Copper-based catalysts are widely employed in the catalytic conversion of aromatic compounds to phenolic derivatives. However, single-atom copper catalysts often exhibit limited reactivity and stability. In this study, we addressed these limitations by loading Cu onto NaY zeolite via ion exchange to synthesize a CuY catalyst, followed by Yb modification. By optimizing the Yb content, we significantly enhanced the anisole conversion rate and guaiacol yield. Catalyst characterization revealed that Yb species modulate the electronic structure of copper, favoring the formation of abundant Cu+ species. This electronic modification promotes the catalytic generation of hydroxyl radicals (˙OH) from hydrogen peroxide, thereby accelerating the reaction kinetics. Furthermore, Yb incorporation into CuY induced the formation of oxygen vacancies, which improved hydroxyl radical adsorption and facilitated the generation of metal-oxo species. These synergistic effects collectively increased the reaction's overall conversion efficiency. Under optimized reaction conditions, the Yb/CuY catalyst achieved an anisole conversion of 56.2% and an ortho-selectivity of 74.6%, clearly outperforming previous reports.
Tuo Zheng,Haiyan Fan,Jia Zhao,Jile Fu,Songshou Ye,Sajid Ali,Nuowei Zhang,Jinbao Zheng,Binghui Chen
In diesel adsorption desulfurization, the coordination bonding between the adsorbent and sulfur compounds is interfered by aromatic compounds in diesel. Transition metal cation exchanged zeolites Y has exhibits exceptional anti-interference performance. In this work, the influence of electron configuration on coordination bonding is explored, specifically between the adsorbent and substrate, using both experimental and DFT theoretical methods. Initially, NiY, CuY and ZnY were synthesized and evaluated for their desulfurization performance in model solution (sulfur content: 25 ppmw dibenzothiophene [DBT]) with two toluene concentrations (1 w% and 3 w%). It is found that CuY showed the highest performance with retention rate at 70.2 %. Subsequently, DFT calculations revealed the binding energy between Cu(II) and DBT was −2.71 eV, higher than Ni(II) and Zn(II), and that between Cu(II) and toluene was −1.75 eV, lower than Ni(II) and Zn(II), indicating that the highest binding energy difference was responsible for the best adsorption capability. Apart from these, wave function analysis show the electron configuration between Cu(II) and DBT had the highest binding energy difference. Finally, the impact of electron configuration on adsorption performance is further investigated by modulating the electron configuration of Ni(II) to enhance/suppress its adsorption capability. According to the findings of this study, tuning the electron configuration is an effective strategy to develop materials in adsorptive desulfurization particularly for extra low sulfur content.
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