4.7 Article

Nanoporous Zn(OH)2/ZnO Particles for pH-Independent Methylene Blue Wastewater Treatment

Journal

ACS APPLIED NANO MATERIALS
Volume 6, Issue 9, Pages 7487-7498

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsanm.3c00664

Keywords

methylene blue; Zn(OH)2; ZnO; octahedral nanoparticles; adsorbent; structure-performance; NH4F

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By tuning the phase and pore structure of zinc hydroxide/zinc oxide (Zn(OH)2/ZnO) nanostructures, the pH limitations in the adsorption of methylene blue (MeB) are overcome by achieving pH-independent interfacial pore-filling reactions.
Although zinc-based nanocomposites have good methylene blue (MeB) adsorption capabilities, their efficiency is heavily limited by pH. This is troubling because large-scale pH adjustment is not economically viable when treating huge volumes of MeB-polluted water. In this study, we eliminate this limitation by tuning the phase and pore structure of zinc hydroxide/zinc oxide (Zn(OH)2/ZnO) nanostructures to allow for interfacial pore-filling adsorption reactions that are pH-independent. The physicochemical optimization is achieved using different reaction temperatures and ammonium fluoride (NH4F) dopant concentrations under hydrothermal conditions. The phase and microstructure of the Zn(OH)2/ZnO nanostructures are characterized using C-potential, SEM, XPS, XRD, Tauc plots, FT-IR, and BET analysis. At 80 and 120 degrees C and without NH4F doping, lambda-Zn(OH)2/ZnO nanosheets were generated with a high specific surface area and pore volume but low MeB removal capacity. However, the addition of NH4F creates solid and porous beta-Zn(OH)2/ZnO polyhedrons with high activity. In particular, 120 degrees C and 1.0 g of NH4F produce highly porous beta-Zn(OH)2/ZnO octahedral nanoparticles (i.e., 120-1) with a high concentration of 6-nm-sized pores, which were crucial for MeB interfacial pore-filling from pH 3 to pH 10. The adsorption kinetics is fast and governed by the Langmuir, pseudo-second-order, and intraparticle diffusion models. 120-1 can be immobilized on a chelating polymer such as polyacrylonitrile (PAN) to generate a flexible membrane with high performance. Our study shows that careful control of the pore structure and phase of Zn(OH)2 in Zn(OH)2/ZnO nanostructures overcomes the pH limitations.

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