Enhancement of gas storage and separation properties of microporous polymers by simple chemical modifications

Owing to their large surface area and good solvent processability, polymers of intrinsic microporosity (PIMs) have been widely investigated for gas storage and separation processes. In this article, we show how chemically modifying the polymers can fine-tune their properties for specific, targeted applications. We find that converting the archetypal microporous polymer PIM-1 into a polycarboxylate salt enhances its separation capabilities for H2/CO2 mixtures (relevant to hydrogen production), whereas appending multiple amine groups significantly improves gas separation properties for N2/CO2 mixtures (relevant to flue gas treatment). Adsorption-based separation processes have received less attention than size-sieving processes in porous polymeric materials, however they could provide a suitable alternative technology to energy-intensive separation processes such as cryogenic distillation. We also report the hydrogen storage properties of the modified polymers, which we find to depend on the chemical modification carried out. By coupling the simplicity of the proposed chemical modifications with the scalability and porous properties of PIMs, we provide a blueprint to create new multifunctional materials with adapted properties for targeted applications.

[1]  C. Bowen,et al.  Chemical modification of the polymer of intrinsic microporosity PIM-1 for enhanced hydrogen storage , 2020, Adsorption.

[2]  G. Zhu,et al.  Porous Aromatic Frameworks (PAFs). , 2020, Chemical reviews.

[3]  N. Mac Dowell,et al.  Exploring the limits of adsorption-based CO2 capture using MOFs with PVSA – from molecular design to process economics , 2020 .

[4]  Joseph J. Richardson,et al.  Porous Inorganic and Hybrid Systems for Drug Delivery: Future Promise in Combatting Drug Resistance and Translation to Botanical Applications. , 2019, Current medicinal chemistry.

[5]  X. Tan,et al.  High Performance of PIM-1/ZIF-8 Composite Membranes for O2/N2 Separation , 2019, ACS omega.

[6]  J. S. Hoffman,et al.  Polymers with intrinsic microporosity chemical sorbents utilizing primary amine appendance through acid-base and hydrogen bonding interactions. , 2019, ACS applied materials & interfaces.

[7]  S. Brandani,et al.  Gas separation by adsorption: technological drivers and opportunities for improvement , 2019, Current Opinion in Chemical Engineering.

[8]  C. Bowen,et al.  Nanoporous polymer-based composites for enhanced hydrogen storage , 2019, Adsorption.

[9]  Mayur B. Kurade,et al.  Metal–organic frameworks (MOFs) for the removal of emerging contaminants from aquatic environments , 2019, Coordination Chemistry Reviews.

[10]  Craig M. Brown,et al.  Record High Hydrogen Storage Capacity in the Metal-Organic Framework Ni2(m-dobdc) at Near-Ambient Temperatures. , 2018, Chemistry of materials : a publication of the American Chemical Society.

[11]  Dan Zhao,et al.  Advanced Porous Materials in Mixed Matrix Membranes , 2018, Advanced materials.

[12]  Neil B. McKeown,et al.  Gas Permeation Properties, Physical Aging, and Its Mitigation in High Free Volume Glassy Polymers. , 2018, Chemical reviews.

[13]  Hao Li,et al.  Recent advances in gas storage and separation using metal–organic frameworks , 2018 .

[14]  R. Mokaya,et al.  Oxygen-rich microporous carbons with exceptional hydrogen storage capacity , 2017, Nature Communications.

[15]  C. Bowen,et al.  Hydrogen storage in polymer-based processable microporous composites , 2017 .

[16]  N. McKeown.  The synthesis of polymers of intrinsic microporosity (PIMs) , 2017, Science China Chemistry.

[17]  Z. Wang,et al.  Polymers of intrinsic microporosity/metal–organic framework hybrid membranes with improved interfacial interaction for high-performance CO2 separation , 2017 .

[18]  Zhongyi Jiang,et al.  Mixed matrix membranes comprising polymers of intrinsic microporosity and covalent organic framework for gas separation , 2017 .

[19]  I. Pinnau,et al.  Soluble Polymers with Intrinsic Porosity for Flue Gas Purification and Natural Gas Upgrading , 2017, Advanced materials.

[20]  Xiao‐Yu Yang,et al.  Applications of Hierarchically Structured Porous Materials from Energy Storage and Conversion, Catalysis, Photocatalysis, Adsorption, Separation, and Sensing to Biomedicine , 2016 .

[21]  M. Hirscher,et al.  The usable capacity of porous materials for hydrogen storage , 2016 .

[22]  M. Hirscher,et al.  Outlook and challenges for hydrogen storage in nanoporous materials , 2016 .

[23]  T. Darwish,et al.  Hydrogen Storage in the Expanded Pore Metal–Organic Frameworks M2(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn) , 2016 .

[24]  Z. Bao,et al.  Chiral polymers of intrinsic microporosity: selective membrane permeation of enantiomers. , 2015, Angewandte Chemie.

[25]  Nuno Bimbo,et al.  High volumetric and energy densities of methane stored in nanoporous materials at ambient temperatures and moderate pressures , 2015 .

[26]  D. F. Kennedy,et al.  Gas-separation membranes loaded with porous aromatic frameworks that improve with age. , 2015, Angewandte Chemie.

[27]  Zafer Kahveci,et al.  Application of pyrene-derived benzimidazole-linked polymers to CO2 separation under pressure and vacuum swing adsorption settings , 2014 .

[28]  M. Sevilla,et al.  Energy storage applications of activated carbons: supercapacitors and hydrogen storage , 2014 .

[29]  T. Mays,et al.  Isosteric enthalpies for hydrogen adsorbed on nanoporous materials at high pressures , 2014, Adsorption.

[30]  Paul A. Webley,et al.  Adsorption technology for CO2 separation and capture: a perspective , 2014, Adsorption.

[31]  Christopher R. Mason,et al.  Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification , 2014, Macromolecules.

[32]  Nuno Bimbo,et al.  Analysis of optimal conditions for adsorptive hydrogen storage in microporous solids , 2013 .

[33]  T. Mays,et al.  Supercritical hydrogen adsorption in nanostructured solids with hydrogen density variation in pores , 2013, Adsorption.

[34]  Hasmukh A. Patel,et al.  Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous covalent organic polymers , 2013, Nature Communications.

[35]  T. Mays,et al.  Analysis of hydrogen storage in nanoporous materials for low carbon energy applications. , 2011, Faraday discussions.

[36]  Andrew I. Cooper,et al.  Chemical tuning of CO2 sorption in robust nanoporous organic polymers , 2011 .

[37]  Rajamani Krishna,et al.  Porous Polymer Networks: Synthesis, Porosity, and Applications in Gas Storage/Separation , 2010 .

[38]  Chongli Zhong,et al.  Molecular simulation of carbon dioxide/methane/hydrogen mixture adsorption in metal-organic frameworks. , 2006, The journal of physical chemistry. B.

[39]  Neil B. McKeown,et al.  Solution‐Processed, Organophilic Membrane Derived from a Polymer of Intrinsic Microporosity , 2004 .

[40]  Heping Ma,et al.  Novel lithium-loaded porous aromatic framework for efficient CO2 and H2 uptake , 2013 .

[41]  P. Llewellyn,et al.  Is the bet equation applicable to microporous adsorbents , 2007 .

[42]  Alan L. Myers,et al.  Thermodynamics of mixed‐gas adsorption , 1965 .