太原理工大学李立博团队报道了柱状层状MOFs中孔环境对乙烯一步提纯的调节。相关研究成果发表在2024年12月19日出版的《中国化学》。

由于C₂H₆、C₂H₄和C₂H₂的物理和化学性质极其相似，一步从C2三元混合物中纯化乙烯非常具有挑战性。

该文中，研究人员通过使用孔工程策略对柱配体进行功能化，开发了一系列柱层状MOF材料((Ni(BTC)(Bipy), Ni(BTC)(3-Me-Bipy)和 Ni(BTC)(3-NH2-Bipy))。单组分吸附等温线测量表明，这些材料优先吸附C₂H₆和C₂H₂，从而实现了三种C2烃的一步纯化以获得C₂H₄。通过在柱上引入官能团，CH/CH的选择性提高了10%以上，而CH/CH选择性提高了300%以上。具体而言，Ni(BTC)(3-NH2-Bipy)对C₂H₆/C₂H₄（50/50，V/V）的选择性为1.5，对C₂H₂/C₂H₄（1/99，V/V）为5.16。

在环境条件下，Ni(BTC)(3-NH2-Bipy)对C₂H²的吸附容量达到121.6 cm³/g，与许多经典材料（包括TJT-100、Azole-Th-1和MOF-808-Bzz，通常用于从C2三元混合物中纯化C₂H₄）相比，Ni(BTC)(3-NH2-Bipy)表现出优异的C₂H₂吸附容量和C₂H₂/C₂H₄选择性。动态突破实验表明，在三元C2混合物中，Ni(BTC)(3-NH2-Bipy)优先捕获C₂H₆和C₂H₂，实现了C₂H₄的一步纯化。

附：英文原文

Title: Modulation of the Pore Environment in Pillar-Layered MOFs for One-Step Purification of Ethylene

Author: Yi Wang, Jian Tan, Yongheng Ren, Yang Chen, Jinping Li, Libo Li

Issue&Volume: 2024-12-19

Abstract: Due to the extremely similar physical and chemical properties of C2H6, C2H4, and C2H2, purifying ethylene from the C2 ternary mixture in one-step is very challenging. In this work, we developed a series of pillar-layered MOF materials ((Ni(BTC)(Bipy), Ni(BTC)(3-Me-Bipy), and Ni(BTC)(3-NH2-Bipy)) through the functionalization of pillar ligands using pore engineering strategies. Single-component adsorption isotherm measurements demonstrate that these materials preferentially adsorb C2H6 and C2H2, thereby achieving one-step purification of the three C2 hydrocarbons to obtain C2H4. By introducing functional groups on the pillars, the selectivity for CH/CH increased by over 10%, while the selectivity for CH/CH increased by more than 300%. Specifically, Ni(BTC)(3-NH2-Bipy) exhibits a selectivity of 1.5 for C2H6/C2H4 (50/50, V/V) and 5.16 for C2H2/C2H4 (1/99, V/V). Under ambient conditions, the adsorption capacity of Ni(BTC)(3-NH2-Bipy) for C2H2 reached 121.6 cm3/g, Ni(BTC)(3-NH2-Bipy) exhibits superior C2H2 adsorption capacity and C2H2/C2H4 selectivity compared to many classic materials, including TJT-100, Azole-Th-1, and MOF-808-Bzz, commonly used for C2H4 purification from C2 ternary mixtures. Dynamic breakthrough experiments indicate that in a ternary C2 mixture, Ni(BTC)(3-NH2-Bipy) preferentially captures C2H6 and C2H2, enabling one-step purification of C2H4.

DOI: 10.1002/cjoc.202400977

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.202400977