Fabrication of adsorbents with enhanced CuI stability: Creating a superhydrophobic microenvironment through grafting octadecylamine

doi:10.1016/j.cjche.2022.05.005

Abstract

Abstract: In atmospheric conditions, Cu^I is easily oxidized to Cu^II due to the coexistence of moisture and oxygen. The poor oxidation inhibition of Cu^I restricts the practical application of Cu^I-containing materials. Herein we introduce an approach to construct a superhydrophobic microenvironment in Cu^I-functionalized metal–organic frameworks by coordinatedly grafting organic amine compounds onto open metal sites (OMSs), which can hinder the accessibility of moisture to pores thereby enhancing the stability of Cu^I. As a proof of concept, MIL-101(Cr) with abundant OMSs and octadecylamine (OA) with long hydrophobic alkyl groups are used as carrier and surface coating. As superhydrophobic porous materials, the resultant Cu^IM-OA exhibits improved Cu^I stability in addition to retaining high crystallinity and intact porosity while almost all Cu^I is oxidized in hydrophilic Cu^IM upon exposure in a humid atmosphere for 30 h. Cu^IM-OA owns excellent adsorption desulfurization performance (ADS) with regard to thiophene, benzothiophene, and 4,6-dimethyl dibenzothiophene. Even from hydrated fuel, the adsorption performance of Cu^IM-OA maintains well while the adsorption capacity of Cu^IM decreases to 7% after 4 cycles. The remarkable moisture resistance, Cu^I stability, and high porosity make the current adsorbent Cu^IM-OA highly promising for the practical ADS process.

Key words: π-Complexation, Metal–organic frameworks, Superhydrophobicity, Cu^I stability, Adsorptive desulfurization (ADS)

摘要： In atmospheric conditions, Cu^I is easily oxidized to Cu^II due to the coexistence of moisture and oxygen. The poor oxidation inhibition of Cu^I restricts the practical application of Cu^I-containing materials. Herein we introduce an approach to construct a superhydrophobic microenvironment in Cu^I-functionalized metal–organic frameworks by coordinatedly grafting organic amine compounds onto open metal sites (OMSs), which can hinder the accessibility of moisture to pores thereby enhancing the stability of Cu^I. As a proof of concept, MIL-101(Cr) with abundant OMSs and octadecylamine (OA) with long hydrophobic alkyl groups are used as carrier and surface coating. As superhydrophobic porous materials, the resultant Cu^IM-OA exhibits improved Cu^I stability in addition to retaining high crystallinity and intact porosity while almost all Cu^I is oxidized in hydrophilic Cu^IM upon exposure in a humid atmosphere for 30 h. Cu^IM-OA owns excellent adsorption desulfurization performance (ADS) with regard to thiophene, benzothiophene, and 4,6-dimethyl dibenzothiophene. Even from hydrated fuel, the adsorption performance of Cu^IM-OA maintains well while the adsorption capacity of Cu^IM decreases to 7% after 4 cycles. The remarkable moisture resistance, Cu^I stability, and high porosity make the current adsorbent Cu^IM-OA highly promising for the practical ADS process.

关键词: π-Complexation, Metal–organic frameworks, Superhydrophobicity, Cu^I stability, Adsorptive desulfurization (ADS)

Zida Ma, Yuxia Li, Mengmeng Jin, Xiaoqin Liu, Linbing Sun. Fabrication of adsorbents with enhanced Cu^I stability: Creating a superhydrophobic microenvironment through grafting octadecylamine[J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 41-48.

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Fabrication of adsorbents with enhanced Cu^I stability: Creating a superhydrophobic microenvironment through grafting octadecylamine

Fabrication of adsorbents with enhanced Cu^I stability: Creating a superhydrophobic microenvironment through grafting octadecylamine

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