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

Abstract

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.

Cu+-Doped PVA-Derived Mesoporous Carbon@Diatomite Adsorbent for Selective Adsorption Desulfurization

“…3 Therefore, the development of high-performance adsorbents was indispensable to SADS technology. Even though a catalog of high-performance adsorbents, such as metal oxides, 4 molecular sieves, 5 porous carbon, 6 metal− organic skeleton (MOF), 7 and so on, has been developed so far, their separation from fuels after use is more difficult or causes serious loss, hindering their practical application. 8 Up to date, the transition metal Cu was assumed to be the distinguished adsorbing active species oriented to adsorption desulfurization due to the existence of interaction with S in aromatic sulfides through π-complexation.…”

Design of High-Humidity-Proof Hierarchical Porous P-ZIF-67(Co)-Polymer Composite Materials by Surface Modification for Highly Efficient Volatile Organic Compound Adsorption

“…Nevertheless, Zhou’s work shows that hydrophobic ligands could not completely prevent crystal structure destruction due to water occupation. Jin et al and Li et al , demonstrated the feasibility of surface hydrophobicity modification of MOFs from hydrophilic to superhydrophobic by the chemical vapor deposition (CVD) of PDMS. At the same time, Guo et al prepared a high-performance composite, NbOFFIVE-1-Ni@PA, based on polyacrylate (PA).…”

Steric effects of alkyl dibenzothiophenes: The root cause of frustrating efficacy of heterogeneous desulfurization for real diesel

“…[1][2][3] At present, the allowable S-content is restricted to 10 ppm or lower in many countries. [4][5][6] Further, S-free oil is vital in fuel cell development toward carbon emission abatement and neutralization. Hydrodesulfurization (HDS) is a conventional process for the removal of some S-components, for example, mercaptans, thioethers, and thiophenes.…”

“…Thus, fuel desulfurization is a must in petroleum refinery 1–3 . At present, the allowable S‐content is restricted to 10 ppm or lower in many countries 4–6 . Further, S‐free oil is vital in fuel cell development toward carbon emission abatement and neutralization.…”