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Research Article

New insight into pyrrolic-N site effect towards the first NIR window absorption of pyrrolic-N-rich carbon dots

Fitri Aulia Permatasari1,2, Reza Umami1, Citra Deliana Dewi Sundari3,4, Tirta Rona Mayangsari2,5, Atthar Luqman Ivansyah3,6, Fahdzi Muttaqien2,6,7,8, Takashi Ogi9, Ferry Iskandar1,2,8( )
Department of Physics, Faculty Mathematics and Natural Sciences, Institut Teknologi Bandung, Jalan Ganesha 10, Bandung, West Java 40132, Indonesia
Collaboration Research Center for Advanced Energy Materials, National Research and Innovation Agency - Institut Teknologi Bandung, Jalan Ganesha 10, Bandung, West Java 40132, Indonesia
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung, West Java 40132, Indonesia
Department of Chemistry Education, UIN Sunan Gunung Djati Bandung, Jl. Cimincrang, Bandung, West Java 40292, Indonesia
Department of Chemistry, Universitas Pertamina, Jakarta 12220, Indonesia
Master Program in Computational Science, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung, West Java 40132, Indonesia
Instrumentation and Computational Physics Research Group, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung 40132, Indonesia
Research Center for Nanoscience and Nanotechnology, Institut Teknologi Bandung, Jalan Ganesha 10, Bandung, West Java 40132, Indonesia
Chemical Engineering Program, Department of Advanced Science and Engineering, Graduate School of Advanced Science and Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan
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Graphical Abstract

Pyrrolic-N-rich carbon dots exhibit a first near infrared (NIR) window absorption with high photothermal conversion of more than 50%. The mid-site pyrrolic-N is crucial to tailor the absorption spectrum and is entangled in the topological and electronic properties of carbon dots.

Abstract

Controlled C–N configurations, i.e., pyrrolic-N, pyridinic-N, and graphitic-N, are promising strategies to tailor the carbon dots’ (CDs) optical properties into the first near infrared (NIR) window (650–900 nm), a responsive range for biomedical application. However, a deep understanding of the role of the C–N configuration in the CDs’ properties is still challenging and thought-provoking owing to their complex structure. Here, an underlying pyrrolic-N concentration and position effect on the pyrrolic-N-rich CDs’ absorption was comprehensively elucidated based on the integrated experimental and computational studies. The as-synthesized pyrrolic-N-rich CDs exhibit a first NIR window absorption centered at 650 nm with high photothermal conversion. Pyrrolic-N concentrations from 1.4% to 11.3% and positions (edge and mid-site) were systematically investigated. A mid-site pyrrolic-N was subsequently generated after the pyrrolic-N concentration more than 10%. Edge-site pyrrolic-N induces a frontier orbital hybridization, reducing bandgap energy, while mid-site pyrrolic-N plays a critical role in inducing a first NIR window absorption owing to their high charge transfer. Also, pyrrolic-N-rich CDs inherit a bowl-like topological feature, elevating the CDs’ layer thickness as much as 0.71 nm. This study shed light on the design and optimization of pyrrolic-N on CDs for the first NIR window responsive materials in any biomedical application.

Keywords

absorptioncarbon dotscharge transferfirst near infrared (NIR) windowfrontier orbital hybridizationmid-site pyrrolic-N

Electronic Supplementary Material

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Nano Research
Volume 16 Issue 4,
April 2023
Pages 6001-6009
DOI: 10.1007/s12274-022-5131-7
Cite this article:
Permatasari FA, Umami R, Dewi Sundari CD, et al. New insight into pyrrolic-N site effect towards the first NIR window absorption of pyrrolic-N-rich carbon dots. Nano Research, 2023, 16(4): 6001-6009. https://doi.org/10.1007/s12274-022-5131-7
Topics:
Carbon quantum dotsElectron energy levels Graphene quantum dots

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Received: 04 August 2022
Revised: 29 September 2022
Accepted: 01 October 2022
Published: 11 January 2023
© Tsinghua University Press 2022
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