Floret-like Fe–N_x nanoparticle-embedded porous carbon superstructures from a Fe-covalent triazine polymer boosting oxygen electroreduction

Abstract

Fe–N_x nanoparticles-embedded porous carbons with a desirable superstructure have attracted immense attention as promising catalysts for electrochemical oxygen reduction reaction. Herein, we employed Fe-coordinated covalent triazine polymer for the fabrication of Fe–N_x nanoparticle-embedded porous carbon nanoflorets (Fe/N@CNFs) employing a hypersaline-confinement-conversion strategy. Presence of tailored N types within the covalent triazine polymer interwork in high proportions contributes to the generation of Fe/N coordination and subsequent Fe–N_x nanoparticles. Owing to the utilization of NaCl crystals, the resultant Fe/N@CNF-800 which was generated by pyrolysis at 800 °C showed nanoflower structure and large specific surface area, which remarkably suppressed the agglomeration of high catalytic active sites. As expect, the Fe/N@CNF-800 exhibited unexpected oxygen reduction reaction catalytic performance with an ultrahigh half-wave potential (0.89 V vs. reversible hydrogen electrode), a dominant 4e^– transfer approach and great cycle stability (> 92% after 100000 s). As a demonstration, the Fe/N-PCNF-800-assembled zinc–air battery delivered a high open circuit voltage of 1.51 V, a maximum peak power density of 164 mW·cm^–2, as well as eminent rate performance, surpassing those of commercial Pt/C. This contribution offers a valuable avenue to exploit efficient metal nanoparticles-based carbon catalysts towards energy-related electrocatalytic reactions and beyond.

Graphical abstract

Keywords

Fe–N_x nanoparticles / hypersaline-confinement conversion / floret-like carbon / covalent triazine polymers / oxygen reduction reaction

References

[1] Wang Y J, Zhao N, Fang B, Li H, Bi X T, Wang H. Carbon-supported Pt-based alloy electrocatalysts for the oxygen reduction reaction in polymer electrolyte membrane fuel cells: particle size, shape, and composition manipulation and their impact to activity. Chemical Reviews, 2015, 115(9): 3433–3467

[2] Shao M H, Chang Q W, Dodelet J P, Chenitz R. Recent advances in electrocatalysts for oxygen reduction reaction. Chemical Reviews, 2016, 116(6): 3594–3657

[3] Jiao Y, Zheng Y, Jaroniec M, Qiao S Z. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chemical Society Reviews, 2015, 44(8): 2060–2086

[4] Kang G S, Lee G, Cho S Y, Joh H I, Lee D C, Lee S. Recycling of waste tires by synthesizing N-doped carbon-based catalysts for oxygen reduction reaction. Applied Surface Science, 2021, 548: 149027–149031

[5] Ge F, Qiao Q G, Chen X, Wu Y. Probing the catalytic activity of M-N₄-xO_x embedded graphene for the oxygen reduction reaction by density functional theory. Frontiers of Chemical Science and Engineering, 2021, 15(5): 1206–1216

[6] Sun J, Guo N K, Song T S, Hao Y R, Sun J W, Xue H, Wang Q. Revealing the interfacial electron modulation effect of CoFe alloys with CoC_x encapsulated in N-doped CNTs for superior oxygen reduction. Advanced Powder Materials, 2022, 1(3): 100023–100029

[7] Peng J H, Tao P, Song C Y, Shang W, Deng T, Wu J B. Structural evolution of Pt-based oxygen reduction reaction electrocatalysts. Chinese Journal of Catalysis, 2022, 43(1): 47–58

[8] Peng W, Yang X X, Mao L C, Jin J H, Yang S L, Zhang J J, Li G. ZIF-67-derived Co nanoparticles anchored in N doped hollow carbon nanofibers as bifunctional oxygen electrocatalysts. Chemical Engineering Journal, 2021, 407: 127157–127167

[9] Han J X, Bao H L, Wang J Q, Zheng L R, Sun S R, Wang Z L, Sun C W. 3D N-doped ordered mesoporous carbon supported single-atom Fe–N–C catalysts with superior performance for oxygen reduction reaction and zinc–air battery. Applied Catalysis B: Environmental, 2021, 280: 119411–119420

[10] Pan Y L, Liu S, Sun K, Chen X, Wang B, Wu K, Cao X, Cheong W C, Shen R, Han A, Chen Z, Zheng L, Luo J, Lin Y, Liu Y, Wang D, Peng Q, Zhang Q, Chen C, Li Y. A bimetallic Zn/Fe polyphthalocyanine-derived single-atom Fe–N₄ catalytic site: a superior trifunctional catalyst for overall water splitting and Zn–air batteries. Angewandte Chemie International Edition, 2018, 57(28): 8614–8618

[11] Yang Z, Yan X, Tang Z, Peng W, Zhang J, Tong Y, Li J, Zhang J. Facile synthesis of hemin-based Fe–N–C catalyst by MgAl-LDH confinement effect for oxygen reduction reaction. Applied Surface Science, 2022, 573: 151505–151513

[12] Qiao M, Wang Y, Wang Q, Hu G, Mamat X, Zhang S, Wang S. Hierarchically ordered porous carbon with atomically dispersed Fe–N₄ for ultraefficient oxygen reduction reaction in proton-exchange membrane fuel cells. Angewandte Chemie International Edition, 2020, 59(7): 2688–2694

[13] Zheng Y, Song H, Chen S, Yu X H, Zhu J X, Xu J S, Zhang K A I, Zhang C, Liu T. Metal-free multi-heteroatom-doped carbon bifunctional electrocatalysts derived from a covalent triazine polymer. Small, 2020, 16(47): 2004342–2004352

[14] Yu X H, Zheng Y, Zhang H P, Wang Y F, Fan X S, Liu T X. Fast-recoverable, self-healable, and adhesive nanocomposite hydrogel consisting of hybrid nanoparticles for ultrasensitive strain and pressure sensing. Chemistry of Materials, 2021, 33(15): 6146–6157

[15] Yu X H, Zheng Y, Wang Y F, Zhang H P, Song H, Li Z B, Fan X S, Liu T X. Facile fabrication of highly stretchable, stable, and self-healing ion-conductive sensors for monitoring human motions. Chemistry of Materials, 2022, 34(3): 1110–1120

[16] Xu J, Zhu C, Song S, Fang Q, Zhao J, Shen Y. A nanocubicle-like 3D adsorbent fabricated by in situ growth of 2D heterostructures for removal of aromatic contaminants in water. Journal of Hazardous Materials, 2022, 423: 127004–127012

[17] Ding F, Yu Z, Chen X, Chen X, Chen C, Huang Y, Yang Z, Zou C, Yang K, Huang S. High-performance supercapacitors based on reduced graphene oxide-wrapped carbon nanoflower with efficient transport pathway of electrons and electrolyte ions. Electrochimica Acta, 2019, 306: 549–557

[18] Li H, Du K, Xiang C, An P, Shu X, Dang Y, Wu C, Wang J, Du W, Zhang J, Li S, Tian H, Wang S, Xia H. Controlled chelation between tannic acid and Fe precursors to obtain N, S co-doped carbon with high density Fe-single atom-nanoclusters for highly efficient oxygen reduction reaction in Zn–air batteries. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2020, 8(33): 17136–17149

[19] Gan Z, Shu C, Deng C, Du W, Huang B, Tang W. Confinement of Pt NPs by hollow-porous-carbon-spheres via pore regulation with promoted activity and durability in the hydrogen evolution reaction. Nanoscale, 2021, 13(43): 18273–18280

[20] Shu C, Tan Q, Deng C, Du W, Gan Z, Liu Y, Fan C, Jin H, Tang W, Yang X, Yang X, Wu Y. Hierarchically mesoporous carbon spheres coated with a single atomic Fe–N–C layer for balancing activity and mass transfer in fuel cells. Carbon Energy, 2022, 4(1): 1–11

[21] Chung D Y, Yoo J M, Sung Y. Highly durable and active Pt-based nanoscale design for fuel-cell oxygen-reduction electrocatalysts. Advanced Materials, 2018, 30(42): 1704123–1704142

[22] Zong W, Chui N B, Tian Z H, Li Y Y, Yang C, Rao D W, Wang W, Huang J J, Wang J T, Lai F, Liu T. Ultrafine MoP nanoparticle splotched nitrogen-doped carbon nanosheets enabling high-performance 3D-printed potassium-ion hybrid capacitors. Advanced Science, 2021, 8(7): 2004142–2004152

[23] Kamiya K. Selective single-atom electrocatalysts: a review with a focus on metal-doped covalent triazine frameworks. Chemical Science, 2020, 11(32): 8339–8349

[24] Jiao L, Hu Y, Ju H, Wang C, Gao M R, Yang Q, Zhu J, Yu S H, Jiang H L. From covalent triazine-based frameworks to N-doped porous carbon/reduced graphene oxide nanosheets: efficient electrocatalysts for oxygen reduction. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2017, 5(44): 23170–23178

[25] He Y, Gehrig D, Zhang F, Lu C, Zhang C, Cai M, Wang Y, Laquai F, Zhuang X, Feng X. Highly efficient electrocatalysts for oxygen reduction reaction based on 1D ternary doped porous carbons derived from carbon nanotube directed conjugated microporous polymers. Advanced Functional Materials, 2016, 26(45): 8255–8265

[26] Ma Y, Chen W, Jiang Z, Tian X, Guo X, Chen G, Jiang Z J. NiFe-nanoparticles supported on N-doped graphene hollow spheres entangled with self-grown N-doped carbon nanotubes for liquid electrolyte/flexible all-solid-state rechargeable zinc–air batteries. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2022, 10(23): 12616–12631

[27] Zheng Y, Chen S, Zhang K A I, Guan J, Yu X, Peng W, Song H, Zhu J, Xu J, Fan X, Zhang C, Liu T. Template-free construction of hollow mesoporous carbon spheres from a covalent triazine framework for enhanced oxygen electroreduction. Journal of Colloid and Interface Science, 2022, 608: 3168–3177

[28] Wang W, Chen W, Miao P, Luo J, Wei Z, Chen S. NaCl crystallites as dual-functional and water-removable templates to synthesize a three-dimensional graphene-like macroporous Fe–N–C catalyst. ACS Catalysis, 2017, 7(9): 6144–6149

[29] Zheng Y, Qing F L, Huang Y, Xu X H. Tunable and practical synthesis of thiosulfonates and disulfides from sulfonyl chlorides in the presence of tetrabutylammonium iodide. Advanced Synthesis & Catalysis, 2016, 358(21): 3477–3481

[30] Zhu C, Fang Q, Liu R, Dong W, Song S, Shen Y. Insights into the crucial role of electron and spin structures in heteroatom-doped covalent triazine frameworks for removing organic micropollutants. Environmental Science & Technology, 2022, 56(10): 6699–6709

[31] Chen S, Zheng Y, Zhang B, Feng Y, Zhu J, Xu J, Zhang C, Feng W, Liu T. Cobalt, nitrogen-doped porous carbon nanosheet-assembled flowers from metal-coordinated covalent organic polymers for efficient oxygen reduction. ACS Applied Materials & Interfaces, 2019, 11(1): 1384–1393

[32] Zhang X, Mollamahale Y B, Lyu D, Liang L, Yu F, Qing M, Du Y, Zhang X, Tian Z Q, Shen P K. Molecular-level design of Fe–N–C catalysts derived from Fe-dual pyridine coordination complexes for highly efficient oxygen reduction. Journal of Catalysis, 2019, 372: 245–257

[33] Zhao X, Pachfule P, Li S, Langenhahn T, Ye M, Tian G, Schmidt J, Thomas A. Silica-templated covalent organic framework-derived Fe-N-doped mesoporous carbon as oxygen reduction electrocatalyst. Chemistry of Materials, 2019, 31(9): 3274–3280

[34] Ding W, Li L, Xiong K, Wang Y, Li W, Nie Y, Chen S, Qi X, Wei Z. Shape fixing via salt recrystallization: a morphology-controlled approach to convert nanostructured polymer to carbon nanomaterial as a highly active catalyst for oxygen reduction reaction. Journal of the American Chemical Society, 2015, 137(16): 5414–5420

[35] Zheng Y, Chen S, Yu X, Li K, Ni X, Ye L. Nitrogen-doped carbon spheres with precisely-constructed pyridinic-N active sites for efficient oxygen reduction. Applied Surface Science, 2022, 598: 153786–153793

[36] Zheng Y, Ni X, Li K, Yu X, Song H, Chen S, Khan N A, Wang D, Zhang C. Multi-heteroatom-doped hollow carbon nanocages from ZIF-8@CTP nanocomposites as high-performance anodes for sodium-ion batteries. Composites Communications, 2022, 32: 101116–101122

[37] Zong W, Guo H, Ouyang Y, Mo L, Zhou C, Chao G, Hofkens J, Xu Y, Wang W, Miao Y E, He G, Parkin I P, Lai F, Liu T. Topochemistry-driven synthesis of transition-metal selenides with weakened van der Waals force to enable 3D-printed Na-ion hybrid capacitors. Advanced Functional Materials, 2022, 32(13): 2110016–2110025

[38] Zhang X, Wang F, Dou L, Cheng X, Si Y, Yu J, Ding B. Ultrastrong, superelastic, and lamellar multiarch structured ZrO₂-Al₂O₃ nanofibrous aerogels with high-temperature resistance over 1300 °C. ACS Nano, 2020, 14(11): 15616–15625

[39] Liu S, Xu J, Zhu J, Chang Y, Wang H, Liu Z, Xu Y, Zhang C, Liu T. Leaf-inspired interwoven carbon nanosheet/nanotube homostructures for supercapacitors with high energy and power densities. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2017, 5(37): 19997–20004

[40] Fan F, Zhou H, Yan R, Yang C, Zhu H, Gao Y, Ma L, Cao S, Cheng C, Wang Y. Anchoring Fe–N–C sites on hierarchically porous carbon sphere and CNT interpenetrated nanostructures as efficient cathodes for zinc–air batteries. ACS Applied Materials & Interfaces, 2021, 13(35): 41609–41618

[41] Unni S M, Devulapally S, Karjule N, Kurungot S. Graphene enriched with pyrrolic coordination of the doped nitrogen as an efficient metal-free electrocatalyst for oxygen reduction. Journal of Materials Chemistry, 2012, 22(44): 23506–23513

[42] Xing Z, Jin R, Chen X, Chen B, Zhou J, Tian B, Li Y, Fan D. Self-templating construction of N, P-co-doped carbon nanosheets for efficient eletreocatalytic oxygen reduction reaction. Chemical Engineering Journal, 2021, 410: 128015–128020

[43] Zhu T, Feng Q, Liu S, Zhang C. Metallogel-derived 3D porous carbon nanosheet composites as an electrocatalyst for oxygen reduction reaction. Composites Communications, 2020, 20: 100376–100380

[44] Zheng Y, Chen S, Zhang K, Zhu J, Xu J, Zhang C, Liu T. Ultrasound-triggered assembly of covalent triazine framework for synthesizing heteroatom-doped carbon nanoflowers boosting metal-free bifunctional electrocatalysis. ACS Applied Materials & Interfaces, 2021, 13(11): 13328–13337

[45] Zhang R Q, Ma A, Liang X, Zhao L M, Zhao H, Yuan Z Y. Cobalt nanoparticle decorated N-doped carbons derived from a cobalt covalent organic framework for oxygen electrochemistry. Frontiers of Chemical Science and Engineering, 2021, 15(6): 1550–1560

[46] Zhang S, Liu X, Li Z, Hao L, Wang P, Zou X, Liu Z, Zhang G, Zhang C Y. Iron and iodine co-doped triazine-based frameworks with efficient oxygen reduction reaction in alkaline and acidic media. ACS Sustainable Chemistry & Engineering, 2019, 7(13): 11787–11794

[47] Yuan K, Sfaelou S, Qiu M, Lützenkirchen-Hecht D, Zhuang X, Chen Y, Yuan C, Feng X, Scherf U. Synergetic contribution of boron and Fe–N_x species in porous carbons toward efficient electrocatalysts for oxygen reduction reaction. ACS Energy Letters, 2018, 3(1): 252–260

[48] Zheng Y, Chen S, Lu H, Zhang C, Liu T. 3D honeycombed cobalt, nitrogen co-doped carbon nanosheets via hypersaline-protected pyrolysis towards efficient oxygen reduction. Nanotechnology, 2020, 31(36): 364003

[49] Zheng Y, Chen S, Song H, Guo H, Zhang K A I, Zhang C, Liu T. Nitrogen-doped hollow carbon nanoflowers from a preformed covalent triazine framework for metal-free bifunctional electrocatalysis. Nanoscale, 2020, 12(27): 14441–14447

[50] Guan C, Sumboja A, Zang W, Qian Y, Zhang H, Liu X, Liu Z, Zhao D, Pennycook S J, Wang J. Decorating Co/CoN_x nanoparticles in nitrogen-doped carbon nanoarrays for flexible and rechargeable zinc–air batteries. Energy Storage Materials, 2019, 16: 243–250

Acknowledgment

The authors are grateful for the financial support from the National Natural Science Foundation of China (Grant Nos. 51872147 and 22006131).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2232-5 and is accessible for authorized users.

RIGHTS & PERMISSIONS

2022 Higher Education Press