S-doped Carbon Nanotube Catalysts for Efficient Electrosynthesis of H2O2 over A Wide pH Range

doi:10.6023/A25020058

Abstract

Hydrogen peroxide (H₂O₂), a green oxidizing agent, is extensively utilized across diverse industries, including wastewater treatment and disinfection. The direct electrochemical synthesis of H₂O₂ via the two-electron oxygen reduction reaction (2e⁻-ORR) presents a sustainable and environmentally friendly alternative to the conventional anthraquinone process, which suffers from high energy consumption and complex multi-step reactions. In this study, sulfur-doped carbon nanotube materials (S-CNTs) were successfully synthesized by utilizing sublimed sulfur as the sulfur source and carbon nanotubes as the carbon carrier, heated at 750 ℃ in an H₂/Ar atmosphere for sulfurization and annealing. For comparison, oxygen-doped carbon nanotubes (O-CNTs) and pure carbon nanotubes (CNTs) were also prepared. The results demonstrate that S-CNTs catalysts exhibit outstanding 2e⁻-ORR performance in both alkaline and neutral environments. In alkaline conditions, the selectivity for H₂O₂ exceeds 80%, with a peak value of 93% over a wide potential range of 0.20~0.60 V (vs. RHE), while in neutral conditions, the selectivity is 87%, within a potential range of 0.20~0.50 V (vs. RHE). Furthermore, in a flow-cell configuration utilizing commercial RuIr@Ti as the anode, the H₂O₂ yield reached 6.16 mmol•cm^-2•h^-1 with a cumulative concentration of 30.8 mmol•L^-1 under alkaline conditions, while under neutral conditions, the yield was 5.82 mmol•cm^-2•h^-1 with over 80% Faradaic efficiency. The incorporation of sulfur into the carbon nanotube catalysts effectively modulated the coordination environment and electronic structure, while the introduction of defect sites provided an ideal active center and robust structural foundation. The electronic structure modulation of the carbon substrate and the enhancement of water dissociation via sulfur-doped carbon nanotube catalysts not only significantly reduced the reaction overpotential across a wide pH range but also facilitated the production of high-concentration hydrogen peroxide, thereby improving synthesis efficiency. This study offers a novel and cost-effective approach for the development of efficient non-metal-doped carbon materials as electrocatalysts for the two-electron reduction of O₂ to H₂O₂ and suggests promising applications in the field of energy and environmental technologies.

Key words: carbon nanotubes, doping, alkaline, neutral, oxygen reduction, hydrogen peroxide

Cite this article

Zijing Huo, Shengjian Lin, Qingsong Chen, Junheng Huang. S-doped Carbon Nanotube Catalysts for Efficient Electrosynthesis of H₂O₂ over A Wide pH Range[J]. Acta Chimica Sinica, 2025, 83(5): 439-444.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 4

Figure 1. Schematic representation of the synthesis of S-CNTs (a); TEM (b, c and d), and HRTEM (e, f) images of S-CNTs, (f) is a zoomed-in view of the boxed area in (e); High-angle annular dark field (HAADF) and corresponding elemental energy-dispersive X-ray spectroscopy (EDS) mapping images of S-CNTs (g)

Figure 2. XRD (a) and Raman (b) patterns of S-CNTs, O-CNTs and CNTs, and high-resolution XPS spectra of C 1s (c) and S 2p (d) of S-CNTs

Figure 3. LSV curves of S-CNTs catalysts tested at RRDE (0.1 mol•L-1 KOH) (a), electron transfer number and selectivity (b), Tafel Slope and Cdl comparisons of CNTs, O-CNTs and S-CNTs catalysts (c); LSV curves of S-CNTs catalysts tested at RRDE (0.1 mol•L-1 Na2SO4) (d), electron transfer number and selectivity (e), Tafel Slope and Cdl comparisons of CNTs, O-CNTs and S-CNTs catalysts (f)

Figure 4. LSV curves (in 1 mol•L-1 KOH solution) (a), Faradaic efficiency and yield (b) for S-CNTs catalysts tested in alkaline three-electrode flow cell; LSV curves (in 1 mol•L-1 Na2SO4) (c), Faradaic efficiency and yield (d) for S-CNTs catalysts tested in neutral three-electrode flow cell

References 36

[1]	Zhang, X.; Xia, Y.; Xia, C.; Wang, H. T. Trends Chem. 2020, 2, 942.
[2]	Ciriminna, R.; Albanese, L.; Meneguzzo, F.; Pagliaro, M. ChemSusChem. 2016, 9, 3374. doi: 10.1002/cssc.201600895 pmid: 27813285
[3]	Campos-Martin, J. M.; Blanco-Brieva, G.; Fierro, J. L. G. Angew. Chem. Int. Ed. 2006, 45, 6962.
[4]	Lee, B. H.; Shin, H.; Rasouli, A. S.; Choubisa, H.; Ou, P. F.; Dorakhan, R.; Grigioni, I.; Lee, G. H.; Shirzadi, E.; Miao, R. K.; Wicks, J.; Park, S.; Lee, H. S.; Zhang, J. Q.; Chen, Y. J.; Chen, Z.; Sinton, D.; Hyeon, T.; Sung, Y. E.; Sargent, E. H. Nat. Catal. 2023, 6, 234.
[5]	Yi, Y.; Wang, L.; Li, G.; Guo, H. Catal. Sci. Technol. 2016, 6, 1593.
[6]	Yang, S.; Verdaguer-Casadevall, A.; Arnarson, L.; Silvioli, L.; Čolić, V.; Frydendal, R.; Rossmeisl, J.; Chorkendorff, I.; Stephens, I. E. L. ACS Catal. 2018, 8, 4064.
[7]	Xu, J. W.; Zheng, X. L.; Feng, Z. P.; Lu, Z. Y.; Zhang, Z. W.; Huang, W.; Li, Y. B.; Vuckovic, D.; Li, Y. Q.; Dai, S.; Chen, G. X.; Wang, K. C.; Wang, H. S.; Chen, J. K.; Mitch, W.; Cui, Y. Nat. Sustain. 2021, 4, 233.
[8]	Qi, J.; Du, Y. D.; Yang, Q.; Jiang, N.; Li, J. C.; Ma, Y.; Ma, Y. J.; Zhao, X.; Qiu, J. S. Nat. Commun. 2023, 14, 6263.
[9]	Chen, X.; Yan, H. J.; Xia, D. G. Acta Chim. Sinica. 2017, 75, 189 (in chinese). doi: 10.6023/A16080451
	(陈鑫, 鄢慧君, 夏定国, 化学学报, 2017, 75, 189.) doi: 10.6023/A16080451
[10]	Liu, J. C.; Li, C. Y.; Liu, Y. Z.; Wang, Y. J.; Fang, Q. R. Acta Chim. Sinica. 2023, 81, 884 (in chinese).
	(刘建川, 李翠艳, 刘耀祖, 王钰杰, 方千荣, 化学学报, 2023, 81, 884.) doi: 10.6023/A23040132
[11]	Shui, Z. Y.; Yu, S. L.; Lu, W.; Xu, L. Y.; Liu, Q. Y.; Zhao, W.; Liu, Y. L. Acta Chim. Sinica. 2024, 82, 1039 (in chinese).
	(税子怡, 于思乐, 陆伟, 许留云, 刘庆叶, 赵炜, 刘益伦, 化学学报, 2024, 82, 1039.) doi: 10.6023/A24050152
[12]	Wang, Y.; Lei, X.; Zhang, B.; Bai, B.; Das, P.; Azam, T.; Xiao, J. P.; Wu, Z. S. Angew. Chem. Int. Ed. 2024, 63, e202316903.
[13]	Zheng, Z.; Ng, Y. H.; Wang, D. W.; Amal, R. Adv. Mater. 2016, 28, 9949.
[14]	Jirkovský, J. S.; Panas, I.; Ahlberg, E.; Halasa, M.; Romani, S.; Schiffrin, D. J. J. Am. Chem. Soc. 2011, 133, 19432. doi: 10.1021/ja206477z pmid: 22023652
[15]	Kang, B.; Xu, B.; Chen, Z.; Li, F.; Wang, Y. Appl. Catal. B: Environ. 2025, 360, 124528.
[16]	Dan, M.; Zhong, R.; Hu, S.; Wu, H.; Zhou, Y.; Liu, Z. Q. Chem Catal. 2022, 2, 1919.
[17]	Tang, H. T.; Tang, Z. J.; Li, R. L.; Tian, L.; Wang, R.; Pu, S.; Liu, Z. Q. Appl. Catal. B: Environ. 2024, 358, 124436.
[18]	Wu, K. H.; Wang, D.; Lu, X. Y.; Zhang, X. F.; Xie, Z. L.; Liu, Y. F.; Su, B. J.; Chen, J. M.; Su, D. S.; Qi, W.; Guo, S. J. Chem. 2020, 6, 1443.
[19]	Lu, X. Y.; Wang, D.; Wu, K. H.; Guo, X. L.; Qi, W. J. Colloid Interf. Sci. 2020, 573, 376.
[20]	Chen, Y. H.; Zhen, C.; Chen, Y. B.; Zhao, H.; Wang, Y. D.; Yue, Z. Y.; Wang, Q. S.; Li, J.; Gu, M. D.; Cheng, Q. Q.; Yang, H. Angew. Chem. Int. Ed. 2024, 63, e202407163.
[21]	Lu, Z. Y.; Chen, G. X.; Siahrostami, S.; Chen, Z. H.; Liu, K.; Xie, J.; Liao, L.; Wu, T.; Lin, D. C.; Liu, Y. Y.; Jaramillo, T. F.; Norskov, J. K.; Cui, Y. Nat. Catal. 2018, 1, 156.
[22]	Chen, G. B.; Wang, T.; Liu, P.; Liao, Z. Q.; Zhong, H. X.; Wang, G.; Zhang, P. P.; Yu, M. H.; Zschech, E.; Chen, M. W.; Zhang, J.; Feng, X. L. Energy Environ. Sci. 2020, 13, 2849.
[23]	Zhang, J. Y.; Zhang, G.; Jin, S. Y.; Zhou, Y. J.; Ji, Q. H.; Lan, H. C.; Liu, H. J.; Qu, J. H. Carbon. 2020, 163, 154.
[24]	Perazzolo, V.; Durante, C.; Pilot, R.; Paduano, A.; Zheng, J.; Rizzi, G. A.; Martucci, A.; Granozzi, G.; Gennaro, A. Carbon. 2015, 95, 949.
[25]	Wang, D.; Feng, B.; Zhang, X. X.; Liu, Y. N.; Pei, Y.; Qiao, M. H.; Zong, B. N. Acta Chim. Sinica. 2022, 80, 772 (in chinese). doi: 10.6023/A22010030
	(王丹, 封波, 张晓昕, 刘亚楠, 裴燕, 乔明华, 宗保宁, 化学学报, 2022, 80, 772.) doi: 10.6023/A22010030
[26]	Chen, S. C.; Chen, Z. H.; Siahrostami, S.; Kim, T. R.; Nordlund, D.; Sokaras, D.; Nowak, S.; To, J. W. F.; Higgins, D.; Sinclair, R.; Norskov, J. K.; Jaramillo, T. F.; Bao, Z. A. ACS Sustain. Chem. Eng. 2018, 6, 311.
[27]	Zhang, K.; Tian, L.; Yang, J.; Wu, F.; Wang, L.; Tang, H.; Liu, Z. Q. Angew. Chem. Int. Ed. 2024, 63, e202317816.
[28]	Chen, Y.; Jiang, X.; Xu, J.; Lin, D.; Xu, X. Environ. Funct. Mater. 2023, 2, 275.
[29]	Li, Y.; Liu, Y.; Peng, X.; Zhao, Z.; Li, Z.; Yang, B.; Zhang, Q.; Lei, L.; Dai, L.; Hou, Y. Angew. Chem. Int. Ed. 2025, 64, e202413159.
[30]	Liu, X.; Kumar, P. V.; Chen, Q.; Zhao, L.; Ye, F.; Ma, X.; Liu, D.; Chen, X.; Dai, L.; Hu, C. Appl. Catal. B: Environ. 2022, 316, 121618.
[31]	Ferrari, A. C.; Rodil, S. E.; Robertson, J. Diam. Relat. Mater. 2003, 12, 905.
[32]	Xia, Y.; Zhao, X. H.; Xia, C.; Wu, Z. Y.; Zhu, P.; Kim, J. Y. T.; Bai, X. W.; Gao, G. H.; Hu, Y. F.; Zhong, J.; Liu, Y. Y.; Wang, H. T. Nat. Commun. 2021, 12, 4225.
[33]	Jin, Y.; Li, F.; Li, T.; Xing, X.; Fan, W.; Zhang, L.; Hu, C. Appl. Catal. B: Environ. 2022, 302, 120824.
[34]	Ren, L.; Liu, J.; Zhao, Y.; Wang, Y.; Lu, X.; Zhou, M.; Zhang, G.; Liu, W.; Xu, H.; Sun, X. Adv. Funct. Mater. 2023, 33, 2210509.
[35]	Mun, Y.; Lee, S.; Kim, K.; Kim, S.; Lee, S.; Han, J. W.; Lee, J. J. Am. Chem. Soc. 2019, 141, 6254.
[36]	Chen, H.; Chen, R.; Yang, S.; Ding, D.; Li, X.; Long, X.; Zhao, T.; Du, Y.; Liu, M.; Tan, J.; Chen, Y. Chem. Eng. J. 2022, 446, 137257.

硫掺杂碳纳米管催化剂用于宽pH范围高效电合成H₂O₂

S-doped Carbon Nanotube Catalysts for Efficient Electrosynthesis of H₂O₂ over A Wide pH Range

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 4

References 36

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Xu Zhang, Xin Guo, Jiyang Zhang, Jihong Liu, Jiapeng Zhu, Chaoyang Huang, Ming Li, Guixiao Jia, Shengli An. Influence Research of Decentralized LiMn₆ on Structural Stability and Oxidation Mechanism of Li_1.17Ni_0.17Fe_0.17Mn_0.49O₂ Layered Cathode Materials [J]. Acta Chimica Sinica, 2025, 83(4): 369-376.
[2]	Yunxin Hou, Fen Hu, Shengjian Lin, Qingsong Chen, Zhenhai Wen. NiTe Nanocatalyst for Efficient Electrochemical Synthesis of H₂O₂ [J]. Acta Chimica Sinica, 2025, 83(4): 326-331.
[3]	Guowei Hu, Xiaohuan Wang, Zhipeng Yuan, Yaer Xinba, Hexige Wuliji. Effect of Ag Doping on the Photocatalytic Performance of Bismuth Ferrite-based Compounds [J]. Acta Chimica Sinica, 2025, 83(3): 229-236.
[4]	Rong Chen, Baosheng Wei. Overview on Low-oxidation-state Alkaline Earth Organometallic Chemistry [J]. Acta Chimica Sinica, 2025, 83(2): 139-151.
[5]	Jian Kang, Zixuan Shi, Jingmei Li. Preparation of Highly Antimicrobial Composites and Study of Photocatalytic Antimicrobial Properties Driven by LED Light [J]. Acta Chimica Sinica, 2024, 82(9): 962-970.
[6]	Guangzheng Huang, Kunwei Li, Yannan Luo, Qiang Zhang, Yuanlong Pan, Honglin Gao. Hydrothermal Treatment for Constructing K Doping and Surface Defects in g-C₃N₄ Nanosheets Promote Photocatalytic Hydrogen Production [J]. Acta Chimica Sinica, 2024, 82(3): 314-322.
[7]	Ziyi Shui, Sile Yu, Wei Lu, Liuyun Xu, Qingye Liu, Wei Zhao, Yilun Liu. Bifunctional Electrocatalysts of Mn-doped Co₃O₄ for Oxygen Reduction and Oxygen Evolution Reactions in Alkaline Medium [J]. Acta Chimica Sinica, 2024, 82(10): 1039-1049.
[8]	Jingyan Wang, Haiyan Ma. Syntheses of Sodium and Potassium Complexes Based on Pyridine-2,6-diyl-bis(methylene)-bridged Bis(aminophenolate) Ligands and Catalytic Ring-opening Polymerization of rac-Lactide [J]. Acta Chimica Sinica, 2024, 82(10): 1058-1068.
[9]	Ping Li, Qiyu Yang, Jing Zeng, Ran Zhang, Qiuyan Chen, Fei Yan. Effect of Fluorine Doping on the Performance of Reversible Solid Oxide Cells and Related Kinetic Studies [J]. Acta Chimica Sinica, 2024, 82(1): 36-45.
[10]	Yuying Zhang, Xiao Cai, Weigang Hu, Guangjun Li, Yan Zhu. Pd and Hg Atoms Co-doped HgPdAu₂₃(PET)₁₈ Nanocluster^★ [J]. Acta Chimica Sinica, 2023, 81(7): 703-708.
[11]	Jiangmin Jiang, Xinran Zheng, Yating Meng, Wenjie He, Yaxin Chen, Quanchao Zhuang, Jiaren Yuan, Zhicheng Ju, Xiaogang Zhang. Research on the Preparation and Potassium Storage Performance of F, N Co-doped Porous Carbon Nanosheets [J]. Acta Chimica Sinica, 2023, 81(4): 319-327.
[12]	Juan Wang, Huamin Xiao, Ding Xie, Yuanru Guo, Qingjiang Pan. Density Functional Theory Study of Structures of Copper-doped and Graphitic Carbon Nitride-combined Zinc Oxides and Their Boosted Nitrogen Dioxide-sensing Performance [J]. Acta Chimica Sinica, 2023, 81(11): 1493-1499.
[13]	Jinjing Liu, Na Yang, Li Li, Zidong Wei. Theoretical Study on the Regulation of Oxygen Reduction Mechanism by Modulating the Spatial Structure of Active Sites on Platinum^★ [J]. Acta Chimica Sinica, 2023, 81(11): 1478-1485.
[14]	Rui Liu, Bin Meng, Junli Hu, Jun Liu. Polycyclic Aromatic Hydrocarbon Molecule with Ultra-low LUMO/HOMO Energy Levels^★ [J]. Acta Chimica Sinica, 2023, 81(10): 1295-1300.
[15]	Guoqiang Zhang, Jinghao Huo, Xin Wang, Shouwu Guo. P-doped TiO₂/C Nanotubes as Anodes for High-performance Li-ion Capacitors [J]. Acta Chimica Sinica, 2023, 81(1): 6-13.

硫掺杂碳纳米管催化剂用于宽pH范围高效电合成H2O2