単一原子・電子で構造化された金ナノクラスターのスピン触媒活性の相関を解明（Scientists Uncover Spin-Catalytic Activity Correlation in Single-atom and -electron Tailored Gold Nanoclusters）

2025-04-14 中国科学院(CAS)

＜関連情報＞

• https://english.cas.cn/newsroom/research_news/phys/202504/t20250414_1041205.shtml
• https://www.science.org/doi/10.1126/sciadv.adu1996

磁性マルチシェル金ナノ粒子の最内殻原子を除去することで、CO2からCO2へのほぼ単一変換が可能になる Remove the innermost atom of a magnetic multi-shell gold nanoparticle for near-unity conversion of CO2 to CO

Guoqing Bian, Dong Chen, Yuping Chen, Wei Zhang, […], and Zhikun Wu
Science Advances  Published:9 Apr 2025
DOI:https://doi.org/10.1126/sciadv.adu1996

Abstract

Few reports on paramagnetic metal nanoparticles with atomic precision and their difficult tailoring retard the insightful investigation of metal nanoparticle paramagnetism. Herein, we introduced a thiol-iodine mixture ligand–protecting strategy to successfully synthesize multi-shell paramagnetic [Au₁₂₇I₄(TBBT)₄₈ (I: iodine, TBBT: 4-tert-butylphenylthiolate)]. The innermost Au atom was successfully removed via thiol induction without altering the structure framework to produce diamagnetic Au₁₂₆I₄(TBBT)₄₈ with local ligand arrangement changed (butterfly effect), which could be further transformed into paramagnetic [Au₁₂₆I₄(TBBT)₄₈]⁺ via hydrogen peroxide oxidation. The spin populations of both paramagnetic nanoparticles are more densely distributed on surface iodine than sulfur. Diamagnetic Au₁₂₆I₄(TBBT)₄₈ exhibited a Faradaic efficiency of ~100% at −0.57 volt during the electrocatalytic reduction of carbon dioxide to carbon monoxide, while paramagnetic Au₁₂₇I₄(TBBT)₄₈ and [Au₁₂₆I₄(TBBT)₄₈]⁺ exhibited the maximum Faradaic efficiency of 87% at −0.67 volt and 90% at −0.57 volt, respectively, indicating the spin-catalytic activity correlation.