:3. Gratzel M. 2005. Dye-sensitized solid-state heterojunction solar cells. MRS Bulletin 30:23. Greenham NC, Peng X, Alivisatos AP. 1996. Charge separation and transport in conjugated-polymer/semiconductornanocrystal composites studied by photoluminescence quenching and photoconductivity. Physical Review 54:17628. Guay P, Stanseld BL, Rochefort A. 2004. On the control of carbon nanostructures for hydrogen storage applications. Carbon 42:2187. Hameed A, Gondal MA. 2004. Laser induced photocatalytic generation of hydrogen and oxygen over NiO and TiO2. Journal of Molecular Catalysis 219:109. Hameed A, Gondal MA, Yamani ZH, Yahya AH. 2005. Signicance of pH measurements in photocatalytic splitting of water using 355 nm UV laser. Journal of Molecular Catalysis 227:241. Han H, Zan L, Zhong J, Zhao X. 2005a. A novel hybrid nanocrystalline TiO2 electrode for the dye-sensitized nanocrystalline solar cells. Journal of Materials Science 40:4921. Han H, Zhao X, Liu J. 2005b. Enhancement in photoelectric conversion properties of the dye-sensitized nanocrystalline solar cells based on the hybrid TiO2 electrode. Journal of the Electrochemical Society 152:A164. Hirscher H, Becher M, Haluska M, Dettla.-Weglikowska U, Quintel A, Duesberg GS, Choi YM, Downers P, Hulman M, Roth S, Stepanek I, Bernier P. 2001. Hydrogen storage in sonicated carbon materials. Applied Physics 72:129. Huot J, Liang G, Schulz R. 2001. Mechanically alloyed metal hydride systems. Journal of Alloys and Compounds 72:187. Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

634

S. S. MAO AND X. CHEN

Huynh WU, Peng X, Alivisatos AP. 1999. CdSe nanocrystal rods/poly(3-hexylthiophene) composite photovoltaic devices. Advanced Materials 11:923. Imamura H, Sakasai N, Kajii Y. 1996. Hydrogen absorption of Mg-based composites prepared by mechanical milling: factors aecting its characteristics. Journal of Alloys and Compounds 232:218. Imamura H, Sakasai N, Fujinaga T. 1997. Characterization and hydriding properties of Mg-graphite composites prepared by mechanical grinding as new hydrogen storage materials. Journal of Alloys and Compounds 253254:34. Imamura H, Takesue Y, Akimoto T, Tabata S. 1999. Hydrogen-absorbing magnesium composites prepared by mechanical grinding with graphite: eects of additives on composite structures and hydriding properties. Journal of Alloys and Compounds 293295:564. Imamura H, Tabata S, Takesue Y, Sakata Y, Kamazaki S. 2000. Hydriding-dehydriding behavior of magnesium composites obtained by mechanical grinding with graphite carbon. International Journal of Hydrogen Energy 25:837. Iwakura C, Nohara S, Inoue H, Fukumoto Y. 1996. Surface modication of MgNi alloy with graphite by ball-milling for use in nickel-metal hydride batteries. Chemical Communications 15:1831. Iwakura C, Inoue H, Zhang SG, Nohara S, Yorimitsu K, Kuramoto N, Morikawa T. 1999a. Raman and X-ray photoelectron spectroscopic investigations on a new electrode material for nickel-metal hydride batteries: MgNigraphite composites prepared by ballmilling. Journal of the Electrochemical Society 146:1659. Iwakura C, Inoue H, Zhang SG, Nohara S. 1999b. A new electrode material for nickelmetal hydride batteries: MgNi graphite composites prepared by ball-milling. Journal of Alloys and Compounds 293295:653. Kalyanasundaram K, Gratzel M. 1998. Applications of functionalized transition metal complexes in photonic and optoelectronic devices. Coordination Chemistry Reviews 77:347. Khan SUM, Akikusa J. 1998. Stability and photoresponse of nanocrystalline n-TiO2 and n-TiO2/Mn2O3 thin lm electrodes during water splitting reactions. Journal of the Electrochemical Society 145:89. Khan SUM, Al-Shahry M, Ingler WB Jr. 2002. Ecient photochemical water splitting by a chemically modied n-TiO2. Science 297:2243. Kinoshita K. 1990. Particle size eects for oxygen reduction on highly dispersed platinum in acid electrolytes. Journal of the Electrochemical Society 137:845. Kirchheim R, Mutschele T, Kieninger W, Gleiter H, Birringer R, Koble TD. 1988. Hydrogen in amorphous and nanocrystalline metals. Materials Science and Engineering 99:457. Kongkanand A, Kuwabata S, Girishkumar G, Kamat P. 2006. Single-wall carbon nanotubes supported platinum nanoparticles with improved electrocatalytic activity for oxygen reduction reaction. Langmuir 22:2392. Kudo A. 2003. Photocatalyst materials for water splitting. Catalysis Survey from Asia 7:31. Li WZ, Liang CH, Zhou WJ, Qiu JS, Zhou ZH, Sun GQ, Xin Q. 2003. Preparation and characterization of multiwalled carbon nanotube-supported platinum for cathode catalysts of direct methanol fuel cells. Journal of Physical Chemistry 107:6292. Liang G, Huot J, Boily S, Neste AV, Schulz R. 1999. Hydrogen storage properties of the mechanically milled MgH2-V nanocomposite. Journal of Alloys and Compounds 291:295. Liang G, Huot J, Boily S, Schulz R. 2000. Hydrogen desorption kinetics of a mechanically milled MgH2+5 at.% V. Journal of Alloys and Compounds 305:239. Lim SH, Luo J, Zhong Z, Ji W, Lin J. 2005. Room-temperature hydrogen uptake by TiO2 nanotubes. Inorganic Chemistry 44:4124. Lindgren T, Mwabora JM, Avendano E, Jonsson J, Hoel A, Granqvist CG, Lindquist SE. 2003. Photoelectrochemical and optical properties of nitrogen doped titanium dioxide lms prepared by reactive DC magnetron sputtering. Journal of Physical Chemistry 107:5709. Liu C, Fan YY, Liu M, Cong HT, Cheng HM, Dresselhaus MS. 1999. Hydrogen storage in single-walled carbon nanotubes at room temperature. Science 286:1127. Liu ZL, Lin XH, Lee JY, Zhang WD, Han M, Gan LM. 2002. Preparation and characterization of platinum-based electrocatalysts on multiwalled carbon nanotubes for proton exchange membrane fuel cells. Langmuir 18:4054. Luo H, Takata T, Lee Y, Zhao J, Domen K, Yan Y. 2004. Photocatalytic activity enhancing for titanium dioxide by co-doping with bromine and chlorine. Chemistry of Materials 16:846. Macak JM, Tsuchiya H, Ghicov A, Schmuki P. 2005. Dye-sensitized anodic TiO2 nanotubes. Electrochemistry Communications 7:1133. Mao WL, Mao HK, Goncharov AF, Struzhkin VV, Guo QZ, Hu JZ, Shu JF, Hemley RJ, Somayazulu M, Zhao YX. 2002. Hydrogen clusters in clathrate hydrate. Science 297:2247. Markovic NM, Ross PN. 2000. Electrocatalysts by design: from the tailored surface to a commercial catalyst. Electrochimica Acta 45:4101. Markovic N, Gasteiger H, Ross PN. 1997. Kinetics of oxygen reduction on Pt(hkl) electrodes: implications for the crystallite size eect with supported Pt electrocatalysts. Journal of the Electrochemical Society 144:1591. Matsumoto Y, Unal U, Tanaka N, Kudo A, Kato H. 2004. Electrochemical approach to evaluate the mechanism of photocatalytic water splitting on oxide photocatalysts. Journal of Solid State Chemistry 177:4205. Moon SC, Mametsuka H, Tabata S, Suzuki E. 2000. Photocatalytic production of hydrogen from water using TiO2 and B/TiO2. Catalysis Today 58:125. Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

SELECTED NANOTECHNOLOGIES FOR RENEWABLE ENERGY APPLICATIONS

635

Mor GK, Shankar K, Paulose M, Varghese OK, Grimes CA. 2005. Enhanced photocleavage of water using titania nanotube arrays. Nano Letters 5:191. Mor GK, Shankar K, Paulose M, Varghese OK, Grimes CA. 2006. Use of highly-ordered TiO2 nanotube arrays in dyesensitized solar cells. Nano Letters 6:215. Mukerjee S, Srinivasan S, Soriaga MP, McBreen J. 1995. Role of structural and electronic properties of Pt and Pt alloys on electrocatalysis of oxygen reduction. Journal of the Electrochemical Society 142:1409. Murray CB, Kagan CR, Bawendi MG. 2000. Synthesis and characterization of monodisperse nanocrystals and closepacked nanocrystal assemblies. Annual Review of Materials Science 30:545. Mutschele T, Kirchheim R. 1987a. Segregation and diusion of hydrogen in grain boundaries of palladium. Scripta Metallurgica et Materialia 21:135. Mutschele T, Kirchheim R. 1987b. Hydrogen as a probe for the average thickness of a grain boundary. Scripta Metallurgica et Materialia 21:1101. Nijkamp MG, Raaymakers JEMJ, van Dillen AJ, de Jong KP. 2001. Hydrogen storage using physisorptionmaterials demands. Applied Physics 72:619. Nohara S, Inoue H, Fukumoto Y, Iwakura C. 1997. Eect of surface modication of an MgNi alloy with graphite by ball-milling on the rate of hydrogen absorption. Journal of Alloys and Compounds 252:L16. Nozik AJ. 2001. Spectroscopy and hot electron relaxation dynamics in semiconductor quantum wells and quantum dots. Annual Review of Physical Chemistry 52:193. Nozik AJ. 2002. Quantum dot solar cells. Physica E 14:115. Ohsaki Y, Masaki N, Kitamura T, Wada Y, Okamoto T, Sekino T, Niihara K, Yanagida S. 2005. Dye-sensitized TiO2 nanotube solar cells: fabrication and electronic characterization. Physical Chemistry and Chemical Physics 7:4157. Petukhov AV, Akemann W, Friedrich KA, Stimming U. 1998. Kinetics of electrooxidation of a CO monolayer at the platinum/electrolyte interface. Surface Science 402404:182. Rosi N, Eddaoudi M, Vodak D, Eckert J, OKee.e M, Yaghi OM. 2003. Hydrogen storage in microporous metalorganic frameworks. Science 300:1127. Rowsell J, Spenser E, Eckert J, Howard JAK, Yaghi OM. 2005. Gas adsorption sites in a large-pore metal-organic framework. Science 309:1350. Rzepka M, Lamp P, de la Casa-Lillo MA. 1998. Physisorption of hydrogen on microporous carbon and carbon nanotubes. Journal of Physical Chemistry 102:10849. Salvador P. 1998. Thermodynamic and kinetic considerations about water splitting and competitive reactions in a photoelectrochemical cell. New Journal of Chemistry 12:35. Sato S, White JM. 1980. Photodecomposition of water over Pt/TiO2 catalysts. Chemical Physics Letters 72:83. Sayama K, Arakawa H. 1997. Eect of carbonate salt addition on the photocatalytic decomposition of liquid water over Pt-TiO2 catalyst. Faraday Transactions 93:1647. Schwarz A, Hartig KJ, Geto. N. 1986. Surface eects on thin polycrystalline n-type titanium dioxide layers for water splitting. Advances in Hydrogen Energy 5:643. Shaheen SE, Ginley DS, Jabbour GE. 2005. Organic based photovoltaics: toward low-cost power generation. MRS Bulletin 30:10. Shevchenko EV, Talapin DV, Murray CB, OBrien S. 2006a. Structural characterization of self-assembled multifunctional binary nanoparticle superlattices. Journal of the American Chemical Society 128:3620. Shevchenko EV, Talapin DV, Kotov NA, OBrien S, Murray CB. 2006b. Structural characterization of self-assembled multifunctional binary nanoparticle superlattices. Nature 439:55. Sluiter MHF, Adachi H, Belosludov RV, Belosludov VR, Kawazoe Y. 2004. Ab initio study of hydrogen storage in hydrogen hydrate clathrates. Materials Transactions 45:1452. Somani PR, Dionigi C, Murgia M, Palles D, Nozar P, Ruani G. 2005. Solid-state dye PV cells using inverse opal TiO2 lms. Solar Energy Materials and Solar Cells 87:513. Stan G, Cole MW. 1998. Hydrogen adsorption in nanotubes. Journal of Low Temperature Physics 110:539. Strobel R, Jorissen L, Schliermann T, Trapp V, Schutz W, Bohmhammel K, Wolf G, Garche J. 1999. Hydrogen adsorption on carbon materials. Journal of Power Sources 84:221. Takabayashi S, Nakamura R, Nakato Y. 2004. A nano-modied Si/TiO2 composite electrode for ecient solar water splitting. Journal of Photochemistry and Photobiology 166:107. Tributsch H. 2004. Dye sensitization solar cells: a critical assessment of the learning curve. Coordination Chemistry Reviews 248:1511. Tryk DA, Fujishima A, Honda K. 2000. Recent topics in photoelectrochemistry: achievements and future prospects. Electrochimica Acta 45:2363. Wang X, Mahesh S, Yan Y. 2005. CNT-based electrodes with high eciency for PEMFCs. Electrochemical and Solid State Letters 8:A42. Wang C, Waje M, Wang X, Tang JM, Haddon RC, Yan Y. 2004. Proton exchange membrane fuel cells with carbon nanotube based electrodes. Nano Letters 4:345. Williams KA, Eklund PC. 2000. Monte Carlo simulations of H2 physisorption in nite-diameter carbon nanotube ropes. Chemical Physics Letters 320:352. Published in 2007 by John Wiley & Sons, Ltd. Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er

636

S. S. MAO AND X. CHEN

Xiang XD, Sun X, Briceno G, Lou Y, Wang KA, Chang H, Wallace-Freedman WG, Chen SW, Schultz PG. 1995. A combinatorial approach to materials discovery. Science 268:1738 Yamakata A, Ishibashi TA, Onishi H. 2003a. Pressure dependence of electron- and hole-consuming reactions in photocatalytic water splitting on Pt/TiO2 studied by time-resolved IR absorption spectroscopy. International Journal of Photoenergy 5:7. Yamakata A, Ishibashi TA, Onishi H. 2003b. Kinetics of the photocatalytic water-splitting reaction on TiO2 and Pt/TiO2 studied by time-resolved infrared absorption spectroscopy. Journal of Molecular Catalysis 199:85. Ye Y, Ahn CC, Witham C, Fultz B, Liu J, Rinzler AG, Colbert D, Smith KA, Smalley RE. 1999. Hydrogen adsorption and cohesive energy of single-walled carbon nanotubes. Applied Physics Letters 74:2307. Zaluska A, Zaluski L, Strom-Olsen JO. 1999. Nanocrystalline magnesium for hydrogen storage. Journal of Alloys and Compounds 288:217. Zaluska A, Zaluski L, Strom-Olsen JO. 2001. Structure, catalysis and atomic reactions on the nano-scale: a systematic approach to metal hydrides for hydrogen storage. Applied Physics 72:157. Zukalova M, Zukal A, Kavan L, Nazeeruddin MK, Liska P, Gratzel M. 2005. Organized mesoporous TiO2 lms exhibiting greatly enhanced performance in dye-sensitized solar cells. Nano Letters 5:1789. Zuttel A, Sudan P, Mauron Ph, Kiyobayashi T, Emmenegger Ch, Schlapbach L. 2002. Hydrogen storage in carbon nanostructures. International Journal of Hydrogen Energy 27:203.

Published in 2007 by John Wiley & Sons, Ltd.

Int. J. Energy Res. 2007; 31:619636 DOI: 10.1002/er