<br>单原子M-N4和M-OH（M=Mn、Fe、Co、Ni）位点协同操控臭氧活化机制：理论预测与实验验证,Environmental Science & Technology

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单原子M-N4和M-OH（M=Mn、Fe、Co、Ni）位点协同操控臭氧活化机制：理论预测与实验验证
Environmental Science & Technology ( IF 10.8 ) Pub Date : 2024-05-15 , DOI: 10.1021/acs.est.4c00812
Guangfei Yu _{1,

2,

3} , Jing Wang _{1,

2} , Zhaomeng Xu _{1,

2} , Hongbin Cao _{1,

2} , Qin Dai ₃ , Yiqiu Wu _{1,

2} , Yongbing Xie _{1,

2}

Affiliation

碳基单原子催化剂(SACs)已逐渐被引入多相催化臭氧化(HCO)领域，但催化剂表面O ₃活化的界面机制仍不明确，特别是表面羟基(M–OH)的作用）在金属部位。在此，我们将理论计算与实验验证相结合，全面研究了一系列具有N掺杂纳米碳基底（MN ₄ –NCs，其中M = Mn、Fe、Co、Ni）的常规SAC结构上的O ₃活化机制。金属原子和M-OH对O ₃活化途径的协同操纵效应受到特别关注。 O ₃倾向于直接与MnN ₄ –NC、FeN ₄ –NC和NiN ₄ –NC催化剂上的金属原子相互作用，其中MnN ₄ –NC因其相对较低的O ₃活化能垒而具有最好的催化活性（ 0.62 eV）和更活跃的表面吸附氧（O _ads ）。在CoN ₄ –NC催化剂上，O ₃与金属位点的直接相互作用在能量上是不可行的，但是O ₃可以通过M-OH位点的直接或间接参与被活化以生成O _ad或HO ₂物种。实验结果表明，MnN ₄ -NC和CoN ₄ -NC催化剂催化臭氧氧化对羟基苯甲酸时，40 min内分别去除了90.7%和82.3%的总有机碳（TOC）。磷酸盐淬灭、催化剂表征和 EPR 测量进一步支持了理论预测。这一贡献为SACs上O ₃活化机制提供了基础见解，其方法和理念可能有助于未来的环境催化研究。

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Synergetic Manipulation Mechanism of Single-Atom M–N4 and M–OH (M = Mn, Fe, Co, Ni) Sites for Ozone Activation: Theoretical Prediction and Experimental Verification

Carbon-based single-atom catalysts (SACs) have been gradually introduced in heterogeneous catalytic ozonation (HCO), but the interface mechanism of O₃ activation on the catalyst surface is still ambiguous, especially the effect of a surface hydroxyl group (M–OH) at metal sites. Herein, we combined theoretical calculations with experimental verifications to comprehensively investigate the O₃ activation mechanisms on a series of conventional SAC structures with N-doped nanocarbon substrates (MN₄–NCs, where M = Mn, Fe, Co, Ni). The synergetic manipulation effect of the metal atom and M–OH on O₃ activation pathways was paid particular attention. O₃ tends to directly interact with the metal atom on MnN₄–NC, FeN₄–NC, and NiN₄–NC catalysts, among which MnN₄–NC has the best catalytic activity for its relatively lower activation energy barrier of O₃ (0.62 eV) and more active surface-adsorbed oxygen species (O_ads). On the CoN₄–NC catalyst, direct interaction of O₃ with the metal site is energetically infeasible, but O₃ can be activated to generate O_ads or HO₂ species from direct or indirect participation of M–OH sites. The experimental results showed that 90.7 and 82.3% of total organic carbon (TOC) was removed within 40 min during catalytic ozonation of p-hydroxybenzoic acid with MnN₄–NC and CoN₄–NC catalysts, respectively. Phosphate quenching, catalyst characterization, and EPR measurement further supported the theoretical prediction. This contribution provides fundamental insights into the O₃ activation mechanism on SACs, and the methods and ideals could be helpful for future studies of environmental catalysis.

更新日期：2024-05-15

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