Carboxymethyl cellulose improved adsorption capacity of polypyrrole/CMC composite nanoparticles for removal of reactive dyes: Experimental optimization and DFT calculation.

In this study, polypyrrole/carboxymethyl cellulose nanocomposite particles (PPy/CMC NPs) were synthesized and applied for removal of reactive red 56 (RR56)and reactive blue 160 (RB160) as highly toxic dyes. The amount of CMC was found significantly effective on the surface adsorption efficiency. Different optimization methods including the genetic programming, response surface methodology, and artificial neural network (ANN) were used to optimize the effect of different parameters including pH, adsorption time, initial dye concentration and adsorbent dose. The maximum adsorption of RR56 and RB160 were found under the following optimum conditions: pH of 4 and 5, adsorption time of 55 min and 52 min for RR56 and RB160, respectively, initial dye concentration of 100 mg/L and adsorbent dose of 0.09 g for both dyes. were obtained for RR56 and RB160, respectively. Also, the results indicated that ANN method could predict the experimental adsorption data with higher accuracy than other methods. The analysis of ANN results indicated that the adsorbent dose is the main factor in RR56 removal, followed by time, pH and initial concentration, respectively. However, initial concentration mostly determines the RB160 removal process. The isotherm data for both dyes followed the Langmuir isotherm model with a maximum adsorption capacity of 104.9 mg/g and 120.7 mg/g for RR56 and RB160, respectively. In addition, thermodynamic studies indicated the endothermic adsorption process for both studied dyes. Moreover, DFT calculations were carried out to obtain more insight into the interactions between the dyes and adsorbent. The results showed that the hydrogen bondings and Van der Waals interactions are dominant forces between the two studied dyes and PPy/CMC composite. Furthermore, the interaction energies calculated by DFT confirmed the experimental adsorption data, where PPy/CMC resulted in higher removal of both dyes compared to PPy. The developed nanocomposite showed considerable reusability up to 3 cylces of the batch adsorption process.