A computational survey of metal-free polyimide-based photocatalysts within the single-stranded polymer model

Jong Hun Park; Aloysius Soon; Ji Hwan Lee

doi:10.1016/j.mcat.2020.111184

A computational survey of metal-free polyimide-based photocatalysts within the single-stranded polymer model

Jong Hun Park, Aloysius Soon, Ji Hwan Lee

Department of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

Eco-friendly production of hydrogen using the solar water-splitting reaction is one of the key technologies for clean energy generation. In this work, using hybrid density-functional theory calculations, we survey a number of isolated polyimide chains for prospective candidates as metal-free organic photocatalysts, given their known excellent thermal stability and chemical resistance. We evaluate their capability to split water following the three key requirements for a good photocatalyst: (1) proper HOMO/LUMO energy levels with respect to the water redox potential, (2) appropriate energy gap sizes for the maximum usability of visible light, and (3) the ability to separate the charge carriers (electron and hole) optimally. Using the well-reported graphitic carbon nitride (g-C₃N₄) as benchmark, we find that both PMDA-ODA and BTDA-ODA polyimides are most promising, with a favourable HOMO–LUMO energy gap and well-separated electron and hole localized on each monomer fragment of the polyimide strand. From our optical response calculations, these PMDA-ODA and BTDA-ODA polyimides are also found to be better absorbers of visible light than e.g. g-C₃N₄. This study will provide a good theoretical platform for optimizing the next-generation metal-free polymeric photocatalysts for hydrogen production from water under visible light.

Original language	English
Article number	111184
Journal	Molecular Catalysis
Volume	497
DOIs	https://doi.org/10.1016/j.mcat.2020.111184
Publication status	Published - 2020 Dec

Bibliographical note

Funding Information:
We gratefully acknowledge support from the NRF Creative Materials Discovery Program (2018M3D1A1058536) and the Yonsei University Future-leading Research Initiative (Y2019-22-0099). Computational resources have been kindly provided by the Australian National Computational Infrastructure and the KISTI Supercomputing Center (KSC-2020-CRE-0040). We thank Y.-K. Jung for fruitful discussions.

Funding Information:
We gratefully acknowledge support from the NRF Creative Materials Discovery Program ( 2018M3D1A1058536 ) and the Yonsei University Future-leading Research Initiative ( Y2019-22-0099 ). Computational resources have been kindly provided by the Australian National Computational Infrastructure and the KISTI Supercomputing Center (KSC-2020-CRE-0040). We thank Y.-K. Jung for fruitful discussions.

Publisher Copyright:
© 2020 Elsevier B.V.

All Science Journal Classification (ASJC) codes

Catalysis
Process Chemistry and Technology
Physical and Theoretical Chemistry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.mcat.2020.111184

Cite this

@article{98da6c8c466049ef8d68c3fe395001f2,

title = "A computational survey of metal-free polyimide-based photocatalysts within the single-stranded polymer model",

abstract = "Eco-friendly production of hydrogen using the solar water-splitting reaction is one of the key technologies for clean energy generation. In this work, using hybrid density-functional theory calculations, we survey a number of isolated polyimide chains for prospective candidates as metal-free organic photocatalysts, given their known excellent thermal stability and chemical resistance. We evaluate their capability to split water following the three key requirements for a good photocatalyst: (1) proper HOMO/LUMO energy levels with respect to the water redox potential, (2) appropriate energy gap sizes for the maximum usability of visible light, and (3) the ability to separate the charge carriers (electron and hole) optimally. Using the well-reported graphitic carbon nitride (g-C3N4) as benchmark, we find that both PMDA-ODA and BTDA-ODA polyimides are most promising, with a favourable HOMO–LUMO energy gap and well-separated electron and hole localized on each monomer fragment of the polyimide strand. From our optical response calculations, these PMDA-ODA and BTDA-ODA polyimides are also found to be better absorbers of visible light than e.g. g-C3N4. This study will provide a good theoretical platform for optimizing the next-generation metal-free polymeric photocatalysts for hydrogen production from water under visible light.",

author = "Park, {Jong Hun} and Aloysius Soon and Lee, {Ji Hwan}",

note = "Funding Information: We gratefully acknowledge support from the NRF Creative Materials Discovery Program (2018M3D1A1058536) and the Yonsei University Future-leading Research Initiative (Y2019-22-0099). Computational resources have been kindly provided by the Australian National Computational Infrastructure and the KISTI Supercomputing Center (KSC-2020-CRE-0040). We thank Y.-K. Jung for fruitful discussions. Funding Information: We gratefully acknowledge support from the NRF Creative Materials Discovery Program ( 2018M3D1A1058536 ) and the Yonsei University Future-leading Research Initiative ( Y2019-22-0099 ). Computational resources have been kindly provided by the Australian National Computational Infrastructure and the KISTI Supercomputing Center (KSC-2020-CRE-0040). We thank Y.-K. Jung for fruitful discussions. Publisher Copyright: {\textcopyright} 2020 Elsevier B.V.",

year = "2020",

month = dec,

doi = "10.1016/j.mcat.2020.111184",

language = "English",

volume = "497",

journal = "Molecular Catalysis",

issn = "2468-8231",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - A computational survey of metal-free polyimide-based photocatalysts within the single-stranded polymer model

AU - Park, Jong Hun

AU - Soon, Aloysius

AU - Lee, Ji Hwan

N1 - Funding Information: We gratefully acknowledge support from the NRF Creative Materials Discovery Program (2018M3D1A1058536) and the Yonsei University Future-leading Research Initiative (Y2019-22-0099). Computational resources have been kindly provided by the Australian National Computational Infrastructure and the KISTI Supercomputing Center (KSC-2020-CRE-0040). We thank Y.-K. Jung for fruitful discussions. Funding Information: We gratefully acknowledge support from the NRF Creative Materials Discovery Program ( 2018M3D1A1058536 ) and the Yonsei University Future-leading Research Initiative ( Y2019-22-0099 ). Computational resources have been kindly provided by the Australian National Computational Infrastructure and the KISTI Supercomputing Center (KSC-2020-CRE-0040). We thank Y.-K. Jung for fruitful discussions. Publisher Copyright: © 2020 Elsevier B.V.

PY - 2020/12

Y1 - 2020/12

N2 - Eco-friendly production of hydrogen using the solar water-splitting reaction is one of the key technologies for clean energy generation. In this work, using hybrid density-functional theory calculations, we survey a number of isolated polyimide chains for prospective candidates as metal-free organic photocatalysts, given their known excellent thermal stability and chemical resistance. We evaluate their capability to split water following the three key requirements for a good photocatalyst: (1) proper HOMO/LUMO energy levels with respect to the water redox potential, (2) appropriate energy gap sizes for the maximum usability of visible light, and (3) the ability to separate the charge carriers (electron and hole) optimally. Using the well-reported graphitic carbon nitride (g-C3N4) as benchmark, we find that both PMDA-ODA and BTDA-ODA polyimides are most promising, with a favourable HOMO–LUMO energy gap and well-separated electron and hole localized on each monomer fragment of the polyimide strand. From our optical response calculations, these PMDA-ODA and BTDA-ODA polyimides are also found to be better absorbers of visible light than e.g. g-C3N4. This study will provide a good theoretical platform for optimizing the next-generation metal-free polymeric photocatalysts for hydrogen production from water under visible light.

AB - Eco-friendly production of hydrogen using the solar water-splitting reaction is one of the key technologies for clean energy generation. In this work, using hybrid density-functional theory calculations, we survey a number of isolated polyimide chains for prospective candidates as metal-free organic photocatalysts, given their known excellent thermal stability and chemical resistance. We evaluate their capability to split water following the three key requirements for a good photocatalyst: (1) proper HOMO/LUMO energy levels with respect to the water redox potential, (2) appropriate energy gap sizes for the maximum usability of visible light, and (3) the ability to separate the charge carriers (electron and hole) optimally. Using the well-reported graphitic carbon nitride (g-C3N4) as benchmark, we find that both PMDA-ODA and BTDA-ODA polyimides are most promising, with a favourable HOMO–LUMO energy gap and well-separated electron and hole localized on each monomer fragment of the polyimide strand. From our optical response calculations, these PMDA-ODA and BTDA-ODA polyimides are also found to be better absorbers of visible light than e.g. g-C3N4. This study will provide a good theoretical platform for optimizing the next-generation metal-free polymeric photocatalysts for hydrogen production from water under visible light.

UR - http://www.scopus.com/inward/record.url?scp=85091978260&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85091978260&partnerID=8YFLogxK

U2 - 10.1016/j.mcat.2020.111184

DO - 10.1016/j.mcat.2020.111184

M3 - Article

AN - SCOPUS:85091978260

SN - 2468-8231

VL - 497

JO - Molecular Catalysis

JF - Molecular Catalysis

M1 - 111184

ER -

A computational survey of metal-free polyimide-based photocatalysts within the single-stranded polymer model

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

UN SDGs

Access to Document

Other files and links

Fingerprint

Cite this