Visible-Light-Active Mixed-Valent Copper-Ion-Coordinated 2,5-Dimercapto-1,3,4-thiadiazole-Based p-Type Metallopolymer

Iranna Udachyan, Pradeepa Kumara, R. S. Vishwanath, Sakthivel Kandaiah

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

Visible-light-active coordination metallopolymer and metal-organic frameworks have gained substantial attention in recent years, owing to their tunable electronic properties. Herein, we present a novel copper-ion-containing metallopolymer, which exhibits visible-light absorption and p-type photoelectrochemical behavior. The functional thiadiazole-based metallopolymer thin films were prepared by using both chemical and electrochemical methods on fluorine-doped tin oxide substrates. XPS, Raman, and FTIR spectral investigations evidence the presence of Cu(II), Cu(I), Cu−S, and disulfide (S−S)2− linkages in the polymeric network. The swift photoresponses, repeatable photovoltage of approximately 55 mV with zero applied current, and high photocurrent values at different bias potentials (ca. 24 μA cm−2 @ −0.6 V vs. Ag/AgCl in 0.1 KCl) in acidic electrolytes (0.5 M H2SO4) suggest that this metallopolymer as an acid-stable p-type photocathode material. In contrast, the electropolymerized non-metallated polymers exhibit n-type photoactivity. Photoelectrochemical sensing studies reveal the analyte-induced reduction in photoactivity.

Original languageEnglish
Pages (from-to)3847-3853
Number of pages7
JournalChemElectroChem
Volume5
Issue number24
DOIs
StatePublished - 10 Dec 2018
Externally publishedYes

Keywords

  • metallopolymers
  • p-type semiconductor
  • photocathodes
  • photoelectrochemical sensing
  • thiadiazoledithiol

ASJC Scopus subject areas

  • Catalysis
  • Electrochemistry

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