• Open Access
  • Article

Metal-Free Conjugated Polyphenothiazine Nanostructures as Visible Light Active Photocatalyst for Selective Aerobic Oxidation of Sulfides

  • Rituporn Gogoi †,*,   
  • Swadhin Kumar Jena †,   
  • Astha Singh,   
  • Kajal Sharma,   
  • Rajesh Kumar,   
  • Prem Felix Siril *

Received: 19 Dec 2025 | Revised: 26 Feb 2026 | Accepted: 10 Mar 2026 | Published: 17 Mar 2026

Abstract

Phenothiazine (PTZ) and its derivatives have been widely explored for photocatalytic molecular oxygen activation in various chemical transformations due to their high reduction potential. However, their photocatalytic activity is restricted to UV light irradiation because of a wide band gap (~3.56 eV). In this work, we report a single-step polymerization of PTZ to synthesize nanostructured polyphenothiazene (PPTZ). The resulting PPTZ exhibits a significantly reduced band gap (~2 eV), enabling efficient visible-light absorption. Furthermore, polymerization using different oxidizing agents modulates the morphology of PPTZ nanoparticles, leading to distinct photocatalytic performances. As a metal-free photocatalyst, PPTZ nanoparticles demonstrate excellent activity toward the selective aerobic oxidation of sulfides (SAOS) under visible-light irradiation. High sulfide conversions of up to 99% with selectivity exceeding 99% were achieved. Moreover, the photocatalyst is recyclable for at least three consecutive cycles without any significant loss in performance, highlighting PPTZ-based nanomaterials as promising visible-light-active photocatalysts for SAOS reactions.

Graphical Abstract

References 

  • 1.

    Li, Q.; Li, F. Recent Advances in Molecular Oxygen Activation via Photocatalysis and Its Application in Oxidation Reactions. Chem. Eng. J. 2021, 421, 129915. https://doi.org/10.1016/j.cej.2021.129915.

  • 2.

    Liu, K.-J.; Deng, J.-H.; Yang, J.; et al. Selective Oxidation of (Hetero)Sulfides with Molecular Oxygen under Clean Conditions. Green Chem. 2020, 22, 433–438. https://doi.org/10.1039/C9GC03713F.

  • 3.

    Zhao, L.; Yang, P.; Shi, S.; et al. Activation of Molecular Oxygen for Alcohol Oxidation over Vanadium Carbon Catalysts Synthesized via the Heterogeneous Ligand Strategy. ACS Catal. 2022, 12, 15249–15258. https://doi.org/10.1021/acscatal.2c04601.

  • 4.

    Dang, X.; Yang, R.; Wang, Z.; et al. Efficient Visible-Light Activation of Molecular Oxygen to Produce Hydrogen Peroxide Using P Doped g-C3N4 Hollow Spheres. J. Mater. Chem. A 2020, 8, 22720–22727. https://doi.org/10.1039/D0TA07794A.

  • 5.

    Gogoi, R.; Jena, S.K.; Singh, A.; et al. Mechanically Pulverized Covalent Organic Framework as a Metal-Free Photocatalyst for Fenton-like Degradation of Organic Pollutants and Hexavalent Chromium Reduction. J. Environ. Chem. Eng. 2024, 12, 112006. https://doi.org/10.1016/J.JECE.2024.112006.

  • 6.

    Casado-Sánchez, A.; Gómez-Ballesteros, R.; Tato, F.; et al. Pt(II) Coordination Complexes as Visible Light Photocatalysts for the Oxidation of Sulfides Using Batch and Flow Processes. Chem. Commun. 2016, 52, 9137–9140. https://doi.org/10.1039/C6CC02452A.

  • 7.

    Lang, X.; Zhao, J.; Chen, X. Visible-Light-Induced Photoredox Catalysis of Dye-Sensitized Titanium Dioxide: Selective Aerobic Oxidation of Organic Sulfides. Angew. Chem. Int. Ed. 2016, 55, 4697–4700. https://doi.org/10.1002/ANIE.201600405.

  • 8.

    Serviou, S.K.; Gkizis, P.L.; Sánchez, D.P.; et al. Expanding the Use of Benzothioxanthene Imides to Photochemistry: Eco-Friendly Aerobic Oxidation of Sulfides to Sulfoxides. ChemSusChem 2024, 17, e202400903. https://doi.org/10.1002/cssc.202400903.

  • 9.

    Elanthendral, M.; Vennila, P.; Venkatesh, G. Design, Synthesis, and Photo Physical Characterization of Phenyl-(Benzo) Phenothiazine-Based Organic Photosensitizes for Dye-Sensitized Solar Cells. J. Phys. Chem. Solids 2026, 208, 113010. https://doi.org/10.1016/j.jpcs.2025.113010.

  • 10.

    Bandishti, M.; Pramanik, C.; Roychowdury, A.; et al. A Concise Review of Phenothiazine Based Antipsychotic Drugs and Their Syntheses. J. Heterocycl. Chem. 2026, 63, 106–129. https://doi.org/10.1002/jhet.70115.

  • 11.

    Park, J.H.; Ko, K.C.; Kim, E.; et al. Photocatalysis by Phenothiazine Dyes: Visible-Light-Driven Oxidative Coupling of Primary Amines at Ambient Temperature. Org. Lett. 2012, 14, 5502–5505. https://doi.org/10.1021/ol302584y.

  • 12.

    Discekici, E.H.; Treat, N.J.; Poelma, S.O.; et al. A Highly Reducing Metal-Free Photoredox Catalyst: Design and Application in Radical Dehalogenations. Chem. Commun. 2015, 51, 11705–11708. https://doi.org/10.1039/C5CC04677G.

  • 13.

    Ando, H.; Takamura, H.; Kadota, I.; et al. Strongly Reducing Helical Phenothiazines as Recyclable Organophotoredox Catalysts. Chem. Commun. 2024, 60, 4765–4768. https://doi.org/10.1039/D4CC00904E.

  • 14.

    Wang, X.; Wang, F.; Sang, Y.; et al. Full-Spectrum Solar-Light-Activated Photocatalysts for Light–Chemical Energy Conversion. Adv. Energy Mater. 2017, 7, 1700473. https://doi.org/10.1002/aenm.201700473.

  • 15.

    Dadashi-Silab, S.; Pan, X.; Matyjaszewski, K. Phenyl Benzo[b]Phenothiazine as a Visible Light Photoredox Catalyst for Metal-Free Atom Transfer Radical Polymerization. Chem. A Eur. J. 2017, 23, 5972–5977. https://doi.org/10.1002/chem.201605574.

  • 16.

    Zhou, J.; Mao, L.; Wu, M.-X.; et al. Extended Phenothiazines: Synthesis, Photophysical and Redox Properties, and Efficient Photocatalytic Oxidative Coupling of Amines. Chem. Sci. 2022, 13, 5252–5260. https://doi.org/10.1039/D2SC01086K.

  • 17.

    Gogoi, R.; Dutt, S.; Siril, P.F. Conjugated Polymer-Based Nanocomposites as Photocatalysts. In Conjugated Polymers Nanostructures for Energy Conversion and Storage Applications; Wiley: Hoboken, NJ, USA, 2021; pp 267–296. https://doi.org/10.1002/9783527820115.CH8.

  • 18.

    Wang, R.; Zhou, C.; Huang, X.; et al. Phenylphenothiazine-Based Porous Organic Polymers as Visible-Light Heterogeneous Photocatalysts for Switchable Bromoalkylation and Cyclopropanation of Unactivated Terminal Alkenes. ACS Sustain. Chem. Eng. 2022, 10, 4650–4659. https://doi.org/10.1021/acssuschemeng.2c00054.

  • 19.

    Wang, W.; Wang, H.; Tang, X.; et al. Phenothiazine-Based Covalent Organic Frameworks with Low Exciton Binding Energies for Photocatalysis. Chem. Sci. 2022, 13, 8679–8685. https://doi.org/10.1039/D2SC02503E.

  • 20.

    Liu, Y.; Jiang, X.; Chen, L.; et al. Rational Design of a Phenothiazine-Based Donor–Acceptor Covalent Organic Framework for Enhanced Photocatalytic Oxidative Coupling of Amines and Cyclization of Thioamides. J. Mater. Chem. A 2023, 11, 1208–1215. https://doi.org/10.1039/D2TA07177K.

  • 21.

    Ghosh, S.; Kouamé, N.A.; Ramos, L.; et al. Conducting Polymer Nanostructures for Photocatalysis under Visible Light. Nat. Mater. 2015, 14, 505–511. https://doi.org/10.1038/nmat4220.

  • 22.

    Gogoi, R.; Singh, A.; Moutam, V.; et al. Revealing the Unexplored Effect of Residual Iron Oxide on the Photoreforming Activities of Polypyrrole Nanostructures on Plastic Waste and Photocatalytic Pollutant Degradation. J. Environ. Chem. Eng. 2022, 10, 106649. https://doi.org/10.1016/j.jece.2021.106649.

  • 23.

    Wang, X.; Li, G.; Han, Y.; et al. Facile Synthesis of Polyphenothiazine as a High-Performance p-Type Cathode for Rechargeable Lithium Batteries. ChemSusChem 2021, 14, 3174–3181. https://doi.org/10.1002/cssc.202101008.

  • 24.

    Maheu, C.; Cardenas, L.; Puzenat, E.; et al. UPS and UV Spectroscopies Combined to Position the Energy Levels of TiO2 Anatase and Rutile Nanopowders. Phys. Chem. Chem. Phys. 2018, 20, 25629–25637. https://doi.org/10.1039/C8CP04614J.

  • 25.

    Khoirun Nisa, Q.A.; Son, D.H.; Kim, J.H. A Step-by-Step Strategy to Enhancing the Photovoltaic Performance of Indandione-Based Polymers. Dye. Pigment. 2022, 207, 110760. https://doi.org/10.1016/j.dyepig.2022.110760.

  • 26.

    Singh, A.; Jena, S.K.; Siril, P.F.; et al. COFfee: A Coffee Waste@Anthraquinone COF Nanocomposite as a Photocatalyst for Green Hydrogen Production. ACS Sustain. Resour. Manag. 2026, 3, 45–51. https://doi.org/10.1021/acssusresmgt.5c00454.

  • 27.

    Li, Q.; Lan, X.; An, G.; et al. Visible-Light-Responsive Anthraquinone Functionalized Covalent Organic Frameworks for Metal-Free Selective Oxidation of Sulfides: Effects of Morphology and Structure. ACS Catal. 2020, 10, 6664–6675. https://doi.org/10.1021/acscatal.0c00290.

  • 28.

    Yang, Y.; Chen, M.; Li, H.; et al. The Degree of Crystallinity Exhibiting a Spatial Distribution in Polymer Films. Eur. Polym. J. 2018, 107, 303–307. https://doi.org/10.1016/j.eurpolymj.2018.08.041.

  • 29.

    Korolev, Y.M.; Ozkan, S.Z. Synthesis and X-Ray Diffraction Study of Polyphenothiazine. Dokl. Phys. Chem. 2009, 429, 223–226. https://doi.org/10.1134/S0012501609110025.

  • 30.

    Wang, X.; Zhang, L. Kinetic Study of Hydroxyl Radical Formation in a Continuous Hydroxyl Generation System. RSC Adv. 2018, 8, 40632–40638. https://doi.org/10.1039/C8RA08511K.

  • 31.

    Gogoi, R.; Dohling, H.M.; Singh, A.; et al. Visible Light Enhanced Photosynthesis of C-C Bonds Using PdO/Pd@PEDOT Nanocomposite. J. Catal. 2022, 414, 109–124. https://doi.org/10.1016/j.jcat.2022.08.027.

  • 32.

    Singh, A.; Surial, S.; Jena, S.K.; et al. Sulfone Based Conjugated Porous Organic Polymer-Immobilized Electrospun Nanofibers for Continuous-Flow Photoreduction of Hexavalent Chromium. Chem. Eng. J. Adv. 2026, 2, 100026. https://doi.org/10.1016/j.cejgas.2026.100026.

  • 33.

    Zhao, Z.Y.; Wang, S.J.; Mi, L.B.; et al. Perylene Diimide-Based Hyper-Cross-Linked Polymers for Visible-Light-Driven Selective Organic Sulfide Oxidation. Sep. Purif. Technol. 2025, 359, 130543. https://doi.org/10.1016/J.SEPPUR.2024.130543.

  • 34.

    Dong, X.; Xu, H.; Hao, H.; et al. Selective Photocatalytic Oxidation of Sulfides with Dioxygen over Carbazole–Fluorene Conjugated Microporous Polymers. J. Colloid Interface Sci. 2022, 608, 882–892. https://doi.org/10.1016/J.JCIS.2021.10.047.

  • 35.

    Zhang, F.; Ma, X.; Dong, X.; et al. Inserting Acetylene into an Olefin-Linked Covalent Organic Framework for Boosting the Selective Photocatalytic Aerobic Oxidation of Sulfides. Chem. Eng. J. 2023, 451, 138802. https://doi.org/10.1016/J.CEJ.2022.138802.

  • 36.

    Ji, G.; Yang, Z.; Yu, X.; et al. Photosensitive Hyper-Cross-Linked Polymers Derived from Three-Dimensional Ringlike Arenes: Promising Catalysts for Singlet-Oxygen Generation. ACS Sustain. Chem. Eng. 2020, 8, 16320–16326. https://doi.org/10.1021/acssuschemeng.0c06025.

  • 37.

    Shan, H.; Zhang, Z.; Jiang, Y.; et al. Two-Dimensional Porphyrin-Based Covalent Organic Frameworks for Heterogeneous Photocatalysis: Influence of Pore Size on Photocatalytic Performance. Sep. Purif. Technol. 2025, 363, 132102. https://doi.org/10.1016/J.SEPPUR.2025.132102.

  • 38.

    Xie, Q.; Chen, A.; Gao, Z.; et al. Regulating Conformational Locking in Covalent Organic Framework for Selective and Recyclable Photocatalytic Transformation. Small 2024, 20, 2405550. https://doi.org/10.1002/smll.202405550.

  • 39.

    Lei, H.; Zhu, C.; Lin, L.; et al. Rational Modulation of Covalent Organic Frameworks Heterogeneous Catalyst: Structural Cationization Effect on Accelerating Photocatalytic Oxidation Process. Appl. Catal. B Environ. Energy 2025, 361, 124654. https://doi.org/10.1016/J.APCATB.2024.124654.

  • 40.

    Wang, Z.; Qi, Z.; Wang, S.; et al. Porphyrin Based Covalent Organic Frameworks via Self-Polycondensation for Heterogeneous Photocatalysis. J. Colloid Interface Sci. 2025, 683, 736–745. https://doi.org/10.1016/J.JCIS.2024.12.205.

  • 41.

    Zhang, H.; Huang, Q.; Zhang, W.; et al. Benzodithiophenedione-Based Conjugated Microporous Polymer Catalysts for Aerobic Oxidation Reactions Driven by Visible-Light. ChemPhotoChem 2019, 3, 645–651. https://doi.org/10.1002/CPTC.201900095.

  • 42.

    Dong, X.; Huang, F.; Wang, Y.; et al. Selective Oxidation of Sulfides by Pyrene-π-Anthraquinone Conjugated Microporous Polymer Photocatalysis. Mater. Today Energy 2023, 38, 101443. https://doi.org/10.1016/J.MTENER.2023.101443.

Share this article:
How to Cite
Gogoi, R.; Jena, S. K.; Singh, A.; Sharma, K.; Kumar, R.; Siril, P. F. Metal-Free Conjugated Polyphenothiazine Nanostructures as Visible Light Active Photocatalyst for Selective Aerobic Oxidation of Sulfides. Photocatalysis 2026, 2 (1), 1. https://doi.org/10.53941/photocatalysis.2026.100001.
RIS
BibTex
Copyright & License
article copyright Image
Copyright (c) 2026 by the authors.