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Principles of Photoelectrochemical Cells

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Photoelectrochemical Hydrogen Production

Part of the book series: Electronic Materials: Science & Technology ((EMST,volume 102))

Abstract

In this chapter, the basic principles of photoelectrochemical water splitting are reviewed. After a brief introduction of the photoelectrochemical cell and the electrochemical reactions involved, the electronic structure and properties of semiconductors are discussed. The emphasis is on metal oxide semiconductors, and special attention is given to the presence of ionic point defects in these materials. This is followed by a closer look at the semiconductor/electrolyte interface. The energy conversion efficiency and different definitions of the quantum efficiency are treated next. The chapter concludes with a brief outline of the material’s requirements and challenges facing the development of highly efficient photoelectrodes.

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Notes

  1. 1.

    Note that the sign of the potential for the oxidation half-reactions is opposite from that usually encountered in the literature, which usually lists these reactions as reduction reactions.

  2. 2.

    The valence band of a semiconductor is analogous to the highest occupied molecular orbital (HOMO) in a molecule, whereas the conduction band is the solid state analogue of the lowest unoccupied molecular orbital (LUMO).

  3. 3.

    An example of a native substituent is a site exchange of A and B cations in a ternary compound such as AB x O y .

  4. 4.

    An “aliovalent” dopant has different charge than the ion that it replaces.

  5. 5.

    Anion interstitials normally only occur in oxides with the fluorite structure, which can be viewed as an fcc base lattice of cations in which the interstitial sites are occupied by anions.

  6. 6.

    Note that the octahedrally coordinated Bi sites (103 pm) are clearly too large for W, and would cause the W6+ to “rattle,” which is energetically very unfavorable.

  7. 7.

    monolayer (ML) corresponds to ~1015 atoms/cm2.

  8. 8.

    “Amphoteric” means that the semiconductor surface can either donate or accept a proton, i.e., it can act both as a Brønsted acid and as a Brønsted base.

  9. 9.

    Note that in highly doped semiconductors (>1019 cm−3) and metals, C SC can exceed C H so that any change in the applied potential will fall across the Helmholtz layer instead of the depletion layer.

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Acknowledgments

The author gratefully acknowledges Fatwa F. Abdi for critical reading of the manuscript, and the NWO-ACTS Sustainable Hydrogen program (project 053.61.009) and the European Commission’s Framework 7 program (NanoPEC, Project 227179) for support.

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  1. Faculty of Applied Sciences, Department Chemical Engineering/Materials for Energy Conversion and Storage, Delft University of Technology, 5045, 2600 GA, Delft, The Netherlands

    Roel van de Krol

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  1. Dept. Chemical Technology, Particle Technology Group, Delft University of Technology, Julianalaan 136, Delft, 2628 BL, Netherlands

    Roel van de Krol

  2. Fac. Sciences de Base, Inst. Sciences et Ingénierie Chimiques, Ecole polytechnique fédérale de Lausanne, CH G1 525, Lausanne, 1015, Switzerland

    Michael Grätzel

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van de Krol, R. (2012). Principles of Photoelectrochemical Cells. In: van de Krol, R., Grätzel, M. (eds) Photoelectrochemical Hydrogen Production. Electronic Materials: Science & Technology, vol 102. Springer, Boston, MA. https://doi.org/10.1007/978-1-4614-1380-6_2

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