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

Hussain, Zakir; Ojha, Ruchika; Martin, L.; Bond, Alan M.; Ramanathan, Rajesh; Bansal, Vipul

doi:10.1007/s42247-019-00026-8

Cited by 17 publications

(39 citation statements)

References 55 publications

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“…The rich electrical, chemical, magnetic, and optoelectronic properties of charge-transfer complexes based on 7,7,8,8-tetracyanoquinodimethane (TCNQ) has seen substantial interest in using these materials for a range of applications ( Figure S1, Supplementary Materials show the chemical structure of TCNQ) [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 ]. The pioneering work led by Dunbar, Miller, Robson, and Bond have seen the development of several strategies including physical [ 9 , 10 ], photochemical [ 11 , 12 , 13 ], vapor deposition [ 9 , 14 , 15 ], electrochemical [ 5 , 13 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ], and wet-chemical synthesis methods [ 19 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ] for the fabrication of TCNQ-based charge transfer complexes. The resultant materials have been used as sensors [ 14 , 15 , 37 , 38 ], photocatalysts […”

Section: Introductionmentioning

confidence: 99%

“…The pioneering work led by Dunbar, Miller, Robson, and Bond have seen the development of several strategies including physical [ 9 , 10 ], photochemical [ 11 , 12 , 13 ], vapor deposition [ 9 , 14 , 15 ], electrochemical [ 5 , 13 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ], and wet-chemical synthesis methods [ 19 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ] for the fabrication of TCNQ-based charge transfer complexes. The resultant materials have been used as sensors [ 14 , 15 , 37 , 38 ], photocatalysts [ 19 , 23 , 24 , 25 , 26 , 29 , 30 , 31 , 32 , 33 , 35 , 36 ], data storage systems [ 39 ...…”

Section: Introductionmentioning

confidence: 99%

“…Specifically, the fabrication of phase I CuTCNQ using this approach involves exposing a piece of Cu foil (Cu 0 ) to acetonitrile (MeCN) solution of neutral TCNQ 0 at or close to ambient temperature. A spontaneous redox reaction results in the oxidation of metallic Cu 0 to Cu + ion and reduction of TCNQ 0 to TCNQ 1− ion, leading to the crystallization of CuTCNQ on the surface of the metal foil [ 13 , 30 , 32 , 33 , 35 ]. However, this well-established route has a limitation—during the fabrication of CuTCNQ in MeCN, two parallel processes occur, viz.…”

Section: Introductionmentioning

confidence: 99%

“…A potential strategy to shift the equilibrium of the reaction would be to increase the temperature of the reaction during synthesis. However, in the case of CuTCNQ, increasing the reaction temperature and exposing CuTCNQ to higher temperatures for a prolonged time results in a physicochemical change in the material where the conductive phase I CuTCNQ gets converted to less conductive phase II CuTCNQ [ 7 , 35 ]. This would mean that the resulting CuTCNQ would not be equally suitable for electronics or catalysis applications.…”

Section: Introductionmentioning

confidence: 99%

“…This would mean that the resulting CuTCNQ would not be equally suitable for electronics or catalysis applications. For instance, phase I CuTCNQ has been shown to be a good catalyst that is useful for the photocatalytic degradation of organic dyes [ 23 , 24 ], reduction of ferricyanide [ 30 , 32 , 33 , 35 ], and reduction of hexavalent chromium [ 25 ]. In contrast, some of these reactions were significantly slow when less conductive phase II CuTCNQ was employed as a catalyst [ 35 ].…”

Section: Introductionmentioning

confidence: 99%

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Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis

et al. 2021

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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% (v/v) 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.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis

et al. 2021

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LSPR‐Induced Catalytic Enhancement Using Bimetallic Copper Fabrics Prepared by Galvanic Replacement Reactions

Anderson

O’Mullane

Gaspera

et al. 2019

Adv Materials Inter

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A simple galvanic replacement (GR) reaction‐based strategy to create copper‐based bimetallic fabrics for photoreductive catalysis is reported. It is shown that a nanostructured Cu@Fabric can be easily converted into bimetallic Cu‐Au@Fabric and Cu‐Ag@Fabric through a spontaneous electroless process that involves simple exposure of copper fabrics to the aqueous solutions of gold and silver ions. The nanoscale hierarchical ordering of cotton fabrics combined with their high porosity and wettability make them outstanding supports for catalyst recovery and reusability. The deposition of miniscule quantities of expensive noble metals on readily available Cu not only reduces the overall catalyst cost, but also plays a major role in improving the catalyst stability and reusability over several cycles through minimizing Cu oxidation. The synergistic effects of the localized surface plasmon resonance (LSPR) properties of Cu, Au, and Ag allow these bimetallic fabrics into highly active visible light photocatalysts. Mechanistic investigation of the photocatalytic activity provides in‐depth information on the electron transfer processes occurring at the catalyst/ reactant interface, revealing electron transport as the rate‐limiting step, which could be overcome under visible light photoillumination conditions. The outcomes enhance the understanding of template‐supported bimetallic nanostructures for LSPR‐induced photocatalysis applications, offering new potential to design multifunctional fabrics for various applications.

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Metal–Organic Charge Transfer Complexes of Pb(TCNQ)₂ and Pb(TCNQF₄)₂ as New Catalysts for Electron Transfer Reactions

Hussain

Zou

Murdoch

et al. 2020

Adv Materials Inter

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The fundamental properties and applications of organic charge transfer complexes based on Pb(TCNQ)2 (Pb = lead, TCNQ = 7,7,8,8‐tetracyanoquinodimethane) and its fluorinated derivatives are relatively unknown. Here, a facile solid–liquid approach for the synthesis of Pb(TCNQ)2 and Pb(TCNQF4)2 is reported. These materials are thoroughly analyzed to obtain insights into their unique morphological, vibrational and optical properties, the latter extending across the UV–Vis–IR region. Subsequently, the catalytic potential of these materials is evaluated by employing a model redox reaction, which revealed two orders of magnitude higher catalytic activity of the fluorinated derivative over non‐fluorinated Pb(TCNQ)2 crystals. Overall, the work presented here adds a new member to the growing yet limited library of metal–organic charge transfer complexes and validates the outstanding redox catalysis performance of this group of materials.

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

Cited by 17 publications

References 55 publications

Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis

Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis

LSPR‐Induced Catalytic Enhancement Using Bimetallic Copper Fabrics Prepared by Galvanic Replacement Reactions

Metal–Organic Charge Transfer Complexes of Pb(TCNQ)₂ and Pb(TCNQF₄)₂ as New Catalysts for Electron Transfer Reactions

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

Cited by 17 publications

References 55 publications

Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis

Increased Crystallization of CuTCNQ in Water/DMSO Bisolvent for Enhanced Redox Catalysis

LSPR‐Induced Catalytic Enhancement Using Bimetallic Copper Fabrics Prepared by Galvanic Replacement Reactions

Metal–Organic Charge Transfer Complexes of Pb(TCNQ)2 and Pb(TCNQF4)2 as New Catalysts for Electron Transfer Reactions

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Metal–Organic Charge Transfer Complexes of Pb(TCNQ)₂ and Pb(TCNQF₄)₂ as New Catalysts for Electron Transfer Reactions