Abstract:
Currently, due to urbanization and rapid development, environmental pollution through
industrial effluents and unattended disposal of anthropogenic wastes causes health
problems and harms the ecosystem in general. Industrial effluents from tanneries, textiles,
breweries, metallurgy, dyeing factories, and agro-processing are polluting environmental
waters with heavy metals and synthetic dyes. One of the common organic dyes used for
coloring paper, cotton, leather, and plastics is methylene blue (MB). However, consuming
high levels of MB can result in various health problems, such as respiratory and
gastrointestinal issues, eye irritation, and tissue necrosis. Similarly, heavy metals like
arsenic, cadmium, and chromium can be harmful to the kidney, liver, brain, and may even
cause cancer. Chromium exists in nature mainly in two forms: Cr(III) and Cr(VI), with
Cr(VI) being significantly more hazardous than Cr(III). The main objective of this study
was to investigate the effectiveness of manganese oxide coffee husk (CH) and khat
leftover (KL) biochar nanocomposites and magnetic CH and KL biochar nanocomposites
for the removal of MB and Cr(VI) from water.
Each biomass, CH and KL, was pyrolyzed at 300 °C for 1 h to produce the pristine
biochars. Similarly, 25 g of each biomass was treated with 12.5 mmol of KMnO4 before
being pyrolyzed for 1 h at 300 °C to produce the manganese oxide CH biochar
nanocomposite (MnOx-CHBNC) and manganese oxide KL biochar nanocomposite
(MnOx-KLBNC). They were characterized by XRD, SEM, FTIR, and BET. The results
showed that the adsorbents are amorphous, and the activated biochars are more porous
and contain various functional groups such as C-O, C=C, O-H, C-H, and R-MnOx.
Additionally, the batch adsorption experiments revealed that MnOx-CHBNC and MnOx
KLBNC have higher efficiency in removing MB and Cr(VI) compared to their pristine
biochars. Under the optimized conditions, MnOx-CHBNC exhibited a MB removal
efficiency of 99.27% with a maximum adsorption capacity (qm) of 39.52 mg g-1.
Similarly, MnOx-KLBNC showed a MB removal efficiency of 98.28% with a qm of
43.47 mg g-1. The Cr(VI) removal efficiency of MnOx-CHBNC was 99.63% with a qm of
72.99 mg g-1, while that of MnOx-KLBNC was 99.84% with a qm of 109.84 mg g-1.
Similarly, magnetic CH biochar nanocomposites (Fe3O4-CHBNC) and magnetic KL
biochar nanocomposites (Fe3O4-KLBNC) were synthesized by pretreating 25 g of
biomass with a 12.5 mmol mixture of FeS and FeCl3 at a 1:1 molar ratio, followed by
iii
pyrolyzing at 300 °C for 1 h. The resulting products were characterized using XRD,
FTIR, SEM, and BET. The results showed that the adsorbents are amorphous, and the
magnetic biochar nanocomposites are more porous and contain various functional groups
such as C-O, C=C, O-H, C-H, and Fe-O. The resulting nanocomposites exhibited a
maximum MB removal efficiency of 99.10% and 99.23% with Fe3O4-CHBNC and
Fe3O4-KLBNC, respectively, with qm of 51.02 and 78.13 mg g-1. Additionally, the Cr(VI)
removal efficiencies were determined to be 99.83% for Fe3O4-CHBNC and 99.86% for
Fe3O4-KLBNC, with their Cr(VI) qm values of 109.89 and 151.52 mg g-1, respectively.
The study on the regeneration of the adsorbents found that, except for MnOx-CHBNC in
the MB removal test, all adsorbents were effective for the removal of MB and Cr(VI)
over six successive cycles. However, MnOx-CHBNC can effectively be used for three
successive MB removals from water. Therefore, MnOx-CHBNC, MnOx-KLBNC, Fe3O4
CHBNC, and Fe3O4-KLBNC can serve as alternative adsorbents for the removal of MB
and Cr(VI) from water.