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Selective Recovery and Recycling of Germanium for the Design of Sustainable Zeolite Catalysts

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    Research Article

    Selective Recovery and Recycling of Germanium for the Design of Sustainable Zeolite Catalysts
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    • Jin Zhang
      Jin Zhang
      Department of Physical and Macromolecular Chemistry & Charles University Center of Advanced Materials, Faculty of Science, Charles University, Hlavova 2030, 12843 Prague 2, Czech Republic
      More by Jin Zhang
    • Qiudi Yue
      Qiudi Yue
      Department of Physical and Macromolecular Chemistry & Charles University Center of Advanced Materials, Faculty of Science, Charles University, Hlavova 2030, 12843 Prague 2, Czech Republic
      More by Qiudi Yue
      Orcidhttp://orcid.org/0000-0003-2046-5238
    • Michal Mazur
      Michal Mazur
      Department of Physical and Macromolecular Chemistry & Charles University Center of Advanced Materials, Faculty of Science, Charles University, Hlavova 2030, 12843 Prague 2, Czech Republic
      More by Michal Mazur
      Orcidhttp://orcid.org/0000-0001-5044-5284
    • Maksym Opanasenko
      Maksym Opanasenko
      Department of Physical and Macromolecular Chemistry & Charles University Center of Advanced Materials, Faculty of Science, Charles University, Hlavova 2030, 12843 Prague 2, Czech Republic
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    • Mariya V. Shamzhy*
      Mariya V. Shamzhy
      Department of Physical and Macromolecular Chemistry & Charles University Center of Advanced Materials, Faculty of Science, Charles University, Hlavova 2030, 12843 Prague 2, Czech Republic
      *Email: [email protected]
      More by Mariya V. Shamzhy
      Orcidhttp://orcid.org/0000-0002-1979-6817
    • Jiři Čejka
      Jiři Čejka
      Department of Physical and Macromolecular Chemistry & Charles University Center of Advanced Materials, Faculty of Science, Charles University, Hlavova 2030, 12843 Prague 2, Czech Republic
      More by Jiři Čejka
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    ACS Sustainable Chemistry & Engineering

    Cite this: ACS Sustainable Chem. Eng. 2020, 8, 22, 8235–8246
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    https://doi.org/10.1021/acssuschemeng.0c01336
    Published May 8, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Germanosilicate zeolites with extra-large-/multidimensional pore systems have a high potential for catalytic applications. However, their insufficient hydrothermal stability, high cost, and lack of strong acid sites limit their use. This work presents a synthetic approach involving post-synthesis degermanation/germanium recycling and remetalation steps for the cost-efficient preparation of Brønsted and Lewis acid zeolite catalysts. Optimization of degermanation conditions (i.e., pH and duration of the leaching treatment) allowed to recover up to 78–94% germanium from ITH, IWW, and UTL zeolites. Further metalation of hydrolyzed IWW zeolites resulted in a set of Al-, Ti-, and Sn-substituted catalysts showing enhanced activity in model acid-catalyzed reactions, such as 1-hexanol tetrahydropyranylation, 1-octene epoxidation, and Baeyer–Villiger oxidation of cyclohexanone. Noticeably, the phase selectivity of zeolite formation upon germanium recycling strongly depended on the method for parent zeolite separation from the leaching solution. In contrast to microfiltration, which produces a versatile source of germanium for the preparation of various zeolites, filtration leads to the formation of germanosilicates with the topology of the parent zeolite regardless of recycling conditions. Such a “memory effect” was rationalized based on the characterization of the germanium source and crystallization products using a combination of techniques (e.g., X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy).

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.0c01336.

    • XRD patterns and N2 adsorption/desorption isotherms of original germanosilicate zeolites; HRTEM images of leaching solution and GeO2filt and GeO2microfilt samples; XRD patterns of germanosilicate zeolites before and after acidic leaching; XRD patterns, N2 adsorption/desorption isotherms, and FTIR spectra of parent IWW, degermanated, and metallated IWW/Mepost zeolites; FTIR spectra of IWW/Mepost zeolites retaining adsorbed pyridine at different temperatures; conversion versus time profiles for 1-hexanol in THP reaction, 1-ocetene in epoxidation reaction, and cyclohexanone in BVO reaction over catalysts under investigation; SEM images of zeolite catalysts under study; and description of Py-FTIR and catalytic experiments (PDF)

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    This article is cited by 26 publications.

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    6. Mengting Jin, Ondřej Veselý, Christopher James Heard, Martin Kubů, Petr Nachtigall, Jiří Čejka, Lukáš Grajciar. The Role of Water Loading and Germanium Content in Germanosilicate Hydrolysis. The Journal of Physical Chemistry C 2021, 125 (43) , 23744-23757. https://doi.org/10.1021/acs.jpcc.1c06873
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    10. Jin Zhang, Talat Zakeri, Qiudi Yue, Martin Kubů, Roman Barakov, Jan Přech, Maksym Opanasenko, Mariya Shamzhy. Lewis acid zeolite catalysts via chemical modification of extra-large pore germanosilicates. Catalysis Today 2024, 440 , 114825. https://doi.org/10.1016/j.cattod.2024.114825
    11. Poonam Rani, Jin Zhang, Yuqi Zhang, Maksym Opanasenko, Mariya Shamzhy. Zeolite-catalyzed one-pot sucrose-to-HMF transformation: Ge outperforms Sn, Zr, and Al sites. Microporous and Mesoporous Materials 2024, 378 , 113234. https://doi.org/10.1016/j.micromeso.2024.113234
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    13. Jiuxing Jiang. Synthesis of Germanosilicates. 2024, 87-118. https://doi.org/10.1002/9783527839384.ch4
    14. Mingming Peng, Yuhong Zhao, Hao Xu, Jingang Jiang, Peng Wu. Double Four Ring Units‐Containing Zeolites: Synthesis, Structural Modification and Catalytic Applications. Chemistry – A European Journal 2024, 30 (15) https://doi.org/10.1002/chem.202303657
    15. Taiki Hayashi, Takamichi Matsuno, Kazuyuki Kuroda, Atsushi Shimojima. Utilization of cage germoxanes as templates for tuning pore characteristics of siloxane-based materials. Chemistry Letters 2024, 53 (3) https://doi.org/10.1093/chemle/upae025
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    21. Roman Barakov, Nataliya Shcherban, Oleg Petrov, Daniel N. Rainer, Martin Kubů, Jiri Cejka, Mariya Shamzhy, Maksym Opanasenko. Optimization of Zr-Al-Usy and Zr-Al-Beta Zeolites Catalysts for a One-Pot Cascade Transformation of Furfural to Γ-Valerolactone. 2023https://doi.org/10.2139/ssrn.4494099
    22. Sharon E. Ashbrook, Russell Morris, Cameron M. Rice. Understanding the synthesis and reactivity of ADORable zeolites using NMR spectroscopy. Current Opinion in Colloid & Interface Science 2022, 61 , 101634. https://doi.org/10.1016/j.cocis.2022.101634
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    26. Maksym Opanasenko, Mariya Shamzhy, Yunzheng Wang, Wenfu Yan, Petr Nachtigall, Jiří Čejka. Synthesis and Post‐Synthesis Transformation of Germanosilicate Zeolites. Angewandte Chemie 2020, 132 (44) , 19548-19557. https://doi.org/10.1002/ange.202005776
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    ACS Sustainable Chemistry & Engineering

    Cite this: ACS Sustainable Chem. Eng. 2020, 8, 22, 8235–8246
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acssuschemeng.0c01336
    Published May 8, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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