Enhancing oxidation resistance of Cu(I) by tailoring microenvironment in zeolites for efficient adsorptive desulfurization

• Published in: Nature communications Vol. 11; no. 1; pp. 3206 - 9
• Main Authors: Li, Yu-Xia, Shen, Jia-Xin, Peng, Song-Song, Zhang, Jun-Kai, Wu, Jie, Liu, Xiao-Qin, Sun, Lin-Bing
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 25.06.2020; Nature Publishing Group; Nature Portfolio
• Subjects: 140/146; 147/135; 147/143; 639/638/224; 639/638/263; Adsorptivity; Coexistence; Copper; Desulfurization; Desulfurizing; Fuels; Humanities and Social Sciences; Hydrophobic surfaces; Hydrophobicity; Moisture; multidisciplinary; Oxidation; Oxidation resistance; Oxygen; Polydimethylsiloxane; Science; Science (multidisciplinary); Sulfur; Sulfur compounds; Sulfur removal; Zeolites
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-17042-6

The zeolite Cu(I)Y is promising for adsorptive removal of thiophenic sulfur compounds from transportation fuels. However, its application is seriously hindered by the instability of Cu(I), which is easily oxidized to Cu(II) even under atmospheric environment due to the coexistence of moisture and oxygen. Here, we report the adjustment of zeolite microenvironment from hydrophilic to superhydrophobic status by coating polydimethylsiloxane (yielding Cu(I)Y@P), which isolates moisture entering the pores and subsequently stabilizes Cu(I) despite the presence of oxygen. Cu(I) in Cu(I)Y@P is stable upon exposure to humid atmosphere for 6 months, while almost all Cu(I) is oxidized to Cu(II) in Cu(I)Y for only 2 weeks. The optimized Cu(I)Y@P material after moisture exposure can remove 532 μmol g −1 of thiophene and is much superior to Cu(I)Y (116 μmol g −1 ), regardless of similar uptakes for unexposed adsorbents. Remarkably, Cu(I)Y@P shows excellent adsorption capacity of desulfurization for water-containing model fuel. Zeolite Cu(I)Y is attractive for adsorptive removal of sulfur compounds from fuel, however practical application is limited by instability of Cu(I). Here the authors use a coating to achieve superhydrophobicity in the zeolite, leading to improved Cu(I) stability against oxidation and thiophene removal.