Trifunctional robust electrocatalysts based on 3D Fe/N-doped carbon nanocubes encapsulating Co₄N nanoparticles for efficient battery-powered water electrolyzers

Abstract

Herein, we have designed a highly active and robust trifunctional electrocatalyst derived from Prussian blue analogs, where Co₄N nanoparticles are encapsulated by Fe embedded in N-doped carbon nanocubes to synthesize hierarchically structured Co₄N@Fe/N–C for rechargeable zinc–air batteries and overall water-splitting electrolyzers. As confirmed by theoretical and experimental results, the high intrinsic oxygen reduction reaction, oxygen evolution reaction, and hydrogen evolution reaction activities of Co₄N@Fe/N–C were attributed to the formation of the heterointerface and the modulated local electronic structure. Moreover, Co₄N@Fe/N–C induced improvement in these trifunctional electrocatalytic activities owing to the hierarchical hollow nanocube structure, uniform distribution of Co₄N, and conductive encapsulation by Fe/N–C. Thus, the rechargeable zinc–air battery with Co₄N@Fe/N–C delivers a high specific capacity of 789.9 mAh g⁻¹ and stable voltage profiles over 500 cycles. Furthermore, the overall water electrolyzer with Co₄N@Fe/N–C achieved better durability and rate performance than that with the Pt/C and IrO₂ catalysts, delivering a high Faradaic efficiency of 96.4%. Along with the great potential of the integrated water electrolyzer powered by a zinc–air battery for practical applications, therefore, the mechanistic understanding and active site identification provide valuable insights into the rational design of advanced multifunctional electrocatalysts for energy storage and conversion.

Keywords

battery-powered electrolyzers / hierarchical structure / Prussian blue analog / trifunctional electrocatalyst / zinc–air battery

References

[1] Chu S, Majumdar A. Opportunities and challenges for a sustainable energy future. Nature. 2012; 488 (7411): 294- 303.

[2] Yang H, Han X, Douka AI, et al. Advanced oxygen electrocatalysis in energy conversion and storage. Adv Funct Mater. 2021; 31 (12): 2007602.

[3] Candelaria SL, Shao Y, Zhou W, et al. Nanostructured carbon for energy storage and conversion. Nano Energy. 2012; 1 (2): 195- 220.

[4] You B, Sun Y. Innovative strategies for electrocatalytic water splitting. Acc Chem Res. 2018; 51 (7): 1571- 1580.

[5] Anantharaj S, Ede SR, Karthick K, et al. Precision and correctness in the evaluation of electrocatalytic water splitting: revisiting activity parameters with a critical assessment. Energy Environ Sci. 2018; 11 (4): 744- 771.

[6] Liu Q, Liu R, He C, et al. Advanced polymer-based electrolytes in zinc-air batteries. eScience. 2022; 2 (5): 453- 466.

[7] Han X, Li N, Kang YB, et al. Unveiling trifunctional active sites of a heteronanosheet electrocatalyst for integrated cascade battery/electrolyzer systems. ACS Energy Lett. 2021; 6 (7): 2460- 2468.

[8] Li H, Li Q, Wen P, et al. Colloidal cobalt phosphide nanocrystals as trifunctional electrocatalysts for overall water splitting powered by a zinc-air battery. Adv Mater. 2018; 30 (9): 1705796.

[9] Wu M, Zhang G, Tong H, et al. Cobalt (II) oxide nanosheets with rich oxygen vacancies as highly efficient bifunctional catalysts for ultra-stable rechargeable Zn-air flow battery. Nano Energy. 2021; 79: 105409.

[10] Wang Y, Kong B, Zhao D, Wang H, Selomulya C. Strategies for developing transition metal phosphides as heterogeneous electrocatalysts for water splitting. Nano Today. 2017; 15: 26- 55.

[11] Oh HS, Nong HN, Reier T, et al. Electrochemical catalyst—support effects and their stabilizing role for IrO_x nanoparticle catalysts during the oxygen evolution reaction. J Am Chem Soc. 2016; 138 (38): 12552- 12563.

[12] Nguyen TT, Balamurugan J, Kim DH, Kim NH, Lee JH. Hierarchical 3D oxygenated cobalt vanadium selenide nanosheets as advanced electrode for flexible zinc-cobalt and zinc-air batteries. Small. 2020; 16 (48): 2004661.

[13] Park HS, Seo E, Yang J, Lee Y, Kim BS, Song HK. Bifunctional hydrous RuO₂ nanocluster electrocatalyst embedded in carbon matrix for efficient and durable operation of rechargeable zinc-air batteries. Sci Rep. 2017; 7: 7150.

[14] Fu J, Liang R, Liu G, et al. Recent progress in electrically rechargeable zinc-air batteries. Adv Mater. 2019; 31 (31): 1805230.

[15] Dai S, Chou JP, Wang KW, et al. Platinum-trimer decorated cobalt-palladium core-shell nanocatalyst with promising performance for oxygen reduction reaction. Nat Commun. 2019; 10: 440.

[16] Sasaki K, Marinkovic N, Isaacs HS, Adzic RR. Synchrotron-based in situ characterization of carbon-supported platinum and platinum monolayer electrocatalysts. ACS Catal. 2016; 6 (1): 69- 76.

[17] Zhang J, Zhou Q, Tang Y, Zhang L, Li Y. Zinc-air batteries: are they ready for prime time? Chem Sci. 2019; 10 (39): 8924- 8929.

[18] Wagh NK, Shinde SS, Lee CH, et al. Densely colonized isolated Cu-N single sites for efficient bifunctional electrocatalysts and rechargeable advanced Zn-air batteries. Appl Catal B. 2020; 268: 118746.

[19] Hua B, Sun YF, Li M, et al. Stabilizing double perovskite for effective bifunctional oxygen electrocatalysis in alkaline conditions. Chem Mater. 2017; 29 (15): 6228- 6237.

[20] Niu H, Xia C, Huang L, et al. Rational design and synthesis of one-dimensional platinum-based nanostructures for oxygen-reduction electrocatalysis. Chin J Catal. 2022; 43 (6): 1459- 1472.

[21] Meng F, Zhong H, Bao D, Yan J, Zhang X. In situ coupling of strung Co₄N and intertwined N-C fibers toward free-standing bifunctional cathode for robust, efficient, and flexible Zn-Air batteries. J Am Chem Soc. 2016; 138 (32): 10226- 10231.

[22] Gao Y, Xiao Z, Kong D, Iqbal R, Yang QH, Zhi L. N, P co-doped hollow carbon nanofiber membranes with superior mass transfer property for trifunctional metal-free electrocatalysis. Nano Energy. 2019; 64: 103879.

[23] Liu H, Guan J, Yang S, et al. Metal-organic-framework-derived Co₂P nanoparticle/multi-doped porous carbon as a trifunctional electrocatalyst. Adv Mater. 2020; 32 (36): 2003649.

[24] Wang Z, Liu H, Ge R, et al. Phosphorus-doped Co₃O₄ nanowire array: a highly efficient bifunctional electrocatalyst for overall water splitting. ACS Catal. 2018; 8 (3): 2236- 2241.

[25] Zheng X, Han X, Zhang Y, et al. Controllable synthesis of nickel sulfide nanocatalysts and their phase-dependent performance for overall water splitting. Nanoscale. 2019; 11 (12): 5646- 5654.

[26] Xu H, Zhu J, Wang P, et al. Fe-Co-P multi-heterostructure arrays for efficient electrocatalytic water splitting. J Mater Chem A. 2021; 9 (43): 24677- 24685.

[27] Zhu C, Yin Z, Lai W, et al. Fe-Ni-Mo nitride porous nanotubes for full water splitting and Zn-air batteries. Adv Energy Mater. 2018; 8 (36): 1802327.

[28] Bai Z, Li S, Fu J, et al. Metal-organic framework-derived nickel cobalt oxysulfide nanocages as trifunctional electrocatalysts for high efficiency power to hydrogen. Nano Energy. 2019; 58: 680- 686.

[29] Wang Y, Yuan H, Liu F, Hu T. A triphasic nanocomposite with a synergetic interfacial structure as a trifunctional catalyst toward electrochemical oxygen and hydrogen reactions. J Mater Chem A. 2021; 9 (11): 7114- 7121.

[30] Hu Q, Wang Z, Huang X, et al. A unique space confined strategy to construct defective metal oxides within porous nanofibers for electrocatalysis. Energy Environ Sci. 2020; 13 (12): 5097- 5103.

[31] Xuan C, Lei W, Wang J, et al. Sea urchin-like Ni-Fe sulfide architectures as efficient electrocatalysts for the oxygen evolution reaction. J Mater Chem A. 2019; 7 (19): 12350- 12357.

[32] Wang Y, Wang Y, Gao H, Huang Z, Hao Q, Liu B. Interface-induced contraction of core-shell Prussian blue analogues toward hollow Ni-Co-Fe phosphide nanoboxes for efficient oxygen evolution electrocatalysis. Chem Eng J. 2023; 451 (Part 1): 138515.

[33] Jeong DI, Choi HW, Woo S, et al. Electronic structure modification and N-doped carbon shell nanoarchitectonics of Ni₃FeN@NC for overall water splitting performance evaluation. J Mater Chem A. 2022; 10 (31): 16704- 16713.

[34] Zeng Y, Lu XF, Zhang SL, Luan D, Li S, Lou XW. Construction of Co-Mn Prussian blue analog hollow spheres for efficient aqueous Zn-ion batteries. Angew Chem Int Ed. 2021; 60 (41): 22189- 22194.

[35] Wang T, He Y, Liu Y, et al. A ZIF-triggered rapid polymerization of dopamine renders Co/N-codoped cage-in-cage porous carbon for highly efficient oxygen reduction and evolution. Nano Energy. 2021; 79: 105487.

[36] Liu X, Qin J, Zhang X, et al. The mechanisms of HSA@PDA/Fe nanocomposites with enhanced nanozyme activity and their application in intracellular H₂O₂ detection. Nanoscale. 2020; 12 (47): 24206- 24213.

[37] Han Y, Wu X, Zhang X, Zhou Z, Lu C. Dual functional biocomposites based on polydopamine modified cellulose nanocrystal for Fe³⁺-pollutant detecting and autoblocking. ACS Sustainable Chem Eng. 2016; 4 (10): 5667- 5673.

[38] Xu N, Hu A, Pu X, et al. Fe (III)-chelated polydopamine nanoparticles for synergistic tumor therapies of enhanced photothermal ablation and antitumor immune activation. ACS Appl Mater Interfaces. 2022; 14 (14): 15894- 15910.

[39] Choi HW, Jeong DI, Woo S, et al. Morphology adjustable Co_xN with 3D mesoporous structure and amorphous N-doped carbon for overall water splitting. Appl Surf Sci. 2020; 529: 147177.

[40] Ye G, Wang S, Liu S, He Z, Wang J. Fe induction strategy for hollow porous N-doped carbon with superior performance in oxygen reduction. Chem Commun. 2021; 57 (58): 7108- 7111.

[41] Sun Y, Mao K, Shen Q, et al. Surface electronic structure modulation of cobalt nitride nanowire arrays via selenium deposition for efficient hydrogen evolution. Adv Funct Mater. 2021; 32 (9): 2109792.

[42] Han J, Bao H, Wang JQ, et al. 3D N-doped ordered mesoporous carbon supported single-atom Fe-N-C catalysts with superior performance for oxygen reduction reaction and zinc-air battery. Appl Catal B. 2021; 280: 119411.

[43] Weng W, Zhou J, Gu D, Xiao W. Thermoelectrochemical formation of Fe/Fe₃C@hollow N-doped carbon in molten salts for enhanced catalysis. J Mater Chem A. 2020; 8 (9): 4800- 4806.

[44] Zhang H, Gong Q, Ren S, Arshid MA, Chu W, Chen C. Implication of iron nitride species to enhance the catalytic activity and stability of carbon nanotubes supported Fe catalysts for carbon-free hydrogen production via low-temperature ammonia decomposition. Catal Sci Technol. 2018; 8 (3): 907- 915.

[45] Liu C, Liu L, Tian X, et al. Coupling metal-organic frameworks and g-CN to derive Fe@N-doped graphene-like carbon for peroxymonosulfate activation: upgrading framework stability and performance. Appl Catal B. 2019; 255: 117763.

[46] Kang BK, Choi YJ, Choi HW, et al. Rational design and in-situ formation of nickel-cobalt nitride multi-core/hollow N-doped carbon shell anode for Li-ion batteries. Chem Eng J. 2021; 420 (Part 1): 129630.

[47] Lai Q, Zheng H, Tang Z, et al. Balance of N-doping engineering and carbon chemistry to expose edge graphitic N sites for enhanced oxygen reduction electrocatalysis. ACS Appl Mater Interfaces. 2021; 13 (51): 61129- 61138.

[48] Wang N, Lu B, Li L, et al. Graphitic nitrogen is responsible for oxygen electroreduction on nitrogen-doped carbons in alkaline electrolytes: insights from activity attenuation studies and theoretical calculations. ACS Catal. 2018; 8 (8): 6827- 6836.

[49] Amiinu IS, Liu X, Pu Z, et al. From 3D ZIF nanocrystals to Co-N_x/C nanorod array electrocatalysts for ORR, OER, and Zn-Air batteries. Adv Funct Mater. 2018; 28 (5): 1704638.

[50] Cao B, Veith GM, Neuefeind JC, Adzic RR, Khalifah PG. Mixed close-packed cobalt molybdenum nitrides as non-noble metal electrocatalysts for the hydrogen evolution reaction. J Am Chem Soc. 2013; 135 (51): 19186- 19192.

[51] Lei X, Ye Z, Qie Y, et al. The synthesis, morphology and magnetic properties of (Fe_1−xMn_x)₃N nanoparticles. J Mater Sci. 2019; 30 (1): 277- 283.

[52] Tang C, Zhang Q. Nanocarbon for oxygen reduction electrocatalysis: dopants, edges, and defects. Adv Mater. 2017; 29 (13): 1604103.

[53] Yang C, Shang S, Gu Q, Shang J, Li X. Metal-organic framework-derived carbon nanotubes with multi-active Fe-N/Fe sites as a bifunctional electrocatalyst for zinc-air battery. J Energy Chem. 2022; 66: 306- 313.

[54] Zhao D, Zhuang Z, Cao X, et al. Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation. Chem Soc Rev. 2020; 49 (7): 2215- 2264.

[55] Neergat M, Gunasekar V, Rahul R. Carbon-supported Pd-Fe electrocatalysts for oxygen reduction reaction (ORR) and their methanol tolerance. J Electroanal Chem. 2011; 658 (1-2): 25- 32.

[56] Jiao L, Zhou YX, Jiang HL. Metal-organic framework-based CoP/reduced graphene oxide: high-performance bifunctional electrocatalyst for overall water splitting. Chem Sci. 2016; 7 (3): 1690- 1695.

[57] Pei Z, Tang Z, Liu Z, et al. Construction of a hierarchical 3D Co/N-carbon electrocatalyst for efficient oxygen reduction and overall water splitting. J Mater Chem A. 2018; 6 (2): 489- 497.

[58] Chen Z, Song Y, Cai J, et al. Tailoring the d-band centers enables Co₄N nanosheets to be highly active for hydrogen evolution catalysis. Angew Chem Int Ed. 2018; 57 (18): 5076- 5080.

[59] Chen P, Xu K, Fang Z, et al. Metallic Co₄N porous nanowire arrays activated by surface oxidation as electrocatalysts for the oxygen evolution reaction. Angew Chem. 2015; 127 (49): 14923- 14927.

[60] Yao N, Li P, Zhou Z, et al. Synergistically tuning water and hydrogen binding abilities over Co₄N by Cr doping for exceptional alkaline hydrogen evolution electrocatalysis. Adv Energy Mater. 2019; 9 (41): 1902449.

[61] Yao N, Fan Z, Xia Z, et al. Constructing the CoO/Co₄N heterostructure with an optimized electronic structure to boost alkaline hydrogen evolution electrocatalysis. J Mater Chem A. 2021; 9 (34): 18208- 18212.

[62] Yan X, Liu K, Wang T, et al. Atomic interpretation of high activity on transition metal and nitrogen-doped carbon nanofibers for catalyzing oxygen reduction. J Mater Chem A. 2017; 5 (7): 3336- 3345.

[63] Zhu S, Chen Z, Li B, et al. Nitrogen-doped carbon nanotubes as air cathode catalysts in zinc-air battery. Electrochim Acta. 2011; 56 (14): 5080- 5084.

[64] Kube A, Strunz W, Wagner N, Andreas Friedrich K. Evaluation of electrochemical impedance spectra of batteries (Li-air/Zn-air) for aqueous electrolytes. Electrochim Acta. 2021; 396: 139261.

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