【公開日：2023.07.28】【最終更新日：2023.05.14】

課題データ / Project Data

課題番号 / Project Issue Number

22HK0013

利用課題名 / Title

水中光合成によるナノ材料の作製

利用した実施機関 / Support Institute

北海道大学 / Hokkaido Univ.

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）物質・材料合成プロセス/Molecule & Material Synthesis

【重要技術領域 / Important Technology Area】（主 / Main）量子・電子制御により革新的な機能を発現するマテリアル/Materials using quantum and electronic control to perform innovative functions（副 / Sub）革新的なエネルギー変換を可能とするマテリアル/Materials enabling innovative energy conversion

キーワード / Keywords

電子顕微鏡/Electron microscopy,電子分光,赤外・可視・紫外分光/Infrared and UV and visible light spectroscopy,赤外・可視・紫外分光/Infrared and UV and visible light spectroscopy,表面・界面・粒界制御/ Surface/interface/grain boundary control,太陽電池/ Solar cell,エネルギー貯蔵/ Energy storage

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)

張 麗華

所属名 / Affiliation

北海道大学大学院工学研究院ｴﾈﾙｷﾞｰ・ﾏﾃﾘｱﾙ融合領域研究センター

共同利用者氏名 / Names of Collaborators in Other Institutes Than Hub and Spoke Institutes

Yu Zhehan,山﨑和太郎,大澤雅弥,能登亮太,福島幸大,早野　彩夏,宮下　弘渡,林　學毅,熊井　宏樹

ARIM実施機関支援担当者 / Names of Collaborators in The Hub and Spoke Institutes

大多亮,吉田すずか,鈴木啓太

利用形態 / Support Type

（主 / Main）機器利用/Equipment Utilization（副 / Sub）-

利用した主な設備 / Equipment Used in This Project

HK-101：ダブル球面収差補正走査透過型電子顕微鏡
HK-201：X線光電子分光装置

報告書データ / Report

概要（目的・用途・実施内容）/ Abstract (Aim, Use Applications and Contents)

Based on our early research work, a new pathway of producing variety of metal oxides nanocrystallites (NCs) was reported, which we call it SPSC (Submerged Photo-Synthesis of Crystallites) method. The SPSC method is a photosynthesis technique to create nanoparticles or nano-surface structures of metal oxides only by light irradiating the metal in water under normal temperature and pressure. Although this method has been reported to be effective for Zn, Cu, and Fe, it has not been applied to W or Mo because W and W do not dissolve in water alone, which is essential for SPSC method. In this study, we attempted to dissolve W and Mo by using H₂O₂ beforehand, and then photosynthesize H₂WO₄ and H₂MoO₄ nanoparticles by irradiating the solution with ultraviolet (UV) light. The morphologies of the synthesized nanoparticles were observed, and the reaction mechanism was analyzed.

実験 / Experimental

The SPSC experiment was conducted by submerging metal plate W in H₂O₂ solution under UV illumination. After that, morphologies of the NCs was observed by a FE-SEM and TEM (JEM-2000FX). The nanoparticles were characterized using an X-ray photoelectron spectroscopy (XPS, JEOL, JPS-9200), and a Cs-corrected Scanning Transmission Electron Microscope (Titan3 G2 60-300).

結果と考察 / Results and Discussion

A yellow-green powder of WO₃ was obtained by using the 10% H₂O₂, and a brighter yellow powder of H₂WO₄ was obtained by using the 35% H₂O₂. It was found that WO₃ and H₂WO₄ are nanoparticles with diameters of about 100 nm and 300 nm, respectively. Therefore, the tungsten nano-oxides were successful fabricated by SPSC method by using H₂O₂ solution.
The reaction mechanism of the SPSC process was considered. Firstly, the dissolution of W or Mo into H₂O₂ generally involves a redox reaction. Then, under UV irradiation, H₂O₂ is decomposed into hydroxyl radicals. Finally, it is considered that the dissolved MeO₄^2- reacts with the generated OH radicals  and crystallizes as H₂WO₄ and H₂MoO₄ nanoparticles.

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)

Reference: Souta Fujii, et al. Materials Letters. 302, 130344 (2021) 

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)

1. Zhehan Yu, Mesoporous single crystal titanium oxide microparticles for enhanced visible light photodegradation, Optical Materials, 127, 112297(2022).
   DOI: 10.1016/j.optmat.2022.112297
   
2. Zhehan Yu, Facile modification of TiO2 nanoparticles with H2O2 + NH4F for enhanced visible light photodegradation of rhodamine B and methylene blue, Materials Today Communications, 33, 104213(2022).
   DOI: 10.1016/j.mtcomm.2022.104213
   

口頭発表、ポスター発表および、その他の論文 / Oral Presentations etc.

1. 能登亮太，張麗華，渡辺精一．次亜塩素酸と過酸化水素を用いた水中結晶光合成による機能性酸化銅ナノ表面作製．化学系学協会北海道支部2023年冬季研究発表会．２０２３年１月
2. 林學毅，Melbert Jeem，張麗華，渡辺精一．機能性モリブデン-タングステンナノ酸化物複合材料の水中光合成．令和４年度日本顕微鏡学会北海道支部学術講演会．２０２２年１１月
3. YU Zhehan，張麗華，渡辺精一．Facile Modification of TiO2 Nanoparticles with H2O2 + NH4F for Enhanced Visible Light Photodegradation of Rhodamine B and Methylene Blue．令和４年度日本顕微鏡学会北海道支部学術講演会．２０２２年１１月
4. 早野彩夏，Melbert Jeem，林學毅，張麗華，渡辺精一．水中光照射下におけるドーピング誘起光学的相転移．日本金属学会2022年秋期(第171回)講演大会．２０２２年9月
5. 福島幸大，張麗華，渡辺精一．G-SPSCを用いた結晶Si 太陽電池のZnO-NRs 反射防止層．日本金属学会2022年秋期(第171回)講演大会．２０２２年9月
6. 林學毅，張麗華，渡辺精一．機能性モリブデン-タングステンナノ酸化物複合材料の水中光合成．日本金属学会2022年秋期(第171回)講演大会．２０２２年9月
7. 西村真拓，渡辺精一，張麗華．CuO ナノワイヤーメッシュを用いた太陽光水蒸発の基礎的調査．２０２２年度 日本金属学会・日本鉄鋼協会両北海道支部合同サマーセッション．２０２２年７月
8. 酒井達也，沖中憲之，張麗華，渡辺精一．尿素・グリシン混合燃料を用いた液相燃焼合成によるSr9Al6O18:Sm3+蓄光体の作製．２０２２年度 日本金属学会・日本鉄鋼協会両北海道支部合同サマーセッション．２０２２年７月
9. YU Zhehan，張麗華，渡辺精一．Facile Modification of TiO2 Nanoparticles with H2O2 + NH4F for Enhanced Visible Light Photodegradation of Rhodamine B and Methylene Blue．２０２２年度 日本金属学会・日本鉄鋼協会両北海道支部合同サマーセッション．２０２２年７月

特許 / Patents

特許出願件数 / Number of Patent Applications：0件
特許登録件数 / Number of Registered Patents：0件