Regulating B-Site Metals in Delafossite to Reach Efficient and Selective Peroxymonosulfate Activation for Water Remediation

Abstract

Transition metals (TMs) are excellent active sites to activate peroxymonosulfate (PMS) for water remediation; however, the factors determining the efficiency and selectivity of PMS activation over different TMs remain blurred. Herein, delafossite with different B-site metals (denoted as CuBO 2 , B = Mn, Fe, Co, Cr) was synthesized to activate PMS for Orange I (OI) degradation. Their catalytic activity order followed CuCrO 2 (91.5%) ≈ CuCoO 2 (91.2%) > CuMnO 2 (46.9%) > CuFeO 2 (27.9%); especially the degradation rate (k) of CuCrO 2 (CuCoO 2 ) was 14.0 (12.6)-fold and 30.0 (27.1)-fold higher than that of CuMnO 2 > CuFeO 2 , respectively. Mechanism analysis showed that sulfate radical (SO 4•− ) was the main oxidant responsible for OI degradation in the CuCoO 2 /PMS system, while CuCrO 2 interacted with PMS to execute an electron transfer pathway (ETP) for degrading OI. Experimental and density functional theory calculation results deciphered that the d-band centers of CuCoO 2 (E d = −1.22 eV) and CuCrO 2 (E d = 0.62 eV) were closest to the Fermi level (E F ), thereby facilitating the interfacial electron transfer process and enhancing the PMS activation efficiency. Moreover, it was important to note that the E d value of CuCoO 2 was located below the E F , which led CuCoO 2 to easily lose electrons to PMS, thereby generating sulfate radicals SO 4•− . On the other hand, the E d value of CuCrO 2 was situated above the E F , which facilitated the catalyst to obtain electrons, acting as electron shuttles and driving a nonradical ETP. Finally, the established CuBO 2 -activated PMS systems also exhibited excellent stability and robust resistance against coexisting substances. These findings provided an alternative perspective to understanding the inherent nature of TM-based catalysts for regulating the efficiency and selectivity of PMS activation in water remediation.

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

“…At desired time intervals, the reaction mixture was sampled and centrifuged for further measurement by a UV–vis spectrophotometer at wavelengths of 275, 320, 356, 463, 505, and 554 nm for CIP, MNZ, TC, MO, ARG, and RhB, respectively. The concentration of PMS was measured by a spectrophotometric method using potassium iodide . To evaluate the stability of 3D–Cu-Ti, the used 3D–Cu-Ti alloy was washed with water and dried for subsequent cycling tests.…”