Direct 3D printing of zero valent iron@polylactic acid catalyst for tetracycline degradation with magnetically inducing active persulfate.

Catalyst stability has become a challenging issue for advanced oxidation processes (AOPs). Herein, we report an alternative method based on 3D printing technology to obtain zero-valent iron polylactic acid prototypes (ZVI@PLA) in a single step and without post etching treatment. ZVI@PLA was used to activate persulfate (PS) for the removal of Tetracycline (TC) in recirculating mode under two different heating methodologies, thermal bath and contactless heating promoted by magnetic induction (MIH). The effect of both heating methodologies was systematically analysed by comparing the kinetic constant of the degradation processes. It was demonstrated that the non-contact heating of ZVI by MIH reactivates the surface of the catalyst, renewing the surface iron content exposed to the pollutant solution, which makes the ZVI@PLA catalyst reusable up to 10 cycles with no efficiency reduction. In contrast, by using a conventional thermal bath, the kinetic constant gradually decreases over the 10 cycles, because of the superficial iron consumption, being the kinetic constant 5 times lower in the 10th run compared to MIH experiment. X-ray diffraction and Mössbauer spectroscopy confirmed the presence of metallic iron embedded in the ZVI@PLA prototype, whose crystalline structure remained unchanged for 10th cycles of MIH. Moreover, it was proven that with no contact heating technology at low magnetic fields (12.2 mT), the solution temperature does not increase, but only the surface of the catalyst does. Under these superficial heated conditions, kinetic rate is increased up to 0.016 min compared to the value of 0.0086 min obtained for conventional heating at 20 °C. This increase is explained not only by PS activation by iron leaching but also by the contribution of ZVI in the heterogeneous activation of persulfate.