Metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrids as efficient bifunctional oxygen electrodes for Zn−air batteries

Abstract

The exploration of efficient bifunctional electrocatalysts for oxygen reduction reaction and oxygen evolution reaction is pivotal for the development of rechargeable metal–air batteries. Transition metal phosphides are emerging as promising catalyst candidates because of their superb activity and low cost. Herein, a novel metal phosphonate-derived cobalt/nickel phosphide@N-doped carbon hybrid was developed by a carbothermal reduction of cobalt/nickel phosphonate hybrids with different Co/Ni molar ratios. The metal phosphonate derivation method achieved an intimately coupled interaction between metal phosphides and a heteroatom-doped carbon substrate. The resultant Co₂P/Ni₃P@NC-0.2 enables an impressive electrocatalytic oxygen reduction reaction activity, comparable with those of state-of-the-art Pt/C catalysts in terms of onset potential (0.88 V), 4e^‒ selectivity, methanol tolerance, and long-term durability. Moreover, remarkable oxygen evolution reaction activity was also observed in alkaline conditions. The high activity is ascribed to the N-doping, abundant accessible catalytic active sites, and the synergistic effect among the components. This work not only describes a high-efficiency electrocatalyst for both oxygen reduction reaction and oxygen evolution reaction, but also highlights the application of metal phosphonate hybrids in fabricating metal phosphides with tunable structures, which is of great significance in the energy conversion field.

Key words： metal phosphonate; cobalt/nickel phosphide; N-doped carbon; oxygen electrochemistry; Zn−air battery

Acknowledgements

This work was supported by the Natural Science Foundation of Shandong Province (ZR2019PB013) and the Training Program of Innovation and Entrepreneurship for Undergraduates (CXCY2021161).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2153-3 and is accessible for authorized users.

References

1 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

2 Wang F M, Zhao H M, Ma Y R, Yang Y, Li B, Cui Y Y, Guo Z Y, Wang L. Core-shell-structured Co@Co4N nanoparticles encapsulated into MnO-modified porous N-doping carbon nanocubes as bifunctional catalysts for rechargeable Zn−air batteries. Journal of Energy Chemistry, 2020, 50 : 52– 62

3 Zhao C X, Liu J N, Wang J, Ren D, Li B Q, Zhang Q. Recent advances of noble-metal-free bifunctional oxygen reduction and evolution electrocatalysts. Chemical Society Reviews, 2021, 50( 13): 7745– 7778

4 Zhang J T, Zhao Z H, Xia Z H, Dai L M. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nature Nanotechnology, 2015, 10( 5): 444– 452

5 Cao R G, Lee J S, Liu M L, Cho J. Recent progress in non-precious catalysts for metal−air batteries. Advanced Energy Materials, 2012, 2( 7): 816– 829

6 Guo Y Y, Yuan P F, Zhang J N, Xia H C, Cheng F Y, Zhou M F, Li J, Qiao Y Y, Mu S C, Xu Q. Co₂P-CoN double active centers confined in N-doped carbon nanotube: heterostructural engineering for trifunctional catalysis toward HER, ORR, OER, and Zn−air batteries driven water splitting. Advanced Functional Materials, 2018, 28( 51): 1805641

7 Wang H T, Wang W, Xu Y Y, Asif M, Liu H F, Xia B Y. Ball-milling synthesis of Co₂P nanoparticles encapsulated in nitrogen doped hollow carbon rods as efficient electrocatalysts. Journal of Materials Chemistry A, 2017, 5( 33): 17563– 17569

8 Zhao H, Yuan Z Y. Transition metal-phosphorus-based materials for electrocatalytic energy conversion reactions. Catalysis Science & Technology, 2017, 7( 2): 330– 357

9 Gagnon K J, Perry H P, Clearfield A. Conventional and unconventional metal-organic frameworks based on phosphonate ligands: MOFs and UMOFs. Chemical Reviews, 2012, 112( 2): 1034– 1054

10 Zhao H, Yuan Z Y. Design strategies of transition-metal phosphate and phosphonate electrocatalysts for energy-related reactions. ChemSusChem, 2021, 14( 1): 130– 149

11 Lv X W, Weng C C, Zhu Y P, Yuan Z Y. Nanoporous metal phosphonate hybrid materials as a novel platform for emerging applications: a critical review. Small, 2021, 17( 22): 2005304

12 Zhao H, Weng C C, Ren J T, Ge L, Liu Y P, Yuan Z Y. 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

13 Chen L, Ren J T, Wang Y S, Tian W W, Gao L J, Yuan Z Y. Organic−inorganic cobalt-phosphonate-derived hollow cobalt phosphate spherical hybrids for highly efficient oxygen evolution. ACS Sustainable Chemistry & Engineering, 2019, 7( 15): 13559– 13568

14 Zhou T H, Du Y H, Wang D P, Yin S M, Tu W G, Chen Z, Borgna A, Xu R. Phosphonate-based metal-organic framework derived Co−P−C hybrid as an efficient electrocatalyst for oxygen evolution reaction. ACS Catalysis, 2017, 7( 9): 6000– 6007

15 Jiao J Q, Pan Y, Wang B, Yang W J, Liu S J, Zhang C. Melamine-assisted pyrolytic synthesis of bifunctional cobalt-based core–shell electrocatalysts for rechargeable zinc−air batteries. Journal of Energy Chemistry, 2021, 53 : 364– 371

16 Ren J T, Wang Y S, Chen L, Gao L J, Tian W W, Yuan Z Y. Binary FeNi phosphides dispersed on N,P-doped carbon nanosheets for highly efficient overall water splitting and rechargeable Zn−air batteries. Chemical Engineering Journal, 2020, 389 : 124408

17 Lv X W, Hu Z P, Chen L, Ren J T, Liu Y P, Yuan Z Y. Organic−inorganic metal phosphonate-derived nitrogen-doped core−shell Ni₂P nanoparticles supported on Ni foam for efficient hydrogen evolution reaction at all pH values. ACS Sustainable Chemistry & Engineering, 2019, 7( 15): 12770– 12778

18 Lv X W, Xu W S, Tian W W, Wang H Y, Yuan Z Y. Activity promotion of core and shell in multifunctional core−shell Co₂P@NC electrocatalyst by secondary metal doping for water electrolysis and Zn−air batteries. Small, 2021, 17( 38): 2101856

19 Li D, Baydoun H, Verani C N, Brock S L. Efficient water oxidation using CoMnP nanoparticles. Journal of the American Chemical Society, 2016, 138( 12): 4006– 4009

20 Mendoza-Garcia A, Zhu H Y, Yu Y S, Li Q, Zhou L, Su D, Kramer M J, Sun S H. Controlled anisotropic growth of Co−Fe−P from Co−Fe−O nanoparticles. Angewandte Chemie International Edition, 2015, 54( 33): 9642– 9645

21 Liang X, Zheng B, Chen L, Zhang J, Zhuang Z, Chen B. MOF-derived formation of Ni₂P−CoP bimetallic phosphides with strong interfacial effect toward electrocatalytic water splitting. ACS Applied Materials & Interfaces, 2017, 9( 27): 23222– 23229

22 Lv X W, Tian W W, Liu Y P, Yuan Z Y. Well-defined CoP/Ni₂P nanohybrids encapsulated in a nitrogen-doped carbon matrix as advanced multifunctional electrocatalysts for efficient overall water splitting and zinc−air batteries. Materials Chemistry Frontiers, 2019, 3( 11): 2428– 2436

23 Zhao H, Weng C C, Hu Z P, Ge L, Yuan Z Y. CdS-polydopamine-derived N,S-codoped hierarchically porous carbons as highly active electrocatalyst for oxygen reduction. ACS Sustainable Chemistry & Engineering, 2017, 5( 11): 9914– 9922

24 Tang J, Liu J, Li C L, Li Y Q, Tade M O, Dai S, Yamauchi Y. Synthesis of nitrogen-doped mesoporous carbon spheres with extra-large pores through assembly of diblock copolymer micelles. Angewandte Chemie International Edition, 2015, 54( 2): 588– 593

25 Kudin K N, Ozbas B, Schniepp H C, Prud’homme R K, Aksay I A, Car R. Raman spectra of graphite oxide and functionalized graphene sheets. Nano Letters, 2008, 8( 1): 36– 41

26 Lv X W, Liu Y P, Tian W W, Gao L J, Yuan Z Y. Aluminum and phosphorus codoped “superaerophobic” Co₃O₄ microspheres for highly efficient electrochemical water splitting and Zn−air batteries. Journal of Energy Chemistry, 2020, 50 : 324– 331

27 Wang X S, Vasiliff A, Jiao Y, Zheng Y, Qiao S Z. Electronic and structural engineering of carbon-based metal-free electrocatalysts for water splitting. Advanced Materials, 2019, 31( 13): 1803625

28 Hu L, Hu Y W, Liu R, Mao Y C, Balogun M S, Tong Y X. Co-based MOF-derived Co/CoN/Co₂P ternary composite embedded in N- and P-doped carbon as bifunctional nanocatalysts for efficient overall water splitting. International Journal of Hydrogen Energy, 2019, 44( 23): 11402– 11410

29 Xu K, Sun Y Q, Sun Y M, Zhang Y Q, Jia G C, Zhang Q H, Gu L, Li S Z, Li Y, Fan H J. Yin−Yang harmony: metal and nonmetal dual-doping boosts electrocatalytic activity for alkaline hydrogen evolution. ACS Energy Letters, 2018, 3( 11): 2750– 2756

30 You B, Jiang N, Sheng M, Bhushan M W, Sun Y. Hierarchically porous urchin-like Ni₂P superstructures supported on nickel foam as efficient bifunctional electrocatalysts for overall water splitting. ACS Catalysis, 2016, 6( 2): 714– 721

31 Borghei M, Laocharoen N, Kibena-Põldsepp E, Johansson L S, Campbell J, Kauppinen E, Tammeveski K, Rojas O J, Porous N. P-doped carbon from coconut shells with high electrocatalytic activity for oxygen reduction: alternative to Pt−C for alkaline fuel cells. Applied Catalysis B: Environmental, 2017, 204 : 394– 402

32 Huang S, Meng Y, Cao Y, He S, Li X, Tong S, Wu M. N-, O- and P-doped hollow carbons: metal-free bifunctional electrocatalysts for hydrogen evolution and oxygen reduction reactions. Applied Catalysis B: Environmental, 2019, 248 : 239– 248

33 Zhuang M H, Ou X W, Dou Y B, Zhang L L, Zhang Q C, Wu R Z, Ding Y, Shao M H, Luo Z T. Polymer-embedded fabrication of Co₂P nanoparticles encapsulated in N,P-doped graphene for hydrogen generation. Nano Letters, 2016, 16( 7): 4691– 4698

34 Das D, Nanda K K. One-step, integrated fabrication of Co₂P nanoparticles encapsulated N, P dual-doped CNTs for highly advanced total water splitting. Nano Energy, 2016, 30 : 303– 311

35 Qin Q, Jang H, Li P, Yuan B, Liu X, Cho J. A tannic acid-derived N-, P-codoped carbon-supported iron-based nanocomposite as an advanced trifunctional electrocatalyst for the overall water splitting cells and zinc−air batteries. Advanced Energy Materials, 2019, 9( 5): 1803312

36 Zhang M, Dai Q, Zheng H, Chen M, Dai L. Novel MOF-derived Co@N−C bifunctional catalysts for highly efficient Zn–air batteries and water splitting. Advanced Materials, 2018, 30( 10): 1705431

37 Zhao H, Yuan Z Y. Surface/interface engineering of high-efficiency noble metal-free electrocatalysts for energy-related electrochemical reactions. Journal of Energy Chemistry, 2021, 54 : 89– 104

38 Zhao C X, Liu J N, Li B Q, Ren D, Chen X, Yu J, Zhang Q. Multiscale construction of bifunctional electrocatalysts for long-lifespan rechargeable zinc–air batteries. Advanced Functional Materials, 2020, 30( 36): 2003619

39 Ren J T, Yuan Z Y. 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

40 Shi Y M, Zhang B. Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction. Chemical Society Reviews, 2016, 45( 6): 1529– 1541

41 Li H, Li Q, Wen P, Williams T B, Adhikari S, Dun C C, Lu C, Itanze D, Jiang L, Carroll D L, Donati G L, Lundin P M, Qiu Y, Geyer S M. Colloidal cobalt phosphide nanocrystals as trifunctional electrocatalysts for overall water splitting powered by a zinc-air battery. Advanced Materials, 2018, 30( 9): 1705796

42 He P, Yu X Y, Lou X W. Carbon-incorporated nickel−cobalt mixed metal phosphide nanoboxes with enhanced electrocatalytic activity for oxygen evolution. Angewandte Chemie International Edition, 2017, 56( 14): 3897– 3900

43 Yan L T, Cao L, Dai P C, Gu X, Liu D D, Li L J, Wang Y, Zhao X B. Metal-organic frameworks derived nanotube of nickel−cobalt bimetal phosphides as highly efficient electrocatalysts for overall water splitting. Advanced Functional Materials, 2017, 27( 40): 1703455