Isolated iridium oxide sites on modified carbon nitride for photoreforming of plastic derivatives

The rising concentration of plastics due to extensive disposal and inefficient recycling of plastic waste poses an imminent and critical threat to the environment and ecological systems. Photocatalytic reforming of plastic derivatives to value-added chemicals under ambient conditions proceeds at lower oxidation potential which galvanizes the hydrogen evolution. We report the synthesis of a narrow band gap NCN-functionalized O-bridged carbon nitride (MC) through condensation polymerization of hydrogen-bonded melem (M)-cyameluric acid (C) macromolecular aggregate. The MC scaffold hosts well-dispersed Ir single atom (MCIrSA) sites which catalyze oxidative photoreforming of alkali-treated polylactic acid (PLA) and polyethylene terephthalate (PET) derivatives to produce H<sub>2</sub> at a rate of 147.5 and 29.58 μmol g<sup>-1</sup><sub>cat</sub> h<sup>-1</sup> under AM1.5G irradiation. Solid-state electron paramagnetic resonance (EPR) and time-resolved photoluminescence (TRPL) reveals efficient charge carrier generation and separation in MCIrSA. X-ray absorption spectroscopy (XAS) and Bader charge analysis reveal undercoordinated IrN<sub>2</sub>O<sub>2</sub> SA sites pinned in C<sub>6</sub>N<sub>7</sub> moieties leading to efficient hole quenching. The liquid phase EPR, in situ FTIR and density functional theory (DFT) studies validate the facile generation of •OH radicals due to the evolution of O-Ir-OH transient species with weak Ir--OH desorption energy barrier.

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Publication Details

Journal
Nature Communications
Published
2025-03-24
DOI
https://doi.org/10.1038/s41467-025-57999-w
Citations
25
Primary Topic
Advanced Photocatalysis Techniques
Type
article
Field-Weighted Citation Impact
9.09

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article

Isolated iridium oxide sites on modified carbon nitride for photoreforming of plastic derivatives

Samira Siahrostami, Yimin A. Wu, Kannimuthu Karthick, Abdelrahman M. Askar et al.
25 citations
Nature Communications
Advanced Photocatalysis Techniques
9.09
article

Isolated iridium oxide sites on modified carbon nitride for photoreforming of plastic derivatives

Samira Siahrostami, Yimin A. Wu, Kannimuthu Karthick, Abdelrahman M. Askar, Jianjie Ma, Adam F. G. Leontowich, Angel A. Martı́, Pulickel Madhavapanicker Ajayan, Jiu Wang, Dhwanil Trivedi, Kexin Ling, Soumyabrata Roy, Md Golam Kibria, Michael M. Adachi, Sung‐Fu Hung, Heng Zhao, Ali Shayesteh Zeraati, Jinguang Hu, David Sinton, Wei‐Hsiang Huang, George K. H. Shimizu, Muflih A. Adnan, Kristen A. Miller, Asfaw G. Yohannes, Pawan Kumar, Xiyang Wang, María Molina, Hongguang Zhang
article en
25 citations

Abstract

The rising concentration of plastics due to extensive disposal and inefficient recycling of plastic waste poses an imminent and critical threat to the environment and ecological systems. Photocatalytic reforming of plastic derivatives to value-added chemicals under ambient conditions proceeds at lower oxidation potential which galvanizes the hydrogen evolution. We report the synthesis of a narrow band gap NCN-functionalized O-bridged carbon nitride (MC) through condensation polymerization of hydrogen-bonded melem (M)-cyameluric acid (C) macromolecular aggregate. The MC scaffold hosts well-dispersed Ir single atom (MCIrSA) sites which catalyze oxidative photoreforming of alkali-treated polylactic acid (PLA) and polyethylene terephthalate (PET) derivatives to produce H<sub>2</sub> at a rate of 147.5 and 29.58 μmol g<sup>-1</sup><sub>cat</sub> h<sup>-1</sup> under AM1.5G irradiation. Solid-state electron paramagnetic resonance (EPR) and time-resolved photoluminescence (TRPL) reveals efficient charge carrier generation and separation in MCIrSA. X-ray absorption spectroscopy (XAS) and Bader charge analysis reveal undercoordinated IrN<sub>2</sub>O<sub>2</sub> SA sites pinned in C<sub>6</sub>N<sub>7</sub> moieties leading to efficient hole quenching. The liquid phase EPR, in situ FTIR and density functional theory (DFT) studies validate the facile generation of •OH radicals due to the evolution of O-Ir-OH transient species with weak Ir--OH desorption energy barrier.

Nature CommunicationsVol. 16(1)
National Yang Ming Chiao Tung University (TW), University of Waterloo (CA), University of Calgary (CA), Simon Fraser University (CA), University of Toronto (CA), National Synchrotron Radiation Research Center (TW), Rice University (US), Canadian Light Source (Canada) (CA), Indian Institute of Technology Kanpur (IN)
National Science Foundation, Rice University, Canadian Light Source, McMaster University, Compute Canada, University of Alberta, Indian Institute of Technology Kanpur, Canada First Research Excellence Fund, Canadian Institutes of Health Research, Natural Sciences and Engineering Research Council of Canada, National Research Council Canada
Openalex Percentile: Top 2%
Advanced Photocatalysis Techniques
9.09
DOIOpen Access PDFOpenAlex
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