Phase-controllable cobalt phosphide heterostructure for efficient electrocatalytic hydrogen evolution in water and seawater

Abstract

Cobalt phosphides attract broad attention as alternatives to platinum-based materials towards hydrogen evolution reaction (HER). The catalytic performance of cobalt phosphides largely depends on the phase structure, but figuring out the optimal phase towards HER remains challenging due to their diverse stoichiometries. In our work, a series of cobalt phosphide nanoparticles with different phase structures but similar particle sizes (CoP-Co₂P, Co₂P-Co, Co₂P, and CoP) on a porous carbon network (PC) were accurately synthesized. The CoP-Co₂P/PC heterostructure demonstrates upgraded HER catalytic activity with a low overpotential of 96.7 and 162.1 mV at 10 mA cm^-2 in 1 M KOH and 1 M phosphate-buffered saline solution, respectively, with a long-term (120 h) durability. In addition, the CoP-Co₂P/PC exhibits good HER performance in alkaline seawater, with a small overpotential of 111.2 mV at 10 mA cm⁻² and a low Tafel slope of 64.2 mV dec⁻¹, as well as promising stability. Density functional theory results show that the Co₂P side of the CoP-Co₂P/PC heterostructure has the best Gibbs free energy of each step for HER, which contributes to the high HER activity. This study sets the stage for the advancement of high-performance HER electrocatalysts and the implementation of large-scale seawater electrolysis.

Keywords

cobalt phosphides / electrocatalysts / heterostructures / porous carbon / seawater electrolysis

References

[1] Zhang C, Xu Z, Han N, et al. Superaerophilic/superaerophobic cooperative electrode for efficient hydrogen evolution reaction via enhanced mass transfer. Sci Adv. 2023;9(3):6978.

[2] Jia Z, Yang Y, Wang Q, et al. An ultrafast and stable high-entropy metallic glass electrode for alkaline hydrogen evolution reaction. ACS Mater Lett. 2022;4(8):1389-1396.

[3] Dresp S, Dionigi F, Klingenhof M, Strasser P. Direct electrolytic splitting of seawater: opportunities and challenges. ACS Energy Lett. 2019;4(4):933-942.

[4] Yu L, Zhu Q, Song SW, et al. Non-noble metal-nitride based electrocatalysts for high-performance alkaline seawater electrolysis. Nat Commun. 2019;10(1):5106.

[5] Zhuang L, Li J, Wang K, Li Z, Zhu M, Xu Z. Structural buffer engineering on metal oxide for long-term stable seawater splitting. Adv Funct Mater. 2022;32(25):2201127.

[6] Liu Q, Sun SJ, Zhang LC, et al. N, O-doped carbon foam as metal-free electrocatalyst for efficient hydrogen production from seawater. Nano Res. 2022;15(10):8922-8927.

[7] Wu LB, Zhang FH, Song SW, et al. Efficient alkaline water/seawater hydrogen evolution by a nanorod-nanoparticle-structured Ni-Mon catalyst with fast water-dissociation kinetics. Adv Mater. 2022;34(21):2201774.

[8] Jin HY, Wang XS, Tang C, et al. Stable and highly efficient hydrogen evolution from seawater enabled by an unsaturated nickel surface nitride. Adv Mater. 2021;33(13):2007508.

[9] Shang L, Zhao YX, Kong XY, et al. Underwater super-aerophobic Ni nanoparticle-decorated nickel-molybdenum nitride nanowire arrays for hydrogen evolution in neutral media. Nano Energy. 2020;78:105375.

[10] Dan Z, Liang W, Gong X, et al. Substitutional doping engineering toward W₂N nanorod for hydrogen evolution reaction at high current density. ACS Mater Lett. 2022;4(7):1374-1380.

[11] Chen C, Wang X, Huang Z, et al. Engineering of self-supported electrocatalysts on a three-dimensional nickel foam platform for efficient water electrolysis. Trans Tianjin Univ. 2024;30(2):103-116.

[12] Li Y, Wang T, Asim M, et al. Manipulating spin polarization of defected CO₃O₄ for highly efficient electrocatalysis. Trans Tianjin Univ. 2022;28(3):163-173.

[13] Liu DB, Li XY, Chen SM, et al. Atomically dispersed platinum supported on curved carbon supports for efficient electrocatalytic hydrogen evolution. Nat Energy. 2019;4(6):512-518.

[14] Guo F, Macdonald TJ, Sobrido AJ, Liu L, Feng J, He G. Recent advances in ultralow-Pt-loading electrocatalysts for the efficient hydrogen evolution. Adv Sci. 2023;10(21):2301098.

[15] Chen Y, Li J, Wang N, Zhou Y, Zheng J, Chu W. Plasma-assisted highly dispersed Pt single atoms on Ru nanoclusters electrocatalyst for pH-universal hydrogen evolution. Chem Eng J. 2022;448:137611.

[16] Zhang LL, Lei YT, Xu WJ, et al. Highly active and durable nitrogen-doped CoP/CeO₂ nanowire heterostructures for overall water splitting. Chem Eng J. 2023;460:141119.

[17] Chen X, Cheng Y, Wen Y, et al. CoP/Fe-CO₉S₈ for highly efficient overall water splitting with surface reconstruction and self-termination. Adv Sci. 2022;9(34):2204742.

[18] Du M, Li D, Liu S, Yan J. Transition metal phosphides: a wonder catalyst for electrocatalytic hydrogen production. Chin Chem Lett. 2023;34(9):108156.

[19] Peng X, Yan YJ, Jin X, et al. Recent advance and prospectives of electrocatalysts based on transition metal selenides for efficient water splitting. Adv Sci. 2020;78:105234.

[20] Patra A, Samal R, Rout CS. Promising water splitting applications of synergistically assembled robust orthorhombic CoSe₂ and 2D Ti₃C₂T_x MXene hybrid. Catal Today. 2023;424:113853.

[21] Li K, Zhang J, Wu R, Yu Y, Zhang B. Anchoring CoO domains on CoSe₂ nanobelts as bifunctional electrocatalysts for overall water splitting in neutral media. Adv Sci. 2016;3(6):1500426.

[22] Li Y, Zhao Y, Zhao H, Wang Z, Li H, Gao P. A bifunctional catalyst of ultrathin cobalt selenide nanosheets for plastic-electroreforming-assisted green hydrogen generation. J Mater Chem A. 2022;10(38):20446-20452.

[23] Jiang L, Gu MZ, Wang H, et al. Synergistically regulating the electronic structure of CoS by cation and anion dual-doping for efficient overall water splitting. ChemSusChem. 2023;16(18):e202300592.

[24] Wu F, Yang R, Lu S, Du W, Zhang B, Shi Y. Unveiling partial transformation and activity origin of sulfur vacancies for hydrogen evolution. ACS Energy Lett. 2022;7(12):4198-4203.

[25] Wang H, Xu J, Zhang Q, et al. Advanced ultralow-concentration electrolyte for wide-temperature and high-voltage Li-metal batteries. Adv Funct Mater. 2022;32(23):2112598.

[26] Wang DL, Zhang C, Hu JG, Zhuang T, Lv ZG. Nitriding-reduction fabrication of coralloid CoN/Ni/NiO for efficient electrocatalytic overall water splitting. J Colloid Interface Sci. 2024;655:217-225.

[27] Dang Y, Li X, Chen Z, Ma B, Zhao X, Chen Y. Hierarchical CoO@Mon heterostructure nanowire array as a highly efficient electrocatalyst for hydrogen evolution. Chem Eng J. 2023;477:147154.

[28] Zhang W, Li C, Ji JY, et al. Tailorable carbon cloth electrodes covered with heterostructured Co/CoO/CoN interfaces for scalable electrocatalytic overall water splitting. Chem Eng J. 2023;461:141937.

[29] Wang LL, He W, Yin DD, et al. CoN/MoC embedded in nitrogen-doped multi-channel carbon nanofibers as an efficient acidic and alkaline hydrogen evolution reaction electrocatalysts. Sustain Energy Rev. 2023;181:113354.

[30] Dang Y, Li X, Chen Z, Zhao X, Ma B, Chen Y. Hierarchical Mon@NiFe-LDH heterostructure nanowire array for highly efficient electrocatalytic hydrogen evolution. Small. 2023;19(50):2303932.

[31] Wu W, Ma X, Zhu Y, et al. CO₂P-Fe₂P heterogeneous nanoparticles: efficient hydrogen oxidation/evolution electrocatalysts and surface reconstruction in alkaline media. Chem Eng J. 2023;478:147425.

[32] Zhang B, Shan J, Wang W, Tsiakaras P, Li Y. Oxygen vacancy and core–shell heterojunction engineering of anemone-like CoP@CoOOH bifunctional electrocatalyst for efficient overall water splitting. Small. 2022;18(12):2106012.

[33] Wu JC, Yang XB, Zhang J, et al. Surface engineering of Ni₂P/CoP nanosheet heterojunctions by the formation of F-doped carbon layers for boosting urea-rich water electrolysis. J Power Sources. 2022;548:232065.

[34] Huang G, Hu M, Xu XT, et al. Optimizing heterointerface of CO₂P-Co_xO_y nanoparticles within a porous carbon network for deciphering superior water splitting. Small Struct. 2023;4(6):2200235.

[35] Callejas JF, Read CG, Popczun EJ, McEnaney JM, Schaak RE. Nanostructured CO₂P electrocatalyst for the hydrogen evolution reaction and direct comparison with morphologically equivalent CoP. Chem Mater. 2015;27(10):3769-3774.

[36] Kumaravel S, Karthick K, Sankar SS, et al. Recent progresses in engineering of Ni and Co based phosphides for effective electrocatalytic water splitting. Chemelectrochem. 2021;8(24):4638-4685.

[37] Liu B, Zhong B, Li F, et al. CO₂P/CoP heterostructures with significantly enhanced performance in electrocatalytic hydrogen evolution reaction: synthesis and electron redistribution mechanism. Nano Res. 2023;16(11):12830-12839.

[38] Li D, Cheng H, Hao X, et al. Wood-derived freestanding carbon-based electrode with hierarchical structure for industrial-level hydrogen production. Adv Mater. 2024;36(4):2304917.

[39] Zhou M, Jiang X, Kong W, et al. Synergistic effect of dual-doped carbon on MO₂C nanocrystals facilitates alkaline hydrogen evolution. Nano-Micro Lett. 2023;15(1):166.

[40] Jiang H, Yan L, Zhang S, et al. Electrochemical surface restructuring of phosphorus-doped carbon@MoP electrocatalysts for hydrogen evolution. Nano-Micro Lett. 2021;13(1):215.

[41] Zhu J, Cheng J, Dailly A, Cai M, Beckner M, Shen PK. One-pot synthesis of Pd nanoparticles on ultrahigh surface area 3D porous carbon as hydrogen storage materials. Int J Hydrogen Energy. 2014;39(27):14843-14850.

[42] Guo RH, Gao LL, Zhang YJ, Zhang XT, Ma MM, Hu TP. Enhancing hydrazine-assisted hydrogen production by constructing CoP-CO₂P bifunctional catalysts. Appl Surf Sci. 2023;617:156602.

[43] Chen L, Ren JT, Yuan ZY. Interface engineering for boosting electrocatalytic performance of CoP-CO₂P polymorphs for all-pH hydrogen evolution reaction and alkaline overall water splitting. Sci China Mater. 2022;65(9):2433-2444.

[44] Song H, Yu J, Tang Z, Yang B, Lu S. Halogen-doped carbon dots on amorphous cobalt phosphide as robust electrocatalysts for overall water splitting (Adv. Energy mater. 14/2022). Adv Energy Mater. 2022;12(14):2270059.

[45] Xu W, Fan G, Zhu S, et al. Electronic structure modulation of nanoporous cobalt phosphide by carbon doping for alkaline hydrogen evolution reaction. Adv Funct Mater. 2021;31(48):2107333.

[46] Ji L, Wang J, Teng X, Meyer TJ, Chen Z. CoP nanoframes as bifunctional electrocatalysts for efficient overall water splitting. ACS Catal. 2020;10(1):412-419.

[47] Yang J, Guo DH, Zhao SL, et al. Cobalt phosphides nanocrystals encapsulated by P-doped carbon and married with P-doped graphene for overall water splitting. Small. 2019;15(10):1804546.

[48] Li Y, Zhou L, Guo S. Noble metal-free electrocatalytic materials for water splitting in alkaline electrolyte. EnergyChem. 2021;3(2):100053.

[49] Jiang E, Li J, Li X, et al. MoP-MO₂C quantum dot heterostructures uniformly hosted on a heteroatom-doped 3D porous carbon sheet network as an efficient bifunctional electrocatalyst for overall water splitting. Chem Eng J. 2022;431:133719.

[50] Kim S, Choi C, Hwang J, et al. Interaction mediator assisted synthesis of mesoporous molybdenum carbide: Mo-valence state adjustment for optimizing hydrogen evolution. ACS Nano. 2020;14(4):4988-4999.

[51] Bai H, Chen D, Ma Q, et al. Atom doping engineering of transition metal phosphides for hydrogen evolution reactions. Electrochem Energy Rev. 2022;5(suppl 2):24.

[52] Fan X, Li B, Zhu C, Yan F, Zhang X, Chen Y. Nitrogen and sulfur co-doped carbon-coated Ni₃S₂/MoO₂ nanowires as bifunctional catalysts for alkaline seawater electrolysis. Small. 2024;20(26):2309655.

[53] Song T, Zhang X, Postolek K, Yang P. N-doped carbon layer promoted charge separation/transfer in WP/g-C₃N₄ heterostructures for efficient H₂ evolution and 4-nitrophenol removal. Carbon. 2023;202:378-388.

[54] Li J, Hu Y, Huang X, Zhu Y, Wang D. Bimetallic phosphide heterostructure coupled with ultrathin carbon layer boosting overall alkaline water and seawater splitting. Small. 2023;19(20):2206533.

[55] Liu X, Chi J, Mao H, Wan L. Principles of designing electrocatalyst to boost reactivity for seawater splitting. Adv Energy Mater. 2023;13(31):2301438.

RIGHTS & PERMISSIONS

2024 The Author(s). Electron published by Harbin Institute of Technology and John Wiley & Sons Australia, Ltd.