低锰负载下 Si-O-Mn 键的稳定和圆形电子金属-载体相互作用增强催化臭氧化消除 CH3SH,Environmental Science & Technology

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低锰负载下 Si-O-Mn 键的稳定和圆形电子金属-载体相互作用增强催化臭氧化消除 CH3SH
Environmental Science & Technology ( IF 10.8 ) Pub Date : 2022-02-23 , DOI: 10.1021/acs.est.1c07065
Dingren Ma ₁ , Weiqi Liu ₁ , Yajing Huang ₁ , Dehua Xia _{1,

2} , Qiyu Lian ₁ , Chun He _{1,

2}

Affiliation

甲硫醇（CH _{3 ）的催化臭氧化}SH）可以有效控制这种难闻的含硫挥发性有机化合物（S-VOC）。构建电子金属-载体相互作用（EMSI）配位结构以最大化活性位点数量并增加活性位点的内在活性是提高催化性能的有效手段。在这项工作中，PSBA-15（煅烧前的 SBA-15）上丰富的 Si-OH 基团用于锚定 Mn，形成基于 Si-O-Mn 的 EMSI 配位结构。详细表征和理论模拟表明，强 EMSI 效应显着调整和稳定 Mn 3d 态的电子结构，导致 Si-O-Mn 键上的富电子中心促进臭氧（O ₃) 和 (Si-O-)Mn-O 键上的缺电子中心吸附大量 CH ₃ SH 并伴随其自身的氧化降解。原位拉曼和原位傅里叶变换红外 (FTIR) 分析表明，3.0Mn-PSBA 上的催化臭氧化产生原子氧 (AOS/*O) 和活性氧 (ROS/ ^• O ₂^– ) 以实现 CH 的有效分解₃ SH 转化为 CO ₂ /SO ₄^2–。此外，CH ₃ SH 获得的电子在贫电子中心被转移，以维持 Mn ^2+/3+ → Mn ⁴⁺ → Mn的氧化还原循环。^{2+/3+通过内部键桥，从而实现了CH}₃ SH的高效稳定降解，降解时间延长至180 min。因此，通过EMSI效应合理设计具有丰富活性位点和优化固有活性的催化剂，可以为提高催化性能和消除恶臭气体提供巨大潜力。

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Enhanced Catalytic Ozonation for Eliminating CH3SH via Stable and Circular Electronic Metal–Support Interactions of Si–O–Mn Bonds with Low Mn Loading

Catalytic ozonation of methyl mercaptan (CH₃SH) can effectively control this unbearable odorous sulfur-containing volatile organic compound (S-VOC). The construction of an electronic metal–support interaction (EMSI) coordination structure to maximize the number of active sites and increase the intrinsic activity of active sites is an effective means to improve catalytic performance. In this work, the abundant Si–OH groups on PSBA-15 (SBA-15 before calcination) were used to anchor Mn to form a Si–O–Mn-based EMSI coordination structure. Detailed characterizations and theoretical simulations reveal that the strong EMSI effect significantly adjusts and stabilizes the electronic structure of Mn 3d states, resulting in an electron-rich center on the Si–O–Mn bond to promote the specific adsorption/activation of ozone (O₃) and an electron-poor center on the (Si–O−)Mn–O bond to adsorb a large amount of CH₃SH accompanied by its own oxidative degradation. In situ Raman and in situ Fourier transform infrared (FTIR) analyses identify that catalytic ozonation over 3.0Mn-PSBA generates atomic oxygen species (AOS/*O) and reactive oxygen species (ROS/^•O₂^–) to achieve efficient decomposition of CH₃SH into CO₂/SO₄^2–. Furthermore, the electrons obtained from CH₃SH in electron-poor centers are transferred to maintain the redox cycle of Mn^2+/3+ → Mn⁴⁺ → Mn^2+/3+ through the internal bond bridge, thus accomplishing the efficient and stable degradation of CH₃SH prolonged to 180 min. Therefore, the rational design of catalysts with abundant active sites and optimized inherent activity via the EMSI effect can provide significant potential to improve catalytic performance and eliminate odorous gases.

更新日期：2022-02-23

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