金属-有机骨架材料CO2捕获性能的大规模计算筛选

doi:10.11949/j.issn.0438-1157.20181079

化工学报 ›› 2019, Vol. 70 ›› Issue (3): 1135-1143.DOI: 10.11949/j.issn.0438-1157.20181079

• 材料化学工程与纳米技术 • 上一篇下一篇

金属-有机骨架材料CO₂捕获性能的大规模计算筛选

王磊¹(),方桂英²(),阳庆元¹()

1. 北京化工大学有机无机复合材料国家重点实验室，北京 100029
2. 江西农业大学理学院，江西南昌 330045

收稿日期:2018-09-26 修回日期:2018-12-10 出版日期:2019-03-05 发布日期:2019-03-05
通讯作者: 方桂英,阳庆元
作者简介:<named-content content-type="corresp-name">王磊</named-content>（1993—），男，硕士研究生，<email>evacolin@163.com</email>|方桂英（1964—），女，学士，副教授，<email>guiyingfang1012@163.com</email>|阳庆元（1976—），男，博士，教授，<email>qyyang@mail.buct.edu.cn</email>
基金资助:
国家重大基础研究计划项目(2016YFA0201701);中央高校基本科研业务费专项资金(buctrc201727)

Performance of metal-organic frameworks for CO₂ capture from large-scale computational screening

Lei WANG¹(),Guiying FANG²(),Qingyuan YANG¹()

1. State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
2. School of Sciences, Jiangxi Agricultural University, Nanchang 330045, Jiangxi, China

Received:2018-09-26 Revised:2018-12-10 Online:2019-03-05 Published:2019-03-05
Contact: Guiying FANG,Qingyuan YANG

摘要/Abstract

摘要：

全球性温室效应形势的日趋严重，迫切需要研究和开发可用于CO₂捕集的高性能材料。对于含有双铜船桨型片段(Cu₂(COO)₄)的MOF材料，因其结构中含有配位不饱和的Cu金属位点，在低压区域的CO₂捕获方面展现出优异的性能。目前，大规模计算筛选工作主要是基于传统的分子力场，无法对此类Cu-MOFs中主客体分子间的相互作用进行准确描述。基于量化计算获得的精确分子力场，利用Monte Carlo分子模拟方法考察了常温常压条件下763个基于Cu-OMS的MOF材料对CO₂存储和CO₂/N₂的分离行为。不仅筛选出潜在的高性能材料，而且揭示出了材料的结构与其性能之间的关系和具有优良性能的材料结构特征，可为面向特定应用的新材料设计和合成提供理论参考。

关键词: 金属-有机骨架材料, Cu开放金属位点, 吸附, 分离, 分子模拟, 大规模筛选

Abstract:

The global greenhouse effect situation is becoming more and more serious, and there is an urgent need to research and develop high-performance materials that can be used for CO₂ capture. Metal?organic frameworks (MOFs) containing an inorganic unit of copper paddle-wheel (Cu₂(COO)₄) have excellent performance in CO₂ capture in low pressure region because of their coordinatively unsaturated Cu sites. However, large-scale computational screening work available so far mainly used conventional molecular force field, which cannot accurately describe the host-guest molecules involved in current study. Thus, on the basis of accurate molecular force fields derived from quantum mechanics calculations, grand canonical Monte Carlo simulation method was adopted to investigate CO₂ storage and CO₂/N₂ separation behaviors of 763 MOFs with Cu-OMS under ambient conditions. Not only were promising MOFs found through large-scale screening, but the established structure-performance relationships and the structural characteristics of high-performance materials were revealed, providing a theoretical foundation for design and synthesis of new materials for targeted applications.

Key words: metal-organic frameworks, open Cu sites, adsorption, separation, molecular simulation, large-scale screening

中图分类号:

TQ 028.8

王磊, 方桂英, 阳庆元. 金属-有机骨架材料CO₂捕获性能的大规模计算筛选[J]. 化工学报, 2019, 70(3): 1135-1143.

Lei WANG, Guiying FANG, Qingyuan YANG. Performance of metal-organic frameworks for CO₂ capture from large-scale computational screening[J]. CIESC Journal, 2019, 70(3): 1135-1143.

图/表 8

表1 描述MOFs中Cu开放金属位点和CO2分子之间特殊作用的Morse势能参数

Table 1 Morse potential parameter for describing specific interactions between CO2 molecules and open Cu sites of MOFs

Atom pair	D₀/(kJ/mol)	R₀/nm	α
Cu-CO_2-O^[31]	1.0113	0.3313	10.5781

图1 N2在Cu-BTC和Cu-TDPAT(a), ZJU-8a和ZJNU-40a(b)中的模拟吸附等温线与实验值对比

Fig.1 Comparison of simulated adsorption isotherms of N2 in Cu-BTC and Cu-TDPAT(a), ZJU-8a and ZJNU-40a(b) with experimental data

图2 常温常压下763个Cu-OMS MOFs中CO2吸附量的模拟构效关系：材料最大孔径(a)，无限稀释吸附热(b)

Fig.2 Gravimetric CO2 uptakes of 763 MOFs with Cu-OMS versus largest cavity diameter (LCD) (a), zero-coverage isosteric heat of adsorption (Qst0) (b) under ambient conditions

图3 常温常压下763种Cu-OMS MOF材料的CO2吸附性能与材料孔体积(a)、材料孔隙率(b)、比表面积(c)、吸附度(d)之间的

Fig.3 Relationships of CO2 uptake of 763 Cu-OMS-containing MOFs under ambient conditions with pore volume(a), fraction(b), accessible surface area(c) and adsorbility (AD)(d)(Uptakes are colored by value of AD in (a), (b) and (c))

图4 298 K和0.1 MPa条件下CO2在MAJJUF材料的微观吸附结构

Fig.4 Microscopic adsorption structures of CO2 molecules in MAJJUF and 298 K and 0.1 MPa

图5 常温常压下763种Cu-OMS MOF材料的CO2/N2分离选择性与1/ΔAD的关系

Fig.5 Relationship between CO2/N2 selectivity of 763 Cu-OMS-containing MOFs and 1/ΔAD at ambient conditions

图6 298 K和0.1 MPa下MOF材料的CO2/N2(15:85)选择性与其CO2吸附量之间的关系（正方形代表本工作中筛选出的两种前景材料;三角形代表目前文献中已经报道的最佳材料)

Fig.6 CO2/N2 (15:85) separation performance of 763 MOFs with Cu-OMS at 298K and 0.1 MPa(Squares represent top 2 MOFs identified in this work; triangles denote some of best MOFs experimentally reported in literature)

图7 298 K和0.1 MPa条件下CO2和N2在NEYRIU材料的微观吸附结构(蓝色代表N2分子)

Fig.7 Microscopic adsorption structures of CO2 and N2 molecules in NEYRIU and 298 K and 0.1 MPa(N2 molecule is colored by blue)

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金属-有机骨架材料CO₂捕获性能的大规模计算筛选

Performance of metal-organic frameworks for CO₂ capture from large-scale computational screening

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