Dual-function CoNi-LDH hollow porous spheres for morphology-driven adsorptive removal and photo-oxidative degradation of anionic dyes

Abstract

The layered double hydroxides (LDHs) emerged as a class of low-cost potential adsorbents for organic pollutant separation, whereas the deep study of organic dye separation regulated by LDH hollow morphology under ambient conditions is still lacking. To address this gap, ZIF-67, Bulk-CoNi-LDH, and HPS-CoNi-LDH materials of different morphology and porosity were synthesized and investigated in the dye separation process. Methyl orange (MO), congo-red (CR), methylene blue (MB), and rhodamine B (Rhb) dyes were selected as model dye pollutants. The spectroscopic and structural analysis reveals the HPS-CoNi-LDH exhibits less-aggregated 2D nanosheets, high BET surface area of 163.2 m²/g, large pore size of 12.29 nm, greater positive surface charges (27.5 mV), superior optical (2.18 eV), and charge-separation capabilities as compared to Bulk-CoNi-LDH, Which provides potential sites for adsorptive and photo-degradation for anionic dyes under natural sunlight. Therefore, it achieves a remarkable removal efficiency of 92.6% for methyl orange (15 ppm) with a superior kinetic rate of 3.0$\times$10⁻² min⁻¹ within 90 min, outperforming Bulk-CoNi-LDH and ZIF-67 having removal efficiency of 71.7% and 40.8%, and kinetic rate of 1.35$\times$10⁻² and 0.5$\times$10⁻² min⁻¹, respectively. Poor removal efficiency and kinetic by ZIF-67 was mainly due to its smaller pore size (1.16 nm) and surface-confined charges (6.13 mV). Additionally, HPS-CoNi-LDH exhibits superb selectivity (at a ppm level) and excellent recyclability under ambient conditions. The mechanism of photo-catalytic reaction is discussed. These results delineate the hollow morphological LDH structure could be a worthy candidate for selective wastewater treatment and useful for sustainable conditions, which points the way to other crucial anionic micropollutant remediation.