Dual-site engineering of N vacancies and K single-atoms in C3N4: Enabling spatial charge transfer channels for photocatalysis

Graphitic carbon nitride (C3N4) is a promising photocatalyst due to its suitable band gap and polymer properties, but its efficiency is limited by the poor separation of photoinduced electron/hole (e–/h+) pairs. To address this issue, we propose creating N vacancies within the layers and bridging K...

Full description

Saved in:
Bibliographic Details
Main Authors: Xiao Xu, Yao Xiao, Xuelian Xu, Sónia A.C. Carabineiro, Junjiang Zhu
Format: Article
Language:English
Published: Elsevier 2025-05-01
Series:Journal of Materiomics
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S2352847824002089
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1849709469931405312
author Xiao Xu
Yao Xiao
Xuelian Xu
Sónia A.C. Carabineiro
Junjiang Zhu
author_facet Xiao Xu
Yao Xiao
Xuelian Xu
Sónia A.C. Carabineiro
Junjiang Zhu
author_sort Xiao Xu
collection DOAJ
description Graphitic carbon nitride (C3N4) is a promising photocatalyst due to its suitable band gap and polymer properties, but its efficiency is limited by the poor separation of photoinduced electron/hole (e–/h+) pairs. To address this issue, we propose creating N vacancies within the layers and bridging K single-atoms between the C3N4 layers through the self-assembly of potassium citrate and melamine–urea monomers. The introduction of N vacancies disrupts the symmetry of C3N4, promoting electron transfer along the delocalized π-conjugated network, while the presence of K atoms provides channels for electron transfer between the layers by forming NKN bridges, thereby leading to significant enhancement in the separation and transfer of e–/h+ pairs across spatial dimension. As expected, the co-modified C3N4, with N vacancies and K single-atoms (designated as CN-K-VN), exhibits excellent photocatalytic performance, with reaction rate constant of 9.69 × 10−2 min−1 (7.39 × 10−2 min−1 in real water environment) for tetracycline, achieving 80% degradation of tetracycline within 20 min. The reaction mechanism, as well as the toxicity of the degradation intermediates, is deeply discussed. This study provides a strategy to enhance the spatial separation of electrons for photocatalyst, highlighting its significance role in photocatalysis.
format Article
id doaj-art-cb90ea699f784ea993774d76b692e2a8
institution DOAJ
issn 2352-8478
language English
publishDate 2025-05-01
publisher Elsevier
record_format Article
series Journal of Materiomics
spelling doaj-art-cb90ea699f784ea993774d76b692e2a82025-08-20T03:15:17ZengElsevierJournal of Materiomics2352-84782025-05-0111310096910.1016/j.jmat.2024.100969Dual-site engineering of N vacancies and K single-atoms in C3N4: Enabling spatial charge transfer channels for photocatalysisXiao Xu0Yao Xiao1Xuelian Xu2Sónia A.C. Carabineiro3Junjiang Zhu4Hubei Key Laboratory of Biomass Fibers and Eco-dyeing & Finishing, School of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan, 430200, ChinaHubei Key Laboratory of Biomass Fibers and Eco-dyeing & Finishing, School of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan, 430200, ChinaHubei Key Laboratory of Biomass Fibers and Eco-dyeing & Finishing, School of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan, 430200, ChinaLAQV-REQUIMTE, Department of Chemistry, NOVA School of Science and Technology, Universidade NOVA de Lisboa, Largo da Torre, 2829-516, Caparica, PortugalHubei Key Laboratory of Biomass Fibers and Eco-dyeing & Finishing, School of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan, 430200, China; Corresponding author.Graphitic carbon nitride (C3N4) is a promising photocatalyst due to its suitable band gap and polymer properties, but its efficiency is limited by the poor separation of photoinduced electron/hole (e–/h+) pairs. To address this issue, we propose creating N vacancies within the layers and bridging K single-atoms between the C3N4 layers through the self-assembly of potassium citrate and melamine–urea monomers. The introduction of N vacancies disrupts the symmetry of C3N4, promoting electron transfer along the delocalized π-conjugated network, while the presence of K atoms provides channels for electron transfer between the layers by forming NKN bridges, thereby leading to significant enhancement in the separation and transfer of e–/h+ pairs across spatial dimension. As expected, the co-modified C3N4, with N vacancies and K single-atoms (designated as CN-K-VN), exhibits excellent photocatalytic performance, with reaction rate constant of 9.69 × 10−2 min−1 (7.39 × 10−2 min−1 in real water environment) for tetracycline, achieving 80% degradation of tetracycline within 20 min. The reaction mechanism, as well as the toxicity of the degradation intermediates, is deeply discussed. This study provides a strategy to enhance the spatial separation of electrons for photocatalyst, highlighting its significance role in photocatalysis.http://www.sciencedirect.com/science/article/pii/S2352847824002089C3N4N vacanciesK single-atomSpatial separation of electronsPhotocatalysis
spellingShingle Xiao Xu
Yao Xiao
Xuelian Xu
Sónia A.C. Carabineiro
Junjiang Zhu
Dual-site engineering of N vacancies and K single-atoms in C3N4: Enabling spatial charge transfer channels for photocatalysis
Journal of Materiomics
C3N4
N vacancies
K single-atom
Spatial separation of electrons
Photocatalysis
title Dual-site engineering of N vacancies and K single-atoms in C3N4: Enabling spatial charge transfer channels for photocatalysis
title_full Dual-site engineering of N vacancies and K single-atoms in C3N4: Enabling spatial charge transfer channels for photocatalysis
title_fullStr Dual-site engineering of N vacancies and K single-atoms in C3N4: Enabling spatial charge transfer channels for photocatalysis
title_full_unstemmed Dual-site engineering of N vacancies and K single-atoms in C3N4: Enabling spatial charge transfer channels for photocatalysis
title_short Dual-site engineering of N vacancies and K single-atoms in C3N4: Enabling spatial charge transfer channels for photocatalysis
title_sort dual site engineering of n vacancies and k single atoms in c3n4 enabling spatial charge transfer channels for photocatalysis
topic C3N4
N vacancies
K single-atom
Spatial separation of electrons
Photocatalysis
url http://www.sciencedirect.com/science/article/pii/S2352847824002089
work_keys_str_mv AT xiaoxu dualsiteengineeringofnvacanciesandksingleatomsinc3n4enablingspatialchargetransferchannelsforphotocatalysis
AT yaoxiao dualsiteengineeringofnvacanciesandksingleatomsinc3n4enablingspatialchargetransferchannelsforphotocatalysis
AT xuelianxu dualsiteengineeringofnvacanciesandksingleatomsinc3n4enablingspatialchargetransferchannelsforphotocatalysis
AT soniaaccarabineiro dualsiteengineeringofnvacanciesandksingleatomsinc3n4enablingspatialchargetransferchannelsforphotocatalysis
AT junjiangzhu dualsiteengineeringofnvacanciesandksingleatomsinc3n4enablingspatialchargetransferchannelsforphotocatalysis