Theoretical Chemistry Accounts

, 136:130 | Cite as

Development of hydrophilicity on the proton exchange using sulfonic acid on PEEK in the presence of water: a density functional theory study

  • Taeyoon Kim
  • Yongju Kwon
  • Junbae Lee
  • Dongwoo Lee
  • Hyun Suk Shin
  • Min Cho
  • Soonchul Kwon
Regular Article


The introduction of a protogenic group such as sulfonic acid enables the operation of polymer electrolyte membrane for fuel cells at intermediate temperatures (> 100 °C) and very low humidity. It has been reported that the addition of a strongly acidic sulfonic acid group to hydrophobic polyether ether ketone (PEEK) creates the water permeability and proton transfer. In order to understand how sulfonic acid develops hydrophilicity, we conducted density functional theory calculations to determine the adsorption affinity of water for sulfonated PEEK (SPEEK), which represents the binding energy and band gap between HOMO (highest occupied molecular orbital) of SPEEK and LUMO (lowest unoccupied molecular orbital) of water molecules. Moreover, we designed disulfonated PEEKs (DSPEEK) with cis- and trans-conformations and found that cis-DSPEEK exhibits higher adsorption affinity for water with strong hydrogen bonds. This is attributed to the narrow energy gap of water molecules on cis-DSPEEK. Furthermore, we investigated proton adsorption in the presence of water to determine the effect of hydrophilic environment on the proton exchange in SPEEK. We found that cis-DSPEEK shows high repulsion for hydrogen transfer and moderate adsorption affinity for protons. Theoretical findings confirm that sulfonation ultimately yields hydrophilicity and developed proton transfer ability for PEEK, leading to a suitable structure for preferable proton exchange membrane.


PEEK Adsorption Hydrophilicity Proton transfer Density functional theory 



This subject is supported by Korea Ministry of Environment (MOE) as “Public Technology Program based on Environmental Policy” (Grant Number: 2016000200003).

Author contributions

The manuscript was written through the contributions of all authors. All the authors have given approval to the final version of the manuscript.

Compliance with ethical standards

Conflict of interest

The authors declares that they have no conflict of interest.


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Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.Department of Civil and Environmental EngineeringPusan National UniversityBusanRepublic of Korea
  2. 2.Division of Biotechnology, Advanced Institute of Environment and Bioscience, College of Environmental and Bioresource SciencesChonbuk National UniversityIksanRepublic of Korea

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