Hayashi Mikio, Lee Dennis T, de Mello Matheus Dorneles, Boscoboinik J Anibal, Tsapatsis Michael
Department of Chemical and Biomolecular Engineering, & Institute for NanoBioTechnology, Johns Hopkins University, 3400 N. Charles Street, Baltimore, MD, 21218, USA.
Science & Innovation Center, Mitsubishi Chemical Corporation, 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa, 227-8502, Japan.
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9316-9320. doi: 10.1002/anie.202100173. Epub 2021 Mar 12.
Vapor-phase treatment of ZIF-8 membranes with manganese(II) acetylacetonate (Mn(acac) ) allows permselectivity tuning. Propylene/propane selectivity increases from 31 to 210 after the Mn(acac) treatment at 165 °C for 30 min, while selectivities increase from 14.6 to 242 for H /CH , from 2.9 to 38 for CO /CH , from 2.4 to 29 for CO /N , and from 2.9 to 7.5 for O /N , after Mn(acac) treatment at 175 °C for 30 min. Stable equimolar propylene/propane mixture selectivity of 165 at ambient temperature and 4 bar equimolar feed with a propylene flux of 8.3×10 mol m s is established. A control experiment excludes thermal treatment alone causing these changes. XPS analysis reveals the presence of Mn(acac) on the outer surface of the vapor-treated ZIF-8 membranes while no other changes are detectable by X-ray diffraction and infrared spectroscopy.
用乙酰丙酮锰（Mn(acac)₂）对ZIF-8膜进行气相处理可实现渗透选择性调节。在165 °C下用Mn(acac)₂处理30分钟后，丙烯/丙烷选择性从31增加到210，而在175 °C下用Mn(acac)₂处理30分钟后，H₂/CH₄选择性从14.6增加到242，CO₂/CH₄选择性从2.9增加到38，CO₂/N₂选择性从2.4增加到29，O₂/N₂选择性从2.9增加到7.5。在环境温度和4 bar等摩尔进料条件下，建立了稳定的等摩尔丙烯/丙烷混合物选择性为165且丙烯通量为8.3×10⁻⁷ mol m⁻² s⁻¹的情况。对照实验排除了仅热处理导致这些变化的可能性。X射线光电子能谱（XPS）分析表明，气相处理后的ZIF-8膜外表面存在Mn(acac)₂，而X射线衍射和红外光谱未检测到其他变化。
