Bifunctional Fe for Induced Graphitization and Catalytic Ozonation Based on a Fe/N-Doped Carbon-Al_2O_3 Framework: Theoretical Calculations Guided Catalyst Design and Optimization

摘要

Heterogeneous catalytic ozonation is regarded as a feasible technology in advanced wastewater treatment. Catalytic performance, mass transfer, and mechanical strength are the key elements for large-scale applications of catalysts. To optimize those elements, Fe was selected for its dual role in graphitization and catalytic ozonation. A Fe/N-doped micron-scale carbon-Al_2O_3 framework (CAF) was designed and applied to a fluidized catalytic process for the treatment of secondary effluent from coal gasification. The chemical oxygen demand removal rate constant and the hydroxyl radical generation efficiency (R_(ct)) of the Fe/N- doped CAF were 190% and 429% higher than those of pure ozone, respectively. Theoretical calculations revealed that higher Fe valence promoted ozone decomposition, which implied increasing Fe~Ⅲ content for further catalyst optimization. The rate constant and R_(ct) with a higher Fe~Ⅲ-proportion catalyst were increased by 13% and 16%, respectively, compared to those with the lower one. Molecular dynamics and density functional theory calculations were performed to analyze the reaction kinetics qualitatively and quantitatively. The energy barrier corresponding to Fe~Ⅲ configuration was 1.32 kcal mol~(-1), 27% lower than that for Fe~Ⅱ configuration. These theoretical calculations guided the catalyst optimization and provided a novel solution for designing ozonation catalysts. The Fe/N-doped CAF demonstrated a great potential for practical applications.