Ultrafine-Mn2O3@N-doped porous carbon hybrids derived from Mn-MOFs: Dual-reaction centre catalyst with singlet oxygen-dominant oxidation process

Ultrafine-Mn2O3@N-doped porous carbon hybrids derived from Mn-MOFs: Dual-reaction centre catalyst with singlet oxygen-dominant oxidation process
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由 Mn-MOF 衍生的超细 Mn2O3@N 掺杂多孔碳杂化物:具有单线态氧主导氧化过程的双反应中心催化剂

DOI:
10.1016/j.cej.2021.132299
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发表时间:
2022-02
影响因子:
15.1
通讯作者:
Philippe François-Xavier Corvini
Philippe François-Xavier Corvini
中科院分区:
工程技术1区
文献类型:
--
作者:
Zhiqun Xie;Zhiping Lyu;Jinnan Wang;Aimin Li;Philippe François-Xavier Corvini

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以1 O2和O2-·为主要活性氧物种,以Mn-MOFs为原料,制备了超细Mn2O3@N掺杂多孔碳杂化材料[Mn2O3@NC]。阳离子-π键和N-Mn络合作用导致富电子Mn中心的形成,为过氧单硫酸根的活化提供电子,产生自由基,并通过链反应生成1 O2。值得注意的是,氮掺杂的碳壳的多孔结构不仅可以促进自由基重组产生1 O2,而且还提供了有机物的吸附位。另一方面,N掺杂碳壳作为贫电子中心,可以促进有机中间体自由基通过π -π反应、C-O-Mn键和C-N-Mn键向富电子Mn中心的电子转移,促进Mn的氧化还原,避免过一硫酸盐的无效分解。由于双反应中心的协同作用和1 O2的强氧化能力,Mn2O3@NC在低剂量(0.033 g/L)下实现了BPA的高矿化。
Ultrafine-Mn2O3@N-doped porous carbon hybrids [Mn2O3@NC] derived from Mn-MOFs was constructed with1O2and O2−•as main Reactive oxygen species (ROS). Cation-π bonds and N-Mn complexation induced the formation of electron-rich Mn centre which provided electron for peroxymonosulfate activation to produce radicals, accompanying with generation of1O2via chain reaction. Notably, the porous structure of N-doped carbon shell could not only facilitate free radical recombination for generation of1O2but also provide adsorption sites for organics. On the other hand, as electron-poor centre, N-doped carbon shell could improve the electrons transfer from organic intermediate radicals to electron-rich Mn centre via π -π reaction, C-O-Mn and C-N-Mn bonds, which promote the redox of Mn to avoid peroxymonosulfate invalid decomposition. Being attributed to synergistic effects of dual-reaction centres and strong oxidation ability of1O2, Mn2O3@NC achieved high mineralization of BPA at low-dose peroxymonosulfate (0.033 g/L).
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