福建师范大学陈邦林团队报道了含氟阴离子的空间划分孔金属-有机骨架用于基准C₂H₂/CO₂分离。相关研究成果发表在2024年6月11日出版的《美国化学会杂志》。

C₂H₂与C₂H₂/CO₂或C₂H₂/CO₂/CH₄混合物的有效分离对于实现高纯度C₂H₂（>99%）至关重要，这对于生产当代商品化学品至关重要。

该文中，研究人员介绍了一种金属-有机框架，ZNU-12，其具有由无机氟化阴离子形成的空间划分孔，用于高效的C₂H₂/CO₂或C₂H₂/CO₂/CH₄分离。该框架由氟化SiF₆^2–阴离子划分为三个不同的笼状物，能够同时实现高的C₂H₂容量（在298K和1.0bar下为176.5 cm³/g）和优异的C₂H₂对CO₂（13.4）和CH₄（233.5）的选择性。

值得注意的是，通过高回收率的吸附-解吸突破实验循环，我们从C₂H₂/CO₂（v/v=50/50）和C₂H₂/CO₂/CH₄（v/v=1/1/1、1/1/2或1/1/8）混合物中获得了创纪录的C₂H₂生产率（132.7、105.9、98.8和80.0 L/kg，纯度99.5%）。理论计算表明，在受限空腔中，C₂H₂和两个六氟硅酸盐（SiF₆^2-）阴离子之间存在有效的“2+2”协同氢键。

附：英文原文

Title: Metal–Organic Framework with Space-Partition Pores by Fluorinated Anions for Benchmark C2H2/CO2 Separation

Author: Yuanbin Zhang, Yan Han, Binquan Luan, Lingyao Wang, Wenlei Yang, Yunjia Jiang, Teng Ben, Yabing He, Banglin Chen

Issue&Volume: June 11, 2024

Abstract: The efficient separation of C2H2 from C2H2/CO2 or C2H2/CO2/CH4 mixtures is crucial for achieving high-purity C2H2 (>99%), essential in producing contemporary commodity chemicals. In this report, we present ZNU-12, a metal–organic framework with space-partitioned pores formed by inorganic fluorinated anions, for highly efficient C2H2/CO2 and C2H2/CO2/CH4 separation. The framework, partitioned by fluorinated SiF62– anions into three distinct cages, enables both a high C2H2 capacity (176.5 cm3/g at 298 K and 1.0 bar) and outstanding C2H2 selectivity over CO2 (13.4) and CH4 (233.5) simultaneously. Notably, we achieve a record-high C2H2 productivity (132.7, 105.9, 98.8, and 80.0 L/kg with 99.5% purity) from C2H2/CO2 (v/v = 50/50) and C2H2/CO2/CH4 (v/v = 1/1/1, 1/1/2, or 1/1/8) mixtures through a cycle of adsorption–desorption breakthrough experiments with high recovery rates. Theoretical calculations suggest the presence of potent “2 + 2” collaborative hydrogen bonds between C2H2 and two hexafluorosilicate (SiF62–) anions in the confined cavities.

DOI: 10.1021/jacs.4c03442

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c03442