尿素诱导温和相变策略调控α-MnO2微结构以增强新污染物催化臭氧氧化效能

doi:10.1016/S1872-2067(25)64889-3

催化学报

• •

尿素诱导温和相变策略调控α-MnO₂微结构以增强新污染物催化臭氧氧化效能

朱培新^a, 肖梦瑶^a, 陈茜茜^c,*, 罗旌崧^d, 房中^d, 陈龙^d, 赵慧楠^a, 何春^a,b, 田双红^a,b,*

^a中山大学环境科学与工程学院, 广东广州 510275;
^b广东省环境污染治理与修复重点实验室, 广东广州 510275;
^c香港城市大学材料科学与工程学院, 中国香港;
^d中国化学南方建设投资有限公司, 广东广州 516000

收稿日期:2025-09-01 接受日期:2025-09-01
通讯作者: ^*电子信箱: xixichen@cityu.edu.hk, chenxixi8117@163.com (陈茜茜), tshuangh@mail.sysu.edu.cn (田双红).
基金资助:
国家重点研发计划(2024YFC3712500); 国家自然科学基金(22376229); 广东省基础与应用基础研究基金(2023A1515010037).

Microstructure modulation of α-MnO2 via mild urea-induced phase transition for enhanced catalytic ozonation of emerging contaminants

Peixin Zhu^a, Mengyao Xiao^a, Xixi Chen^c,*, Jingsong Luo^d, Zhong Fang^d, Long Chen^d, Huinan Zhao^a, Chun He^a,b, Shuanghong Tian^a,b,*

^aSchool of Environmental Science & Engineering, Sun Yat-sen University, Guangzhou 510275, Guangdong, China;
^bGuangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation, Guangzhou 510275, Guangdong, China;
^cDepartment of Materials Science and Engineering, City University of Hong Kong, Hong Kong, China;
^dChina National Chemical Southern Construction Investment Co., Ltd., Guangzhou 516000, Guangdong, China

Received:2025-09-01 Accepted:2025-09-01
Contact: ^*E-mail: xixichen@cityu.edu.hk, chenxixi8117@163.com (X. Chen), tshuangh@mail.sysu.edu.cn (S. Tian).
Supported by:
National Key Research and Development Program of China (2024YFC3712500), the National Natural Science Foundation of China (22376229), and the Guangdong Basic and Applied Basic Research Foundation (2023A1515010037).

摘要/Abstract

摘要： 以抗生素为代表的新兴污染物由于具有难降解特性难以被传统工艺彻底去除,广泛残留于水环境中,其生物毒性对生态环境和人体健康构成严重威胁.对此,非均相催化臭氧氧化因其反应条件温和、操作简便、适应性强且二次污染少等特点极具应用价值.该技术的核心在于催化剂表面对臭氧的吸附与活化,而氧空位(Ov)的构建能够有效增强臭氧的吸附与电子转移.晶面工程是改变电子结构并产生大量金属氧化物缺陷的有效方法.因此,通过微观结构调控设计具有丰富缺陷的高效催化剂,成为催化臭氧氧化领域的重要研究方向.本研究通过一种温和的尿素辅助热处理策略,成功构建了富含氧空位的α-MnO₂(310)/Mn₃O₄异质结催化剂,同时实现了异质结与晶面工程的协同调控,为开发高效稳定的臭氧催化剂提供了新思路.
本研究通过控制制备条件(温度值和尿素投加量), 获得以下不同的MnX-YU催化剂组成(X代表制备温度, Y代表尿素与α-MnO2(310)的质量比): α-MnO2, 不同比例的α-MnO2(310)/Mn3O4异质结与Mn3O4; 其中成功构建了富含氧空位(OV)的α-MnO2(310)/Mn3O4异质结材料(Mn400-0.125U), 该材料由48.6%的α-MnO2(310)和51.4%的Mn3O4组成. 通过X-射线衍射(XRD)、扫描电镜、透射电镜(TEM)、X-射线光电子能谱(XPS)、固相电子自旋共振与Raman等表征手段, 证明了该材料基于α-MnO2(310)晶面较低的氧空位形成能及异质结界面效应实现了高浓度氧空位的构筑. 此外, 通过H2-程序升温还原、电化学阻抗谱与循环伏安法的测试, Mn400-0.125U最易被还原, 流动氧数量最多, 同时具备最高的本征界面电导率最大的电子转移和氧化还原反应能力, 以上特点非常有利于催化臭氧氧化性能的发挥. 因此, Mn400-0.125U在催化臭氧氧化去除新污染物的过程中表现出卓越性能, 其对磺胺甲噁唑(SMZ)的降解速率常数高达7.7×10‒2 min‒1, 分别是α-MnO2(310) , Mn3O4和单独臭氧氧化体系的1.8倍、1.6倍和3.3倍. 该材料还具有超低投加量(0.1 g/L)、较宽pH适应性(3.5–10.5)和强抗水体基质干扰能力(去除率损失≤12.4%)等显著操作优势. 在连续五次循环实验中Mn400-0.125U催化臭氧氧化SMZ的去除率始终超过86.9%, 并且通过其反应前后的XRD, TEM, 高分辨TEM与XPS对比发现Mn400-0.125U在反应过后具有显著的结构和化学稳定性, 证实了Mn400-0.125U的卓越运行稳定性. 机理实验和理论计算共同表明, 材料中丰富的氧空位与其适宜的亲水性协同作用, 实现了臭氧的无能垒活化和分解, 并通过链式反应产生多种活性物种. Mn400-0.125U在催化臭氧氧化SMZ的过程中以电子转移、表面氧原子(O*)和单线态氧(1O2)为主的非自由基途径起主导作用, 而自由基途径(•O2‒/•OH)的贡献很小, 仅仅起到了次要作用.
综上, 本工作为通过晶面工程与异质结协同调控策略构建富氧空位等缺陷催化剂提供了新方法, 显著提升了催化臭氧氧化体系的活性与稳定性, 对高效水处理技术的开发具有重要推动作用. 该研究成果为设计高性能非均相催化剂及深入理解表面缺陷促进的氧化机制提供了理论和实验依据.

关键词: 晶面调控, 异质结, 锰基催化剂, 氧空位, 催化臭氧化

Abstract: While facet engineering and heterostructure construction are recognized as effective strategies for enhancing catalytic performance through defect creation, their integration remains scarce and challenging. This study develops a mild urea-assisted thermal strategy to construct an oxygen vacancy (OV)-rich α-MnO2(310)/Mn3O4 heterojunction (Mn400-0.125U), comprising 48.6% α-MnO2 with preferentially exposed (310) facets and 51.4% Mn3O4. The low OV formation energy on (310) facets coupled with heterojunction interfaces effects leads to a high OV concentration. Mn400-0.125U demonstrated exceptional catalytic ozonation performance, achieving a sulfamethoxazole degradation rate constant (7.7×10–2 min–1), which is 1.8-, 1.6-, and 3.3-fold higher than those of α-MnO2, Mn3O4, and single ozonation, respectively. Operational advantages include ultralow catalyst dosage (0.1 g/L), broad pH adaptability (3.5–10.5), and remarkable resilience against aqueous matrix interference (≤ 12.4% efficiency loss). Both experimental and theoretical calculations demonstrate that the abundant OVs, combined with the proper hydrophilicity of Mn400-0.125U, synergistically trigger barrier-free activation and decomposition of ozone, subsequently generating a series of reactive species via chain reactions. A hybrid oxidation regime was identified where the non-radical pathway mediated by electron-transfer, O* (surface oxygen atoms), and 1O2 predominates over radical pathways (•O2–/•OH). This work establishes a facile coupled modulation protocol for creating defect-rich manganese oxides applied in catalytic ozonation of emerging contaminants.

Key words: Facet engineering, Heterojunction, Manganese-based catalysts, Oxygen vacancy, Catalytic ozonation

朱培新, 肖梦瑶, 陈茜茜, 罗旌崧, 房中, 陈龙, 赵慧楠, 何春, 田双红. 尿素诱导温和相变策略调控α-MnO₂微结构以增强新污染物催化臭氧氧化效能[J]. 催化学报, DOI: 10.1016/S1872-2067(25)64889-3.

Peixin Zhu, Mengyao Xiao, Xixi Chen, Jingsong Luo, Zhong Fang, Long Chen, Huinan Zhao, Chun He, Shuanghong Tian. Microstructure modulation of α-MnO2 via mild urea-induced phase transition for enhanced catalytic ozonation of emerging contaminants[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(25)64889-3.

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尿素诱导温和相变策略调控α-MnO₂微结构以增强新污染物催化臭氧氧化效能

Microstructure modulation of α-MnO2 via mild urea-induced phase transition for enhanced catalytic ozonation of emerging contaminants

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