Effects and Mechanisms of Cu Species in Fe-MOFs on Fenton-Like Catalytic Activity and Stability

Fe-based MOFs (Fe-MOFs) are deemed promising Fenton-like catalysts due to their well-developed pores and accessible active sites. However, their inferior catalytic activity, iron leaching, and low H 2 O 2 utilization always hinder their application as Fe-based MOF catalysts. In this work, we manipulated the structure of Fe-oxo nodes in MIL-88B(Fe) via a Cu I species substitution method, affording a mixed-valence (Cu-incorporated Fe-MOFs) with highly improved Fenton-like performance. It is found that the Cu I serves as a shuttle to promote transfer between Fe II /Fe III, inducing the formation of a larger amount of stable Fe II sites, which was proven by experimental and DFT calculation results. A linear relationship was observed for the Fenton-like performance and the amount of Cu I species for the catalysts. The corresponding value of the • OH formation is 2.17 eV for Cu-incorporated MIL-88B(Fe), which is significantly lower than that of MIL-88B(Fe) (2.69 eV). Meanwhile, the enriched Cu I species suppress Fe species leaching during the catalytic reaction. The Fe-ion leakage of 0.4Cu@MIL-88B is very tiny (0.01–0.03 mg/L), significantly less than that of MIL-88B (2.00–3.02 mg/L). At the same time, H 2 O 2 utilization for 0.4Cu@ MIL-88B(Fe) is 88%, which is almost 4.4 times that of pure MIL-88B(Fe). This work provides insights into the rational design of Fe-MOFs as promising Fenton-like catalysts for wastewater treatment.