Zn/Cu单晶转换MOF材料的CO2/CH4分离性能研究

doi:10.11949/0438-1157.20200287

摘要/Abstract

摘要：

CO₂的捕获和分离具有重要的工业和环境意义。采用溶剂热法，以羧基和路易斯碱位点功能修饰的配体和锌离子构筑了阴离子型金属有机框架材料{[Zn₂(N)·(DMF)₃·(CH₃)₂NH₂]·(DMF)₂}_n (NEM-7-Zn)。为了提高骨架的稳定性，通过金属离子置换工艺，将NEM-7-Zn转化为高稳定性的铜基框架材料NEM-7-Cu。采用EA、PXRD、TGA及比表面积分析等技术对多孔材料进行综合表征，并测定了NEM-7-Cu对二氧化碳、乙炔和甲烷单组分气体的吸附等温线。实验结果表明，NEM-7-Cu不仅具有较高的CO₂ 吸附性能（74 cm³·g^-1），更表现出优异的CO₂/CH₄（11.5）和C₂H₂/CH₄（7.1）吸附选择性。通过巨正则Monte Carlo方法（GCMC）计算得到CO₂在NEM-7-Cu中的主要吸附位点为功能基团羧基与路易斯碱位点附近以及Cu的金属团簇附近。

关键词: 金属-有机框架材料, 金属离子置换（Zn/Cu）, CO₂, CO₂/CH₄

Abstract:

The adsorption and separation of CO₂ are of great importance from both industrial and environmental points of view. A metal-organic framework {[Zn₂(N)·(DMF)₃·(CH₃)₂NH₂]·(DMF)₂}_n (NEM-7-Zn) was synthesized by nitrogen sites and —COO^- groups decorated ligand. In order to improve the stability, the metal center of NEM-7-Zn was converted from Zn to Cu through metal ion exchange, which resulted in a stable skeleton (NEM-7-Cu). The synthesized materials were characterized by analysis techniques including EA, PXRD, TGA and specific surface area analysis. Single-component adsorption isotherms for acetylene and carbon dioxide on NEM-7-Cu was determined. Gas adsorption test results show that, NEM-7-Cu possesses high CO₂ uptake (74 cm³·g^-1) and selectivities for CO₂/CH₄ (11.5) and C₂H₂/CH₄(7.1). Grand canonical Monte Carlo (GCMC) simulations revealed the strong CO₂ adsorption sites exist near the Cu^Ⅱ cluster sites, the uncoordinated —COO^- groups and the Lewis basic nitrogen sites.

Key words: metal-organic framework, metathesis of zinc with copper, CO₂, CO₂/CH₄

中图分类号:

O 611.4

刘增欣,王依军,郝春莲,刘秀萍. Zn/Cu单晶转换MOF材料的CO₂/CH₄分离性能研究[J]. 化工学报, 2021, 72(S1): 546-553.

LIU Zengxin,WANG Yijun,HAO Chunlian,LIU Xiuping. Metal-organic frameworks: metathesis of zinc(Ⅱ) with copper(Ⅱ) for efficient CO₂/CH₄ separation[J]. CIESC Journal, 2021, 72(S1): 546-553.

图/表 6

图1 NEM-7-Zn的晶体结构羧基和氮修饰的配体(a)；锌的次级结构单元(b)；沿C轴方向的NEM-7-Zn结构堆积图(c)(锌:蓝绿色；碳:橘红色；氧:红色；氮:蓝色)

Fig.1 Structural representation of NEM-7-Zn tetracarboxylate linker (a); Coordination environments of the metal centers in the secondary building units (b); Packing mode presentation of NEM-7-Zn (c)

图2 NEM-7-Zn、模拟NEM-7-Zn单晶、蓝色离子交换后制备的NEM-7-Cu、活化后的NEM-7-Cu、活化后的NEM-7-Zn的XRD谱图(a)；配体H5N、NEM-7-Zn、金属中心转换之后的NEM-7-Cu及活化后的红外吸收光谱(b)

Fig.2 XRD patterns of NEM-7-Zn (simulated from X-ray crystal diffraction data) and NEM-7-Zn and as-synthesized NEM-7-Cu samples, activated NEM-7-Cu, activated NEM-7-Zn, respectively(a); FT-IR spectra of ligand H5N, NEM-7-Zn and NEM-7-Cu in the as-synthesized, and activated adsorbed states (b)

图3 NEM-7-Zn和金属离子交换后的NEM-7-Cu晶体图(a); 金属锌转化为金属铜的动力学过程曲线(b)；金属锌(c)转化为金属铜(d)的EDX能谱图

Fig.3 Photographs of the NEM-7-Zn sample before and after the metal-ion metathesis (a); Kinetic profiles of the framework metal ion exchange of Zn2+ in NEM-7-Zn with Cu2+ (b); EDX for the conversion of NEM-7-Zn (c) to NEM-7-Cu(d)

图4 77 K条件下NEM-7-Zn和NEM-7-Cu的氮气吸附等温线(a)；NEM-7-Cu的孔径分布(b)

Fig.4 The N2 adsorption isotherm in NEM-7-Zn and NEM-7-Cu at 77 K(a); Pore size distribution for NEM-7-Cu evaluated by using N2 adsorption data measured at 77 K (b)

图5 NEM-7-Cu的吸附曲线和吸附热273 K和298 K条件下CO2(a)、C2H2(b)和CH4(c)的吸附曲线；C2H2、CO2 和CH4的吸附热(d)

Fig.5 The adsorption isotherms and isosteric heats of adsorption of NEM-7-Cu CO2 (a)，C2H2 (b) and CH4 (c) adsorption isotherms in NEM-7-Cu at 273 K and 298 K; The isosteric heats of adsorption of C2H2, CO2 and CH4 (d)

图6 273 K和0.1 bar条件下通过GCMC模拟的CO2在NEM-7-Cu的吸附密度图(a)；通过IAST计算NEM-7-Cu的CO2/CH4(b)和C2H2/CH4的吸附选择性(c)

Fig.6 Density distribution of CO2 molecules in the unit cell of NEM-7-Cu at 273 K and 0.1 bar simulated by GCMC (a)；Adsorption selectivities of NEM-7-Cu calculated by the IAST method for mixtures of CO2/CH4 (b) and C2H2/CH4 (c)

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Zn/Cu单晶转换MOF材料的CO₂/CH₄分离性能研究

Metal-organic frameworks: metathesis of zinc(Ⅱ) with copper(Ⅱ) for efficient CO₂/CH₄ separation

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