Faculty Profiles - MATSUDA Ryotaro

Three-Dimensional Visualization of Adsorption Distribution in a Single Crystalline Particle of a Metal–Organic Framework Open Access

Emina Yamada, Hirotoshi Sakamoto, Hirosuke Matsui, Tomoya Uruga, Kunihisa Sugimoto, Minh-Quyet Ha, Hieu-Chi Dam, Ryotaro Matsuda, Mizuki Tada

Journal of the American Chemical Society Vol. 146 ( 13 ) page： 9181 - 9190 2024.3

Effect of pore size on heat release from CO2 adsorption in MIL-101, MOF-177, and UiO-66

Gunjan Auti, Yuki Kametani, Hibiki Kimura, Soumyadeep Paul, Wei-Lun Hsu, Shinpei Kusaka, Ryotaro Matsuda, Takashi Uemura, Shohei Chiashi, Hirofumi Daiguji

Journal of Materials Chemistry A Vol. 11 ( 37 ) page： 20043 - 20054 2023.9

Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

Understanding the relationship between the geometry of metal-organic frameworks (MOFs) and the CO2 enthalpy of adsorption is of utmost importance to control CO2 adsorption/desorption in MOFs and the associated heat...

DOI： 10.1039/d3ta03018k

Subambient temperature swing adsorption utilizing cold energy from liquefied natural gas

Yukino Kuwabara, Takaya Tokunaga, Tatsuya Moriyama, Masahisa Koizumi, Shiho Mizuno, Takuro Hagino, Shinpei Kusaka, Ryotaro Matsuda, Tomoyuki Yajima, Yoshiaki Kawajiri

International Journal of Greenhouse Gas Control Vol. 126 2023.6

Language：English Publishing type：Research paper (scientific journal)

This study proposes a CO2 capture process by temperature swing adsorption (TSA) using latent heat of evaporation for liquefied natural gas (LNG) as a cold energy source, which is currently unused and discarded into seawater. The proposed subambient process has several advantages: (1) the total energy cost can be saved by the LNG cold energy; (2) the equilibrium capacity of CO2 at subambient temperature can be increased substantially; and (3) water in the flue gas which would lead to deterioration of the adsorbent can be removed by a pretreatment step utilizing LNG cold energy. For the adsorbent in the TSA system, zeolite 13X, MIL-101, UiO-66, and CPL-1, which are considered effective for CO2 adsorption in the subambient, were considered and adsorption isotherm data were obtained at subambient conditions. Comparisons of these adsorbents were carried out using a rigorous dynamic model of the TSA process. It was found that CPL-1 gives a high recovery rate of 70% and purity of 95%. It was also found that the proposed system has the potential to capture up to 6% of the CO2 emitted from Japan.

DOI： 10.1016/j.ijggc.2023.103910

Creation of single molecular conjugates of metal-organic cages and DNA. International journal

Toshinobu Nakajo, Shinpei Kusaka, Haruka Hiraoka, Kohei Nomura, Noriaki Matsubara, Rintaro Baba, Yuki Yoshida, Kosuke Nakamoto, Masakazu Honma, Hiroaki Iguchi, Takayuki Uchihashi, Hiroshi Abe, Ryotaro Matsuda

Chemical communications (Cambridge, England) Vol. 59 ( 33 ) page： 4974 - 4977 2023.4

Language：English Publishing type：Research paper (scientific journal)

Here we report the development of an equimolar conjugate of a metal-organic cage (MOC) and DNA (MOC-DNA). Several MOC-DNA conjugates were assembled into a programmed structure by coordinating with a template DNA having a complementary base sequence. Moreover, conjugation with the MOC drastically enhanced the permeability of DNA through the lipid bilayer, presenting great potential as a drug delivery system.

DOI： 10.1039/d3cc00460k

An Open-shell, Luminescent, Two-Dimensional Coordination Polymer with a Honeycomb Lattice and Triangular Organic Radical

Kimura Shun, Uejima Motoyuki, Ota Wataru, Sato Tohru, Kusaka Shinpei, Matsuda Ryotaro, Nishihara Hiroshi, Kusamoto Tetsuro

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 143 ( 11 ) page： 4329 - 4338 2021.3

Modulation of Self-Assembly Enhances the Catalytic Activity of Iron Porphyrin for CO2 Reduction

Tasaki Masahiro, Okabe Yuki, Iwami Hikaru, Akatsuka Chiharu, Kosugi Kento, Negita Kohei, Kusaka Sinpei, Matsuda Ryotaro, Kondo Mio, Masaoka Shigeyuki

SMALL 2021.3

Molecular motion in the nanospace of MOFs upon gas adsorption investigated by in situ Raman spectroscopy Reviewed

Shinpei Kusaka, Yasuaki Nakajima, Akihiro Hori, Akira Yonezu, Kenta Kikushima, Wataru Kosaka, Yunsheng Ma, Ryotaro Matsuda

Faraday Discussions Vol. 225 ( 0 ) page： 70 - 83 2021.2

Language：English Publishing type：Research paper (scientific journal)

Molecular motions taking place in the nanospace of metal-organic frameworks (MOFs) are an interesting research subject, although not yet fully investigated. In this work, we utilized in situ Raman spectroscopy in the ultralow-frequency region to investigate the libration motion (including the rotational motion of phenylene rings) of MOFs, in particular [Cu2(bdc)2(dabco)] (Cu-JAST-1), where bdc = 1,4-benzenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane. The libration mode of Cu-JAST-1 was found to be significantly suppressed by the adsorption of various guest molecules, such as CO2, Ar, and N2. In addition, an appreciable correlation between the libration mode and adsorption equilibrium time was identified, which provides useful novel tools in the design of MOFs acting as molecular adsorption and separation materials.

DOI： 10.1039/d0fd00002g

Tuning Gate-Opening of a Flexible Metal–Organic Framework for Ternary Gas Sieving Separation

Qiubing Dong, Xin Zhang, Shuang Liu, Rui Biao Lin, Yanan Guo, Yunsheng Ma, Akira Yonezu, Rajamani Krishna, Gongpin Liu, Jingui Duan, Ryotaro Matsuda, Wanqin Jin, Banglin Chen

Angewandte Chemie - International Edition Vol. 59 ( 50 ) page： 22756 - 22762 2020.12

Publishing type：Research paper (scientific journal)

In comparison with the fast development of binary mixture separations, ternary mixture separations are significantly more difficult and have rarely been realized by a single material. Herein, a new strategy of tuning the gate-opening pressure of flexible MOFs is developed to tackle such a challenge. As demonstrated by a flexible framework NTU-65, the gate-opening pressure of ethylene (C H ), acetylene (C H ), and carbon dioxide (CO ) can be regulated by temperature. Therefore, efficient sieving separation of this ternary mixture was realized. Under optimized temperature, NTU-65 adsorbed a large amount of C H and CO through gate-opening and only negligible amount of C H . Breakthrough experiments demonstrated that this material can simultaneously capture C H and CO , yielding polymer-grade (>99.99 %) C H from single breakthrough separation. 2 4 2 2 2 2 2 2 2 4 2 2 2 2 4

DOI： 10.1002/anie.202011802

Trapping and Releasing of Oxygen in Liquid by Metal–Organic Framework with Light and Heat

Masashi Fujimura, Shinpei Kusaka, Ayaka Masuda, Akihiro Hori, Yuh Hijikata, Jenny Pirillo, Yunsheng Ma, Ryotaro Matsuda

Small 2020.11

Publishing type：Research paper (scientific journal)

Nanoporous materials can adsorb small molecules into their nanospaces. However, the trapping of light gas molecules dissolved in solvents suffers from low concentration and poor adsorption affinity. Here, the reversible trapping and releasing of dissolved oxygen are shown through integrating photosensitization and chemical capturing abilities into a metal–organic framework (MOF), MOMF-1. 9,10-Di(4-pyridyl)anthracene (dpa) ligands in MOMF-1 generates singlet oxygen from triplet oxygen under photoirradiation without additional photosensitizers, and successively reacts with it to produce anthracene endoperoxide, forming MOMF-2, which is proved crystallographically. The reverse reaction also proceeds quantitatively by heating MOMF-2. Moreover, MOMF-1 exhibits excellent water resistance, and completely removes oxygen of ppm order concentrations in water. The new material shown in this report allows controlling of the amount of dissolved oxygen, which can be applicable in various fields relating to numerous oxidation phenomena.

DOI： 10.1002/smll.202004351

Molecular simulation study on the flexibility in the interpenetrated metal-organic framework LMOF-201 using reactive force field

Ankit Agrawal, Mayank Agrawal, Donguk Suh, Yunsheng Ma, Ryotaro Matsuda, Akira Endo, Wei Lun Hsu, Hirofumi Daiguji

Journal of Materials Chemistry A Vol. 8 ( 32 ) page： 16385 - 16391 2020.8

Publishing type：Research paper (scientific journal)

Framework flexibility is one of the most important characteristics of metal-organic frameworks (MOFs), making them highly suitable for adsorption applications. There have been a limited number of computational efforts to study flexible MOFs in the literature, and they are mostly focused on MIL-53. We studied a flexible MOF known as LMOF-201, which was found to exhibit guest-induced flexible properties; however, the mechanism of the appearance of flexibility is still unclear. First, we validated our simulation results by reproducing the experimental isotherm and powder X-ray diffraction measurements of experimental structures using grand canonical Monte Carlo (GCMC) and reactive force field (ReaxFF) molecular dynamics (MD) simulations. Then, we demonstrated the importance of the presence of a carbonyl oxygen atom in LMOF-201 to induce flexibility. The mechanism determined in this study will enable LMOF-201 to be considered for adsorption applications in the future.

DOI： 10.1039/c9ta12065c

Augmenting the Carbon Dioxide Uptake and Selectivity of Metal-Organic Frameworks by Metal Substitution: Molecular Simulations of LMOF-202

Ankit Agrawal, Mayank Agrawal, Donguk Suh, Shubo Fei, Amer Alizadeh, Yunsheng Ma, Ryotaro Matsuda, Wei Lun Hsu, Hirofumi Daiguji

ACS Omega Vol. 5 ( 28 ) page： 17193 - 17198 2020.7

Publishing type：Research paper (scientific journal)

Metal organic frameworks (MOFs) are promising porous materials for the adsorption of CO2. Here, we report the study of a luminescent MOF (LMOF), called LMOF-202. We have employed Grand Canonical Monte Carlo (GCMC) simulations to understand and explain the adsorption phenomena inside LMOF-202, and based on the phenomena happening at the molecular level, we have varied the metal ions in LMOF-202 to increase the CO2 affinity and selectivity of the material. We show that the CO2 adsorption capacity and selectivity can be increased by approximately 1.5 times at 1 bar and 298 K by changing the metal ion from Zn to Ba. We also report the feasibility of using this material to capture CO2 from flue gas under realistic conditions (1 bar and 298 K). This work shows that LMOF-202 merits further consideration as a carbon capture adsorbent.

DOI： 10.1021/acsomega.0c01267

Pseudo-Gated Adsorption with Negligible Volume Change Evoked by Halogen-Bond Interaction in the Nanospace of MOFs Reviewed International journal

Prakash Kanoo, Ryotaro Matsuda, Hiroshi Sato, Liangchun Li, Nobuhiko Hosono, Susumu Kitagawa

Chemistry - A European Journal Vol. 26 ( 10 ) page： 2148 - 2153 2020.2

Language：English Publishing type：Research paper (scientific journal)

The enhancement of gas adsorption utilizing weak interactions in porous compounds is highly demanding for the design of energy-efficient storage materials. Here, we present a rational design for such an adsorption process by using synergistic functions between dynamic motion in a local module and weak but specific host–guest interactions, that is, halogen-bond (XB) interactions in metal–organic frameworks (MOFs). We designed a new porous coordination polymer (PCP), that is, Br-PCP, the pore surfaces of which are decorated with −CH Br groups and could be useful for interaction with CO molecules. In accordance with our anticipation, in-situ studies suggest that the adsorption step at approximately 54 kPa during CO adsorption is indeed facilitated by XB interactions with little change in the structural volume. This approach of integrating flexible XB modules in rigid PCPs is applicable for designing advanced gas storage systems. 2 2 2

DOI： 10.1002/chem.201904703

Swift and efficient nuclear spin conversion of molecular hydrogen confined in Prussian blue analogs

Yuta Ohtsubo, Akio Mishima, Akihiro Hori, Ryotaro Matsuda, Ryo Ohtani, Masaaki Ohba

Chemistry Letters Vol. 49 ( 2 ) page： 149 - 152 2020.2

Language：English Publishing type：Research paper (scientific journal)

The ortho-isomer of molecular hydrogen (o-H ) was converted to the para-isomer (p-H ) within 600 s by using Prussian blue analogs, {M [Cr (CN) ] } (MCr; M = Mn and Ni), as nuclear-spin conversion catalysts. The swift conversion was confirmed by in-situ Raman micro-spectroscopy under an H gas atmosphere (100 kPa) in a low temperature range (2090 K). The o-p ratio observed in MCr deviated from the theoretical value based on the Boltzmann distribution of H in a free rotational state to the para-rich proportion, which suggested the promotion of the o-p conversion at higher temperature. 2 2 3 6 2 2 2 II III

DOI： 10.1246/cl.190829

Direct observation of dimethyl sulfide trapped by MOF proving efficient removal of sulfur impurities

Masashi Morita, Akira Yonezu, Shinpei Kusaka, Akihiro Hori, Yunsheng Ma, Ryotaro Matsuda

RSC Advances Vol. 10 ( 8 ) page： 4710 - 4714 2020.1

Language：English Publishing type：Research paper (scientific journal)

Here, we report the adsorptive removal of trace amounts of dimethyl sulfide (DMS) using metal-organic frameworks (MOFs). Cu -based MOFs with open metal sites (OMSs), [Cu (btc) ] (HKUST-1), where btc = 1,3,5-benzenetricarboxylate, and without OMSs, [Cu (bdc) (dabco)] (Cu-JAST-1), where bdc = 1,4-benzenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane, were investigated for the removal of DMS to compare their performance with that of Ag-Y zeolite, which is currently widely used in industry. HKUST-1 exhibited a considerably higher adsorption capacity for DMS than the other adsorbents, which was confirmed by breakthrough measurements. The adsorption state of DMS with HKUST-1 was directly revealed by single-crystal X-ray diffraction (SXRD) analysis and in situ Raman spectroscopy. In addition, it was shown that DMS can be removed by HKUST-1 even under humid conditions. 2+ 3 2 2 2

DOI： 10.1039/c9ra09702c

Accelerated C<inf>2</inf>H<inf>2</inf>/CO<inf>2</inf> Separation by a Se-Functionalized Porous Coordination Polymer with Low Binding Energy Reviewed International journal

Qiubing Dong, Yanan Guo, Haifei Cao, Suna Wang, Ryotaro Matsuda, Jingui Duan

ACS Applied Materials and Interfaces Vol. 12 ( 3 ) page： 3764 - 3772 2020.1

Language：English Publishing type：Research paper (scientific journal)

High-quality pure acetylene (C H ) is a kind of crucial starting material for various value-added products. However, selective capture of C H from the main impurity of CO via porous absorbents is a great challenge, as they possess extremely similar kinetic diameters and boiling points, as well as the explosive and reactive properties of C H . Herein, we report a porous coordination polymer (PCP), (NTU-55), which assembled from the coordination between a Cu dimer and a newly designed ligand with a nonmetal selenium (Se) site. Static single-component adsorption and dynamic breakthrough experiments reveal that desolvated NTU-55 can completely adsorb C H from the C H /CO mixture (1/4, v/v) at 298 K, along with higher C H capacity and much lower binding energy. The origin of this separation, as comprehensively revealed by density functional theory (DFT) calculations, is derived from the interaction discriminatory of C H and CO toward accessible Se and Cu adsorption sites. To the best of our knowledge, this is the first time to find the positive effect of nonmetal Se sites for selective C H capture. 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

DOI： 10.1021/acsami.9b20623

Grafting free carboxylic acid groups onto the pore surface of 3d porous coordination polymers for high proton conductivity Reviewed

Yuanmeng Tian, Gan Liang, Tao Fan, Jin Shang, Shanshan Shang, Yunsheng Ma, Ryotaro Matsuda, Mingxian Liu, Man Wang, Liangchun Li, Susumu Kitagawa

Chemistry of Materials Vol. 31 ( 20 ) page： 8494 - 8503 2019.10

Publishing type：Research paper (scientific journal)

Copyright © 2019 American Chemical Society. Development of proton conduction materials with a high performance via functionalization of porous coordination polymers (PCPs) is challenging yet promising. Herein, a facile and efficient method to synthesize multicarboxylate-group-functionalized rigid ligands has been developed. Interestingly, when utilizing these ligands to prepare PCPs, the peripheral carboxylate groups of the ligands selectively coordinate to the metal ions for constructing the PCP frameworks while ortho-dicarboxylic acid groups on the central benzene ring remain free in the pores. Single-crystal X-ray diffractions and various gas sorption analyses reveal the characteristics of high-density free carboxylic acid groups in the pores of these PCPs, not only forming hydrogen-bond clusters and three-dimensional hydrogen-bond networks potentially, but also stimulating the flexibility of these very robust PCP frameworks. Based on this unique structure, the PCP functionalized with four free carboxylic acids on every ligand (TJU-102) exhibits a high proton conductivity of 5.26 × 10-2 S cm-1 at 90 °C and 98% relative humidity. The activation energy for proton conduction of TJU-102 is ca. 0.59 eV, suggesting that the conduction mechanism is predominantly vehicular.

DOI： 10.1021/acs.chemmater.9b02924