金属—有机骨架材料中天然气存储的分子模拟研究及MOF-5的实验合成
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摘要
金属—有机骨架材料(Metal-Organic Frameworks,MOFs)是一类类似于沸石的新型多孔材料,具有多样性的结构组成、较大的比表面积和孔隙率、可裁剪性的孔等特点,可应用于气体储存、分离及催化等领域。计算化学不仅可以突破传统方法的局限性,而且还可为最佳吸附材料的设计和最优操作条件的确定提供理论依据,实现从以经验为主向定量、定向制备的转变,从而节省大量繁杂的实验研究。本工作主要针对甲烷存储这一热门话题,通过分子模拟手段分析其在材料中的吸附机理,从而设计具有更高甲烷存储量的新材料。此外,为了进一步设计新材料,我们进行了实验合成的探索研究。其主要研究内容如下:
1、针对具有最大甲烷存储量的金属—有机骨架材料(MOFs)PCN-14,采用质心分布图研究了甲烷在其中的吸附机理。结果表明,PCN-14中主要存在两个吸附位,其中金属簇—苯基区域中靠近苯环的位置为第一吸附位,蒽基上方为第二吸附位。两个吸附位均与有机配体有关,有机配体较之金属簇在CH_4的吸附中发挥着重要的作用。
2、在此基础上,我们通过改变PCN-14的有机配体,设计了具有高存储量的新型MOF材料PCN-M1和PCN-M2。通过模拟290 K时的吸附等温线,发现新材料PCN-M1和PCN-M2的吸附性能比PCN-14增强很多。在3.5 PMa时,PCN-M1、PCN-M2的吸附量分别达到了246 v/v、257 v/v,比PCN-14增加了7%、12%。本章接着模拟了298 K和3.5 MPa时的吸附,PCN-M2对甲烷的吸附量达到了241v/v,超过了DOE标准180 v/v的34%。
3、为了进一步验证上述分子模拟结果,需要实验合成上述新材料并对其结构特性以及吸附性能进行研究,从而开发具有更高甲烷存储量的MOF材料。但是由于本实验室之前并没有过实验合成MOF材料的经验,所以本人选择合成晶体结构相对简单、合成步骤简易的MOF-5材料,为本实验室开展实验合成MOF材料做前期探索工作,为建立分子模拟—实验合成共同筛选高性能甲烷存储材料机制作前期准备。
Metal-Organic Frameworks (MOFs), commonly recognized as "soft" analogues of zeolites, is a new class of nanoporous materials. MOFs, with extremely high porosity, chemical diversity, and as tailored materials with well-defined pore size, are promising materials for gases storage, separation, and catalyst, etc. Computational chemistry can not only overcome the limitations of traditional methods, but also provides theoretical guidance for the design of optimal adsorbents and the determination of optimal industrial operation conditions, which also saves a lot of time for complicated experimental works. In this work, a systematic study was carried out on methane storage in MOFs using molecular simulation technique, and the new material was designed by investigating the adsorption mechanism in MOFs. Furthermore, we also synthesized a MOF material named MOF-5. The main contents and findings are summarized as follows:
(1) An effective method denoted as "center of mass probability distributions" was employed to study the methane adsorption mechanism in metal-organic framework PCN-14 which shows the highest methane storage capacity to date, finding that this material has two adsorption sites for methane molecules, and the organic linkers play an important role in adsorption.
(2) Based on this point, two new materials named PCN-M1 and PCN-M2 were designed by modifying the organic linkers of PCN-14. The newly designed MOF materials have a methane storage capacity of ca. 246 and 257 v/v at 290 K and 3.5 MPa, which is 7 % and 12 % higher than that of PCN-14. On the other hand, it has a methane capacity of ca. 241 v/v at 298 K and 3.5 MPa in PCN-M2, which is 34 % over the DOE target (180 v/v).
(3) In order to further verify the simulation results mentioned above, we should experimentally synthesize the new designed materials and investigate their structural characteristics, as well as the adsorption performance. Thus, we can develop a higher amount of methane stored MOF materials. However, as the limited ability in synthesis of MOF materials in our laboratory, we have to synthesize a relatively simple material (MOF-5) firstly, as the preliminary exploration work.
1、针对具有最大甲烷存储量的金属—有机骨架材料(MOFs)PCN-14,采用质心分布图研究了甲烷在其中的吸附机理。结果表明,PCN-14中主要存在两个吸附位,其中金属簇—苯基区域中靠近苯环的位置为第一吸附位,蒽基上方为第二吸附位。两个吸附位均与有机配体有关,有机配体较之金属簇在CH_4的吸附中发挥着重要的作用。
2、在此基础上,我们通过改变PCN-14的有机配体,设计了具有高存储量的新型MOF材料PCN-M1和PCN-M2。通过模拟290 K时的吸附等温线,发现新材料PCN-M1和PCN-M2的吸附性能比PCN-14增强很多。在3.5 PMa时,PCN-M1、PCN-M2的吸附量分别达到了246 v/v、257 v/v,比PCN-14增加了7%、12%。本章接着模拟了298 K和3.5 MPa时的吸附,PCN-M2对甲烷的吸附量达到了241v/v,超过了DOE标准180 v/v的34%。
3、为了进一步验证上述分子模拟结果,需要实验合成上述新材料并对其结构特性以及吸附性能进行研究,从而开发具有更高甲烷存储量的MOF材料。但是由于本实验室之前并没有过实验合成MOF材料的经验,所以本人选择合成晶体结构相对简单、合成步骤简易的MOF-5材料,为本实验室开展实验合成MOF材料做前期探索工作,为建立分子模拟—实验合成共同筛选高性能甲烷存储材料机制作前期准备。
Metal-Organic Frameworks (MOFs), commonly recognized as "soft" analogues of zeolites, is a new class of nanoporous materials. MOFs, with extremely high porosity, chemical diversity, and as tailored materials with well-defined pore size, are promising materials for gases storage, separation, and catalyst, etc. Computational chemistry can not only overcome the limitations of traditional methods, but also provides theoretical guidance for the design of optimal adsorbents and the determination of optimal industrial operation conditions, which also saves a lot of time for complicated experimental works. In this work, a systematic study was carried out on methane storage in MOFs using molecular simulation technique, and the new material was designed by investigating the adsorption mechanism in MOFs. Furthermore, we also synthesized a MOF material named MOF-5. The main contents and findings are summarized as follows:
(1) An effective method denoted as "center of mass probability distributions" was employed to study the methane adsorption mechanism in metal-organic framework PCN-14 which shows the highest methane storage capacity to date, finding that this material has two adsorption sites for methane molecules, and the organic linkers play an important role in adsorption.
(2) Based on this point, two new materials named PCN-M1 and PCN-M2 were designed by modifying the organic linkers of PCN-14. The newly designed MOF materials have a methane storage capacity of ca. 246 and 257 v/v at 290 K and 3.5 MPa, which is 7 % and 12 % higher than that of PCN-14. On the other hand, it has a methane capacity of ca. 241 v/v at 298 K and 3.5 MPa in PCN-M2, which is 34 % over the DOE target (180 v/v).
(3) In order to further verify the simulation results mentioned above, we should experimentally synthesize the new designed materials and investigate their structural characteristics, as well as the adsorption performance. Thus, we can develop a higher amount of methane stored MOF materials. However, as the limited ability in synthesis of MOF materials in our laboratory, we have to synthesize a relatively simple material (MOF-5) firstly, as the preliminary exploration work.
引文
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