Formation of an ion-free crystalline carbon nitride and its reversible intercalation with ionic species and molecular water

Suter, Theo; Miller, Thomas S.; Cockcroft, Jeremy K.; Aliev, Abil E.; Wilding, Martin C.; Sella, Andrea; Corà, Furio; Howard, Christopher A.; McMillan, Paul F.

doi:10.1039/c8sc05232h

Cited by 43 publications

(89 citation statements)

References 45 publications

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“…Rapid water transport that more closely resembles the directional transport of single H 2 O molecules through AQP channels has been reported within subnanometerdiameter carbon nanotubes (CNTs) embedded in lipid membranes (14)(15)(16)(17). Here, we report diffusion of single H 2 O molecules on a time scale equal to that in AQP channels across the interlayer spacing and through the aligned C 12 N 12 H 3 ring pores within the stacked graphene-like layers of crystalline carbon nitride with a polytriazine imide (PTI) structure (18)(19)(20). The molecules undergo a sequence of orientation reversals choreographed by H-bonding interactions with ─N═ and ─NH═ species surrounding the ring voids within the carbon nitride layers to provide a transport mechanism that resembles that of H 2 O molecules transiting through biological AQP channels.…”

Section: Introductionmentioning

confidence: 63%

“…These layered structures contained Li + and Cl − or Br − ions intercalated between the stacked carbon nitride sheets or within the C 12 N 12 rings, partially replacing H + in the case of Li + ions ( 18 – 20 ). Samples of intercalant-free IF-PTI were then produced by extracting the included ions into water followed by drying ( 19 ). Chemical analysis results were consistent with a layer composition C 6 N 9 H 3 (table S1).…”

Section: Resultsmentioning

confidence: 99%

“…Our crystalline PTI starting materials for this study were obtained by reacting dicyandiamide in eutectic LiCl/KCl or LiBr/KBr molten salt mixtures. These layered structures contained Li + and Cl − or Br − ions intercalated between the stacked carbon nitride sheets or within the C 12 N 12 rings, partially replacing H + in the case of Li + ions (18)(19)(20). Samples of intercalant-free IF-PTI were then produced by extracting the included ions into water followed by drying (19).…”

Section: Synthesis and Characterization Of Intercalant-free (If-)-ptimentioning

confidence: 99%

“…The intercalated Li + and halide ions were removed by continuously washing the samples in H 2 O via Sohxlet extraction over a period of 15 to 21 days. The result was a fully deintercalated crystalline PTI material (IF-PTI) with a layered structure and composition C 6 N 9 H 3 (19). The reversible uptake of atmospheric H 2 O was determined by TGA and FTIR spectroscopy with changes in layer stacking and interlayer spacings studied by powder XRD.…”

Section: Sample Preparationmentioning

confidence: 99%

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Aquaporin-like water transport in nanoporous crystalline layered carbon nitride

et al. 2020

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Designing next-generation fuel cell and filtration devices requires the development of nanoporous materials that allow rapid and reversible uptake and directed transport of water molecules. Here, we combine neutron spectroscopy and first-principles calculations to demonstrate rapid transport of molecular H2O through nanometer-sized voids ordered within the layers of crystalline carbon nitride with a polytriazine imide structure. The transport mechanism involves a sequence of molecular orientation reversals directed by hydrogen-bonding interactions as the neutral molecules traverse the interlayer gap and pass through the intralayer voids that show similarities with the transport of water through transmembrane aquaporin channels in biological systems. The results suggest that nanoporous layered carbon nitrides can be useful for developing high-performance membranes.

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Section: Introductionmentioning

confidence: 63%

Section: Resultsmentioning

confidence: 99%

Section: Synthesis and Characterization Of Intercalant-free (If-)-ptimentioning

confidence: 99%

Section: Sample Preparationmentioning

confidence: 99%

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Aquaporin-like water transport in nanoporous crystalline layered carbon nitride

et al. 2020

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“…poly(triazine imide) or LiBr . poly(triazine imide) may be also regarded to this class. Synthesis, properties and application of metal intercalated carbon nitrides may be found in the review …”

Section: Introductionmentioning

confidence: 99%

Ionic Carbon Nitrides in Solar Hydrogen Production and Organic Synthesis: Exciting Chemistry and Economic Advantages

Savateev

Antonietti

2019

ChemCatChem

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Molecular photoredox complexes from the platinum group paved the way of organic photocatalysis. However, high price and difficulties related to removal and recycling hamper application of such complexes on the larger scale. Carbon nitride semiconductor photocatalysts are deprived at large extent of such limitations. Herein, we summarize application of ionic carbon nitrides in photocatalysis. A salt-like structure of ionic carbon nitrides comprising negatively charged poly (heptazine imide) anion and positively charged alkali metal cations gives rise to a number of unique properties and high activity in photocatalysis. The performance of ionic carbon nitrides in H 2 generation is up to 100 times higher compared with the covalent graphitic carbon nitrides. Eleven photocatalytic reactions mediated by ionic carbon nitrides and their long-lived radicals are reviewed. Economy of using carbon nitride photocatalysts in comparison with the photoredox complexes from the platinum group has been analyzed.

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Nafion Matrix and Ionic Domain Tuning for High‐Performance Composite Proton Exchange Membranes

Smith

Foglia

Clancy

et al. 2023

Adv Funct Materials

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Although proton exchange membranes (PEMs) are widely deployed in an array of commercial applications, limitations linked to their proton conductivity, water retention, and gas permeability still limit ultimate device performance. While ex situ studies have shown additives can enhance membrane stability and mass transport, to date few have demonstrated that these performance enhancements are maintained when tested in commercially relevant electrochemical technologies, such as fuel cells or electrolyzers. Herein, a new multifunctional additive, 2D poly(triazine imide) (PTI), is demonstrated for composite PEMs, which is shown to boost proton conductivity by 37% under optimal high relative humidity (RH) conditions and 67% at low RHs. PTI also enables major improvements (over 55%) in both current and power densities in industrially relevant PEM fuel cells (PEMFCs). Most importantly, in situ and ex situ characterization suggests that the enhanced performance is due to polymer aggregate‐PTI clusters that form with increasing 2D character and improved long‐range connectivity, while acid‐base interactions with pyridinic nitrogen facilitate the critical proton hopping mechanism at all RHs. Hence, this work offers both a new membrane concept with proven benefits for important electrochemical technologies, as well as design principles for future optimization of proton transport and water management within PEMs.

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Formation of an ion-free crystalline carbon nitride and its reversible intercalation with ionic species and molecular water

Abstract: Crystalline layered carbon nitrides can be inter-converted by simple ion exchange process allowing their properties to be tuned.

Cited by 43 publications

References 45 publications

Aquaporin-like water transport in nanoporous crystalline layered carbon nitride

Aquaporin-like water transport in nanoporous crystalline layered carbon nitride

Ionic Carbon Nitrides in Solar Hydrogen Production and Organic Synthesis: Exciting Chemistry and Economic Advantages

Nafion Matrix and Ionic Domain Tuning for High‐Performance Composite Proton Exchange Membranes

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