Hydrogen storage in polymer-based processable microporous composites

Rochat, Sébastien; Polak-Kraśna, Katarzyna; Tian, Mi; Holyfield, Leighton; Mays, Timothy J.; Bowen, Christopher R.; Burrows, Andrew D.

doi:10.1039/c7ta05232d

Cited by 52 publications

(48 citation statements)

References 40 publications

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“…On average, the determined BET surface area was 761 m 2 g -1 , which is within the expected range for thin films made of PIM-1. [17,33] At a pressure of 100 kPa, the hydrogen uptake of the polymer was similarly found to be constant over time. Within the experimental error of such measurements, the average hydrogen uptake at 100 kPa and 77 K is 0.81 wt%, which is consistent with values reported in prior articles.…”

Section: Resultsmentioning

confidence: 90%

“…PIM-1 was prepared and characterised according to published procedures, [17,33] and a polymer with a number-average molecular weight (Mn) of 55 000 g mol -1 and a polydispersity index of 5.1 was obtained. Self-standing PIM-1 films were prepared by casting chloroform solutions (2 wt%) in covered glass Petri dishes (20 cm diameter) to allow slow evaporation over 1-2 days.…”

Section: Methodsmentioning

confidence: 99%

“…[12,19,29,30] Our group recently studied the capacity of PIM-1 for hydrogen storage and its mechanical properties, [31,32] and demonstrated that its relatively limited surface area and hydrogen uptake capacity can be significantly enhanced by addition of high-surface area fillers. [33] An important parameter to consider when evaluating these materials is their long-term behaviour and stability. For example, the ultimate target for durability issued by the U.S. Department of Energy (DoE) mentions 1500 charging/discharging cycles over 15 years.…”

Section: Introductionmentioning

confidence: 99%

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Assessment of the long-term stability of the polymer of intrinsic microporosity PIM-1 for hydrogen storage applications

Rochat

Polak-Kraśna

Tian

et al. 2019

International Journal of Hydrogen Energy

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Polymers of intrinsic microporosity, such as PIM-1, advantageously combine high surface areas with good processability, which are attractive properties for hydrogen storage applications. Here we address the lack of data on the long-term mechanical stability and hydrogen uptake capacity of PIM-1 in a study carried out over 400 days. Our results show that most mechanical and surface properties of PIM-1 remain stable over this time. In particular, the mechanical strength and elasticity are maintained, and the surface area remains constant over the course of our observations. In contrast, we detected a small but statistically significant decrease of the hydrogen storage capacity of the material over time, particularly in the first stages of aging. We attribute this phenomenon to the slow rearrangement of the polymer scaffold in the solid state. Taken together, our experiments demonstrate that PIM-1 possesses the long-term stability required for realistic applications in hydrogen storage or in gas separation.

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Section: Resultsmentioning

confidence: 90%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Assessment of the long-term stability of the polymer of intrinsic microporosity PIM-1 for hydrogen storage applications

Rochat

Polak-Kraśna

Tian

et al. 2019

International Journal of Hydrogen Energy

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“…For example, a series of poly(aryleneethynylene) MOPs were prepared by varying the “strut” length in the network through a Sonogashira–Hagihara crosscoupling route, and it was demonstrated that the average micropore size, the micropore volume, and the BET surface area could be finely tuned. On account of the well‐defined porosities and large surface areas, MOPs demonstrate excellent performance for gas storage and gas separation . Moreover, MOPs with incorporated heteroatoms such as S, N, O have unique physical and chemical characteristics, which can be rationally applied in catalysis, photoconductivity devices, sensors, and energy‐storage materials .…”

Section: C/n Molar Ratio Band Gap and Catalytic Rate Constants Of Smentioning

confidence: 99%

Band Structure Engineering of Schiff‐Base Microporous Organic Polymers for Enhanced Visible‐Light Photocatalytic Performance

Xiao

Huang

Zhao

et al. 2019

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Recently, microporous organic polymers (MOPs) such as hypercrosslinked polymers, [1,2] polymers of intrinsic microporosity (PIMs), [3,4] and covalent organic frameworks (COFs) [5,6] have attracted increasing scientific and practical interest. The structures and properties of these materials, which are synthesized by bottom-up methods, can be adjusted via the rational choice of the aromatic units with a range of functional groups. For example, a series of poly(aryleneethynylene) MOPs were prepared by varying the "strut" length in the network through a Sonogashira-Hagihara crosscoupling route, [7,8] and it was demonstrated that the average micropore size, the micropore volume, and the BET surface area could be finely tuned. On account of the well-defined porosities and large surface areas, MOPs demonstrate excellent performance for gas storage and gas separation. [9][10][11][12] Moreover, MOPs with incorporated heteroatoms such as S, N, O have unique physical and Schiff-base networks (SBNs), as typical examples of nitrogen-doped microporous organic polymers (MOPs), exhibit promising application prospects owing to their stable properties and tunable chemical structures. However, their band structure engineering, which plays a key role in optical properties, remains elusive due to the complicated mechanisms behind energy level adjustment. In this work, a series of SBNs are fabricated by tailoring the ratio of p-phthalaldehyde and o-phthalaldehyde in the Schiff-base chemistry reaction with melamine, resulting in a straightforward as well as continuous tuning of their band gaps ranging from 4. 4 to 1.4 eV. Consequently, SBNs can be successfully used as photocatalysts with excellent visible-light photocatalytic activity even under metal-free conditions. Significantly, electronic structures of SBNs are systematically studied by electrochemical and spectroscopic characterizations, demonstrating that the enhanced performance is ascribed to proper band structure and improved charge separation ability. More importantly, in combination with theoretical calculations, the band structure regulation mechanism and band structure-photocatalytic property relationship are deeply disclosed. The results obtained from this study will not only furnish SBN materials with excellent performance for solar energy conversion, but also open up elegant protocols for the molecular engineering of MOPs with desirable band structures.

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“…A maximum excess hydrogen uptake of 1.66 wt % at 32 bar for powder and 1.59 wt % at 29 bar for the film were reported. Later, Rochat et al . reported on the mechanical properties and hydrogen uptake capacity of composite‐based PIM‐1 containing the porous aromatic framework, PAF‐1.…”

Section: Introductionmentioning

confidence: 99%

The Effect of Thermal Treatment on the Hydrogen‐Storage Properties of PIM‐1

et al. 2019

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There has been recent interest in polymers of intrinsic microporosity (PIMs) for solid‐state hydrogen‐storage materials; however, the gas‐sorption properties and conditions for hydrogen uptake are relatively unexplored. PIM‐1 has been synthesised using the condensation reaction between 3,3,3,3‐tetramethyl‐1,1‐spirobisindane‐5,5,6,6‐tetraol and 2,3,5,6‐tetrafluorophthalonitrile as precursors. The synthesised PIM‐1 was annealed at different temperatures for varying times and then characterised for hydrogen uptake at both ambient and cryogenic temperatures. The excess hydrogen PCT isotherms have been measured to high pressure (320 bar) for the first time and the effect of different annealing conditions on the hydrogen capacity is reported.

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Hydrogen storage in polymer-based processable microporous composites

Abstract: Microporous polymer-based membranes (PIM-1) doped with a porous aromatic framework (PAF-1) combine mechanical flexibility with enhanced hydrogen uptake capacities: they can potentially store up to 6.7 wt% H2 at 77 K.

Cited by 52 publications

References 40 publications

Assessment of the long-term stability of the polymer of intrinsic microporosity PIM-1 for hydrogen storage applications

Assessment of the long-term stability of the polymer of intrinsic microporosity PIM-1 for hydrogen storage applications

Band Structure Engineering of Schiff‐Base Microporous Organic Polymers for Enhanced Visible‐Light Photocatalytic Performance

The Effect of Thermal Treatment on the Hydrogen‐Storage Properties of PIM‐1

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