Chemical modification of the polymer of intrinsic microporosity PIM-1 for enhanced hydrogen storage
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Chemical modification of the polymer of intrinsic microporosity PIM‑1 for enhanced hydrogen storage Mi Tian1,5 · Sébastien Rochat2,3 · Hamish Fawcett1 · Andrew D. Burrows2 · Christopher R. Bowen4 · Timothy J. Mays1 Received: 17 September 2019 / Revised: 28 April 2020 / Accepted: 8 May 2020 © The Author(s) 2020
Abstract A detailed investigation has been carried out of the pre-polymerisation modification of the polymer of intrinsic microporosity PIM-1 by the addition of two methyl (Me) groups to its spirobisindane unit to create a new chemically modified PIM-1 analogue, termed MePIM. Our work explores the effects of this modification on the porosity of PIM-1 and hence on its gas sorption properties. MePIM was successfully synthesised using either low (338 K) or high (423 K) temperature syntheses. It was observed that introduction of methyl groups to the spirobisindane part of PIM-1 generates additional microporous spaces, which significantly increases both surface area and hydrogen storage capacity. The BET surface area (N2 at 77 K) was increased by ~ 12.5%, resulting in a ~ 25% increase of hydrogen adsorption after modification. MePIM also maintains the advantages of good processability and thermal stability. This work provides new insights on a facile polymer modification that enables enhanced gas sorption properties. Keywords Hydrogen storage · Porous polymers · Polymer of intrinsic microporosity · PIM-1 · Modified PIM-1
1 Introduction The preparation of new porous polymer membranes is receiving increasing attention by both academia and industry as a result of their potential for a number of important Electronic supplementary material The online version of this article (https://doi.org/10.1007/s10450-020-00239-y) contains supplementary material, which is available to authorized users. * Timothy J. Mays [email protected] 1
Department of Chemical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, UK
2
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK
3
Department of Engineering Mathematics, School of Chemistry, Bristol Composites Institute, University of Bristol, Bristol BS8 1UB, UK
4
Department of Mechanical Engineering, University of Bath, Claverton Down, Bath BA2 7AY, UK
5
Present Address: College of Engineering, Mathematics and Physical Sciences, University of Exeter, Harrison Building, Streatham Campus, N Park Rd, Exeter EX4 4QF, UK
applications. These include hydrogen storage (Rochat et al. 2017), hydrogen production and separation (Xu et al. 2017), CO2 separation and storage (Budd et al. 2005), and waste gas treatment (Kim et al. 2016). Solvent-processable adsorbents are advantageous over powders in terms of safety, handling and practical ease of large-scale manufacturing. Polymers of intrinsic microporosity (PIMs) are a widely investigated class of polymers with backbones composed of rigid ladder-like sequences with sites of contortion, which prohibits efficient packing in the solid state and creates a large free volume. Consequently
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