1. School of Materials Science and Engineering, Liaocheng University, Liaocheng 252000, China 2. Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), School of Materials Science and Engineering, Nankai University, Tianjin 3000350, China
The low cost and highly efficient construction of electrocatalysts has attracted significant attention owing to the use of clean and sustainable energy technologies. In this work, cobalt nanoparticle decorated N-doped carbons (Co@NC) are synthesized by the pyrolysis of a cobalt covalent organic framework under an inert atmosphere. The Co@NC demonstrates improved electrocatalytic capabilities compared to N-doped carbon without the addition of Co nanoparticles, indicating the important role of cobalt. The well-dispersed active sites (Co–Nx) and the synergistic effect between the carbon matrix and Co nanoparticles greatly enhance the electrocatalytic activity for the oxygen reduction reaction. In addition, the Co content has a significant effect on the catalytic activity. The resulting Co@NC-0.86 exhibits a superb electrocatalytic activity for the oxygen reduction reaction in an alkaline electrolyte in terms of the onset potential (0.90 V), half-wave potential (0.80 V) and the limiting current density (4.84 mA·cm–2), and a high selectivity, as well as a strong methanol tolerance and superior durability, these results are comparable to those of the Pt/C catalyst. Furthermore, the superior bifunctional activity of Co@NC-0.86 was also confirmed in a home-built Zn-air battery, signifying the possibility for application in electrode materials and in current energy conversion and storage devices.
H X Zhang, J Y Liang, B W Xia, Y Li, S F Du. Ionic liquid modified Pt/C electrocatalysts for cathode application in proton exchange membrane fuel cells. Frontiers of Chemical Science and Engineering, 2019, 13(4): 695–701 https://doi.org/10.1007/s11705-019-1838-8
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X F Peng, Z H Wang, Z Wang, Y X Pan. Multivalent manganese oxides with high electrocatalytic activity for oxygen reduction reaction. Frontiers of Chemical Science and Engineering, 2018, 12(4): 790–797 https://doi.org/10.1007/s11705-018-1706-y
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R Hao, J T Ren, X W Lv, W Li, Y P Liu, Z Y Yuan. N-Doped porous carbon hollow microspheres encapsulated with iron-based nanocomposites as advanced bifunctional catalysts for rechargeable Zn-air battery. Journal of Energy Chemistry, 2020, 49: 14–21 https://doi.org/10.1016/j.jechem.2020.01.007
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S H Yin, J Yang, Y Han, G Li, L Y Wan, Y H Chen, C Chen, X M Qu, Y X Jiang, S G Sun. Construction of highly active metal-containing nanoparticles and FeCo-N4 composite sites for the acidic oxygen reduction reaction. Angewandte Chemie International Edition, 2020, 59(49): 21976–21979 https://doi.org/10.1002/anie.202010013
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J T Ren, Z Y Yuan. A universal route to N-coordinated metals anchored on porous carbon nanosheets for highly efficient oxygen electrochemistry. Journal of Materials Chemistry A, 2019, 7(22): 13591–13601 https://doi.org/10.1039/C9TA03300A
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L M Wu, B X Ni, R Chen, P C Sun, T H Chen. A general approach for hierarchically porous metal/N/C nanosphere electrocatalysts: nano-confined pyrolysis of in situ-formed amorphous metal-ligand complexes. Journal of Materials Chemistry A, 2020, 8(40): 21026–21035 https://doi.org/10.1039/D0TA07029G
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C Medard, M Lefevre, J Dodelet, F Jaouen, G Lindbergh. Oxygen reduction by Fe-based catalysts in PEM fuel cell conditions: activity and selectivity of the catalysts obtained with two Fe precursors and various carbon supports. Electrochimica Acta, 2006, 51(16): 3202–3213 https://doi.org/10.1016/j.electacta.2005.09.012
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H G Wang, C C Weng, Z Y Yuan. Insights into efficient transition metal-nitrogen/carbon oxygen reduction electrocatalysts. Journal of Energy Chemistry, 2021, 56: 470–485 https://doi.org/10.1016/j.jechem.2020.08.030
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L M Zhao, H M Liu, Y Du, X Liang, W J Wang, H Zhao, W Z Li. An ionic liquid as a green solvent for high potency synthesis of 2D covalent organic frameworks. New Journal of Chemistry, 2020, 44(36): 15410–15414 https://doi.org/10.1039/D0NJ01478H
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X Liang, H M Liu, Y Du, W Z Li, M Wang, B Ge, L M Zhao. Terbium functionalized covalent organic framework for selective and sensitive detection of LVX based on fluorescence enhancement. Colloids and Surfaces A, 2020, 606: 125429 https://doi.org/10.1016/j.colsurfa.2020.125429
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R K Sharma, P Yadav, M Yadav, R Gupta, P Rana, A Srivastava, R Zbořil, R S Varma, M Antonietti, M B Gawande. Recent development of covalent organic frameworks (COFs): synthesis and catalytic (organic-electro-photo) applications. Materials Horizons, 2020, 7(2): 411–454 https://doi.org/10.1039/C9MH00856J
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D Rodríguez-San-Miguel, C Montoro, F Zamora. Covalent organic framework nanosheets: preparation, properties and applications. Chemical Society Reviews, 2020, 49(8): 2291–2302 https://doi.org/10.1039/C9CS00890J
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H Li, F Q Chen, X Y Guan, J L Li, C Y Li, B Tang, V Valtchev, Y S Yan, S L Qiu, Q R Fang. Three-dimensional triptycene-based covalent organic frameworks with ceq or acs topology. Journal of the American Chemical Society, 2021, 143(1): 2654–2659 https://doi.org/10.1021/jacs.0c12499
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X Cui, S Lei, A C Wang, L K Gao, Q Zhang, Y K Yang, Z Q Lin. Emerging covalent organic frameworks tailored materials for electrocatalysis. Nano Energy, 2020, 70: 104525 https://doi.org/10.1016/j.nanoen.2020.104525
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Y Yusran, Q R Fang, V Valtchev. Electroactive covalent organic frameworks: design, synthesis, and applications. Advanced Materials, 2020, 32(44): 2002038 https://doi.org/10.1002/adma.202002038
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D Wang, T Qiu, W Guo, Z Liang, H Tabassum, D Xia, R Zou. Covalent organic framework-based materials for energy applications. Energy & Environmental Science, 2021, 14(2): 688–728 https://doi.org/10.1039/D0EE02309D
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J Wang, J R Wang, S Y Qi, M W Zhao. Stable multifunctional single-atom catalysts resulting from the synergistic effect of anchored transition-metal atoms and host covalent-organic frameworks. Journal of Physical Chemistry C, 2020, 124(32): 17675–17683 https://doi.org/10.1021/acs.jpcc.0c04360
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S J Wei, Y Wang, W X Chen, Z Li, W C Cheong, Q H Zhang, Y Gong, L Gu, C Chen, D S Wang, et al.. Atomically dispersed Fe atoms anchored on COF-derived N-doped carbon nanospheres as efficient multi-functional catalysts. Chemical Science (Cambridge), 2020, 11(3): 786–790 https://doi.org/10.1039/C9SC05005A
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S Roy, S Mari, M K Sai, S C Sarma, S Sarkar, S C Peter. Highly efficient bifunctional oxygen reduction/evolution activity of a non-precious nanocomposite derived from a tetrazine-COF. Nanoscale, 2020, 12(44): 22718–22734 https://doi.org/10.1039/D0NR05337F
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Y Z Zhu, W C Peng, Y Li, G L Zhang, F B Zhang, X B Fan. Modulating the electronic structure of single-atom catalysts on 2D nanomaterials for enhanced electrocatalytic performance. Small Methods, 2019, 3(9): 1800438 https://doi.org/10.1002/smtd.201800438
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S Kandambeth, A Mallick, B Lukose, M V Mane, T Heine, R Banerjee. Construction of crystalline 2D covalent organic frameworks with remarkable chemical (acid/base) stability via a combined reversible and irreversible route. Journal of the American Chemical Society, 2012, 134(48): 19524–19527 https://doi.org/10.1021/ja308278w
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H Zhao, Z P Hu, Y P Zhu, L Ge, Z Y Yuan. P-doped mesoporous carbons for high-efficiency electrocatalytic oxygen reduction. Chinese Journal of Catalysis, 2019, 40(9): 1366–1374 https://doi.org/10.1016/S1872-2067(19)63363-2
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H Zhao, C C Weng, J T Ren, L Ge, Y P Liu, Z Y Yuan. Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts. Chinese Journal of Catalysis, 2020, 41(2): 259–267 https://doi.org/10.1016/S1872-2067(19)63455-8
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Z Yang, C Zhao, Y Qu, H Zhou, F Zhou, J Wang, Y Wu, Y Li. Trifunctional self-supporting cobalt-embedded carbon nanotube films for ORR, OER, and HER triggered by solid diffusion from bulk metal. Advanced Materials, 2019, 31(12): 1808043 https://doi.org/10.1002/adma.201808043
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X W Lv, Y Liu, Y S Wang, X L Liu, Z Y Yuan. Encapsulating vanadium nitride nanodots into N,S-codoped graphitized carbon for synergistic electrocatalytic nitrogen reduction and aqueous Zn-N2 battery. Applied Catalysis B: Environmental, 2021, 280: 119434 https://doi.org/10.1016/j.apcatb.2020.119434
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C C Weng, J T Ren, Z P Hu, Z Y Yuan. Nitrogen-doped defect-rich graphitic carbon nanorings with CoOx nanoparticles as highly efficient electrocatalyst for oxygen electrochemistry. ACS Sustainable Chemistry & Engineering, 2018, 6(11): 15811–15821 https://doi.org/10.1021/acssuschemeng.8b04406
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T Ouyang, Y Q Ye, C Y Wu, K Xiao, Z Q Liu. Heterostructures comprised of Co/β-Mo2C-encapsulated N-doped carbon nanotubes as bifunctional electrodes for water splitting. Angewandte Chemie International Edition, 2019, 58(15): 4923–4928 https://doi.org/10.1002/anie.201814262
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A Aijaz, J Masa, C Rösler, W Xia, P Weide, A J R Botz, R A Fischer, W Schuhmann, M Muhler. Co@Co3O4 encapsulated in carbon nanotube-grafted nitrogen-doped carbon polyhedra as an advanced bifunctional oxygen electrode. Angewandte Chemie International Edition, 2016, 55(12): 4087–4091 https://doi.org/10.1002/anie.201509382
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Q Wang, Z Y Zhou, Y J Lai, Y You, J G Liu, X L Wu, E Terefe, C Chen, L Song, M Rauf, et al.Phenylenediaminebased FeNx/C catalyst with high activity for oxygen reduction in acid medium and its active-site probing. Journal of the American Chemical Society, 2014, 136(31): 10882–10885 https://doi.org/10.1021/ja505777v
30
M Lefèvre, E Proietti, F Jaouen, J P Dodelet. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science, 2009, 324(5923): 71–74 https://doi.org/10.1126/science.1170051
31
L Lai, J R Potts, D Zhan, L Wang, C K Poh, C Tang, H Gong, Z Shen, J Lin, R S Ruoff. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy & Environmental Science, 2012, 5(7): 7936–7942 https://doi.org/10.1039/c2ee21802j
32
D Guo, R Shibuya, C Akiba, S Saji, T Kondo, J Nakamura. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science, 2016, 351(6271): 361–365 https://doi.org/10.1126/science.aad0832
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G Wu, K L More, C M Johnston, P Zelenay. High performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science, 2011, 332(6028): 443–447 https://doi.org/10.1126/science.1200832
34
J Y Cheon, J H Kim, J H Kim, K C Goddeti, J Y Park, S H Joo. Intrinsic relationship between enhanced oxygen reduction reaction activity and nanoscale work function of doped carbons. Journal of the American Chemical Society, 2014, 136(25): 8875–8878 https://doi.org/10.1021/ja503557x
35
Y T Zhang, P Wang, J Yang, S S Lu, K K Li, G Y Liu, Y F Duan, J S Qiu. Decorating ZIF-67-derived cobalt–nitrogen doped carbon nanocapsules on 3D carbon frameworks for efficient oxygen reduction and oxygen evolution. Carbon, 2021, 177: 344–356 https://doi.org/10.1016/j.carbon.2021.02.052
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Y J Sa, S O Park, G Y Jung, T J Shin, H Y Jeong, S K Kwak, S H Joo. Heterogeneous Co–N/C electrocatalysts with controlled cobalt site densities for the hydrogen evolution reaction: structure-activity correlations and kinetic insights. ACS Catalysis, 2019, 9(1): 83–97 https://doi.org/10.1021/acscatal.8b03446
37
Y Liu, C Y Song, Y C Wang, W H Cao, Y P Lei, Q G Feng, Z Chen, S J Liang, L Xu, L L Jiang. Rational designed Co@N-doped carbon catalyst for high-efficient H2S selective oxidation by regulating electronic structures. Chemical Engineering Journal, 2020, 401: 126038 https://doi.org/10.1016/j.cej.2020.126038
38
Y Tan, C Xu, G Chen, X Fang, N Zheng, Q Xie. Facile synthesis of manganese-oxide-containing mesoporous nitrogen-doped carbon for efficient oxygen reduction. Advanced Functional Materials, 2012, 22(21): 4584–4591 https://doi.org/10.1002/adfm.201201244
39
S Liu, Z Wang, S Zhou, F Yu, M Yu, C Y Chiang, W Zhou, J Zhao, J Qiu. Metal-organic-framework-derived hybrid carbon nanocages as a bifunctional electrocatalyst for oxygen reduction and evolution. Advanced Materials, 2017, 29(31): 1700874–1700883 https://doi.org/10.1002/adma.201700874
40
H B Yang, J W Miao, S F Hung, J Z Chen, H B Tao, X Z Wang, L P Zhang, R Chen, J J Gao, H M Chen, et al.. Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: development of highly efficient metal-free bifunctional electrocatalyst. Science Advances, 2016, 2(4): e1501122 https://doi.org/10.1126/sciadv.1501122
41
J Masa, W Xia, M Muhler, W Schuhmann. On the role of metals in nitrogen-doped carbon electrocatalysts for oxygen reduction. Angewandte Chemie International Edition, 2015, 54(35): 10102–10120 https://doi.org/10.1002/anie.201500569
