【公開日：2025.06.10】【最終更新日：2025.05.07】
課題データ / Project Data
課題番号 / Project Issue Number
24NM5281
利用課題名 / Title
Ultra-High Surface Area Carbon Materials Design for Energy Storage
利用した実施機関 / Support Institute
物質・材料研究機構 / NIMS
機関外・機関内の利用 / External or Internal Use
内部利用（ARIM事業参画者以外）/Internal Use (by non ARIM members)
技術領域 / Technology Area
【横断技術領域 / Cross-Technology Area】（主 / Main）計測・分析/Advanced Characterization（副 / Sub）-
【重要技術領域 / Important Technology Area】（主 / Main）高度なデバイス機能の発現を可能とするマテリアル/Materials allowing high-level device functions to be performed（副 / Sub）-
キーワード / Keywords
Porous carbons, MOF, fullerene assemblies,X線回折/ X-ray diffraction,電子分光/ Electron spectroscopy
利用者と利用形態 / User and Support Type
利用者名（課題申請者）/ User Name (Project Applicant)
スレスタ ロック クマール
所属名 / Affiliation
物質・材料研究機構
共同利用者氏名 / Names of Collaborators in Other Institutes Than Hub and Spoke Institutes
ARIM実施機関支援担当者 / Names of Collaborators in The Hub and Spoke Institutes
利用形態 / Support Type
（主 / Main）機器利用/Equipment Utilization（副 / Sub）,技術補助/Technical Assistance
利用した主な設備 / Equipment Used in This Project
NM-202：硬X線光電子分光分析装置（HAX-PES/XPS）
NM-210：温度可変型粉末X線回折装置_Cu1_NTS
NM-212：卓上型粉末回折計_Cu_ASC_NC1
NM-649：FE-SEM+EDX [SU8230]
NM-225：X線光電子分光分析装置（XPS-Quantera SXM）
報告書データ / Report
概要（目的・用途・実施内容）/ Abstract (Aim, Use Applications and Contents)
We presented a novel approach for synthesizing and characterizing metal−organic frameworks on fullerene (MOFOF) composites, achieved through the integration of coordination chemistry and supramolecular chemistry principles. The MOFOF showed the superior sensitivity for acid vapors.
実験 / Experimental
MOF crystals were grown on the self-assembled fullerene nanotubes (FNT) by solution-based chemistry. Self-assembled FNT crystals were prepared following the commonly used LLIP method using mesitylene as the “good” solvent and methanol as the “bad” solvent. The assembly of fullerene into FNT is generally driven by the molecular interactions and self-organization tendencies of the fullerene molecules, where the inherent curvature of the fullerene structure, along with solvent composition, treatment conditions, and temperature, influences the assembly process to form the tubular structures. In the synthesis of the MOFOF composites, specific conditions were carefully selected to optimize the quality and functionality of the resulting materials. The method for MOFOF synthesis involves in situ growth of ZIF-67 onto FNTox at room temperature under ultrasonication. The synthesis temperature of 25 °C and noncontinuous sonication and hand shaking (∼10 s) at 1 min intervals were selected to facilitate the controlled growth of the ZIF-67 crystals on the FNTox surface without causing degradation of the self-assembled fullerene tubular structure. Separate Co(NO3)2· 6H2O (2 mM; 10 mL) and ligand-modulator (Mim + TEA; 16 mM each; 10 mL) solutions were prepared in water. First, the Co2+ solution was added to a dispersion of FNTox (100 mg/mL) in water. The slurry was held under sonication for 5 min with shaking by hand (∼10 s) at 1 min intervals. Mim + TEA solution was then added rapidly, and the same sonication-shaking regime continued for an additional 15 min. The resulting purple-brown solid was collected by centrifugation, then washed with water and methanol (three times), and dried at 80 °C for 12 h under reduced pressure. The composition (MOF: FNTox: or Co2+: C60) of the MOFOF composites was varied by varying the quantity of FNTox used. MOFOF composites with varying Co2+/C60 ratios (e.g., 0.5, 1.0, 1.5, and 2.0) are respectively referred to in this work as MOFOF-0.5, MOFOF-1.0, MOFOF-1.5, and MOFOF-2.0. The observed MOFOF composites were characterized using XRD, XPS, and SEM.
結果と考察 / Results and Discussion
MOFOFs with different compositions were successfully prepared. MOFOF samples were obtained by the in situ growth of ZIF-67 (a typical MOF) onto the surface-modified FNT at room temperature under ultrasonication. The FNT morphology was maintained with only minor decomposition, even following the growth of ZIF-67 crystals onto the surface of the FNTox. The newly prepared MOFOF composites indicate that ZIF-67 particles grow only at the surfaces of FNTox with no nonattached particles visible, indicating robust attachment and homogeneous distribution. The uniform distribution of ZIF-67 particles on the FNTox surfaces and at their interiors is significant for the composite’s functional properties, as it ensures maximum surface area and accessibility for various (e.g., catalytic or adsorptive) interactions. Predictably, the quantity of ZIF-67 particles varies according to the increasing ratio of the ZIF-67 precursors. ZIF-67 particles at the exterior of FNTox, especially for MOFOF-2.0, indicate that there is an optimum Co2+/C60 ratio (i.e., Co2+/C60: 1/1) for successful in situ incorporation of ZIF-67 on the FNTox in the MOFOF composites.
図・表・数式 / Figures, Tables and Equations
その他・特記事項（参考文献・謝辞等） / Remarks(References and Acknowledgements)
A new porous MOFOF composite with a uniform distribution of ZIF-67, a typical MOF, grown on self-assembled fullerene nanotube (FNT), was synthesized following a two-step in situ method. By varying the ratio of FNT and MOF precursors, in particular, the Co2+/C60 ratio, the distribution and interconnectedness of the MOFOF components can be controlled by this simple room temperature synthesis procedure using a standard ultrasound bath sonication. The resulting MOFOFs possess large specific surface areas based on micro- and mesopore channels, contain defect sites for binding of guest molecules, and show excellent sensitivity for acid vapor sensing when applied in QCM sensing layers.
成果発表・成果利用 / Publication and Patents
論文・プロシーディング（DOIのあるもの） / DOI (Publication and Proceedings)
-
Biswa Nath Bhadra, Metal–Organic Framework on Fullerene (MOFOF) as a Hierarchical Composite by the Integration of Coordination Chemistry and Supramolecular Chemistry, ACS Applied Materials & Interfaces, 16, 41363-41370(2024).
DOI: https://doi.org/10.1021/acsami.4c09747
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Mandira Pradhananga Adhikari, Ultrahigh surface area self-nitrogen-doped nanoporous carbon materials from Macrotyloma uniflorum (Horse gram) seed for high-performance supercapacitor applications, Journal of Power Sources, 631, 236239(2025).
DOI: https://doi.org/10.1016/j.jpowsour.2025.236239
口頭発表、ポスター発表および、その他の論文 / Oral Presentations etc.
特許 / Patents
特許出願件数 / Number of Patent Applications：2件
特許登録件数 / Number of Registered Patents：0件