Novel carbon based bioactive nanocomposites of aniline/indole copolymer for  removal  of  cationic dyes from aqueous solution: kinetics and isotherms

2020-02-27 20:23:43

 

 

Mona Rouhi, Moslem Mansour Lakouraj, Hamed Tashakkorianb and Vahid Hasantabar


Introduction
Nowadays one of the main concerns of the environmentalist is the massive consumption of various dyes in coloring technologies of textiles and goods that lead to harmful effects on aquatic life other and living organisms.1–3 Dyes which are used  in industries can find their way into water streams and soil; therefore, finding a way to remove dyes prior to discharge is necessary.

 

Among organic dyes, cationic dyes such as methylene blue (MB) and malachite green (MG) have shown the highest toxicity for microorganisms. These cationic dyes are usually used for coloring paper, for dying cotton, wool and silk, as temporary hair colorants, and as coating for paper stock.6,7 MB can cause an increase of heart rate, vomiting, cyanosis, jaundice, quadriplegia, mental confusion, and tissue necrosis in humans. Consuming fish contaminated with MG poses a significant threat to human health due to its adverse effect on the immune and reproductive system and its carcinogenic, mutagenic, genotoxic, and teratogenic properties.

 

So far, different kinds of technologies such as separation, chemical oxidation, coagulation and flocculation, photocatalytic degradation, and adsorption have been used for dye removal in wastewater treatment. Adsorption is now the most convenient method due to its effectiveness, simplicity, economy and lack of secondary pollution.
Along these lines, carbon-based materials are one of the most common adsorbents due to their high surface area and porous structure and can provide an inexpensive and interesting way for the impressive removal of various organic compounds from wastewater.12,13 Among them, graphene oxide (GO), with plentiful hydrophilic groups on its surface including hydroxyl, epoxide and carboxylic groups and with a large surface area, is an exceptional adsorbent. The electrostatic charge–charge inter- action of GO with the adsorbate makes it a suitable  candidate  for charged species.2,14 Also, functional carbon nanotubes (CNT- COOH) due to their remarkable properties such as large area, small size, and hollow and layered structures have attracted great interest as a new type of adsorbent for removing many kinds of organic and inorganic pollutants.15,16 Furthermore, carbon nanotubes (CNTs) and graphene-based nanocomposites have shown cytotoxicity to bacteria and have found antibacterial applications.17–20 They disturb the  bacterial  membrane  physically via oxidative stress and show antibacterial activity due to their nanostructures which may result in physical damage to cell membranes, leading to the loss of bacterial membrane integrity and the leakage of RNA.

 

In this work, in continuation of our ongoing works,23 novel bioactive nanocomposites of conductive functional polymers based on graphene oxide and carboxylated carbon nanotubes were synthesized and their potential practical application in the removal of organic pollutants having a hazardous effect on the environment, such as the cationic dyes methylene blue and malachite green, from aqueous solution was studied. The impact of some experimental factors such as dosage of adsorbents, pH, dye concentration and contact time on their adsorption power was investigated. Furthermore, the antibacterial activity of these nanocomposites was explored for possible microbial decont- amination of infected water.


Experimental
Materials
Aniline was provided by Merck (Germany) and was doubly distilled in the presence of zinc dust in order to eliminate possible oxidation impurities. Indole, methylene blue (MB), malachite green (MG), graphene oxide (GO) and functionalized carbon nanotubes (CNT-COOH) were purchased from Sigma- Aldrich (Germany) and used as-received. Ammonium persulfate (APS), sodium dodecyl sulfate (SDS), chloroform, hydrochloric acid (37%), and ammonia solution (28%) were purchased from Merck (Germany) and were used without further purification. Stock solutions of dyes were prepared by dissolving the powder in distilled water.


Synthesis of poly(aniline-co-indole), P(ANI-co-IN)
The copolymer of aniline and indole was prepared by radical oxidative polymerization of aniline and indole at a molar ratio
of 1 : 1 at 0 1C. To a solution of 1 g of aniline dissolved in 20 mL of HCl (1 M) the mixture of 1 g of indole in 10 mL of CHCl3 was added. Polymerization was initiated after the addition of 25 mL of APS aqueous solution; the latter solution was added in a dropwise manner over 30 min. Polymerization was carried out over 12 h at 01C.  The dark black powder wasfiltered and washed several times with distilled water and methanol until the filtrate became colorless. The obtained polymer was further dried in a vacuum oven at 50 1C for 24 h.


Synthesis of the nanocomposite based on poly(aniline-co- indole) and GO
The mixture of 1 g of pure aniline (ANI) and 12.5  mL of HCl  (1 M) was stirred in an ice bath. 1 g of indole was dissolved in CHCl3 and added to the above solution. Next, a certain amount of GO and SDS dispersed in water was added. Lastly, 30 mL of saturated aqueous solution of ammonium persulfate (APS) was slowly added dropwise. After the mixture was stirred for about 12 h in an ice bath, the precipitated product was collected and washed several times with distilled water until the washing fluid was neutral. Finally, the obtained P(ANI-co-IN)/GO com- posite was dried in air at 80 1C for 12 h.

 

Synthesis of the nanocomposite based on poly(aniline-co-indole) and CNT-COOH
A mixture of 1 g of pure aniline (ANI) and 12.5 mL of HCl (1 M) was stirred in an ice bath. Then the solution of 1 g of indole in CHCl3 was added to the above mixture. After that, CNT-COOH dispersed in SDS and water was added. Then, 30 mL of water saturated solution of ammonium persulfate (APS) was slowly added dropwise. After the mixture was  stirred  for  about 12  h in an ice bath, the precipitated product was collected and  washed several times with distilled water. Finally, the obtained P(ANI-co-IN)/CNT-COOH composites were dried in air at 80 1C for 12 h.

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