viii
5.3 Underpotential Deposition (UPD) of Metals and Catalytic
Properties of Surfaces Modified by Metal Adlayers . . . . . . . . . . . . 43
5.3.1 Oxidation of Small Organic Molecules
on Surfaces Modified by UPD Adlayers . . . . . . . . . . . . . . . 49
5.3.2 Hydrogen Evolution on Surfaces Modified
by UPD Adlayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.3.3 Oxygen Reduction Reaction on Surfaces
Modified by UPD Adlayers . . . . . . . . . . . . . . . . . . . . . . . . . 52
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
6 Important Electrocatalytic Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6.1 Oxygen Reduction Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6.1.1 The d-Band Theory of Surface Reactivity . . . . . . . . . . . . . . 63
6.2 Hydrogen Evolution Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
6.3 Hydrogen Oxidation Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
6.3.1 CO Tolerance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
6.4 Methanol Oxidation Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
6.5 Ethanol Oxidation Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
6.6 Formic Acid Oxidation Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6.7 Oxygen Evolution Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7 Platinum Monolayer Electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.1 Concept of Pt Monolayer Electrocatalysts . . . . . . . . . . . . . . . . . . . . 83
7.2 Synthesis of Pt Monolayer Catalysts by Galvanic
Displacement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
7.3 Other Syntheses of Pt Monolayer Electrocatalysts . . . . . . . . . . . . . 87
7.3.1 Pd-Pt Catalyst Synthesized in Ethanol . . . . . . . . . . . . . . . . . 88
7.3.2 Synthesis of Pt ML by Surface Mediated Growth . . . . . . . . . 89
7.3.3 Characterization of Pt Monolayer Electrocatalysts . . . . . . . 90
7.4 In Situ FTIR and Synchrotron X-Ray Absorption
Spectroscopies, and Hydrodynamic Rotating Disk
Electrode Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
7.4.1 In situ FTIR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 93
7.4.2 X-Ray Absorption Spectroscopy . . . . . . . . . . . . . . . . . . . . . 94
7.4.3 Rotating Disk Electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
8 Catalytic Properties of Pt Monolayer Electrocatalysts . . . . . . . . . . . . 101
8.1 Oxygen Reduction Reaction (ORR) . . . . . . . . . . . . . . . . . . . . . . . . 101
8.1.1 Pt Monolayer on Extended Areas Single Crystals . . . . . . . . 101
8.1.2 Pt Monolayer Shell on Nanoparticle Cores . . . . . . . . . . . . . 105
8.1.3 Effects of Composition, Shape, and Size of Cores . . . . . . . 107
8.1.4 Modifications of Pt Monolayer Surfaces . . . . . . . . . . . . . . . 126
Contents
5.3 Underpotential Deposition (UPD) of Metals and Catalytic
Properties of Surfaces Modified by Metal Adlayers . . . . . . . . . . . . 43
5.3.1 Oxidation of Small Organic Molecules
on Surfaces Modified by UPD Adlayers . . . . . . . . . . . . . . . 49
5.3.2 Hydrogen Evolution on Surfaces Modified
by UPD Adlayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.3.3 Oxygen Reduction Reaction on Surfaces
Modified by UPD Adlayers . . . . . . . . . . . . . . . . . . . . . . . . . 52
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
6 Important Electrocatalytic Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6.1 Oxygen Reduction Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
6.1.1 The d-Band Theory of Surface Reactivity . . . . . . . . . . . . . . 63
6.2 Hydrogen Evolution Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
6.3 Hydrogen Oxidation Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
6.3.1 CO Tolerance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
6.4 Methanol Oxidation Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
6.5 Ethanol Oxidation Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
6.6 Formic Acid Oxidation Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6.7 Oxygen Evolution Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
7 Platinum Monolayer Electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.1 Concept of Pt Monolayer Electrocatalysts . . . . . . . . . . . . . . . . . . . . 83
7.2 Synthesis of Pt Monolayer Catalysts by Galvanic
Displacement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
7.3 Other Syntheses of Pt Monolayer Electrocatalysts . . . . . . . . . . . . . 87
7.3.1 Pd-Pt Catalyst Synthesized in Ethanol . . . . . . . . . . . . . . . . . 88
7.3.2 Synthesis of Pt ML by Surface Mediated Growth . . . . . . . . . 89
7.3.3 Characterization of Pt Monolayer Electrocatalysts . . . . . . . 90
7.4 In Situ FTIR and Synchrotron X-Ray Absorption
Spectroscopies, and Hydrodynamic Rotating Disk
Electrode Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
7.4.1 In situ FTIR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 93
7.4.2 X-Ray Absorption Spectroscopy . . . . . . . . . . . . . . . . . . . . . 94
7.4.3 Rotating Disk Electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
8 Catalytic Properties of Pt Monolayer Electrocatalysts . . . . . . . . . . . . 101
8.1 Oxygen Reduction Reaction (ORR) . . . . . . . . . . . . . . . . . . . . . . . . 101
8.1.1 Pt Monolayer on Extended Areas Single Crystals . . . . . . . . 101
8.1.2 Pt Monolayer Shell on Nanoparticle Cores . . . . . . . . . . . . . 105
8.1.3 Effects of Composition, Shape, and Size of Cores . . . . . . . 107
8.1.4 Modifications of Pt Monolayer Surfaces . . . . . . . . . . . . . . . 126
Contents