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

Volume 32 Issue 1

Jan. 2025

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文章导航 > 矿物冶金与材料学报（英文） > 2025 > 32(1): 169-181

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., 32(2025), No. 1, pp. 169-181. https://doi.org/10.1007/s12613-024-2953-1

Cite this article as:

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., 32(2025), No. 1, pp. 169-181. 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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[1]	Y.C. Yang, Q.L. Zhu, X.W. Peng, et al., Hydrogels for the removal of the methylene blue dye from wastewater: A review, Environ. Chem. Lett., 20(2022), No. 4, p. 2665. doi: 10.1007/s10311-022-01414-z
[2]	X.T. Huo, R.X. Chai, L.Z. Gou, M. Zhang, and M. Guo, Facile synthesis of composite polyferric magnesium–silicate–sulfate coagulant with enhanced performance in water and wastewater, Int. J. Miner. Metall. Mater., 31(2024), No. 3, p. 574. doi: 10.1007/s12613-023-2704-8
[3]	X.D. Du and M.H. Zhou, Strategies to enhance catalytic performance of metal–organic frameworks in sulfate radical-based advanced oxidation processes for organic pollutants removal, Chem. Eng. J., 403(2021), art. No. 126346. doi: 10.1016/j.cej.2020.126346
[4]	J.L. Wang and S.Z. Wang, Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants, Chem. Eng. J., 334(2018), p. 1502. doi: 10.1016/j.cej.2017.11.059
[5]	J.Q. Wang, B. Hasaer, M. Yang, et al., Anaerobically-digested sludge disintegration by transition metal ions-activated peroxymonosulfate (PMS): Comparison between Co²⁺, Cu²⁺, Fe²⁺ and Mn²⁺, Sci. Total Environ., 713(2020), art. No. 136530. doi: 10.1016/j.scitotenv.2020.136530
[6]	P.D. Hu and M.C. Long, Cobalt-catalyzed sulfate radical-based advanced oxidation: A review on heterogeneous catalysts and applications, Appl. Catal. B Environ., 181(2016), p. 103. doi: 10.1016/j.apcatb.2015.07.024
[7]	J.S. Yuan, Y. Zhang, X.Y. Zhang, L. Zhao, H.L. Shen, and S.G. Zhang, Template-free synthesis of core–shell Fe₃O₄@MoS₂@mesoporous TiO₂ magnetic photocatalyst for wastewater treatment, Int. J. Miner. Metall. Mater., 30(2023), No. 1, p. 177. doi: 10.1007/s12613-022-2473-9
[8]	G.J. Lv, T. Wang, X.Y. Zou, et al., Highly dispersed copper oxide-loaded hollow Fe-MFI zeolite for enhanced tetracycline degradation, Colloids Surf. A, 655(2022), art. No. 130250. doi: 10.1016/j.colsurfa.2022.130250
[9]	W.J. Peng, L.X. Cai, Y.N. Lu, and Y.Y. Zhang, Preparation of Mn–Co-MCM-41 molecular sieve with thermosensitive template and its degradation performance for rhodamine B, Catalysts, 13(2023), No. 6, art. No. 991. doi: 10.3390/catal13060991
[10]	Q.Y. Yi, J.L. Tan, W.Y. Liu, H. Lu, M.Y. Xing, and J.L. Zhang, Peroxymonosulfate activation by three-dimensional cobalt hydroxide/graphene oxide hydrogel for wastewater treatment through an automated process, Chem. Eng. J., 400(2020), art. No. 125965. doi: 10.1016/j.cej.2020.125965
[11]	Z.Y. Yang, X. Li, Y.Z. Huang, et al., Facile synthesis of cobalt-iron layered double hydroxides nanosheets for direct activation of peroxymonosulfate (PMS) during degradation of fluoroquinolones antibiotics, J. Clean. Prod., 310(2021), art. No. 127584. doi: 10.1016/j.jclepro.2021.127584
[12]	C.L. He, Y. Liu, M.W. Qi, et al., A functionalized activated carbon adsorbent prepared from waste amidoxime resin by modifying with H₃PO₄ and ZnCl₂ and its excellent Cr(VI) adsorption, Int. J. Miner. Metall. Mater., 31(2024), No. 3, p. 585. doi: 10.1007/s12613-023-2737-z
[13]	T.H. Ma, H.X. Li, X.G. Liu, et al., Preparation of cobalt and nitrogen-doped porous carbon composite catalysts from ZIF-9 and their outstanding Fenton-like catalytic properties towards methylene blue, ChemistrySelect, 8(2023), No. 18, art. No. e202204785. doi: 10.1002/slct.202204785
[14]	C.G. Hu and L.M. Dai, Doping of carbon materials for metal-free electrocatalysis, Adv. Mater., 31(2019), No. 7, art. No. e1804672. doi: 10.1002/adma.201804672
[15]	Y. Gao, Q. Wang, G.Z. Ji, and A.M. Li, Degradation of antibiotic pollutants by persulfate activated with various carbon materials, Chem. Eng. J., 429(2022), art. No. 132387. doi: 10.1016/j.cej.2021.132387
[16]	W.Q. Huang, S. Xiao, H. Zhong, M. Yan, and X. Yang, Activation of persulfates by carbonaceous materials: A review, Chem. Eng. J., 418(2021), art. No. 129297. doi: 10.1016/j.cej.2021.129297
[17]	S.J. Zhang, X.W. Huo, S.Z. Xu, et al., Original sulfur-doped carbon materials synthesized by coffee grounds for activating persulfate to BPA degradation: The key role of electron transfer, Process. Saf. Environ. Prot., 168(2022), p. 1219. doi: 10.1016/j.psep.2022.10.073
[18]	S.Y. Liu, C. Lai, B.S. Li, et al., Heteroatom doping in metal-free carbonaceous materials for the enhancement of persulfate activation, Chem. Eng. J., 427(2022), art. No. 131655. doi: 10.1016/j.cej.2021.131655
[19]	C.L. Ding, Z. Liu, S.Y. Pan, et al., Activation of peroxydisulfate via Fe@sulfur-doped carbon-supported nanocomposite for degradation of norfloxacin: Efficiency and mechanism, Chem. Eng. J., 460(2023), art. No. 141729. doi: 10.1016/j.cej.2023.141729
[20]	J.L. Li, W.H. Zhu, Y. Gao, et al., The catalyst derived from the sulfurized Co-doped metal–organic framework (MOF) for peroxymonosulfate (PMS) activation and its application to pollutant removal, Sep. Purif. Technol., 285(2022), art. No. 120362. doi: 10.1016/j.seppur.2021.120362
[21]	Y.W. Li, Q. Wu, R.C. Ma, et al., A Co-MOF-derived Co₉S₈@NS-C electrocatalyst for efficient hydrogen evolution reaction, RSC Adv., 11(2021), No. 11, p. 5947. doi: 10.1039/D0RA10864B
[22]	T. Yamada, Y. Kubo, and N. Kimizuka, Introduction of thiourea into metal–organic frameworks by immersion technique and their phase transition characteristics, Chem. Lett., 46(2017), No. 1, p. 115. doi: 10.1246/cl.160910
[23]	M.A. Asgari, M. Moradi, M.J. Eshraghi, and S. Hajati, A comparison between microwave reflection loss of MIL-53 derived Fe₂O₃ and MOF-71-derived Co₃O₄ through direct and indirect heat treatment, Synth. Met., 295(2023), art. No. 117337. doi: 10.1016/j.synthmet.2023.117337
[24]	J.Q. Dong, Z.Q. Gong, Y.Z. Chen, et al., Organic microstructure-induced hierarchically porous g-C₃N₄ photocatalyst, Sci. China Mater., 66(2023), No. 8, p. 3176. doi: 10.1007/s40843-022-2463-8
[25]	D. Chisca, L. Croitor, O. Petuhov, E.B. Coropceanu, and M.S. Fonari, MOF-71 as a degradation product in single crystal to single crystal transformation of new three-dimensional Co(II) 1, 4-benzenedicarboxylate, CrystEngComm, 18(2016), No. 1, p. 38. doi: 10.1039/C5CE02094H
[26]	L.C. Yin, J. Liang, G.M. Zhou, F. Li, R. Saito, and H.M. Cheng, Understanding the interactions between lithium polysulfides and N-doped graphene using density functional theory calculations, Nano Energy, 25(2016), p. 203. doi: 10.1016/j.nanoen.2016.04.053
[27]	J. Li, H. Li, W. Xie, et al., Flame-assisted synthesis of O-coordinated single-atom catalysts for efficient electrocatalytic oxygen reduction and hydrogen evolution reaction, Small Methods, 6(2022), No. 1, art. No. e2101324. doi: 10.1002/smtd.202101324
[28]	Z.Z. Du, X.J. Chen, W. Hu, et al., Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries, J. Am. Chem. Soc., 141(2019), No. 9, p. 3977. doi: 10.1021/jacs.8b12973
[29]	K.K. Qiu, Y.J. Zhang, L. Wang, M.Y. Wu, J.Y. Jin, and W.Q. Shi, N-functionalized Ti₂C MXene as a high-performance adsorbent for strontium ions: A first-principles study, J. Phys. Chem. C, 127(2023), No. 23, p. 11167. doi: 10.1021/acs.jpcc.3c00849
[30]	T. Lu and F.W. Chen, Multiwfn: A multifunctional wavefunction analyzer, J. Comput. Chem., 33(2012), No. 5, p. 580. doi: 10.1002/jcc.22885
[31]	Y.Y. Liu, Z.R. Min, J.C. Jiang, et al., Molybdenum, cobalt sulfide-modified N-, S-doped graphene from low-temperature molecular pyrolysis: Mutual activation effect for hydrogen evolution, ACS Sustainable Chem. Eng., 7(2019), No. 24, p. 19442. doi: 10.1021/acssuschemeng.9b04219
[32]	X.C. Feng, Z.J. Xiao, H.T. Shi, et al., How nitrogen and sulfur doping modified material structure, transformed oxidation pathways, and improved degradation performance in peroxymonosulfate activation, Environ. Sci. Technol., 56(2022), No. 19, p. 14048. doi: 10.1021/acs.est.2c04172
[33]	D.H. Duan, W.W. Zhao, K.X. Chen, et al., MOF-71 derived layered Co–CoP/C for advanced Li–S batteries, J. Alloys Compd., 886(2021), art. No. 161203. doi: 10.1016/j.jallcom.2021.161203
[34]	Y. Zhou, W.H. Lv, B.L. Zhu, et al., Template-free one-step synthesis of g-C₃N₄ nanosheets with simultaneous porous network and S-doping for remarkable visible-light-driven hydrogen evolution, ACS Sustainable Chem. Eng., 7(2019), No. 6, p. 5801. doi: 10.1021/acssuschemeng.8b05374
[35]	C.A. Téllez S, E. Hollauer, M.A. Mondragon, and V.M. Castaño, Fourier transform infrared and Raman spectra, vibrational assignment and ab initio calculations of terephthalic acid and related compounds, Spectrochim. Acta Part A: Mol. Biomol. Spectrosc., 57(2001), No. 5, p. 993. doi: 10.1016/S1386-1425(00)00428-5
[36]	S.A. Abrori, N.L.W. Septiani, F.N. Hakim, et al., Non-enzymatic electrochemical detection for uric acid based on a glassy carbon electrode modified with MOF-71, IEEE Sens. J., 21(2021), No. 1, p. 170. doi: 10.1109/JSEN.2020.3014298
[37]	M. Mouanga, L. Ricq, and P. Berçot, Effects of thiourea and urea on zinc–cobalt electrodeposition under continuous current, J. Appl. Electrochem., 38(2008), No. 2, p. 231. doi: 10.1007/s10800-007-9430-1
[38]	Y.P. Guo, Z.Q. Zeng, Y.L. Li, Z.G. Huang, and Y. Cui, In-situ sulfur-doped carbon as a metal-free catalyst for persulfate activated oxidation of aqueous organics, Catal. Today, 307(2018), p. 12. doi: 10.1016/j.cattod.2017.05.080
[39]	S.Z. Wang and J.L. Wang, Peroxymonosulfate activation by Co9S8@ S and N co-doped biochar for sulfamethoxazole degradation, Chem. Eng. J., 385(2020), art. No. 123933. doi: 10.1016/j.cej.2019.123933
[40]	G. Zhang, P. Wang, W.T. Lu, et al., Co nanoparticles/Co, N, S tri-doped graphene templated from in-situ-formed Co, S co-doped g-C₃N₄ as an active bifunctional electrocatalyst for overall water splitting, ACS Appl. Mater. Interfaces, 9(2017), No. 34, p. 28566. doi: 10.1021/acsami.7b08138
[41]	J. Tang, R.R. Salunkhe, H. Zhang, et al., Bimetallic metal-organic frameworks for controlled catalytic graphitization of nanoporous carbons, Sci. Rep., 6(2016), art. No. 30295. doi: 10.1038/srep30295
[42]	Q.Q. Ren, Z.Y. Wu, S. Hu, et al., Sulfur self-doped char with high specific capacitance derived from waste tire: Effects of pyrolysis temperature, Sci. Total Environ., 741(2020), art. No. 140193. doi: 10.1016/j.scitotenv.2020.140193
[43]	X.G. Duan, K. O’Donnell, H.Q. Sun, Y.X. Wang, and S.B. Wang, Sulfur and nitrogen co-doped graphene for metal-free catalytic oxidation reactions, Small, 11(2015), No. 25, p. 3036. doi: 10.1002/smll.201403715
[44]	J. Deng, Y.J. Ge, C.Q. Tan, et al., Degradation of ciprofloxacin using α-MnO₂ activated peroxymonosulfate process: Effect of water constituents, degradation intermediates and toxicity evaluation, Chem. Eng. J., 330(2017), p. 1390. doi: 10.1016/j.cej.2017.07.137
[45]	Z.L. Wu, Z.K. Xiong, R. Liu, et al., Pivotal roles of N-doped carbon shell and hollow structure in nanoreactor with spatial confined Co species in peroxymonosulfate activation: Obstructing metal leaching and enhancing catalytic stability, J. Hazard. Mater., 427(2022), art. No. 128204. doi: 10.1016/j.jhazmat.2021.128204
[46]	M.X. Lu, G.Y. Kang, and Y.J. Deng, Construction of mesoporous S-doped Co₃O₄ with abundant oxygen vacancies as an efficient activator of PMS for organic dye degradation, CrystEngComm, 25(2023), No. 18, p. 2767. doi: 10.1039/D3CE00067B
[47]	H.X. Li, S.D. Xu, J. Du, J.H. Tang, and Q.W. Zhou, Cu@Co-MOFs as a novel catalyst of peroxymonosulfate for the efficient removal of methylene blue, RSC Adv., 9(2019), No. 17, p. 9410. doi: 10.1039/C9RA01143A
[48]	Z.L. Wu, Y.P. Wang, Z.K. Xiong, et al., Core–shell magnetic Fe₃O₄@Zn/Co-ZIFs to activate peroxymonosulfate for highly efficient degradation of carbamazepine, Appl. Catal. B: Environ., 277(2020), art. No. 119136. doi: 10.1016/j.apcatb.2020.119136
[49]	F. Ghanbari and M. Moradi, Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: Review, Chem. Eng. J., 310(2017), p. 41. doi: 10.1016/j.cej.2016.10.064
[50]	W.X. Qin, G.D. Fang, Y.J. Wang, and D.M. Zhou, Mechanistic understanding of polychlorinated biphenyls degradation by peroxymonosulfate activated with CuFe₂O₄ nanoparticles: Key role of superoxide radicals, Chem. Eng. J., 348(2018), p. 526. doi: 10.1016/j.cej.2018.04.215
[51]	J.K. Tan, X.D. Zhang, Y.W. Lu, X. Li, and Y.M. Huang, Role of interface of metal–organic frameworks and their composites in persulfate-based advanced oxidation process for water purification, Langmuir, 40(2024), No. 1, p. 21. doi: 10.1021/acs.langmuir.3c02877
[52]	Y.W. Yu, H.Y. Quan, Z.X. Zhang, et al., Nonradical pathway dominated activation of peroxymonosulfate by ZnFe₂O₄/C composites to eliminate tetracycline hydrochloride: Insight into the cycle of Zn/Fe and electron transfer, Sep. Purif. Technol., 322(2023), art. No. 124336. doi: 10.1016/j.seppur.2023.124336
[53]	J.L. Wang and S.Z. Wang, Effect of inorganic anions on the performance of advanced oxidation processes for degradation of organic contaminants, Chem. Eng. J., 411(2021), art. No. 128392. doi: 10.1016/j.cej.2020.128392
[54]	J.B. Sun, D.J. Zhang, D.S. Xia, and Q. Li, Orange peels biochar doping with Fe–Cu bimetal for PMS activation on the degradation of bisphenol A: A synergy of ${\mathrm{SO}}_4^{- } \cdot$, · OH, ¹O₂ and electron transfer, Chem. Eng. J., 471(2023), art. No. 144832. doi: 10.1016/j.cej.2023.144832
[55]	S.Z. Wang, J. Hu, and J.L. Wang, Degradation of sulfamethoxazole using PMS activated by cobalt sulfides encapsulated in nitrogen and sulfur Co-doped graphene, Sci. Total Environ., 827(2022), art. No. 154379. doi: 10.1016/j.scitotenv.2022.154379
[56]	H.X. Li, Z.X. Yang, S. Lu, et al., Nano-porous bimetallic CuCo-MOF-74 with coordinatively unsaturated metal sites for peroxymonosulfate activation to eliminate organic pollutants: Performance and mechanism, Chemosphere, 273(2021), art. No. 129643. doi: 10.1016/j.chemosphere.2021.129643
[57]	W.K. Zhu, D. Kim, M.S. Han, et al., Fibrous cellulose nanoarchitectonics on N-doped carbon-based metal-free catalytic nanofilter for highly efficient advanced oxidation process, Chem. Eng. J., 460(2023), art. No. 141593. doi: 10.1016/j.cej.2023.141593
[58]	H.X. Li, J. Zhang, Y.Z. Yao, X.R. Miao, J.L. Chen, and J.H. Tang, Nanoporous bimetallic metal-organic framework (FeCo-BDC) as a novel catalyst for efficient removal of organic contaminants, Environ. Pollut., 255(2019), art. No. 113337. doi: 10.1016/j.envpol.2019.113337
[59]	W. Zhang, M. Li, W.T. Shang, et al., Singlet oxygen dominated core–shell Co nanoparticle to synergistically degrade methylene blue through efficient activation of peroxymonosulfate, Sep. Purif. Technol., 308(2023), art. No. 122849. doi: 10.1016/j.seppur.2022.122849
[60]	L.Y. Wu, P.P. Guo, X. Wang, H.Y. Li, A.Z. Li, and K.Y. Chen, Mechanism study of CoS₂/Fe(III)/peroxymonosulfate catalysis system: The vital role of sulfur vacancies, Chemosphere, 288(2022), art. No. 132646. doi: 10.1016/j.chemosphere.2021.132646
[61]	Z. Zhu, Z.X. Liu, X. Tang, et al., Sulfur-doped g-C₃N₄ for efficient photocatalytic CO₂ reduction: Insights by experiment and first-principles calculations, Catal. Sci. Technol., 11(2021), No. 5, p. 1725. doi: 10.1039/D0CY02382E
[62]	X.X. Wang, C.Y. Zhang, D.H. Li, et al., Theoretical study of local S coordination environment on Fe single atoms for peroxymonosulfate-based advanced oxidation processes, J. Hazard. Mater., 454(2023), art. No. 131469. doi: 10.1016/j.jhazmat.2023.131469
[63]	S.Q. Li, Y.J. Hou, Q.M. Chen, X.D. Zhang, H.Y. Cao, and Y.M. Huang, Promoting active sites in MOF-derived homobimetallic hollow nanocages as a high-performance multifunctional nanozyme catalyst for biosensing and organic pollutant degradation, ACS Appl. Mater. Interfaces, 12(2020), No. 2, p. 2581. doi: 10.1021/acsami.9b20275
[64]	S.Z. Wang, H.Y. Liu, and J.L. Wang, Nitrogen, sulfur and oxygen co-doped carbon-armored Co/Co9S8 rods (Co/Co9S8@N–S–O–C) as efficient activator of peroxymonosulfate for sulfamethoxazole degradation, J. Hazard. Mater., 387(2020), art. No. 121669. doi: 10.1016/j.jhazmat.2019.121669
[65]	X.Q. Zhou, M.Y. Luo, C.Y. Xie, et al., Tunable S doping from Co₃O₄ to Co₉S₈ for peroxymonosulfate activation: Distinguished radical/nonradical species and generation pathways, Appl. Catal. B Environ., 282(2021), art. No. 119605. doi: 10.1016/j.apcatb.2020.119605
[66]	S.Z. Wang and J.L. Wang, High efficient activation of peroxymonosulfate by Co9S8 anchored in N, S, O co-doped carbon composite for degradation of sulfamethoxazole: Effect of sulfur precursor and sulfur doping content, Chem. Eng. J., 434(2022), art. No. 134824. doi: 10.1016/j.cej.2022.134824
[67]	G.S. Zhang, J.Y. Gao, J. Wang, H.F. Lin, J.X. Xu, and L. Wang, ZIF-67/melamine derived hollow N-doped carbon/Co₉S₈ polyhedron to activate peroxymonosulfate for degradation of tetracycline, J. Environ. Chem. Eng., 11(2023), No. 2, art. No. 109355. doi: 10.1016/j.jece.2023.109355
[68]	Y. Jiang, J. Wang, B. Liu, et al., Superhydrophilic N, S, O-doped Co/CoO/Co₉S₈@carbon derived from metal-organic framework for activating peroxymonosulfate to degrade sulfamethoxazole: Performance, mechanism insight and large-scale application, Chem. Eng. J., 446(2022), art. No. 137361. doi: 10.1016/j.cej.2022.137361
[69]	Y.K. Long, S. Li, Y.P. Su, et al., Sulfur-containing iron nanocomposites confined in S/N co-doped carbon for catalytic peroxymonosulfate oxidation of organic pollutants: Low iron leaching, degradation mechanism and intermediates, Chem. Eng. J., 404(2021), art. No. 126499. doi: 10.1016/j.cej.2020.126499
[70]	Y. Gao, T.W. Wu, C.D. Yang, et al., Activity trends and mechanisms in peroxymonosulfate-assisted catalytic production of singlet oxygen over atomic metal–N–C catalysts, Angew. Chem. Int. Ed Engl., 60(2021), No. 41, p. 22513. doi: 10.1002/anie.202109530
[71]	G.X. Zhu, J.L. Zhu, Q. Liu, et al., ${\mathrm{HPO}}_4^{2-} $ enhanced catalytic activity of N, S, B, and O-codoped carbon nanosphere-armored Co₉S₈ nanoparticles for organic pollutants degradation via peroxymonosulfate activation: Critical roles of superoxide radical, singlet oxygen and electron transfer, Phys. Chem. Chem. Phys., 23(2021), No. 9, p. 5283. doi: 10.1039/D0CP04773B