Early-time photodynamics of ruthenium-based photocatalysts for light-induced hydrogen generation

Qing Pan

Research output: ThesisPhD Thesis - Research UT, graduation UT

Abstract

This thesis aims to provide a fundamental understanding of the early-time photodynamics of a series of Ru/M (M = Pd or Pt) bimetallic photocatalysts for light-induced hydrogen generation. This class of complexes adopts a general structure involving a Ru(II) center coordinated to two peripheral ligands and one bridging ligand, which bonds to a catalytic metal center as schematically shown in Figure 1. Photoexcitation of the complexes leads to intra-molecular electron transfer processes, which are investigated by using ultrafast time-resolved spectroscopic techniques. The excited state photodynamics are systematically studied considering the individual building blocks of the complexes (i.e. peripheral/bridging ligands and the catalytic moiety). The knowledge obtained in this thesis facilitates interpreting the structure-reactivity relationship, allowing the photophysical exploration of other analogous complexes, and guiding the optimization of new photocatalysts with improved photocatalytic efficiency. This thesis is organized in the following way: •Chapter 1 provides a general background of photocatalytic hydrogen generation, coordination complexes, and time-resolved spectroscopy. In particular, the prototype complex [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) is introduced in detail to provide key concepts which are frequently referred to in later chapters. •Chapter 2 discusses the methodological aspects of transient absorption, which is the main technique used in this thesis. •Chapter 3 explores the impact of the bridging ligand on the excited state properties of two analogous Ru/Pd complexes. •Chapter 4 investigates the critical role played by the catalytic moiety in the early-time photodynamics of two analogous Ru/Pd and Ru/Pt complexes. •Chapter 5 studies the influence of the peripheral ligands on the photodynamics for a series of Ru/Pt complexes. •Chapter 6 focuses on the photodynamics of a new Ru/Pt complex whose design is based on the knowledge obtained in previous chapters. •Chapter 7 extends the discussion of Chapter 4 by applying time-resolved X-ray absorption spectroscopy to investigate the catalytic Pt center of a Ru/Pt complex. •Chapter 8 summarizes the main conclusions obtained from the previous chapters, and presents an outlook overview.
LanguageEnglish
Awarding Institution
  • University of Twente
Supervisors/Advisors
  • Herek, Jennifer Lynn, Supervisor
  • Huijser, Jannetje Maria, Advisor
Thesis sponsors
Award date27 Oct 2016
Place of PublicationEnschede
Publisher
Print ISBNs978-90-365-4165-7
DOIs
StatePublished - 27 Oct 2016

Fingerprint

Ruthenium
Photocatalysts
Hydrogen
Ligands
Excited states
2,2'-Dipyridyl
X ray absorption spectroscopy
Photoexcitation
Coordination Complexes
Metals
Spectroscopy
Electrons

Keywords

  • METIS-318104
  • IR-101551

Cite this

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title = "Early-time photodynamics of ruthenium-based photocatalysts for light-induced hydrogen generation",
abstract = "This thesis aims to provide a fundamental understanding of the early-time photodynamics of a series of Ru/M (M = Pd or Pt) bimetallic photocatalysts for light-induced hydrogen generation. This class of complexes adopts a general structure involving a Ru(II) center coordinated to two peripheral ligands and one bridging ligand, which bonds to a catalytic metal center as schematically shown in Figure 1. Photoexcitation of the complexes leads to intra-molecular electron transfer processes, which are investigated by using ultrafast time-resolved spectroscopic techniques. The excited state photodynamics are systematically studied considering the individual building blocks of the complexes (i.e. peripheral/bridging ligands and the catalytic moiety). The knowledge obtained in this thesis facilitates interpreting the structure-reactivity relationship, allowing the photophysical exploration of other analogous complexes, and guiding the optimization of new photocatalysts with improved photocatalytic efficiency. This thesis is organized in the following way: •Chapter 1 provides a general background of photocatalytic hydrogen generation, coordination complexes, and time-resolved spectroscopy. In particular, the prototype complex [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) is introduced in detail to provide key concepts which are frequently referred to in later chapters. •Chapter 2 discusses the methodological aspects of transient absorption, which is the main technique used in this thesis. •Chapter 3 explores the impact of the bridging ligand on the excited state properties of two analogous Ru/Pd complexes. •Chapter 4 investigates the critical role played by the catalytic moiety in the early-time photodynamics of two analogous Ru/Pd and Ru/Pt complexes. •Chapter 5 studies the influence of the peripheral ligands on the photodynamics for a series of Ru/Pt complexes. •Chapter 6 focuses on the photodynamics of a new Ru/Pt complex whose design is based on the knowledge obtained in previous chapters. •Chapter 7 extends the discussion of Chapter 4 by applying time-resolved X-ray absorption spectroscopy to investigate the catalytic Pt center of a Ru/Pt complex. •Chapter 8 summarizes the main conclusions obtained from the previous chapters, and presents an outlook overview.",
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language = "English",
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Early-time photodynamics of ruthenium-based photocatalysts for light-induced hydrogen generation. / Pan, Qing.

Enschede : University of Twente, 2016. 157 p.

Research output: ThesisPhD Thesis - Research UT, graduation UT

TY - THES

T1 - Early-time photodynamics of ruthenium-based photocatalysts for light-induced hydrogen generation

AU - Pan,Qing

PY - 2016/10/27

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N2 - This thesis aims to provide a fundamental understanding of the early-time photodynamics of a series of Ru/M (M = Pd or Pt) bimetallic photocatalysts for light-induced hydrogen generation. This class of complexes adopts a general structure involving a Ru(II) center coordinated to two peripheral ligands and one bridging ligand, which bonds to a catalytic metal center as schematically shown in Figure 1. Photoexcitation of the complexes leads to intra-molecular electron transfer processes, which are investigated by using ultrafast time-resolved spectroscopic techniques. The excited state photodynamics are systematically studied considering the individual building blocks of the complexes (i.e. peripheral/bridging ligands and the catalytic moiety). The knowledge obtained in this thesis facilitates interpreting the structure-reactivity relationship, allowing the photophysical exploration of other analogous complexes, and guiding the optimization of new photocatalysts with improved photocatalytic efficiency. This thesis is organized in the following way: •Chapter 1 provides a general background of photocatalytic hydrogen generation, coordination complexes, and time-resolved spectroscopy. In particular, the prototype complex [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) is introduced in detail to provide key concepts which are frequently referred to in later chapters. •Chapter 2 discusses the methodological aspects of transient absorption, which is the main technique used in this thesis. •Chapter 3 explores the impact of the bridging ligand on the excited state properties of two analogous Ru/Pd complexes. •Chapter 4 investigates the critical role played by the catalytic moiety in the early-time photodynamics of two analogous Ru/Pd and Ru/Pt complexes. •Chapter 5 studies the influence of the peripheral ligands on the photodynamics for a series of Ru/Pt complexes. •Chapter 6 focuses on the photodynamics of a new Ru/Pt complex whose design is based on the knowledge obtained in previous chapters. •Chapter 7 extends the discussion of Chapter 4 by applying time-resolved X-ray absorption spectroscopy to investigate the catalytic Pt center of a Ru/Pt complex. •Chapter 8 summarizes the main conclusions obtained from the previous chapters, and presents an outlook overview.

AB - This thesis aims to provide a fundamental understanding of the early-time photodynamics of a series of Ru/M (M = Pd or Pt) bimetallic photocatalysts for light-induced hydrogen generation. This class of complexes adopts a general structure involving a Ru(II) center coordinated to two peripheral ligands and one bridging ligand, which bonds to a catalytic metal center as schematically shown in Figure 1. Photoexcitation of the complexes leads to intra-molecular electron transfer processes, which are investigated by using ultrafast time-resolved spectroscopic techniques. The excited state photodynamics are systematically studied considering the individual building blocks of the complexes (i.e. peripheral/bridging ligands and the catalytic moiety). The knowledge obtained in this thesis facilitates interpreting the structure-reactivity relationship, allowing the photophysical exploration of other analogous complexes, and guiding the optimization of new photocatalysts with improved photocatalytic efficiency. This thesis is organized in the following way: •Chapter 1 provides a general background of photocatalytic hydrogen generation, coordination complexes, and time-resolved spectroscopy. In particular, the prototype complex [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) is introduced in detail to provide key concepts which are frequently referred to in later chapters. •Chapter 2 discusses the methodological aspects of transient absorption, which is the main technique used in this thesis. •Chapter 3 explores the impact of the bridging ligand on the excited state properties of two analogous Ru/Pd complexes. •Chapter 4 investigates the critical role played by the catalytic moiety in the early-time photodynamics of two analogous Ru/Pd and Ru/Pt complexes. •Chapter 5 studies the influence of the peripheral ligands on the photodynamics for a series of Ru/Pt complexes. •Chapter 6 focuses on the photodynamics of a new Ru/Pt complex whose design is based on the knowledge obtained in previous chapters. •Chapter 7 extends the discussion of Chapter 4 by applying time-resolved X-ray absorption spectroscopy to investigate the catalytic Pt center of a Ru/Pt complex. •Chapter 8 summarizes the main conclusions obtained from the previous chapters, and presents an outlook overview.

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M3 - PhD Thesis - Research UT, graduation UT

SN - 978-90-365-4165-7

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