2018 Fiscal Year Annual Research Report
先端エネルギーと医療応用のための多機能性ナノポーラス材料の理論設計と実験的創製
| Project/Area Number |
17H03122
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| Research Institution | Tohoku University |
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Principal Investigator |
ベロスルドフ ロディオン 東北大学, 金属材料研究所, 准教授 (10396517)
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| Co-Investigator(Kenkyū-buntansha) |
松田 亮太郎 名古屋大学, 工学研究科, 教授 (00402959)
川添 良幸 東北大学, 未来科学技術共同研究センター, 名誉教授 (30091672)
竹谷 敏 国立研究開発法人産業技術総合研究所, 計量標準総合センター, 上級主任研究員 (40357421)
大村 亮 慶應義塾大学, 理工学部(矢上), 教授 (70356666)
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| Project Period (FY) |
2017-04-01 – 2020-03-31
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| Keywords | Nanoporous materials / Clathrate hydrate / Metal-organic framework / Computer simulation / guest-host interaction / gas storage/separation / thermodynamic properties |
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| Outline of Annual Research Achievements |
Phase diagram of H2S+CH4 hydrate was reconstructed. The presence of 20 mol % H2S into the gas phase reduces hydrate formation pressure more than in one order in magnitude. Small content of H2S can start hydrate formation which can use for significant reduction of H2S content in sour gas mixture. The electronic structures of the various porphyrin and phthalocyanine-based platforms were estimated using DFT and time-dependent DFT calculations. It was shown that the TDDFT-predicted energies correlate well with the amount of HF exchange present in the LC-BP86 and LC-wPBE functional providing the best agreement between theory and experiment. Theoretical modelling of CO2 adsorption into Mn3(Hpdc)2(pdc)2 and Mg3(Hpdc)2(pdc)2 revealed the formation of unique chain CO2 structures. The filling order of local sites by CO2 varies for each compound, resulting in significant differences in host-guest energetics and in the observed experimentally S-shaped sorption isotherm in case of MnMOF. The interpenetration effect on stability of ZnMOF structures (proposed in the 1st year) was studied. Substitution of biphenyl by porphyrin moieties prevent framework adhesion due to increasing distance between ligands. It was shown that introduction of porphyrin improved the CH4 adsorption. The first-principles calculations were used to estimate the weak interaction energies between 1,7-dipyrene-aza-BODIPYs and nanocarbon materials. It was demonstrated that the pyrene substituents were ineffective at promoting and directing complex formation with nanocarbon materials which support the experimental data.
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| Current Status of Research Progress |
Current Status of Research Progress
2: Research has progressed on the whole more than it was originally planned.
Reason
The melting process of CO2 clathrate hydrate immersed in the ice phase with various cavity occupation ratios is being investigated. The phase diagram of and composition of He-H2O system are being studied using the LJ parameters of interaction obtained during the first year of current project. Based on experimental suggestions the thermodynamic conditions of hydrate formation with 1,3,3,3-Tetrafluoropropene (HFO-1234ze(E)) and the role of guest-host and guest-guest interactions on stability of this hydrate are being studied. The encapsulation of C60 molecules into experimentally proposed ZnMOF with thieno-[2,3-b]thiophene ligand and the guest-host interaction is being studied.
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| Strategy for Future Research Activity |
1)The investigation of the self-preservation effect (an anomalously low dissociation rate) will be performed. The simulation of the most stable structure of the binary X+CO2, Y+O3 and Z+CH4 hydrates immersed in the ice phase will be investigated.
2)The design of organic linkers that will assemble the individual nanocage and nanobarrel supramolecules into crystalline structure will be performed. This will also include the design of linkers that have the possibility to change their length via light irradiation. The thermodynamic and dynamic stability of the empty framework will be investigated.
3)The proposed MOF structures will be studied for storage QDs. These will include the encapsulation of QDs having 1.5 nm size and low Cd concentration, QD interaction with MOF and the effect of the framework on the optical spectra of QDs will be studied. The thermodynamic stability of selected MOFs will be studied and the QDs effect on their stability will be investigated.
4)The most promising structures will be selected and proposed to experimental groups for experimental synthesis and investigation of their storage capacity.
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