Preparation of gold clusters deposited catalysts using microwave and application for selective functionalization using molecular oxygen

• Project/Area Number: 18K05203
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 34030:Green sustainable chemistry and environmental chemistry-related
• Research Institution: Yokohama National University (2020); Tokyo Metropolitan University (2018-2019)
• Principal Investigator: TAKETOSHI Ayako 横浜国立大学, 大学院工学研究院, 非常勤教員 (50533056)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2020: ¥520,000 (Direct Cost: ¥400,000、Indirect Cost: ¥120,000); Fiscal Year 2019: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: 触媒 / 金クラスター / 金ナノ粒子 / 酸素酸化 / マイクロ波

Outline of Final Research Achievements

Gold clusters, which are smaller than 2 nm in diameter, could be deposited on metal oxide having high microwave absorption efficiency such as MnO2 by Deposition-precipitation method followed by microwave irradiation though the degree of reduction is still insufficient at 50%.
Selective esterification of aliphatic aldehydes and alcohols with ethanol in the absence of a base is a more difficult reaction than that with methanol. Gold nanoparticles on ZnO were found to be the most effective catalyst for the oxidative　esterification of octanal and 1-octanol to ethyl octanoate without a base. Au/ZnO exhibited the highest catalytic activity in both batch and flow reactors.

Academic Significance and Societal Importance of the Research Achievements

金触媒調製時、担体のマイクロ波吸収効率が高い場合、マイクロ波加熱により還元まで行うことが、クラスターサイズの金を担持するのに有効であるとわかった。今後さらなる条件検討により還元度合を制御できれば、金クラスター触媒の一般的な調製法となることが期待できる。エチルエステル合成については、現行のプロセスではアルデヒドから2工程必要だが、金触媒を用いることにより1工程に短縮でき、化学プロセスのシンプル化につながる。

Research Products

• [Journal Article] Gold Nanoparticles Supported on Nb2O5 for Low-Temperature CO Oxidation and as Cathode Materials for Li-ion Batteries (2020)
  • Author(s): Dien Luong Xuan、Truong Quang Duc、Murayama Toru、Chinh Huynh Dang、Taketoshi Ayako、Honma Itaru、Haruta Masatake、Ishida Tamao
  • Journal Title: Applied Catalysis A: General Volume: 603 Pages: 117747-117747
  • DOI: 10.1016/j.apcata.2020.117747
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] 金触媒：ナノ粒子の世界 (2020)
  • Author(s): 竹歳絢子, 石田玉青
  • Journal Title: 理科教室 Volume: 63 Pages: 82-85
  • Peer Reviewed
• [Journal Article] 担持金ナノ粒子触媒を用いる高選択的酸化反応 (2020)
  • Author(s): 竹歳絢子, 石田玉青
  • Journal Title: 触媒 Volume: 62 Pages: 99-105
  • Peer Reviewed
• [Journal Article] Oxidative esterification of aliphatic aldehydes and alcohols with ethanol over gold nanoparticle catalysts in batch and continuous flow reactors (2019)
  • Author(s): Taketoshi Ayako、Ishida Tamao、Murayama Toru、Honma Tetsuo、Haruta Masatake
  • Journal Title: Applied Catalysis A: General Volume: 585 Pages: 117169-117169
  • DOI: 10.1016/j.apcata.2019.117169
  • Peer Reviewed
• [Journal Article] Importance of Size and Contact Structure of Gold Nanoparticles for the Genesis of Unique Catalytic Processes (2019)
  • Author(s): Ishida Tamao、Murayama Toru、Taketoshi Ayako、Haruta Masatake
  • Journal Title: Chemical Reviews Volume: 120 Issue: 2 Pages: 464-525
  • DOI: 10.1021/acs.chemrev.9b00551
  • Peer Reviewed / Open Access
• [Journal Article] 金ナノ粒子触媒によるエチルエステルの効率合成 (2019)
  • Author(s): 竹歳絢子, 石田玉青
  • Journal Title: AROMA RESEARCH Volume: 20 Pages: 10-11
• [Journal Article] Supported gold cluster catalysts prepared by solid grinding using a non-volatile organogold complex for low-temperature CO oxidation and the effect of potassium on gold particle size (2019)
  • Author(s): Dien Luong Xuan, Ishida Tamao, Taketoshi Ayako, Truong Duc Q., Dang Chinh Huynh, Honma Tetsuo, Murayama Toru, Haruta Masatake
  • Journal Title: Applied Catalysis B: Environmental Volume: 241 Pages: 539-547
  • DOI: 10.1016/j.apcatb.2018.09.053
  • Peer Reviewed / Int'l Joint Research
• [Presentation] 置換ハイドロキシアパタイト担持金触媒による3,4-diacetoxybut-1-eneの異性化反応－強い金属―担体相互作用(SMSI)の効果－ (2020)
  • Author(s): 中山晶皓, 袖永竜生, Yuvaraj Gangarajura, 竹歳絢子, 村山徹, 本間徹生, 坂口紀史, 嶋田哲也, 高木慎介, 春田正毅, Junhu Wang, 石田玉青
  • Organizer: 第126回触媒討論会
• [Presentation] 置換ハイドロキシアパタイト担持金ナノ粒子触媒によるアルケンの異性化反応－強い金属―担体相互作用(SMSI)と置換イオンの効果－ (2020)
  • Author(s): 中山晶皓, 袖永竜生, Yuvaraj Gangarajura, 竹歳絢子, 村山徹, 本間徹生, 坂口紀史, 嶋田哲也, 高木慎介, 春田正毅, Junhu Wang, 石田玉青
  • Organizer: 第10回CSJ化学フェスタ
• [Presentation] Selective oxidation of furfural derivatives over Au/Nb2O5 (2020)
  • Author(s): Chihiro Mochizuki, Mingyue Lin, Ayako Taketoshi, Hiroki Miura, Kiyotaka Nakajima, Tamao Ishida, Tetsuya Shishido, Masatake Haruta, Toru Murayama
  • Organizer: TMU-CU Symposium 2020
  • Int'l Joint Research
• [Presentation] 担持金ナノ粒子触媒を用いたフルフラール酸化反応における担体が与える影響と金粒子サイズの効果 (2020)
  • Author(s): 望月ちひろ，Lin Mingyue 竹歳絢子,石田玉青，宍戸哲也, 中島清隆，春田正毅，村山徹
  • Organizer: 第125回触媒討論会
• [Presentation] Effects of the size of nanoparticulate gold and their support on selective oxidation of furfural to furoic acid (2019)
  • Author(s): Chihiro Mochizuki, Mingyue Lin, Ayako Taketoshi, Tamao Ishida, Masatake Haruta, Toru Murayama
  • Organizer: The 8th Asia-Pacific Congress on Catalysis
  • Int'l Joint Research
• [Presentation] フルフラール選択的酸化反応における担持金ナノ粒子触媒の担体・サイズ効果 (2019)
  • Author(s): 望月ちひろ, 竹歳絢子, 石田玉青, 春田正毅, 村山 徹
  • Organizer: 第62回石油学会年会
• [Presentation] 担持金ナノ粒子触媒における金ナノ粒子の電子状態がフルフラール酸化反応に与える影響 (2019)
  • Author(s): 望月ちひろ, Lin Mingyue, 竹歳絢子, 石田玉青, 中島清隆, 春田正毅, 村山徹
  • Organizer: 第124回触媒討論会
• [Presentation] ハイドロキシアパタイト担持金ナノ粒子触媒による脂肪族アルデヒドの酸化的エステル化－カチオンおよびアニオン置換効果－ (2019)
  • Author(s): 竹歳絢子, GANGARAJULA, Yuvaraj, 袖永竜生, 村山徹, WANG, Junhu, 春田正毅, 石田玉青
  • Organizer: 第124回触媒討論会
• [Presentation] Oxidative Esterification of Aliphatic Aldehydes or Alcohols with Ethanol Catalyzed by Gold Nanoparticles (2018)
  • Author(s): Ayako Taketoshi, Tamao Ishida, Toru Murayama, Masatake Haruta
  • Organizer: International Symposium on Gold Chemistry 2018
  • Int'l Joint Research / Invited
• [Presentation] Catalytic oxidation of furfural by nanoparticulate gold catalysts (2018)
  • Author(s): Chihiro Mochizuki, Ayako Taketoshi, Tamao Ishida, Masatake Haruta, Toru Murayama
  • Organizer: International Symposium on Gold Chemistry 2018
  • Int'l Joint Research
• [Presentation] Oxidative Esterification of Aliphatic Aldehydes by Gold Nanoparticle Catalysts in a Continuous Flow Reactor (2018)
  • Author(s): Ayako Taketoshi, Tamao Ishida, Toru Murayama, Masatake Haruta
  • Organizer: The 8th International Conference on Gold Science, Technology and its Applications (GOLD2018)
  • Int'l Joint Research
• [Presentation] Effect of the Support and the Size of Gold Nanoparticles on Catalytic Oxidation of Furfural (2018)
  • Author(s): Chihiro Mochizuki, Ayako Taketoshi, Tamao Ishida, Masatake Haruta, Toru Murayama
  • Organizer: The 3rd International Symposium on Hydrogen Energy-based Society
  • Int'l Joint Research
• [Presentation] 担持金ナノ粒子触媒による脂肪族アルデヒド、アルコールの酸化的エステル 化 (2018)
  • Author(s): 竹歳絢子, 石田玉青, 村山 徹, 春田正毅
  • Organizer: 第 122 回触媒討論会
• [Presentation] フルフラール酸化における金ナノ粒子触媒の担体・サイズ効果 (2018)
  • Author(s): 望月ちひろ, 竹歳絢子, 石田玉青, 春田正毅, 村山 徹
  • Organizer: 第 51 回酸化反応討論会 2018