催化学报

催化学报 ›› 2027, Vol. 92: 428-441.DOI: 10.1016/S1872-2067(26)65238-2

• 论文 • 上一篇    下一篇

B→Co电子供给诱导硼化钴Lewis碱性Co位点实现过一硫酸盐选择性内层活化

魏浩然a,1, 赵薇b,1, 张俊磊a,*, 尉国佳a, 杨方d, 王小兵e, 熊梧琬f, 李世杰c,*   

  1. a西北工业大学材料科学与工程学院, 陕西西安 710072;
    b云南大学生态与环境科学学院, 云南大学高原湖泊生态与治理研究院, 云南昆明 650500;
    c浙江海洋大学国家海洋设施养殖工程技术研究中心, 浙江省临港石化污染控制重点实验室, 浙江舟山 316000;
    d上海工程技术大学机械与汽车工程学院, 上海 201620;
    e韶关学院化学与土木工程学院, 广东韶关 512005;
    f肇庆学院环境与化学工程学院, 广东肇庆 526061
  • 收稿日期:2026-05-25 接受日期:2026-07-10 出版日期:2027-01-18 发布日期:2026-10-30
  • 通讯作者: *电子信箱: jlzhang2018@163.com (张俊磊), lishijie@zjou.edu.cn (李世杰).
  • 作者简介:1共同第一作者.
  • 基金资助:
    国家自然科学基金(52300218); 云南省基础研究计划(202401CF070197); 云南省“兴滇英才支持计划”青年专项.

B→Co electron donation programs Lewis-basic sites in cobalt boride for selective inner-sphere peroxymonosulfate activation

Haoran Weia,1, Wei Zhaob,1, Junlei Zhanga,*, Guojia Yua, Fang Yangd, Xiaobing Wange, Wuwan Xiongf, Shijie Lic,*   

  1. aSchool of Materials Science and Engineering, Northwestern Polytechnical University, Xi’ an 710072, Shaanxi, China;
    bSchool of Ecology and Environmental Science, Institute for Ecological Research and Pollution Control of Plateau Lakes, Yunnan University, Kunming 650500, Yunnan, China;
    cNational Engineering Research Center for Marine Aquaculture, Zhejiang Key Laboratory of Pollution Control for Port-Petrochemical Industry, Zhejiang Ocean University, Zhoushan 316000, Zhejiang, China;
    dSchool of Mechanical and Automotive Engineering, Shanghai University of Engineering Science, Shanghai 201620, China;
    eSchool of Chemistry and Civil Engineering, Shaoguan University, Shaoguan 512005, Guangdong, China;
    fSchool of Environmental and Chemical Engineering, Zhaoqing University, Zhaoqing 526061, Guangdong, China
  • Received:2026-05-25 Accepted:2026-07-10 Online:2027-01-18 Published:2026-10-30
  • Contact: *E-mail: jlzhang2018@163.com (J. Zhang), lishijie@zjou.edu.cn (S. Li).
  • About author:1 Contributed equally to this work.
  • Supported by:
    National Natural Science Foundation of China (52300218), the Yunnan Fundamental Research Projects (202401CF070197) and Yunnan Xingdian Talent Support Program.

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摘要： 过一硫酸盐(PMS)高级氧化技术可生成硫酸根自由基、羟基自由基和单线态氧等活性物种, 在抗生素、染料及其他难降解新污染物去除中具有重要应用潜力. 然而, 传统PMS活化多依赖自由基路径, 反应选择性较低, 易受Cl−, HCO3−和天然有机质等水体基质影响, 并可能降低氧化剂利用效率甚至诱发副产物风险. 相比之下, 以单线态氧和界面电子转移为核心的非自由基路径通常具有更好的污染物选择性和环境适应性, 但催化剂表面电子结构如何调控PMS吸附、内层电子转移和活性氧物种选择性仍不清晰. 因此, 发展兼具高活性、稳定性和选择性的新型PMS活化材料, 并阐明其Lewis酸碱耦合调控机制, 对面向复杂水体的新兴污染物治理具有重要意义.
本文以硼化钴(CoxB)为PMS活化催化剂, 并以Co3O4和Co2O3为参照, 系统考察其土霉素(OTC)降解活性、循环稳定性、污染物适用范围、复杂水体适应性和连续流运行性能. 研究提出, B→Co电子供给可增强表面Co位点的Lewis碱性, 使其与PMS中亲电性的氧原子发生更强的内层相互作用, 从而促进界面电子转移和O–O键极化, 并将反应选择性导向以1O2为主的非自由基路径. 在相同条件下, CoxB/PMS体系可在20 min内去除99.0%的OTC, 表观一级反应速率常数达到0.309 min–1, 分别约为Co3O4/PMS和Co2O3/PMS的2.4倍和5.4倍; 其单位催化剂摩尔降解速率为14.48 min–1·mol·L–1, 优于多种已报道钴基PMS活化体系. 稳定性测试显示, CoxB连续使用15次后仍保持97.6%的OTC去除性能, 而Co3O4和Co2O3在前4次循环中分别出现44.1%和32.9%的活性损失. 该体系还可高效去除亚甲基蓝、甲基橙、酸性品红、罗丹明B、金霉素、四环素、强力霉素和左氧氟沙星等多种染料与抗生素. 在雨水、河水和自来水中, CoxB/PMS仍保持较高OTC去除率, 并可在pH = 3.4–9.1范围内稳定运行; 腐殖酸仅造成有限抑制, NO3−影响较小, HPO42−和CO32−表现出中等抑制, 而Cl−和HCO3−抑制更明显, 揭示了体系在复杂水体中的适用边界. 连续流实验进一步表明, CoxB/PMS可在30 h内维持>99%的OTC去除率, 总处理体积为1.8 L. X-射线光电子能谱结果显示, PMS活化过程中Co价态发生可恢复的动态调节, B–Co和晶格结构保持相对稳定; 开路电位和原位红外结果表明, Co–B框架有利于PMS加入后的界面电荷重分布, 并显著扰动S–O和O–O振动. 猝灭实验、电子顺磁共振和糠醇探针共同证明, 1O2为主要活性物种, 其相对贡献约为49%, 而·SO4−, ·O2−和·OH的相对贡献分别约为25.4%, 21.5%和4.1%; 糠醇在1, 3和5 min内的表观消耗率分别达到79.4%, 93.3%和99.1%. 液相色谱-质谱及毒性预测表明, OTC可经侧链转化、四环骨架断裂、芳香环氧化开环及进一步碎片化生成低分子量产物, 且主要中间产物的发育毒性和致突变性风险整体低于母体OTC. 密度泛函理论计算进一步表明, Co3B(103)表面对PMS的S–O吸附更强(吸附能为−2.985 eV), 电势决定步骤能垒低于Co3O4(110) (2.792 vs. 3.037 eV), 与实验中更快动力学和更高1O2选择性相一致.
综上, 本文证明了通过金属硼化物中Lewis酸碱耦合调控表面电子结构, 可实现稳定的选择性非自由基PMS活化. 该策略为高效水处理氧化催化剂的设计提供了新的电子结构调控思路, 也为后续硼化物催化剂的可控制备、真实水体适应性评价和连续流放大应用奠定了基础.

关键词: Lewis酸碱耦合, 硼化钴, 过一硫酸盐活化, 非自由基氧化, 新污染物降解

Abstract: Peroxymonosulfate (PMS)-based advanced oxidation processes are promising for contaminant removal but are often limited by nonselective radical pathways. Here we show that selective PMS activation can be achieved by regulating Lewis acid-base interactions in cobalt boride (CoxB). Electron donation from boron to cobalt modifies the electronic structure of surface Co sites, generating Lewis-basic centers that interact strongly with electrophilic oxygen atoms in PMS. This interaction promotes inner-sphere electron transfer and favors selective 1O2 generation while suppressing radical-mediated reactions. Under optimized conditions, the CoxB/PMS system removes 99.0% of oxytetracycline within 20 min, delivering a kinetic constant of 0.309 min–1 and a molar degradation rate of 14.48 min–1·mol·L–1, outperforming representative cobalt oxides. The catalyst also shows strong stability, retaining 97.6% activity after 15 cycles and sustaining > 99% removal efficiency in continuous-flow operation for 30 h (1.8 L throughput). X-ray photoelectron spectroscopy measurements reveal reversible Co valence modulation during PMS activation, whereas density functional theory calculations indicate stronger PMS adsorption and a lower potential-determining barrier on CoxB relative to Co3O4. Together, these results identify Lewis-basic Co sites as key centers for selective non-radical PMS activation and provide a strategy for designing efficient boride-based oxidation catalysts.

Key words: Lewis acid-base coupling, Cobalt boride, Peroxymonosulfate activation, Non-radical pathway, Emerging contaminant degradation