催化作用
氧化物
化学
锆
选择性
分子
激进的
猝灭(荧光)
碳纤维
纳米复合材料
电子转移
化学计量学
金属
光化学
无机化学
化学工程
材料科学
有机化学
纳米技术
物理
量子力学
复合数
工程类
复合材料
荧光
作者
Xiaoyang Li,Jiahang Liu,Ruolin Lv,Yingying Chu,Lu Lv,Junhe Lu,Weiming Zhang
标识
DOI:10.1016/j.cej.2023.142369
摘要
Self-quenching of radicals and their non-selective attack on co-existing substrates result in the low oxidant utilization efficiency in Fenton and Fenton-like systems. Herein, we developed a novel octahedral carbon-encapsulated zirconium oxide catalyst (ZrO2-C) featured by large specific surface area (219.5 m2/g), highly-dispersed sub-5 nm active sites, and strong metal-support interactions. The catalyst shows outstanding performance for peroxymonosulfate (PMS) activation, and a two-step catalytic mechanism is proposed. First, it interacts with PMS via inner-sphere coordination to form a metastable surface complex (Stage I); then, the reactive complex reacts with selected molecules via oxygen-atom-transfer route (Stage II). Surprisingly, only 1.21 PMS molecules was consumed for each molecule of carbamazepine (CBZ), almost close to the stoichiometric ratio. Based on a quantitative structure–activity relationship between the reaction rates and the molecular structures of fourteen substituted phenols, we demonstrated that this catalytic process was highly selective towards electron-rich compounds, that is, only those organics with EHOMO values higher than ca. −6.52 eV could be oxidized. Overall, this study provides mechanistic insights into the catalytic selectivity of Zr-based catalysts and advances their further application in Fenton-like systems.
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