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

Mengzhen Song; Jingru Han; Yingzhi Wang; Lungang Chen; YanYan Chen; Xiaoyuan Liao

doi:10.1021/acsami.3c05928

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

ACS Appl Mater Interfaces. 2023 Aug 2;15(30):36201-36213. doi: 10.1021/acsami.3c05928. Epub 2023 Jul 19.

Authors

Mengzhen Song¹, Jingru Han¹, Yingzhi Wang¹, Lungang Chen², YanYan Chen³, Xiaoyuan Liao¹

Affiliations

¹ College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, Tianjin 300222, China.
² Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, China.
³ State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan, Shanxi 030001, China.

PMID: 37464747
DOI: 10.1021/acsami.3c05928

Abstract

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 H₂O₂ 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, H₂O₂ 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.

Keywords: Cu-incorporated; Fe-MOFs; Fenton-like; H2O2 utilization; stability.