Adjusting accommodation microenvironment for Cu+ to enhance oxidation inhibition for thiophene capture

• Published in: AIChE journal Vol. 67; no. 10
• Main Authors: Li, Yu‐Xia, Jin, Meng‐Meng, Shi, Shu, Qi, Shi‐Chao, Liu, Xiao‐Qin, Sun, Lin‐Bing
• Format: Journal Article
• Language: English
• Published: Hoboken, USA John Wiley & Sons, Inc 01.10.2021; American Institute of Chemical Engineers
• Subjects: absorption; Activated carbon; Adsorptivity; composite materials; computational chemistry; Copper; Copper oxides; environmental engineering; fuels; Hydrophobicity; Moisture; Oxidation; Polydimethylsiloxane; Silica; Silicon dioxide; Stability
• ISSN: 0001-1541; 1547-5905
• DOI: 10.1002/aic.17368

Cu+‐containing materials have great potentials in various applications like adsorptive desulfurization. Nevertheless, their applications are severely obstructed by poor stability of Cu+ in air. Here, we first clarify the mechanism of Cu+ oxidation by first‐principle calculations and demonstrate that moisture accelerates Cu+ oxidation dramatically. Then, the microenvironment of Cu2O‐modified HKUST‐1, a typical metal‐organic framework, is adjusted from hydrophilic to hydrophobic with polydimethylsiloxane coating (producing Cu2O@HK@P). This isolates moisture from pores and enhances the stability of Cu+ significantly even under oxygen atmosphere. Cu+ in Cu2O@HK@P preserves well after exposed to air for 6 months, while Cu2O@HK lose almost all Cu+ for 2 weeks. The optimal Cu2O@HK@P can remove 540 μmol g−1 of thiophene from hydrous fuel, which is much superior to Cu2O@HK (227 μmol g−1) and most reported adsorbents. Our strategy can also be applied to stabilize Cu+ in various materials including zeolite, mesoporous silica, and activated carbon.