Abstract
Rational designing of metal-free carbon nitride based photocatalysts can lead to an excellent optical response and a higher photocatalytic activity driven by visible and solar light. This combines green photocatalytic technology with greener materials prepared by facile approaches for environmental remediation. Herein we report utilization of star photocatalyst g-C3N4 (CN) to form highly efficient hetero-assemblies along with acidified g-C3N4 (ACN), polyaniline (PANI), reduced graphene oxide (RGO) and biochar. By use of these organic semiconductors we synthesize g-C3N4/ACN/RGO@Biochar (GARB), g-C3N4/PANI/RGO@Biochar (GPRB) and ACN/PANI/RGO@Biochar (APRB) nano-assemblies with different optical response and band edge positions for a better charge flow and reduced recombination of carriers. These synthesized catalysts were used for visible light powered degradation of 2,4-Dichlorophenoxy acetic acid (2,4-D) and ibuprofen (IBN). APRB performs the best and degrades 99.7% and 98.4% of 2,4-D and IBN (20 mg L−1) under Xe lamp exposure in 50 min and retention of high activity in natural sunlight. Optical analysis, photoelectrochemical response and radical quenching studies show both hydroxyl and superoxide radical anions as major reactive species and a Z-scheme photocatalytic mechanism. RGO acts as an electron mediator and protects higher positioned bands of PANI and ACN in APRB for a remarkable photocatalytic activity for a metal free material. The degradation pathway was analyzed by LC-MS analysis and 42% and 40% total organic carbon was removed in 2 h for 2,4-D and IBN degradation respectively. The toxicity of degraded products was analyzed by analyzing viability of human peripheral blood cells with retaining of 99.1% cells.
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•Metal free organic semiconductors based nano-assemblies as photocatalysts.•Utilizing g-C3N4, acidified C3N4, PANI for designing efficient photocatalyst.•Z-scheme mechanism-high spectral response and charge separation.•Excellent photo-degradation of Ibuprofen and 2,4-D under artificial and solar light.•Complete mineralization and no toxicity on human PBL cells.