Photocatalytic activity of micron-scale brass on emerging pollutant degradation in water: mechanism elucidation and removal efficacy assessment

Abstract

Alloys or smelted metal mixtures have served as cornerstones of human civilization. The advent of smelted copper and tin, i.e., bronze, in the 4^th millennium B.C. in Mesopotamia has pioneered the preparation of other metal composites, such as brass (i.e., mixture of copper and zinc), since the bronze age. The contemporary use of these alloys has expanded beyond using their physical strength. The catalytic chemistry of micron-scale brass or copper–zinc alloy can be utilized to effectively degrade emerging contaminants (ECs) in water, which are presenting significant risks to human health and wildlife. Here, we examine the photocatalytic activity of a commercially available micro-copper–zinc alloy (KDF® 55, MicroCuZn), made with earth abundant metals, for oxidative removal of two ECs. The micron-scale brass is independently characterized for its morphology, which confirms that it has the β-brass phase and that its plasmonic response is around 475 nm. Estriol (E3), a well-known EC, is removed from water with ultraviolet (UV) radiation catalyzed by MicroCuZn and H₂O₂–MicroCuZn combinations. The synergy between H₂O₂, UV, and MicroCuZn enhances hydroxyl radical (˙OH) generation and exhibit a strong pseudo-first-order kinetic degradation of E3 with a decay constant of 1.853 × 10⁻³ min⁻¹ (r² = 0.999). Generation of ˙OH is monitored with N,N-dimethyl-4-nitrosoaniline (pNDA) and terephthalic acid (TA), which are effective ˙OH scavengers. X-ray photoelectron spectroscopy analysis has confirmed ZnO/CuO–Cu₂O film formation after UV irradiation. The second EC studied here is Δ9-tetrahydrocannabinol or THC, a psychotropic compound commonly consumed through recreational or medicinal use of marijuana. The exceptionally high solids–water partitioning propensity of THC makes adsorption the dominant removal mechanism, with photocatalysis potentially supporting the removal efficacy of this compound. These results indicate that MicroCuZn can be a promising oxidative catalyst especially for degradation of ECs, with possible reusability of this historically significant material with environmentally-friendly attributes.