制备可实现优异亚甲基蓝降解的 Co/S 共掺杂碳催化剂

李海旭; 何浩波; 姜天男; 杜云飞; 吴芷尘; 徐良; 王新洁; 刘晓光; 余万华; 薛文东

doi:10.1007/s12613-024-2953-1

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文章导航 > 矿物冶金与材料学报（英文） > 2025 > 二校

Haixu Li, Haobo He, Tiannan Jiang, Yunfei Du, Zhichen Wu, Liang Xu, Xinjie Wang, Xiaoguang Liu, Wanhua Yu, and Wendong Xue, Preparation of Co/S co-doped carbon catalysts for excellent methylene blue degradation, Int. J. Miner. Metall. Mater.,(2025). https://doi.org/10.1007/s12613-024-2953-1

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Haixu Li, Haobo He, Tiannan Jiang, Yunfei Du, Zhichen Wu, Liang Xu, Xinjie Wang, Xiaoguang Liu, Wanhua Yu, and Wendong Xue, Preparation of Co/S co-doped carbon catalysts for excellent methylene blue degradation, Int. J. Miner. Metall. Mater.,(2025). https://doi.org/10.1007/s12613-024-2953-1

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研究论文

制备可实现优异亚甲基蓝降解的 Co/S 共掺杂碳催化剂

1)
北京科技大学材料科学与工程学院, 北京 100083, 中国
2)
北京金裕通达耐火材料科技有限公司, 北京 100085, 中国

通讯作者:
刘晓光 E-mail: liuxg@ustb.edu.cn

文章亮点

(1)为了改变两者之间的结合方式，使用了两种不同的方法混合了MOF-71和硫脲，明确了酒精蒸发法混合原料可以生成氢键并促进S在碳骨架内外均匀分布。

(2)催化剂和过氧单硫酸盐（PMS）在4 min内降解95.6%的亚甲基蓝（MB）。

(3)通过理论计算得出C–S–C位点可以吸附PMS，然后与Co–S位点共活化PMS。

(4)在亚甲基蓝降解过程中，¹O₂起主要降解作用，SO₄⁻·和·OH起辅助作用。

中文摘要

通过在 800°C 高温下热解 MOF-71 和硫脲混合物制备了 S 和 Co 共掺杂碳催化剂，MOF-71 与硫脲的质量比为 1:0.1，可有效活化过一硫酸盐 (PMS) 以降解亚甲基蓝 (MB)。研究发现了两种不同混合路线对甲基溴降解性能的影响。其中，通过醇溶剂蒸发（MOF-AEP）混合路线得到的催化剂可在 4 min内降解 95.60% 的亚甲基蓝（50 mg/L）（降解率：K = 0.78 min^-1），比直接研磨法得到的催化剂（MOF-DGP，80.97%，K= 0.39 min^-1）更快。X 射线光电子能谱显示，MOF-AEP 的 Co–S 位点（43.39at%）少于 MOF-DGP（54.73at%），MOF-AEP 中的 C–S–C 比例（13.56at%）高于 MOF-DGP（10.67at%）。密度泛函理论计算表明，当硫以 C–S–C 形式掺杂在碳骨架上时，钴对 PMS 的吸附能为-2.94 eV，高于以 Co–S 键形式掺杂在钴旁边时的吸附能（-2.86 eV）。因此，与 Co–S 相比，C–S–C 位点可能对活化 PMS 有更大的贡献。此外，还研究了降解参数，包括 pH 值和 MOF-AEP 的用量。最后，自由基淬灭实验和电子顺磁共振（EPR）测量结果表明，在降解 MB 的过程中，¹O₂可能是主要催化物种，而 · O²⁻可能是次要催化物种。

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Research Article

Preparation of Co/S co-doped carbon catalysts for excellent methylene blue degradation

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Abstract

Abstract

S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800°C at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate (PMS) for methylene blue (MB) degradation. The effects of two different mixing routes were identified on the MB degradation performance. Particularly, the catalyst obtained by the alcohol solvent evaporation (MOF-AEP) mixing route could degrade 95.60% MB (50 mg/L) within 4 min (degradation rate: K = 0.78 min^–1), which was faster than that derived from the direct grinding method (MOF-DGP, 80.97%, K = 0.39 min^–1). X-ray photoelectron spectroscopy revealed that the Co–S content of MOF-AEP (43.39at%) was less than that of MOF-DGP (54.73at%), and the proportion of C–S–C in MOF-AEP (13.56at%) was higher than that of MOF-DGP (10.67at%). Density functional theory calculations revealed that the adsorption energy of Co for PMS was −2.94 eV when sulfur was doped as C–S–C on the carbon skeleton, which was higher than that when sulfur was doped next to cobalt in the form of Co–S bond (−2.86 eV). Thus, the C–S–C sites might provide more contributions to activate PMS compared with Co–S. Furthermore, the degradation parameters, including pH and MOF-AEP dosage, were investigated. Finally, radical quenching experiments and electron paramagnetic resonance (EPR) measurements revealed that ¹O₂ might be the primary catalytic species, whereas · O²⁻ might be the secondary one in degrading MB.
- advanced oxidation process;
- alcohol solvent evaporation;
- hydrogen bond;
- S and Co co-doped carbon catalysts;
- wastewater remediation

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