Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis
Controlling the kinetics of CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) crystallization has been a major challenge, as CuTCNQ crystallizing on Cu foil during synthesis in conventional solvents such as acetonitrile simultaneously dissolves into the reaction medium. In this work, we address this...
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doaj-871f043c57fe44d29c2cd3d451ec19ff2021-04-08T23:04:28ZengMDPI AGNanomaterials2079-49912021-04-011195495410.3390/nano11040954Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox CatalysisZakir Hussain0Ayman Nafady1Samuel R. Anderson2Abdullah M. Al-Enizi3Asma A. Alothman4Rajesh Ramanathan5Vipul Bansal6Ian Potter NanoBioSensing Facility, NanoBiotechnology Research Laboratory (NBRL), School of Science, RMIT University, GPO Box 2476, Melbourne, VIC 3000, AustraliaChemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi ArabiaIan Potter NanoBioSensing Facility, NanoBiotechnology Research Laboratory (NBRL), School of Science, RMIT University, GPO Box 2476, Melbourne, VIC 3000, AustraliaChemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi ArabiaChemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi ArabiaIan Potter NanoBioSensing Facility, NanoBiotechnology Research Laboratory (NBRL), School of Science, RMIT University, GPO Box 2476, Melbourne, VIC 3000, AustraliaIan Potter NanoBioSensing Facility, NanoBiotechnology Research Laboratory (NBRL), School of Science, RMIT University, GPO Box 2476, Melbourne, VIC 3000, AustraliaControlling the kinetics of CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) crystallization has been a major challenge, as CuTCNQ crystallizing on Cu foil during synthesis in conventional solvents such as acetonitrile simultaneously dissolves into the reaction medium. In this work, we address this challenge by using water as a universal co-solvent to control the kinetics of crystallization and growth of phase I CuTCNQ. Water increases the dielectric constant of the reaction medium, shifting the equilibrium toward CuTCNQ crystallization while concomitantly decreasing the dissolution of CuTCNQ. This allows more CuTCNQ to be controllably crystallized on the surface of the Cu foil. Different sizes of CuTCNQ crystals formed on Cu foil under different water/DMSO admixtures influence the solvophilicity of these materials. This has important implications in their catalytic performance, as water-induced changes in the surface properties of these materials can make them highly hydrophilic, which allows the CuTCNQ to act as an efficient catalyst as it brings the aqueous reactants in close vicinity of the catalyst. Evidently, the CuTCNQ synthesized in 30% (<i>v</i>/<i>v</i>) water/DMSO showed superior catalytic activity for ferricyanide reduction with 95% completion achieved within a few minutes in contrast to CuTCNQ synthesized in DMSO that took over 92 min.https://www.mdpi.com/2079-4991/11/4/954metal–organic semiconductorCuTCNQcharge-transfer complexco-solventredox catalysis |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Zakir Hussain Ayman Nafady Samuel R. Anderson Abdullah M. Al-Enizi Asma A. Alothman Rajesh Ramanathan Vipul Bansal |
spellingShingle |
Zakir Hussain Ayman Nafady Samuel R. Anderson Abdullah M. Al-Enizi Asma A. Alothman Rajesh Ramanathan Vipul Bansal Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis Nanomaterials metal–organic semiconductor CuTCNQ charge-transfer complex co-solvent redox catalysis |
author_facet |
Zakir Hussain Ayman Nafady Samuel R. Anderson Abdullah M. Al-Enizi Asma A. Alothman Rajesh Ramanathan Vipul Bansal |
author_sort |
Zakir Hussain |
title |
Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis |
title_short |
Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis |
title_full |
Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis |
title_fullStr |
Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis |
title_full_unstemmed |
Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis |
title_sort |
increased crystallization of cutcnq in water/dmso bisolvent for enhanced redox catalysis |
publisher |
MDPI AG |
series |
Nanomaterials |
issn |
2079-4991 |
publishDate |
2021-04-01 |
description |
Controlling the kinetics of CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) crystallization has been a major challenge, as CuTCNQ crystallizing on Cu foil during synthesis in conventional solvents such as acetonitrile simultaneously dissolves into the reaction medium. In this work, we address this challenge by using water as a universal co-solvent to control the kinetics of crystallization and growth of phase I CuTCNQ. Water increases the dielectric constant of the reaction medium, shifting the equilibrium toward CuTCNQ crystallization while concomitantly decreasing the dissolution of CuTCNQ. This allows more CuTCNQ to be controllably crystallized on the surface of the Cu foil. Different sizes of CuTCNQ crystals formed on Cu foil under different water/DMSO admixtures influence the solvophilicity of these materials. This has important implications in their catalytic performance, as water-induced changes in the surface properties of these materials can make them highly hydrophilic, which allows the CuTCNQ to act as an efficient catalyst as it brings the aqueous reactants in close vicinity of the catalyst. Evidently, the CuTCNQ synthesized in 30% (<i>v</i>/<i>v</i>) water/DMSO showed superior catalytic activity for ferricyanide reduction with 95% completion achieved within a few minutes in contrast to CuTCNQ synthesized in DMSO that took over 92 min. |
topic |
metal–organic semiconductor CuTCNQ charge-transfer complex co-solvent redox catalysis |
url |
https://www.mdpi.com/2079-4991/11/4/954 |
work_keys_str_mv |
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