2017 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, 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 / thermodynamic properties |
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| Outline of Annual Research Achievements |
We have performed molecular modeling of structural, guest distribution and hydrate formation conditions of H2S, CH4, CO2 and CO2 + CH4 gas hydrates. Obtained results agree with the known experimental data. Ozone storage capacity in clathrate hydrates was studied. The promising p-T conditions and gas compositions for formation of O3 containing hydrates from O3 + O2 + N2 + CO2 gas mixtures were suggested. The CO2, C2H2 adsorption isotherms of proposed nanocage and nanobarrel structures was estimated. It was found that for CO2/C2H2 gas mixture the 20% separation ability was observed for conjugated structures with high porosity at low-pressure conditions. The proposed nanocage and nanobarrels motifs was modified in order to obtain the pore size for encapsulation CdSe quantum dots (QDs) with 1.5 nm size. Six (four) naphtalocyanine-type fragments were combined to form non-conjugated and conjugated nanocages (nanobarrels) connected by sp3 carbon groups and benzene, respectively. All nanostructures were optimized and their dynamic stability was calculated. MOF structures with low density, large surface area were designed by using large molecular building blocks with linkers having large surface area such as the well-known binuclear carboxylate complexes having an octahedral geometry (Zn2(R)4L2). The biphenyl connected to the Zn metals through pyridine molecules and terphenyldicarboxylate are selected as L and R ligands, respectively. To increase the pore size biphenyl and phenyl motifs were replaced by porphyrins in the L and R ligands.
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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 CO and N2 adsorption isotherms of proposed nanocage and nanobarrel structures are being estimated using Monte Carlo simulations.
The estimation of QD interaction with proposed nanocages and nanobarrels having appropriate porosity is being performed. The effect of framework on the electronic properties of QDs is being studied.
The thermodynamic stability of MOF structures in which the biphenyl and phenyl motifs were replaced by porphyrin in the L and R ligands is being investigated.
Based on experimental suggestions the thermodynamic conditions of hydrate formation with HFC245fa and the role of guest-host and guest-guest interactions on stability of this hydrate are being studied.
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| Strategy for Future Research Activity |
1)The simulation of the thermodynamic and dynamic properties of the binary X+CO2 , X+CH4 and Z+CH4 hydrates with the possibility of multiple filling of cavities by guests (X= SO2, H2S and O2 molecules and Z=He and Xe atoms) will be studied.
2)The functionalization of organic ligands in proposed nanocages and nanobarrels will be performed. Functionalization of the proposed by substituting Zn metals for the transition-metal ions will be also studied.
3)The guest-guest interaction inside the nanoporous structures will be estimated and its role in absorption ability of these structures will be evaluated.
4)The investigation of the catenation effect on the thermodynamic stability of MOF structure formation in order to realize the optimal ratio between pore volume and surface area will be performed. The CH4, CO2, C2H2, CO, and N2 adsorption isotherms of the proposed structures will be estimated.
5)The experimental synthesis and detailed analysis of selected clathrate hydrates and MOF structures will be performed.
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