Simultaneous removal of nitrate nitrogen and orthophosphate by electroreduction and electrochemical precipitation.

Electrochemical methods can effectively remove nitrate nitrogen (NO3-N) and orthophosphate phosphorus (PO4-P) from wastewater. This work proposed a process for the simultaneous removal of NO3-N and PO4-P by combining electroreduction with electrochemically-induced calcium phosphate precipitation, and its performance and mechanisms were studied. For the treatment of 100 mg L-1 NO3-N and 5 mg L-1 PO4-P, NO3-N removal of 60-90% (per cathode area: 0.25-0.38 mg h-1 cm-2) and 80-90% (per cathode area: 0.33-0.38 mg h-1 cm-2) could be acquired within 3 h in single-chamber cell (SCC) and dual-chamber cell (DCC), while P removal was 80-98% (per cathode area: 0.10-0.12 mg h-1 cm-2) in SCC after 30 min and 98% (per cathode area: 0.37 mg h-1 cm-2) in DCC within 10 min. The faster P removal in DCC was due to the higher pH and more abundant Ca2+ in the cathode chamber of DCC, which was caused by the cation exchange membrane (CEM). Interestingly, NO3-N reduction enhanced P removal because more OH- can be produced by nitrate reduction than hydrogen evolution for an equal-charge reaction. For 10 mg L-1 PO4-P in SCC, when the initial NO3-N was 0, 20, 100, and 500 mg L-1, the P removal efficiencies after 1 h treatment were < 10%, 45-55%, 86-99%, and above 98% respectively. An increase in Ca2+ concentration also promoted P removal. However, Ca and P inhibited nitrate reduction in SCC at the relatively low initial Ca/P, as CaP on the cathode limited the charge or mass transfer process. The removal efficiency of NO3-N in SCC after 3 h reaction can reduce by about 17%, 40%, and 34% for Co3O4/Ti, Co/Ti, and TiO2/Ti. The degree of inhibition of P on NO3-N removal was related to the content and composition of CaP deposited on the cathode. On the cathode, the lower the deposited Ca and P, and the higher the deposited Ca/P molar ratio, the weaker the inhibition of P on NO3-N removal. Especially, P had little or even no inhibition on nitrate reduction when treated in DCC instead of SCC or under high initial Ca/P. It is speculated that under these conditions, a high local pH and local high concentration Ca2+ layer near the cathode led to a decrease in CaP deposition and an increase in Ca/P molar ratio on the cathode. High initial concentrations of NO3-N might also be beneficial in reducing the inhibition of P on nitrate reduction, as few CaP with high Ca/P molar ratios were deposited on the cathode. The evaluation of the real wastewater treatment was also conducted.

Facile Fabrication of Magnetic Microrobots Based on Spirulina Templates for Targeted Delivery and Synergistic Chemo-Photothermal Therapy.

Magnetic microrobots can be actuated in fuel-free conditions and are envisioned for biomedical applications related to targeted delivery and therapy in a minimally invasive manner. However, mass fabrication of microrobots with precise propulsion performance and excellent therapeutic efficacy is still challenging, especially in a predictable and controllable manner. Herein, we propose a facile technique for mass production of magnetic microrobots with multiple functions using Spirulina ( Sp.) as biotemplate. Core-shell-structured Pd@Au nanoparticles (NPs) were synthesized in Sp. cells by electroless deposition, working as photothermal conversion agents. Subsequently, the Fe3O4 NPs were deposited onto the surface of the obtained (Pd@Au)@ Sp. particles via a sol-gel process, enabling them to be magnetically actuated. Moreover, the anticancer drug doxorubicin (DOX) was loaded on the (Pd@Au)/Fe3O4@ Sp. microrobots, which endows them with additional chemotherapeutic efficacy. The as-prepared biohybrid (Pd@Au)/Fe3O4@ Sp.-DOX microrobots not only possess efficient propulsion performance with the highest speed of 526.2 µm/s under a rotating magnetic field but also have enhanced synergistic chemo-photothermal therapeutic efficacy. Furthermore, they can be structurally disassembled into individual particles under near-infrared (NIR) laser irradiation and exhibit pH- and NIR-triggered drug release. These intriguing properties enable the microrobots to be a very promising and efficient platform for drug loading, targeted delivery, and chemo-photothermal therapy.