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Density Functional Theory Mechanistic Study on H(2)O(2) Production Using an Organic Semiconductor Epindolidione

[Image: see text] Organic semiconductors have recently emerged as promising catalytic materials for oxygen reduction to hydrogen peroxide, H(2)O(2), a chemical of great importance in industry as well as biology. While examples of organic semiconductor-mediated photocatalytic and electrocatalytic pro...

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Autores principales: Wadnerkar, Nitin, Gueskine, Viktor, Głowacki, Eric Daniel, Zozoulenko, Igor
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7681785/
https://www.ncbi.nlm.nih.gov/pubmed/33166157
http://dx.doi.org/10.1021/acs.jpca.0c08496
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author Wadnerkar, Nitin
Gueskine, Viktor
Głowacki, Eric Daniel
Zozoulenko, Igor
author_facet Wadnerkar, Nitin
Gueskine, Viktor
Głowacki, Eric Daniel
Zozoulenko, Igor
author_sort Wadnerkar, Nitin
collection PubMed
description [Image: see text] Organic semiconductors have recently emerged as promising catalytic materials for oxygen reduction to hydrogen peroxide, H(2)O(2), a chemical of great importance in industry as well as biology. While examples of organic semiconductor-mediated photocatalytic and electrocatalytic processes for H(2)O(2) production become more numerous and improve in performance, fundamental understanding of the reaction mechanisms at play have been explored far less. The aim of the present work is to computationally test hypotheses of how selective oxygen reduction to H(2)O(2) generally occurs on carbonyl dyes and pigments. As an example material, we consider epindolidione (EPI), an industrial pigment with demonstrated semiconductor properties, which photocatalytic activity in oxygen reduction reaction (ORR) and thereby producing hydrogen peroxide (H(2)O(2)) in low pH environment has been recently experimentally demonstrated. In this work, the ability of the reduced form of EPI, viz. EPI-2H (which was formed after a photoinduced 2e(–)/2H(+) process), to reduce molecular triplet oxygen to peroxide and the possible mechanism of this reaction are computationally investigated using density functional theory. In the main reaction pathway, the reduction of O(2) to H(2)O(2) reaction occurs via abstraction of one of the hydrogen atoms of EPI-2H by triplet dioxygen to produce an intermediate complex consisting of the radicals of hydrogen peroxide (HOO(•)) and EPI-H(•) at the initial stage. HOO(•) thus released can abstract another hydrogen atom from EPI-H(•) to produce H(2)O(2) and regenerates EPI; otherwise, it can enter another pathway to abstract hydrogen from a neighboring EPI-2H to form EPI-H(•) and H(2)O(2). EPI, after reduction, thus plays in ORR the role of hydrogen atom transfer (HAT) agent via its OH group, similar to anthraquinone in the industrial process, while HAT from its amino hydrogen is found unfavorable.
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spelling pubmed-76817852020-11-24 Density Functional Theory Mechanistic Study on H(2)O(2) Production Using an Organic Semiconductor Epindolidione Wadnerkar, Nitin Gueskine, Viktor Głowacki, Eric Daniel Zozoulenko, Igor J Phys Chem A [Image: see text] Organic semiconductors have recently emerged as promising catalytic materials for oxygen reduction to hydrogen peroxide, H(2)O(2), a chemical of great importance in industry as well as biology. While examples of organic semiconductor-mediated photocatalytic and electrocatalytic processes for H(2)O(2) production become more numerous and improve in performance, fundamental understanding of the reaction mechanisms at play have been explored far less. The aim of the present work is to computationally test hypotheses of how selective oxygen reduction to H(2)O(2) generally occurs on carbonyl dyes and pigments. As an example material, we consider epindolidione (EPI), an industrial pigment with demonstrated semiconductor properties, which photocatalytic activity in oxygen reduction reaction (ORR) and thereby producing hydrogen peroxide (H(2)O(2)) in low pH environment has been recently experimentally demonstrated. In this work, the ability of the reduced form of EPI, viz. EPI-2H (which was formed after a photoinduced 2e(–)/2H(+) process), to reduce molecular triplet oxygen to peroxide and the possible mechanism of this reaction are computationally investigated using density functional theory. In the main reaction pathway, the reduction of O(2) to H(2)O(2) reaction occurs via abstraction of one of the hydrogen atoms of EPI-2H by triplet dioxygen to produce an intermediate complex consisting of the radicals of hydrogen peroxide (HOO(•)) and EPI-H(•) at the initial stage. HOO(•) thus released can abstract another hydrogen atom from EPI-H(•) to produce H(2)O(2) and regenerates EPI; otherwise, it can enter another pathway to abstract hydrogen from a neighboring EPI-2H to form EPI-H(•) and H(2)O(2). EPI, after reduction, thus plays in ORR the role of hydrogen atom transfer (HAT) agent via its OH group, similar to anthraquinone in the industrial process, while HAT from its amino hydrogen is found unfavorable. American Chemical Society 2020-11-09 2020-11-19 /pmc/articles/PMC7681785/ /pubmed/33166157 http://dx.doi.org/10.1021/acs.jpca.0c08496 Text en © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Wadnerkar, Nitin
Gueskine, Viktor
Głowacki, Eric Daniel
Zozoulenko, Igor
Density Functional Theory Mechanistic Study on H(2)O(2) Production Using an Organic Semiconductor Epindolidione
title Density Functional Theory Mechanistic Study on H(2)O(2) Production Using an Organic Semiconductor Epindolidione
title_full Density Functional Theory Mechanistic Study on H(2)O(2) Production Using an Organic Semiconductor Epindolidione
title_fullStr Density Functional Theory Mechanistic Study on H(2)O(2) Production Using an Organic Semiconductor Epindolidione
title_full_unstemmed Density Functional Theory Mechanistic Study on H(2)O(2) Production Using an Organic Semiconductor Epindolidione
title_short Density Functional Theory Mechanistic Study on H(2)O(2) Production Using an Organic Semiconductor Epindolidione
title_sort density functional theory mechanistic study on h(2)o(2) production using an organic semiconductor epindolidione
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7681785/
https://www.ncbi.nlm.nih.gov/pubmed/33166157
http://dx.doi.org/10.1021/acs.jpca.0c08496
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