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Catalytic deconstruction of organic additive-containing plastics

Nature Chemical Engineering volume 2, pages 220–228 (2025)Cite this article

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Abstract

Plastics waste ends up in landfills, oceans and incinerators, posing major environmental and human health threats. Catalytic deconstruction is emerging as a key technological solution to handle complex plastics and has successfully converted virgin polymers into various products. Here we investigate the resilience of chemical deconstruction technologies to organic additives, which are ubiquitous in plastics. We study catalyst–additive interactions experimentally and via first-principles calculations for plastics additives representative of entire classes. We reveal two deactivation mechanisms and demonstrate that most recently developed catalysts are inadequate for polyolefin conversion due to poisoning caused by the strong adsorption of many additives or their small fragments. We also identify conditions and catalysts that can circumvent the challenge of deconstruction in the presence of additives.

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Fig. 1: Product yields from 76LDPE hydrocracking with 2 wt% select additives using a Ni/HBEA catalyst.
Fig. 2: Reactivity data of LDPE with various additives under melt catalytic pyrolysis conditions.
Fig. 3: Product distributions.
Fig. 4: Desorption profile of BHT over solid-acid materials.
Fig. 5: ATR–FTIR spectra of I-3114 on HZSM-5.
Fig. 6: Correlation between conversion, reaction temperature and desorption temperature of additives on various catalytic materials used for catalytic upcycling of polyolefins.

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All data is available in the main text or the supplementary materials. Source Data are provided with this paper, including the atomic coordinates of the optimized computational models.

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Acknowledgements

This work was funded by the Center for Plastics Innovation, an Energy Frontier Research Center, funded by the US Deptartment of Energy, Office of Science, Office of Basic Energy Sciences (award no. DE-SC0021166 to J.N.), National Science Foundation (grant no. OIA–2119754 to S.N.), Graduate Research Fellowship through the National Science Foundation (grant no. 1940700. to B.C.V.), Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the US Deptartment of Energy, Office of Science, Office of Basic Energy Sciences (award no. DE-SC0001004 to E.S. and P.Y.). This research used instruments in the Advanced Materials Characterization Lab (AMCL). The TGA-MS equipment was supported by the Center for Plastics Innovation, an Energy Frontier Research Center, funded by the US Deptartment of Energy, Office of Science, Office of Basic Energy Sciences (award no. DE-SC0021166). The Department of Energy’s Office of Energy Efficient and Renewable Energy’s Advanced Manufacturing Office supported the microwave instrumentation (award no. DE-EE0007888-8.3). We are grateful to S. Caratzoulas for useful discussions, and J. Sun for her assistance with the synthesis and characterization of the ruthenium on carbon catalyst.

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Author notes

  1. These authors contributed equally: Sean Najmi, Esun Selvam, Brandon Vance.

Authors and Affiliations

  1. Center for Plastics Innovation, University of Delaware, Newark, DE, USA

    Jacqueline Ngu, Esun Selvam, Brandon Vance & Dionisios G. Vlachos

  2. Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA

    Jacqueline Ngu, Sean Najmi, Esun Selvam, Brandon Vance, Piaoping Yang & Dionisios G. Vlachos

  3. Delaware Energy Institute, University of Delaware, Newark, DE, USA

    Sean Najmi & Dionisios G. Vlachos

Authors
  1. Jacqueline Ngu
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Contributions

J.N., S.N., E.S., B.V. and D.G.V. contributed to the conceptualization and methodology. J.N., S.N., E.S., B.V., P.Y. and D.G.V. all contributed to the investigation. D.G.V. acquired funding and supervised the project. J.N., S.N., E.S., B.V., P.Y. and D.G.V. composed the original draft and contributed to reviewing and editing.

Corresponding author

Correspondence to Dionisios G. Vlachos.

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Competing interests

J.N., S.N., E.S., B.V. and D.G.V are inventors on a patent application (US CIP patent application no. 18/948,419) related to the catalytic cracking of additives under microwave irradiation filed by the University of Delaware. The remaining authors declare no competing interests.

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Peer review information

Nature Chemical Engineering thanks Zhiqiang Niu, Salar Tavakkol and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Table 1 List of organic additives, IUPAC names, abbreviations, structures and main functions of additives studied in this work
Full size table

Supplementary information

Supplementary Information

Supplementary Materials, Text, Figs. 1–38, Tables 1–6 and references.

Supplementary Data 1

Atomic coordinates of BT on a BAS.

Supplementary Data 2

Atomic coordinates of BT on a nickel site.

Supplementary Data 3

Atomic coordinates of HALS on a BAS.

Source data

Source Data Fig. 1

Statistical Source Data.

Source Data Fig. 2

Statistical Source Data.

Source Data Fig. 3

Statistical Source Data.

Source Data Fig. 4

Statistical Source Data.

Source Data Fig. 5

Statistical Source Data.

Source Data Fig. 6

Statistical Source Data.

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Ngu, J., Najmi, S., Selvam, E. et al. Catalytic deconstruction of organic additive-containing plastics. Nat Chem Eng 2, 220–228 (2025). https://doi.org/10.1038/s44286-025-00187-w

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