Aqueous proton transfer across single-layer graphene

Aqueous proton transfer across single-layer graphene

Proton transfer across single-layer graphene proceeds with large computed energy barriers and is therefore thought to be unfavourable at room temperature unless nanoscale holes or dopants are introduced, or a potential bias is applied. Here we subject single-layer graphene supported on fused silica...

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Main Authors: Achtyl, Jennifer L., Unocic, Raymond R., Xu, Lijun, Cai, Yu, Raju, Muralikrishna, Zhang, Weiwei, Sacci, Robert L., Vlassiouk, Ivan V., Fulvio, Pasquale F., Ganesh, Panchapakesan, Wesolowski, David J., Dai, Sheng, van Duin, Adri C. T., Neurock, Matthew, Geiger, Franz M.
Format: Online
Language:English
Published: Nature Pub. Group 2015
Online Access:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4382684/
id pubmed-4382684
recordtype oai_dc
spelling pubmed-43826842015-04-07 Aqueous proton transfer across single-layer graphene Achtyl, Jennifer L. Unocic, Raymond R. Xu, Lijun Cai, Yu Raju, Muralikrishna Zhang, Weiwei Sacci, Robert L. Vlassiouk, Ivan V. Fulvio, Pasquale F. Ganesh, Panchapakesan Wesolowski, David J. Dai, Sheng van Duin, Adri C. T. Neurock, Matthew Geiger, Franz M. Article Proton transfer across single-layer graphene proceeds with large computed energy barriers and is therefore thought to be unfavourable at room temperature unless nanoscale holes or dopants are introduced, or a potential bias is applied. Here we subject single-layer graphene supported on fused silica to cycles of high and low pH, and show that protons transfer reversibly from the aqueous phase through the graphene to the other side where they undergo acid–base chemistry with the silica hydroxyl groups. After ruling out diffusion through macroscopic pinholes, the protons are found to transfer through rare, naturally occurring atomic defects. Computer simulations reveal low energy barriers of 0.61–0.75 eV for aqueous proton transfer across hydroxyl-terminated atomic defects that participate in a Grotthuss-type relay, while pyrylium-like ether terminations shut down proton exchange. Unfavourable energy barriers to helium and hydrogen transfer indicate the process is selective for aqueous protons. Nature Pub. Group 2015-03-17 /pmc/articles/PMC4382684/ /pubmed/25781149 http://dx.doi.org/10.1038/ncomms7539 Text en Copyright © 2015, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved. http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
repository_type Open Access Journal
institution_category Foreign Institution
institution US National Center for Biotechnology Information
building NCBI PubMed
collection Online Access
language English
format Online
author Achtyl, Jennifer L.
Unocic, Raymond R.
Xu, Lijun
Cai, Yu
Raju, Muralikrishna
Zhang, Weiwei
Sacci, Robert L.
Vlassiouk, Ivan V.
Fulvio, Pasquale F.
Ganesh, Panchapakesan
Wesolowski, David J.
Dai, Sheng
van Duin, Adri C. T.
Neurock, Matthew
Geiger, Franz M.
spellingShingle Achtyl, Jennifer L.
Unocic, Raymond R.
Xu, Lijun
Cai, Yu
Raju, Muralikrishna
Zhang, Weiwei
Sacci, Robert L.
Vlassiouk, Ivan V.
Fulvio, Pasquale F.
Ganesh, Panchapakesan
Wesolowski, David J.
Dai, Sheng
van Duin, Adri C. T.
Neurock, Matthew
Geiger, Franz M.
Aqueous proton transfer across single-layer graphene
author_facet Achtyl, Jennifer L.
Unocic, Raymond R.
Xu, Lijun
Cai, Yu
Raju, Muralikrishna
Zhang, Weiwei
Sacci, Robert L.
Vlassiouk, Ivan V.
Fulvio, Pasquale F.
Ganesh, Panchapakesan
Wesolowski, David J.
Dai, Sheng
van Duin, Adri C. T.
Neurock, Matthew
Geiger, Franz M.
author_sort Achtyl, Jennifer L.
title Aqueous proton transfer across single-layer graphene
title_short Aqueous proton transfer across single-layer graphene
title_full Aqueous proton transfer across single-layer graphene
title_fullStr Aqueous proton transfer across single-layer graphene
title_full_unstemmed Aqueous proton transfer across single-layer graphene
title_sort aqueous proton transfer across single-layer graphene
description Proton transfer across single-layer graphene proceeds with large computed energy barriers and is therefore thought to be unfavourable at room temperature unless nanoscale holes or dopants are introduced, or a potential bias is applied. Here we subject single-layer graphene supported on fused silica to cycles of high and low pH, and show that protons transfer reversibly from the aqueous phase through the graphene to the other side where they undergo acid–base chemistry with the silica hydroxyl groups. After ruling out diffusion through macroscopic pinholes, the protons are found to transfer through rare, naturally occurring atomic defects. Computer simulations reveal low energy barriers of 0.61–0.75 eV for aqueous proton transfer across hydroxyl-terminated atomic defects that participate in a Grotthuss-type relay, while pyrylium-like ether terminations shut down proton exchange. Unfavourable energy barriers to helium and hydrogen transfer indicate the process is selective for aqueous protons.
publisher Nature Pub. Group
publishDate 2015
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4382684/
_version_ 1613206625936474112

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