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Title: Strong Differential Monovalent Anion Selectivity in Narrow Diameter Carbon Nanotube Porins

Abstract

Inner pores of carbon nanotubes combine extremely fast water transport and ion selectivity that could potentially be useful for high-performance water desalination and separation applications. In this study, we used dye-quenching halide assays and stopped-flow spectrometry to determine intrinsic permeability of three small monovalent halide anions (chloride, bromide, iodide) and one pseudohalide anion (thiocyanate) through narrow 0.8 nm-diameter carbon nanotube porins (CNTPs). These measurements revealed unexpectedly strong differential ion selectivity with permeabilities of different ions varying by up to two orders of magnitude. Removal of the negative charge from the nanotube entrance increased anion permeability by only a relatively small factor, indicating that electrostatic repulsion was not a major determinant of CNTP selectivity. First principle molecular dynamics simulations revealed that the origin of this strong differential ion selectivity is partial dehydration of anions upon entry into the narrow CNTP channels.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [2];  [2]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Southeast Univ., Nanjing (China)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of California, Merced, CA (United States)
  4. Southeast Univ., Nanjing (China)
  5. Yale Univ., New Haven, CT (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); Scientific Research Foundation of Graduate School of Southeast University; Postgraduate Research & Practice Innovation Program of Jiangsu Province; China Scholarship Council
OSTI Identifier:
1657683
Report Number(s):
LLNL-JRNL-799503
Journal ID: ISSN 1936-0851; 1002151
Grant/Contract Number:  
AC52-07NA27344; AC02-05CH11231; SC0019112; YBJJ1802; KYCX18_0067; CSC 201806090020
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 14; Journal Issue: 5; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nanofluidics; carbon nanotube porins; halide anions; ion selectivity; ion channels

Citation Formats

Li, Zhongwu, Li, Yuhao, Yao, Yun-Chiao, Aydin, Fikret, Zhan, Cheng, Chen, Yunfei, Elimelech, Menachem, Pham, Tuan Anh, and Noy, Aleksandr. Strong Differential Monovalent Anion Selectivity in Narrow Diameter Carbon Nanotube Porins. United States: N. p., 2020. Web. doi:10.1021/acsnano.0c02423.
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Li, Zhongwu, Li, Yuhao, Yao, Yun-Chiao, Aydin, Fikret, Zhan, Cheng, Chen, Yunfei, Elimelech, Menachem, Pham, Tuan Anh, & Noy, Aleksandr. Strong Differential Monovalent Anion Selectivity in Narrow Diameter Carbon Nanotube Porins. United States. https://doi.org/10.1021/acsnano.0c02423
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Li, Zhongwu, Li, Yuhao, Yao, Yun-Chiao, Aydin, Fikret, Zhan, Cheng, Chen, Yunfei, Elimelech, Menachem, Pham, Tuan Anh, and Noy, Aleksandr. Wed . "Strong Differential Monovalent Anion Selectivity in Narrow Diameter Carbon Nanotube Porins". United States. https://doi.org/10.1021/acsnano.0c02423. https://www.osti.gov/servlets/purl/1657683.
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@article{osti_1657683,
title = {Strong Differential Monovalent Anion Selectivity in Narrow Diameter Carbon Nanotube Porins},
author = {Li, Zhongwu and Li, Yuhao and Yao, Yun-Chiao and Aydin, Fikret and Zhan, Cheng and Chen, Yunfei and Elimelech, Menachem and Pham, Tuan Anh and Noy, Aleksandr},
abstractNote = {Inner pores of carbon nanotubes combine extremely fast water transport and ion selectivity that could potentially be useful for high-performance water desalination and separation applications. In this study, we used dye-quenching halide assays and stopped-flow spectrometry to determine intrinsic permeability of three small monovalent halide anions (chloride, bromide, iodide) and one pseudohalide anion (thiocyanate) through narrow 0.8 nm-diameter carbon nanotube porins (CNTPs). These measurements revealed unexpectedly strong differential ion selectivity with permeabilities of different ions varying by up to two orders of magnitude. Removal of the negative charge from the nanotube entrance increased anion permeability by only a relatively small factor, indicating that electrostatic repulsion was not a major determinant of CNTP selectivity. First principle molecular dynamics simulations revealed that the origin of this strong differential ion selectivity is partial dehydration of anions upon entry into the narrow CNTP channels.},
doi = {10.1021/acsnano.0c02423},
journal = {ACS Nano},
number = 5,
volume = 14,
place = {United States},
year = {Wed Apr 29 00:00:00 EDT 2020},
month = {Wed Apr 29 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acsnano.0c02423
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