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Electrochemistry at Semiconductor and Oxidized Metal Electrodes

30 Nov 1980-
TL;DR: In this paper, the authors present a theoretical analysis of the energy levels at the surface of a delectable deformed deformed metal deformed by Mott-Schottky Plots.
Abstract: 1. The Solid and the Solution.- 1.1. The Solid.- 1.1.1. Donors, Acceptors, and Traps.- 1.1.2. Energy Levels at the Surface.- 1.1.3. Conductance in Solids.- 1.2. The Solution.- 1.2.1. Introduction.- 1.2.2. The Electrode Fermi Energy as a Function of the Redox Couples in Solution.- 1.2.3. The Relation between the Hydrogen and the Vacuum Scales of Energy.- 1.2.4. Fluctuating Energy Levels in Solution.- 1.2.5. The Energy Levels Associated with Two-Equivalent Ions.- 1.2.6. Conductance in Liquids.- 2. The Solid/Liquid Interface.- 2.1. Surface Ions and Their Energy Levels.- 2.1.1. Adsorption.- 2.1.2. Surface States at the Solid/Liquid Interface.- 2.2. Double Layers at the Solid/Liquid Interface.- 2.2.1. General.- 2.2.2. The Gouy Layer.- 2.2.3. The Helmholtz Double Layer.- 2.2.4. The Space Charge Double Layer in the Semiconductor.- 2.3. Theoretical Predictions of the Energy Levels of Band Edges.- 2.4. The Band Model of the Solid/Solution Interface.- 3. Theory of Electron and Hole Transfer.- 3.1. Introduction.- 3.1.1. General.- 3.1.2. The Activation Energy in Electrode Reactions.- 3.2. Classical Model.- 3.3. The Energy Level Model of Charge Transfer.- 3.3.1. General.- 3.3.2. The Metal Electrode.- 3.3.3. The Semiconductor Electrode.- 3.4. Qualitative Description of Electrode Processes Using the Band Model.- 3.4.1. The Behavior of the Metal Electrode.- 3.4.2. The Behavior of the Semiconductor Electrode.- 3.4.3. The Transition between Semiconductor and Metallic Behavior.- 4. Measurement Techniques.- 4.1. Capacity Measurements.- 4.1.1. Introduction.- 4.1.2. Measurement Theory.- 4.1.3. Analysis.- 4.1.4. Complex Mott-Schottky Plots.- 4.1.5. Determination of Band Edges.- 4.2. Measurements of the Current/Voltage Characteristics.- 4.2.1. General Techniques Voltammetry.- 4.2.2. Rotating Electrodes.- 4.2.3. Illumination.- 4.3. Other Techniques.- 4.3.1. Techniques for Vs Measurement.- 4.3.2. Techniques to Determine Surface Species or Phases.- 4.3.3. Techniques to Study Electrode Reactions.- 5. The Properties of the Electrode and Their Effect on Electrochemical Measurements.- 5.1. The Behavior of the Perfect Crystal.- 5.1.1. The Helmholtz Double Layer: The Surface Charges on the Electrode.- 5.1.2. The Space Charge Region of the Perfect Crystal.- 5.2. The Behavior of Electrode Defects.- 5.2.1. Introduction.- 5.2.2. Deviations of Mott-Schottky Plots Due to Bulk Flaws.- 5.2.3. Current Flow Associated with Bulk Flaws.- 5.3. Observed Flat Band Potentials for Various Semiconductors.- 6. Observations of Charge Transfer at an Inert Semiconductor Electrode.- 6.1. Introduction.- 6.2. Majority Carrier Capture.- 6.2.1. Direct Carrier Transfer to Ions in Solution.- 6.2.2. Indirect Electron Transfer to Ions in Solution.- 6.3. Minority Carrier Capture.- 6.3.1. Minority Carrier Capture on Two-Equivalent Species: Radical Formation and Current Doubling.- 6.3.2. Minority Carrier Capture by One-Equivalent Ions.- 6.3.3. Photocatalysis.- 6.4. Intrinsic Surface States and Recombination Centers.- 6.4.1. Intrinsic Surface States as Carrier Transfer Centers.- 6.4.2. Intrinsic Surface States and Ions in Solution as Recombination Centers.- 6.5. Carrier Injection.- 6.5.1. Direct Electron and Hole Injection.- 6.5.2. Injection by Tunneling.- 6.5.3. Injection by Optically Excited Ions: Dye Injection.- 6.6. High-Current, High-Voltage Processes.- 6.6.1. Introduction.- 6.6.2. High Currents with Accumulation Layers.- 6.6.3. Tunneling and Breakdown on Non-Transition-Metal Semiconductors.- 6.6.4. Practical Electrodes.- 6.7. Analysis of Complicated Electrode Reactions using the Tools of Semiconductor Electrochemistry.- 6.7.1. The Photocatalytic Oxidation of Formic Acid.- 6.7.2. Analysis of the Energy Levels of Two-Equivalent Species.- 6.7.3. The Reduction of Iodine on CdS.- 7. Chemical Transformation in the Electrode Reaction.- 7.1. Introduction.- 7.2. Inner Sphere Changes during Redox Reactions at an Inert Electrode.- 7.3. Adsorption onto and Absorption into the Electrode.- 7.3.1. Adsorption of Water, Hydrogen, and Oxygen.- 7.3.2. Adsorption of Electrolyte Ions.- 7.3.3. Action of Deposited Species.- 7.3.4. Movement of Impurities and Defects into the Electrode.- 7.4. Corrosion.- 7.4.1. Introduction.- 7.4.2. Theory and Observations of Semiconductor Corrosion.- 7.4.3. Stabilizing Agents to Prevent Corrosion.- 8. Coated Electrodes.- 8.1. Introduction.- 8.1.1. The Band Model for Oxide Films.- 8.1.2. Thin Films.- 8.1.3. The Structure of Thick Films.- 8.2. Current Transport through Oxide Films.- 8.2.1. Thin Oxide Layers.- 8.2.2. Model of Electronic Conduction through Thick Coherent Layers.- 8.2.3. Semiconducting Oxide Layers on Metal Electrodes.- 8.2.4. Insulating Layers on Metal and Semiconductor Electrodes.- 8.3. Deposition of Reaction Products on Semiconductor Electrodes.- 9. Applications of Semiconductor Electrodes.- 9.1. Solar Energy Conversion.- 9.1.1. Introduction.- 9.1.2. Photovoltaic Cells.- 9.1.3. Conversion of Optical to Chemical Energy.- 9.1.4. Corrosion of PEC Cells.- 9.1.5. The Future Potential of PEC Solar Cells.- 9.2. Electrocatalysis on Semiconductors.- 9.2.1. General.- 9.2.2. Surface State Additives and Narrow Bands in Electrocatalysis.- 9.3. New Devices.- 9.4. Electropolishing of Semiconductors.- References.- References to Review Articles and Books.- Author Index.

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Abstract: The civilian, commercial, and defense sectors of most advanced industrialized nations are faced with a tremendous set of environmental problems related to the remediation of hazardous wastes, contaminated groundwaters, and the control of toxic air contaminants. For example, the slow pace of hazardous waste remediation at military installations around the world is causing a serious delay in conversion of many of these facilities to civilian uses. Over the last 10 years problems related to hazardous waste remediation have emerged as a high national and international priority.

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Journal ArticleDOI
28 Feb 2014-Science
TL;DR: It is demonstrated that a nanoporous morphology effectively suppresses bulk carrier recombination without additional doping, manifesting an electron-hole separation yield of 0.90 at 1.23 volts (V) versus the reversible hydrogen electrode (RHE).
Abstract: Bismuth vanadate (BiVO4) has a band structure that is well-suited for potential use as a photoanode in solar water splitting, but it suffers from poor electron-hole separation. Here, we demonstrate that a nanoporous morphology (specific surface area of 31.8 square meters per gram) effectively suppresses bulk carrier recombination without additional doping, manifesting an electron-hole separation yield of 0.90 at 1.23 volts (V) versus the reversible hydrogen electrode (RHE). We enhanced the propensity for surface-reaching holes to instigate water-splitting chemistry by serially applying two different oxygen evolution catalyst (OEC) layers, FeOOH and NiOOH, which reduces interface recombination at the BiVO4/OEC junction while creating a more favorable Helmholtz layer potential drop at the OEC/electrolyte junction. The resulting BiVO4/FeOOH/NiOOH photoanode achieves a photocurrent density of 2.73 milliamps per square centimenter at a potential as low as 0.6 V versus RHE.

2,361 citations

Journal ArticleDOI
TL;DR: In this paper, a critical review highlights some key factors influencing the efficiency of heterogeneous semiconductors for solar water splitting (i.e. improved charge separation and transfer, promoted optical absorption, optimized band gap position, lowered cost and toxicity, and enhanced stability and water splitting kinetics).
Abstract: There is a growing interest in the conversion of water and solar energy into clean and renewable H2 fuels using earth-abundant materials due to the depletion of fossil fuel and its serious environmental impact. This critical review highlights some key factors influencing the efficiency of heterogeneous semiconductors for solar water splitting (i.e. improved charge separation and transfer, promoted optical absorption, optimized band gap position, lowered cost and toxicity, and enhanced stability and water splitting kinetics). Moreover, different engineering strategies, such as band structure engineering, micro/nano engineering, bionic engineering, co-catalyst engineering, surface/interface engineering of heterogeneous semiconductors are summarized and discussed thoroughly. The synergistic effects of the different engineering strategies, especially for the combination of co-catalyst loading and other strategies seem to be more promising for the development of highly efficient photocatalysts. A thorough understanding of electron and hole transfer thermodynamics and kinetics at the fundamental level is also important for elucidating the key efficiency-limiting step and designing highly efficient solar-to-fuel conversion systems. In this review, we provide not only a summary of the recent progress in the different engineering strategies of heterogeneous semiconductors for solar water splitting, but also some potential opportunities for designing and optimizing solar cells, photocatalysts for the reduction of CO2 and pollutant degradation, and electrocatalysts for water splitting.

1,489 citations

Journal ArticleDOI
TL;DR: In this paper, the authors focused on the materials-related issues in the development of high-efficiency photo-electrochemical cells (PECs), in terms of semiconducting and electrochemical properties and their impact on the performance of PECs.

1,424 citations


Cites background or methods from "Electrochemistry at Semiconductor a..."

  • ...The Nat-band potential may be modi5ed to the desired level through surface chemistry [48,49]....

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  • ...1, the optimal band gap for highperformance photo-electrodes is∼ 2 eV [10,22,27,51,58,59]....

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  • ...Recent e3orts in the development of vehicles fuelled by hydrogen, either directly or through hydrogen fuel cells, may serve as examples of T. Bak et al. / International Journal of Hydrogen Energy 27 (2002) 991–1022 993 Nomenclature A irradiated area (m2) a Anode=photo-anode AM air mass c speed of light in vacuo (2:99793×108 m=s) c cathode=photo-cathode Dye photo-sensitizer at ground state Dye∗ dye at excited state Dye+ dye at charged state e elementary charge (1:602 × 10−19 C) e′ quasi-free electron E energy (eV) EB potential energy related to the bias (EB = eVbias) Ec energy of the bottom of the conduction band (eV) EF Fermi energy (eV) Eg band gap (eV) Ei threshold energy (eV) E(H+=H2) energy of the redox couple H+=H2 (eV) E(O2=H2O) energy of the redox couple O2=H2O (eV) Eloss energy loss (eV) El electrolyte En;d free enthalpy of electrochemical oxidation (per one electron hole) (eV) Ep;d free enthalpy of electrochemical reduction (per one electron) (eV) Ev energy of the top of the valence band (eV) EMF electromotive force (open circuit voltage) (V) F Faraday constant (F = eNA) (9:648 × 104 C mol−1) G Gibbs energy (free enthalpy) (kJ mol−1) G0 standard Gibbs energy (standard free enthalpy) (kJ mol−1) MGa free enthalpy of anodic decomposition (kJ mol−1) MGc free enthalpy of cathodic decomposition (kJ mol−1) MGloss free energy losses related with anodic and cathodic over-potentials MG(H2O) free energy of H2O formation h Planck constant (6:626 × 10−34 J s) h: quasi-free electron hole H+ hydrogen ion (can be considered as hydronion ion H3O+) HPE hybrid photo-electrode I current (A) IPCE incident photon-to-current e0ciency Ir incidence of solar irradiance (W m−2) i concentration of ionic charge carriers (cm−3) J Nux density (amount of some quantity Nowing across a given area—often unit area perpendicular to the Now—per unit time, e.g. number of particles) (m−2 s−1) Jg Nux density of absorbed photons (m−2 s−1) M metal MOx metal oxide (x corresponds to oxygen stoichiometry) N number of photons NA Avogadro number (6:022 × 1023 mol−1) Ne3 e0cient number of incidents N (E) distribution of photons with respect to energy (s−1 m−2 eV−1) Ntot total number of incidents NHE normal hydrogen electrode n concentration of electrons (cm−3) OH− hydroxyl ion PC polycrystalline specimen PEC photo-electrochemical cell p concentration of electron holes (cm−3) pH −log [H+] R Universal gas constant (8:3144 J mol−1K−1) R resistance (Q) R(H2) rate of hydrogen generation (mol s−1) S surface area (m2) SC single crystal TF thin 5lm t time Ua anodic over-potential (V) Uc cathodic over-potential (V) Ufb Nat band potential (V) Vbias bias voltage (V) VB surface potential (corresponding to band curvature) (V) Vn;d cathodic decomposition potential (V) Vp;d anodic decomposition potential (V) VH potential drop across the Helmholtz layer (V) Vh potential drop across the hybrid photoelectrode (V) Vph(Si) photo-voltage across the Si cell (V) Vph (TiO2) photo-voltage across the oxide photoelectrode (V) x number (related to nonstoichiometry in chemical formulas) X anion in salts, such as Cl− or SO2−4 z number of electrons (electron holes) [H+] concentration of hydrogen ions (M) M di3erence electrical conductivity (Q−1 cm−1) i mobility of ionic charge carriers (cm2 V−1 s−1) 994 T. Bak et al. / International Journal of Hydrogen Energy 27 (2002) 991–1022 n mobility of electrons (cm2 V−1 s−1) p mobility of electron holes (cm2 V−1 s−1) g fraction of e0cient solar irradiance ch chemical e0ciency of irradiation QE quantum e0ciency wavelength (nm) i threshold wavelength v frequency (Hz) angle (rad) work function (eV) a work function of photo-anode (eV) el work function of electrolyte (eV) how close is the hydrogen age....

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  • ...The Nat-band potential, Ufb, is the potential that has to be imposed over the electrode=electrolyte interface in order to make the bands Nat [22,51,58]....

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  • ...Philips et al. [70] have observed that, although the addition of 30 mol% V to TiO2 results in a reduction in the band gap to 1:99 eV, the formation of (Ti0:7V0:3)O2 had a detrimental e3ect on the photo-activity due to a substantial increase in the Nat band potential by ∼ 1 V)....

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Journal ArticleDOI
TL;DR: The present review tries to give a comprehensive and most up to date view to the field, with an emphasis on the currently most investigated anodic TiO2 nanotube arrays.
Abstract: In the present review we try to give a comprehensive and most up to date view to the field, with an emphasis on the currently most investigated anodic TiO2 nanotube arrays. We will first give an overview of different synthesis approaches to produce TiO2 nanotubes and TiO2 nanotube arrays, and then deal with physical and chemical properties of TiO2 nanotubes and techniques to modify them. Finally, we will provide an overview of the most explored and prospective applications of nanotubular TiO2.

984 citations