skip to main content


This content will become publicly available on December 1, 2024

Title: Search for a Grotthuss mechanism through the observation of proton transfer
Abstract The transport of protons is critical in a variety of bio- and electro-chemical processes and technologies. The Grotthuss mechanism is considered to be the most efficient proton transport mechanism, generally implying a transfer of protons between ‘chains’ of host molecules via elementary reactions within the hydrogen bonds. Although Grotthuss proposed this concept more than 200 years ago, only indirect experimental evidence of the mechanism has been observed. Here we report the first experimental observation of proton transfer between the molecules in pure and 85% aqueous phosphoric acid. Employing dielectric spectroscopy, quasielastic neutron, and light scattering, and ab initio molecular dynamic simulations we determined that protons move by surprisingly short jumps of only ~0.5–0.7 Å, much smaller than the typical ion jump length in ionic liquids. Our analysis confirms the existence of correlations in these proton jumps. However, these correlations actually reduce the conductivity, in contrast to a desirable enhancement, as is usually assumed by a Grotthuss mechanism. Furthermore, our analysis suggests that the expected Grotthuss-like enhancement of conductivity cannot be realized in bulk liquids where ionic correlations always decrease conductivity.  more » « less
Award ID(s):
2102425
NSF-PAR ID:
10421878
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Communications Chemistry
Volume:
6
Issue:
1
ISSN:
2399-3669
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Currently, completely abiotic channel systems that concurrently reproduce the high selectivity and high permeation rate of natural protein channels are rare. Here, we provide one such biomimetic channel system, i.e., a novel family of helically folded hybrid amide foldamers that can serve as powerful artificial proton channels to mimic key transport features of the exceptionally selective Matrix‐2 (M2) proton channels. Possessing an angstrom‐scale tubular pore 3 Å in diameter, these low water permeability artificial channels transport protons at a rate 1.22 and 11 times as fast as gramicidin A and M2 channels, respectively, with exceptionally high selectivity factors of 167.6, 122.7, and 81.5 over Cl, Na+, and K+ions. Based on the experimental and computational findings, we propose a novel proton transport mechanism where a proton may create a channel‐spanning water chain from two or more short water chains to facilitate its own transmembrane flux via the Grotthuss mechanism.

     
    more » « less
  2. Abstract

    Currently, completely abiotic channel systems that concurrently reproduce the high selectivity and high permeation rate of natural protein channels are rare. Here, we provide one such biomimetic channel system, i.e., a novel family of helically folded hybrid amide foldamers that can serve as powerful artificial proton channels to mimic key transport features of the exceptionally selective Matrix‐2 (M2) proton channels. Possessing an angstrom‐scale tubular pore 3 Å in diameter, these low water permeability artificial channels transport protons at a rate 1.22 and 11 times as fast as gramicidin A and M2 channels, respectively, with exceptionally high selectivity factors of 167.6, 122.7, and 81.5 over Cl, Na+, and K+ions. Based on the experimental and computational findings, we propose a novel proton transport mechanism where a proton may create a channel‐spanning water chain from two or more short water chains to facilitate its own transmembrane flux via the Grotthuss mechanism.

     
    more » « less
  3. We used equilibrium and non-equilibrium atomistic simulations to probe the influence of anion chemistry on the true conductivity, dynamical correlations, and ion transport mechanisms in polymeric ionic liquids. An inverse correlation was found between anion self-diffusivities, ionic mobilities, and the anion size for spherical anions. While some larger asymmetric anions had higher diffusivities than smaller spherical anions, their diffusivities and mobilities did not exhibit a direct correlation to the anion volumes. The conductivity and anion dynamical correlations also followed the same trends as displayed by the diffusivity and mobility of anions. All the systems we examined displayed positively correlated motion among anions, suggesting a contribution that enhances the conductivity beyond the ideal Nernst–Einstein value. Analysis of ion transport mechanisms demonstrated very similar hopping characteristics among the spherical anions despite differences in their sizes.

     
    more » « less
  4. Abstract

    Ionic liquids (ILs) have shown to be promising additives to the catalyst layer to enhance oxygen reduction reaction in polymer electrolyte fuel cells. However, fundamental understanding of their role in complex catalyst layers in practically relevant membrane electrode assembly environment is needed for rational design of highly durable and active platinum-based catalysts. Here we explore three imidazolium-derived ionic liquids, selected for their high proton conductivity and oxygen solubility, and incorporate them into high surface area carbon black support. Further, we establish a correlation between the physical properties and electrochemical performance of the ionic liquid-modified catalysts by providing direct evidence of ionic liquids role in altering hydrophilic/hydrophobic interactions within the catalyst layer interface. The resulting catalyst with optimized interface design achieved a high mass activity of 347 A g−1Ptat 0.9 V under H2/O2, power density of 0.909 W cm−2under H2/air and 1.5 bar, and had only 0.11 V potential decrease at 0.8 A cm−2after 30 k accelerated stress test cycles. This performance stems from substantial enhancement in Pt utilization, which is buried inside the mesopores and is now accessible due to ILs addition.

     
    more » « less
  5. As known, small HCl–water nanoclusters display a particular dissociation behaviour, whereby at least four water molecules are required for the ionic dissociation of HCl. In this work, we examine how intermolecular interactions promote the ionic dissociation of such nanoclusters. To this end, a set of 45 HCl–water nanoclusters with up to four water molecules is introduced. Energy decomposition analysis based on absolutely localized molecular orbitals (ALMO-EDA) is employed in order to study the importance of frozen interaction, dispersion, polarization, and charge-transfer for the dissociation. The vertical ALMO-EDA scheme is applied to HCl–water clusters along a proton-transfer coordinate varying the amount of spectator water molecules. The corresponding ALMO-EDA results show a clear preference for the dissociated cluster only in the presence of four water molecules. Our analysis of adiabatic ALMO-EDA results reveals a push–pull mechanism for the destabilization of the HCl bond based on the synergy between forward and backward charge-transfer. 
    more » « less