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California is committed to 33 percent energy from renewable resources by 2020. With that deadline fast approaching, researchers across the state are busy exploring options.

Solar energy is attractive but for widespread adoption, it requires transformation into a storable form. This week in ACS Central Science, researchers report that nanowires made from multiple metal oxides could put solar ahead in this race.

One way to harness solar power for broader use is through photoelectrochemical (PEC) water splitting that provides hydrogen for fuel cells. Many materials that can perform the reaction exist, but most of these candidates suffer from issues, ranging from efficiency to stability and cost.

Peidong Yang and colleagues designed a system where nanowires from one of the most commonly used materials (TiO2) acts as a “host” for “guest” nanoparticles from another oxide called BiVO4. BiVO4 is a newly introduced material that is among the best ones for absorbing light and performing the water splitting reaction, but does not carry charge well while TiO2 is stable, cheap and an efficient charge carrier but does not absorb light well.

Together with a unique studded nanowire architecture, the new system works better than either material alone.

The authors state their approach can be used to improve the efficiencies of other photoconversion materials.

Synopsis

We report the use of Ta:TiO2|BiVO4 as a photoanode for use in solar water splitting cells. This host−guest system makes use of the favorable band alignment between the two semiconductors. The nanowire architecture allows for simultaneously high light absorption and carrier collection for efficient solar water oxidation.

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Metal oxides that absorb visible light are attractive for use as photoanodes in photoelectrosynthetic cells. However, their performance is often limited by poor charge carrier transport. We show that this problem can be addressed by using separate materials for light absorption and carrier transport. Here, we report a Ta:TiO2|BiVO4 nanowire photoanode, in which BiVO4 acts as a visible light-absorber and Ta:TiO2 acts as a high surface area electron conductor. Electrochemical and spectroscopic measurements provide experimental evidence for the type II band alignment necessary for favorable electron transfer from BiVO4 to TiO2. The host–guest nanowire architecture presented here allows for simultaneously high light absorption and carrier collection efficiency, with an onset of anodic photocurrent near 0.2 V vs RHE, and a photocurrent density of 2.1 mA/cm2 at 1.23 V vs RHE.

Introduction


Harnessing energy from sunlight is a means of meeting the large global energy demand in a cost-effective and environmentally benign manner. However, to provide constant and stable power on demand, it is necessary to convert sunlight into an energy storage medium.(1) An example of such a method is the production of hydrogen by photoelectrochemical (PEC) water splitting. The direct splitting of water can be achieved using a single semiconductor; however, due to the voltage requirement of the water splitting reaction and the associated kinetic overpotentials, only wide-band-gap materials can perform overall water splitting, limiting the efficiency due to insufficient light absorption.(2) To address this issue, a dual-band-gap z-scheme system can be utilized, with a semiconductor photoanode and photocathode to perform the respective oxidation and reduction reactions.(3) This approach allows for the use of lower-band-gap materials that can absorb complementary portions of the solar spectrum and yield higher solar-to-fuel efficiencies.(4, 5) In this integrated system, the charge flux is matched in both light absorbers of the photoelectrochemical cell. Therefore, the overall performance is determined by the limiting component. In most photoelectrosynthetic cells, this limiting component is the semiconductor photoanode.(6)
Metal oxides have been heavily researched as photoanode materials since few conventional light absorber materials are stable at the highly oxidizing conditions required for water oxidation.(7) However, the most commonly studied binary oxide, TiO2, has a band gap that is too large to absorb sunlight efficiently (∼3.0 eV), consequently limiting its achievable photocurrent.(8) While promising work has recently been done on stabilizing conventional light absorbers such as Si,(9) GaAs,(10) and InP,(11) the photovoltage obtained by these materials thus far has been insufficient to match with smaller-band-gap photocathode materials such as Si and InP in a dual absorber photoelectrosynthetic cell.(12, 13) Additionally, these materials have high production and processing costs. Small-band-gap metal oxides that absorb visible light and can be inexpensively synthesized, such as WO3, Fe2O3, and BiVO4, are alternative materials that hold promise to overcome these limitations.(14-16) Among these metal oxides, BiVO4 has emerged as one of the most promising materials due to its relatively small optical band gap of ∼2.5 eV and its negative conduction band edge (∼0 V versus RHE).(17, 18) Under air mass 1.5 global (AM1.5G) solar illumination, the maximum achievable photocurrent for water oxidation using BiVO4 is ∼7 mA/cm2.(16) However, the water oxidation photocurrent obtained in practice for BiVO4 is substantially lower than this value, mainly due to poor carrier transport properties, with electron diffusion lengths shorter than the film thickness necessary to absorb a substantial fraction of light.(17)
One approach for addressing this problem is to use two separate materials for the tasks of light absorption and carrier transport. To maximize performance, a conductive and high surface area support material (“host”) is used, which is coated with a highly dispersed visible light absorber (“guest”). This architecture allows for efficient use of absorbed photons due to the proximity of the semiconductor liquid junction (SCLJ). This strategy has been employed in dye sensitized (DSSC) and quantum dot sensitized solar cells (QDSSC).(19, 20) Using a host–guest scheme can improve the performance of photoabsorbing materials with poor carrier transport but relies upon appropriate band alignment between the host and guest. Namely, the electron affinity of the host should be larger, to favor electron transfer from guest to host without causing a significant loss in open-circuit voltage.(21) Nanowire arrays provide several advantages for use as the host material as they allow high surface area loading of the guest material, enhanced light scattering for improved absorption, and one-dimensional electron transport to the back electrode.(22) Therefore, nanowire arrays have been used as host materials in DSSCs, QDSSCs, and hybrid perovskite solar cells.(23-25) In photoelectrosynthetic cells, host–guest architectures have been utilized for oxide photoanodes such as Fe2O3|TiSi2,(26) Fe2O3|WO3,(27) Fe2O3|SnO2,(28) and Fe2TiO5|TiO2.(29) For BiVO4, it has been studied primarily with WO3|BiVO4,(30-32) ZnO|BiVO4,(33) and anatase TiO2|BiVO4.(34) While attractive for its electronic transport properties, ZnO is unstable in aqueous environments, and WO3 has the disadvantage of having a relatively positive flatband potential (∼0.4 V vs RHE)(14) resulting in potential energy losses for electrons as they are transferred from BiVO4 to WO3, thereby limiting the photovoltage of the combined system. Performance in the low potential region is critical for obtaining high efficiency in photoelectrosynthetic cells when coupled to typical p-type photocathode materials such as Si or InP.(12, 13) TiO2 is stable in a wide range of pH and has a relatively negative flat band potential (∼0.2 V vs RHE)(7) which does not significantly limit the photovoltage obtainable from BiVO4, while still providing a driving force for electron transfer. While TiO2 has intrinsically low mobility, doping TiO2 with donor type defects could increase the carrier concentration and thus the conductivity. Indeed, niobium and tantalum doped TiO2 have recently been investigated as potential transparent conductive oxide (TCO) materials.(35, 36) A host material with high carrier concentration could also ensure low contact resistance with the guest material.(37)
Using a solid state diffusion approach based on atomic layer deposition (ALD), we have previously demonstrated the ability to controllably and uniformly dope TiO2.(38) In this study we demonstrate a host–guest approach using Ta-doped TiO2 (Ta:TiO2) nanowires as a host and BiVO4 as a guest material. This host–guest nanowire architecture allows for simultaneously high light absorption and carrier collection efficiency, with an onset of anodic photocurrent near 0.2 V vs RHE, and a photocurrent of 2.1 mA/cm2 at 1.23 V vs RHE. We show that the synergistic effect of the host–guest structure results in higher performance than either pure TiO2 or BiVO4. We also experimentally demonstrate thermodynamically favorable band alignment between TiO2 and BiVO4 using spectroscopic and electrochemical methods, and study the band edge electronic structure of the TiO2 and BiVO4 using X-ray absorption and emission spectroscopies.

Article adapted from a American Chemical Society news release. To Read the FULL release, please click on the link provided below.

Publication: TiO2/BiVO4 Nanowire Heterostructure Photoanodes Based on Type II Band Alignment. Resasco, J et al. ACS Central Science (3 February, 2016): Click here to view.

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