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

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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.

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Acknowledgments

V.B. thanks the Australian Research Council (ARC) for a Future Fellowship (FT140101285). V.B., R.R., L.L.M., and A.M.B. acknowledge the ARC for funding this project though an ARC Discovery (DP170103477) Grant. The authors are appreciative of the generous support of the Ian Potter Foundation towards establishing the Sir Ian Potter NanoBioSensing Facility at RMIT University. R.R. acknowledges RMIT University for a Vice Chancellor Fellowship. Authors acknowledge the support from the RMIT Microscopy and Microanalysis Facility (RMMF) for technical assistance and providing access to characterization facilities.

Funding sources

V.B.: Australian Research Council (ARC), Future Fellowship (FT140101285).

V.B., R.R., L.L.M., A.M.B.: ARC, Discovery Grant (DP170103477).

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Authors and Affiliations

  1. Ian Potter NanoBioSensing Facility, NanoBiotechnology Research Laboratory, School of Science, RMIT University, GPO Box 2476, Melbourne, VIC, 3001, Australia

    Zakir Hussain, Rajesh Ramanathan & Vipul Bansal

  2. School of Chemistry, Monash University, 17 Rainforest Walk, Clayton, VIC, 3800, Australia

    Ruchika Ojha, Lisandra L. Martin & Alan M. Bond

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  1. Zakir Hussain
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The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

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Correspondence to Rajesh Ramanathan or Vipul Bansal.

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Hussain, Z., Ojha, R., Martin, L.L. et al. Controlling the morphological and redox properties of the CuTCNQ catalyst through solvent engineering. emergent mater. 2, 35–44 (2019). https://doi.org/10.1007/s42247-019-00026-8

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