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Catalytic conversion of mixed polyolefins under mild atmospheric pressure

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  • Corresponding author: jiaoning@pku.edu.cn
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    1. ■ Under atmospheric pressure and mild conditions with O2 or air as the oxidant.
    2. ■ Compatible with HDPE, LDPE, PS, PP, and mixed polyolefins.
    3. ■ Economical and recoverable metal catalyst.
  • The chemical recycling of polyolefin presents a considerable challenge, especially as upcycling methods struggle with the reality that plastic wastes typically consist of mixtures of polyethylene (PE), polystyrene (PS), and polypropylene (PP). We report a catalytic aerobic oxidative approach for polyolefins upcycling with the corresponding carboxylic acids as the product. This method encompasses three key innovations. First, it operates under atmospheric pressure and mild conditions, using O2 or air as the oxidant. Second, it is compatible with high-density polyethylene, low-density polyethylene, PS, PP, and their blends. Third, it uses an economical and recoverable metal catalyst. It has been demonstrated that this approach can efficiently degrade mixed wastes of plastic bags, bottles, masks, and foam boxes.
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  • [1] Geyer, R., Jambeck, J.R., and Law, K.L. (2017). Production, use, and fate of all plastics ever made. Sci. Adv. 3(7): e1700782. https://doi.org/10.1126/sciadv.1700782.

    View in Article CrossRef Google Scholar

    [2] Nicholson, S.R., Rorrer, N.A., Carpenter, A.C., et al. (2021). Manufacturing energy and greenhouse gas emissions associated with plastics consumption. Joul. 5(3): 673–686. https://doi.org/10.1016/j.joule.2020.12.027.

    View in Article CrossRef Google Scholar

    [3] Chamas, A., Moon, H., Zheng, J., et al. (2020). Degradation rates of plastics in the environment. ACS Sustain. Chem. Eng. 8(9): 3494–3511. https://doi.org/10.1021/acssuschemeng.9b06635.

    View in Article CrossRef Google Scholar

    [4] Patrício Silva, A.L., Prata, J.C., Walker, T.R., et al. (2021). Increased plastic pollution due to COVID-19 pandemic: challenges and recommendations. Chem. Eng. J. 405: 126683. https://doi.org/10.1016/j.cej.2020.126683.

    View in Article CrossRef Google Scholar

    [5] MacLeod, M., Arp, H.P.H., Tekman, M.B., et al. (2021). The global threat from plastic pollution. Scienc. 373(6550): 61–65. https://doi.org/10.1126/science.abg5433.

    View in Article CrossRef Google Scholar

    [6] Moens, E.K.C., De Smit, K., Marien, Y.W., et al. (2020). Progress in reaction mechanisms and reactor technologies for thermochemical recycling of poly(methyl methacrylate). Polymer. 12(8): 1667. https://doi.org/10.3390/polym12081667.

    View in Article CrossRef Google Scholar

    [7] De Smit, K., Wieme, T., Marien, Y.W., et al. (2022). Multi-scale reactive extrusion modelling approaches to design polymer synthesis, modification and mechanical recycling. React. Chem. Eng. 7(2): 245–263. https://doi.org/10.1039/D1RE00556A.

    View in Article CrossRef Google Scholar

    [8] Ceretti, D.V.A., Edeleva, M., Cardon, L., et al. (2023). Molecular pathways for polymer degradation during conventional processing, additive manufacturing, and mechanical recycling. Molecule. 28(5): 2344. https://doi.org/10.3390/molecules28052344.

    View in Article CrossRef Google Scholar

    [9] Ellis, L.D., Rorrer, N.A., Sullivan, K.P., et al. (2021). Chemical and biological catalysis for plastics recycling and upcycling. Nat. Catal. 4(7): 539–556. https://doi.org/10.1038/s41929-021-00648-4.

    View in Article CrossRef Google Scholar

    [10] Korley, L.T.J., Epps, T.H., Helms, B.A., et al. (2021). Toward polymer upcycling—adding value and tackling circularity. Scienc. 373(6550): 66–69. https://doi.org/10.1126/science.abg4503.

    View in Article CrossRef Google Scholar

    [11] Kosloski-Oh, S.C., Wood, Z.A., Manjarrez, Y., et al. (2021). Catalytic methods for chemical recycling or upcycling of commercial polymers. Mater. Horiz. 8(4): 1084–1129. https://doi.org/10.1039/D0MH01286F.

    View in Article CrossRef Google Scholar

    [12] Jehanno, C., Alty, J.W., Roosen, M., et al. (2022). Critical advances and future opportunities in upcycling commodity polymers. Natur. 603(7903): 803–814. https://doi.org/10.1038/s41586-021-04350-0.

    View in Article CrossRef Google Scholar

    [13] Zhang, M.-Q., Wang, M., Sun, B., et al. (2022). Catalytic strategies for upvaluing plastic wastes. Che. 8(11): 2912–2923. https://doi.org/10.1016/j.chempr.2022.08.004.

    View in Article CrossRef Google Scholar

    [14] Partenheimer, W. (2003). Valuable oxygenates by aerobic oxidation of polymers using metal/bromide homogeneous catalysts. Catal. Toda. 81(2): 117–135. https://doi.org/10. 1016/S0920-5861(03)00124-X.

    View in Article CrossRef Google Scholar

    [15] Jing, Y., Wang, Y., Furukawa, S., et al. (2021). Towards the circular economy: converting aromatic plastic waste back to arenes over a Ru/Nb2O5 catalyst. Angew. Chem. Int. Ed. 60(10): 5527–5535. https://doi.org/10.1002/anie.202011063.

    View in Article CrossRef Google Scholar

    [16] Pifer, A. and Sen, A. (1998). Chemical recycling of plastics to useful organic compounds by oxidative degradation. Angew. Chem. Int. Ed. 37(23): 3306–3308. https://doi.org/10.1002/(SICI)1521-3773(19981217)37:23<3306::AID-ANIE3306>3.0.CO;2-B.

    View in Article CrossRef Google Scholar

    [17] Bäckström, E., Odelius, K., and Hakkarainen, M. (2017). Trash to treasure: microwave-assis- € ted conversion of polyethylene to functional chemicals. Ind. Eng. Chem. Res. 56(50): 14814–14821. https://doi.org/10.1021/acs.iecr.7b04091.

    View in Article CrossRef Google Scholar

    [18] Bäckström, E., Odelius, K., and Hakkarainen, M. (2019). Designed from recycled: turning poly- € ethylene waste to covalently attached polylactide plasticizers. ACS Sustain. Chem. Eng. 7(12): 11004–11013. https://doi.org/10.1021/acssuschemeng.9b02092.

    View in Article CrossRef Google Scholar

    [19] Xu, Z., Munyaneza, N.E., Zhang, Q., et al. (2023). Chemical upcycling of polyethylene, polypropylene, and mixtures to high-value surfactants. Scienc. 381(6658): 666–671. https://doi.org/10.1126/science.adh0993.

    View in Article CrossRef Google Scholar

    [20] Anuar Sharuddin, S.D., Abnisa, F., Wan Daud, W.M.A., et al. (2016). A review on pyrolysis of plastic wastes. Energy Convers. Manag. 115: 308–326. https://doi.org/10.1016/j.enconman.2016.02.037.

    View in Article CrossRef Google Scholar

    [21] Al-Salem, S.M., Antelava, A., Constantinou, A., et al. (2017). A review on thermal and catalytic pyrolysis of plastic solid waste (PSW). J. Environ. Manag. 197: 177–198. https://doi.org/10.1016/j.jenvman.2017.03.084.

    View in Article CrossRef Google Scholar

    [22] Munir, D., Irfan, M.F., and Usman, M.R. (2018). Hydrocracking of virgin and waste plastics: A detailed review. Renew. Sustain. Energy Rev. 90: 490–515. https://doi.org/10.1016/j.rser.2018.03.034.

    View in Article CrossRef Google Scholar

    [23] Liu, S., Kots, P.A., Vance, B.C., et al. (2021). Plastic waste to fuels by hydrocracking at mild conditions. Sci. Adv. 7(17): eabf8283. https://doi.org/10.1126/sciadv.abf8283.

    View in Article CrossRef Google Scholar

    [24] Hackler, R.A., Lamb, J.V., Peczak, I.L., et al. (2022). Effect of macro- and microstructures on catalytic hydrogenolysis of polyolefins. Macromolecule. 55(15): 6801–6810. https://doi.org/10.1021/acs.macromol.2c00805.

    View in Article CrossRef Google Scholar

    [25] Chen, S., Tennakoon, A., You, K.-E., et al. (2023). Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis. Nat. Catal. 6(2): 161–173. https://doi.org/10.1038/s41929-023-00910-x.

    View in Article CrossRef Google Scholar

    [26] Lee, W.-T., Bobbink, F.D., van Muyden, A.P., et al. (2021). Catalytic hydrocracking of synthetic polymers into grid-compatible gas streams. Cell Rep. Phys. Sci. 2(2): 100332. https://doi.org/10.1016/j.xcrp.2021.100332.

    View in Article CrossRef Google Scholar

    [27] Wu, X., Tennakoon, A., Yappert, R., et al. (2022). Size-controlled nanopticles embedded in a mesoporous architecture leading to efficient and selective hydrogenolysis of polyolefins. J. Am. Chem. Soc. 144(12): 5323–5334. https://doi.org/10.1021/jacs.1c11694.

    View in Article CrossRef Google Scholar

    [28] Zichittella, G., Ebrahim, A.M., Zhu, J., et al. (2022). Hydrogenolysis of polyethylene and polypropylene into propane over cobalt-based catalysts. JACS A. 2(10): 2259–2268. https://doi.org/10.1021/jacsau.2c00402.

    View in Article CrossRef Google Scholar

    [29] Tennakoon, A., Wu, X., Paterson, A.L., et al. (2020). Catalytic upcycling of high-density polyethylene via a processive mechanism. Nat. Catal. 3(11): 893–901. https://doi.org/10.1038/s41929-020-00519-4.

    View in Article CrossRef Google Scholar

    [30] Wang, K., Jia, R., Cheng, P., et al. (2023). Highly selective catalytic oxi-upcycling of polyethylene to aliphatic dicarboxylic acid under a mild hydrogen-free process. Angew. Chem. Int. Ed. 62(29): e202301340. https://doi.org/10.1002/anie.202301340.

    View in Article CrossRef Google Scholar

    [31] Jia, X., Qin, C., Friedberger, T., et al. (2016). Efficient and selective degradation of polyethylenes into liquid fuels and waxes under mild conditions. Sci. Adv. 2(6): e1501591. https://doi.org/10.1126/sciadv.1501591.

    View in Article CrossRef Google Scholar

    [32] Ellis, L.D., Orski, S.V., Kenlaw, G.A., et al. (2021). Tandem heterogeneous catalysis for polyethylene depolymerization via an olefin-intermediate process. ACS Sustain. Chem. Eng. 9(2): 623–628. https://doi.org/10.1021/acssuschemeng.0c07612.

    View in Article CrossRef Google Scholar

    [33] Zhang, F., Zeng, M., Yappert, R.D., et al. (2020). Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization. Scienc. 370(6515): 437–441. https://doi.org/10.1126/science.abc5441.

    View in Article CrossRef Google Scholar

    [34] Li, H., Wu, J., Jiang, Z., et al. (2023). Hydroformylation of pyrolysis oils to aldehydes andalcohols from polyolefin waste. Scienc. 381(6658): 660–666. https://doi.org/10.1126/science.adh1853.

    View in Article CrossRef Google Scholar

    [35] Kanbur, U., Zang, G., Paterson, A.L., et al. (2021). Catalytic carbon-carbon bond cleavage and carbon-element bond formation give new life for polyolefins as biodegradable surfactants. Che. 7(5): 1347–1362. https://doi.org/10.1016/j.chempr.2021.03.007.

    View in Article CrossRef Google Scholar

    [36] Fazekas, T.J., Alty, J.W., Neidhart, E.K., et al. (2022). Diversification of aliphatic C–H bonds in small molecules and polyolefins through radical chain transfer. Scienc. 375(6580): 545–550. https://doi.org/10.1126/science.abh4308.

    View in Article CrossRef Google Scholar

    [37] Conk, R.J., Hanna, S., Shi, J.X., et al. (2022). Catalytic deconstruction of waste polyethylene with ethylene to form propylene. Scienc. 377(6614): 1561–1566. https://doi.org/10.1126/science.add1088.

    View in Article CrossRef Google Scholar

    [38] Wang, N.M., Strong, G., DaSilva, V., et al. (2022). Chemical recycling of polyethylene by tandem catalytic conversion to propylene. J. Am. Chem. Soc. 144(40): 18526–18531. https://doi.org/10.1021/jacs.2c07781.

    View in Article CrossRef Google Scholar

    [39] Jie, X., Li, W., Slocombe, D., et al. (2020). Microwave-initiated catalytic deconstruction of plastic waste into hydrogen and high-value carbons. Nat. Catal. 3(11): 902–912. https:c.org/10.1038/s41929-020-00518-5.

    View in Article CrossRef Google Scholar

    [40] Jiao, X., Zheng, K., Chen, Q., et al. (2020). Photocatalytic conversion of waste plastics into C2 fuels under simulated natural environment conditions. Angew. Chem. Int. Ed. 59(36): 15497–15501. https://doi.org/10.1002/anie.201915766.

    View in Article CrossRef Google Scholar

    [41] Rabot, C., Chen, Y., Bijlani, S., et al. (2023). Conversion rate of polyethylenes into fungal secondary metabolites. Angew. Chem. Int. Ed. 62(4): e202214609. https://doi.org/10.1002/anie.202214609.

    View in Article CrossRef Google Scholar

    [42] Oh, S. and Stache, E.E. (2022). Chemical upcycling of commercial polystyrene via catalystcontrolled photooxidation. J. Am. Chem. Soc. 144(13): 5745–5749. https://doi.org/10. 1021/jacs.2c01411.

    View in Article CrossRef Google Scholar

    [43] Huang, Z., Shanmugam, M., Liu, Z., et al. (2022). Chemical recycling of polystyrene to valuable chemicals via selective acid-catalyzed aerobic oxidation under visible light. J. Am. Chem. Soc. 144(14): 6532–6542. https://doi.org/10.1021/jacs.2c01410.

    View in Article CrossRef Google Scholar

    [44] Li, T., Vijeta, A., Casadevall, C., et al. (2022). Bridging plastic recycling and organic catalysis: photocatalytic deconstruction of polystyrene via a C–H oxidation pathway. ACS Catal. 12(14): 8155–8163. https://doi.org/10.1021/acscatal.2c02292.

    View in Article CrossRef Google Scholar

    [45] Qin, Y., Zhang, T., Ching, H.V., et al. (2022). Integrated strategy for the synthesis of aromatic building blocks via upcycling of real-life plastic wastes. Che. 8(9): 2472–2484. https://doi.org/10.1016/j.chempr.2022.06.002.

    View in Article CrossRef Google Scholar

    [46] Cao, R., Zhang, M.-Q., Hu, C., et al. (2022). Catalytic oxidation of polystyrene to aromatic oxygenates over a graphitic carbon nitride catalyst. Nat. Commun. 13(1): 4809. https://doi.org/10.1038/s41467-022-32510-x.

    View in Article CrossRef Google Scholar

    [47] Zhang, G., Zhang, Z., and Zeng, R. (2021). Photoinduced FeCl3-catalyzed alkyl aromatics oxidation toward degradation of polystyrene at room temperature. Chin. J. Chem. 39(12): 3225–3230. https://doi.org/10.1002/cjoc.202100420.

    View in Article CrossRef Google Scholar

    [48] Wang, M., Wen, J., Huang, Y., et al. (2021). Selective degradation of styrene-related plastics catalyzed by iron under visible light. ChemSusChe. 14(22): 5049–5056. https://doi.org/10.1002/cssc.202101762.

    View in Article CrossRef Google Scholar

    [49] Meng, J., Zhou, Y., Li, D., et al. (2023). Degradation of plastic wastes to commercial chemicals and monomers under visible light. Sci. Bull. 68(14): 1522–1530. https://doi.org/10. 1016/j.scib.2023.06.024.

    View in Article CrossRef Google Scholar

    [50] Urgoitia, G., Herrero, M.T., and SanMartin, R. (2022). Metal-catalyzed, photo-assisted selective transformation of tertiary alkylbenzenes and polystyrenes into carbonyl compounds. ChemSusChe. 15(17): e202200940. https://doi.org/10.1002/cssc.202200940.

    View in Article CrossRef Google Scholar

    [51] Zhang, W., Kim, S., Wahl, L., et al. (2023). Low-temperature upcycling of polyolefins into liquid alkanes via tandem cracking-alkylation. Scienc. 379(6634): 807–811. https://doi.org/10. 1126/science.ade7485.

    View in Article CrossRef Google Scholar

    [52] Sullivan, K.P., Werner, A.Z., Ramirez, K.J., et al. (2022). Mixed plastics waste valorization through tandem chemical oxidation and biological funneling. Scienc. 378(6616): 207–211. https://doi.org/10.1126/science.abo4626.

    View in Article CrossRef Google Scholar

    [53] Qiu, X., Sang, Y., Wu, H., et al. (2021). Cleaving arene rings for acyclic alkenylnitrile synthesis. Natur. 597(7874): 64–69. https://doi.org/10.1038/s41586-021-03801-y.

    View in Article CrossRef Google Scholar

    [54] Liu, M., Zhang, Z., Yan, J., et al. (2020). Aerobic oxidative cleavage and esterification of C(OH)–C bonds. Che. 6(12): 3288–3296. https://doi.org/10.1016/j.chempr.2020.09.006.

    View in Article CrossRef Google Scholar

    [55] Smaligo, A.J., Swain, M., Quintana, J.C., et al. (2019). Hydrodealkenylative C(sp3)–C(sp2) bond fragmentation. Scienc. 364(6441): 681–685. https://doi.org/10.1126/science.aaw4212.

    View in Article CrossRef Google Scholar

    [56] Roque, J.B., Kuroda, Y., Göttemann, L.T., et al. (2018). Deconstructive fluorination of cyclic amines by carbon-carbon cleavage. Scienc. 361(6398): 171–174. https://doi.org/10.1126/science.aat6365.

    View in Article CrossRef Google Scholar

    [57] Reisenbauer, J.C., Green, O., Franchino, A., et al. (2022). Late-stage diversification of indole skeletons through nitrogen atom insertion. Scienc. 377(6610): 1104–1109. https://doi.org/10.1126/science.add1383.

    View in Article CrossRef Google Scholar

    [58] Xu, Y., Qi, X., Zheng, P., et al. (2019). Deacylative transformations of ketones via aromatization-promoted C–C bond activation. Natur. 567(7748): 373–378. https://doi.org/10.1038/ s41586-019-0926-8.

    View in Article CrossRef Google Scholar

    [59] Woo, J., Christian, A.H., Burgess, S.A., et al. (2022). Scaffold hopping by net photochemical carbon deletion of azaarenes. Scienc. 376(6592): 527–532. https://doi.org/10.1126/science.abo4282.

    View in Article CrossRef Google Scholar

    [60] Rahimi, A., Ulbrich, A., Coon, J.J., et al. (2014). Formic-acid-induced depolymerization of oxidized lignin to aromatics. Natur. 515(7526): 249–252. https://doi.org/10.1038/nature13867.

    View in Article CrossRef Google Scholar

    [61] Hahladakis, J.N., Velis, C.A., Weber, R., et al. (2018). An overview of chemical additives present in plastics: migration, release, fate and environmental impact during their use, disposal and recycling. J. Hazard Mater. 344: 179–199. https://doi.org/10.1016/j.jhazmat.2017.10.014.

    View in Article CrossRef Google Scholar

    [62] Ilton, E.S., Post, J.E., Heaney, P.J., et al. (2016). XPS determination of Mn oxidation states in Mn (hydr)oxides. Appl. Surf. Sci. 366: 475–485. https://doi.org/10.1016/j.apsusc.2015.12.159.

    View in Article CrossRef Google Scholar

    [63] Biesinger, M.C., Payne, B.P., Grosvenor, A.P., et al. (2011). Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni. Appl. Surf. Sci. 257(7): 2717–2730. https://doi.org/10.1016/j.apsusc.2010.10.051.

    View in Article CrossRef Google Scholar

    [64] Xu, T., Li, G., and Zhao, L. (2018). Ni-Co-S/Co(OH)2 nanocomposite for high energy density all-solid-state asymmetric supercapacitors. Chem. Eng. J. 336: 602–611. https://doi.org/10.1016/j.cej.2017.12.065.

    View in Article CrossRef Google Scholar

    [65] Reed, G.H., Leigh, J.S., Jr., et al. (1971). Electron paramagnetic relaxation and EPR line shapes of manganous ion complexes in aqueous solutions. Frequency and ligand dependence. J. Chem. Phys. 55(7): 3311–3316. https://doi.org/10.1063/1.1676582.

    View in Article CrossRef Google Scholar

    [66] Partenheimer, W. (2001). The structure of metal/bromide catalysts in acetic acid/water mixtures and its significance in autoxidation. J. Mol. Catal. A-Chem. 174(1): 29–33. https://doi.org/10.1016/S1381-1169(01)00169-8.

    View in Article CrossRef Google Scholar

    [67] Partenheimer, W. (1995). Methodology and scope of metal/bromide autoxidation of hydrocarbons. Catal. Toda. 23(2): 69–158. https://doi.org/10.1016/0920-5861(94)00138-R.

    View in Article CrossRef Google Scholar

    [68] Maity, A., Hyun, S.-M., and Powers, D.C. (2018). Oxidase catalysis via aerobically generated hypervalent iodine intermediates. Nat. Chem. 10(2): 200–204. https://doi.org/10.1038/ nchem.2873.

    View in Article CrossRef Google Scholar

    [69] Larkin, D.R. (1990). The role of catalysts in the air oxidation of aliphatic aldehydes. J. Org. Chem. 55(5): 1563–1568. https://doi.org/10.1021/jo00292a035.

    View in Article CrossRef Google Scholar

  • Cite this article:

    Binzhi Zhao, Hui Tan, Jie Yang, Xiaohui Zhang, Zidi Yu, Hanli Sun, Jialiang Wei, Xinyi Zhao, Yufeng Zhang, Lili Chen, Dali Yang, Jin Deng, Yao Fu, Zheng Huang, Ning Jiao. Catalytic conversion of mixed polyolefins under mild atmospheric pressure[J]. The Innovation, 2024, 5(2). https://doi.org/10.1016/j.xinn.2024.100586
    Binzhi Zhao, Hui Tan, Jie Yang, Xiaohui Zhang, Zidi Yu, Hanli Sun, Jialiang Wei, Xinyi Zhao, Yufeng Zhang, Lili Chen, Dali Yang, Jin Deng, Yao Fu, Zheng Huang, Ning Jiao. Catalytic conversion of mixed polyolefins under mild atmospheric pressure[J]. The Innovation, 2024, 5(2). https://doi.org/10.1016/j.xinn.2024.100586

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