Highly permeable and selective mixed-matrix membranes for hydrogen separation containing PAF-1

Hou, Rujing; Ghanem, Bader S.; Smith, Stefan J. D.; Doherty, Cara M.; Setter, Caitlin J.; Wang, Huanting; Pinnau, Ingo; Hill, Matthew R.

doi:10.1039/d0ta05071g

Cited by 38 publications

(18 citation statements)

References 36 publications

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“…In fact, it has been shown to improve membrane permeability, selectivity, or sometimes both. This improvement has been detected both for pure non-TR-able polymers [33] and also for thermally rearrangeable ones [34][35][36][37].…”

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confidence: 74%

Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement

et al. 2021

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Mixed matrix membranes (MMMs) consisting of a blend of a hydroxypolyamide (HPA) matrix and variable loads of a porous polymer network (PPN) were thermally treated to induce the transformation of HPA to polybenzoxazole (β-TR-PBO). Here, the HPA matrix was a hydroxypolyamide having two hexafluoropropyilidene moieties, 6FCl-APAF, while the PPN was prepared by reacting triptycene (TRP) and trifluoroacetophenone (TFAP) in a superacid solution. The most probable size of the PPN particles was 75 nm with quite large distributions. The resulting membranes were analyzed by SEM and AFM. Up to 30% PPN loads, both SEM and AFM images confirmed quite planar surfaces, at low scale, with limited roughness. Membranes with high hydrogen permeability and good selectivity for the gas pairs H2/CH4 and H2/N2 were obtained. For H2/CO2, selectivity almost vanished after thermal rearrangement. In all cases, their hydrogen permeability increased with increasing loads of PPN until around 30% PPN with ulterior fairly abrupt decreasing of permeability for all gases studied. Thermal rearrangement of the MMMs resulted in higher permeabilities but lower selectivities. For all the membranes and gas pairs studied, the balance of permeability vs. selectivity surpassed the 1991 Robeson’s upper bound, and approached or even exceeded the 2008 line, for MMMs having 30% PPN loads. In all cases, the HPA-MMMs before thermal rearrangement provided good selectivity versus permeability compromise, similar to their thermally rearranged counterparts but in the zone of high selectivity. For H2/CH4, H2/N2, these nonthermally rearranged MMMs approach the 2008 Robeson’s upper bound while H2/CO2 gives selective transport favoring H2 on the 1991 Robeson’s bound. Thus, attending to the energy cost of thermal rearrangement, it could be avoided in some cases especially when high selectivity is the target rather than high permeability.

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confidence: 74%

Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement

et al. 2021

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“…Notably, this also exceeded the performance of several native and composite membranes fabricated from other advanced high fractional free volume polymers (Figure ) . These included pure membranes (thermal rearranged (TR), TPIM-1, PIM-Trip-TB, and PIM-EA-TB) ,, and composite membranes (PTMSP/PAF-1, PIM-1/ p -DCX, and TPIM-2/PAF-1). , All of these membrane performance details can be found in Table S5.…”

Section: Resultsmentioning

confidence: 99%

“…These included pure membranes (thermal rearranged (TR), TPIM-1, PIM-Trip-TB, and PIM-EA-TB) 18,19,51 and composite membranes (PTMSP/PAF-1, PIM-1/p-DCX, and TPIM-2/PAF-1). 46,52 All of these membrane performance details can be found in Table S5. Significant enhancement in gas selectivities is relatively rare among for high free volume polymer MMMs as the addition of porous additives usually increases the speed of guest transport, although not much in terms of improving the size-sieving effect.…”

Section: ■ Introductionmentioning

confidence: 99%

Greatly Enhanced Gas Selectivity in Mixed-Matrix Membranes through Size-Controlled Hyper-cross-linked Polymer Additives

Hou

O’Loughlin

Ackroyd

et al. 2020

Ind. Eng. Chem. Res.

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Membrane technology without a phase-change process has demonstrated its low-cost, high-energy-efficiency advantages. High fractional free volume polymers of intrinsic microporosity (PIMs), such as poly(1-trimethylsilyl-1-propyne) (PTMSP), are known for high permeability but disappointing gas selectivity. Porous aromatic frameworks and hyper-cross-linked polymers (HCPs) are effective membrane additives; however, prior works have examined their performance through chemical interactions and other material characteristics. Using a recently developed facile and scalable controlled HCP synthesis method, the size effect of these additives can now be investigated. In this work, HCPs with gradually increasing molecular weight/particle size were combined to investigate the performance and mixing/dispersion behavior in PTMSP mixed-matrix membranes. Unexpectedly, the largest dispersible additive (V125E) resulted in a membrane with drastically higher selectivity (H 2 /CH 4 = +690%) and similar H 2 permeability, which is a performance above the 2015 upper bound for H 2 gas pairs. With identical additive affinity/compatibility, we demonstrate the benefit of size-controlled HCP additives for enhancing membrane performance.

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“…Owing to the sufficient HCP-PTMSP interaction and efficient dispersion of the HCP particles, H 2 /CH 4 and H 2 /N 2 selectivity were enhanced by 690% and 540%, reaching up to 22 and 30, respectively. The same group also added PAF-1 additives into the highly permeable TPIM-2 polymer matrix, leading to simultaneous improvement in the H 2 permeability, H 2 /N 2 selectivity, and long-term stability of the MMM [ 126 ]. PAF-1 was also used to elevate the H 2 separation performance of PIM-1 membranes.…”

Section: Mixed-matrix Membranes For Hydrogen Separationmentioning

confidence: 99%

Recent Progress in Mixed-Matrix Membranes for Hydrogen Separation

et al. 2021

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Membrane separation is a compelling technology for hydrogen separation. Among the different types of membranes used to date, the mixed-matrix membranes (MMMs) are one of the most widely used approaches for enhancing separation performances and surpassing the Robeson upper bound limits for polymeric membranes. In this review, we focus on the recent progress in MMMs for hydrogen separation. The discussion first starts with a background introduction of the current hydrogen generation technologies, followed by a comparison between the membrane technology and other hydrogen purification technologies. Thereafter, state-of-the-art MMMs, comprising emerging filler materials that include zeolites, metal-organic frameworks, covalent organic frameworks, and graphene-based materials, are highlighted. The binary filler strategy, which uses two filler materials to create synergistic enhancements in MMMs, is also described. A critical evaluation on the performances of the MMMs is then considered in context, before we conclude with our perspectives on how MMMs for hydrogen separation can advance moving forward.

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Highly permeable and selective mixed-matrix membranes for hydrogen separation containing PAF-1

Abstract:
As the potential for a Hydrogen economy re-emerges globally, its distribution is a key enabling capability to master. One option is to utilise the existing reticulated natural gas infrastructure, mixing...

Cited by 38 publications

References 36 publications

Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement

Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement

Greatly Enhanced Gas Selectivity in Mixed-Matrix Membranes through Size-Controlled Hyper-cross-linked Polymer Additives

Recent Progress in Mixed-Matrix Membranes for Hydrogen Separation

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Highly permeable and selective mixed-matrix membranes for hydrogen separation containing PAF-1

Abstract: As the potential for a Hydrogen economy re-emerges globally, its distribution is a key enabling capability to master. One option is to utilise the existing reticulated natural gas infrastructure, mixing...

Cited by 38 publications

References 36 publications

Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement

Hydrogen Recovery by Mixed Matrix Membranes Made from 6FCl-APAF HPA with Different Contents of a Porous Polymer Network and Their Thermal Rearrangement

Greatly Enhanced Gas Selectivity in Mixed-Matrix Membranes through Size-Controlled Hyper-cross-linked Polymer Additives

Recent Progress in Mixed-Matrix Membranes for Hydrogen Separation

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Abstract:
As the potential for a Hydrogen economy re-emerges globally, its distribution is a key enabling capability to master. One option is to utilise the existing reticulated natural gas infrastructure, mixing...