单线态氧(1O2)在化学领域得到了广泛的应用,生物医学和环境。然而,通过双氧活化生产高浓度的1O2仍然是一个挑战。在这里,碳负载的稀土氧化物纳米团簇和单原子催化剂系统(称为RE2O3/RE-C,RE=La,Ce,Pr,Nd,Sm,Eu,Gd,TB,Dy,Ho,呃,Tm,Yb,卢,Sc和Y)形态相似,结构,和物理化学特性被构造为激活溶解氧(DO)以增强1O2的产生。实验揭示了催化活性的趋势和机理,并通过理论分析和计算得到了证明。1O2生成活性趋势为Gd2O3/Gd-C>Er2O3/Er-C>Sm2O3/Sm-C>原始碳(C)。超过95.0%的常见抗生素(环丙沙星,氧氟沙星,诺氟沙星和卡马西平)可以在60分钟内通过Gd2O3/Gd-C去除。密度泛函理论计算表明,Gd2O3纳米团簇和Gd单原子表现出适度的·O2-吸附能,以提高1O2的产量。这项研究提供了一种通用的策略,以提高氧气活化中的1O2生产,以供将来应用,并揭示了通过稀土氧化物纳米团簇和稀土单原子生产1O2的基本机制的自然本质。
Singlet oxygen (1O2) is extensively employed in the fields of chemical, biomedical and environmental. However, it is still a challenge to produce high- concentration 1O2 by dioxygen activation. Herein, a system of carbon-supported rare-earth oxide nanocluster and single atom catalysts (named as RE2O3/RE-C, RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y) with similar morphology, structure, and physicochemical characteristic are constructed to activate dissolved oxygen (DO) to enhance 1O2 production. The catalytic activity trends and mechanisms are revealed experimentally and are also proven by theoretical analyses and calculations. The 1O2 generation activity trend is Gd2O3/Gd-C>Er2O3/Er-C>Sm2O3/Sm-C>pristine carbon (C). More than 95.0% of common antibiotics (ciprofloxacin, ofloxacin, norfloxacin and carbamazepine) can be removed in 60 min by Gd2O3/Gd-C. Density functional theory calculations indicate that Gd2O3 nanoclusters and Gd single atoms exhibit the moderate adsorption energy of ·O2- to enhance 1O2 production. This study offers a universal strategy to enhance 1O2 production in dioxygen activation for future application and reveals the natural essence of basic mechanisms of 1O2 production via rare-earth oxide nanoclusters and rare-earth single atoms.