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Photoelectrochemical Measurements

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Photoelectrochemical Hydrogen Production

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

Abstract

This chapter presents an overview of several photoelectrochemical characterization techniques and the equipment needed to carry out these measurements. It starts with a detailed description of the photoelectrochemical cell and its components. A few selected cell designs are shown and discussed, and several considerations for choosing suitable photoelectrode substrates, electrolyte solutions, and counter and reference electrodes are given. This is followed by a description of two experimental setups for photocurrent measurements, one for measurements under simulated sunlight and one for wavelength-dependent (monochromatic) measurements. The components of these setups are described, with special emphasis given to the inner workings of the potentiostat and the various types and specifications of solar simulators. The information that can be obtained from photocurrent measurements, such as photocurrent onset potentials, performance limiting factors, and quantum efficiencies is described next. The final section reviews the principles, equipment, and practical considerations for Mott–Schottky measurements. Common pitfalls of impedance measurements are outlined, and several strategies and precautions to avoid or minimize measurement errors are given.

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Notes

  1. 1.

    Examples of optimization parameters for photoelectrode synthesis are deposition temperature, substrate cleaning method, additives used to optimize the boiling point, surface tension, water content or viscosity of a solution, postdeposition heat treatments to improve the crystallinity, dipping as-prepared samples in a precursor solution to improve interparticle contacts, etc.

  2. 2.

    Most photoelectrochemical cells used in PEC research are designed to study the properties of a single photoelectrode. PEC cells in which more than one electrode is illuminated at once (e.g., tandem cells) are somewhat more complicated and will not be considered here.

  3. 3.

    Except for a small dip around ~1400 nm, depending on the purity grade.

  4. 4.

    A 50 mm, 3 mm thick window of UV-grade fused silica costs ~40 EUR (in 2010). Note that fused silica is often incorrectly referred to as “quartz,” which is the crystalline form of SiO2 that shows slightly better transmission than fused silica at a much higher price.

  5. 5.

    Factors that may contribute to the total overpotential include slow charge transfer across the Helmholtz layer, slow reaction kinetics due to preceding or subsequent reaction steps, mass transport limitations (diffusion, convection, migration), and removal of the solvation sheet of water molecules (dipoles) surrounding each ion.

  6. 6.

    Each ion is surrounded by a solvation sheath of water molecules (see Sect. 2.6.2). The size and charge of the central ion determine the configuration of the surrounding molecules, and this in turn determines the interaction strength of the ion with neighboring ions in the solution.

  7. 7.

    For a more detailed description of the working principle of the differential amplifiers, buffers, and power amplifiers shown in Fig. 3.6, the reader is referred to the excellent classic text on electronics by Horowitz and Hill [23].

  8. 8.

    The modulation input is used for, e.g., impedance measurements, which will be discussed later.

  9. 9.

    Most proprietary software packages include support for several types of frequency response analyzers, sometimes even for models made by other manufacturers.

  10. 10.

    The AM1.5D spectrum only contains the direct contributions over a 5° field of view, and has an integrated intensity of 768 W/m2.

  11. 11.

    In exceptional cases, ignition of a high-power gas discharge lamp can even destroy electronic equipment. This has happened once in the author’s laboratory to a Solartron 1286 potentiostat after switching on an older type 450 W Xe lamp.

  12. 12.

    Monochromators have both entrance and exit slits. It is recommended to use the same width for both slits.

  13. 13.

    The situation is a bit complicated in a three-electrode system since the potential of the counter electrode is not known. One can argue that for a counter-electrode with a low overpotential for H2 evolution, the potential of the counter electrode should be close to that of the reversible hydrogen potential – provided that the concentration of dissolved hydrogen is high enough. This can be easily verified by a separate measurement of V WE –V CE during a three-electrode linear sweep voltammogram. One particular test in the author’s laboratory showed that at a current density >0.5 mA/cm2, the potential of a coiled Pt wire electrode approached that of the reversible hydrogen electrode to within ~0.1 V. At lower current densities, however, deviations as large as 1 V were observed.

  14. 14.

    In contrast to photocurrent measurements, discontinuities in the ICPE spectrum can be easily avoided by using the same combination of wavelength range and long pass filters while measuring the light intensity with the calibrated photodiode.

  15. 15.

    There are several other, more complicated elements available to describe the various processes that can occur in a photoelectrochemical cell, such as the Warburg element (to model diffusion), the Constant Phase Element (CPE, used to describe processes that have a distribution of time constants or activation energies), and transmission lines (to model porous electrodes [47]). Porous electrodes and CPE elements that represent nonideal capacitive elements are briefly discussed below. For more detailed information, the reader is referred to the literature [48, 49].

  16. 16.

    Preconditioning steps are, e.g., removal of the dc component of the signal by passing it through a high pass filter (a capacitor), or amplification/attenuation of the signal by a certain fixed factor. These steps are often necessary to ensure that the signal falls within the range that the FRA can handle internally. These steps do not (and should not) influence the final measurement results.

  17. 17.

    When writing one’s own measurement software, it should be realized that the FRA simply divides the voltage signals at both input channels – it does not know what these signals represent. Since the (voltage) signal that represents the current is given by I monitor × R i (Fig. 3.6), the FRA reports the impedance as V/(I × R i) – it does not “know” the value of the range resistor R i. The software should therefore multiply the reported value by R i to obtain the actual impedance.

  18. 18.

    The value of kT/e at room temperature is ~25 mV.

  19. 19.

    This membrane forms the junction between the internal solution of the reference electrode and the electrolyte of the PEC cell.

  20. 20.

    The donors/acceptors are then no longer shallow, but deep.

  21. 21.

    Note that a semicircle in the Z′ vs. Z″ (Nyquist) plot is only observed in the presence of a resistive element in parallel to the space charge capacitance.

  22. 22.

    CPE elements are usually indicated by the letter Q, analogous to the letters R and C used for resistive and capacitive elements, respectively.

  23. 23.

    A bulk or surface state with a single, discrete energy level is probably better described by a single additional RC component instead of a CPE element.

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Acknowledgments

The author gratefully acknowledges 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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Correspondence to Roel van de Krol .

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Editors and Affiliations

  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). Photoelectrochemical Measurements. 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_3

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