Bian Guoqing, Chen Dong, Chen Yuping, Zhang Wei, Fang Liang, You Qing, Wang Runguo, Gu Wanmiao, Zhou Yue, Yan Nan, Zhuang Shengli, Ji Shiyu, Zhou Meng, Wang Chengming, Liao Lingwen, Tang Qing, Yang Jun, Wu Zhikun
Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences, Hefei, Anhui 230031, P. R. China.
Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, P. R. China.
Sci Adv. 2025 Apr 11;11(15):eadu1996. doi: 10.1126/sciadv.adu1996. Epub 2025 Apr 9.
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 [AuI(TBBT) (I: iodine, TBBT: 4-tert-butylphenylthiolate)]. The innermost Au atom was successfully removed via thiol induction without altering the structure framework to produce diamagnetic AuI(TBBT) with local ligand arrangement changed (butterfly effect), which could be further transformed into paramagnetic [AuI(TBBT)] via hydrogen peroxide oxidation. The spin populations of both paramagnetic nanoparticles are more densely distributed on surface iodine than sulfur. Diamagnetic AuI(TBBT) exhibited a Faradaic efficiency of ~100% at -0.57 volt during the electrocatalytic reduction of carbon dioxide to carbon monoxide, while paramagnetic AuI(TBBT) and [AuI(TBBT)] exhibited the maximum Faradaic efficiency of 87% at -0.67 volt and 90% at -0.57 volt, respectively, indicating the spin-catalytic activity correlation.
关于具有原子精度的顺磁性金属纳米颗粒及其难以定制的报道很少，这阻碍了对金属纳米颗粒顺磁性的深入研究。在此，我们引入了一种硫醇-碘混合配体保护策略，成功合成了多壳层顺磁性[AuI(TBBT)]（I：碘，TBBT：4-叔丁基苯硫醇盐）。通过硫醇诱导成功去除了最内层的金原子，而不改变结构框架，从而产生了具有局部配体排列变化的抗磁性AuI(TBBT)（蝴蝶效应），其可通过过氧化氢氧化进一步转化为顺磁性[AuI(TBBT)]。两种顺磁性纳米颗粒的自旋布居在表面碘上的分布比在硫上更密集。抗磁性AuI(TBBT)在将二氧化碳电催化还原为一氧化碳的过程中，在-0.57伏时表现出约100%的法拉第效率，而顺磁性AuI(TBBT)和[AuI(TBBT)]分别在-0.67伏和-0.57伏时表现出87%和90%的最大法拉第效率，表明了自旋催化活性相关性。
