CH4/N2 adsorption separation research of MOFs with divalent Cr/Mo/Ni unsaturated metal sites

doi:10.11949/j.issn.0438-1157.20180302

Abstract

Abstract:

Based on the strong interaction energy between the coordinatively unsaturated metal sites (UMSs) and the gas molecules, M-BTC(M=Cr, Mo, Ni), isostructural with HKUST-1 (Cu-BTC), were successfully synthesized via the coordination reaction of the high activity divalent metal (Cr²⁺/Mo²⁺/Ni²⁺) and organic ligand (H₃BTC), and then to gain insight into the impact of gas-metal interactions on the selective adsorption of CH₄ from N₂ by comparing with classical materials (Cu-BTC). The results show the good CH₄ selective adsorption properties of M-BTC (M=Cr, Mo, Ni) with UMSs. Among these materials, Ni-BTC with unsaturated Ni²⁺ sites presents the highest adsorption heat value for CH₄, leading to the excellent CH₄/N₂ adsorption separation properties; but the Cr-BTC with high Cr²⁺ activity shows the lower ability for CH₄/N₂ separation than Cu-BTC. Combined the IAST calculation results, we verified the ability for the selective adsorption of CH₄ molecules on M-BTC (M=Cr, Mo, Ni) and Cu-BTC followed as Ni-BTC > Mo-BTC > Cu-BTC > Cr-BTC.

Key words: methane, nitrogen, adsorption, adsorbents, coordinatively unsaturated metal sites

摘要：

基于金属有机骨架材料中金属空配位对气体的强吸附作用，利用具有较高活性的二价金属Cr²⁺/Mo²⁺/Ni²⁺与均苯三酸（H₃BTC）配位合成了HKUST-1（Cu-BTC）同构系列材料M-BTC（M=Cr、Mo、Ni），并与Cu-BTC对比分析了该类型材料中不同金属空配位对甲烷和氮气的吸附性能。实验结果显示，此三种材料均具有较好的甲烷选择吸附性，其中含Ni²⁺金属空位的Ni-BTC以其尤为突出的甲烷吸附热值而呈现较好的CH₄/N₂分离潜力；Cr²⁺空配位虽具有较强活性，但是对于甲烷的选择性吸附性能却低于含Cu²⁺空位的Cu-BTC材料。结合吸附选择性IAST计算分析得到此三种含较高活性不饱和金属空配位的MOFs材料对于甲烷选择性吸附作用能顺序为：Ni-BTC > Mo-BTC > Cu-BTC > Cr-BTC。

关键词: 甲烷, 氮气, 吸附, 吸附剂, 不饱和金属空配位

CLC Number:

TQ028.8

JIA Xiaoxia, WANG Li, YUAN Ning, YANG Jiangfeng, LI Jinping. CH₄/N₂ adsorption separation research of MOFs with divalent Cr/Mo/Ni unsaturated metal sites[J]. CIESC Journal, 2018, 69(9): 3896-3904.

贾晓霞, 王丽, 元宁, 杨江峰, 李晋平. 二价铬/钼/镍空配位MOFs的CH₄/N₂吸附分离研究[J]. 化工学报, 2018, 69(9): 3896-3904.

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CH₄/N₂ adsorption separation research of MOFs with divalent Cr/Mo/Ni unsaturated metal sites

二价铬/钼/镍空配位MOFs的CH₄/N₂吸附分离研究

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