Citation: Ya-Qi CUI, Jiao-Xing XU, Mei-Lin WANG, Lun-Hui GUAN. Surface Oxidation of Single-walled-carbon-nanotubes with Enhanced Oxygen Electroreduction Activity and Selectivity[J]. Chinese Journal of Structural Chemistry, ;2021, 40(5): 533-539. doi: 10.14102/j.cnki.0254–5861.2011–3157 shu

Surface Oxidation of Single-walled-carbon-nanotubes with Enhanced Oxygen Electroreduction Activity and Selectivity

Ya-Qi CUI ^{a, b} ,
Jiao-Xing XU ^{a, b,,} ,
Mei-Lin WANG ^{a, b} ,
Lun-Hui GUAN ^{a, b,,}

a.
College of Chemistry and Materials Science, Fujian Normal University, Fuzhou 350007, China
b.
CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350108, China

Corresponding author: Jiao-Xing XU, xujx_1220@fjirsm.ac.cn Lun-Hui GUAN, guanlh@fjirsm.ac.cn
Received Date: 24 February 2021
Accepted Date: 1 March 2021

Fund Project: the Science and Technology Planning Project of Fujian Province 2018J01023the STS Project of Fujian Province 2018T 3024

Figures(3)

Electrochemical oxygen reduction reaction (ORR) with 2-electron process is an alternative for decentralized H₂O₂ production, but it remains high challenging to develop highly active and selective catalysts for this process. In this work, we present a selective and efficient nonprecious electrocatalyst, prepared through an easily scalable mild oxidation of single-walled carbon nanotubes (SWNTs) with different oxidative acids including sulfur acid, nitride acid and mixed sulfuric/nitric acids, respectively. The high-degree oxidized SWNTs treated by mixed acids exhibit the highest activity and selectivity of electroreduction of oxygen to synthesize H₂O₂ at low overpotential in alkaline and neutral media. Spectroscopic characterizations suggested that the C–O is vital for catalyzing 2-electron ORR, providing an insightful understanding of defected carbon surface as the active catalytic sites for 2-electron ORR.
- electrocatalysts,
- hydrogen peroxide production,
- oxygen reduction reaction
1. [1]
  Xia, C.; Xia, Y.; Zhu, P.; Fan, L.; Wang, H. Direct electrosynthesis of pure aqueous H₂O₂ solutions up to 20% by weight using a solid electrolyte. Science 2019, 366, 226–231. doi: 10.1126/science.aay1844
2. [2]
  Jiang, K.; Zhao, J.; Wang, H. Catalyst design for electrochemical oxygen reduction toward hydrogen peroxide. Adv. Funct. Mater. 2020, 30, 2003321. doi: 10.1002/adfm.202003321
3. [3]
  Ciriminna, R.; Albanese, L.; Meneguzzo, F.; Pagliaro, M. Hydrogen peroxide: a key chemical for today's sustainable development. Chemsuschem. 2016, 9, 3374–3381. doi: 10.1002/cssc.201600895
4. [4]
  Campos-Martin, J. M., Blanco-Brieva, G., Fierro, J. L. Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process. Angew. Chem. Int. Ed. 2006, 45, 6962–6984. doi: 10.1002/anie.200503779
5. [5]
  Yang, S.; Verdaguer-Casadevall, A.; Arnarson, L.; Silvioli, L.; Čolić, V.; Frydendal, R.; Rossmeisl, J.; Chorkendorff, I.; Stephens, I. E. L. Toward the decentralized electrochemical production of H₂O₂: a focus on the catalysis. ACS Catalysis 2018, 8, 4064–4081. doi: 10.1021/acscatal.8b00217
6. [6]
  Siahrostami, S.; Villegas, S. J.; Bagherzadeh Mostaghimi, A. H.; Back, S.; Farimani, A. B.; Wang, H. Persson, K. A.; Montoya, J. A review on challenges and successes in atomic-scale design of catalysts for electrochemical synthesis of hydrogen peroxide. ACS Catalysis 2020, 10, 7495–7511. doi: 10.1021/acscatal.0c01641
7. [7]
  Stamenkovic, V.; Mun, B. S.; Mayrhofer, K. J. J.; Ross, P. N.; Markovic, N. M.; Rossmeisl, J.; Greeley, J.; Nørskov, J. K. Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angew. Chem. Int. Ed. 2006, 45, 2897–2901. doi: 10.1002/anie.200504386
8. [8]
  Viswanathan, V.; Hansen, H. A.; Rossmeisl, J.; Nørskov, J. K.; Unifying the 2e^- and 4e^- reduction of oxygen on metal surfaces. J. Phys. Chem. Lett. 2012, 3, 2948–2951. doi: 10.1021/jz301476w
9. [9]
  Siahrostami, S.; Verdaguer-Casadevall, A.; Karamad, M.; Deiana, D.; Malacrida, P.; Wickman, B.; Escudero-Escribano, M.; Paoli, E. A.; Frydendal, R.; Hansen, T. W.; Chorkendorff, I.; Stephens, I. E. L.; Rossmeisl, J. Enabling direct H₂O₂ production through rational electrocatalyst design. Nature Mater. 2013, 12, 1137–1143. doi: 10.1038/nmat3795
10. [10]
  Verdaguer, C. A.; Deiana, D.; Karamad, M.; Siahrostami, S.; Malacrida, P.; Hansen, T. W.; Rossmeisl, J.; Chorkendorff, I.; Stephens, I. E. L. Trends in the electrochemical synthesis of H₂O₂: enhancing activity and selectivity by electrocatalytic site engineering. Nano Lett. 2014, 14, 1603–1608. doi: 10.1021/nl500037x
11. [11]
  Shen, R.; Chen, W.; Peng, Q.; Lu, S.; Zheng, L.; Cao, X.; Wang, Y.; Zhu, W.; Zhang, J.; Zhuang, Z.; Chen, C.; Wang, D.; Li, Y. High-concentration single atomic Pt sites on hollow CuS_x for selective O₂ reduction to H₂O₂ in acid solution. Chem. 2019, 5, 2099–2110. doi: 10.1016/j.chempr.2019.04.024
12. [12]
  Pang, Y.; Wang, K.; Xie, H.; Sun, Y.; Titirici, M. M.; Chai, G. L. Mesoporous carbon hollow spheres as efficient electrocatalysts for oxygen reduction to hydrogen peroxide in neutral electrolytes. ACS Catalysis 2020, 10, 7434–7442 doi: 10.1021/acscatal.0c00584
13. [13]
  Zhang, J.; Zhang, G.; Jin, S.; Zhou, Y.; Ji, Q.; Lan, H.; Liu, H.; Qu, J. Graphitic N in nitrogen-doped carbon promotes hydrogen peroxide synthesis from electrocatalytic oxygen reduction. Carbon 2020, 163, 154–161. doi: 10.1016/j.carbon.2020.02.084
14. [14]
  Chen, S.; Chen, Z.; Siahrostami, S.; Kim, T. R.; Nordlund, D.; Sokaras, D.; Nowak, S.; To, J. W.; Higgins, D.; Sinclair, R. Defective carbon-based materials for the electrochemical synthesis of hydrogen peroxide. ACS Sustain. Chem., Eng. 2018, 6, 311–317. doi: 10.1021/acssuschemeng.7b02517
15. [15]
  Yuan, K.; Luetzenkirchen, H. D.; Li, L. B.; Shuai, L.; Li, Y. Z.; Cao, R.; Qiu, M.; Zhuang, X. D.; Leung, M. K. H.; Chen, Y. W.; Scherf, U. Boosting oxygen reduction of single iron active sites via geometric and electronic engineering: nitrogen and phosphorus dual coordination. J. Am. Chem. Soc. 2020, 142, 2404–2412. doi: 10.1021/jacs.9b11852
16. [16]
  Tang, C.; Jiao, Y.; Shi, B. Y.; Liu, J. N.; Xie, Z. H.; Chen, X.; Zhang, Q. Coordination tunes selectivity: two-electron oxygen reduction on high-loading molybdenum single-atom catalysts. Angew. Chem. Int. Ed. 2020, 59, 9171–9176. doi: 10.1002/anie.202003842
17. [17]
  Kulkarni, A.; Siahrostami, S.; Patel, A.; Nørskov, J. K. Understanding catalytic activity trends in the oxygen reduction reaction. Chem. Rev. 2018, 118, 2302–2312. doi: 10.1021/acs.chemrev.7b00488
18. [18]
  Feng, X.; Bai, Y.; Liu, M.; Li, Y.; Yang, H.; Wang, X.; Wu, C. Untangling respective effects of heteroatom-doped carbon materials in batteries, supercapacitors and ORR to design high-performance materials. Energy, Environ. Sci. 2021, DOI: 10.1039/D1EE00166C. doi: 10.1039/D1EE00166C
19. [19]
  Gong, K.; Du, F.; Xia, Z.; Durstock, M.; Dai, L. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 2009, 323, 760–764. doi: 10.1126/science.1168049
20. [20]
  Liu, X.; Dai, L. Carbon-based metal-free catalysts. Nature Rev. Mater. 2016, 1, 16064. doi: 10.1038/natrevmats.2016.64
21. [21]
  Perazzolo, V.; Durante, C.; Pilot, R.; Paduano, A.; Zheng, J.; Rizzi, G. A.; Martucci, A.; Granozzi, G.; Gennaro, A. Nitrogen and sulfur doped mesoporous carbon as metal-free electrocatalysts for the in situ production of hydrogen peroxide. Carbon 2015, 95, 949–963. doi: 10.1016/j.carbon.2015.09.002
22. [22]
  Jia, N.; Yang, T.; Shi, S.; Chen, X.; An, Z.; Chen, Y.; Yin, S.; Chen, P. N, F-Codoped carbon nanocages: an efficient electrocatalyst for hydrogen peroxide electroproduction in alkaline and acidic solutions. ACS Sustain. Chem. , Eng. 2020, 8, 2883–2891. doi: 10.1021/acssuschemeng.9b07047
23. [23]
  Lu, Z.; Chen, G.; Siahrostami, S.; Chen, Z.; Liu, K.; Xie, J.; Liao, L.; Wu, T.; Lin, D.; Liu, Y.; Jaramillo, T. F.; Nørskov, J. K.; Cui, Y. High-efficiency oxygen reduction to hydrogen peroxide catalysed by oxidized carbon materials. Nature Catal. 2018, 1, 156–162. doi: 10.1038/s41929-017-0017-x
24. [24]
  Kim, H. W.; Ross, M. B.; Kornienko, N.; Zhang, L.; Guo, J.; Yang, P.; McCloskey, B. D. Efficient hydrogen peroxide generation using reduced graphene oxide-based oxygen reduction electrocatalysts. Nat. Catal. 2018, 1, 282–290. doi: 10.1038/s41929-018-0044-2
25. [25]
  Kosynkin, D. V.; Higginbotham, A. L.; Sinitskii, A. L.; Jay R.; Dimiev, A. P. B.; Katherine, T.; James, M. Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons. Nature 2009, 458, 872–U5. doi: 10.1038/nature07872
26. [26]
  Hu, R. T.; Wu, C. X.; Hou, K.; Xia, C.; Yang, J.; Guan, L. H.; Li, Y. Tailoring the electrocatalytic oxygen reduction reaction pathway by tuning the electronic states of single-walled carbon nanotubes. Carbon 2019, 147, 35–42. doi: 10.1016/j.carbon.2019.02.067
27. [27]
  Briggs, D.; Fairley, N. XPS of chemically modified low-density polyethylene surfaces: observations on curve-fitting the C 1s spectrum. Surf. Interface Anal. 2002, 33, 283–290. doi: 10.1002/sia.1212
28. [28]
  Kharlamova, M. V. Advances in tailoring the electronic properties of single-walled carbon nanotubes. Prog. Mater. Sci. 2016, 77, 125–211. doi: 10.1016/j.pmatsci.2015.09.001
29. [29]
  Fantini, C.; Jorio, A.; Souza, M.; Strano, M. S.; Dresselhaus, M. S.; Pimenta, M. A. Optical transition energies for carbon nanotubes from resonant Raman spectroscopy: environment and temperature effects. Phy. Rev. Lett. 2004, 93, 147406. doi: 10.1103/PhysRevLett.93.147406
30. [30]
  Brown, S. D. M.; Jorio, A.; Dresselhaus, M. S.; Dresselhaus, G. Observations of the D-band feature in the Raman spectra of carbon nanotubes. Phys. Rev. B 2001, 64, 073403. doi: 10.1103/PhysRevB.64.073403
31. [31]
  Bachilo, S. M.; Strano, M. S.; Kittrell, C.; Hauge, R. H.; Smalley, R. E.; Weisman, R. B. Structure-assigned optical spectra of single-walled carbon nanotubes. Science 2002, 298, 2362–2365.
32. [32]
  Wang, Y.; Liu, D.; Zhang, H.; Wang, J.; Du, R.; Li, T. T.; Qian, J.; Hu, Y.; Huang, S. Methylation-induced reversible metallic-semiconducting transition of single-walled carbon nanotube arrays for high-performance field-effect transistors. Nano Lett. 2020, 20, 496–501. doi: 10.1021/acs.nanolett.9b04219
33. [33]
  Jorio, A.; Souza Filho, A. G.; Dresselhaus, G.; Dresselhaus, M. S.; Swan, A. K.; Ünlü, M. S.; Goldberg, B. B.; Pimenta, M. A.; Hafner, J. H.; Lieber, C. M.; Saito, R. G-band resonant Raman study of 62 isolated single-wall carbon nanotubes. Phys. Rev. B 2002, 65, 155412. doi: 10.1103/PhysRevB.65.155412
34. [34]
  Maniwa, Y.; Fujiwara, R.; Kira, H.; Tou, H.; Kataura, H.; Suzuki, S.; Achiba, Y.; Nishibori, E.; Takata, M.; Sakata, M.; Fujiwara, A.; Suematsu, H. Thermal expansion of single-walled carbon nanotube (SWNT) bundles: X-ray diffraction studies. Phys. Rev. B 2001, 64, 241402. doi: 10.1103/PhysRevB.64.241402
35. [35]
  Kawasaki, S.; Matsuoka, Y.; Yokomae, T.; Nojima, Y.; Okino, F.; Touhara, H.; Kataura, H. XRD and TEM study of high pressure treated single-walled carbon nanotubes and C60-peapods. Carbon 2005, 43, 37–45. doi: 10.1016/j.carbon.2004.08.018
36. [36]
  Chen, J.; Yao, B.; Li, C.; Shi, G. An improved Hummers method for eco-friendly synthesis of graphene oxide. Carbon 2013, 64, 225–229. doi: 10.1016/j.carbon.2013.07.055
37. [37]
  Chen, C.; Zhang, X.; Zhou, Z. Y.; Yang, X. D.; Zhang, X. S.; Sun, S. G. Highly active Fe, N co-doped graphene nanoribbon/carbon nanotube composite catalyst for oxygen reduction reaction. Electrochim. Acta 2016, 222, 1922–1930. doi: 10.1016/j.electacta.2016.12.005
38. [38]
  Kim, H. W.; Bukas, V. J.; Park, H.; Park, S.; Diederichsen, K. M.; Lim, J.; Cho, Y. H.; Kim, J.; Kim, W.; Han, T. H.; Voss, J.; Luntz, A. C.; McCloskey, B. D. Mechanisms of two-electron and four-electron electrochemical oxygen reduction reactions at nitrogen-doped reduced graphene oxide. ACS Catal. 2019, 10, 852–863.
39. [39]
  Kundu, S.; Wang, Y.; Xia, W.; Muhler, M. Thermal stability and reducibility of oxygen-containing functional groups on multiwalled carbon nanotube surfaces: a quantitative high-resolution xps and tpd/tpr study. J. Phys. Chem. C 2008, 112, 16869–16878. doi: 10.1021/jp804413a
1. [1]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
2. [2]
  Guoliang Gao , Guangzhen Zhao , Guang Zhu , Bowen Sun , Zixu Sun , Shunli Li , Ya-Qian Lan . Recent advancements in noble-metal electrocatalysts for alkaline hydrogen evolution reaction. Chinese Chemical Letters, 2025, 36(1): 109557-. doi: 10.1016/j.cclet.2024.109557
3. [3]
  Yanan Zhou , Li Sheng , Lanlan Chen , Wenhua Zhang , Jinlong Yang . Axial coordinated iron-nitrogen-carbon as efficient electrocatalysts for hydrogen evolution and oxygen redox reactions. Chinese Chemical Letters, 2025, 36(1): 109588-. doi: 10.1016/j.cclet.2024.109588
4. [4]
  Qiyan Wu , Ruixin Zhou , Zhangyi Yao , Tanyuan Wang , Qing Li . Effective approaches for enhancing the stability of ruthenium-based electrocatalysts towards acidic oxygen evolution reaction. Chinese Chemical Letters, 2024, 35(10): 109416-. doi: 10.1016/j.cclet.2023.109416
5. [5]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
6. [6]
  Shaojie Ding , Henan Wang , Xiaojing Dai , Yuru Lv , Xinxin Niu , Ruilian Yin , Fangfang Wu , Wenhui Shi , Wenxian Liu , Xiehong Cao . Mn-modulated Co–N–C oxygen electrocatalysts for robust and temperature-adaptative zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100302-100302. doi: 10.1016/j.cjsc.2024.100302
7. [7]
  Qin Cheng , Ming Huang , Qingqing Ye , Bangwei Deng , Fan Dong . Indium-based electrocatalysts for CO₂ reduction to C1 products. Chinese Chemical Letters, 2024, 35(6): 109112-. doi: 10.1016/j.cclet.2023.109112
8. [8]
  Jiao Li , Chenyang Zhang , Chuhan Wu , Yan Liu , Xuejian Zhang , Xiao Li , Yongtao Li , Jing Sun , Zhongmin Su . Defined organic-octamolybdate crystalline superstructures derived Mo₂C@C as efficient hydrogen evolution electrocatalysts. Chinese Chemical Letters, 2024, 35(6): 108782-. doi: 10.1016/j.cclet.2023.108782
9. [9]
  Kunsong Hu , Yulong Zhang , Jiayi Zhu , Jinhua Mai , Gang Liu , Manoj Krishna Sugumar , Xinhua Liu , Feng Zhan , Rui Tan . Nano-engineered catalysts for high-performance oxygen reduction reaction. Chinese Chemical Letters, 2024, 35(10): 109423-. doi: 10.1016/j.cclet.2023.109423
10. [10]
  Jialin Cai , Yizhe Chen , Ruiwen Zhang , Cheng Yuan , Zeyu Jin , Yongting Chen , Shiming Zhang , Jiujun Zhang . Interfacial Pt-N coordination for promoting oxygen reduction reaction. Chinese Chemical Letters, 2025, 36(2): 110255-. doi: 10.1016/j.cclet.2024.110255
11. [11]
  Jiajun Wang , Guolin Yi , Shengling Guo , Jianing Wang , Shujuan Li , Ke Xu , Weiyi Wang , Shulai Lei . Computational design of bimetallic TM₂@g-C₉N₄ electrocatalysts for enhanced CO reduction toward C₂ products. Chinese Chemical Letters, 2024, 35(7): 109050-. doi: 10.1016/j.cclet.2023.109050
12. [12]
  Qiyan Wu , Qing Li . Topologically close-packed intermetallic alloy electrocatalysts for CO₂ reduction towards high value-added multi-carbon chemicals. Chinese Chemical Letters, 2025, 36(1): 110384-. doi: 10.1016/j.cclet.2024.110384
13. [13]
  Jing Cao , Dezheng Zhang , Bianqing Ren , Ping Song , Weilin Xu . Mn incorporated RuO₂ nanocrystals as an efficient and stable bifunctional electrocatalyst for oxygen evolution reaction and hydrogen evolution reaction in acid and alkaline. Chinese Chemical Letters, 2024, 35(10): 109863-. doi: 10.1016/j.cclet.2024.109863
14. [14]
  Liyong Ding , Zhenhua Pan , Qian Wang . 2D photocatalysts for hydrogen peroxide synthesis. Chinese Chemical Letters, 2024, 35(12): 110125-. doi: 10.1016/j.cclet.2024.110125
15. [15]
  Yufeng Wu , Mingjun Jing , Juan Li , Wenhui Deng , Mingguang Yi , Zhanpeng Chen , Meixia Yang , Jinyang Wu , Xinkai Xu , Yanson Bai , Xiaoqing Zou , Tianjing Wu , Xianyou Wang . Collaborative integration of Fe-N_x active center into defective sulfur/selenium-doped carbon for efficient oxygen electrocatalysts in liquid and flexible Zn-air batteries. Chinese Chemical Letters, 2024, 35(9): 109269-. doi: 10.1016/j.cclet.2023.109269
16. [16]
  Guan-Nan Xing , Di-Ye Wei , Hua Zhang , Zhong-Qun Tian , Jian-Feng Li . Pd-based nanocatalysts for oxygen reduction reaction: Preparation, performance, and in-situ characterization. Chinese Journal of Structural Chemistry, 2023, 42(11): 100021-100021. doi: 10.1016/j.cjsc.2023.100021
17. [17]
  Min Song , Qian Zhang , Tao Shen , Guanyu Luo , Deli Wang . Surface reconstruction enabled o-PdTe@Pd core-shell electrocatalyst for efficient oxygen reduction reaction. Chinese Chemical Letters, 2024, 35(8): 109083-. doi: 10.1016/j.cclet.2023.109083
18. [18]
  Yi Zhou , Yanzhen Liu , Yani Yan , Zonglin Yi , Yongfeng Li , Cheng-Meng Chen . Enhanced oxygen reduction reaction on La-Fe bimetal in porous N-doped carbon dodecahedra with CNTs wrapping. Chinese Chemical Letters, 2025, 36(1): 109569-. doi: 10.1016/j.cclet.2024.109569
19. [19]
  Chenhao Zhang , Qian Zhang , Yezhou Hu , Hanyu Hu , Junhao Yang , Chang Yang , Ye Zhu , Zhengkai Tu , Deli Wang . N-doped carbon confined ternary Pt₂NiCo intermetallics for efficient oxygen reduction reaction. Chinese Chemical Letters, 2025, 36(3): 110429-. doi: 10.1016/j.cclet.2024.110429
20. [20]
  Zhipeng Wan , Hao Xu , Peng Wu . Selective oxidation using in-situ generated hydrogen peroxide over titanosilicates. Chinese Journal of Structural Chemistry, 2024, 43(6): 100298-100298. doi: 10.1016/j.cjsc.2024.100298

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(458)
HTML views(16)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142