Updated on 2023/10/12

写真a

 
SHIMOYAMA Yuto
 
Organization
Institutes of Innovation for Future Society Designated assistant professor
Title
Designated assistant professor
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Degree 3

  1. 博士(学術) ( 2022.3   東京大学 ) 

  2. 修士(工学) ( 2019.3   筑波大学 ) 

  3. 学士(工学) ( 2017.3   筑波大学 ) 

Research Interests 6

  1. water electrolysis

  2. polyoxometalate

  3. 電解アンモニア合成

  4. oxygen reduction reaction

  5. homogeneous catalyst

  6. ionic crystal

Research Areas 1

  1. Nanotechnology/Materials / Inorganic/coordination chemistry  / polyoxometalate

Research History 5

  1. Nagoya University   Institute of Innovation for Future Society   Designated assistant professor

    2023.10

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  2. ENEOS株式会社 中央技術研究所   先進技術研究所   チーフスタッフ

    2022.4 - 2023.9

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  3. Graduate school of Arts and Sciences, The University of Tokyo

    2020.4 - 2022.3

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  4. Graduate school of Arts and Sciences, The University of Tokyo

    2019.3 - 2020.4

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  5. Graduate School of Pure and Applied Sciences, University of Tsukuba

    2017.4 - 2019.3

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Education 3

  1. Graduate school of Arts and Sciences, The University of Tokyo

    2019.4 - 2022.3

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  2. Graduate School of Pure and Applied Sciences, University of Tsukuba   Graduate School of Pure and Applied Sciences

    2017.4 - 2019.3

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  3. University of Tsukuba   College of Engineering Sciences

    2013.4 - 2017.3

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Awards 10

  1. 井上研究奨励賞

    2022.12   井上科学振興財団   第39回井上研究奨励賞

    下山雄人

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  2. 優秀ポスター賞

    2021.10   日本化学会   第11回CSJ化学フェスタ

    下山雄人, 内田研究室

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  3. 優秀ポスター賞

    2020.10   日本化学会   第10回CSJ化学フェスタ

    下山雄人(所属:内田研究室)

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  4. 優秀ポスター賞

    2019.10   日本化学会   第9回CSJ化学フェスタ

    下山雄人(所属:内田研究室)

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  5. 修士論文発表優秀賞

    2019.3   筑波大学 数理物質研究科  

    下山雄人(所属:神原・桑原研究室)

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  6. Excellent Poster Award

    2018.9   Tsukuba Global Science Week

    下山雄人(所属:神原・桑原研究室)

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  7. 卒業生総代

    2017.3   筑波大学  

    下山雄人

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  8. 学長表彰

    2017.3   筑波大学  

    下山雄人

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  9. サイエンス・インカレ・コンソーシアム奨励賞

    2016.3   第5回サイエンス・インカレ

    下山雄人(所属:神原・桑原研究室)

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  10. 優秀賞

    2016.1   筑波大学   2015年度先導的研究者体験プログラム

    下山雄人 (所属:神原・桑原研究室)

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Papers 11

  1. Polyoxocationic antimony oxide cluster with acidic protons Reviewed

    Yuki Watanabe, Kim Hyeon-Deuk, Takafumi Yamamoto, Masayoshi Yabuuchi, Olesia M. Karakulina, Yasuto Noda, Takuya Kurihara, I-Ya Chang, Masanobu Higashi, Osamu Tomita, Cedric Tassel, Daichi Kato, Jingxin Xia, Tatsuhiko Goto, Craig M. Brown, Yuto Shimoyama, Naoki Ogiwara, Joke Hadermann, Artem M. Abakumov, Sayaka Uchida, Ryu Abe, Hiroshi Kageyama

    SCIENCE ADVANCES   Vol. 8 ( 24 )   2022.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER ASSOC ADVANCEMENT SCIENCE  

    The success and continued expansion of research on metal-oxo clusters owe largely to their structural richness and wide range of functions. However, while most of them known to date are negatively charged polyoxometalates, there is only a handful of cationic ones, much less functional ones. Here, we show an all-inorganic hydroxyiodide [H(10.)7Sb(32.1)O(44)][H2.1Sb2.1I8O6][Sb0.76I6](2)center dot 25H(2)O (HSbOI), forming a face-centered cubic structure with cationic Sb32O44 clusters and two types of anionic clusters in its interstitial spaces. Although it is submicrometer in size, electron diffraction tomography of HSbOI allowed the construction of the initial structural model, followed by powder Rietveld refinement to reach the final structure. The cationic cluster is characterized by the presence of acidic protons on its surface due to substantial Sb3+ deficiencies, which enables HSbOI to serve as an excellent solid acid catalyst. These results open up a frontier for the exploration and functionalization of cationic metal-oxo clusters containing heavy main group elements.

    DOI: 10.1126/sciadv.abm5379

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  2. Oxygen Evolution Reaction Driven by Charge Transfer from a Cr Complex to Co-Containing Polyoxometalate in a Porous Ionic Crystal Reviewed

    Yuto Shimoyama, Naoki Ogiwara, Zhewei Weng, Sayaka Uchida

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 144 ( 7 ) page: 2980 - 2986   2022.2

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    Considerable efforts have been devoted to developing oxygen evolution reaction (OER) catalysts based on transition metal oxides. Polyoxometalates (POMs) can be regarded as model compounds of transition metal oxides, and cobalt-containing POMs (Co-POMs) have received significant interest as candidates. Nanocomposites based on Co-POMs have been reported to show high OER activities due to synergistic effects among the components; however, the role of each component is unclear due to its complex structure. Herein, we utilize porous ionic crystals (PICs) based on Co-POMs, which enable a composition-structure-function relationship to be established to understand the origin of the synergistic catalysis. Specifically, a Keggin-type POM [alpha-CoW12O40](6-) and a Cr complex [Cr3O(OOCCH2CN)(6)(H2O)(3)](+) are implemented as PIC building blocks for the OER under nonbasic conditions. The potentially OER-active but highly soluble [alpha-CoW12O40](6-) was successfully anchored in the crystalline PIC matrix via Coulomb interactions and hydrogen bonding induced by polar cyano groups of the Cr complex. The PIC exhibits efficient and sustained OER catalytic activity, while each building block is inactive. The Tafel slope of the linear sweep voltammetry curve and the relatively large kinetic isotope effect value suggest that elementary steps closely related to the OER rate involve single-electron and proton transfer reactions. Electrochemical and spectroscopic studies clearly show that the synergistic catalysis originates from the charge transfer from the Cr complex to [alpha-CoW12O40](6-); the increased electron density of [alpha-CoW12O40](6-) may increase its basicity and accelerate proton abstraction as well as enhance electron transfer to stabilize the reaction intermediates adsorbed on [alpha-CoW12O40](6-).

    DOI: 10.1021/jacs.1c10471

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  3. Photocatalytic Water Oxidation by Phosphotungstate and Mg-Al Layered Double Hydroxide Hybrid Reviewed

    Akinobu Miyoshi, Yuto Shimoyama, Hiroto Mogi, Hiroki Ubukata, Naoki Hirayama, Ayu Tanaka, Kenji Arai, Soichiro Morita, Tatsuto Yui, Sayaka Uchida, Teruki Motohashi, Yoshiyuki Inaguma, Hiroshi Kageyama, Kazuhiko Maeda

    CHEMISTRY LETTERS   Vol. 51 ( 2 ) page: 107 - 110   2022.2

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

    Immobilization of phosphotungstate ([PW12O40](3-)) in the interlayer space of a Mg-Al layered double hydroxide (LDH) resulted in an absorption edge at similar to 350 nm, different from the pristine LDH or the POM (either in aqueous solution or in the solid state). The obtained hybrid showed enhanced photocatalytic activity for water oxidation in the presence of Ag+ as an electron acceptor.

    DOI: 10.1246/cl.210621

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  4. Front Cover: Formation of Mixed‐Valence Luminescent Silver Clusters via Cation‐Coupled Electron‐Transfer in a Redox‐Active Ionic Crystal Based on a Dawson‐type Polyoxometalate with Closed Pores (Eur. J. Inorg. Chem. 16/2021)

    Naoya Haraguchi, Tomoki Okunaga, Yuto Shimoyama, Naoki Ogiwara, Soichi Kikkawa, Seiji Yamazoe, Miki Inada, Takashi Tachikawa, Sayaka Uchida

    European Journal of Inorganic Chemistry   Vol. 2021 ( 16 ) page: 1530 - 1530   2021.4

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    Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    DOI: 10.1002/ejic.202100253

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  5. Formation of Mixed-Valence Luminescent Silver Clusters via Cation-Coupled Electron-Transfer in a Redox-Active Ionic Crystal Based on a Dawson-type Polyoxometalate with Closed Pores Reviewed

    Naoya Haraguchi, Tomoki Okunaga, Yuto Shimoyama, Naoki Ogiwara, Soichi Kikkawa, Seiji Yamazoe, Miki Inada, Takashi Tachikawa, Sayaka Uchida

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY   Vol. 2021 ( 16 ) page: 1531 - 1535   2021.4

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

    A redox-active ionic crystal based on a Dawson-type polyoxometalate (POM) [alpha-(P2W18O62)-O-VI](6-) is utilized to form and stabilize small mixed-valence luminescent silver clusters without the aid of protecting ligands at room temperature. A reduced ionic crystal of Cs3H5[Cr3O(OOCH)(6)(etpy)(3)](3)[alpha-(P2W5W13O62)-W-V-O-VI] . 5H(2)O (etpy=4-ethylpyridine) is formed by a cation-coupled electron-transfer (CCET) reaction with sodium ascorbate as a reducing reagent to provide electrons and Cs+ as counter cations of POM. Then, silver is introduced via ion-exchange between Cs+ and Ag+ jointly with CCET reaction: X-ray photoelectron spectroscopy and elemental analysis show that the ionic crystal is oxidized via electron-transfer from the POM (W5+) to Ag+, and [(Ag1.5Ag1.5I)-Ag-0]H-4.5[Cr3O(OOCH)(6)(etpy)(3)](3)[alpha-(P2W3W15O62)-W-V-O-VI] . 7H(2)O is formed. Photoluminescence and X-ray absorption fine structure suggest that the silver species exist as mixed-valence luminescent clusters with an average formula of [Ag-4](2+) probably in a tetrahedral geometry.

    DOI: 10.1002/ejic.202100101

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  6. Role of Pyridinic Nitrogen in the Mechanism of the Oxygen Reduction Reaction on Carbon Electrocatalysts Reviewed

    Kotaro Takeyasu, Moeko Furukawa, Yuto Shimoyama, Santosh K. Singh, Junji Nakamura

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 60 ( 10 ) page: 5121 - 5124   2021.3

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

    The introduction of pyridinic nitrogen (pyri-N) into carbon-based electrocatalysts for the oxygen reduction reaction is considered to create new active sites. Herein, the role of pyri-N in such catalysts was investigated from a mechanistic viewpoint using carbon black (CB)-supported pyri-N-containing molecules as model catalysts; the highest activity was observed for 1,10-phenanthroline/CB. X-ray photoemission spectroscopy showed that in acidic electrolytes, both pyri-N atoms of 1,10-phenanthroline could be protonated to form pyridinium ions (pyri-NH+). In O-2-saturated electrolytes, one of the pyri-NH+ species was reduced to pyri-NH upon the application of a potential; no such reduction was observed in N-2-saturated electrolytes. This behavior was ascribed to electrochemical reduction of pyri-NH+ occurring simultaneously with the thermal adsorption of O-2, as supported by DFT calculations. According to these calculations, the coupled reduction was promoted by hydrophobic environments.

    DOI: 10.1002/anie.202014323

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  7. Structure-function Relationships of Porous Ionic Crystals (PICs) Based on Polyoxometalate Anions and Oxo-centered Trinuclear Metal Carboxylates as Counter Cations Reviewed

    Yuto Shimoyama, Sayaka Uchida

    CHEMISTRY LETTERS   Vol. 50 ( 1 ) page: 21 - 30   2021.1

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    Authorship:Lead author   Language:English   Publisher:CHEMICAL SOC JAPAN  

    Unique structures and functions of porous ionic crystals (PICs) based on polyoxometalate (POM) anions, which are different from typical porous crystalline materials such as zeolites and metal-organic frameworks (MOFs), can be summarized as follows. (i) Crystal structures of PICs are often flexible since Coulomb interaction works isotropically in a long-range, so that structural transformation occurs to adapt to specific guest molecules. (ii) POMs show reversible redox properties leading to the formation of "redox-active" porous materials. (iii) Ionic building blocks create strong electrostatic fields in the pore, which are suitable for accommodating and stabilizing polar guests and ionic intermediates. (iv) Various cations can be incorporated as counter cations of POMs to fine-tune the functions. The crystal structures and functions of PICs can be controlled by the appropriate choice of molecular cations (macrocations) as ionic building blocks as well as the symmetry, size, and charge of POMs. In particular, oxo-centered trinuclear metal (M-III) carboxylates with a general formula of [M3O(OOCR)(6)(L)(3)](+) as macrocations allow controlling the crystal structures of PICs through the bridging ligands (R) and terminal ligands (L). The fine-tuned structures of PICs lead to unique functions in gas/solvent sorption/separation, heterogeneous catalysis, redox-induced ion-uptake/release, synthesis of mixed-valance metal nanoclusters, and so on.

    DOI: 10.1246/cl.200603

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  8. Isostructural mesoporous ionic crystals as a tunable platform for acid catalysis Reviewed

    Yuto Shimoyama, Zhewei Weng, Naoki Ogiwara, Takashi Kitao, Yuji Kikukawa, Sayaka Uchida

    DALTON TRANSACTIONS   Vol. 49 ( 30 ) page: 10328 - 10333   2020.8

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    Eleven isostructural mesoporous ionic crystals (meso-PICs) are synthesized. The initial activities of the Barbier-Grignard reaction, which is a typical C-C bond formation reaction, catalyzed by the meso-PICs are dependent on the acid dissociation constant of the aqua ions of Mn+ and the types of polyoxometalates, which construct the meso-PICs.

    DOI: 10.1039/d0dt01202e

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  9. Amorphous High-Surface-Area Aluminum Hydroxide-Bicarbonates for Highly Efficient Methyl Orange Removal from Water Reviewed

    Yuki Kinoshita, Yuto Shimoyama, Yoichi Masui, Yoshiteru Kawahara, Kenji Arai, Teruki Motohashi, Yasuto Noda, Sayaka Uchida

    LANGMUIR   Vol. 36 ( 22 ) page: 6277 - 6285   2020.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    Amorphous high-surface-area aluminum hydroxide-bicarbonates were synthesized starting from AlCl3, base, and bicarbonate in water. Composites with a chemical formulas of [Al13O4(mu-OH)(24)(H2O)(6.5)(OH)(5.5)](HCO3)(1.5) (I-NaOH) and [Al13O4(mu- OH)(24)(H2O)(6)(OH)(6)](HCO3) (I-NH3) were obtained by the use of NaOH/NaHCO3 and NH3/NH4HCO3 as base/bicarbonate, respectively. The surface area of the composites was highly dependent on the pH level of the synthetic solution, and composites with high surface areas (ca. 200 m(2) g(-1)) were obtained around pH 7-8. Pore-size distributions determined from the N-2 adsorption isotherms showed that I-NH3 and I-NaOH possess mainly large (pore radius r(p) > 3 nm) and small (r(p) < 3 nm) pores, respectively, despite similar surface areas. While SEM images showed that both I-NH3 and I-NaOH were aggregates of nanoparticles, the particles were more fused in I-NaOH, which is in line with the existence of small pores and the use of a stronger base (NaOH), which would facilitate the dehydration condensation reaction. The composites were applied as adsorbents to remove methyl orange (MO) from water. The time course of MO adsorption was readily fitted with a pseudo-second-order model, and over 90% MO removal was attained within 10 min with I-NH3, while I-NaOH showed much less MO removal (26%). The MO adsorption isotherm of I-NH3 was reproduced with a Langmuir model with an adsorption capacity of 154 mg g(-1). Notably, the aluminum hydroxide-bicarbonates could not absorb methylene blue, which is a cationic dye, while anions (MO and PO43-) were readily absorbed. Solid-state Al-27 MAS NMR spectra showed that the concentration of 5-coordinated aluminum species, which may serve as guest binding sites, was higher for I-NH3. These results show that electrostatic interaction between anionic MO and coordinatively unsaturated 5-coordinated cationic aluminum species and the large external surface area of I-NH3 contribute to the highly efficient MO adsorption.

    DOI: 10.1021/acs.langmuir.0c00021

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  10. Mechanistic Study of Pd/Ag Dual-Catalyzed Cross-Dehydrogenative Coupling of Perfluoroarenes with Thiophenes Reviewed

    Yuto Shimoyama, Junpei Kuwabara, Takaki Kanbara

    ACS CATALYSIS   Vol. 10 ( 5 ) page: 3390 - 3397   2020.3

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    The mechanism of the Pd/Ag dual-catalyzed cross-dehydrogenative coupling (CDC) between perfluoroarenes and thiophenes was clarified. The exact role of the catalytic resting state of the homo-biaryl-Pd(II) complex, which was previously overlooked in Pd/Ag dual-catalyzed CDC, was carefully investigated. Detailed experimental studies indicated that a homo-biaryl-Pd(II) complex occurred in the catalytic off-cycle as a resting state and prevented the homocoupling of perfluoroarenes. In addition, these studies indicated that the C-H bond activation steps of perfluoroarenes and thiophenes proceeded by different mechanisms. While the C-H bond of perfluoroarenes was immediately activated by Ag(I) salts, the C-H bond of thiophenes was activated by the Pd(II) catalyst. Kinetic studies revealed that the Pd(II)-C-H activation of thiophenes is most likely the rate-determining step.

    DOI: 10.1021/acscatal.9b05326

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  11. Synthesis of Conjugated Polymers Containing Octafluorobiphenylene Unit via Pd-Catalyzed Cross-Dehydrogenative-Coupling Reaction Reviewed

    Hideaki Aoki, Hitoshi Saito, Yuto Shimoyama, Junpei Kuwabara, Takeshi Yasuda, Takaki Kanbara

    ACS MACRO LETTERS   Vol. 7 ( 1 ) page: 90 - 94   2018.1

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    Polycondensation via Pd-catalyzed cross-dehydrogenative-coupling reaction of 2,2',3,3',5,5',6,6'-octafluorobiphenyl with thiophene analogues was studied. The synthetic protocol, in which employment of prefunctionalized starting monomers was fully avoided, allowed straightforward access to an alternating pi-conjugated polymer. The addition of K2CO3 to the catalytic system promotes the cross-coupling reaction and suppresses the undesired homocoupling reaction, producing the corresponding donor acceptor type pi-conjugated polymers with minor homocoupling defects. The reaction also proceeded using O-2 as the terminal oxidant, resulting in lower loading of the Ag oxidant. The obtained polymer was evaluated as an emitting material for an organic light-emitting diode.

    DOI: 10.1021/acsmacrolett.7b00887

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KAKENHI (Grants-in-Aid for Scientific Research) 1

  1. メソ多孔性イオン結晶-金属クラスター触媒による協奏的なCO2光還元反応系の構築

    Grant number:20J14672  2020.4 - 2022.3

    日本学術振興会  科学研究費助成事業 特別研究員奨励費  特別研究員奨励費

    下山 雄人

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    昨年度末に、分子性カチオン[Cr3O(OOCCH2CN)6(H2O)3]+ (Cr-CN)とCoを中心に内包したポリ酸[α-CoW12O40]6-(CoW)からなる新規の多孔性イオン結晶 K2[Cr3O(OOCCH2CN)6(H2O)3]4[α-CoW12O40]・32H2O(I)を得た。また、この結晶Iが電気化学的な酸素生成反応(Oxygen Evolution Reaction, OER: 2H2O→O2 + 4H+ + 4e-)に対して触媒活性を示すことも昨年度末に確認した。
    本年度は、この結晶IのOER触媒特性の詳細を実験的に検討した。結晶Iと原料であるCr-CN、CoWのOER触媒活性をpH1およびpH5.6の電解液中で測定した結果、原料(Cr-CN、CoW)はOER触媒としてほとんど機能しない一方で、結晶Iは効率的なOER触媒として機能することが明らかとなった。更に、結晶IとCoW単体のCoW1分子に当たりの触媒活性を算出すると、結晶IはCoWの40倍程度の触媒活性を持つことが分かった。結晶Iの特異的なOER触媒活性の起源を明らかにするために電気化学的、分光学的な解析を実施した。その結果、分子性カチオンCr-CNから活性点となるポリ酸CoWに電子が供与されていることが特異的な活性発現の重要な要因であることが明らかになった。この成果はJournal of The American Chemical Societyに掲載した。
    この結晶Iの電気化学的な触媒活性について、更に検討を進めた結果、電気化学的な還元反応に対しても特異的な触媒特性を示すことを見出した。現在はこの詳細を解析している。
    また、ポリ酸の光触媒利用を共同研究で進め、層状複水酸化物とポリ酸を組み合わせることで光触媒的な酸素発生触媒能が向上することを見出し、共著論文として公表した。

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Industrial property rights 1

  1. 酸素還元触媒とその活性化方法、および燃料電池触媒

    中村 潤児, 近藤 剛弘, 渋谷 陸, 下山 雄人

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    Applicant:国立大学法人 筑波大学

    Application no:特願2017-008910  Date applied:2017.1

    Announcement no:特開2017-127863  Date announced:2017.7

    Patent/Registration no:特許第6804760号  Date registered:2020.12 

    J-GLOBAL

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Social Contribution 2

  1. リバネス ジュニアドクター育成塾 NEST 講師

    リバネス株式会社  2019.4 - 2021.3

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    Type:Research consultation

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  2. 竹園高校 探Q活動 研究指導員

    竹園高校  2017.4 - 2019.3

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