Incorporation of lanthanide atom into the titanium−oxo cluster structure is an effective strategy for exploring novel photoelectrode materials. Herein, we synthesized and characterized three lanthanide-doped titanium−oxo clusters (Ln-TOCs): [Ti 4 La(μ 3 -O) 3 (O i Pr) 2 (C 6 H 5 COO) 11 ]·3CH 3 CN ( 1 ), [Ti 4 Eu 2 (μ 3 -O) 4 (acac) 2 (C 6 H 5 COO) 13 ] ( 2, acac = acetylacetonate), and [Ti 7 Ce(μ 2 -O) 2 (μ 3 -O) 5 (O i Pr) 2 (C 6 H 5 COO) 15 ]·CH 3 CN ( 3 ). These Ln−TOCs display strong UV-light absorption and extended visible light absorption, which can be ascribed to the doping of lanthanides and benzoates. As electrode precursors for photoelectric responses, these Ln doped clusters exhibit clear photocurrent responses. Moreover, cluster 3 shows the highest photocurrent intensity because of Ce(IV)/Ce(III) redox reaction . This work not only enriches the Ln−TOCs family, but also promotes the development of novel titanium-based photoelectric active materials.
Substituted polycyclic aromatic hydrocarbons (SPAHs) are being intensively investigated, considering their high toxicity. Additionally, the mechanism of the effect of substituents on the removal of SPAHs and the activation of Ce(III) ions on peroxymonosulfate (PMS) have not been explored. Here we evaluated the removal efficiency of SPAHs in the oxidation system constructed by Ce(Ⅲ) ions and PMS, with emphasized the effect of substituents on SPAHs degradation. Ce(Ⅲ) has high catalytic performance for PMS, and the degradation percentage of all pollutants was higher than 92%. The significantly negative correlation between the reaction rate constants of SPAHs and the highest occupied molecular orbital-the lowest unoccupied molecular orbital gap, confirms that substituents lead to the differences in the degradation of SPAHs. The generation of reactive oxygen species (SO 4 •− , • OH, and 1 O 2 ) is based on the electron transfer between Ce(Ⅲ) and PMS, and the contribution of ROS to substituted naphthalene varies due to the role of substituents. The Ce(Ⅳ)/Ce(Ⅲ) cycle accelerates the activation of PMS. Based on the transformation products and condensed Fukui function, the possible degradation pathways are inferred. In addition, inorganic anions and organic matter have little effect on the Ce(Ⅲ)/PMS system, which is a prerequisite for applying this system to real-world waste-water for SPAHs removal. This work demonstrates a new model of the degradation mechanism of SPAHs in the Ce(Ⅲ)/PMS system.
Graphical Redox flow battery : A Zn−Ce redox flow battery based on choline chloride ethylene glycol deep eutectic solvent was studied. The open-circuit voltage of the battery reaches 2.2 V, and the coulombic efficiency of the battery is stable at about 84 %, which may provide theoretical support for the development of large-scale energy storage system. Compared with conventional aqueous and ionic liquid electrolytes, deep eutectic solvent (DES) are considered as electrolyte for redox flow batteries because they have a wider electrochemical window and relatively low price. In this study, Ce IV /Ce III and Zn II /Zn redox couples are used as the positive and negative active materials, respectively, in an electrolyte consisting of choline chloride ethylene glycol (ethaline). The structure of Ce III in the positive electrolyte is inferred through spectrum detection. Ce IV /Ce III and Zn II /Zn redox couples show a stable potential difference of 2.2 V (vs. Ag) through cyclic voltammetry. The charge and discharge performance of battery was tested at different current densities. In addition, battery performance was evaluated at different temperatures and concentrations of cerium in the electrolyte. Consequently, at a current density of 0.5 mA cm −2 at room temperature and using 1.0 m Ce III , the battery performance reaches the best coulombic efficiency of 84 %.
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