Published Papers - NAKAGAWA Tessui

Delayed ammonia release of ammonia borane hydrolysis by citric acid

Shimizu Y.

International Journal of Hydrogen Energy ( International Journal of Hydrogen Energy )  82   733 - 739   2024.09 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Investigation of Water Quality/Quantity and Effective Utilization of Condensed Water from Dehumidifier in Okinawa as a Model Case

IZUMI Jin, NAKAGAWA Tessui, ASADA Shoji, YOSHIMOTO Takamitsu, KINOSHITA Koichiro, YONEKURA Isao, KOSHIRO Norihiro, OSHIO Aiko, FUKUMOTO Kozo

Journal of Japan Society on Water Environment ( Japan Society on Water Environment )  47 ( 1 ) 47 - 53   2024.01 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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<p>In many developing countries with high temperatures and humidity are suffering from a shortage of safe drinking water. In such countries, dehumidifiers are often used to prevent the growth of rust and mold. The water generated from the dehumidifier (DHW) is often discarded because most people feel that this water is dirty. We continuously investigated the water quality and quantity in Okinawa, which is a hot and humid area, for ～1.5 years. As a result, we found that the water from a dehumidifier (average 11.730 mg L^-1, Main component: TOC 6.985 mg L^-1, NH₄⁺ 3.760 mg L^-1) contained less impurities than tap water (119.821 mg L^-1, Main component: Cl^- 34.315 mg L^-1, Ca²⁺ 28.636 mg L^-1, Na⁺ 25.658 mg L^-1, SO₄^2- 23.293 mg L^-1) throughout the whole year. A compressor-type dehumidifier can generate water of about 62% of rated dehumidification capacity on average annually (6.22 L d^-1) in a closed room, which is superior to a zeolite-type dehumidifier (3.16 L day^-1, about 39% of rating on average annually) . These results show that water generated by dehumidifiers can be used for many purposes such as drinking water with a proper water purification treatment.</p>

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Development of continuous measurement system for hydrogen and impurity gases using detector tube.

Shimizu Y, Miyagi A, Nakagawa T

The Review of scientific instruments ( Review of Scientific Instruments )  94 ( 9 ) 095114-1 - 095114-6   2023.09 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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A relatively accurate, inexpensive, simple, and continuous quantification system for hydrogen and impurity gas(es) using a detector tube was developed in this study. Additionally, different detector tubes can be applied to measure different types of gases in a wide range from ppm order to % level. We optimized this system and evaluated its accuracy as well as the behavior of released H2 and impurity (NH3) gases from a hydrolysis of ammonia borane using a Pt/Al2O3 catalyst. The accuracy of hydrogen quantitation achieved by this system was comparable to that of commercial mass flow meters, and the accuracy of ammonia quantitation was 10% or 5% relative standard deviation, which depends on the detector tube. The concentration of released NH3 was evaluated by image analysis with a time-lapse video of the detector tube and succeeded in analyzing from ppm to % order. The H2 and NH3 release behaviors agreed with pH, and the percentage of reaction was estimated by NMR measurement of the reacted solution. These results confirmed the accuracy of this system.

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Fundamental Properties of Ammonia Borane Aqueous Solution: Dissolution Enthalpy of Solution, Freezing Points and Solubility Curve, Thermal analysis, Stability and Phase Diagram

Yoshihiro SHIMIZU, Reiya TAMAKI, Ankit Kumar TRIPATHI, Shuji TAKAMINE, Ye TIAN, Ko KISHIMOTO, Tasuku TERUYA, Yuri UNTEN, Hina SHINJO, Tessui NAKAGAWA

Journal of the Japan Institute of Energy ( Japan Institute of Energy )  102 ( 7 ) 65 - 76   2023.07 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Hydrogen carrier by ammonia borane-ammonia system with low-vapor pressure

Fangqin Guo , Yufeng Wang , Shuji Takamine , Ko Kishimoto , Tomoyuki Ichikawa , Hiroki Miyaoka , Yoshihiro Shimizu , Tessui Nakagawa , Takayuki Ichikawa

International Journal of Hydrogen Energy ( Elsevier )  102 ( 7 ) 65 - 76   2023.04 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Recyclable Dehydrogenation/Regeneration of Ammonia Borane Nanoconfined in Amino-Functionalized ZIF-8 with 3-Amino-1,2,4-triazole

Guan-Lin Li , Ankit Kumar Tripathi , Hao Chan , Sung-Tzu Chen , Jui-Ting Chang , Tessui Nakagawa , Cheng-Yu Wang

ACS Sustainable Chem. Eng. ( ACS )  11 ( 16 ) 6143 - 6152   2023.04 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Structural Properties of (Ti, Zr)(Mn, Cr)₂M[0.1] (M = None, Fe, Co, Ni, and Cu) Hydrogen Storage Alloys : Composition Distribution and Occupied Site of Doped Element

Nakagawa Tessui, Heshiki Daichi, Higa Hiroki, Kawakami Junko, Kobayashi Riki, Hanada Nobuko, Ikeda Kazutaka, Otomo Toshiya, Ofuchi Hironori, Ishida Masayoshi

MATERIALS TRANSACTIONS ( 公益社団法人 日本金属学会 )  62 ( 6 ) 899 - 904   2021.03 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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<p>CO₂ tolerance of hydrogen storage alloys of AB₂-type (C14 Laves phase) Ti_0.515Zr_0.485Mn_1.2Cr_0.8<i>M</i>_0.1 (AB₂-M, <i>M</i> = none, Fe, Co, Ni, and Cu) depends on dopant <i>M</i>. Since our goal is to clarify this mechanism, we determined the elemental analysis using X-ray absorption spectroscopy (XAS), scanning electron microscope (SEM) coupled with energy dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (XRD), and neutron powder diffraction (NPD) with Rietveld refinement in this study. As a result of XAS analysis, a strong evidence of all doped elements occupying B site in AB₂ was obtained. SEM-EDX showed inhomogeneous composition with vacancy in B site and linear correlation of Ti/Zr and Mn/Cr ratio. The peak width in XRD patterns of AB₂-M depends on the magnitude of homogeneity, therefore the Rietveld analysis using NPD patterns could not be well refined. Thus, homogeneity is not important but element of B site would be important for CO₂ tolerance as well as AB₅ type alloys.</p>

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Surface-Controlled Conversion of Ammonia Borane from Boron Nitride

Tessui Nakagawa, Hiroki Uesato, Anthony K. Burrell, Takayuki Ichikawa, Hiroki Miyaoka, Benjamin L. Davis, Yoshitsugu Kojima

energies ( MDPI )  13 ( 21 ) 5569-1 - 5569-9   2020.10 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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“One-pot regeneration”, which is simple regneneration method of ammonia borane (AB) using hydrazine and liquid ammonia, enables conversion of AB from hexagonal boron nitride (h-BN) after milling hydrogenation. Solution 11B-NMR revealed the presence of AB after NH3/N2H4 treatment of milled h-BN (BNHx) although the yield of AB was less than 5%. The conversion mechanism was clarified as B-H bonds on the h-BN surface created by ball-milling under hydrogen pressure have an ability to form AB, which was confirmed by Thermogravimetry-Residual Gas Analysis (TG-RGA) and Infrared (IR) analysis. The reaction routes are also the same as regeneration route of polyborazylene because intermediates of AB such as (B(NH2)3 and hydrazine borane were found by solution 11B-NMR after soaking BNHx in liquid NH3 and hydrazine, respectively. Because of the fact that all reactions proceed on the h-BN surface and no reaction proceeds when neat h-BN is treated, breaking of B3N3 ring structure and then creation of B-H bond is the key issue to increase conversion yield of AB.

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Top-down approach using supercritical carbon dioxide ball milling for producing sub-10 nm Bi2Te3 grains

Mohamed Atwa, 中川鉄水, 與那嶺亮, David C. Lloyd, Makoto Schreiber, 宮崎 康次, 竹内恒博, 岡田佳憲

Applied Physics Express   13   067002-1 - 067002-5   2020.05 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Electronic structure of octagonal boron nitride nanotubes

Lauren Takahashi, Tessui Nakagawa, Keisuke Takahashi

International Journal of Quantum Chemistry ( John Wiley and Sons Inc. )  118 ( 11 ) e25542(1) - e25542(7)   2018.06 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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The effect of an octagonal lattice configuration on a boron nitride nanotube is explored using first principle calculations. Calculations show that the formational energy of an octagonal boron nitride nanotube (o-BNNT) is an exothermic reaction. Boron and nitrogen atoms within an o-BNNT have an average of 2.88 electrons and 9.09 electrons, respectively, indicating ionic-like bonding. In addition, the electronic structure of the octagonal boron nitride nanotube shows semiconductive properties, while h-BNNT is reported to be an insulator. Additional o-BNNTs with varying diameters are calculated where the results suggest that the diameter has an effect on the binding energy and bandgap of the o-BNNT. The defect sites of the o-BNNT are reactive against hydrogen where a boron defect is particularly reactive. Thus, this work suggests that physical and chemical properties of a boron nitride nanotube can be tailored and tuned by controlling the lattice configuration of the nanotube.

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Effect of CO2 on hydrogen absorption in Ti-Zr-Mn-Cr based AB(2) type alloys

Nobuko Hanada, Hirotaka Asada, Tessui Nakagawa, Hiroki Higa, Masayoshi Ishida, Daichi Heshiki, Tomohiro Toki, Itoko Saita, Kohta Asano, Yumiko Nakamura, Akitoshi Fujisawa, Shinichi Miura

JOURNAL OF ALLOYS AND COMPOUNDS ( ELSEVIER SCIENCE SA )  705   507 - 516   2017.05 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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The effect of CO2 on hydrogen absorption has been investigated for AB2 type alloys of Ti0.515Zr0.485Mn1.2Cr0.8 (Ti-Zr-Mn-Cr) and Ti0.515Zr0.485Mn1.2Cr0.8M0.1 (Ti-Zr-Mn-Cr-M, M = Fe, Co, or Ni) in order to develop metal hydrides for a hydrogen purification and storage system. A magnitude of CO2 poisoning tolerance was evaluated by comparing hydrogen absorption properties before and after CO2 exposure. As the results, an order of CO2 tolerance was Ti-Zr-Mn-Cr-Ni &lt; Ti-Zr-Mn-Cr &lt; Ti-Zr-Mn-CrCo &lt; Ti-Zr-Mn-Cr-Fe. It suggests that the AB(2) alloys have dependence of additive 3d-transition elements on CO2 tolerance. Ti-Zr-Mn-Cr-Fe has the highest CO2 tolerance among them. The additive of Fe and Co improves tolerance of CO2 poisoning for hydrogen absorption properties. On the other hand, Ni element in AB(2) alloy decreases CO2 tolerance. The estimated enthalpy change between CO2 and the alloys surface was comparable to the formation of metal oxide. And the CO2-exposed AB(2) alloys after reacting with hydrogen desorbed methane gas. Therefore, CO2 would dissociate to CO and O on the surface of alloys, and then oxygen atom reacts with the alloys. (C) 2017 Elsevier B. V. All rights reserved.

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Synthesis, structural characterization, and hydrogen desorption properties of Na[Al(NH2BH3)(4)]

Yuki Nakagawa, Keita Shinzato, Tessui Nakagawa, Keita Nakajima, Shigehito Isobe, Kiyotaka Goshome, Hiroki Miyaoka, Takayuki Ichikawa

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY ( PERGAMON-ELSEVIER SCIENCE LTD )  42 ( 9 ) 6173 - 6180   2017.03 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Na[Al(NH2BH3)(4)], a mixed-metal amidoborane, was synthesized by ball-milling (solid method) and the chemical reaction in THF (solution method). Solid method has a tendency to remain unreacted NaAlH4 and AB. In the solution method, the partial decomposition of Na[Al(NH2BH3)(4)] would proceed during mixing in THF. The local structural characterization of as-synthesized material was performed by MAS NMR and FT-IR. While Na[Al(NH2BH3)(4)] desorbed hydrogen in two steps as reported, the results of structural characterization suggested that the hydrogen desorption in the 2nd step would originate from the Al-N-B H phase. Effect of hydrogen pressure during ball-milling was also investigated for nNH(3)BH(3)-NaAlH4 (n = 1, 4) composites. In the case of n = 4, Na[Al(NH2BH3)(4)] was formed under both Ar and H-2 atmosphere. However, in the case of n =1, Na[Al(NH2BH3)(4)] only formed under H-2 atmosphere, whereas most of H-2 was desorbed during ball-milling under Ar atmosphere. Thus, the hydrogen pressure is necessary for the synthesis in the case of n = 1. Potential energy diagram of AB-NaAlH4 system was described. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

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Dependence of constituent elements of AB(5) type metal hydrides on hydrogenation degradation by CO2 poisoning

Nobuko Hanada, Tessui Nakagawa, Hirotaka Asada, Masayoshi Ishida, Keisuke Takahashi, Shigehito Isobe, Itoko Saita, Kohta Asano, Yumiko Nakamura, Akitoshi Fujisawa, Shinichi Miura

JOURNAL OF ALLOYS AND COMPOUNDS ( ELSEVIER SCIENCE SA )  647   198 - 203   2015.10 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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LaNi5-based AB(5) type alloy has high tolerance to CO2 poisoning for hydrogen purification and storage from 20 to 25% CO2 mixed gas. To elucidate the CO2 poisoning factors of AB(5) type alloys, which are LaNi5, CaNi5, LaCo5, and MmNi(4.025)Co(0.4)Mn(0.275)Al(0.3) (Mm-Ni), the dependence of the constituent elements has been investigated on hydrogenation degradation by CO2 poisoning. The tendency of CO2 poisoning magnitude is CaNi5 &lt; LaNi5 &lt;&lt; Mm-Ni &lt; LaCo5, which was evaluated by the hydrogenation rate and capacity under CO2 partial pressure and after CO2 exposure. The Ni element of B site in CaNi5 and LaNi5 is an important role to maintain higher tolerance of CO2 poisoning compared to Co element in LaCo5. Moreover, the element of A site effects on CO2 poisoning magnitude in AB(5) type alloy. The experimental tendency of CO2 poisoning magnitude is consistent with the theoretical CO2 adsorption energy on the (1010) surface plane of -1.39, -2.05, and -2.68 eV for CaNi5, LaNi5, and LaCo5, respectively. CO2 adsorbs on B site with electron charge transfer from AB(5) alloys to carbon. Not only Ni element in B site but also Ca element in A site decreases the energy of CO2 adsorption on B site in AB(5) type alloys. (C) 2015 Elsevier B.V. All rights reserved.

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Physical, structural, and dehydrogenation properties of ammonia borane in ionic liquids

Tessui Nakagawa, Anthony K. Burrell, Rico E. Del Sesto, Michael T. Janicke, Adam L. Nekimken, Geraldine M. Purdy, Biswajit Paik, Rui-Qin Zhong, Troy A. Semelsberger, Benjamin L. Davis

RSC ADVANCES ( ROYAL SOC CHEMISTRY )  4 ( 42 ) 21681 - 21687   2014.04 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Ionic liquids (ILs) are excellent solvents for the dehydrogenation of ammonia borane (AB); however, the basic properties that allow efficient dehydrogenation are still unclear. In this report, density, viscosity, melting/freezing/glass transition temperature, solubility, and the dehydrogenation properties, including impurity gas quantification, of AB-imidazolium-based IL solutions were studied. Note that ILs can solubilize 32–35 wt% of AB, and the liquid AB–IL solutions have densities of ∼0.9 g cm−3, viscosities similar to motor oil (100–250 cP), and glass transition temperatures below −50 °C. AB–ILs are stable at room temperature for several weeks with minimal hydrogen generation, although some hydrolysis occurs immediately upon mixing as a result of trace water content. Between 80 and 130 °C, more than 2 mol H2/AB are desorbed from AB–ILs with limited impurity emissions. Furthermore, there is no reaction between AB and ILs upon dehydrogenation, and structural analysis reveals a complex solid solution.

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Synthesis of Calcium Borohydride by Milling Hydrogenation of Hydride and Boride

Tessui Nakagawa, Takayuki Ichikawa, Hiroki Miyaoka, Masami Tsubota, Yoshitsugu Kojima

J. Japan Inst. Met. Mater. ( The Japan Institute of Metals and Materials )  77 ( 12 ) 609 - 614   2013.12 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Microstructure and hydrogen desorption characteristics of hydrogenated ScH2-MBn (M = Mg and Ca) systems synthesized by mechanical milling

Tessui Nakagawa, Takayuki Ichikawa, Keiji Shimoda, Masami Tsubota, Hiroki Miyaoka, Shigehito Isobe, Tetsuo Honma, Shinji Michimura, Fumitoshi Iga, Somei Ohnuki, Yoshitsugu Kojima

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY ( PERGAMON-ELSEVIER SCIENCE LTD )  38 ( 16 ) 6744 - 6749   2013.04 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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The mixtures of scandium hydride ScH2 and metal boride MBn, which is MgB2 or CaB6, were hydrogenated by mechanical milling under hydrogen pressure at room temperature. ScH2–MgB2 and ScH2–CaB6 desorbed 3.4 and 2.3 mass% of H2, respectively, with peaks below 300 °C. The results of synchrotron radiation X-ray powder diffraction and X-ray absorption spectroscopy at the Sc K-edge indicated that ScB2 was produced by milling. Fourier-transform infrared spectroscopy suggested that hydrogen was stored as B–H bonds in the as-milled samples. Nuclear magnetic resonance spectroscopy clarified the presence of metal borohydrides M(BH4)2 (M = Mg and Ca) in the as-milled ScH2–MBn mixtures. These results indicate that M(BH4)2 is synthesized by milling the ScH2–MBn mixtures under hydrogen pressure at room temperature, and hydrogen was desorbed from M(BH4)2. The by-products of M(BH4)2 are MgH2 in the M = Mg case, which was observed by transmission electron microscopy, and ScB2 in both cases.

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Comparative Study of Structural Changes in NH3BH3, LiNH2BH3, and KNH2BH3 During Dehydrogenation Process

Keiji Shimoda, Koichi Doi, Tessui Nakagawa, Yu Zhang, Hiroki Miyaoka, Takayuki Ichikawa, Masataka Tansho, Tadashi Shimizu, Anthony K. Burrell, Yoshitsugu Kojima

JOURNAL OF PHYSICAL CHEMISTRY C ( American Chemical Society )  116 ( 9 ) 5957 - 5964   2012.03 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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The thermal decomposition pathways of ammonia borane (AB, NH3BH3), lithium amidoborane (LiAB, LiNH2BH3), and potassium amidoborane (KAB, KNH2BH3) have been investigated in detail by using solid state 11B MAS NMR spectroscopy. During the first decomposition process of AB, the complex structural entities were observed, which have been attributed to polyaminoborane (PAB, (NH2BH2)n). On the other hand, polyiminoborane (PIB, (NHBH)n) formed in the second process showed a single 3-fold coordination IIIB signal above 125 °C, suggesting a [—B═N—]n network structure. LiAB and KAB did not show the PAB-like structure, and the PIB-like structure was directly formed by the hydrogen desorption. Quantitative analyses of the 11B NMR spectra suggested that the general route of the thermal decomposition of alkali metal amidoboranes (LiAB, NaAB, and KAB) is similar. Also, 39K MAS NMR spectra of KAB and its decomposition products indicated the formation of KH and an amorphous K–N–B–H phase during the hydrogen release.

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Improved hydrogen release from ammonia-borane with ZIF-8

Rui-Qin Zhong, Ru-Qiang Zou, Tessui Nakagawa, Michael Janicke, Troy A. Semelsberger, Anthony K. Burrell, Rico E. Del Sesto

Inorganic Chemistry ( PERGAMON-ELSEVIER SCIENCE LTD )  51 ( 5 ) 2728 - 2730   2012.02 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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The promotion for hydrogen release from ammonia–borane (AB) was observed in the presence of ZIF-8. Even at concentrations of ZIF-8 as low as 0.25 mol %, a reduction of the onset temperature for dehydrogenation accompanies an increase in both the rate and amount of hydrogen released from AB.

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Regeneration of Ammonia Borane Spent Fuel by Direct Reaction with Hydrazine and Liquid Ammonia

Andrew D. Sutton , Anthony K. Burrell , David A. Dixon , Edward B. Garner , John C. Gordon , Tessui Nakagawa , Kevin C. Ott , Pierce Robinson , Monica Vasiliu

SCIENCE ( American Association for the Advancement of Science )  331 ( 6023 ) 1426 - 1429   2011.03 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Ammonia borane (H3N-BH3, AB) is a lightweight material containing a high density of hydrogen (H2) that can be readily liberated for use in fuel cell–powered applications. However, in the absence of a straightforward, efficient method for regenerating AB from dehydrogenated polymeric spent fuel, its full potential as a viable H2 storage material will not be realized. We demonstrate that the spent fuel type derived from the removal of greater than two equivalents of H2 per molecule of AB (i.e., polyborazylene, PB) can be converted back to AB nearly quantitatively by 24-hour treatment with hydrazine (N2H4) in liquid ammonia (NH3) at 40°C in a sealed pressure vessel.

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Potassium(I) Amidotrihydroborate: Structure and Hydrogen Release

Himashinie V. K. Diyabalanage , Tessui Nakagawa , Roshan P. Shrestha , Troy A. Semelsberger , Benjamin L. Davis , Brian L. Scott , Anthony K. Burrell , William I. F. David , Kate R. Ryan , Martin Owen Jones , Peter P. Edwards

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY ( AMERICAN CHEMICAL SOCIETY )  132 ( 34 ) 11836 - 11837   2010.09 [ Peer Review Accepted ]

Type of publication: Research paper (scientific journal)

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Potassium(I) amidotrihydroborate (KNH2BH3) is a newly developed potential hydrogen storage material representing a completely different structural motif within the alkali metal amidotrihydroborate group. Evolution of 6.5 wt % hydrogen starting at temperatures as low as 80 °C is observed and shows a significant change in the hydrogen release profile, as compared to the corresponding lithium and sodium compounds. Here we describe the synthesis, structure, and hydrogen release characteristics of KNH2BH3.

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