Microscopic Revelation of Charge-Trapping Sites in Polymeric Carbon Nitrides for Enhanced Photocatalytic Activity by Correlating with Chemical and Electronic Structures

DIpak B. Nimbalkar, Monika Stas, Sheng-Shu Hou, Shyue Chu Ke, Jih-Jen Wu

Research output: Contribution to journalArticle

Abstract

The influences of chemical and electronic structures on the photophysical properties of polymeric carbon nitrides (PCNs) photocatalysts, which govern the microscopic mechanisms of the superior photocatalytic activity under visible-light irradiation, have been resolved in this work. Time-resolved photoluminescence and in situ electron paramagnetic resonance measurements indicate that the photoexcited electrons in the fractured PCNs swiftly transfer to the C2p-localized states where the trapped photoelectrons exhibit longer lifetime compared to those in the ordinary PCNs. Moreover, the structure deviation at the carbon (Cb) atoms around the bridging sites of heptazine ring units, where trapped photoelectrons are localized, has been determined in the fractured PCNs based on the 13C solid-state nuclear magnetic resonance spectra and the density functional theory calculations. Accordingly, the formation of fractured PCNs by breaking the in-plane hydrogen bonds at a high temperature is a promising strategy for the enhancement of photocatalytic activity.

Original languageEnglish
Pages (from-to)19087-19095
Number of pages9
JournalACS Applied Materials and Interfaces
Volume11
Issue number21
DOIs
Publication statusPublished - 2019 May 29

Fingerprint

Charge trapping
Carbon nitride
Electronic structure
Photoelectrons
Photocatalysts
Density functional theory
Paramagnetic resonance
Photoluminescence
Hydrogen bonds
Carbon
Nuclear magnetic resonance
cyanogen
Irradiation
Atoms
Electrons
Temperature

All Science Journal Classification (ASJC) codes

  • Materials Science(all)

Cite this

@article{cc03efb12f304eb387613dc90404ff99,
title = "Microscopic Revelation of Charge-Trapping Sites in Polymeric Carbon Nitrides for Enhanced Photocatalytic Activity by Correlating with Chemical and Electronic Structures",
abstract = "The influences of chemical and electronic structures on the photophysical properties of polymeric carbon nitrides (PCNs) photocatalysts, which govern the microscopic mechanisms of the superior photocatalytic activity under visible-light irradiation, have been resolved in this work. Time-resolved photoluminescence and in situ electron paramagnetic resonance measurements indicate that the photoexcited electrons in the fractured PCNs swiftly transfer to the C2p-localized states where the trapped photoelectrons exhibit longer lifetime compared to those in the ordinary PCNs. Moreover, the structure deviation at the carbon (Cb) atoms around the bridging sites of heptazine ring units, where trapped photoelectrons are localized, has been determined in the fractured PCNs based on the 13C solid-state nuclear magnetic resonance spectra and the density functional theory calculations. Accordingly, the formation of fractured PCNs by breaking the in-plane hydrogen bonds at a high temperature is a promising strategy for the enhancement of photocatalytic activity.",
author = "Nimbalkar, {DIpak B.} and Monika Stas and Sheng-Shu Hou and Ke, {Shyue Chu} and Jih-Jen Wu",
year = "2019",
month = "5",
day = "29",
doi = "10.1021/acsami.9b02494",
language = "English",
volume = "11",
pages = "19087--19095",
journal = "ACS applied materials & interfaces",
issn = "1944-8244",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Microscopic Revelation of Charge-Trapping Sites in Polymeric Carbon Nitrides for Enhanced Photocatalytic Activity by Correlating with Chemical and Electronic Structures

AU - Nimbalkar, DIpak B.

AU - Stas, Monika

AU - Hou, Sheng-Shu

AU - Ke, Shyue Chu

AU - Wu, Jih-Jen

PY - 2019/5/29

Y1 - 2019/5/29

N2 - The influences of chemical and electronic structures on the photophysical properties of polymeric carbon nitrides (PCNs) photocatalysts, which govern the microscopic mechanisms of the superior photocatalytic activity under visible-light irradiation, have been resolved in this work. Time-resolved photoluminescence and in situ electron paramagnetic resonance measurements indicate that the photoexcited electrons in the fractured PCNs swiftly transfer to the C2p-localized states where the trapped photoelectrons exhibit longer lifetime compared to those in the ordinary PCNs. Moreover, the structure deviation at the carbon (Cb) atoms around the bridging sites of heptazine ring units, where trapped photoelectrons are localized, has been determined in the fractured PCNs based on the 13C solid-state nuclear magnetic resonance spectra and the density functional theory calculations. Accordingly, the formation of fractured PCNs by breaking the in-plane hydrogen bonds at a high temperature is a promising strategy for the enhancement of photocatalytic activity.

AB - The influences of chemical and electronic structures on the photophysical properties of polymeric carbon nitrides (PCNs) photocatalysts, which govern the microscopic mechanisms of the superior photocatalytic activity under visible-light irradiation, have been resolved in this work. Time-resolved photoluminescence and in situ electron paramagnetic resonance measurements indicate that the photoexcited electrons in the fractured PCNs swiftly transfer to the C2p-localized states where the trapped photoelectrons exhibit longer lifetime compared to those in the ordinary PCNs. Moreover, the structure deviation at the carbon (Cb) atoms around the bridging sites of heptazine ring units, where trapped photoelectrons are localized, has been determined in the fractured PCNs based on the 13C solid-state nuclear magnetic resonance spectra and the density functional theory calculations. Accordingly, the formation of fractured PCNs by breaking the in-plane hydrogen bonds at a high temperature is a promising strategy for the enhancement of photocatalytic activity.

UR - http://www.scopus.com/inward/record.url?scp=85066847145&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85066847145&partnerID=8YFLogxK

U2 - 10.1021/acsami.9b02494

DO - 10.1021/acsami.9b02494

M3 - Article

VL - 11

SP - 19087

EP - 19095

JO - ACS applied materials & interfaces

JF - ACS applied materials & interfaces

SN - 1944-8244

IS - 21

ER -