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Contents
Author Biographies
Chapter 1

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The Potential Contribution of Photoelectrochemistry in the

Global Energy Future
Bruce Parkinson and John Turner
1.1
1.2
1.3
1.4

History
Solar Hydrogen
New Materials
Commercial Viability of Photoelectrolysis as a Route
to Hydrogen
1.5 Photoelectrochemical Reduction of Carbon Dioxide
1.6 Summary and Conclusions
Acknowledgement
References
Chapter 2

Kinetics and Mechanisms of Light-Driven Reactions at

Semiconductor Electrodes: Principles and Techniques
Laurence Peter
2.1
2.2

Introduction
Conventional and Nanostructured Photoelectrodes
2.2.1 Conventional Semiconductor Electrodes
2.2.2 Potential and Charge Distribution at the
Semiconductor-Electrolyte Junction
2.2.3 Collection of Minority Carriers at the
Illuminated Semiconductor-Electrolyte
Junction
2.2.4 Nanostructured and Mesoporous Electrodes

RSC Energy and Environment Series No. 9

Photoelectrochemical Water Splitting: Materials, Processes and Architectures
Edited by Hans-Joachim Lewerenz and Laurence Peter
r The Royal Society of Chemistry 2013
Published by the Royal Society of Chemistry, www.rsc.org

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2.3

Rate Constants and Reaction Orders

2.3.1 Electrode Kinetics at Metal Electrodes
2.3.2 Kinetics of Minority Carrier Reactions at
Semiconductor Electrodes
2.3.3 The Concept of Overpotential for Minority
Carrier Reactions
2.3.4 Competition between Charge Transfer and
Recombination
2.4 Determination of Rate Constants from Transient
Photocurrents
2.5 Intensity-Modulated Photocurrent Spectroscopy
2.6 Photoelectrochemical Impedance Spectroscopy
2.7 Following Interfacial Electron Transfer using
Microwave Reectivity Measurements
2.8 Potential and Light-Modulated Absorption
Spectroscopy
2.9 Conclusions and Outlook
Acknowledgements
References

Chapter 3

Structured Materials for Photoelectrochemical Water

Splitting
James MCKone and Nathan Lewis
3.1
3.2

3.3

Introduction
Interplay between Materials Properties and Device
Characteristics
3.2.1 Light Absorption and Collection of
Photogenerated Carriers in Crystalline
Semiconductors
3.2.2 Open-Circuit Photovoltage at Structured
Semiconductors
3.2.3 Electrochemical Transport at Structured
Semiconductors
3.2.4 Catalysis at Structured Semiconductors
3.2.5 Outlook
Review of Recently Demonstrated Advantages of
Structured Materials for Photoelectrochemical Water
Splitting
3.3.1 Metal Oxide Photoelectrodes
3.3.2 High Aspect-Ratio Structures
3.3.3 Water Splitting by Colloidal Particles
3.3.4 Water Splitting Catalysis by Structured
Materials

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3.3.5

Advances in Modeling Heterogeneous

Catalysis
3.3.6 Broader Considerations Beyond Small
Acknowledgements
References
Chapter 4

Tandem Photoelectrochemical Cells for Water Splitting

Kevin Sivula and Michael Gratzel
Introduction and Motivation for Using Multiphoton
Systems
4.2 Strategies and Limitations of Multi-Absorber Systems
4.2.1 Brute Force Strategies
4.2.2 The Tandem Cell Concept
4.2.3 The D4 Strategy and its Potential
4.2.4 D4 Device Architectures
4.3 PV/PV Strategies
4.4 Photoelectrode/PV Systems
4.4.1 Advantages and Operation of a Photoanode/
PV Tandem Cell
4.4.2 Photoanode/PV Examples
4.4.3 The Photoanode/DSSC Tandem Cell
4.5 Photoanode/Photocathode Systems
4.6 Practical Device Design Considerations
4.7 Summary and Outlook
Acknowledgement
References

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4.1

Chapter 5

Particulate Oxynitrides for Photocatalytic Water Splitting

Under Visible Light
Kazuhiko Maeda and Kazunuri Domen
5.1
5.2
5.3

Introduction
Oxynitrides Having Early-Transition Metal Cations
Improvement of Water Reduction Activity of
d0-(Oxy)nitrides
5.4 Ge3N4, a Typical Metal Nitride with d10 Electronic
Conguration
5.5 GaN-ZnO and ZnGeN2-ZnO Solid Solutions
5.6 Two-Step Water Splitting Mimicking Natural
Photosynthesis in Green Plants
5.7 Photoelectrochemical Water Splitting Using
d0-Oxynitrides
5.8 Conclusions
References

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Chapter 6

Contents

Rapid Screening Methods in the Discovery and Investigation

of New Photocatalyst Compositions
Allen Bard, Heung Chan Lee, Kevin Leonard,
Hyun Seo Park and Shijun Wang
6.1
6.2
6.3

Introduction
Rapid Synthesis on Arrays
Rapid Screening with SECM
6.3.1 Method
6.3.2 Guidelines
6.3.3 Data Analysis
6.4 Rapid Screening with Electrocatalysts
6.5 Follow-Up Studies with Large Electrodes
6.6 Correlation of Doping Eects and Theory
References

Chapter 7

Oxygen Evolution and Reduction Catalysts: Structural and

Electronic Aspects of Transition Metal Based Compounds
and Composites
Sebastian Fiechter and Peter Bogdano
7.1

Introduction
7.1.1 Chemical Energy Storage
7.1.2 Oxidation and Reduction Catalysts
in Nature
7.2 Oxygen Evolving Catalysts an Inorganic
Approach
7.2.1 Structural Features
7.2.2 Preparation Routes and Phase
Formation
7.2.3 Electrochemical Behavior and
Structure-function Analysis
7.3 Functionalization of Electrode Surfaces and
In-Operando studies
7.3.1 In-Line Synchrotron Radiation X-ray
Photoelectron Spectroscopy
7.3.2 In-Situ X-ray Absorption Spectroscopy
7.4 Integrated Concepts and Challenges in Catalysts
Characterization
7.5 Summary and Outlook
Acknowledgements
References

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Contents

Chapter 8

The Group III-Nitride Material Class: from Preparation to

Perspectives in Photoelectrocatalysis
Ramon Collazo and Nikolaus Dietz

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Introduction
8.1.1 Properties of the Binaries InN, GaN, AlN and
their Ternaries
8.1.2 Band Gap Alignments for InN-GaN-AlN-InN
Alloys and Heterostructures
8.2 Fabrication of Epitaxial Alloys and Heterostructures
8.2.1 Epitaxial Growth Techniques
8.2.2 Substrate Issues
8.3 The AlxGa1-xN System: from the Binaries to Ternary
Alloys and Heterostructures
8.3.1 Properties of Epitaxial GaN-AlN Alloys
8.3.2 Ternary AlGaN Alloys and Heterostructures
8.3.3 Point Defects in AlGaN Alloys: Electrical
Properties
8.4 The InxGa1-xN System
8.4.1 Gallium-rich Ternary InGaN Alloys and
Heterostructures
8.4.2 InN and Indium-Rich InGaN Epilayers and
Heterostructures
8.5 Present Challenges in Materials Improvement and
Materials Integration
8.6 InGaN-based Photoelectrochemical Cells for
Hydrogen Generation
8.7 Conclusions
Acknowledgement
References
Chapter 9

Epitaxial III-V Thin Film Absorbers: Preparation, Ecient

InP Photocathodes and Routes to High Eciency Tandem
Structures
Thomas Hannappel, Matthias M May and
Hans-Joachim Lewerenz
9.1
9.2
9.3

General Introduction
Introduction to III-V Materials
Epitaxial III-V Systems for Solar Energy
Conversion
9.3.1 Eciency Considerations and Multi-Junction
Absorbers
9.3.2 Band Alignment

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Contents

9.3.3 Water Splitting with III-V Semiconductors

9.3.4 III-V Heteroepitaxy
9.4 Preparation of Epitaxial III-V Thin Film Absorbers
Using Optical In Situ Control
9.4.1 Optical In Situ Control: Reectance
Anisotropy Spectroscopy
9.4.2 Metal-Organic Chemical Vapor Deposition
9.5 InP(100) Absorbers: Heterostructures and
Photocathodes
9.5.1 InP-based Heterostructures
9.5.2 Surface-Functionalized InP(100) for
Ecient Hydrogen Evolution
9.6 GaP(100) and Hetero-Interfaces
9.6.1 GaP Preparation
9.6.2 Interface Formation with Water
9.6.3 The GaP(N,As)/Si Tandem System
9.6.4 Micro- and Nanostructured Systems
9.7 Synopsis
Acknowledgements
References
Chapter 10 Photoelectrochemical Water Splitting: A First Principles
Approach
Anders Hellman
10.1
10.2

Introduction
Capture of the Photon
10.2.1 Band Gap Design
10.2.2 Plasmon-Assisted Photon Absorption
10.3 ElectronHole Separation
10.4 Charge Transfer
10.5 Surface Reaction (Electrochemical Conversion)
10.5.1 Pourbaix Surface Diagrams
10.5.2 Reaction Mechanism
10.5.3 Overpotential
10.6 Conclusion and Outlook
Acknowledgements
References
Chapter 11 Electro- and Photocatalytic Reduction of CO2:
The Homogeneous and Heterogeneous Worlds Collide?
David Boston, Kai-Ling Huang, Norma de Tacconi, Noseung
Myung, Frederick MacDonell and Krishnan Rajeshwar
11.1

Introduction and Scope

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11.2
11.3

Thermodynamics of CO2 Reduction

Energetics of CO2 Reduction
11.3.1 General Remarks
11.3.2 Band Energy Positions of Selected Oxide
Semiconductors and CO2 Redox Potentials
11.3.3 Molecular Orbital Energy Diagram for
Ru(phen)321 Compared with CO2 Redox
Potentials
11.4 Electrocatalytic CO2 Reduction with Molecular
Catalysts
11.4.1 Pyridine for Electrocatalytic Reduction of CO2
11.4.2 Rhenium Polypyridyl Complexes for
Electrocatalytic Reduction of CO2
11.4.3 Ruthenium Polypyridyl Complexes for
Electrocatalytic Reduction of CO2
11.5 Electrocatalytic Materials Inspired by Fuel Cell
Electrode Nanocomposites
11.5.1 Pt-carbon Black-TiO2 Nanocomposite
Films Containing Highly Dispersed Pt
Nanoparticles as Applied to CO2
Electroreduction
11.6 Transition Metal Complexes for Photocatalytic CO2
Reduction
11.6.1 Catalysts for Reduction of CO2 to CO or
HCOO
11.6.2 Deeper Reduction Using a Hybrid System
11.7 Photocatalytic CO2 Reduction using Semiconductor
Nanoparticles
11.7.1 Syngas as Precursor in Fisher-Tropsch
Process for Production of Synthetic Fuels
11.7.2 Photogeneration of Syngas Using
AgBiW2O8 Semiconductor Nanoparticles
11.7.3 Photoreduction of CO2 using Cu2O as
Semiconductor and Pyridine as Solution
Co-Catalyst
11.8 Concluding Remarks and Future Directions
Acknowledgements
References

Chapter 12 Key Intermediates in the Hydrogenation and Electrochemical

Reduction of CO2
Klaas Jan Schouten and Marc Koper
12.1

Introduction

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12.2
12.3

CO2 Fixation in the Calvin Cycle

The Mechanisms of CO2 Reduction Using
Heterogeneous Catalysis
12.3.1 Carbon Monoxide Synthesis via the Reverse
Water-Gas Shift Reaction
12.3.2 Methanation of Carbon Dioxide
12.3.3 Methanol Synthesis
12.3.4 Synthesis of Hydrocarbons
12.4 The Mechanisms of CO2 Reduction Using
Homogeneous Catalysis
12.4.1 Synthesis of Formic Acid
12.4.2 Synthesis of Other Products
12.5 Mechanisms of the Electrochemical Reduction
of CO2
12.5.1 Homogeneous Electrocatalysis
12.5.2 Heterogeneous Electrocatalysis
12.5.3 Photoelectrochemical CO2
Reduction
12.6 Discussion and Conclusions
References

Chapter 13 Novel Approaches to Water Splitting by Solar Photons

Arthur J. Nozik
Introduction and Previous History of
Photoelectrochemical Water Splitting/
Photoelectrolysis
13.2 Detailed Balance Thermodynamic Calculations of
Solar Water-Splitting PCEs
13.2.1 Conventional Solar Cells at One Sun
Intensity
13.2.2 Tandem Semiconductor Structures for
Water Splitting
13.2.3 Power Conversion Eciencies Based on
Utilization of Hot Electron-Hole Pairs and
Singlet Fission
13.3 Buried Junctions and Other Novel Approaches
13.3.1 Buried p-n Junctions in a Tandem Cell
13.3.2 Buried p-n Junctions in a Texas Instruments
System for H2O Splitting
13.3.3 Buried p-n Junctions using Nanocrystals
(Quantum Dots, Quantum Wires, and
Nanorods)
Acknowledgements
References

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Chapter 14 Light Harvesting Strategies Inspired by Nature

Evgeny Ostrumov, Chanelle Jumper and Gregory Scholes

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14.1
14.2

Introduction
Weakly-Coupled Chromophores: Forster Resonance
Energy Transfer Theory
14.3 Multi-Subunit Protein Complexes: Generalized
Forster Theory
14.4 Quantum Coherence in LH Proteins
14.5 Strategies of Photoadaptation and Photoprotection
14.6 Summary of the Strategies Adopted by Natural
Systems
Acknowledgements
References
Chapter 15 Electronic Structure and Bonding of Water to Noble Metal
Surfaces
Hirohito Ogasawara and Anders Nilsson
15.1
15.2

Introduction
H-up, H-down and Partially Dissociated Water
Layers
15.3 Competition Between Thermal Dissociation and
Desorption
15.4 Electronic Structure and Bonding Mechanism
15.5 Conclusions
Acknowledgements
References
Chapter 16 New Perspectives and a Review of Progress
Hans-Joachim Lewerenz and Laurence Peter
16.1
16.2

Introduction
Advanced Photonics
16.2.1 Surface Plasmons
16.2.2 Coupled Forster Excitation Energy Transfer
16.2.3 Levy Processes
16.3 Electrodes Structural Aspects
16.4 A Note on Electronic Properties of Transition
Metal Oxides
16.5 Looking Back
16.5 Progress Towards Light Driven Water Splitting
Acknowledgements
References
Subject Index

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