Controlling the morphological and redox properties of the CuTCNQ catalyst through solvent engineering

Zakir Hussain, Ruchika Ojha, Lisa Martin, Alan Bond, rajesh ramanathan, Vipul Bansal

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The solution-based synthesis of the coordination polymer, CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which exists in two phases, has predominately used acetonitrile (MeCN) as the solvent. However, our knowledge on the growth and properties of CuTCNQ in other solvents remains limited. In this work, the synthesis of CuTCNQ on Cu foil in two protic (MeOH, EtOH) as well as four aprotic (MeCN, DMSO, DMF, THF) solvents has allowed us to obtain new insights into the important role of the reaction medium in the spontaneous crystallization of CuTCNQ in discrete morphologies and phases. A new electrochemical method for phase identification also has been developed to support this study. Findings reveal that (i) the solvents with higher dielectric constants favor CuTCNQ crystallization; (ii) irrespective of the solvent, use of high temperature (60 °C vs. 25 °C in conventional synthesis) promotes CuTCNQ crystallization and facilitate conversion of phase I to phase II; (iii) phase I CuTCNQ possess enhanced redox catalysis (ferricyanide reduction by thiosulfate) performance over phase II CuTCNQ; and (iv) the amount of catalyst is not necessarily the most important factor for driving catalytic reactions, and other factors, such as, morphology, redox characteristics and solvent in which the CuTCNQ is synthesized may dictate the overall catalytic performance. These findings emphasize the importance of understanding the influence of parameters, such as, solvent and temperature in CuTCNQ synthesis as a means of providing materials with improved catalytic activity.
Original languageEnglish
Number of pages10
JournalEmergent Materials
DOIs
Publication statusAccepted/In press - 2019

Keywords

  • Catalysis
  • Metal-organic semiconductor
  • CuTCNQ
  • Charge-transfer complex
  • Morphological control

Cite this

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title = "Controlling the morphological and redox properties of the CuTCNQ catalyst through solvent engineering",
abstract = "The solution-based synthesis of the coordination polymer, CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which exists in two phases, has predominately used acetonitrile (MeCN) as the solvent. However, our knowledge on the growth and properties of CuTCNQ in other solvents remains limited. In this work, the synthesis of CuTCNQ on Cu foil in two protic (MeOH, EtOH) as well as four aprotic (MeCN, DMSO, DMF, THF) solvents has allowed us to obtain new insights into the important role of the reaction medium in the spontaneous crystallization of CuTCNQ in discrete morphologies and phases. A new electrochemical method for phase identification also has been developed to support this study. Findings reveal that (i) the solvents with higher dielectric constants favor CuTCNQ crystallization; (ii) irrespective of the solvent, use of high temperature (60 °C vs. 25 °C in conventional synthesis) promotes CuTCNQ crystallization and facilitate conversion of phase I to phase II; (iii) phase I CuTCNQ possess enhanced redox catalysis (ferricyanide reduction by thiosulfate) performance over phase II CuTCNQ; and (iv) the amount of catalyst is not necessarily the most important factor for driving catalytic reactions, and other factors, such as, morphology, redox characteristics and solvent in which the CuTCNQ is synthesized may dictate the overall catalytic performance. These findings emphasize the importance of understanding the influence of parameters, such as, solvent and temperature in CuTCNQ synthesis as a means of providing materials with improved catalytic activity.",
keywords = "Catalysis, Metal-organic semiconductor, CuTCNQ, Charge-transfer complex, Morphological control",
author = "Zakir Hussain and Ruchika Ojha and Lisa Martin and Alan Bond and rajesh ramanathan and Vipul Bansal",
year = "2019",
doi = "10.1007/s42247-019-00026-8",
language = "English",
journal = "Emergent Materials",
issn = "2522-5731",
publisher = "Springer",

}

Controlling the morphological and redox properties of the CuTCNQ catalyst through solvent engineering. / Hussain, Zakir; Ojha, Ruchika; Martin, Lisa; Bond, Alan; ramanathan, rajesh ; Bansal, Vipul.

In: Emergent Materials, 2019.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Controlling the morphological and redox properties of the CuTCNQ catalyst through solvent engineering

AU - Hussain, Zakir

AU - Ojha, Ruchika

AU - Martin, Lisa

AU - Bond, Alan

AU - ramanathan, rajesh

AU - Bansal, Vipul

PY - 2019

Y1 - 2019

N2 - The solution-based synthesis of the coordination polymer, CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which exists in two phases, has predominately used acetonitrile (MeCN) as the solvent. However, our knowledge on the growth and properties of CuTCNQ in other solvents remains limited. In this work, the synthesis of CuTCNQ on Cu foil in two protic (MeOH, EtOH) as well as four aprotic (MeCN, DMSO, DMF, THF) solvents has allowed us to obtain new insights into the important role of the reaction medium in the spontaneous crystallization of CuTCNQ in discrete morphologies and phases. A new electrochemical method for phase identification also has been developed to support this study. Findings reveal that (i) the solvents with higher dielectric constants favor CuTCNQ crystallization; (ii) irrespective of the solvent, use of high temperature (60 °C vs. 25 °C in conventional synthesis) promotes CuTCNQ crystallization and facilitate conversion of phase I to phase II; (iii) phase I CuTCNQ possess enhanced redox catalysis (ferricyanide reduction by thiosulfate) performance over phase II CuTCNQ; and (iv) the amount of catalyst is not necessarily the most important factor for driving catalytic reactions, and other factors, such as, morphology, redox characteristics and solvent in which the CuTCNQ is synthesized may dictate the overall catalytic performance. These findings emphasize the importance of understanding the influence of parameters, such as, solvent and temperature in CuTCNQ synthesis as a means of providing materials with improved catalytic activity.

AB - The solution-based synthesis of the coordination polymer, CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which exists in two phases, has predominately used acetonitrile (MeCN) as the solvent. However, our knowledge on the growth and properties of CuTCNQ in other solvents remains limited. In this work, the synthesis of CuTCNQ on Cu foil in two protic (MeOH, EtOH) as well as four aprotic (MeCN, DMSO, DMF, THF) solvents has allowed us to obtain new insights into the important role of the reaction medium in the spontaneous crystallization of CuTCNQ in discrete morphologies and phases. A new electrochemical method for phase identification also has been developed to support this study. Findings reveal that (i) the solvents with higher dielectric constants favor CuTCNQ crystallization; (ii) irrespective of the solvent, use of high temperature (60 °C vs. 25 °C in conventional synthesis) promotes CuTCNQ crystallization and facilitate conversion of phase I to phase II; (iii) phase I CuTCNQ possess enhanced redox catalysis (ferricyanide reduction by thiosulfate) performance over phase II CuTCNQ; and (iv) the amount of catalyst is not necessarily the most important factor for driving catalytic reactions, and other factors, such as, morphology, redox characteristics and solvent in which the CuTCNQ is synthesized may dictate the overall catalytic performance. These findings emphasize the importance of understanding the influence of parameters, such as, solvent and temperature in CuTCNQ synthesis as a means of providing materials with improved catalytic activity.

KW - Catalysis

KW - Metal-organic semiconductor

KW - CuTCNQ

KW - Charge-transfer complex

KW - Morphological control

U2 - 10.1007/s42247-019-00026-8

DO - 10.1007/s42247-019-00026-8

M3 - Article

JO - Emergent Materials

JF - Emergent Materials

SN - 2522-5731

ER -