Abstract

The direct utilization of solar light for synthetic photochemistry is a sustainable and efficient technological goal. Herein we report the first in-depth study on the use of the inexpensive organic photocatalyst eosin Y for solar photocatalysis by demonstrating the oxidative coupling of benzylic amines to form imines, a class of valuable intermediates in chemical synthesis. By the use of a unique experimental setup with a custom-built variable-intensity solar light simulator, replication of a natural-sunlight environment was achieved. The relative significance of different variables on the reaction rate constant was quantitatively evaluated through comprehensive experimental design. Reaction kinetics and mechanistic information were obtained using both a batch reactor and a spinning-disc reactor. A maximum pseudo-first-order rate constant of 1.59 × 10–3 s–1 was obtained at a maximum turnover frequency of 192 h–1 through optimization of the reaction conditions. Experiments carried out using a spinning-disc reactor confirmed that the reaction was not mass-transfer-limited but rather photon-transfer-limited.
LanguageEnglish
Article number7b01754
Pages9826–9835
Number of pages10
JournalACS Sustainable Chemistry and Engineering
Volume5
Issue number11
Early online date18 Sep 2017
DOIs
StatusPublished - 6 Nov 2017

Fingerprint

Eosine Yellowish-(YS)
Amines
Rate constants
Imines
Photocatalysis
Photochemical reactions
Batch reactors
Photocatalysts
Reaction kinetics
Design of experiments
Reaction rates
Mass transfer
Photons
Simulators
photochemistry
reaction kinetics
experimental design
reaction rate
simulator
mass transfer

Cite this

@article{9dbb258f14164ab69354f3f1778df5d0,
title = "An In-Depth Study of the Use of Eosin Y for the Solar Photocatalytic Oxidative Coupling of Benzylic Amines",
abstract = "The direct utilization of solar light for synthetic photochemistry is a sustainable and efficient technological goal. Herein we report the first in-depth study on the use of the inexpensive organic photocatalyst eosin Y for solar photocatalysis by demonstrating the oxidative coupling of benzylic amines to form imines, a class of valuable intermediates in chemical synthesis. By the use of a unique experimental setup with a custom-built variable-intensity solar light simulator, replication of a natural-sunlight environment was achieved. The relative significance of different variables on the reaction rate constant was quantitatively evaluated through comprehensive experimental design. Reaction kinetics and mechanistic information were obtained using both a batch reactor and a spinning-disc reactor. A maximum pseudo-first-order rate constant of 1.59 × 10–3 s–1 was obtained at a maximum turnover frequency of 192 h–1 through optimization of the reaction conditions. Experiments carried out using a spinning-disc reactor confirmed that the reaction was not mass-transfer-limited but rather photon-transfer-limited.",
author = "Tibbetts, {Joshua D.} and Carbery, {David R.} and Emanuelsson, {Emma A.C.}",
year = "2017",
month = "11",
day = "6",
doi = "10.1021/acssuschemeng.7b01754",
language = "English",
volume = "5",
pages = "9826–9835",
journal = "ACS Sustainable Chemisty and Engineering",
issn = "2168-0485",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - An In-Depth Study of the Use of Eosin Y for the Solar Photocatalytic Oxidative Coupling of Benzylic Amines

AU - Tibbetts, Joshua D.

AU - Carbery, David R.

AU - Emanuelsson, Emma A.C.

PY - 2017/11/6

Y1 - 2017/11/6

N2 - The direct utilization of solar light for synthetic photochemistry is a sustainable and efficient technological goal. Herein we report the first in-depth study on the use of the inexpensive organic photocatalyst eosin Y for solar photocatalysis by demonstrating the oxidative coupling of benzylic amines to form imines, a class of valuable intermediates in chemical synthesis. By the use of a unique experimental setup with a custom-built variable-intensity solar light simulator, replication of a natural-sunlight environment was achieved. The relative significance of different variables on the reaction rate constant was quantitatively evaluated through comprehensive experimental design. Reaction kinetics and mechanistic information were obtained using both a batch reactor and a spinning-disc reactor. A maximum pseudo-first-order rate constant of 1.59 × 10–3 s–1 was obtained at a maximum turnover frequency of 192 h–1 through optimization of the reaction conditions. Experiments carried out using a spinning-disc reactor confirmed that the reaction was not mass-transfer-limited but rather photon-transfer-limited.

AB - The direct utilization of solar light for synthetic photochemistry is a sustainable and efficient technological goal. Herein we report the first in-depth study on the use of the inexpensive organic photocatalyst eosin Y for solar photocatalysis by demonstrating the oxidative coupling of benzylic amines to form imines, a class of valuable intermediates in chemical synthesis. By the use of a unique experimental setup with a custom-built variable-intensity solar light simulator, replication of a natural-sunlight environment was achieved. The relative significance of different variables on the reaction rate constant was quantitatively evaluated through comprehensive experimental design. Reaction kinetics and mechanistic information were obtained using both a batch reactor and a spinning-disc reactor. A maximum pseudo-first-order rate constant of 1.59 × 10–3 s–1 was obtained at a maximum turnover frequency of 192 h–1 through optimization of the reaction conditions. Experiments carried out using a spinning-disc reactor confirmed that the reaction was not mass-transfer-limited but rather photon-transfer-limited.

UR - https://doi.org/10.1021/acssuschemeng.7b01754

U2 - 10.1021/acssuschemeng.7b01754

DO - 10.1021/acssuschemeng.7b01754

M3 - Article

VL - 5

SP - 9826

EP - 9835

JO - ACS Sustainable Chemisty and Engineering

T2 - ACS Sustainable Chemisty and Engineering

JF - ACS Sustainable Chemisty and Engineering

SN - 2168-0485

IS - 11

M1 - 7b01754

ER -