Study of the Direct Red 81 Dye/Copper(II)-Phenanthroline System

Molecules. 2018 Jan 25;23(2):242. doi: 10.3390/molecules23020242.


Recovered papers contain several chromophores, such as wood lignin and dyes. These have to be eliminated during paper recycling in order to produce white paper. Hydrogen peroxide under alkaline conditions is generally used to decolorize lignin, but its effect on dyes is limited. Copper(II)-phenanthroline (Cu-Phen) complexes can activate the oxidation of lignin by hydrogen peroxide. Hydrogen peroxide may also be activated during recycled fiber bleaching, thus enhancing its color-stripping efficiency towards unoxidizable azo dyes. The purpose of this paper was to determine the effect of Cu-Phen complexes on a model azo dye, Direct Red 81 (DR81), in aqueous solution. Different Cu-Phen solutions (with different initial Cu:Phen molar ratios) were prepared and mixed with the dye at different pHs. The geochemical computer program PHREEQC allowed precise calculation of the theoretical distribution between different possible coordinates (CuPhenOH⁺, Cu(Phen)₂2+, CuPhen(OH)₂, Cu(Phen)₃2+, etc.) depending on pH and initial concentrations. UV-vis spectroscopic measurements were correlated with the major species theoretically present in each condition. The UV absorbance of the system was mainly attributed to the Cu-Phen complex and the visible absorbance was only due to the dye. Cu-Phen appeared to reduce the color intensity of the DR81 dye aqueous solution under specific conditions (more effective at pH 10.7 with Cu:Phen = 1:1), probably owing to the occurrence of a coordination phenomenon between DR81 and Cu-Phen. Hence, the ligand competition between phenanthroline and hydroxide ions would be disturbed by a third competitor, which is the dye molecule. Further investigation proved that the DR81 dye is able to form a complex with copper-phenanthroline, leading to partial color-stripping. This new "color-stripping effect" may be a new opportunity in paper and textile industries for wastewater treatment.

Keywords: Direct Red 81 azo dye; EPR spectroscopy; UV-vis spectroscopy; color-stripping; coordination; copper(II)-phenanthroline; speciation simulation.

MeSH terms

  • Azo Compounds / chemistry*
  • Copper / chemistry*
  • Hydrogen-Ion Concentration
  • Molecular Structure
  • Phenanthrolines / chemistry*
  • Spectrophotometry, Ultraviolet
  • Temperature


  • Azo Compounds
  • Phenanthrolines
  • Copper
  • Direct Red 81