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Dirhodium(II,II) Complexes as Photocatalysts in Homogenous Solution and Photoelectrochemical Cells for Hydrogen Evolution.

Record Type:	Language materials, manuscript : Monograph/item
Title/Author:	Dirhodium(II,II) Complexes as Photocatalysts in Homogenous Solution and Photoelectrochemical Cells for Hydrogen Evolution./
Author:	Huang, Jie.
Description:	1 online resource (145 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 85-04, Section: B.
Contained By:	Dissertations Abstracts International85-04B.
Subject:	Chemistry. -
Online resource:	click for full text (PQDT)
ISBN:	9798380589642

Dirhodium(II,II) Complexes as Photocatalysts in Homogenous Solution and Photoelectrochemical Cells for Hydrogen Evolution.
Huang, Jie.

Dirhodium(II,II) Complexes as Photocatalysts in Homogenous Solution and Photoelectrochemical Cells for Hydrogen Evolution. - 1 online resource (145 pages)

Source: Dissertations Abstracts International, Volume: 85-04, Section: B.

Thesis (Ph.D.)--The Ohio State University, 2023.

Includes bibliographical references

Energy demands from increasing population are expected to double by 2050 and more than triple by the end of 2100. The urgent need for renewable and carbon-free energy sources demands scientists to pursue alternative ways to replace petroleum, coal, and natural gas as energy sources. Solar fuels have the potential to serve as an outstanding source of energy, since the energy from sunlight that reaches the Earth every hour is 173,000 terawatts. One key factor required to utilize solar fuels is to increase the ability of the light-harvesting process and the chemical bond-forming reactivity of photocatalysts. This dissertation demonstrates the design and characterization of dirhodium Rh2(II,II) complexes for photocatalysis with red light and the effect of ligand modification on the electronic structure and steric hindrance on the systems, as well as their ability for solar energy storage through the production of hydrogen, a clean fuel.In Chapter 4, a series of three dirhodium complexes with varying electron donating abilities of the formamidinate ligands were synthesized with general formula cis- [Rh2(DPhB)2(bncn)2](BF4)2 (DPhB = diphenyl-formamidinate, bncn = benzo[c]cinnoline). These complexes were found to act as single-molecule photocatalysts for H2 production in the presence of 0.1 M p-toluenesulfonic acid and the sacrificial electron donor BNAH (1- benzyl-1,4-dihydronicotinamide). The most efficient catalyst in this series is able to achieve turnover numbers (TONs) up to 250 upon 24 h irradiation with red light. The one-component catalytic system does not require any other catalyst, electron relay, or light absorber. Upon excitation, these complexes are able to store two electrons on each molecule after two stepwise reductive quenching steps by BNAH and provide protonation sites for the catalysis to generate H2 to proceed. These properties are essential for the complexes to act as single-molecule photocatalysts. The substitution of the bridging ligands affects the electronic properties and the driving force for reductive quenching of the excited state, which play a role on the efficiency of hydrogen production. The complexes absorb light strongly from the ultraviolet to the near-infrared, making them broad-spectrum photosensitizers that can harness solar photons throughout a greater sunlight energy range than commonly used sensitizers.The excited state reduction potential of the dirhodium complexes and their ability to serve as a single-molecule photocatalyst make them suitable dyes for the p-type photocathodes in dye-sensitized photoelectro-chemical cells (DSPECs). For this purpose, in Chapter 5, a new Rh2(II,II) dimer was designed and prepared with carboxylate anchoring groups on the formamidinate ligands for attachment onto a NiO photocathode. This complex successfully injected holes into NiO upon irradiation with red light with the charge recombination times of 44 ns and 5.7 μs measured using transient absorption spectroscopy. The irradiation of the Rh2-NiO assembly, with 655 nm light (53 mW cm-2 ) on the photocathode in a DSPEC in the presence of p-toluenesulfonic acid (0.1 M), produces the photocurrent of 52 μA cm-2 at -0.2 V vs Ag/AgCl. In addition, H2 was produced with Faradaic efficiencies up to 85  5% after 2.5 hours of irradiation without photoelectrode degradation. The electronic absorption spectrum of the Rh2-NiO photoelectrode shows a broad feature in the visible range that extends to 800 nm, making it a good dye to harvest sunlight. This work presents the first single-molecule photocatalyst, acting as both the light absorber and catalytic center on NiO, which is able to generate hydrogen from acidic solutions with red light when anchored to a p-type semiconductor, providing a promising new system for solar fuel production.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2024

Mode of access: World Wide Web

ISBN: 9798380589642Subjects--Topical Terms:

593913
Chemistry.
Subjects--Index Terms:

Dirhodium complexesIndex Terms--Genre/Form:

554714
Electronic books.

Dirhodium(II,II) Complexes as Photocatalysts in Homogenous Solution and Photoelectrochemical Cells for Hydrogen Evolution.
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653 $a Photochemistry
653 $a Transient absorption
653 $a Photocatalysts
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