Semiconductor electrode electrochemical potential

B) Electrochemically-assisted photocatalysis As discussed above, photocatalytic processes are electrochemical in nature. A clever enhancement approach involves the application of a judiciously selected potential bias to a semiconductor electrode. The potential promotes a better charge-separation, thus decreasing the electron-hole recombination and increasing the yield of the target processes. This approach is called electrochemically... 

When a semiconductor electrode is immersed in an electrolyte, the semiconductor-liquid junction is thus established. As a result, electrons flow from semiconductor to the electrolyte rmtil the equilibrium is achieved (Fig. 2.4). The electrolyte solution contains redox couple. The charge transfer develops an interfacial electric held and thus electrostatic potential builds up. The electrostatic potential balances the electrochemical potential between electrolyte solution and semiconductor. The electrochemical potential is observed throughout the system after equilibrium stage is achieved. It is also referred as Fermi level [38, 39, 42]. 

After starting his own laboratory in 1982, the author built microwave measurement facilities with his collaborators and resumed research on microwave electrochemical phenomena. While the potential of combining photoelectrochemistry with microwave conductivity techniques became evident very soon,6,7 it was some time before microwave experiments could be performed at semiconductor electrodes under better-defined microwave technical conditions.8... 

The (photo)electrochemical behavior of p-InSe single-crystal vdW surface was studied in 0.5 M H2SO4 and 1.0 M NaOH solutions, in relation to the effect of surface steps on the crystal [183]. The pH-potential diagram was constructed, in order to examine the thermodynamic stability of the InSe crystals (Fig. 5.12). The mechanism of photoelectrochemical hydrogen evolution in 0.5 M H2SO4 and the effect of Pt modification were discussed. A several hundred mV anodic shift of the photocurrent onset potential was observed by depositing Pt on the semiconductor electrode. 

It follows from the Franck-Condon principle that in electrochemical redox reactions at metal electrodes, practically only the electrons residing at the highest occupied level of the metal s valence band are involved (i.e., the electrons at the Fermi level). At semiconductor electrodes, the electrons from the bottom of the condnc-tion band or holes from the top of the valence band are involved in the reactions. Under equilibrium conditions, the electrochemical potential of these carriers is eqnal to the electrochemical potential of the electrons in the solution. Hence, mntnal exchange of electrons (an exchange cnrrent) is realized between levels having the same energies. 

Because of the excess holes with an energy lower than the Fermi level that are present at the n-type semiconductor surface in contact with the solution, electron ttansitions from the solution to the semiconductor electrode are facilitated ( egress of holes from the electrode to the reacting species ), and anodic photocurrents arise. Such currents do not arise merely from an acceleration of reactions which, at the particular potential, will also occur in the dark. According to Eq. (29.6), the electrochemical potential, corresponds to a more positive value of electrode potential (E ) than that which actually exists (E). Hence, anodic reactions can occur at the electrode even with redox systems having an equilibrium potential more positive than E (between E and E ) (i.e., reactions that are prohibited in the dark). 

The photoelectrolysis of H2O can be performed in cells being very similar to those applied for the production of electricity. They differ only insofar as no additional redox couple is used in a photoelectrolysis cell. The energy scheme of corresponding systems, semiconductor/liquid/Pt, is illustrated in Fig. 9, the upper scheme for an n-type, the lower for a p-type electrode. In the case of an n-type electrode the hole created by light excitation must react with H2O resulting in 02-formation whereas at the counter electrode H2 is produced. The electrolyte can be described by two redox potentials, E°(H20/H2) and E (H20/02) which differ by 1.23 eV. At equilibrium (left side of Fig. 9) the electrochemical potential (Fermi level) is constant in the whole system and it occurs in the electrolyte somewhere between the two standard energies E°(H20/H2) and E°(H20/02). The exact position depends on the relative concentrations of H2 and O2. Illuminating the n-type electrode the electrons are driven toward the bulk of the semiconductor and reach the counter electrode via the external circuit at which they are consumed for Hj-evolution whereas the holes are dir tly... 

Basic properties of semiconductors and phenomena occurring at the semiconductor/electrolyte interface in the dark have already been discussed in Sections 2.4.1 and 4.5.1. The crucial effect after immersing the semiconductor electrode into an electrolyte solution is the equilibration of electrochemical potentials of electrons in both phases. In order to quantify the dark- and photoeffects at the semiconductor/electrolyte interface, a common reference level of electron energies in both phases has to be defined. 

The electrochemical potential of an electron in a solid defines the Fermi energy (cf. Eq. 3.1.9). The Fermi energy of a semiconductor electrode (e ) and the electrolyte energy level (credox) are generally different before contact of both phases (Fig. 5.60a). After immersing the semiconductor electrode into the electrolyte, an equilibrium is attained ... 

GaAs, CuInS2, CuInSe2- Semiconductor electrodes have received increasing attention as a consequence of their potential application in photoelectrochemical energy conversion devices. In order to achieve optimum efficiency, the knowledge of the surface composition plays a crucial role. Surface modifications may occur during operation of the photo electrode, or may be the result of a chemical or electrochemical treatment process prior to operation. 

It is the electrode potential

electrochemical experiments it represents a potential difference between two identical metallic contacts of an electrochemical circuit. Such a circuit, whose one element is a semiconductor electrode, is shown schematically in Fig. 2. Besides the semiconductor electrode, it includes a reference electrode whose potential is taken, conventionally, as zero in reckoning the electrode potential (for details, see the book by Glasstone, 1946). The potential q> includes potential drops across the interfaces, i.e., the Galvani potentials at contacts—metal-semiconductor interface, semiconductor-electrolyte interface, etc., and also, if current flows in the circuit, ohmic potential drops in metal, semiconductor, electrolyte, and so on. (These ohmic drops are negligibly small under experimental conditions considered below.)... 

The symbols in parentheses denote the electrochemical potential levels for the corresponding reaction (the level Fdec is a particular case of the level Fred0J for a redox reaction, in which the electrode material is destructed). Once Fdec is calculated (from tabular values of thermodynamic characteristics of substances involved see, for example, Latimer, 1952), the equilibrium potentials of the reactions of anodic [Pg.286]

While many of the standard electroanalytical techniques utilized with metal electrodes can be employed to characterize the semiconductor-electrolyte interface, one must be careful not to interpret the semiconductor response in terms of the standard diagnostics employed with metal electrodes. Fundamental to our understanding of the metal-electrolyte interface is the assumption that all potential applied to the back side of a metal electrode will appear at the metal electrode surface. That is, in the case of a metal electrode, a potential drop only appears on the solution side of the interface (i.e., via the electrode double layer and the bulk electrolyte resistance). This is not the case when a semiconductor is employed. If the semiconductor responds in an ideal manner, the potential applied to the back side of the electrode will be dropped across the internal electrode-electrolyte interface. This has two implications (1) the potential applied to a semiconducting electrode does not control the electrochemistry, and (2) in most cases there exists a built-in barrier to charge transfer at the semiconductor-electrolyte interface, so that, electrochemical reversible behavior can never exist. In order to understand the radically different response of a semiconductor to an applied external potential, one must explore the solid-state band structure of the semiconductor. This topic is treated at an introductory level in References 1 and 2. A more complete discussion can be found in References 3, 4, 5, and 6, along with a detailed review of the photoelectrochemical response of a wide variety of inorganic semiconducting materials. 

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