Heterogeneous Activation of Sulfite by a Three-Dimensional Printed Hierarchically Porous Copper Catalyst for the Degradation of Tetracycline Hydrochloride in Water

Abstract

Sulfite [S(IV)]-based advanced oxidation processes (AOPs) have emerged as a promising strategy to address evergrowing water pollution. In this study, a novel three-dimensional hierarchical porous copper (3D-Cu) catalyst was fabricated via laser 3D printing. The 3D-Cu catalyst demonstrated remarkable efficiency as an S(IV) activator for the efficient removal of tetracycline hydrochloride (TC), comparable to that of copper powder under similar conditions. Impressively, the 3D-Cu catalyst manifested superb stability and reusability, maintaining a high reactivity even after 40 successive cycles. The results indicated that Cu(II) sites functioned as active sites for S(IV) oxidative activation, with the unique 3D hierarchically porous structures enhancing accessibility to these active sites and facilitating the migration of S(IV) and contaminants. Furthermore, ryegrass seeds and Vibrio fischeri exposure experiments suggested that the mineralization process of TC could effectively reduce its biotoxicity. Additionally, the CaSO 3 /3D-Cu system exhibited excellent adaptability to different natural water matrices and was even effective in eliminating contaminants in actual wastewater. Overall, this study provides a new strategy for the preparation of efficient and durable heterogeneous S(IV) activators and advances the application of S(IV)-AOPs in real-world wastewater treatment.

Efficient Degradation of Ciprofloxacin via Peroxymonosulfate Activation over a Hierarchically Porous Cu–Ti Alloy Manufactured by 3D Printing

“…Furthermore, actual wastewater was utilized to validate the applicability of the 3D-Cu-Ti/PMS system through 3D-EEM fluorescence spectroscopy. The 3D-EEM spectra of the actual wastewater revealed three major regions with high fluorescence intensity, attributed to aromatic protein-like substances in the pollutants (Figure g) . However, when treated with the 3D-Cu-Ti/PMS system, the fluorescence intensity of these regions gradually decreased or even disappeared as the reaction time increased to 90 min.…”

“…3D printing, academically known as additive manufacturing, offers extensive flexibility in design, an array of material options, minimal energy consumption, negligible material waste, and fewer byproducts . Moreover, 3D printing enables the fabrication of intricate geometrical structures, a critical requirement for the precise manufacturing of reactors employed in wastewater treatment. , Specifically, selective laser melting (SLM), a powder bed fusion 3D-printing method, has been frequently utilized to fabricate metal-based catalysts with complex structure, extraordinary reactivity, and superior reusability . To date, research pertaining to the development of environmentally benign monolithic catalysts through 3D printing remains scarce, and the utilization of bimetallic alloy catalysts obtained via SLM as a catalytic device for the activation of PMS to degrade CIP in water has been rarely reported.…”