Mechanistic study on metal chalcogenides catalyzed water splitting for efficient hydrogen production

2020 Fiscal Year Annual Research Report

• Project/Area Number: 19F18346
• Research Institution: Waseda University
• Principal Investigator: 野田 優 早稲田大学, 理工学術院, 教授 (50312997)
• Co-Investigator(Kenkyū-buntansha): SENGENI ANANTHARAJ 早稲田大学, 理工学術院, 外国人特別研究員
• Project Period (FY): 2019-04-01 – 2021-03-31
• Keywords: 水電解水素製造 / 電気化学触媒 / 遷移金属カルコゲナイド / カーボンナノチューブ電極 / 水素発生反応 / 酸素発生反応

Outline of Annual Research Achievements

昨年度までに非貴金属系の水電解触媒の多くで表面再構成が重要なことを示してきた。2020年度はこの観点から高機能触媒の開発に取り組んだ。CoSe2をCoSeO3へと前酸化してから表面をCoOOHへ電気化学酸化すると活性なCo2+サイトが増大し高い酸素生成活性を発現すること、Niを不純物として含むCuフォームを1 mM Fe2+を含む1 M KOH水溶液中で電気化学酸化するとNixFe1-xOOHナノニードルがフォーム上に高密度に形成して高い酸素発生活性を発現すること、ニッケル硫化物をアルカリ水溶液中で電気化学酸化すると表面がアモルファスNiSx(OH)yへ再構成され高い水素生成活性を発現すること、ステンレス箔表面からCrを溶解除去したうえで電気化学還元するとNiとMnの水酸化物に表面が再構成し高い水素生成活性を発現することを見出した。また、多分野から水電解研究に参入している中、電気化学評価が不適切に行われている状況を指摘、適切な評価方法を提示した。まず、電気化学インピーダンス分光法はまちまちな条件で行われ触媒活性比較に混乱を生じている状況を指摘、モデル触媒で各条件を検討、全触媒が作用する電位で電荷移動抵抗を求めると触媒活性と良い相関が得られることを示した。また、性能評価に重要なTafelプロットは定常状態のデータに適用すべきところ、多くの研究で簡便な非定常測定である線形掃引ボルタンメトリー(LSV)やサイクリックボルタンメトリー(CV)のデータに適用されてしまっている。実際にLSVとCVでは定常状態データからずれて結果が変わることを示し、定常状態でのデータ取得の重要性を示した。さらに日々膨大に発表される関連論文を精読し、メカニズムと課題を整理したレビュー論文を複数発表した。これらは再エネ電力を用いたCO2フリー水素製造に通じる成果であり、SDG目標7,13に貢献する。

Research Progress Status

令和2年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和2年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Surface amorphized nickel hydroxy sulphide for efficient hydrogen evolution reaction in alkaline medium (2021)
  • Author(s): Anantharaj Sengeni、Sugime Hisashi、Noda Suguru
  • Journal Title: Chemical Engineering Journal Volume: 408 Pages: 127275～127275
  • DOI: 10.1016/j.cej.2020.127275
  • Peer Reviewed / Open Access
• [Journal Article] “The Fe Effect”: A review unveiling the critical roles of Fe in enhancing OER activity of Ni and Co based catalysts (2021)
  • Author(s): Anantharaj Sengeni、Kundu Subrata、Noda Suguru
  • Journal Title: Nano Energy Volume: 80 Pages: 105514～105514
  • DOI: 10.1016/j.nanoen.2020.105514
  • Peer Reviewed / Open Access
• [Journal Article] A review on recent developments in electrochemical hydrogen peroxide synthesis with a critical assessment of perspectives and strategies (2021)
  • Author(s): Anantharaj Sengeni、Pitchaimuthu Sudhagar、Noda Suguru
  • Journal Title: Advances in Colloid and Interface Science Volume: 287 Pages: 102331～102331
  • DOI: 10.1016/j.cis.2020.102331
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Pushing the Limits of Rapid Anodic Growth of CuO/Cu(OH)2 Nanoneedles on Cu for the Methanol Oxidation Reaction: Anodization pH Is the Game Changer (2021)
  • Author(s): Anantharaj Sengeni、Sugime Hisashi、Yamaoka Shohei、Noda Suguru
  • Journal Title: ACS Applied Energy Materials Volume: 4 Pages: 899～912
  • DOI: 10.1021/acsaem.0c02822
  • Peer Reviewed
• [Journal Article] Strategies and Perspectives to Catch the Missing Pieces in Energy‐Efficient Hydrogen Evolution Reaction in Alkaline Media (2021)
  • Author(s): Anantharaj Sengeni、Noda Suguru、Jothi Vasanth Rajendiran、Yi SungChul、Driess Matthias、Menezes Prashanth W.
  • Journal Title: Angewandte Chemie International Edition Volume: 60 Pages: 2～28
  • DOI: 10.1002/anie.202015738
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] The Pitfalls of Using Potentiodynamic Polarization Curves for Tafel Analysis in Electrocatalytic Water Splitting (2021)
  • Author(s): Anantharaj Sengeni、Noda Suguru、Driess Matthias、Menezes Prashanth W.
  • Journal Title: ACS Energy Letters Volume: 6 Pages: 1607～1611
  • DOI: 10.1021/acsenergylett.1c00608
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Nickel selenides as pre-catalysts for electrochemical oxygen evolution reaction: A review (2020)
  • Author(s): Anantharaj Sengeni、Noda Suguru
  • Journal Title: International Journal of Hydrogen Energy Volume: 45 Pages: 15763～15784
  • DOI: 10.1016/j.ijhydene.2020.04.073
  • Peer Reviewed
• [Journal Article] Achieving Increased Electrochemical Accessibility and Lowered Oxygen Evolution Reaction Activation Energy for Co2+ Sites with a Simple Anion Preoxidation (2020)
  • Author(s): Anantharaj Sengeni、Sugime Hisashi、Chen Bozhi、Akagi Natsuho、Noda Suguru
  • Journal Title: The Journal of Physical Chemistry C Volume: 124 Pages: 9673～9684
  • DOI: 10.1021/acs.jpcc.0c00178
  • Peer Reviewed
• [Journal Article] Appropriate Use of Electrochemical Impedance Spectroscopy in Water Splitting Electrocatalysis (2020)
  • Author(s): Anantharaj Sengeni、Noda Suguru
  • Journal Title: ChemElectroChem Volume: 7 Pages: 2297～2308
  • DOI: 10.1002/celc.202000515
  • Peer Reviewed
• [Journal Article] Ultrafast Growth of a Cu(OH)2?CuO Nanoneedle Array on Cu Foil for Methanol Oxidation Electrocatalysis (2020)
  • Author(s): Anantharaj Sengeni、Sugime Hisashi、Noda Suguru
  • Journal Title: ACS Applied Materials & Interfaces Volume: 12 Pages: 27327～27338
  • DOI: 10.1021/acsami.0c08979
  • Peer Reviewed
• [Journal Article] Boosting the oxygen evolution activity of copper foam containing trace Ni by intentionally supplementing Fe and forming nanowires in anodization (2020)
  • Author(s): Anantharaj Sengeni、Sugime Hisashi、Chen Bozhi、Akagi Natsuho、Noda Suguru
  • Journal Title: Electrochimica Acta Volume: 364 Pages: 137170～137170
  • DOI: 10.1016/j.electacta.2020.137170
  • Peer Reviewed
• [Journal Article] Chemical Leaching of Inactive Cr and Subsequent Electrochemical Resurfacing of Catalytically Active Sites in Stainless Steel for High-Rate Alkaline Hydrogen Evolution Reaction (2020)
  • Author(s): Anantharaj Sengeni、Sugime Hisashi、Noda Suguru
  • Journal Title: ACS Applied Energy Materials Volume: 3 Pages: 12596～12606
  • DOI: 10.1021/acsaem.0c02505
  • Peer Reviewed
• [Presentation] Electroanalytical Techniques for water splitting: dos and don’ts (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: International webinar on ‘Electroanalytical Techniques for water splitting: dos and don’ts’ organized by The Department of Physics, Saveetha Engineering College, Chennai, India
  • Int'l Joint Research / Invited
• [Presentation] Cyclic and linear sweep voltammetry: fundamentals and applications (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: International webinar on ‘Cyclic and linear sweep voltammetry: fundamentals and applications’ organized by The Department of Chemistry, Bhaktavatsalam memorial college for women, Chennai, India
  • Int'l Joint Research / Invited
• [Presentation] Developments in Electrocatalytic Water Splitting: Hydrogen Generation and Beyond (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: International webinar on ‘Developments in Electrocatalytic Water Splitting: Hydrogen Generation and Beyond’ organized by The Department of Physics, Kumbagonam Government Arts College, India
  • Int'l Joint Research / Invited
• [Presentation] Oxygen Electrocatalysis: The Holy Grail of Energy Conversion and Storage (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: International webinar on ‘Oxygen Electrocatalysis: The Holy Grail of Energy Conversion and Storage’ organized by The Department of Chemistry, Chennai Institute of Technology, Chennai, India
  • Int'l Joint Research / Invited
• [Presentation] Fundamentals of Electrochemistry (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: An invited lecture on ‘Fundamentals of Electrochemistry’ jointly organized by The Department of Physics, Bharathiar University, Kovai and The Academy of Sciences, Chennai, India
  • Int'l Joint Research / Invited
• [Presentation] Oxygen Electrocatalysis for Sustainable Future (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: An invited lecture on ‘Oxygen Electrocatalysis for Sustainable Future’ jointly organized by The Department of Physics, Bharathiar University, Kovai and The Academy of Sciences, Chennai, India
  • Int'l Joint Research / Invited
• [Presentation] Voltammetry and Electrochemical Impedance Analysis: The Fundamentals (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: An invited lecture on ‘Oxygen Electrocatalysis for Sustainable Future’ jointly organized by Department of Physics, Bharathiar University and The Academy of Sciences, India
  • Int'l Joint Research / Invited
• [Presentation] Electroanalytical Techniques and Electrocatalytic Water Splitting: Best Practices (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: A Keynote Lecture on ‘Voltammetry and Electrochemical Impedance Analysis: The Fundamentals’ jointly organized by Manonmaniyam Sundaranar University and ThermoFischer Scientific, India
  • Int'l Joint Research / Invited
• [Presentation] Recent Advances in the Growth of One-Dimensional Cu-based Nanostructures for Methanol Electrooxidation: Chemical vs. Electrochemical Methods (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: International Conference on Advanced Nanomaterials and Nanostructures (ICANN-2021) organized by The Department of Chemistry, Bharath Institute for Higher Education Research, Chennai, India
  • Int'l Joint Research / Invited
• [Presentation] Voltammetry and Electrochemical Impedance Analyses: Fundamentals and Applications (2020)
  • Author(s): Sengeni Anantharaj
  • Organizer: A short term course on the advanced material characterizations organized by The Department of Ceramic Engineering, IIT Varanasi (BHU), Varanasi, India
  • Int'l Joint Research / Invited
• [Remarks] 代表者・野田ホームページ
  • URL: http://www.f.waseda.jp/noda/index-j.html