单原子活化过一硫酸盐性能更好?与金属氧化物耦合可能更高效

doi:10.1016/S1872-2067(24)60009-4

催化学报 ›› 2024, Vol. 59: 137-148.DOI: 10.1016/S1872-2067(24)60009-4

单原子活化过一硫酸盐性能更好?与金属氧化物耦合可能更高效

张俊磊^a^,^d, 刘文聪^a, 刘彪^b, 段晓光^c, 敖志敏^b^,^*(), 朱明山^a^,^*()

^a暨南大学环境学院, 广东省环境污染与健康重点实验室, 广东广州511443, 中国
^b北京师范大学环境与生态前沿交叉研究院, 广东珠海519087, 中国
^c阿德莱德大学化工学院, 阿德莱德, 澳大利亚
^d西北工业大学材料科学与工程学院, 凝固技术国家重点实验室, 陕西西安710072, 中国

收稿日期:2023-12-22 接受日期:2024-02-26 出版日期:2024-04-18 发布日期:2024-04-15
通讯作者: *电子信箱: zhimin.ao@bnu.edu.cn (敖志敏), zhumingshan@jnu.edu.cn (朱明山).
基金资助:
国家自然科学基金(52300218);国家自然科学基金(22322604);国家自然科学基金(22176041);广东省珠江人才引进计划(2019QN01L148)

Is single-atom catalyzed peroxymonosulfate activation better? Coupling with metal oxide may be better

Junlei Zhang^a^,^d, Wencong Liu^a, Biao Liu^b, Xiaoguang Duan^c, Zhimin Ao^b^,^*(), Mingshan Zhu^a^,^*()

^aGuangdong Key Laboratory of Environmental Pollution and Health, School of Environment, Jinan University, Guangzhou 511443, Guangdong, China
^bAdvanced Interdisciplinary Institute of Environment and Ecology, Beijing Normal University, Zhuhai 519087, Guangdong, China
^cSchool of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia
^dSchool of Materials Science and Engineering, State Key Laboratory of Solidification Processing, Atomic Control & Catalysis Engineering Laboratory, Northwestern Polytechnical University, Xi’an 710072, Shaanxi, China

Received:2023-12-22 Accepted:2024-02-26 Online:2024-04-18 Published:2024-04-15
Contact: *E-mail: zhimin.ao@bnu.edu.cn (Z. Ao); zhumingshan@jnu.edu.cn (M. Zhu).
Supported by:
The National Natural Science Foundation of China(52300218);The National Natural Science Foundation of China(22322604);The National Natural Science Foundation of China(22176041);The Pearl River Talent Recruitment Program of Guangdong Province(2019QN01L148)

摘要/Abstract

摘要：

单原子催化剂(SAC)作为新一代过一硫酸盐(PMS)非均相活化剂, 具有原子利用率高、结构稳定性强等优点, 为新兴有机污染物(EOPs)的高效降解提供了新的解决方案. 然而, SAC的活性位点密度依然受限于严苛的制备工艺等, 而这严重影响PMS的进一步激活. 因此, 发展SAC基PMS高级氧化技术的关键之一在于提升SAC的活性位点密度, 进而增强PMS活化效率. 相比之下, 传统的过渡金属氧化物(MO_x)作为PMS活化剂, 尽管存在金属原子利用率低和金属离子易溶出等问题, 但其表面具有丰富的金属活性位点. 统筹SAC与MO_x的优缺点, 本文提出了一种“新-老”结合策略, 即将传统MO_x与新一代SAC耦合, 发展兼具丰富金属活性位点和优良结构稳定性的PMS活化剂, 实现PMS的高效活化.

本文采用预配位-重结晶-热解路径, 结合金属离子源投加量控制, 制备了具有金属氧化物与单原子组分的Co₃O₄@Co₁/C₃N₅复合PMS非均相活化剂, 并系统研究了其活化PMS降解EOPs的性能. 粉末X射线衍射、X射线光电子能谱、高角环形暗场扫描透射电子显微镜及X射线吸收谱结果表明, Co₃O₄@Co₁/C₃N₅由金属氧化物Co₃O₄和单原子Co₁/C₃N₅组成, 并且Co₃O₄纳米晶体被锚定在Co₁/C₃N₅纳米片表面. 在降解典型EOPs双氯芬酸钠(DCF)的过程中, Co₃O₄@Co₁/C₃N₅活化的PMS体系展现了显著增强的性能. 相比基于Co₃O₄和Co₁/C₃N₅活化的PMS体系, DCF的降解速率分别提高了约28.0倍和2.5倍, 证明Co₃O₄@Co₁/C₃N₅具有显著增强的PMS活化能力. 这主要因为Co₁/C₃N₅和Co₃O₄之间形成的Co₁-O(Co₃O₄)和Co-N(Co₁/C₃N₅)化学键有效地促进了电荷迁移. 结合密度泛函理论计算发现, Co₁/C₃N₅和Co₃O₄之间的强电子相互作用显著强化了PMS的吸附, 降低了PMS分解生成活性物质的能垒. 此外, Co₃O₄@Co₁/C₃N₅具有良好的复杂环境因素(包括pH、共存阴离子以及实际污水等)耐受性和可重复使用性, 证明了其在PMS高级氧化体系中的应用潜力.

综上, 将单原子催化剂与金属氧化物进行耦合, 不仅可能优化电子结构, 增强活性位点的暴露度, 还能通过协同效应, 促进反应中间体的稳定和转化, 从而提升整体的PMS活化性能. 本文研究结果为设计高效催化剂体系提供了参考.

关键词: 单原子催化剂, 金属氧化物, 协同效应, 过一硫酸盐活化, Co₃O₄@Co₁/C₃N₅

Abstract:

Single-atom catalysts (SACs) as a new class of peroxymonosulfate (PMS) activator are still limited by the low metal loading and activity. Here, we introduce a new strategy of interfacial coupling SACs with metal oxides to fine-tune the active single-atom sites and improve the atomic utilization efficiency. Taking Co₃O₄@Co₁/C₃N₅ as a case, the formation of heterostructures enhanced the activity of outer-sphere SACs for PMS activation, further upgrading the kinetics of diclofenac sodium degradation. The degradation rate of the composite increases by up to approximately 28.0 and 2.5 times compared to Co₃O₄and Co₁/C₃N₅, respectively. The Co₁-O (Co₃O₄) and Co-N (Co₁/C₃N₅) bonds between Co₁/C₃N₅ and Co₃O₄ make a tightly coupled interface for charge migration, which synergically optimizes the PMS adsorption configuration toward reactive species generation with lower activation energy. Co₃O₄@Co₁/C₃N₅ also exhibits excellent reusability and can be employed in broad application scenarios.

Key words: Single-atom catalyst, Metal oxide, Synergy, Peroxymonosulfate activation, Co₃O₄@Co₁/C₃N₅

张俊磊, 刘文聪, 刘彪, 段晓光, 敖志敏, 朱明山. 单原子活化过一硫酸盐性能更好?与金属氧化物耦合可能更高效[J]. 催化学报, 2024, 59: 137-148.

Junlei Zhang, Wencong Liu, Biao Liu, Xiaoguang Duan, Zhimin Ao, Mingshan Zhu. Is single-atom catalyzed peroxymonosulfate activation better? Coupling with metal oxide may be better[J]. Chinese Journal of Catalysis, 2024, 59: 137-148.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60009-4

https://www.cjcatal.com/CN/Y2024/V59/I4/137

图/表 5

Fig. 1. (A) The development trend of heterogeneous PMS activators. (B) The DCF degradation rates in the reaction system of Co3O4, Co1/C3N5 or Co3O4@Co1/C3N5 coupled PMS.

Fig. 2. (A) The scheme of Co3O4@Co1/C3N5 preparation. (B) TEM image of Co3O4@Co1/C3N5. (C) HR-TEM image of Co3O4 in Co3O4@Co1/C3N5. (D) HADDF-STEM image of Co1/C3N5 in Co3O4@Co1/C3N5. (E) Co k edge XANES spectra of Co foil, CoO, Co3O4, Co2O3, Co1/C3N5, and Co3O4@Co1/C3N5. (F-G) high-resolution XPS of Co 2p from Co3O4@Co1/C3N5 and Co1/C3N5. The corresponding Fourier transform spectra of Co foil, CoO, Co3O4, Co2O3, Co1/C3N5, and Co3O4@Co1/C3N5 (H), and EXAFS fitting curves at K (I) and R (J) space of Co1/C3N5, respectively.

Fig. 3. The degradation curves (A), rates (B), and mineralization efficiencies (C) of DCF in the system of PMS alone, Co3O4@Co1/C3N5 alone, C3N5 coupled PMS, Co3O4 coupled PMS, Co1/C3N5 coupled PMS or Co3O4@Co1/C3N5 coupled PMS. (D) Comparison of the DCF degradation rate and TOC removal by Co3O4 plus Co1/C3N5 and Co3O4@Co1/C3N5. The degradation curves (E) and TOC removal efficiencies (F) of DCF in various waterbodies (e.g., deionized (DI) water, rain water, tap water, river water, and medical wastewater) over the reaction system of Co3O4@Co1/C3N5 coupled PMS. (G) The adsorption energy Eads of PMS adsorbed on the C3N5, Co1/C3N5, and Co3O4@Co1/C3N5 surfaces, inset showing corresponding relaxed configuration. (H) The pathway of the free radical production process. (I) The relaxed configuration of the free radical production process on the C3N5, Co1/C3N5, and Co3O4@Co1/C3N5 surfaces, where IS, TS and FS represent initial structure, transition structure and final structure of the reaction, respectively. The gray, blue, red, yellow, white, nattier blue spheres in this Fig. are C, N, O, S, H, Co atoms, respectively.

Fig. 4. Effects of scavengers on DCF degradation in the Co3O4@Co1/C3N5 (A), Co1/C3N5 (B) or Co3O4 (C) coupled PMS system. ESR spectra of TEMP-1O2 (D), DMPO-OH/SO4- (E), and DMPO-O2- (F) in the systems of PMS alone, and Co3O4, Co1/C3N5 or Co3O4@Co1/C3N5 coupled PMS, respectively. (G) The proposed mechanism of Co3O4@Co1/C3N5 to activate PMS for PPCPs degradation.

Fig. 5. (A) The degradation products and summarized possible degradation pathways of DCF in the system of Co3O4@Co1/C3N5 coupled PMS. Acute toxicity (B), developmental toxicity (C), bioaccumulation factor (D), and mutagenicity (E) of DCF and corresponding products. (F) Recycling degradation curves of DCF by reusing Co3O4@Co1/C3N5 to activate PMS. (G) XRD patterns of fresh, used, and calcined Co3O4@Co1/C3N5 samples.

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单原子活化过一硫酸盐性能更好?与金属氧化物耦合可能更高效

Is single-atom catalyzed peroxymonosulfate activation better? Coupling with metal oxide may be better

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